CN1788057A - Ink jet ink composition and method for security making - Google Patents
Ink jet ink composition and method for security making Download PDFInfo
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- CN1788057A CN1788057A CN 200480012856 CN200480012856A CN1788057A CN 1788057 A CN1788057 A CN 1788057A CN 200480012856 CN200480012856 CN 200480012856 CN 200480012856 A CN200480012856 A CN 200480012856A CN 1788057 A CN1788057 A CN 1788057A
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Abstract
Disclosed is an ink composition suitable for ink jet printing comprising a luminescent compound, a solvent, and an energy active compound, and optionally a non-luminescent colorant. The energy active compound, when exposed to energy, generates one or more active species that can react with the luminescent compound to alter one or more of the characteristics of the luminescent compound. The luminescent compound can be colored or colorless. Also disclosed is a method for marking substrates comprising providing a mark comprising a luminescent compound and an energy active compound. Further disclosed is a jet ink composition suitable for printing on substrates authentication or security marks which can be rendered unreadable. The luminescence of the mark is quenched and the visible color is changed when irradiated with a light.
Description
Invention field
The present invention relates to contain the ink-jet ink composition of tinting material or luminophor and energy active compound (for example sensitive materials).The ink-jet ink composition is used in stamped mark on the matrix, and energy following time that this mark is exposed to significant quantity changes, thereby for example makes tinting material change luminous or luminophor is changed.The invention still further relates to a kind of in matrix, for example carry out the composition and the method for security printing on metal, glass and the plastics, also relate to and a kind of luminophor (for example fluorescent chemicals) on the matrix can not be read out in colour-change, and then can check the composition and the method for this variation by vision.
Background of invention
For many purposes, printing ink is used for tagged items, for example, be used for determining its verity.This mark (for example, covert indicia) for example is used in the commodity that check will be sold on niche market.These marks are used for preventing to obtain higher profit by following manner: the commodity that will estimate to sell with lower price are with more high price sale.Covert indicia is used and is required this mark not seen by people's naked eyes usually, can not duplicate again after this mark is found simultaneously at all.Usually wish that after this security feature was understood, passivation had just taken place this security feature.For many reasons, this easy and predetermined passivation of mark is given in the security system that has this mark.At first, give this mark a bells and whistles---non-reproduction.Secondly, by passivation, after this mark was finished purposes in the secure network, it can not be transferred on other article or the position.The 3rd, the information that comprises in this mark is destroyed, and undelegated department can not understand or duplicate.
Passivation with security feature may be represented a kind of situation in the some kinds of situations.This situation for example is: these article of possessor of notice article can not be sold in specialized market.The Another reason that makes mark generation passivation is after article are converted to cash, makes these article no longer have value.
Also wish mark is used in production or the distribution condition to carry out process control.For example, can in central dispense equipment, carry out taxonomy of goods by reading identification marking with very high production rate.May also wish in process of production and will come with article difference through the article of a process through another process.Another example of process control is a process monitoring.For example, as the indicator on the product sealed vessel, so just make container be different from the container of disinfecting in a kind of general process control printing ink without this through disinfecting.These methods for example can be, and steam is induced or the method for ultraviolet induction.The color of ink indicia changes usually and the vision indication is provided: article have passed through this process.This visual monitoring may need the on-line operation personnel to come the on-line monitoring product.Therefore the progress that need indicate process with the printing ink and the mark of machine-can read.
Except the component that changes machine-can read, when not needing to read, also wish estimate the component that changes and be used for some application with machine.At present available can provide the mark system of range estimation and fluorescent flag all to need two kinds of independent printing ink, and every kind of printing ink has application apparatus separately.The printing ink that people wish to design a kind of multiple purpose that can be used for---for example colour-change and variations in light---, thus coloured component and fluorescent colorant (as, dyestuff) in unitary system, had simultaneously.Also wish two kinds of dyestuffs are changed simultaneously.So just can for example adopt mark on the jetted ink printing press at the production line that uses single application apparatus.People wish single liquid and single application apparatus are used in the security system structure very much, any forgery (breech) of total system---that is, is usurped liquid to other position---all can be discerned rapidly like this.
By luminous or have color marker can change in the process of Item Value or process status, require this mark not to be read.A kind of method of finishing this purpose is to fade, burn, and perhaps other passes through to apply the method that energy destroys this mark.Traditional dyestuff or pigment need not with the energy direct reaction that is applied.And the level of response between the used energy will depend on its intrinsic stability.When temperature was lower than about 600 ℃, many organic substances can decomposes.Many matrix, promptly plastics and paper are decomposing above beginning under about 150 ℃ temperature.The source of radiation that thermal source commonly used is made up of filament, this filament need feed electric energy and just can be heated.These thermals source are slow to the response of energy requirement, and operate with half-power ready mode usually in practice, and it can more promptly operate in this way.Owing to need to continue energy in ready mode, and the radiating calorific loss can cause inefficiency, and therefore for some automation processes, these equipment of the process of for example classifying on production line are also impracticable.People need that a kind of requirement is more low-yield to come operated system.
According to background technology, people have carried out providing prevailingly the trial of safety label, referring to for example, and United States Patent (USP) 6,441,380; 6,402,986; With 5,837,042.People need a kind of method that the distinctive mark can be provided, and require this mark to produce not can read phenomenon, also need a kind of being suitable in matrix, for example the inkjet ink composition that prints on the distinctive mark.
The invention provides and be suitable for finishing one or more above-mentioned ink composites that need.To make these and other superiority of the present invention and other inventive features apparent by the description of this invention herein.
The invention summary
The present invention has satisfied above-mentioned needs to a great extent, the invention provides a kind of ink composite that is applicable to ink jet printing, and said composition comprises luminophor, solvent, energy active compound and optional not luminescence colorant.In energy following time that the energy active compound is exposed to significant quantity, can produce one or more active substances, and this active substance can react with luminophor, thereby change luminophor and/or one or more characteristics of luminophor not.This luminophor can be coloured or colorless substance for naked eyes.Ink composite also can contain not luminescence colorant.The present invention also provides a kind of ink composite that is applicable to spray ink Printing, and said composition comprises tinting material, solvent and energy active compound.Tinting material can be luminous or luminophore not.Usually, this mark is exposed under the energy of significant quantity to carry out said process.The energy of significant quantity is that reactivity by this mark and this are marked at the maximum time that can expose under the available energy and determine.
The present invention also provides a kind of and is applicable to that on matrix printing can produce the distinctive that not can read phenomenon or the inkjet ink composition of security sign.The invention provides a kind of mark, when this mark is exposed to (fluorescence or the phosphorescence) cancellation of energy its luminous of following time and the visible color also changes.The present invention also provides a kind of inkjet ink composition, it comprise luminous (as, fluorescence) first tinting material, second tinting material, solvent, adhesive resin and the sensitization of pH sensitivity are released-acid compound.The present invention also provides a kind of inkjet ink composition, and it comprises the compound of the release acid of luminous (as, fluorescence) tinting material, solvent, adhesive resin and photosensitivity.
Ink composite of the present invention also can contain one or more adhesive resins and other additive, for example wetting Agent for Printing Inks, softening agent, light blocker, tensio-active agent, wetting agent, thermo-stabilizer, sterilant, tackifier and conductive agent.
The present invention also provides a kind of method of differentiating matrix, and it comprises: (a) provide the discriminating mark with ink composite of the present invention on matrix; (b) read this discriminating mark; (c) will differentiate that mark is exposed under the energy of significant quantity,, thereby obtain discriminating mark after energy-exposure with generation and luminophor and/or the material that reacts of luminescence colorant not; (d) read discriminating mark after this energy-exposure.The present invention also provides a kind of method of mark matrix, it comprises: a kind of mark that comprises luminophor and energy active compound is provided, wherein said energy active compound is exposed to the material that energy following time produces one or more and luminophor reaction, thereby changes the absorption and/or the emission characteristic of luminophor.According to the present invention, when reactive materials reacts and when changing the characteristics of luminescence of luminophor, it can destroy this compound, change the chemistry or the electronic environment of compound, for example, this compound can be transformed into protonated form.
The present invention also provides a kind of safety label with changeable colour to come the method for mark matrix, wherein said colour-change can test out, this method comprises: a kind of mark is provided, its contain macroscopic not luminous (for example, non-blooming) tinting material and fluorescent colorant, wherein said fluorescent colorant only just can produce the emission of luminous (fluorescence) when being subjected to the rayed of first wavelength, thereby become macroscopic material, use this mark of rayed of second wavelength to launch then with this luminous of cancellation (fluorescence), and the color of this (not luminous) tinting material is changed, thereby provide a kind of visual manner to verify that this luminous (fluorescence) emission is by the method for cancellation.The present invention also provides a kind of system that is used to differentiate matrix, and it comprises: (a) ink composite of the present invention; (b) ink-jet printer; (c) matrix; (d) energy, for example, the passivation energy; (e) reading device.
By the description that provides, can make above-mentioned and other advantage of the present invention, and other inventive features becomes apparent herein to the invention preferred embodiment.
The accompanying drawing summary
Fig. 1 describes according to embodiment of the present invention, the reactive materials that the energy active compound is generated and luminophor (for example, luminescence colorant) or the luminescence colorant various reactions or the effect of not having an effect and then can produce, P
1* be exposed to the material of the energy generation of following time of significant quantity for the energy active compound.(I) various reactions or the effect of representing reactive materials and luminophor A to carry out.(II) the various reactions of representing reactive materials and luminescence colorant B not to carry out.(III) representative exists luminophor and not issuable other reaction or effect during luminescence colorant simultaneously in mark.
Fig. 2 illustrates one embodiment of the invention, and this embodiment comprises luminophor and luminescence colorant not, and the wherein observed luminous characteristic variations of luminescence colorant that is subjected to is not controlled, or according to the characteristic variations of luminescence colorant not and change.The wavelength that the representative of x-axle absorbs or launches.The intensity that the representative of y-axle absorbs or launches.A and B represent the absorption and the emmission spectrum of luminophor respectively, and C represents the not absorption spectrum of luminescence colorant.When the reactive materials that is derived from the energy active compound when luminescence colorant does not react, the position of C can be changed to the upper wavelength place, like this, the absorption after the change will be consistent with B or overlapping.Alternatively, the position changeableization of C is to low wavelength place, and like this, the absorption after the change will be consistent with A or overlapping.The variation of the position of C is come out by the direction indication of arrow.According to embodiment of the present invention, the position of C (during beginning) can be at any wavelength place, for example, and less than A, greater than the wavelength place between B or A and the B.
Detailed Description Of The Invention
A kind of ink composite that is applicable to ink jet printing is provided in one embodiment of the invention, and it comprises luminophor, solvent and energy active compound. In energy lower time that this energy active compound is exposed to effective dose, can produce one or more active materials, and this active material can react with luminophor, thereby changes its a kind of or multifrequency nature. This luminophor can be coloured or colourless substance. In addition, this ink composite also can contain not luminescence colorant. In another embodiment, the invention provides a kind of ink composite that is applicable to ink jet printing, it comprises colouring agent, solvent and energy active compound. In energy lower time that this energy active compound is exposed to effective dose, can produce one or more active materials, and this active material can react with colouring agent in mark, thereby changes its a kind of or multifrequency nature. This colouring agent can be luminous or luminescent substance not.
When this energy active compound is exposed to lower time of energy of effective dose, it produces one or more materials, and this material reacts and then changes colouring agent and/or luminophor (for example luminescence colorant) and/or the feature of luminescence colorant not. Some contingent various reactions or effects have been described in signal among Fig. 1. For example, this reaction changes one or more characteristics or the character of colouring agent or luminophor, for example absorbs and/or emission characteristics. For example, in one embodiment, this reaction has changed absorbing wavelength. This reaction can change wavelength under the maximum intensity or the wavelength under the mean intensity. In one embodiment, this reaction can change emissive porwer or emission lifetime. When it changed emission wavelength, it can change the wavelength under the maximum emission intensity, perhaps changes the wavelength under the average emitted intensity. Emissive porwer is increased or reduce. When this reaction changes emission lifetime, emission lifetime is increased or minimizing. In one embodiment, this reaction changes the not Absorption Characteristics of luminescence colorant, for example, and absorbing wavelength or absorption intensity.
In a specific embodiments, reaction can change the absorption characteristic of luminescence colorant and the absorption characteristic of luminescence colorant not; In some embodiments, reaction can change the emission characteristics of luminescence colorant and the emission characteristics of luminescence colorant not. For example, this reaction can change the emissive porwer of luminescence colorant, perhaps changes the not absorbing wavelength of luminescence colorant. This reaction can change the not absorption intensity of luminescence colorant. This reaction can change the emission lifetime of luminescence colorant. This reaction can change the absorbing wavelength of luminescence colorant not or the absorption intensity of luminescence colorant not. If luminescence colorant and not luminescence colorant be present in simultaneously in the mark, then the change of luminescence colorant absorption characteristic also can not exert an influence to absorption or the emission characteristics of luminescence colorant. Can produce simultaneously luminous cancellation or luminous variation phenomenon, and one or more photochemistries can occur individually or simultaneously. Luminous and coloured component of the present invention can be same substance.
Following description is provided, and with it as definition. Luminously refer to any material owing to the excitation energy that absorbs photon, charged particle or chemical change form is launched visible or invisible radiation, but be not attended by high temperataure phenomena, the luminous fluorescence and phosphorescence that comprises. From energy point of view, fluorescence phenomenon is defined as the photon release phenomenon that electronics produces when the lowest vibration pattern of single line molecular-excited state transits to single line molecule ground state. According to the Laporte selection rule, transition is the phenomenon that produces relatively easily, and it can very rapidly occur after electron excitation. Therefore, excite and launch between the time interval---namely, decay time---very short, be generally 10-9-10
-7Second. When the transition in the phosphorescent glow is by three line molecular-excited states during to singlet, this phosphorescent glow can not be accepted by the Laporte rule, so phosphorescent glow is characterised in that and excites and the time interval between the emission is 10 again-5-10
1Second, but many hours phosphorescent glow of experience also is common for inorganic compound. Luminescence colorant of the present invention or compound can show fluorescence phenomenon or phosphorescent glow. Preferably, when using phosphorescent compound, it can produce luminescence phenomenon with rational quantum yield (that is,＞0.1) under 40 ℃ room temperature. More preferably, when using phosphorescent compound, decay time is between 10-5-10
-2Between second. According to the present invention, term " colouring agent " refers to have any material of following characteristics: it is visible coloured or leuco-compounds, and its react or change after can become coloring matter.
Expand according to well-known McLaren, the fluorescent emission phenomenon (F) of the dilution fluorescent material that is recorded by spectrum relates to several parameters: F=K ε bcI, and wherein ε is molar absorption coefficient (extinction coefficient); is quantum efficiency; B is path; The constant of K for considering that all residue (supposing that it is what fix) equipment factors are established. This relational expression only has and could set up very rare fluorogen solution, and under higher concentration because several impact and untenable; For example, especially sample to the self-absorption phenomenon of fluorescent emission. is the ratio of utilizing emitted light quantum count and absorption optical quantum count, and it rule of thumb comes to determine usually. For being considered to epipolic most of molecule, is between 0.2-0.9. Quenching phenomenon can occur when decaying to ground state in (that is, non-phosphorescent intermediate state cross, intermolecular resonance energy transfer etc.) through non-radiative path when the excitation state electronics. Many common environment molecules can impel (comprising water and oxygen) generation of fluorescent quenching phenomenon. It should be understood that the present invention can adopt any mechanism in many known mechanism to operate, use so that fluorescence intensity weakens the degree to hope. Some fluorescence molecules are very responsive to pH. An one example is exactly fluorescein, and when its pH dropped to 7 from 9, quantum efficiency reduced by 0.2. McLaren expands and also can be used for phosphorescent compound as defined above, but decay time relatively lack (as, greater than 10-2Second). In the Electron Relaxation process, the solvable phosphorescence that decay time is long is known from experience the extensive impact that is subject to the intramolecule process.
The invention provides method and inkjet ink composition, it is by reacting with energy (for example, light) and making fluorescence labeling that reversible passivation occur. The present invention also will provide dyestuff (coloured or colourless) mixed provides visible indication in the prescription, can not be read (hereinafter being called cancellation) in order to represent this mark; Perhaps, it can affect with predictable, machine-readable form the photoluminescent property of mark.
According to an embodiment, the invention provides a kind of method and a kind of composition, it can make luminous (fluorescence) mark not be read, and also produces the colour-change that can discern by vision simultaneously.The method of this passivation security feature for example is that completely destroy falls this feature.Under the situation of luminous chemical dye or pigment, this may need to change or destroy the chemical ingredients that causes luminous effect.Therefore, thus being used to make the method for earth complex luminescent component passivation should be that initiating chamical reaction changes earth complex luminescent component or is decomposed into not luminous composition.Can comprise the use tinting material with the method for this variation of visual identification, and this tinting material carries out the visible colour-change being similar to make under the unreadable condition of luminescent marking.The method that realizes this process comprises comes in the colorant combination of outward appearance generation visual change under the described conditions.It can be dyestuff or pigment form, and can comprise in conjunction with any colour-change: a kind of color fade to distinct colors, colourless fade to coloured, or coloured fade to colourless.
If intention certain time after the date manufactured is used this printing ink, then require its component reasonably can keep stable in the time limit.If chien shih solid mark changes during after printing certain, then a kind of mode is that the potential reactive component is bonded in this mark, and energy apply this reactive component when this mark can be activated by selectivity.Can define energy according to radiation (electromagnetism) energy, it comprises all energy that limited by electromagnetic spectrum usually.Radiating capacity uses radiant flux density (unit is for joule/second square metre or be equivalent to watt/square metre) to describe usually, and it is to be applied to measuring of energy usage on the plane surface in the unit time.The Planck equation formula connects the photon of radiating capacity with the discontinuous energy of expression.Based on this relation, radiation flux can further be defined by certain wavelengths.
