CN1009346B - The laser chemistry curing of high-molecular coating - Google Patents

Abstract

A kind of laser chemistry method of solidifying high-molecular coating is wherein carried out Ultra-Violet Laser irradiation to the coating that contains the laser sensitive light trigger of a certain selected wavelength, and the low energy that can reach this coating is solidified.Solidify used total energy by applying the laser pulse of one group of low monopulse flux, significantly reduce to finish.Reduce the monopulse flux during fixed pulse frequency, or fixedly reduce the repetition rate of pulse during the monopulse flux, can further reduce the required total energy of curing of finishing coating.

Description

The laser chemistry curing of high-molecular coating

The present invention relates to the curing of coating and printing ink, more properly say, relate to the laser curing of described coating and printing ink.

Be easy to the coating and the printing ink that carry out the transparent of ultraviolet light polymerization or add pigment, for example, be used to paint and those of Printing industry, because they can be by very fast curing, it is little to solidify requisite space, and can reduce or eliminate the loss of solvent to environment, and they are admitted widely.Ultraviolet coating is made up of a kind of liquid or solid polymkeric substance and/or oligopolymer and/or a kind of monomer and a kind of light trigger usually.Light trigger optionally is added with hydrogen donor, as amine or mercaptan and their congener, comprises the congener of high molecular, so that increase the amount of free radical of initiated polymerization thing chain of being used for.Form a free radical after photoinitiator molecules absorbs a photon, this free radical combines with a monomer or polymkeric substance, the growth of initiated polymerization thing long-chain, thus reach the curing of coating or printing ink.Common ultraviolet lamp system needs every square centimeter of erg-ten or bigger flux, has practical thickness to guarantee solidified coating or film.When this kind of consumption energy is with the curing speed that reaches practicality, if can reduce flux, thereby make that solidifying more film with same luminous energy raises the efficiency, just can obtain bigger superiority.Can freely select optimal wavelength and wavelength bandwidth, also be favourable.In addition, when coating was thicker, usually inner solidified earlier than it on the surface of coating, causes coating wrinkling and surface adhesion force is poor.

Be to remove with stove to desolvate now, thereby drying and/or polymerization are with conventional solvent or based on the coating of the aqueous solution.This stove and accessory occupies sizable space, and needs many relatively energy to ventilate to remove solvent vapour to keep furnace temperature and to ensure.Having the necessity of more uniform curing speed at whole profile depth, as by reducing optical throughput to reach the resultant benifit of photopolymerization, is conspicuous.Now, with ultraviolet lamp dry transparent coating and printing ink, but the light of ozone, heat radiation and useless wavelength all can reduce its effectiveness.The light that these lamps send has only seldom a part of can penetrate common thick pigment coatedly, does not have what commercial value so that be used for this purpose lamp.

The present invention utilizes the Ultra-Violet Laser energy of special selection to finish the curing of the predetermined form of coating and printing ink, and expectation solves some the relevant problems of curing process system with previous coating and printing ink.

On the one hand, the present invention includes a kind of coating material solidified, comprise the method that coating is used for a surface, this coating comprises a liquid or solid polymkeric substance and/or oligopolymer and/or a monomer and at least a light trigger, and coating is carried out irradiation with the Ultra-Violet Laser of at least one predetermined wavelength, wherein select the light of at least one predetermined wavelength for use, make it by at least a light trigger and not by other component institute preferential absorption of coating.When this coating was a kind of form with pigment coating or printing ink, coating also can contain a kind of pigment, and selects the laser of a predetermined wavelength at least, makes pigment reach minimum to the absorption of light.

According to of the present invention, the method for in fact preferentially selecting for use is that laser is imposed on coating with impulse form.More particularly, finishing curing needs 25 laser pulses at least, and another kind of scheme needs 50 pulses at least.It is low-level to wish that used single laser pulse flux remains on, be preferably less than 3 millis burnt/centimetre ²More advantageously, have been found that, reduce the monopulse flux and increase the pulse sum that imposes on coating or printing ink, then can significantly reduce to finish and solidify needed total energy if keep a given pulse-repetition frequency.