A kind of method that energy is applied on the mark matrix is the quantity of radiant energy that applies the UV-light form.Uv-radiation can be compared with the radiating capacity of other longer wavelength has some advantages.For example, some matrix, for example low melting point plastic can not stand the effect of infrared (heat) energy.Uv-radiation can typically refer to UVB or UVC radiation (about 200-350nm), and this ultraviolet ray can be effective especially.Chemical compound lot can be not destroyed after absorbing this regional energy; But, known specific light-sensitive compound absorb behind the described energy degradation rapidly and with medium in exist other more stable molecule react.Because this compound has reactivity to radiating capacity, therefore can select these compounds.In some applications, people wish to have the enhanced reactivity for the energy of given radiation power, and may wish to select the energy to given radiation power to have relatively poor reactive compound in some applications.
In order to improve the reactivity of mark of the present invention to the radiating capacity in the particular wavelength region, a kind of method commonly used is to select suitable light-sensitive compound.The selection of light-sensitive compound can be based on it to the intrinsic chemical reactivity of incident radiation energy and existing the going and finding out what's going on that distributes according to the spectral energy to source of radiation.For example, the known energy active compound of two classes is diaryl group iodized salt and triarylsulfonium salt.It is believed that diaryl group iodized salt is more stable than triarylsulfonium salt under the radiating capacity effect, and it can produce bigger free acid concentration under radiation.But, find that when similar sulfonium salt is compared reactivity mainly is controlled by the molar absorptivity of incident radiation power and this salt.For example, for mainly give off greater than the UV of 300nm can the conventional high-tension mercury vapor arc lamps, ((very a spot of specific absorbance＞320nm) activity is littler than the mixing triarylsulfonium salt of equivalent for very a spot of specific absorbance＞300nm) for the triphenyl sulfonium salt.For further improve salt pair than low-energy light (＞320nm) reactivity can be used known photosensitizers, for example, anthraquinone or tonka bean camphor.
The another kind of method that is used to improve described labeled reactant is, a kind of energy source is provided, and it can transmit bigger radiant flux density in light-sensitive compound has the wavelength region may of strong absorption.For example, in the 300-400nm zone that portable low pressure mercury lamp (Spectroline ENF-260C) produces, the average flux density of transmission is 1 watt of/square centimeter order of magnitude.Electrodeless high voltage mercury lamp (for example, 300 watts of/inch ultraviolet curing unit that produced by fusion system (Fusion System)) can transmit with the radiant flux density that exceeds two or three orders of magnitude.Therefore, can estimate mainly have the energy active compound of absorption to react with back one energy according to different gamma flux density people with the faster speed that exceeds one or two order of magnitude in the 300-400nm wavelength region may.
The energy active compound can be exposed under the energy of any appropriate form.For example, energy may be the radiating capacity of visible light (400-700nm), UV, heat, IR (700-100000nm), X-ray, gamma-radiation, electron beam or its any combination.Optimized light source comprises following light source among the present invention: the most of active input of its emission can be uv-radiation.More preferably mainly launch UVB (280-315nm) or UVC (100-280nm) radiation and need not to launch UVA (315-400nm) radiating light source.Certainly, the present invention also allows to react with the light of any energy, and it comprises nearly UV, visible or infrared light.The example of UV light source includes but not limited to: excimer laser; Low pressure mercury lamp; High pressure (belt electrode or not electroded) mercury lamp; Ultrahigh pressure mercury lamp; High pressure xenon-mercury lamp; High pressure xenon lamp; Low-pressure sodium lamp; High-pressure mercury lamp; LED; Daylight; Diode laser; Low-pressure gaseous discharge lamp; With the swirl stabilization plasma lamp.As seen with the example of IR light emitter except that comprising those radiators that are listed as above, also have following radiator: black matrix light source, for example continuous wave halogen lamp; The halogen photoflash lamp; CO
2Laser apparatus; Incandescent light; Halogen incandescent lamp; With the fluorescent tube bulb.
Other suitable energy includes but not limited to those energy commonly used in the sterilizing process: promptly, and γ, X-ray or high-power electron beam.With regard to the electromagnetic spectrum energy of these light sources, it is normally defined wavelength all energy (that is, less than 10nm) less than UV energy wavelength.More commonly use the energy of electron-volt (eV) expression single particle.Suitably the eV of the energy is 100eV (X-ray)-greater than any value of 1MeV (gamma-radiation).The typical particle energy that obtains in the electron-beam sterilization system is between 80keV-12MeV.
Mark based on these compounds is heated the degradation or the cancellation that can cause luminous composition.Other energy also can be used to activate the component of this prescription.These energy include but not limited to electron beam and high energy excimer laser.
In one embodiment, the invention provides a kind of method and a kind of composition, it can make luminous (fluorescence or phosphorescence) mark not be read, and colour-change also takes place simultaneously, and this colour-change can be discerned by vision.More particularly the invention provides a kind of preparation and a kind of method, it relates to the photoinduction cancellation of using said preparation to promote fluorescence or phosphorescence reagent, also promotes the photoinduction of color to change simultaneously.
In one embodiment, the energy active compound is exposed to the material that the energy of significant quantity produced down and comprises acid.In another embodiment, this material comprises group.Energy active compound according to the present invention is a salt, and for example, this salt comprises the element that is selected from periodic table of elements V, VI or VII family.
In a specific embodiments, this salt is selected from the group of being made up of following material: diazonium salt, salt compounded of iodine, sulfonium salt, selenium salt, ammonium salt, oxidation sulfonium salt, haloid, phosphonium salt, arsenic salt and arbitrary combination thereof.
In specific embodiment, this energy active compound is selected from the group of being made up of following material: thiophene salt, silver salt, poly-borate metal salt, ferrocene salt, thiapyran salt, uranyl compound or salt, thallium salt and arbitrary combination thereof.In another embodiment, this energy active compound is selected from the group that following material is formed: sulfonation imide, diazomethane compound, triaizine compounds or derivatives thereof, sulfonated ester, two sulfones, sulfonation nitride, oxo sulfosalt, nitrosamine and halogenated compound, and arbitrary combination.In one embodiment, this energy active compound is selected from the group of being made up of following material: arone, quinone, transition metal complex, metal carbonyl complex, phosphine oxide, superoxide, S
xO
ySalt is wherein worked as x=1, then y=3,4 or 5; Work as x=2, then y=3,4,5,6,7 or 8; As x=n+2 (n＞0), then y=6, and arbitrary combination.
Can use any suitable energy active compound that produces reactive materials.Be suitable for energy active compound used in this invention, for example light-sensitive compound comprises those absorb light or heat and the material that reacts by the generation free acid.Can carry out in the following manner by the process that produces free acid with light or thermal response: uses various can acting on become charged (ion) and not charged (nonionic) compound through organising, and can further organise become some kinds more specifically the compound of group carry out.
Be not the constraint of wishing to accept opinion or mechanism, but it is believed that under the situation of ionic acid generation body homolysis can cause producing short-life group that it extracts proton from other molecule that exists rapidly.Proton is transferred to rapidly in the anionic component of compound in quick Decomposition, thereby obtains metastable strong acid material.This material continues the reaction process that participation is caused by acid.Body takes place and all is made up of the strongly-acid leavings group that is connected on the carbon atom in most of nonionic acid.Photoinitiation causes going up generation protonation at certain point (for example, carbon atom) of molecule usually, intermolecular reorganization takes place rapidly subsequently, thereby produce reactive strong acid.Be noted that importantly that in any one mechanism as long as there is proton-accept part, then the energy active compound just all is consumed in and produces in the reactive materials.The example of preferred charging cpd is set forth below.
Table 1. diazonium salt
| Example | Reference or source |
| NITRODIAZONIUM FLUOROBORATE | 251 pages of Pappas* |
| The perchloric acid diazonium salt | 251 pages of Pappas |
| The perfluorocarboxylic acid diazonium salt | 251 pages of Pappas |
| The hexafluorophosphoric acid diazonium salt | 251 pages of Pappas |
| The phospho-wolframic acid diazonium salt | 251 pages of Pappas |
| The phospho-molybdic acid diazonium salt | 251 pages of Pappas |
| Tungsten germanic acid diazonium salt | 251 pages of Pappas |
| The tungstosilicic acid diazonium salt | 251 pages of Pappas |
| The molybdenum silicic acid diazonium salt | 251 pages of Pappas |
| The thiazole derivative diazonium salt | CGI 1397-CGI 1311 |
Pappas*，S.Peter，ed.UV Curing：Science and Technology。The II volume; 1985, Technology Marketing Corporation, Norwalk CT.
Table 2. salt compounded of iodine
| Example | The source |
| Two (4-tert-butyl-phenyl) iodine tosilate | Aldrich |
| Phenylbenzene iodo-9,10-dimethoxy anthracene-2-sulfonate | Aldrich |
| Diphenyl iodine hexafluorophosphate | Aldrich |
| Phenylbenzene iodine fluoroform sulphonate | Aldrich |
| Two (4-tert-butyl-phenyl) iodine perfluor-1-fourth sulfonate | Aldrich |
| Phenylbenzene iodine tosilate | Aldrich |
| Phenylbenzene iodine nitrate | Aldrich |
| Two (4-tert-butyl-phenyl) iodine fluoroform sulphonate | Aldrich |
| Phenylbenzene iodine perfluor-1-fourth sulfonate | Aldrich |
| (4-aminomethyl phenyl) [4-(2-methyl-propyl) phenyl] iodine hexafluorophosphate | CGI552 a |
| [4-[(2-hydroxyl tetradecyl) oxo] phenyl] the phenyl-iodide hexafluorophosphate | PC-2508 b |
| Mixed diaryl iodine hexafluoro antimonate | PC-2506 b |
aCiba Specialty Chemicals
bPolyset Company，Mecahnicville，NY
Table 3. sulfonium salt
| Example | The source |
| (4-Phenoxyphenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-methyl thio-phenyl) aminomethyl phenyl sulfonium fluoroform sulphonate | Aldrich |
| (4-chloro-phenyl-) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| 2-naphthyl phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (tert-butoxycarbonyl methoxyl group naphthyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| Thiobis (triphenylsulfonium hexafluorophosphate) solution | Aldrich |
| (4-p-methoxy-phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-tert-butyl-phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| The triphenylsulfonium fluoroform sulphonate | Aldrich |
| (4-fluorophenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-aminomethyl phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-fluorophenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-iodine substituted phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (tert-butoxycarbonyl p-methoxy-phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-phenyl thio-phenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| (4-bromophenyl) phenylbenzene sulfonium fluoroform sulphonate | Aldrich |
| Triphenylsulfonium perfluor-1-fourth sulfonate | Aldrich |
| Three (4-tert-butyl-phenyl) sulfonium fluoroform sulphonate | Aldrich |
| Three (4-tert-butyl-phenyl) sulfonium perfluor-1-fourth sulfonate | Aldrich |
| Dimethyl (4-naphthols) sulfonium fluoroform sulphonate | UR-1106 b |
| Dimethyl (4, the 7-dihydroxy naphthlene) sulfonium fluoroform sulphonate | UR-1107 b |
| Dimethyl (4, the 7-dihydroxy naphthlene) sulfonium 10-camsilate | UR-1113 b |
| Dimethyl (4, the 7-dihydroxy naphthlene) sulfonium nine fluorine fourth sulfonate | UR-1114 b |
| Dimethyl (4, the 7-dihydroxy naphthlene) sulfonium is to toluic acid hydrochloric acid | UR-1115 b |
| Dialkyl phenyl organic acyl group sulfonium salt | Pappas |
| The blended triarylsulfonium salt; Hexafluorophosphate | UVI-6976 a |
| The blended triarylsulfonium salt; Hexafluoro antimonate | UVI-6992 a |
aDow Chemical
bMidori Kogaku Inc.，Ltd.
Other useful salt of table 4.
| Group | Example |
| Selenium oxide salt | |
| Selenium salt | |
| Quaternary ammonium salt | |
| The oxidation sulfonium salt | |
| Haloid | |
| Quaternary alkylphosphonium salt | The tetraphenylphosphoniphenolate bromide |
| Season arsenic salt | Tetraphenyl arsenic bromide |
By showing the combination that negatively charged ion listed among the 1-4 and positively charged ion can form many salt.According to traditional way this salt being named, is the space after the cationic moiety, is anionicsite then.Other unlisted negatively charged ion also can use, and it includes but not limited to: halide complex negatively charged ion of element sb, Sn, Fe, Bi, Al, Ga, In, Ti, Zr, Sc, D, Cr, Hf, Cu, B, P and As and composition thereof; The tetraphenyl borate; Fluorinated sulfonate (that is, trifluoromethanesulfonic acid root, nine fluosulfonic acid roots (nonaflate) etc.) with various carbon chain lengths; Sulfonate radical with various alkyl carbon chain length (that is, butyl, octyl group etc.); With the camphorsulfonic acid root.Operable other various salt among the present invention have been provided below.
Other various salt of table 5.
| Group | Example | Source, title or reference |
| Thiophene salt | S-(2-naphthalene carbonyl methyl) tetramethylene sulfide tosilate | UR-1116 a |
| S-(2-naphthalene carbonyl methyl) tetramethylene sulfide fluoroform sulphonate | UR-1115 a | |
| Silver salt | Halogenation boron polyhedron | 251 pages of Papps |
| Fluorinated alkyl sulfonate | 251 pages of Papps | |
| Poly-borate metal salt | Metal halide | 251 pages of Papps |
| Aromatic halide | 251 pages of Papps | |
| Ferrocene salt | Ferrocene and TiCl 4 | 251 pages of Papps |
| Cumene (cyclopentadiene) closes iron (II) hexafluorophosphate | Aldrich 40，807-7 | |
| Thiapyran salt | 251 pages of Papps | |
| Uranyl compound | Uranyl nitrate | 251 pages of Papps |
| Thallium salt | Fluorinated alkyl sulfonate | 251 pages of Papps |
aAvailable from Midori Kagaku Co., Ltd.
In specific embodiment, salt is selected from the group that is made of following material: diazonium salt, the salt with at least one aryl, the sulfonium salt with at least one aryl and arbitrary combination thereof.The salt that comprises sulphur and iodine by the preferred light-sensitive compound of acidic diazonium salt, salt or the generation of other salt.In these salt, especially effectively as UVI-6976 and UVI-6992 (DowChemical) and the mixing aryl sulfonium salt that is commercially available.Other preferred salt comprises diaryl group iodized salt CGI552 (Ciba Specialty Chemicals) and PC-2506 and PC-2508 (Polyset Company).These salt pair radiating capacity demonstrate very high reactive behavior.
Nonionic energy active (acidic photosensitive) compound also is applicable to the present invention.The example that photoinduced acid generates compound is sulfonation imide, diazomethane compound, triazine, sulphonate and two sulfones.Provided the example of these compounds below.
Table 6. sulfonation imide
| Example | The source |
| N-hydroxyl naphthalimide fluoroform sulphonate | Aldrich#53108-1 |
| N-hydroxyl-5-norbornylene-2, the 3-dicarboximide | Aldrich#53108-1；NKI 101-NDI-109 a |
| N-hydroxyl naphthalimide fluoroform sulphonate | Aldrich |
| Naphthalimide sulfonate | NAI-100，105，106，109 a |
| Succimide base sulfonate | SI-101，105，106，109 a |
aAvailable from Midori Kagaku Co., Ltd.
Table 7. diazomethane
| Example | The source |
| Two (cyclohexyl alkylsulfonyl) diazomethane | UR-1200 a |
| Two (benzenesulfonyl) diazomethane | UR-1201 a |
| Two (2,4-dimethyl benzene alkylsulfonyl) diazomethane | UR-1202 a |
| Two (4-chlorobenzene alkylsulfonyl) diazomethane | UR-1203 a |
| Two (4-anisole alkylsulfonyl) diazomethane | UR-1204 a |
aAvailable from Midori Kagaku Co., Ltd.
Table 8. pyrrolotriazine derivatives
| Example | The source |
| 2-(4-methoxyl-styrene)-4, two (the trichloromethyl)-1,3,5-triazines of 6- | Aldrich#530964 |
| Three [trichloromethyl] s-triazine | TAZ-101 a |
| P-methoxyphenyl [two (trichloromethyl)]-triazine | TAZ-104 a |
| 2,4,6-three (2,4, the 6-tribromophenoxy)-1,3,5-triazines | Dead Sea Bromine Group |
aAvailable from Midori Kagaku Co., Ltd.
Table 9. miscellaneous sulphonate
| Example | Reference and source |
| 2,1, the 4-diazonium naphthoquinone sulphonate | United States Patent (USP) 5,827,634 |
| 2,1, the 5-diazonium naphthoquinone sulphonate | United States Patent (USP) 5,827,634 |
| Sulfonyloxy ketone | United States Patent (USP) 5,827,634 |
| The st-yrax tosylate | United States Patent (USP) 5,827,634 |
| Tert-butyl-phenyl α-(tolysulfonyl oxygen base) acetic ester | United States Patent (USP) 5,827,634 |
| Tertiary butyl α-(tolysulfonyl oxygen base) acetic ester | United States Patent (USP) 5,827,634 |
| Sulfonation nitride derivative | CGI26x family; PAI-101,106,1001 a |
| 4-bromine 2,6-dimethyl benzene sulfocarbolate | United States Patent (USP) 5,827,634 |
| [1,2,3-front three sulfonate group] benzene | PYR-100 b |
aCiba Specialty Chemicals
bAvailable from Midori Kagaku Co., Ltd.
Table 10. halogenated compound
| Example | Reference or source or CAS# |
| 1,1 ,-two [rubigan]-2,2,2-trichloroethane | United States Patent (USP) 5,827,634 |
| 1,1 ,-two [p-methoxyphenyl]-2,2,2-trichloroethane | United States Patent (USP) 5,827,634 |
| 4,4-two chloro-2-(trichloromethyl) diphenyl-carbinols | United States Patent (USP) 5,827,634 |
| 2-chloro-6-(trichloromethyl) pyridine | United States Patent (USP) 5,827,634 |
| The chlordene dimethyl sulfone | United States Patent (USP) 5,827,634 |
| O, O-diethyl-O-(3,5, the 6-trichloro-2-pyridyl) phosphorus thiosulfates | United States Patent (USP) 5,827,634 |
| 1,2,3,4,5, the 6-HEXACHLOROBUTADIENE | United States Patent (USP) 5,827,634 |
| N-(1,1 ,-two [rubigan]-2,2,2-three chloroethyls) ethanamide | United States Patent (USP) 5,827,634 |
| 2, two [the rubigan]-vinylidene chlorides of 2- | United States Patent (USP) 5,827,634 |
| Chloroform | Aldrich |
| 1,2,5,6,9, the 10-hexabromocyclododecane | United States Patent (USP) 5,827,634 |
| 1, the 10-dibromo-decane | United States Patent (USP) 5,827,634 |
| Three [2, the 3-dibromopropyl] isocyanuric acid ester | United States Patent (USP) 5,827,634 |
| Iodoform | Aldrich |
| Bromofom | Aldrich |
| Tribromo-ethanol | Aldrich |
| 2,3-two bromopropionitriles | Aldrich |
| 1, the 2-dibromo-cyclohexane | Aldrich |
| The hot amyl group alcohol of tribromo | Dead Sea Bromine Group |
| PF 5070 | Aldrich |
| Monobromomethane | |
| Methylene bromide | |
| Bromochloromethane |
| Ethylene dibromide | |
| N-amyl bromide | |
| Bromine acetic acid benzyl ester | |
| Monobromo-acetic acid | |
| Bromo ethanoyl bromine | |
| 2-bromo butyric acid | |
| Allyl bromide 98 | |
| 3-bromo-3-butene-1-alcohol | |
| 1-bromo-3-chloropropane | |
| The 2-bromo acid | |
| The 3-bromo acid | |
| 5-bromo valeric acid | |
| Instead-bromostyrene | |
| N-butyl bromide | |
| The hexadecyl bromine | |
| The cetyl pyridinium bromide | |
| Cyclopropyl Bromide | |
| Ring-propyl group monobromomethane | |
| 1, the 4-dibromobutane | |
| 1, the 3-dibromopropane | |
| 2,3-dibromo third-1-alcohol | |
| Monobromethane | |
| The bromo acetic acid ethyl ester | |
| The n-hexyl bromine | |
| Isobutyl bromide | [78-77-3] |
| N-octyl bromide | [75-26-3] |
| Isopropyl bromide | [75-26-3] |
| N-octyl bromide | [111-83-1] |
| Positive propyl bromo | [106-94-5] |
| 1,1,2, the 2-tetrabromoethane | [79-27-6] |
| Vinyl bromide |
| Bromobenzene | |
| 4-bromobenzene acetonitrile | |
| Bromo-2,4 difluorobenzene | |
| 2,4, the 6-bromamide | |
| 2,4, the 6-tribromophenol | |
| Bromamine acid, 1-amino-4-bromine anthracene-2-sulfonic acid | |
| Two-(2-ethylhexyl tetrabromo-phthalate) | [26040-51-7] |
| Two (methyl) tetrabromo-phthalate | [55481-60-2] |
| Two (tribromophenoxy) ethane | [37853-59-1] |
| Bromination trimethylphenyl indane | [155613-93-7] |
| Decabromodiphenyl | [13654-09-6] |
| Decabromodiphynly oxide | [1163-19-5] |
| Decabrominated dipheny base ethane | [137563-36-1] |
| Two bromotrifluoromethane dibromo-cyclohexanes | [3322-93-8] |
| Ethylenebis bromo norcamphane dicarboximide | [52907-07-0] |
| Ethylenebis (tetrabromo-phthalic imide) | [32588-76-4] |
| Octabromodiphenyl ether | [32536-52-0] |
| Pentabromotoluene | [87-83-2] |
| Tetrabromo-bisphenol two (2,3-dibromo propyl ether) | |
| Tetrabromo-bisphenol | |
| Ten tetrabromos, two phenoxy group benzene | |
| Three-dibromopropyl isocyanuric acid ester | |
| The low molecular weight brominated polystyrene | CAS[88497-56-7] |
| Brominated Polystyrene | CAS[88497-56-1] |
| Poly-(the inferior phenylate of dibromo) | CAS[26023-27-8] |
| Poly-(vinylformic acid pentabromobenzyl ester) | CAS[59447-55-1] |
| Poly-(Dowspray 9) | CAS[62354-98-7] |
| The tetrabromobisphenol A carbonic ester oligopolymer, the tribromophenoxy end-blocking | CAS[71342-77-3] |
| Dibromoneopentyl glycol | [3296-90-0] |
| Vinylformic acid pentabromobenzyl ester | [59447-55-1] |
| The pentabromobenzyl bromine | [38521-51-6] |
| Tetrabromo-bisphenol | [79-94-7] |
| Tetrabromo-bisphenol two (allyl ethers) | |
| Tetrabromo-bisphenol two (2-hydroxyethyl ether) | |
| Tetrabromophthalic anhydride | [632-79-1] |
| The tetrabromophthalic anhydride glycol | [7709807-8] |
| The tribromo phenyl maleimide | [59789-51-4] |
| 2,4, the 6-tribromophenol | [118-79-6] |
| Decabromodiphynly oxide | Albemarle，Inc. |
| Tetrabromo two phenoxy group benzene | |
| Ethane-1,2-two (penta-bromophenyl) | |
| Ethene is two-the tetrabromo-phthalic imide | |
| Three-tribromo phenyl triazine | Dead Sea Bromine Group |
Table 11. miscellaneous is charging cpd not
| Group | Example | Reference or source |
| Metal carbonyl complex | Ten manganese carbonyls | 251 pages of Pappas |
| Three carbonyl cyclopentadiene manganese | 251 pages of Pappas | |
| Nitrosamine | Unsaturated nitrosamine | 251 pages of Pappas |
| Two sulfones | Phenylbenzene two sulfones | DS-100 a |
| Amino two sulfones of dimethylbenzene | DS-100 a |
aAvailable from Midori Kagaku Co., Ltd.
In another embodiment, the energy active compound is selected from the group of being made up of following material: the diazomethane compound, have MX on one or more positions of 2,4 and/or 6 of triazine ring
3Substituent pyrrolotriazine derivatives, wherein X is a halogen atom, M is a carbon atom, and arbitrary combination.Preferred example be three [trichloromethyl] s-triazine (TAZ-101, MidoriKogaku).
The compound that generates photosensitive acid is those materials that demonstrate hyperergy, and the material that preferably has good thermostability in printing ink.According to an embodiment, the energy active compound comprises photoabsorption segment and the sulfonic acid group, toluenesulphonic acids group or the trifluoromethanesulfonic acid group that are connected thereon, for example, this energy active compound is selected from the group of being made up of following material: N-hydroxyl naphthalimide fluoroform sulphonate, N-hydroxyl-5-norbornylene-2,3-dicarboximide sulfonate, N-hydroxyphthalimide fluoroform sulphonate, naphthalimido sulfonate, succimide sulfonate and st-yrax tosylate and arbitrary combination thereof.The example of this compound is succimide sulphonate SI-105 (Midori Kogaku), diazomethane Compound D AM-301 (Midori Kogaku), sulfonation nitride CGI263 (CibaSpecialty chemicals), and above mentioned three [trichloromethyl] s-triazine.
According to a specific embodiments of the present invention, the energy active compound is a thiophene salt, and for example, aryl alkyl carbonyl thiophene salt is as S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide tosilate and S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide fluoroform sulphonate.
An example that produces the light-sensitive compound of halogenated acid is a halohydrocarbon, it comprises (1) at least two carbon atom of being appointed as carbon 1 and carbon 2, wherein carbon 1 and carbon 2 are bonded together, and have two halogen atom Direct Bonding at least on carbon 1, and carbon 2 Direct Bonding are on another group, this group for example is an electron-withdrawing group, as cyano group, hydroxyl, fluorine, chlorine, bromine, iodine, phosphonate radical or sulfonate radical; Perhaps (2) at least three carbon atoms that connect successively, described carbon atom is designated as 1,2 and 3, and wherein at least one halogen atom is bonded on the carbon 1, and at least one halogen atom is bonded on the adjacent carbon 2.First type example is a tribromo-ethanol.Second type example is 1, the 2-dibromo-cyclohexane.
According to another embodiment, the energy active compound is selected from the group of being made up of following material: 1,2; 5,6,9; 10-hexabromocyclododecane, tribromo-ethanol, 1; 2-dibromo-cyclohexane, 2,3-two bromopropionitriles, bromo acetic acid benzyl ester, bromo acetic acid, bromo ethanoyl bromine, 2-bromo butyric acid, 2-bromo acid, 2,3-two bromos third-1-alcohol, bromo acetic acid ethyl ester and 1; 1; 2,2-tetrabromoethane, and arbitrary combination.
In another embodiment, the energy active compound is selected from the group of being made up of following material: benzophenone, anthraquinone, dibenzoyl, benzoin ether, Alpha-hydroxy-α, α-dialkyl benzene ethyl ketone and dibasic aromatic series phosphine oxide, and arbitrary combination.For example, the fragrant family of di-substituted aryl phosphine oxide can be two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, phenylbenzene (2,4, the 6-trimethylbenzoyl)-phosphine oxide or its combination.
In addition, it is also in the present invention available to produce the energy or the light-sensitive compound of other type reaction material.For example, light trigger can be used for producing chemical transformation, and this variation can make fluorescence or phosphorescence produce loss and color is changed.Especially, free radical photo-initiation absorbs luminous energy and produces reactive free radical material.For example, known in the art in benzoin ether, uniform bond cleavage takes place in the C-C between phenyl, ketone and the phenylate group, thereby forms two free radical materials.Equally, at Alpha-hydroxy-α, in α-dialkyl benzene ethyl ketone, the C-C generation homolysis between the alkyl of phenyl ketone and hydroxyl-replacement.With the reaction process of medium in, initial energy active compound is destroyed usually to be fallen.
The example of free radical photo-initiation comprises phenyl ketone, for example benzophenone, methyl phenyl ketone and derivative thereof, and all these materials all have the phenyl ketone group; Dibenzoyl; St-yrax; Benzoin ether; Alpha-hydroxy-α, α-dialkyl benzene ethyl ketone; Metal complexes; Phosphine oxide; And benzoquinones.The sequence of suitable radical photoinitiator includes but not limited to the example shown in table 12 and 13.
Table 12. ethanoyl-and benzo-phenyl ketone and derivative thereof
| Example | The source |
| 2 methyl benzophenone | Aldrich 15，753-8 |
| 3-methyldiphenyl ketone | Aldrich 19，805-6 |
| Methyl phenyl ketone | Aldrich A1，070-1 |
| 2-methyl-4 '-(methyl sulfo-)-2-morpholino Propiophenone | Aldrich 40，563-9 |
| 4-phenoxy group acetylbenzene | Aldrich 29，074-2 |
| 4-oxyethyl group acetylbenzene | Aldrich 27，571-9 |
| 3-hydroxyacetyl benzene | Aldrich 32，810-3 |
| 4-hydroxyacetyl benzene | Aldrich 27，856-4 |
| The 3-dihydroxy benaophenonel | Aldrich 22，043-4 |
| The 4-dihydroxy benaophenonel | Aldrich H2，020-2 |
| 4, two (dimethylamino) benzophenone of 4- | Aldrich 14，783-4 |
| Dibenzosuberenone | Aldrich D3，173-7 |
| 2,2-diethoxy acetylbenzene | Aldrich 22，710-2 |
| 4, the 4-dihydroxy benaophenonel | Aldrich D11，050-7 |
| 2,2-dimethoxy-2-phenyl acetyl benzene | Aldrich 19，611-8 |
| 3,3,4, the 4-benzophenone tetracarboxylic dianhydride | Aldrich 26，246-3 |
| 4-benzoyl biphenyl | Aldrich B1，260-1 |
| 2-benzyl-2-(dimethylamino)-4 '-morpholino butyryl radicals benzene | Aldrich 40，564-7 |
| 4, two (diethylamino) benzophenone of 4- | Aldrich 16，032-6 |
| 4-(dimethylamino) benzophenone | Aldrich 14，934-9 |
| 2, the 5-dimethyl benzophenone | Aldrich d14，966-7 |
| 3, the 4-dimethyl benzophenone | Aldrich d14，967-5 |
| Benzophenone | Aldrich B930-0 |
Table 13. miscellaneous phenyl ketone
| Example | The source |
| Anthraquinone | Aldrich A9，000-4 |
| Anthraquinone-2-sulfonic acid sodium salt | Aldrich 12，324-2 |
| Thioxanthene-9-one | Aldrich T3，400-2 |
| EAQ | Aldrich E1，220-6 |
| 2-chlorine thioxanthene-9-one | Aldrich C7，240-4 |
Table 14. dibenzoyl and dibenzoyl derivative
| Example | The source |
| Dibenzoyl | Aldrich B515-1 |
| The toluyl manthanoate | Aldrich M3，050-7 |
| Phenanthrenequione | Aldrich 15，650-7 |
| 4,4-dimethyl diphenyl formyl | Aldrich 14，670-6 |
Table 15. st-yrax and benzoin ether
| Fennel | Aldrich A8，840-9 |
| St-yrax | Aldrich 39，939-6 |
| The st-yrax ethyl ether | Aldrich 17，200-6 |
| Benzoin isobutyl butyl ether | Aldrich 19，578-2 |
| The st-yrax methyl ether | Aldrich B870-3 |
Table 16. Alpha-hydroxy-α, α-dialkyl group acetylbenzene
| Example | The source |
| The 1-hydroxycyclohexylphenylketone | Aldrich 40，561-2 |
| 2-hydroxy-2-methyl Propiophenone | Aldrich 40，565-5 |
Table 17. miscellaneous
| Type | Subtype | Source/example |
| Transition metal complex | Benzene (three carbonyls) chromium | 11，931-8 |
| Ferrocene | Aldrich F40-8 | |
| Benzoquinones | Camphorquinone | Aldrich 12，469-3 |
| Phosphine oxide | Two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides | Irgacure 819 |
| Phenylbenzene (2,4, the 6-trimethylbenzoyl) phosphine oxide | Aldrich |
When having other compound mix especially for the activity that improves some energy active compound or light-sensitive compound, may be to this energy active compound or light-sensitive compound active favourable.These compounds comprise, for example, and the amine synergistic agent and the photosensitizers of replacement.The example of suitable replacement amine synergistic agent is that (DBE, MidoriKogaku), the example of suitable photosensitizers is 3 to (6-dimethylamino) benzylacetic acid ester, 3 '-carbonyl two (7-diethyl amino coumarin).
Should be noted that many common compounds run off in time in the presence of UV light all can demote.But the difference between the generation of these slow demotion processes and rapid reaction material is conspicuous to those skilled in the art.People should infer, and are stable and can to produce the compound of reactive materials frequently in fact identical with reactive photoinitiators to light.
Publication number is the example that discloses energy active (photosensitive) compound in the U.S. Patent application (people such as Vig) of No.2003/0112423A1; Its disclosure is incorporated herein by reference.
Luminophor or tinting material can be selected from dyestuff and pigment class material.It includes but not limited to the material of following type arbitrarily: aromatic series (for example, anthracene); The aromatic series (for example, oil of mirbane) that replaces; Heterocycle (for example, furans, thiophene); Cyanine; Xanthene (for example, fluorescein, rhodamine); Acridine (for example, euchrysine); Azophenlyene (for example, safranine); Naphthols; Porphyrin; Tonka bean camphor; The methylene pyrrole methine; He oxazine; And arbitrary combination.
The light radiation that term " luminescence colorant " is defined as known energy can produce response and be accompanied by the dyestuff or the pigment of emitting (or emission) different-energy light.These energy can use commonly used for this reason and the photofluorometer (Hitach F-4500) of design.All actual projectile energies all are potential available energy, and it comprises that wavelength is the energy in about 100-1500nm scope.The energy of emitting or launching can be any energy in about 300-1000nm wavelength.
Preferred luminescence colorant comprises rare earth metal (for example, lanthanide series metal) the class title complex of launching cold light (emitting fluorescence or phosphorescence) in unique relatively mode.Preferred complexes comprises the chelating organic ligand, for example, and the rare earth coordination title complex.Do not wish to accept the constraint of opinion or mechanism, but it is believed that rare-earth chelates mainly absorbs the incident photon by part.Excited state electronics on the part mainly is transferred on the metal center by non-radiative approach.Electronics from this state through being considered to singlet
5D
0Decay to triplet state
7F
2Transition state, and in this process, launch (visible) photon energy.Preferred rare earth metal center comprises terbium, dysprosium, europium and samarium.In these metals, owing to the competitive non-radiative approach that in transitional function, exists seldom, so quantum yield very high (＞0.5).Rare earth compound based on europium is preferred, and can be commercially available.Total United States Patent (USP) 5,837,042 comprises the example of many rare-earth based luminophors and part type thereof, and these contents all are bonded to herein as a reference.Have example of structure and comprise American Dye Source, Inc. those disclosed example, it comprises: three (dibenzoyl acetone acidic groups)-list (phenanthroline) closes europium (III); Three (phenyl phenacyl ketones)-list (phenanthroline) closes europium (III); Three (phenyl phenacyl ketones)-list (the amino phenanthroline of 5-) close europium (III); Three (dinaphthyl acyl group methane)-list (phenanthroline) closes europium (III); Three (4-bromobenzene formyl radical methane)-list (phenanthroline) closes europium (III); Three (biphenyl formyl radical methane)-list (phenanthroline) closes europium (III); Three (phenyl phenacyl ketones)-list (4,7-phenylbenzene phenanthroline) close europium (III); Three (phenyl phenacyl ketones)-list (4,7-dimethyl phenanthroline) close europium (III); Three (phenyl phenacyl ketones)-list (4,7-dimethyl phenanthroline) close europium (III).Though each comfortable 612nm place emission cold light of these compounds is joined intravital fine variation and is caused having different absorption maximum values at 330-380nm.Said structure is used for illustrating at the similar compound of chelating organic ligand to have very delicate difference usually.Other suitable part type commonly used comprise contain oxo-, amino-, pyrido-, the type of sulfoxide-part, for example, beta diketone; Two pyridines; With the two pyridines of big ring; Crown ether; Phosphine oxide; Sulfonate radical.Other suitable part comprises cyclopentadienyl.