Use two kinds of light triggers in another embodiment, each optionally absorbs the laser of a different setted wavelength each among both, makes a kind of light trigger be used to solidify whole coating, and the another kind of surface that is used for solidified coating.

Usually, pigment coated thickness 〉=0.5 micron; The thickness of Clear coating 〉=2 micron; The thickness of printing-ink≤20 micron.

Laser curing technology of the present invention only needs to contain seldom in coating or the printing ink or do not contain solvent, thereby the requisite space minimum, and the technology that provides a kind of environmental system to allow.In addition, carry out laser curing with technology of the present invention, its cost is the sub-fraction of existing heat curing process only, but also has avoided air dried related problems.Usually the hot stove drying of pigment coating needs sizable space and energy, to keep the ventilation equipment of certain temperature and elimination solvent vapour.

Utilizing the present invention, that flux is low to moderate 0.0001 milli is burnt/centimetre ²The laser pulse of/pulse promptly can be used for the curing of Clear paint.Best flux be 0.002 milli burnt/centimetre ²/ pulse applies 180 subpulses.Under this flux, curable wide 1 meter, the thick 7 microns film of 100 watts of Ultra-Violet Laser lamps, walking speed is 750 meters ²/ minute.This can be solidified (1 meter wide interior light is 200-300 watt/inch by force) and single electronic beam curing with single ultraviolet lamp and compare, the former common walking speed is 80 meters ²/ minute, the latter is 400 meters ²/ minute.Utilize low monopulse flux and multipulse irradiation, can in the curing of transparent polymer coating, obtain high energy efficiency.Solidify for small throughput, available Beer's law is determined the optimum concn of light trigger under required coat-thickness, thereby makes the whole thickness of coating can both obtain solidifying.Utilize the present invention, except that light trigger is required, do not need to use more luminous energy, because consider that from the angle of preferential selection other component in the coating does not produce absorption substantially under selected wavelength.Compare with the coating material solidified flux of using always, this technology reduces flux greatly, and because final required number of photons much less, thereby it is much lower to finish the clean cost of solidified, although produce the cost of a photon than using the ordinary lamps height with laser apparatus.Equally, and compared in the past, the reduction of required flux, then being converted into the material yield that is covered with coating increases greatly.

Have, transmit because the light of laser apparatus output can be grown distance at an easy rate, laser apparatus can be placed on the place away from the coating place.With beam spread and make its enough uniformly technology be to realize easily.

Adding under the situation of pigment coating, the present invention once was used for solidifying 20 microns or the thicker 50%(weight that contains) rutile TiO ₂The business level coating.In this example, absorb under the minimum wavelength at pigment, use the laser penetration coating, reach the completely solidified of coating, used light trigger produces absorption at this wavelength, and can regulate initiator concentration and make energy efficiency the highest.

In solidification process, the most handy nitrogen protection turns usefulness into the resistance of antagonism oxygen, and with very short light pulse, is generally the 20-40 nanosecond order, causes the polymer growth of a specific region in the coating.The successive short pulse combines with low optical throughput, impels to solidify to reach complete.Have been found that at 50% concentration expressed in percentage by volume TiO ₂The time, according to the method described in the present invention, with 3 millis burnt/centimetre ²Flux, its effect with flux be 16 Jiao/centimetre ²The solidification effect of mercury lamp can at room temperature solidify during quite and with laser.This means that 100 watts of laser apparatus can keep 1 meter wide band and move with 50 meters/minute speed.Produce the pigment that absorbs for other in spectrographic ultraviolet region shortwave direction, or thinner coating, as printing ink, finishing the energy that solidifies required unit surface will be still less.

Following Example has provided component contained in the general coating, and these coating are suitable for being cured with method of the present invention.

Clear paint

Be applicable to general Ultra-Violet Laser hardenable coatings of the present invention, may contain, but non-ly be confined to following material:

1. the low-molecular weight polymer of the one or more activation functionality of active copolymer-have (weight-average molecular weight is greater than 500 usually), contain unsaturated reactive center, as acrylate or acrylamide or polyester, polyethers, Synolac, Mierocrystalline cellulose, acrylic resin, Resins, epoxy, silicone resin, urethane, or their arbitrary combination, but be not limited to these.Also available polyenoid/polythiol type system, or be similar to the system of the type that positively charged ion causes, the also system of available anionic initiation.