Compare with all organic light emission dyestuffs, the characteristics of luminescence of rare earth metal complex is that intensity height, emitted energy have narrow energy distribution, and absorbs the energy gap big (Stokes shift) between energy and the emission energy.Most of this compound absorbs the energy in ultra-violet region and launches energy in the visible region.The definite color or the wavelength of the energy of emission depend on rare earth metal itself.For example, the glow color based on the inner complex of terbium, dysprosium, europium and samarium is respectively orange, orange, orange red and red.
Enhancement of the Luminescent Intensity ofthe Novel System Containing Eu from people such as Parra
3+-β-Diketonate Complex Dopesin the Epoxy Resin.J.Appl.Polym.Sci., 83,2716-2726 (2002); People's such as Voloshin Water Enhances Quantum Yield and Lifetime ofluminescence of europium (III) tri-beta-diketonate s inconcentrated touluene and acetonitrile solutions.J.Luminescence, 93, can obtain background technical information among the 191-197 (2001) about some fluorescent material.
According to embodiment of the present invention, luminescence colorant is UV, visible or IR luminescence colorant; Its light emitting region is respectively 200-400nm, 400-700nm and 700-1300nm.
The chemical structure that depends on dyestuff, it absorbs different with emission characteristic also possibility.The present invention relates to all structure types of described dyestuff and pigment.The example of preferred luminescence colorant is rare earth compounding pigment or dyestuff, for example LUMILUX CD331 and LUMILUX CK332 (originating from Honeywell), it is an europium organic ligand title complex, for example, or europium metallo-chelate or europium organic ligand coordinate complex.
Not luminous or secondary tinting material (for example, dyestuff) can be mixed in the ink composite, in order to provide the visible color to mark or in order to change the luminosity of main luminophor (for example, dyestuff).Preferred secondary tinting material is those pH at its place environment materials that color also changes when changing.More preferably the absorption in nearly UV (300-400nm ripple one-tenths) can uncared-for material, so just can not hinder the absorption of energy active or light-sensitive compound, and it is right, and for example daylight has the very photostabilization of high level.The preferred secondary tinting material that Show Color changes under acidic conditions for example is purple 4 (the triarylmethane dye classes of alkalescence, color index 426000), solvent red 49 (xanthene dye class, color index 45170: 1) and solvent orange 3 (azoic dyestuff class, color index 11270: 1).Other example that is suitable for secondary tinting material used in this invention comprises the tinting material in the dye type of listing above, and from the tinting material of for example following dye type: anthraquinone, ditan, thiazine, oxazine, azine, pyronin, sulfo-pyronin, acridine, poly-methine, indigo-blue, nitro and nitroso-group and combination thereof.
In another embodiment, luminophor (for example, luminescent dye) and tinting material (for example, dyestuff) can be same substance.In this embodiment, the reaction of mark and energy changes luminescence activity, simultaneously the main body color is changed.Luminescence activity and/or change in color can take place independently of each other.Be luminophor be again that the preferred example of the luminophor of coloured dyestuff comprises the C.I. solvent red 49, it can be used as Sepisol Fast RedMG (BIMA Corporation) and buys; The azoic dyestuff that fluorescence metal cooperates, for example aluminium: sour alizarin garnet R; With the fluorescence azoic dyestuff, 4-dimethylamino-N-benzylidene-4 '-N-methyl-p-nitroaniline for example.
According to one embodiment of the invention, also can comprise tinting material, for example dyestuff or pigment, it is used to provide the visible color when using the compound of emission invisible light.Above-mentioned energy-inductive colour-change can also be before taking place or is used for strengthening the color (intensity) of mark subsequently in this tinting material.Having at least a kind of tinting material not have in reactive system, can use coloring agent mixture to produce the colour-change of hope.For example, be exposed under the situation that can become colorless under the light, can use white and redness at red stain.The mark of gained can keep the color of white color agents, and the color of gained can fade to white by redness.Preferred this tinting material comprises, do not absorb the material of luminous energy near the emission light of luminophor or excitation wavelength.
Most of commercially available tinting material all has enough stability to light and heat, thereby can stand the short-term time under the ambient lighting condition.To these tinting materials (dyestuff) apply heat or light time its be easy to decompose, but very high from the required energy of cost or safety perspective.An advantage of the invention is the reduction energy requirement, this energy requirement is to change tinting material to provide variation visible or that the machine detection obtains necessary with certain form.Also can produce this superiority by changing color, colour intensity, luminous energy or intensity.To the relatively stable dyestuff of direct acting heat or light can with effective other composition generation chemical reaction of absorb light or heat energy.After having applied light or heat, these light-sensitive compounds are tending towards producing the material of hyperergy---free acid or free electron (free radical), its very easily with medium in other composition react.Serve as a mark, ink composite of the present invention takes place effectively after via the reaction of luminous or coloured dyestuff and these photosensitive components and can detectedly change.
For luminous leucocompound, can change the absorption or the emission characteristic of luminous leucocompound with the reaction of active substance.Absorption characteristic is an absorbing wavelength, for example, and wavelength under the maximum strength or the wavelength under the average intensity.Reaction can change emission characteristic, for example, and emission wavelength, emissive porwer or emission lifetime.Emission wavelength can be the wavelength under maximum strength or the average intensity.This reaction can increase or reduce emissive porwer, perhaps prolongs or shorten emission lifetime.
Ink composite of the present invention comprises appropriate solvent, for example the mixture of organic solvent or one or more organic solvents.Preferably, this organic solvent is a volatile organic solvent.Volatile organic solvent is defined as the material that rate of evaporation is at least 0.2 times of n-butyl acetate (its rate of evaporation is 1.0).
Volatile organic solvent is selected from the group of being made up of following material usually: alcohol, ketone, cyclic ketones, ester, ether, and arbitrary combination.For example, organic solvent is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, acetone, methylethylketone, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, pimelinketone and any arbitrary combination thereof.Preferred primary solvent is to have very big volatile solvent, thereby in the short moistening tag application time, for example 1 minute, preferably less than 10 seconds, is more preferably less than in 2 seconds and just can obtains dry mark from liquid state.These solvents include but not limited to methyl alcohol, ethanol, different/n-propyl alcohol, propyl carbinol, acetone, methylethylketone, vinyl acetic monomer, acetic acid different/n-propyl, pimelinketone or its mixture.In certain embodiments of the invention, if for example used mark is to be placed on the porous matrix, then can use solvent than low volatility.After having used this printing ink, be absorbed into along with solvent that mark will be dry in the hole of matrix.
Ink composite of the present invention can comprise one or more supplementary components, for example, and preferred one or more adhesive resins.In one embodiment, this adhesive resin is a thermoplastic resin.According to one embodiment of the invention, this adhesive resin is selected from the group that following material is formed: acid amides, urethane, ester, Resins, epoxy, ketone resin, vinylpyrrolidone copolymer, vinyl polymer, vinyl butyral multipolymer, acrylic resin, styrene/acrylic resin, celluosic resin, soluble cotton, resol, hydroxystyrene polymers, vinyl alcohol polymer, styrene and arbitrary combination thereof.
Select adhesive resin can give mark best functional performance based on it.But some resin can also be used to strengthen the reactivity of mark to light, and can not hinder the incident of light; Perhaps make mark keep stable to light by absorbing incident light.UV light had radioparent relatively preferably preferred resin for example for cellulose ester, as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate (various Mierocrystalline celluloses all can available from EastmanChemical Inc.).Absorb light and can reduce mark reactive preferred resin of light those materials that to a certain degree unsaturated structure (hydrocarbon) forms of for example serving as reasons.It comprises styrene resin (styrene acrylic resin, vinylbenzene allyl alcohol resin and polyhydroxystyrene resin); Resol; Phenoxy resin; Aromatic series polyketone resin; Aromatic urethane; And aromatic polyamide.
Ink composite of the present invention can comprise that also one or more are selected from the additive by following material: wetting agent, softening agent, Photoresist, tensio-active agent, moistening agent, thermo-stabilizer, sterilant, tackifier and conductive agent.
The printing ink of describing among the present invention can be used according to any suitable mode, preferably uses ink jet printing.Ink jet printing is a technique known, need not to make in this process to produce just to contact between printing device and the matrix of adhering to print character to finish printing.In brief, ink jet printing comprises following technology: droplet of ink stream is ejected on the surface, thereby and the position of regulating drop on this surface, forms the printed images of hope.This contactless typography is particularly suitable for character is applied on the matrix such as glass, metal or plastic containers.
Can use ink jet printing to print covert indicia.In following publication, can find the each side summary of ink jet printing: people's such as Kuhn Scientific American, April, 1979,162-178; With the Phys.Technol.. of Keeling, 12 (5), 196-303 (1981).Various ink discharge devices have been described: U.S. Patent No. 3,060,429,3,298,030,3,373,437,3,416,153 and 3,673,601 in the following document.
Usually, inkjet compositions will be used in the ink jet printing operation and then must satisfy some requirement.It relates to the consistency of viscosity, corrosion stability, solvability, component and the wetting properties of matrix.In addition, printing ink must be rapidly-dry and bear dirty, wear-resisting, can also can not stop up by nozzle, and with the minimum wash machine parts rapidly of just paying.The skilled formulator in this area can obtain the physical properties of the desirable liquid of ink jet process, for example, and viscosity, surface tension and stability of solution.
In one embodiment, the viscosity of ink composite of the present invention under 25 ℃ is about 1.6 centipoises (cps)-Yue 7 centipoises, and resistivity is about 2,000 Ω of about 50 Ω-cm--cm, and the velocity of sound is about 1100 meter per seconds-Yue 1700 meter per seconds.
The present invention can also use the system component that is applicable to continuous ink jet printing (CIJ) process.The printing ink that is used for CIJ need have 1000 little siemens orders of magnitude or bigger solution conductivity.Usually use the additional salt that dissolves in the printing ink carrier to reach this requirement.The add-on of this salt is generally about 0.5-3% weight of ink composite.In some embodiments, advantageously the energy active compound can provide the electroconductibility of hope, therefore needn't use the salt that improves electroconductibility.
According to one embodiment of the invention, this ink composite can be printed on instant dripping on the ink jet printer that prints (DOD).This ink composite viscosity of (usually 25-70 ℃) under the print engine service temperature be the about 300cps of about 3cps-, for example, is the about 120cps of about 4cps-at 25 ℃ times, and resistivity is greater than about 3k Ω-cm, and the surface tension under 25 ℃ is about 25-38 dyne/cm.Printing ink in this embodiment also must pass through long-term strict stability test, thereby guarantees not have in the work-ing life of printing ink the deposited phenomenon of ink component.In this embodiment, the boiling point of printing ink is higher than 200 ℃ usually.
Can use softening agent, for example, belong to the material of following chemical type: dibasic phthalic ester, alkoxyl group-phosphoric acid ester, acyclic polyester, epoxidized oil, dibasic ester and trimellitate.Also can add other modified component in ink composite, for example Photostabilised compound (more generally being called the UV blocker), thermo-stabilizer, moistening agent, sterilant and tackifier are in order to realize desirable functional property.White pigment dispersion (for example, the MICROLITH that in vinyl acetate/vinyl chloride copolymer, forms of titanium dioxide that adds about 15% weight of about 1-
TMThe R-K dispersion) can improve various matrix, the sharpness of the mark on the especially translucent matrix.The moistening agent (for example, originating from the Unidyne NS-1603 of Daikin Industries) that can add about 2% weight of about 0.01-improves the printed dot size on the matrix, and regulates image intensity.In addition, can use the tackifier (for example, trialkoxy silane) of about 5% weight of about 0.01-to improve sticking power to some matrix.
Can also add other component and improve the printing press operability, for example, the wetting agent that adds about 0.5-about 10% can prevent that the printing ink in the printing press is dry too early.The example of wetting agent includes but not limited to glycol ether, esterification lactic acid salt, N-Methyl pyrrolidone, amyl acetate-n, propyl carbonate or methyl-sulphoxide.Can use defoamer about 0.1-about 2.0%, compatible with ink carrier (solvent) (for example, originating from the Tego Foamex N of Tego Chemie Service) to reduce the foam that produces in the CIJ printing press.
It in addition, use Photostabilised compound highly beneficial, because can prevent that the light of energy active compound and setted wavelength from undesirable reaction taking place.For example, can design such individual system, itself and ambient light do not react substantially and react with higher UV luminous energy.In this system, can use Photostabilised compound, its with the home light of 300-400nm (that is, containing UV light hangs down wavelength to about 300nm daylight) the similar energy area of energy in have significant absorption.In addition, can also use the energy active compound that between 250-300nm, has additional remarkable absorption.The existence of Photostabilised compound can consume the incident ambient light energy; But the high energy window still keeps, and wherein, the light (for example, 300nm or lower) with appropriate energy can be passed in the energy active compound by suitable light source.
The structure of Photostabilised compound is made up of light absorbing substructure, and especially this substructure is that aromatic series functional group-this functional group also can find in the energy active compound usually.But according to definition, effective Photostabilised compound does not produce the material that reacts with surrounding medium, as above-mentioned energy active compound.On the contrary, these materials absorb luminous energy usually and with this Conversion of energy for heat and can not be attended by the degradation of structure.For example, the most frequently used, be used in Photostabilised compound-p-methoxycinnamic acid octyl group ester in the protectiveness opalizer-be exposed to light following time the photoisomerization reaction takes place, it transforms back into more stable isomer again gradually when light source is removed then.The example of suitable Photostabilised compound is as follows:
The Photostabilised compound of table 18.
| Type | Subtype | Example |
| 2 cyanoethyl acrylate | Uvinul 3039，3035；UVSOB 320 | |
| Benzophenone | Hydroxyl replaces | Uvinul P25，400，D-49，D- 50；UBSOB 340；Syntase 1200；Maxgard 200；Mark 1535；Cyasorb UV2098， UV2126，UV24，284；Cyagard 531，UV9 |
| Propanedione | The aromatic series propanedione | Givsorb UV-14 |
| Triazine | Uvinul T-150；Tinuvin 1545，1577，400；Cyagard 1164 | |
| Benzotriazole | Hydroxy phenyl | Tinuvin 840，900，928，326， 327，328，384，571，109， 1130，320，99，P；THPEBZT； Norblock 6000，7966； Cyagard UV544 |
| Oxamide | Carbonamidine | Sanduvor 3206，EPO；Givsorb UV-1，UV-2 |
| Benzoic ether | The hydroxy phenyl benzoic ether | Eastman RMB；Escalol 507 |
| The Whitfield's ointment phenylester | Escalol 587 | |
| Benzoic ether is obstructed | Tinuvin 120；Cyasorb UV2908 |
| Benzal | Laurate | Escalol 557；UVSOB A，360 |
| Phenylpropionate | Givsorb UV-15 | |
| The benzylidene malonic acid ester | Cyasorb UV1988 | |
| Fortified phenol | Mark 446 | |
| Phenylpropionate | Givsorb UV-13 | |
| Benzoglyoxaline | Givsorb UV-16；UVSOB HS | |
| Benzoxazinone | Cyagard 3638 | |
| Miscellaneous | Avobenzone | |
| Quercetin | ||
| Metal complexes | Cyasorb 1084 |
Free-radical scavengers also can be used as Photostabilised compound.The example of this scavenging agent comprises hindered amine as light stabilizer (HALS).The object lesson of HALS is Uinul 4049H, Unvinul 4050H and the Uvinul 5050H that is produced by BASF Chemical Inc..
According to the present invention, can carry out mark to any suitable matrix, for example metal, glass and plastics especially polish cylinder of steel, aluminium pot, PET guide plate, vial etc.
In one embodiment, the invention provides a kind of ink composite, it contains about 95% weight of the 30-that has an appointment, preferred about 75% weight of about 40-, the solvent of about 65% weight of 50-more preferably from about, contain about 30% weight of 0-, preferred about 25% weight of about 1-, the adhesive resin of about 20% weight of 5-more preferably from about, contain about 10% weight of the 0.01-that has an appointment, about 5% weight of preferably about 0.1-, the more preferably from about luminophor or the tinting material of about 3% weight of 0.1-, contain about 10% weight of 0-, preferred about 5% weight of 0.01-, more preferably from about the not luminescence colorant of 0.1-2% weight also contains about 15% weight of the 0.1%-that has an appointment, preferred about 10% weight of about 0.1-, more preferably from about the energy active compound of about 5% weight of 0.1-.Solvent is preferably organic solvent, and for example, organic polar solvent is as acetone.Adhesive resin is preferably polyketone resin (for example, the Synthetic Resin SK of DegussaHuls Inc. production).Luminophor is the phosphorescent coloring that comprises europium.Luminescence colorant is not preferably azoic dyestuff, for example, and Chrysolidine Y alkali.Preferably, this ink composite also contains conductive agent, for example, the bromination tetrapropyl ammonium, its amount is about 0.5-5% of ink composite, preferably about 0.5-3%, more preferably from about 0.8-2% weight.This energy active compound is preferably and can reacts the compound that also can be dissolved in the solvent with UVC.The example of energy active compound is a tribromoethyl alcohol.
In another embodiment, this energy active compound and conducting salt can be same substance.For example, can be about 15% with about 0.5-, preferably about 1-about 10%, more preferably from about about 3% weight of 1-with the miscible salt of ink carrier (solvent) (for example, the blended triarylsulfonium salt, UVI-6976 specifically, Dow Chemical produces) replace conducting salt and energy active compound.
In another optional embodiment of above-mentioned prescription, luminophor and coloured component can be same substance.For example, luminophor and coloured dyestuff can be that the energy active compound is had reactive colored oxidation anthracene-radical dye (for example, the ocean alkali of solvent red 49, BASF production is red).With the shortwave light source, for example UVC reacts the color of dyestuff is changed fully---and fade to colourlessly from redness, and almost completely lose fluorescence.Should special combination make system simultaneously not readable for machine and people's naked eyes.The disappearance of marker color provides definite feedback to the viewer, and promptly this mark is invalid.In addition, owing to the printing ink with one-component is more cheap relatively on producing, so this embodiment is favourable.
In one embodiment, the invention provides a kind of ink composite that is applicable to ink jet printing, it comprises not luminescence colorant, solvent and energy active compound.The mark that is made by ink composite is exposed to the following time of energy of significant quantity, for example this not the absorbing wavelength of luminescence colorant change.Can use any not luminescence colorant discussed above.The example of this tinting material is a solvent orange 3.Can use any suitable energy active compound, for example tribromoethyl alcohol.
In yet another embodiment of the present invention, the light that only jetted ink preparation can be become with desired wavelength reacts.The visible colour-change can take place in the mark that is generated by described printing ink, and luminous reduces, the situation just as among the above-mentioned embodiment during with irradiate light.But this ink composite is compared with prescription before, more can prevent the reaction with surround lighting.This ink composite is made up of following ingredients: the 1) polar organic solvent of about 30-about 95% (for example, acetone), and preferably about 40-is about 75%, more preferably from about about 65% weight of 50-; 2) resin that dissolves in the printing ink carrier of about 1-about 30% (for example, Polyvinylpyrolidone (PVP)/vinyl acetate copolymer E-335, ISP Incorporated production); 3) the europium base phosphorescent coloring that dissolves in the printing ink carrier of about 0.01-about 10%, it is about 5% to be preferably about 0.1-, more preferably from about about 3% weight of 0.1-(for example, AMART dyestuff
TMUR-3, Photosecure produces); 4) the coloured dyestuff of yellow azo-type of 0-about 10%, it is about 5% to be preferably about 0.01-, about 2% weight of 0.1-(for example, solvent yellow 56) more preferably from about, color fades to red-brown from yellow after itself and the strong acid generation protonation; 5) radiation has reactivity and dissolves in the printing ink carrier to UVC for the energy active compound of about 0.1-about 15%, this material, and it is about 10% to be preferably about 0.01-, more preferably from about about 5% weight of 0.1-(for example, tribromoethyl alcohol or hexabromocyclododecane); 6) about 5% conducting salt of about 0.5-, preferably about 0.5-is about 3%, about 2% weight of 0.8-(that is, the TBuA hexafluorophosphate) more preferably from about, it is dissolved in ink carrier and has good electrical conductivity therein; 7) the Photostabilised compound of UV of 0-about 15%, preferably about 0.1-is about 10%, more preferably from about about 6% weight of 0.5-(for example, octyl methoxycinnamate, the Escalol 557 that ISP Incorporated produces); 8) the white color divergence body of 0-15%, it is about 15% to be preferably about 5-, about 10% weight of more preferably about 5-(for example, the MicrolithR-K that produces of Ciba, it is the dispersion of titanium dioxide in vinyl acetate/vinyl chloride copolymer), it is used for improving the readability that is marked at various matrix; With 9) wetting agent of 0-about 25%, preferably about 0.5-is about 20%, about 10% weight of 0.5-(for example, acetic acid uncle amyl group ester) more preferably from about, it can prevent that the printing ink in the printing press is dry too early.
According to the prepared mark of ink composite embodiment of the present invention, for example CIJ printing ink has very short time of drying, usually less than 2 seconds, and various pore-free surfaces is all had good sticking power under the room temperature.In addition, in embodiments, it can wash by water.But, resin is changed into different resins by vinyl pyrrolidone/vinyl acetate, for example acrylic resin then can form the water-insoluble mark in a similar fashion.Color can become red-brown by yellow when the mark in the above-mentioned embodiment was subjected to the irradiation in UVC source.Except making the sample colour-darkening, luminous intensity can reduce greatly when dyestuff was subjected to the known radiation that excites in (excitation maximum of europium dyestuff is usually between 350-400nm) rate frequently.
Jetted ink only reacts with the light of desired wavelength in another embodiment of the invention, this embodiment is as follows: the 1) organic solvent of about 40-about 98%, and preferably about 60-is about 95%, more preferably from about about 95% weight of 70-, (for example, tripropylene glycol-monomethyl ether); 2) organic solvent that is used to change viscosity of 0-about 40%, preferably about 3-is about 15%, about 10% weight of 5-more preferably from about, (for example, triglycol); 3) the europium base phosphorescent coloring that dissolves in the printing ink carrier of about 0.01-about 10%, preferably about 0.1-is about 5%, about 3% weight of 0.1-more preferably from about, (for example, LUMILUX CD-331 dyestuff); 4) the coloured dyestuff of azo-type of 0-about 10%, preferably about 0.01-is about 5%, more preferably from about about 2% weight of 0.1-(for example, xanchromatic chrysolidineY alkali, it is easy to strong acid generation protonation to be become by yellow brown); 5) the energy active compound of about 0.1-about 15%, it can react and dissolve in the printing ink carrier under the UVC radiation, and it is about 10% to be preferably about 0.1-, about 5% weight of more preferably about 0.1-, (for example, tribromoethyl alcohol).This printing ink has the desired physical properties of operation in the DOD printing press: for example, viscosity is the about 30cps of about 3cps-under the service temperature (being generally 25-70 ℃) of printing press engine; For example, at 25 ℃ down under the about 120cPs of about 4-, resistivity is greater than about 3K Ω-cm, and is about 25-38 dyne/cm at 25 ℃ of lower surface tension force.The boiling point of this prescription is usually above 200 ℃.
Liquid viscosity properties-correcting agent can comprise any liquid of viscosity greater than 6cps.More preferably, thickening material comprises any liquid of viscosity greater than 20cps.More preferably this liquid thickener is got rid of the molecule of being made up of reactive functional groups again, and this reactive functional groups is epoxide group or unsaturated carbon group (for example, acrylate and vinyl).
Because above-mentioned prescription does not contain adhesive resin, therefore the printed images that obtains should be used in porous matrix, for example on the paper.But, can in DOD printing ink, comprise adhesive resin, also ruled it out not among the present invention.As mentioned above, when using the optical energy irradiation image of about 350-380nm, Stokes shift can take place in it in narrower about 600-630nm zone, thereby sends red light.When with ultraviolet ray, when especially wavelength was lower than this mark of rayed of about 300nm, visible variation-color can take place and become orange/brown by yellow in it.In addition, when by the rayed of about 350-380nm, the luminous intensity of this mark can reduce.
Colour-change of Miao Shuing and fluorescence losses degree depend on many formulation parameters herein, comprise the amount of energy active compound and the ratio between energy active compound and reactive tinting material and the luminophor.Other parameter comprises medium property and offsets the actual energy and the power output of light source.For example, when use is used for the portable 254nm light source of germ-resistant low power (for example can available from Spectroline Incorporated), the weight ratio of energy active compound and (combination dyestuff add luminophor) be 3 or bigger situation under, in several minutes, observe entire reaction and finish.Entire reaction is defined herein as whole visible conversion process---and the Chrysolidine Y basic dye of all yellow forms is converted into brown form, and almost whole fluorescence reduces to below 5 percent of initial value.Use more high-power light source, be similar to the high pressure mercury vapor arc lamps of buying, can make entire reaction realize faster rate by such as the such company of Fusion Systems Incorporated.This system reaches same level of response can be with the time of second order of magnitude or still less, so just can use this mark in high speed processes, for example on fabrication line the product of production is classified.An attendant advantages of this combination partner is that environment, indoor light are had relative satisfactory stability.Under these conditions, the sample that newly prints can be preserved several hours or several days, and color or luminous intensity almost do not change.
Be noted that importantly tinting material in above-mentioned example (that is ChrysolidineY alkali) and luminophor (that is LUMILUX CD-331 dyestuff) can react with energy active compound (that is tribromoethyl alcohol) simultaneously.In fact, the variation of the two all can make the whole luminous intensity of luminophor reduce.Under the situation of luminophor, luminescence phenomenon is directly by cancellation.In addition, the tinting material color fades to brown average energy corresponding to the light that absorbs by yellow increases.Under original state, the tinting material strong absorption produces the interior light of energy area (about 610nm) of luminescence phenomenon, therefore impels observable whole luminous intensity to reduce.
Term " machine-readable " is used to summarize the variation that how monitoring mark and energy react and produced in this article.The electronic measurement technique that is designed for variation of assessment luminous or colour-change has been arranged, and it can be suitably with in the present invention.Use any appropriate means can detect variation, for example, use photorectifier, photographic camera, ccd sensor, cmos sensor, spectrometer and colorimeter.
The present invention also provides a kind of method of differentiating matrix, and it comprises: (a) use ink composite of the present invention that a kind of discriminating mark is provided on matrix; (b) read this discriminating mark; (c) will differentiate that mark is exposed under the passivation energy of significant quantity producing certain material, this material and luminophor or tinting material and/or not the luminescence colorant reaction obtain discriminating mark after energy-exposure; (d) read discriminating mark after this energy-exposure.Be exposed to the passivation light source before or subsequently mark when comparing, read this discriminating mark and can be used for determining luminous intensity or wavelength change.Therefore, this reading device can be made up of the system that obtains illuminated message.The another kind of method of determining the exposure effect of discriminating mark is to measure to be exposed to before the passivation light source or the difference between the mark subsequently.The information that reads this discriminating mark and collected can comprise obtains image luminous or light-contrast base, thereby determines the information that typographic(al) mark contains in modes such as alphanumeric symbol, 1-D bar code, 2-D bar code, data matrix bar codes.Except the information that typographic(al) mark contains, can also determine to be exposed to before the passivation light source or luminous intensity subsequently or the ratio between the contrast gradient.These ratios can be used in the automatic algorithms, mark whether to expose or passivation in order to determine this.Can also use other method to determine to be used in and being marked at before the exposure or the situation after the exposure in this algorithm, and these methods also are not precluded within outside the scope of the present invention.The effect of reading can comprise measures luminophor or the luminescence colorant difference that changes and caused not.This variation can be spectrum change, for example, and absorbing wavelength, absorption intensity, emission wavelength, emissive porwer or emission lifetime.
The present invention also provides a kind of system of differentiating matrix, and it comprises: (a) ink composite of the present invention; (b) ink-jet printer; (c) matrix; (d) the passivation energy; (e) reading device.This reading device of said system can be made up of the secondary reading device of the device of detected electronically mark, excitation light source and possible direct this mark of affirmation.Excitation light source be likely xenon flash lamp or with other luminous light source of corresponding wavelength place, the excitation energy of luminophor zone.Particularly preferably be xenon flash lamp, because its energy that has very high radiation power output and consumption in broad potential excitation wavelength band is less relatively.In addition, these lamps are launched very high power and matrix is exposed under the destructive energy.Can comprise less important reading device in the main reading device, be used for confirming the reliability of this discriminating mark.For example, under the situation of drink pack, traditional bar-code reading device can read the UPC bar code on the packing, and confirms that it is to carry out mark by proper discriminating mark.In addition, the IR transmitter can be determined the shape section packed, and to from differentiating that the information that mark obtains compares to determine its character.This information can be used for also determining what kind of processing is system carried out according to passivation requirement and reading requirement to mark.
The present invention has also brought profitability for the process control under production or the distribution condition.When with the optical energy irradiation of another wavelength, luminescence colorant (for example, dyestuff) responds the visible or invisible light at the setted wavelength place of emission.Can select dyestuff, make its emission wish the light of intensity and energy, thereby available machines used read.Can select the emission light of can be well having an effect with photosensitive device.These systems can overcome and automatic bar code-relevant problem of the process that reads commonly used, for example, depart from, the interference of ambient lighting or the interference of matrix background color.Therefore because carrying out machine easily reads and can use luminescence colorant in automated procedure.For example, in central dispense equipment, can use very high reading rate to read the identification marking of article, thereby it is classified.In process of production, the present invention can come the article through a process with the article difference through another process.
Can use another example of process control of the present invention is process monitoring.The present invention has advantageously provided machine-readable printing ink, and it need not on-line operation person just can indicate the process process.Do not required visible indication in the present invention.Therefore, the present invention makes in the automation process and can use luminescent marking.
Single ink composite during the present invention advantageously provides a kind of multiple purpose that can be used for---for example, colour-change or luminous change---, it not only has coloured component but also has luminescence colorant in unitary system.In preferred embodiments, every kind of tinting material all has reactivity to other independent in system component, and therefore the chemical transformation of wishing takes place in two kinds of tinting materials simultaneously.Just can use single application apparatus like this on production line, for example ink-jet printer is used this mark.In the design of security system, wish very much to use single fluid and single application apparatus, any forgery of total system---that is, is usurped liquid to other position---all can be discerned rapidly like this.
As seen coloured component is exposed to the next meeting of energy and produces colour-change, and this colour-change can influence the intensity of luminous signal and/or the color of emission again.Can provide a kind of advantageous manner that is used for discernable marks article situation to the influence of intensity.For example, the color of visible coloured component migrates to redness by yellow, and the emissive porwer of earth complex luminescent component luminous in the ruddiness zone is descended.It is colourless that second colour-change of bringing out can cause visible component to be changed into by redness, recovers initial luminous.These change all is machine-can read, and therefore makes the present invention have availability in automation process.
Reactive systems of the present invention is favourable, and this is that this energy is used under the lower substrate temperature system is activated because it is compatible with the more effective energy.Photochromic marking takes place reversible change according to embodiments of the present invention.
In one embodiment, the present invention also provides a kind of ink composite, it comprises luminophor, not luminescence colorant and energy active compound, wherein reactive materials reacts (in mark) and makes not that the absorption or the emission characteristic of luminescence colorant change, thereby make the absorption of the not luminescence colorant after the change overlapping or consistent with the absorption or the emission characteristic of luminophor, for example, as shown in Figure 2.
The invention provides some advantages, for example mark is to the good sticking power of matrix, and this printing ink does not contain or do not contain substantially solvent, for example methylethylketone (MEK) or methyl alcohol in embodiments.Also cold-resistant the coagulating of this mark in the embodiment acts on.
The following example further illustrates the present invention, but can not think that certainly it limits invention scope by any way.
Embodiment 1
This embodiment has illustrated that cation light initiator is as the purposes of energy active compound and its luminiferous variation under the UV energy emission.With 100.0g styrene acrylic copolymer JONCRYL
TM611 (Johnson polymkeric substance) are dissolved in the 400.0g acetone and make resin solution, and it is labeled as solution 1.Luminous europium organic coordination compound dyestuff LUMILUX CD-331 with about 1% is dissolved in the solution 1 and makes dye solution.Add different energy active compounds in each solution of picture.In the table 19 these solution have been done summary.
Table 19
| The solution numbering | Solution 1 (% is heavy) | LUMILUX CD-331 (% is heavy) | Additive title and amount (% is heavy) |
| 2 | 99 | 1 | Do not have |
| 3 | 94 | 1 | 5% mixes triarylsulfonium salt (UVI-6976) a |
| 4 | 94 | 1 | 5% diaryl group iodized salt (CGI-552) b |
| 5 | 94 | 1 | 5% Xiuization 4-butyl-phosphonium (TBPBr) c |
| 6 | 89* | 1 | 5% Xiuization tetraphenylphosphoniphenolate (TPPBr) * c |
| 7 | 94 | 1 | 5% benzophenone (BP) c |
| 8 | 94 | 1 | 5％Darocur 1173(1173) b |
| 9 | 94 | 1 | 5％Darocur TPO(TPO) b |
| 10 | 94 | 1 | Lauric acid c |
* 5% ethanol has replaced 5% solution 1, in order to stablize TPPBr.
aDerive from the UVI-6976 of Dow Chemical
bDerive from the CGI-552 of Ciba
cAldrich，Inc.。
Use #8 steel stretching rod that printing ink is stretching in this printing ink that stretches on the aluminium sheet, make the solid tension specimen of each solution in the table 19.Aluminium sheet is cut into little.These are exposed under the hand-held ultraviolet lamp that model is ENF-260c (Spectroline Inc.), and this ultraviolet light fitting is useful on UVA and the independent lamp (incandescent lamp) of UVC radiating.Be provided with down at corresponding ultraviolet lamp, these lamps are launched narrow-band radiated respectively under about 365nm and 254nm.Sample directly is placed under the lamp but does not directly contact, expose 2 minutes in this way with lamp is surperficial.After the exposure, touch this sample even do not have the sensation of alternating temperature.
Use Hitachi F-4500 photofluorometer to measure, assess in order to residue luminous intensity to each sample.With excitation frequency transmitting frequency is made a cubical array, selective exitation maximum value then, thereby the peak area of definite emission.Use this excitation frequency curve plotting figure, it demonstrates has the frequency field of high visible luminescence intensity.The value that integration is determined each sample is carried out in zone below the curve, the emission value that records under this curve representative each frequency in the maximum intensity zone.
For LUMILUX CD-331, excitation wavelength is chosen as 358 nanometers (nm).Integration is carried out in zone in the 600-630nm obtain emtting area.Emissive porwer before emissive porwer after the UV exposure is exposed is removed, and obtains remaining luminous percentage.Table 20 has provided listed each solution of table 19 and has been exposed to the UV light luminous percentage of residue afterwards.
Table 20
| Additive | Remaining luminous percentage after exposing 2 minutes under the UV lamp | ||
| Shortwave (254nm) | Long wave (365nm) | ||
| 2 | Do not have | 86 | 92 |
| 3 | UVI-6976 | 4 | 58 |
| 4 | CGI-552 | 1 | 58 |
| 5 | TBPBr | 76 | 66 |
| 6 | TPPBr | 79 | 83 |
| 7 | BP | 91 | 63 |
| 8 | 1173 | 57 | 67 |
| 9 | TPO | 66 | 80 |
| 10 | Lauric acid | 97 | 94 |
| The average % that acid-producing agent reduces | 98 | 69 | |
| The average % that free radical generating agent reduces | 29 | 30 | |
| The average % that bromine salt reduces | 23 | 31 | |
From the result of table 20 as can be seen, compare as the situation of radical photoinitiator with each bromine salt, ion acid type light trigger is showing very strong superiority aspect the luminous reducing.But, and to compare by the situation of not adding any light-sensitive compound of " nothing " representative, latter two group is better.
Embodiment 2
This embodiment has illustrated that the halo light acid propellant is as the purposes of energy active compound and luminiferous variation under the UV energy emission.Shown in embodiment 1, prepared more several typical solution.Luminous europium organic coordination compound dyestuff LUMILUX CD-331 (Honeywell Corp.) with about 1% is dissolved in the solution 1 and makes dye solution.In each solution, add different energy active compounds.In the table 21 these solution have been done summary.
Table 21.
| The solution numbering | Solution 1 (% is heavy) | LUMILUX CD-331 | Additive title and amount (% is heavy) |
| 11 | 94 | 1 | 5%1,2-dibromo-cyclohexane (DBCH) a |
| 12 | 94 | 1 | 5%1,10-dibromo-decane (DBD) a |
| 13 | 94 | 1 | 5% tribromoethyl alcohol (TBE) a |
| 14 | 94 | 1 | 5% tribromoneoamyl alcohol (TBPA) a |
| 15 | 94 | 1 | Perfluor heptan a |
aAldrich，Inc
According to the description of embodiment 1, the solution effect under identical exposure effect and analysis condition in the his-and-hers watches 21.Provided the result in the table 22.
Table 22.
| Solution | Additive | Remaining luminous percentage after exposing 2 minutes under the UV lamp | |
| Shortwave (254nm) | Long wave (365nm) | ||
| 2 (from embodiment 1) | Do not have | 86 | 92 |
| 11 | DBCH | 2 | 69 |
| 12 | DBD | 77 | 56 |
| 13 | TBE | 1 | 77 |
| 14 | TBPA | 61 | 76 |
| 15 | PF 5070 | 86 | 80 |
Presentation of results in the table 22, the halogenated compound of some type in the present invention, for example DBCH and TBE are favourable.
Embodiment 3
This embodiment has illustrated the purposes of some nonionic light acid-producing agent as the energy active compound.Shown in embodiment 1, prepared more several typical solution.Luminous europium organic coordination compound dyestuff Lumilux CD-331 (Honeywell Corp.) with about 1% is dissolved in the solution 1 and makes dye solution.In each dye solution, add different energy active compounds.In the table 23 these solution have been done summary.
Table 23.
| The solution numbering | Solution 1 (% is heavy) | LUMILUX CD-331 (% is heavy) | Additive title and amount (% is heavy) |
| 16 | 94 | 1 | 5%[1,2,3-three methylsulfonic acids] benzene (PYR-100) a |
| 17 | 94 | 1 | 5% diazomethane compound (DAM-301) a |
| 18 | 94 | 1 | 5% succimide sulphonate (SI 105) a |
| 19 | 94 | 1 | 5% 3 [trichloromethyl] s-triazine (TAZ 100) a |
| 20 | 94 | 1 | 5% sulfonation nitride (CGI-263) b |
aMidori Kogaku，Inc.Ltd.
bDerive from the CGI-263 of Ciba Specialty Chemicals
According to the description of embodiment 1, the solution effect under identical exposure effect and analysis condition in the his-and-hers watches 23.Provided the result in the table 24.
Table 24.
| Solution | Additive | Remaining luminous percentage after exposing 2 minutes under the UV lamp | |
| Shortwave (254nm) | Long wave (365nm) | ||
| 2 (from embodiment 1) | Do not have | 86 | 92 |
| 16 | PYR-100 | 80 | 100 |
| 17 | DAM-301 | 8 | 45 |
| 18 | SI-105 | 18 | 100 |
| 19 | TAZ-100 | 6 | 70 |
| 20 | CGI-263 | 1 | 42 |
As can be seen from Table 24, various other known light-sensitive compounds also can be advantageously used among the present invention, especially when being used in combination with short wavelength's radiating capacity.
Embodiment 4
This embodiment illustrates that some europium dyestuff is according to the purposes in embodiment of the present invention.Shown in embodiment 1, prepared more several typical solution; But, used different europium organic coordination compound luminescent dyes.The dyestuff that contains in each case is 1% weight level.In each case, the dye solution that does not contain light-sensitive compound is compared with the dye solution that contains tribromoethyl alcohol (TBE).Identical with before used Hitachi F-4500 photofluorometer, but is to use the particular dye that combines excitation frequency and transmit frequency range.In the table 25 solution has been done summary with exciting with transmitting frequency.
Table 25.
| The solution numbering | Solution 1 (% is heavy) | TBE (% is heavy) | Luminescent dye title and amount (% is heavy) | Excitation wavelength (nm) | Emission wavelength zone (nm) |
| 21a | 99 | 0 | 1％LUMILUX CD3-9411 | 362 | 600-630 |
| 21b | 94 | 5 | 1％LUMILUX CD3-9411 | 362 | 600-630 |
| 22a | 99 | 0 | 1％LUMILUX CD-332 | 362 | 600-630 |
| 22b | 94 | 5 | 1％LUMILUX CD-332 | 362 | 600-630 |
| 23a | 99 | 0 | 1％LUMILUX CD-316 | 358 | 600-630 |
| 23b | 94 | 5 | 1％LUMILUX CD-316 | 358 | 600-630 |
According to the description of embodiment 1, the solution effect under identical exposure effect and analysis condition in the his-and-hers watches 25.Provided the result in the table 26.
Table 26.
| Solution | Whether there is TBE | The LUMILUX dyestuff | Remaining luminous percentage after exposing 2 minutes under the UV lamp | |
| Shortwave (254nm) | Long wave (365nm) | |||
| 2 (from embodiment 2) | Not | CD-331 | 86 | 92 |
| 13 (from embodiment 2) | Be | CD-331 | 1 | 77 |
| 21a | Not | CDE-9411 | 71 | 81 |
| 21b | Be | CDE-9411 | 2 | 88 |
| 22a | Not | CD-332 | 53 | 66 |
| 22b | Be | CD-332 | 1 | 59 |
| 23a | Not | CD-316 | 67 | 74 |
| 23b | Be | CD-316 | 2 | 73 |
The data declaration of table 26, prescription of the present invention can be had an effect with multiple different europium a metal-organic complex dyestuff well.
Embodiment 5
This embodiment has illustrated that the miscellaneous fluorescence dye is according to the purposes in embodiment of the present invention.Shown in embodiment 4, prepared more several typical solution.Equally, the dyestuff that contains under every kind of situation is 1% weight level.In each case, the dye solution that does not contain light-sensitive compound is compared with the dye solution that contains tribromoethyl alcohol (TBE).In the table 27 these solution have been done summary.
Table 27.
| The solution numbering | Solution 1 (% is heavy) | UVI-6976 (% is heavy) | TBE (% is heavy) | Luminescent dye title and amount (% is heavy) | Excitation wavelength (nm) | Emission wavelength zone (nm) |
| 24a | 99 | 0 | 0 | 1% benzothiazole derivant a | 333 | 400-650 |
| 24b | 94 | 0 | 5 | 1% benzothiazole derivant a | 333 | 400-650 |
| 25a | 99 | 0 | 0 | The ocean solvent red 49 b | 355 | 550-700 |
| 25b | 94 | 0 | 5 | The ocean solvent red 49 b | 355 | 550-700 |
| 26a | 99 | 0 | 0 | The Alberta Huang c | 430 | 450-580 |
| 26b | 94 | 5 | 0 | The Alberta Huang c | 430 | 450-580 |
| 27a | 99 | 0 | 0 | Alkali red 1:1 d | 510 | 530-680 |
| 27b | 94 | 5 | 0 | Alkali red 1:1 d | 510 | 530-680 |
aLumilux CD-333 derives from Honeywell, Inc.
bOcean alkalescence is red, derives from BASF.
cThe solubility toning agent derives from Radiant Colors, Inc.
D pigment HM-13 derives from Radiant Colors, Inc.
According to the description of embodiment 1, the solution effect under identical exposure effect and analysis condition in the his-and-hers watches 25.Provided the result in the table 28.
Table 28.
| Solution | Whether there is initiator | Dyestuff | Remaining luminous percentage after exposing 2 minutes under the UV lamp | |
| Shortwave (254nm) | Long wave (365nm) | |||
| 24a | Not | Benzothiazole derivant | 100 | 92 |
| 24b | Be | Benzothiazole derivant | 58 | 73 |
| 25a | Not | Solvent red 49 | 52 | 80 |
| 25b | Be | Solvent red | 9 | 69 |
| 26a | Not | The Alberta Huang | 100 | 100 |
| 26b | Be | The Alberta Huang | 25 | 20 |
| 27a | Not | Alkalescence is red | 92 | 100 |
| 27b | Be | Alkalescence is red | 30 | 27 |
Use the shortwave light irradiation after 2 minutes, become almost colourless by dark magenta corresponding to the sample of solution 28b.Shine after 4 minutes, the sample of solution 25b becomes colorless.Under similarity condition, after the irradiation, keep its priming color corresponding to the sample of solution 25a.The luminous of this luminescent dye has taken place sightless, machine-readable variation, visible change has taken place in color.
Embodiment 6
This embodiment has illustrated one embodiment of the invention, and wherein color is faded to brown by yellow.Mix each component according to the order shown in the table 29, made pigment dispersion, solution 28.
Table 29. solution 28
| Component | Weight percentage |
| Acetone acetic ester methoxy-propyl titanium dioxide dispersion | 50.0 20.0 30.0 |
aMicrolith R-K derives from Ciba Specialty Chemicals.Mix each component according to the order shown in the table 30, made printing ink, solution 29.
Table 30. solution 29
| Component | Weight percentage |
| Acetone bromination tetrapropyl ammonium | 46.3 1.7 |
| Synthetic resins SK (polyketone resin) solution 28 ChrysolidineY alkali (solvent orange 3) europium organic coordination compound LUMILUX CD-331 2,2, the 2-tribromoethyl alcohol | 15.0 30.0 1.0 1.0 5.0 |
Measured the following character of solution 29.25 ℃ of following viscosity are 3.71 centipoises.The solution resistance rate is 1.520k Ω-cm.The velocity of sound is 1215 meter per seconds.Proportion is 0.982g/mL.
Use #8 wire-wound stretching rod on aluminium sheet, to make tension specimen.According to embodiment 1 described mode, a part of tension specimen is exposed 2 minutes under the shortwave hand-held ultraviolet lamp.Exposed region is become brown by yellow.Measure remaining luminous intensity according to the mode described in the embodiment 1 equally.The residual intensity percentage ratio in coloured zone of gained is less than 5%.
Use the Macbeth colourimeter to measure colour-change.Use instrument to change the observed value that obtains into the CIELAB scale, 65 ° at incident illumination angle, viewing angle is 10 ° etc.The Δ E measured value of observed colour-change is 32.7.
Use Videojet EXCEL
TMThe continuous ink jet printing machine prints this printing ink, has obtained good printing quality.In the manner described above, will under portable short wave ultraviolet light source, shine 2 minutes by the typographic(al) mark that discontinuous liquid is formed.Typographic(al) mark becomes brown, uses the long wave of portable UV lamp to be provided as incident light source, determines almost not have remaining luminous by visible inspection.
Embodiment 7
This embodiment has illustrated one embodiment of the invention, and wherein color becomes purple by pink colour.Make ink composite according to mode similar to Example 6.Mix each component according to the order shown in the table 31 and make printing ink, solution 30.
Table 31. solution 30
| Component | Weight percentage |
| Acetone bromination tetrapropyl ammonium synthetic resins SK solution 31 pararosaniline alkali LUMILUX CD-331 2,2, the 2-tribromoethyl alcohol | 46.8 1.7 15.0 30.0 0.5 1.0 5.0 |
Measured the following character of solution 30.Viscosity is 3.65 centipoises.The solution resistance rate is 1.450k Ω-cm.The velocity of sound is 1190 meter per seconds.Proportion is 0.978g/mL.
Use #8 wire-wound stretching rod on aluminium sheet, to make the tension specimen of printing ink.According to embodiment 1 described mode, a part of tension specimen is exposed 2 minutes under the shortwave hand-held ultraviolet lamp.Exposed region becomes purple by pink colour.Measure remaining luminous intensity according to the mode described in the embodiment 1.The residual intensity percentage ratio in coloured zone of gained is less than 5%.Measure colour-change according to the mode described in the embodiment 6.The Δ E measured value of observed colour-change is 18.5.
Use Videojet EXCEL continuous ink jet printing machine to print this ink composite, obtain good printing quality.In the manner described above, will under portable short wave ultraviolet light source, shine 2 minutes by the typographic(al) mark that discontinuous liquid is formed.Typographic(al) mark becomes purple, uses the long wave of portable UV lamp to be provided as incident light source, determines almost not have remaining luminous by visible inspection.
Embodiment 8
This embodiment has illustrated another embodiment of the invention.Component shown in the table 32 mixed make solution, solution A 1.
Table 32. solution A 1
| Component | Weight percentage |
| Acetone: duplicate fluid #5 (4: 3 mixtures) CAB 553-0.4 (Eastman Chemical) (cellulose acetate butyrate fibre) propylene glycol monomethyl ether acetate polysiloxane surfactant | 89.9 5.0 5.0 0.1 |
To duplicate fluid #5 sex change is ethanol.Add 99.0g solution A 1,1.0g luminescent dye LUMILUX CD-332 makes dye solution A2.Use more fast to light dyestuff LUMILUX CD-331 to make another kind of solution, solution A 3 according to same step.Shown in table 28, the mixing aryl sulfonium salt light trigger UVI-6976 (Dow Chemical) that in the aliquots containig of solution A 2 and A3, adds different levels, whole printing ink A2 was diluted to for 10% (add acetone and compensate the weight difference, to reach 2.0,4.0,6.0 and 8.0% initiator printing ink).
Table 33.CAB 553-0.4 preparation
| Solution | The LUMILUX dyestuff | The UVI-6976 % weight that adds |
| A4 | CD-332 | 2.0 |
| A5 | CD-332 | 4.0 |
| A6 | CD-332 | 6.0 |
| A7 | CD-332 | 8.0 |
| A8 | CD-332 | 10.0 |
| A9 | CD-331 | 0.27 |
| A10 | CD-331 | 0.67 |
| A11 | CD-331 | 1.0 |
| A12 | CD-331 | 1.5 |
| A13 | CD-331 | 2.0 |
Embodiment 9
This embodiment has illustrated another embodiment of the invention.Component shown in the table 34 mixed make solution, solution B 1.
Table 34. solution B 1
| Component | Weight percentage |
| Acetone: duplicate fluid #5 (4: 3 mixtures) JONCRYL 611 (Johnson polymkeric substance) propylene glycol monomethyl ether acetate polysiloxane surfactant | 89.9 5.0 5.0 0.1 |
Add 99.0g solution B 1,1.0g photoluminescence dyestuff Lumilux CD-331 obtains dye solution B2.Shown in table 35, the light trigger UVI-6976 (Dow Chemical) that in the aliquots containig of solution B 2, adds different levels, whole printing ink B2 is diluted to 10% (add acetone and compensate the weight difference, with reach initiator printing ink 2.0,4.0,6.0 and 8.0%).
Table 35.JONCRYL 611 preparations
| Solution | The LUMILUX dyestuff | The UVI-6976 that adds, % weight |
| B3 | CD-331 | 0.27 |
| B4 | CD-331 | 0.67 |
| B5 | CD-331 | 1.0 |
| B6 | CD-331 | 1.5 |
| B7 | CD-331 | 2.0 |
Embodiment 10
This embodiment has illustrated another embodiment of the invention.Component shown in the table 36 mixed make solution, solution C 1.
Table 36. solution C 1
| Component | Weight percentage |
| Acetone: duplicate fluid #5 (3: 1 mixtures) Paraloid B-66 (Rohm and Haas) light trigger UVI-6976 (Dow Chemical) | 83.0 12.0 5.0 |
Shown in table 37, tinting material is joined in the aliquots containig of solution C 1.
Table 37.CAB 553-0.4 prescription
| Solution | Dyestuff | % dyestuff (weight) |
| C2 | Alkalescence purple 4 | 1.0 |
| C3 | Solvent orange 3 | 1.0 |
| C4 | Solvent red 49 | 1.0 |
Embodiment 11
This embodiment has illustrated some character of embodiment of the present invention.The formulations prepared from solutions of preparation will be exposed to the sample under the light among the use embodiment 8,9 and 10.On aluminium sheet, prepare tension specimen.With this tension specimen section of cutting into so that sample generation exposure effect, and to solidifying sample and initial sample compares.According to the effect of exposing of some kinds of modes.Carry sample at the UV solidifying channel that is positioned on the transport substrate (molten system), thereby the 4.0cm sample is suspended in below the cure lamp.This lamp uses the H-type bulb of a 300W/6 inch, and the direction of bulb is perpendicular to throughput direction.Speed with 15 feet per minute clocks is carried sample.Embodiment 8 and 9 sample generation fluorescent quenching phenomenon; And the sample generation colour-change of embodiment 10.
Embodiment 12
This embodiment has illustrated some character of embodiment of the present invention.Use following prescription, make the mark sample according to embodiment 8-10.
Table 38.
| Component | Weight percentage |
| Acetone solvent orange 3 (Keystone, Inc.) Smart DYE TM(PhotoSecure，Inc.) 1JONCRYL 611 (Johnson Wax) acryloid B-66 (Rohm and Haas) (acrylic resin) VI1-0301-02 (Gibraltar Chemical Works, Inc.) 2Light trigger CGI 552 (diaryl group iodized salt), (Ciba Specialty Chemicals) | 65.3 1.0 1.0 4.7 9.7 13.3 5.0 |
1Assert that it is the europium metallo-chelate
2The TiO 2 pigment dispersion
According to the mode identical with all other embodiment (according to the mode among the embodiment 1, on aluminium, stretch and carry out the UV exposure) sample is detected, and the effect after the observation UV exposure, that is, the complete cancellation of fluorescence is also observed color generation noticeable change---become brown by yellow.
Embodiment 13
This embodiment has illustrated one embodiment of the invention, and color becomes redness by yellow in this embodiment, and mark tenable environment light, and for example, the minimizing of colour-change and fluorescence all has sizable tolerance to ambient light.This embodiment has also illustrated an embodiment, in this embodiment luminophor and not luminescence colorant be exposed to energy following time and can be affected.The energy active compound produces certain material, and it reacts and makes the emission of luminophor and the not absorption change of luminescence colorant.
Mix each component according to the order shown in the table 39 and make printing ink, solution 14.
Table 39. solution 14
| Component | Weight percentage |
| Acetic acid uncle amyl group ester acetone octyl methoxycinnamate | 13.6 42.2 2.0 |
| TBuA hexafluorophosphate hexabromocyclododecane solution 28 vinyl pyrrolidones/vinyl acetate copolymer solution, (ISP E-335) europium organic coordination compound, (SMART dyestuff TMUR3, derive from Photosecure) solution yellow 56 2,2, the 2-tribromoethyl alcohol | 1.2 3.0 15.0 20.0 1.0 1.0 1.0 |
Measured the following character of solution 31.Viscosity under 25 ℃ is 3.31 centipoises.Solution resistance rate under 25 ℃ is 911.3 Ω-cm.The velocity of sound under 25 ℃ is 1184 meter per seconds.Use #8 wire-wound stretching rod on aluminium sheet, to make the tension specimen of printing ink.According to embodiment 1 described mode, a part of tension specimen is exposed 4 minutes under the portable UV lamp of shortwave (254nm).Exposed region becomes reddish-brown by pink colour.Equally, measure remaining luminous intensity according to the mode described in the embodiment 1.The residual intensity percentage ratio in the coloured zone of gained is 11.4% of initial strength.
Use the Macbeth colourimeter to measure change in color.Measure and use instrument that transformation of data is the CIELAB scale, 65 ° at incident illumination angle, viewing angle is 10 °.L*, a*, b* are changed to 13.6,22.4 and-26.5, and this expression sample deepening and color migrate to redness by yellow.The Δ E measured value of observed colour-change is 37.3.
To drip sample on the fadometer of outdoor exposure and be exposed under the light being used to simulate.The amount that is passed to the luminous energy of sample is 0.4 watt/square metre, and blackboard temperature is set at 50 ℃.With sample exposure 3 hours and measure the fluorescence of unexposed sample.At least remain 50% luminous intensity, and do not observe colour-change.According to the mode described in the embodiment 1 sample after the fadometer exposure was shone 4 minutes under the portable UV lamp of short wavelength (254nm), then to reddish-brown, the sample after residual intensity is exposed than initial fadomter reduces 70% to color at least by xanthochromia.
Use Videojet EXCEL
TMThe continuous ink jet printing machine prints this printing ink, has obtained good printing quality.In the manner described above, will under portable shortwave UV light source, shine 2 minutes by the typographic(al) mark that discontinuous drop is formed.Typographic(al) mark becomes redness, uses the long wave (365nm) of portable UV lamp to be provided as incident light source, determines almost not have remaining luminous by visible inspection.
At these all reference that will quote herein, comprise that publication, patent application and patent are as a reference incorporated, every piece of document all as independent with concrete document and incorporated, and its full content is bonded to herein.
In description (especially in the content of following claim) to content of the present invention, the term " one (a and an) " that uses and " one (the) " and similarly word should be judged as and covered odd number and plural form, unless indication is arranged herein in addition or can know judgement itself and above-mentioned situation contradiction according to content.Term " comprises ", " having ", " comprising " and " containing " should be judged as open-ended term (that is, expression " including but not limited to "), unless note is arranged in addition.Unless indication is arranged herein in addition, otherwise enumerating of numerical range is intended to as a kind of short-cut method herein, it relates separately to each independent values that drops in this scope, and each independent values all is incorporated in in the specification sheets, just looks like that it is listed the same in this article separately.All methods of Miao Shuing can be operated with any suitable order herein, unless indication is arranged herein in addition, unless perhaps clearly demonstrate itself and above-mentioned situation contradiction in the content.Any or all embodiment that is provided herein or exemplary language (as, " for example ") just to the present invention is described better, invention scope is not made any restriction, unless requirement to some extent in addition.Do not have in the specification sheets term can be considered to represent any failed call but to the very important key element that carries out an invention.
Herein the preferred embodiment of the invention is described, comprises the known enforcement of inventor best mode of the present invention.After the explanation before having read, the modification of those preferred embodiments can become apparent to those skilled in the art.The present inventor estimates that those of skill in the art can rationally utilize these modification, and present inventor's intention is implemented the present invention to be different from specifically described mode herein.Therefore, present invention resides in all modification and the equivalents of the theme described in the claim, this claim is attached to herein and by corresponding law to be ratified.And, above-mentioned key element according to the combination that might mode forms all comprise in the present invention, unless indication arranged herein in addition or obviously contradict with above-mentioned situation according to this paper content.
Claims (157)
1. one kind is applicable to the ink composite in the ink jet printing, it comprises not luminescence colorant of luminophor, solvent and energy active compound and optional one or more, in energy following time that described energy active compound is exposed to significant quantity, produce one or more materials, this material react and make luminophor and/or not the characteristic of luminescence colorant change.
2. ink composite that is applicable to ink jet printing, it comprises tinting material, solvent and energy active compound, in energy following time that described energy active compound is exposed to significant quantity, produce one or more materials, and this material reacts and the characteristic of tinting material is changed.
3. ink composite as claimed in claim 2, wherein tinting material is a luminescence colorant.
4. ink composite as claimed in claim 2, wherein tinting material is luminescence colorant not.
5. ink composite as claimed in claim 1, it also comprises adhesive resin.
6. ink composite as claimed in claim 2, it also comprises adhesive resin.
7. ink composite as claimed in claim 1, wherein said one or more materials react and the absorption characteristic of luminophor are changed.
8. ink composite as claimed in claim 1, wherein said one or more materials react and the emission characteristic of luminophor are changed.
9. ink composite as claimed in claim 8, wherein emission characteristic is an emission wavelength.
10. ink composite as claimed in claim 8, wherein emission characteristic is an emissive porwer.
11. as the ink composite of claim 10, wherein said one or more materials react and emissive porwer are reduced.
Making not 12. ink composite as claimed in claim 1, wherein said one or more materials react, the absorption characteristic of luminophor changes.
13. as the ink composite of claim 12, wherein absorption characteristic is an absorbing wavelength.
14. as the ink composite of claim 12, wherein absorption characteristic is an absorption intensity.
15. ink composite as claimed in claim 2, wherein said one or more materials react and the absorption characteristic of tinting material are changed.
16. as the ink composite of claim 15, wherein absorption characteristic is an absorbing wavelength.
17. as the ink composite of claim 15, wherein absorption characteristic is an absorption intensity.
Make 18. ink composite as claimed in claim 1, wherein said one or more materials react the absorption characteristic of luminophor and not the absorption characteristic of luminescence colorant change.
Make 19. ink composite as claimed in claim 1, wherein said one or more materials react the emission characteristic of luminophor and not the absorption characteristic of luminescence colorant change.
20. as the ink composite of claim 19, wherein said one or more materials react and the emissive porwer of luminophor are changed.
21. as the ink composite of claim 19, wherein said one or more active substances react and make not that the absorbing wavelength of luminescence colorant changes.
22. as the ink composite of claim 10, wherein said one or more active substances react and make not that the absorption intensity of luminescence colorant changes.
23. ink composite as claimed in claim 1, wherein said material comprises acid.
24. ink composite as claimed in claim 1, wherein said material comprises free radical.
25. as the ink composite of claim 23, wherein said energy active compound is a salt.
26. as the ink composite of claim 25, wherein said salt comprises the element of periodic table of elements V, VI or VII family.
27. as the ink composite of claim 25, wherein said salt is selected from the group of being made up of following material: diazonium salt, salt compounded of iodine, sulfonium salt and arbitrary combination thereof with at least one aryl with at least one aryl.
28. as the ink composite of claim 23, wherein said energy active compound is a thiophene salt.
29. as the ink composite of claim 28, wherein said thiophene salt is aryl alkyl carbonyl thiophene salt.
30. as the ink composite of claim 29, wherein said aryl alkyl carbonyl thiophene salt is selected from the group of being made up of following material: S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide tosilate and S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide fluoroform sulphonate.
31. as the ink composite of claim 23, wherein said energy active compound is selected from the group of being made up of following material: the diazomethane compound, have on one or more positions of 2,4 and 6 of triazine ring wherein that X is that halogen atom and M are the substituent pyrrolotriazine derivatives of MX3 and the arbitrary combination thereof of carbon atom.
32. as the ink composite of claim 31, wherein pyrrolotriazine derivatives is three [trichloromethyl] s-triazine.
33. as the ink composite of claim 23, wherein said energy active compound comprises photoabsorption segment and the sulfonic acid group, toluenesulphonic acids group or the trifluoromethanesulfonic acid group that are connected thereon.
34. ink composite as claim 33, wherein said energy active compound is selected from the group of being made up of following material: N-hydroxyl naphthalimide fluoroform sulphonate, N-hydroxyl-5-norbornylene-2,3-dicarboximide sulfonate, N-hydroxyphthalimide fluoroform sulphonate, naphthalimido sulfonate, succimide sulfonate and st-yrax tosylate.
35. ink composite as claim 23, wherein said energy active compound is a halohydrocarbon, it comprises (1) at least two carbon atom of being appointed as carbon 1 and carbon 2, wherein carbon 1 and carbon 2 are bonded together, and have two halogen atom Direct Bonding at least on carbon 1, and carbon 2 Direct Bonding are on cyano group, hydroxyl, fluorine, chlorine, bromine, iodine, phosphonate radical or sulfonate radical; Perhaps (2) at least three carbon atoms that connect successively, described carbon atom is designated as 1,2 and 3, and wherein at least one halogen atom is bonded on the carbon 1, and at least one halogen atom is bonded on the adjacent carbon 2.
36. as the ink composite of claim 35, wherein said energy active compound is selected from the group of being made up of following material: 1,2; 5,6,9; 10-hexabromocyclododecane, tribromo-ethanol, 1; 2-dibromo-cyclohexane, 2; 3-three bromopropionitriles, bromo acetic acid benzyl ester, bromo acetic acid, bromo ethanoyl bromine, 2-bromo butyric acid, 2-bromo acid, 2,3-two bromos third-1-alcohol, bromo acetic acid ethyl ester and 1,1; 2,2-tetrabromoethane and arbitrary combination thereof.
37. ink composite as claim 24, wherein said energy active compound is selected from the group of being made up of following material: benzophenone, anthraquinone, dibenzoyl, benzoin ether, Alpha-hydroxy-α, α-dialkyl benzene ethyl ketone and dibasic aromatic series phosphine oxide and arbitrary combination thereof.
38. as the ink composite of claim 24, wherein said energy active compound is two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, phenylbenzene (2,4, the 6-trimethylbenzoyl)-phosphine oxide or its combination.
39. ink composite as claimed in claim 1, wherein said energy are light, heat, electron beam or its arbitrary combination.
40. ink composite as claimed in claim 1, wherein luminophor is launched in ultraviolet (UV) light district.
41. ink composite as claimed in claim 1, wherein said luminophor is launched at visible region.
42. ink composite as claimed in claim 1, wherein said luminophor is launched in infrared (IR) light district.
43. ink composite as claimed in claim 3, wherein said luminescence colorant is launched in UV light district.
44. ink composite as claimed in claim 3, wherein said luminescence colorant is launched at visible region.
45. ink composite as claimed in claim 3, wherein said luminescence colorant is launched in IR light district.
46. ink composite as claimed in claim 1, wherein said solvent are organic solvent.
47. as the ink composite of claim 46, wherein said organic solvent is a volatile organic solvent.
48. as the ink composite of claim 47, wherein said volatile organic solvent is selected from the group of being made up of following material: alcohol, ketone, cyclic ketones, ester, ether and arbitrary combination thereof.
49. as the ink composite of claim 46, wherein said organic solvent is selected from the group of being made up of following material: methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, acetone, methylethylketone, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, pimelinketone and arbitrary combination thereof.
50. ink composite as claimed in claim 5, wherein adhesive resin is a thermoplastic resin.
51. ink composite as claimed in claim 5, wherein said adhesive resin is selected from the group of being made up of following material: acid amides, urethane, ester, Resins, epoxy, ketone resin, vinylpyrrolidone copolymer, vinyl polymer, vinyl butyral multipolymer, acrylic resin, styrene/acrylic resin, celluosic resin, soluble cotton, resol, hydroxystyrene polymers, vinyl alcohol polymer, vinylbenzene allyl alcohol polymkeric substance and arbitrary combination thereof.
52. ink composite as claimed in claim 2, wherein said material comprises acid.
53. ink composite as claimed in claim 2, wherein said material comprises free radical.
54. ink composite as claimed in claim 2, wherein said energy active compound is a salt.
55. as the ink composite of claim 54, wherein said salt comprises the element of periodic table of elements V, VI or VII family.
56. as the ink composite of claim 54, wherein said salt is selected from the group of being made up of following material: diazonium salt, salt compounded of iodine, sulfonium salt and arbitrary combination thereof with at least one aryl with at least one aryl.
57. as the ink composite of claim 52, wherein said energy active compound is a thiophene salt.
58. as the ink composite of claim 57, wherein said thiophene salt is aryl alkyl carbonyl thiophene salt.
59. as the ink composite of claim 58, wherein said aryl alkyl carbonyl thiophene salt is selected from the group of being made up of following material: S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide tosilate and S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide fluoroform sulphonate.
60. as the ink composite of claim 52, wherein said energy active compound is selected from the group of being made up of following material: the diazomethane compound, have on one or more positions of 2,4 and 6 of triazine ring wherein that X is that halogen atom and M are the substituent pyrrolotriazine derivatives of MX3 and the arbitrary combination thereof of carbon atom.
61. as the ink composite of claim 60, wherein pyrrolotriazine derivatives is three [trichloromethyl] s-triazine.
62. as the ink composite of claim 52, wherein said energy active compound comprises photoabsorption segment and the sulfonic acid group, toluenesulphonic acids group or the trifluoromethanesulfonic acid group that are connected thereon.
63. ink composite as claim 62, wherein said energy active compound is selected from the group of being made up of following material: N-hydroxyl naphthalimide fluoroform sulphonate, N-hydroxyl-5-norbornylene-2,3-dicarboximide sulfonate, N-hydroxyphthalimide fluoroform sulphonate, naphthalimido sulfonate, succimide sulfonate and st-yrax tosylate.
64. ink composite as claim 52, wherein said energy active compound is a halohydrocarbon, it comprises (1) at least two carbon atom of being appointed as carbon 1 and carbon 2, wherein carbon 1 and carbon 2 are bonded together, and have two halogen atom Direct Bonding at least on carbon 1, and carbon 2 Direct Bonding are on cyano group, hydroxyl, fluorine, chlorine, bromine, iodine, phosphonate radical or sulfonate radical; Perhaps (2) at least three carbon atoms that connect successively, described carbon atom is designated as 1,2 and 3, and wherein at least one halogen atom is bonded on the carbon 1, and at least one halogen atom is bonded on the adjacent carbon 2.
65. as the ink composite of claim 64, wherein said energy active compound is selected from the group of being made up of following material: 1,2; 5,6,9; 10-hexabromocyclododecane, tribromo-ethanol, 1; 2-dibromo-cyclohexane, 2; 3-three bromopropionitriles, bromo acetic acid benzyl ester, bromo acetic acid, bromo ethanoyl bromine, 2-bromo butyric acid, 2-bromo acid, 2,3-two bromos third-1-alcohol, bromo acetic acid ethyl ester and 1,1; 2,2-tetrabromoethane and arbitrary combination thereof.
66. ink composite as claim 53, wherein said energy active compound is to be selected from the group of being made up of following material: benzophenone, anthraquinone, dibenzoyl, benzoin ether, Alpha-hydroxy-α, α-dialkyl benzene ethyl ketone and dibasic aromatic series phosphine oxide and arbitrary combination thereof.
67. as the ink composite of claim 53, wherein said energy active compound is two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, phenylbenzene (2,4, the 6-trimethylbenzoyl)-phosphine oxide or its combination.
68. ink composite as claimed in claim 2, wherein said energy are light, heat, electron beam, or its arbitrary combination.
69. ink composite as claimed in claim 2, wherein said solvent are organic solvent.
70. as the ink composite of claim 69, wherein said organic solvent is a volatile organic solvent.
71. as the ink composite of claim 70, wherein said volatile organic solvent is selected from the group of being made up of following material: alcohol, ketone, cyclic ketones, ester, ether and arbitrary combination thereof.
72. as the ink composite of claim 70, wherein said organic solvent is selected from the group of being made up of following material: methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, acetone, methylethylketone, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, pimelinketone and arbitrary combination thereof.
73. ink composite as claimed in claim 6, wherein adhesive resin is a thermoplastic resin.
74. ink composite as claimed in claim 6, wherein said adhesive resin is selected from the group of being made up of following material: acid amides, urethane, ester, Resins, epoxy, ketone resin, vinylpyrrolidone copolymer, vinyl polymer, vinyl butyral multipolymer, acrylic resin, styrene/acrylic resin, celluosic resin, soluble cotton, resol, hydroxystyrene polymers, vinyl alcohol polymer, vinylbenzene allyl alcohol polymkeric substance and arbitrary combination thereof.
75. ink composite as claimed in claim 1, wherein luminophor is a luminescence colorant.
76. ink composite as claimed in claim 1, wherein luminophor is luminous leucocompound.
77. as the ink composite of claim 76, it also comprises adhesive resin.
78. as the ink composite of claim 76, wherein said one or more materials react and the absorption characteristic of luminous leucocompound are changed.
79. as the ink composite of claim 76, wherein said one or more materials react and the emission characteristic of luminous leucocompound are changed.
80. as the ink composite of claim 79, wherein said emission characteristic is an emission wavelength.
81. as the ink composite of claim 79, wherein said emission characteristic is an emissive porwer.
82. as the ink composite of claim 79, wherein said one or more materials react and emissive porwer are descended.
83. as the ink composite of claim 76, wherein said material comprises acid.
84. as the ink composite of claim 76, wherein said material comprises free radical.
85. as the ink composite of claim 76, wherein said energy active compound is a salt.
86. as the ink composite of claim 85, wherein said salt comprises the element of periodic table of elements V, VI or VII family.
87. as the ink composite of claim 85, wherein said salt is selected from the group of being made up of following material: diazonium salt, salt compounded of iodine, sulfonium salt and arbitrary combination thereof with at least one aryl with at least one aryl.
88. as the ink composite of claim 83, wherein said energy active compound is a thiophene salt.
89. as the ink composite of claim 88, wherein said thiophene salt is aryl alkyl carbonyl thiophene salt.
90. as the ink composite of claim 89, wherein said aryl alkyl carbonyl thiophene salt is selected from the group of being made up of following material: S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide tosilate and S-(2-naphthalene carbonyl methyl)-tetramethylene sulfide fluoroform sulphonate.
91. as the ink composite of claim 83, wherein said energy active compound is selected from the group of being made up of following material: the diazomethane compound, have on one or more positions of 2,4 and 6 of triazine ring wherein that X is that halogen atom and M are the substituent pyrrolotriazine derivatives of MX3 and the arbitrary combination thereof of carbon atom.
92. as the ink composite of claim 91, wherein pyrrolotriazine derivatives is three [trichloromethyl] s-triazine.
93. as the ink composite of claim 83, wherein said energy active compound comprises photoabsorption segment and the sulfonic acid group, toluenesulphonic acids group or the trifluoromethanesulfonic acid group that are connected thereon.
94. ink composite as claim 93, wherein said energy active compound is selected from the group of being made up of following material: N-hydroxyl naphthalimide fluoroform sulphonate, N-hydroxyl-5-norbornylene-2,3-dicarboximide sulfonate, N-hydroxyphthalimide fluoroform sulphonate, naphthalimido sulfonate, succimide sulfonate and st-yrax tosylate.
95. ink composite as claim 83, wherein said energy active compound is a halohydrocarbon, it comprises (1) at least two carbon atom of being appointed as carbon 1 and carbon 2, wherein carbon 1 and carbon 2 are bonded together, and have two halogen atom Direct Bonding at least on carbon 1, and carbon 2 Direct Bonding are on cyano group, hydroxyl, fluorine, chlorine, bromine, iodine, phosphonate radical or sulfonate radical; Perhaps (2) at least three carbon atoms that connect successively, described carbon atom is designated as 1,2 and 3, and wherein at least one halogen atom is bonded on the carbon 1, and at least one halogen atom is bonded on the adjacent carbon 2.
96. as the ink composite of claim 95, wherein said energy active compound is selected from the group of being made up of following material: 1,2; 5,6,9; 10-hexabromocyclododecane, tribromo-ethanol, 1; 2-dibromo-cyclohexane, 2; 3-two bromopropionitriles, bromo acetic acid benzyl ester, bromo acetic acid, bromo ethanoyl bromine, 2-bromo butyric acid, 2-bromo acid, 2,3-two bromos third-1-alcohol, bromo acetic acid ethyl ester and 1,1; 2,2-tetrabromoethane and arbitrary combination thereof.
97. ink composite as claim 84, wherein said energy active compound is to be selected from the group of being made up of following material: benzophenone, anthraquinone, dibenzoyl, benzoin ether, Alpha-hydroxy-α, α-dialkyl benzene ethyl ketone and dibasic aromatic series phosphine oxide and arbitrary combination thereof.
98. as the ink composite of claim 84, wherein said energy active compound is two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, phenylbenzene (2,4, the 6-trimethylbenzoyl)-phosphine oxide or its combination.
99. as the ink composite of claim 76, wherein said energy is light, heat, electron beam or its arbitrary combination.
100. as the ink composite of claim 76, wherein said solvent is an organic solvent.
101. as the ink composite of claim 100, wherein said organic solvent is a volatile organic solvent.
102. as the ink composite of claim 101, wherein said volatile organic solvent is selected from the group of being made up of following material: alcohol, ketone, cyclic ketones, ester, ether, and arbitrary combination.
103. as the ink composite of claim 100, wherein said organic solvent is selected from the group of being made up of following material: methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, acetone, methylethylketone, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, pimelinketone and arbitrary combination thereof.
104. ink composite as claimed in claim 1, it also comprises one or more additives, and this additive is selected from the group of being made up of following material: wetting Agent for Printing Inks, softening agent, light blocker, tensio-active agent, wetting agent, thermo-stabilizer, sterilant, tackifier and conductive agent and arbitrary combination thereof.
105. ink composite as claimed in claim 2, it also comprises one or more additives, and this additive is selected from the group of being made up of following material: wetting Agent for Printing Inks, softening agent, light blocker, tensio-active agent, wetting agent, thermo-stabilizer, sterilant, tackifier and conductive agent and arbitrary combination thereof.
106. ink composite as claimed in claim 1, the viscosity under its 25 ℃ is about 1.6 centipoises (cps)-Yue 7 centipoises, and resistivity is about 2,000 Ω of about 50 Ω-cm--cm, and the velocity of sound is about 1100 meter per seconds-Yue 1700 meter per seconds.
107. ink composite as claimed in claim 2, the viscosity under its 25 ℃ is about 1.6 centipoises (cps)-Yue 7 centipoises, and resistivity is about 2,000 Ω of about 50 Ω-cm--cm, and the velocity of sound is about 1100 meter per seconds-Yue 1700 meter per seconds.
108. ink composite as claimed in claim 1, the viscosity under its 25 ℃ is about 4 centipoises-Yue 120 centipoises, and resistivity is greater than about 3K Ω-cm, and the surface tension under 25 ℃ is about 38 dyne of about 25-/cm.
109. ink composite as claimed in claim 2, the viscosity under its 25 ℃ is about 4 centipoises-Yue 120 centipoises, and resistivity is greater than about 3K Ω-cm, and the surface tension under 25 ℃ is about 38 dyne of about 25-/cm.
110. ink composite as claimed in claim 1, its resistivity be greater than about 3K Ω-cm, the surface tension under 25 ℃ is about 38 dyne of about 25-/cm.
111. as the ink composite of claim 110, the viscosity under its 25-70 ℃ is the about 30cps of about 3cps-.
112. ink composite as claimed in claim 2, its resistivity be greater than about 3K Ω-cm, the surface tension under 25 ℃ is about 38 dyne of about 25-/cm.
113. as the ink composite of claim 112, the viscosity under its 25-70 ℃ is the about 30cps of about 3cps-.
114. a method of differentiating matrix, it comprises: (a) use the ink composite of claim 1 that the discriminating mark is provided on matrix; (b) read described discriminating mark; (c) described discriminating mark is exposed under the energy of significant quantity, producing and described luminophor and/or the material that reacts of luminescence colorant not, thereby obtains discriminating mark after energy-exposure; (d) read discriminating mark after this energy-exposure.
115. a method of differentiating matrix, it comprises: (a) use the ink composite of claim 2 that the discriminating mark is provided on matrix; (b) read described discriminating mark; (c) described discriminating mark is exposed under the energy of significant quantity, with the material that produces and described tinting material reacts, thus the discriminating mark after acquisition energy-exposure; (d) read discriminating mark after this energy-exposure.
116. a method of differentiating matrix, it comprises: (a) use the ink composite of claim 1 that the discriminating mark is provided on matrix; (b) read described discriminating mark; (c) described discriminating mark is exposed under the energy of significant quantity, with the material that produces and described not luminescence colorant reacts, thus the discriminating mark after acquisition energy-exposure; (d) read discriminating mark after this energy-exposure.
117. a system that is used to differentiate matrix, it comprises the ink composite of (a) claim 1; (b) ink-jet printer; (c) matrix; (d) the passivation energy; (d) reading device.
118. a system that is used to differentiate matrix, it comprises the ink composite of (a) claim 2; (b) ink-jet printer; (c) matrix; (d) the passivation energy; (d) reading device.
119. the safety label with color changeableization comes the method for mark matrix, wherein said colour-change can test out, this method comprises: a kind of mark that contains macroscopic non-fluorescent colorant and fluorescent colorant is provided, wherein said fluorescent colorant only when being subjected to first wavelength light irradiation just owing to fluorescent emission becomes macroscopic material, this mark of rayed of using second wavelength then is with this fluorescent emission of cancellation, and the color of this non-fluorescent colorant is changed, verify that by visual manner this fluorescent emission is by the method for cancellation thereby provide a kind of.
120. an inkjet ink composition, it comprises the compound of release acid of second tinting material, solvent, adhesive resin and the photosensitivity of fluorescigenic first tinting material, pH susceptibility.
121. the safety label with color changeableization comes the method for mark matrix, this method comprises: a kind of mark that contains macroscopic non-fluorescent colorant and fluorescent colorant is provided, only ability is owing to fluorescent emission becomes macroscopic material to wherein said fluorescent colorant when being subjected to first wavelength light irradiation, and this mark of rayed of using second wavelength then is with this fluorescent emission of cancellation.
122. ink composite as claimed in claim 6, wherein said tinting material are fluorescent colorant, the energy active compound is the compound of the release acid of photosensitivity.
123. ink composite as claimed in claim 3, wherein said luminophor is selected from the group of being made up of following material: anthracene, furans, thiophene, oil of mirbane, cyanine, xanthene, acridine, azophenlyene, naphthols, porphyrin, tonka bean camphor, pyrroles's methine He oxazine and arbitrary combination thereof.
124. as the ink composite of claim 123, wherein said xanthene is fluorescein or rhodamine.
125. as the ink composite of claim 123, wherein said acridine is euchrysine.
126. as the ink composite of claim 123, wherein said azophenlyene is a safranine.
127. ink composite as claimed in claim 1, wherein said luminophor are dyestuff.
128. as the ink composite of claim 127, wherein said dyestuff is selected from the group of being made up of following material: C.I. solvent red 49, fluorescigenic metal complexes azoic dyestuff and fluorescigenic azoic dyestuff and arbitrary combination thereof.
129. as the ink composite of claim 128, wherein said fluorescigenic metal complexes azoic dyestuff is an aluminium: sour alizarin garnet R.
130. as the ink composite of claim 128, wherein said fluorescigenic azoic dyestuff is 4-dimethylamino-N-benzylidene-4 '-N-methyl-p-nitroaniline.
131. ink composite as claimed in claim 1, wherein said luminophor are rare-earth chelates.
132. as the ink composite of claim 131, wherein said rare earth metal is a lanthanon.
133. as the ink composite of claim 132, wherein said rare earth metal is Eu.
134. ink composite as claimed in claim 1, wherein said reactive materials reacts, make not that the absorption or the emission characteristic of luminescence colorant change, thereby make the absorption of the not luminescence colorant after the change or emission characteristic overlapping or consistent with the absorption or the emission characteristic of luminophor.
135. ink composite as claimed in claim 1, it comprises additional not luminescence colorant, in order to a kind of visible color to be provided or to be used for changing the luminosity of luminophor.
136. as the ink composite of claim 135, wherein said additional not luminescence colorant is a titanium dioxide.
137. ink composite as claimed in claim 1, wherein at least a not luminescence colorant is a following substances: when the pH of its environment changed, its color also changed.
138. as the ink composite of claim 137, wherein said at least a not luminescence colorant color under acidic conditions demonstrates variation.
139. as the ink composite of claim 137, wherein said at least a not luminescence colorant is triarylmethane dye, xanthene dyestuff or azoic dyestuff.
140. as the ink composite of claim 139, wherein said triarylmethane dye is a C.I. alkalescence purple 4.
141. as the ink composite of claim 139, wherein said xanthene dyestuff is the C.I. solvent red 49.
142. as the ink composite of claim 139, wherein said azoic dyestuff is a C.I. solvent orange 3.
143. as the ink composite of claim 137, wherein said at least a not luminescence colorant is selected from the group of being made up of following material: anthraquinone, ditan, thiazine, oxazine, azine, pyronin, sulfo-pyronin, acridine, poly-methine, indigo-blue, nitro and nitroso-dye and arbitrary combination thereof.
144. ink composite as claimed in claim 1, wherein said energy active agent is a light trigger.
145. ink composite as claimed in claim 2, wherein said energy active agent is a light trigger.
146. ink composite as claimed in claim 5, it contains the not luminescence colorant of about 10% weight of luminophor, 0-of adhesive resin, about 10% weight of about 0.01-of about 30% weight of solvent, 0-of about 95% weight of the 30-that has an appointment and the energy active compound of about 15% weight of about 0.1%-.
147. as the ink composite of claim 146, wherein said solvent is an organic solvent.
148. as the ink composite of claim 147, wherein said organic solvent is an acetone.
149. as the ink composite of claim 146, wherein said adhesive resin is the polyketone resin.
150. as the ink composite of claim 146, wherein said luminophor is the phosphorescent coloring that comprises europium.
151. as the ink composite of claim 146, wherein luminescence colorant is not an azoic dyestuff.
152. as the ink composite of claim 151, wherein azoic dyestuff is a chrysolidine Y alkali.
153. as the ink composite of claim 146, radiation has reactivity and is dissolvable in water in the solvent wherein said energy active compound to UVC.
154. as the ink composite of claim 146, wherein said energy active compound is a tribromoethyl alcohol.
155. as the ink composite of claim 146, it also comprises conductive agent, the amount of this conductive agent is about 5% weight of about 0.5-of ink composite.
156. as the ink composite of claim 115, wherein said conductive agent is the bromination tetrapropyl ammonium.
157. as the ink composite of claim 19, wherein said luminophor is the europium metallo-chelate, luminescence colorant is not a solvent yellow 56.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45394003P | 2003-03-13 | 2003-03-13 | |
| US60/453,940 | 2003-03-13 | ||
| US10/800,426 | 2004-03-12 |
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| Publication Number | Publication Date |
|---|---|
| CN1788057A true CN1788057A (en) | 2006-06-14 |
| CN100575430C CN100575430C (en) | 2009-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200480012856 Expired - Fee Related CN100575430C (en) | 2003-03-13 | 2004-03-15 | Ink-jet ink composition and safe printing method |
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| Country | Link |
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| CN (1) | CN100575430C (en) |
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| CN102093754A (en) * | 2010-12-08 | 2011-06-15 | 中国人民解放军63975部队 | Dyeing agent for labeling skin |
| CN104349904A (en) * | 2012-06-11 | 2015-02-11 | 锡克拜控股有限公司 | Methods for printing tactile security features |
| CN105273501A (en) * | 2014-06-26 | 2016-01-27 | 马肯依玛士控股公司 | Ink composition for deflected continuous jet printing, in particular for security markings |
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| CN109722160B (en) * | 2018-12-19 | 2020-12-29 | 上海乘鹰新材料有限公司 | High-wear-resistance UV (ultraviolet) photocuring release layer applied to gold stamping material and preparation thereof |
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| CN102093754A (en) * | 2010-12-08 | 2011-06-15 | 中国人民解放军63975部队 | Dyeing agent for labeling skin |
| US9616699B2 (en) | 2012-06-11 | 2017-04-11 | Sicpa Holding Sa | Methods for printing tactile security features |
| CN104349904A (en) * | 2012-06-11 | 2015-02-11 | 锡克拜控股有限公司 | Methods for printing tactile security features |
| CN104349904B (en) * | 2012-06-11 | 2016-09-21 | 锡克拜控股有限公司 | For the method printing tactile security feature |
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| CN106256857A (en) * | 2015-06-17 | 2016-12-28 | 乐凯华光印刷科技有限公司 | A kind of ethyl violet B being applied to offset plate material and the HPLC assay method of content thereof |
| CN106256857B (en) * | 2015-06-17 | 2018-02-16 | 乐凯华光印刷科技有限公司 | It is a kind of applied to the ethyl violet B of offset plate material and its HPLC assay methods of content |
| WO2019120125A1 (en) * | 2017-12-21 | 2019-06-27 | 广州华睿光电材料有限公司 | Composition for preparing organic electronic device, organic electronic device and application thereof |
| CN111868050A (en) * | 2017-12-21 | 2020-10-30 | 广州华睿光电材料有限公司 | Composition for preparing organic electronic device, organic electronic device and application |
| CN111868050B (en) * | 2017-12-21 | 2023-07-25 | 广州华睿光电材料有限公司 | Composition for preparing organic electronic device, organic electronic device and application |
| CN109238522A (en) * | 2018-09-21 | 2019-01-18 | 南开大学 | A kind of wearable flexibility stress sensor and its preparation method and application |
| CN114874238A (en) * | 2021-02-01 | 2022-08-09 | 中国科学院理化技术研究所 | Photosensitizer based on thiadiazole [3,4-g ] quinoxaline structure and synthesis method and application thereof |
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