Reactive thinner-this component can be single, double, three or multi-functional, and also should be low molecular weight substance usually.(general weight-average molecular weight is 50-500.）

3. photoinitiator system-this component will utilize incident light to form free radical or ion to induce.

4. can also contain a kind of amine or derivative, comprise amino acrylates and

5 various additives-these additives generally are used for traditional paint manufacturing, for example, are used as flowing regulator.

6. optional solvent or water.

General photoinitiator system preferably comprises two groups in the following series group:

1. the alkyl benzoin ether-for example, benzoin isobutyl ether is as the commodity EB3 of Fu Laitaili Rameau vigorous special (Fratelli Lamaberti).

2. α-acyl oxime ester-1-phenyl-1,2-propanedione-2-(-neighbour-ethoxy carboxyl) oxime, for example the Ku Anta of Ward-Blanc Ken Suopu (Ward-Blankensop) solidifies 1,5-pentanediol (Quantacure PDO).

3. benzoglyoxaline and a word used for translation thiophene-2-chloromethyl benzimidazole.

4. benzophenone and derivative-benzophenone thereof are right-the phenyl benzophenone, for example, and the tripartite 12(Trigonal 12 of Acker assistant chemistry (AKZO Chemie) company).

5 methyl phenyl ketones and derivative thereof-(α, α-diethoxy acetophenone) diethoxy acetophenone (DEAP) of producing as A Pu John (Upjohn), or 2,2-dimethyl-2-phenyl methyl phenyl ketone, the Ai Jia of Ba-Jie Ji (Ciba-Geigy) product solidifies 651(Irgacure 651 like that), or 2-2-dimethyl-2-hydroxy acetophenone, as not restraining the D1173 that (Merck) produces.

6. hydrogen donor as amine or mercaptan and their congener, comprises polymeric and unsaturated congener, for example, and methyldiethanolamine.

7. ketone-Mi Qiele (ketone of Michler ' s) seldom is used owing to have carinogenicity, and sieve that reaches that also has gram to produce solidifies 1664(Darocure 1664).

8. dibenzoyl ketal-benzyl dimethyl ketal, for example, KB1 and KB60 that Forlan Tai Li-La Mubote (Fratelli-Lamberti) produces.

9. other excludes 2-methyl isophthalic acid-(4-methylbenzene the sulfenyl)-2-morpholine acetone-1 and the 1-benzoyl hexalin of compound-Si Ba-Jie Ji (Ciba-Geigy) product of above-mentioned classification; Acyloxylation phosphine ex hoc genus anne thing.

10. thioxanthone-comprise following compounds:

2 and the 4-chloro thioxanthone, as the CTX of She Wuyin WILLIAMS-DARLING Ton (Sherwin Williams).

2, the 4-diethyl thioxanthone is as DETX.

Isopropyl thioxanthone is as ITX.

2,4-dimethyl thioxanthone is as RTX.

CTX/MDEOA, DETX/MDEOA, ITX/MDEOA and RTX/MDEOA.MDEOA can use ethyl-right-dimethylaminobenzoic acid ester, and ethylpyridine bromide (EPB) and right-dimethyl ethyl aminobenzoate substitute.Other suitable compound has the DETX congener, corresponding polymer and amine and Aminobenzoate.Add pigment coating

Be used for general ultraviolet curable coating of the present invention, usually by above-cited material and the colored pigment that is used for Clear paint, as TiO ₂Form.The light trigger that is used for the TiO 2 pigment system is generally CTX/MDEOA, DETX/MDEOA, ITX/MDEOA and RTX/MDEOA.MDEOA can-dimethylaminobenzoic acid ester, ethylpyridine bromide (EPB) a pair of with ethyl and right-dimethyl ethyl aminobenzoate substitute.Other compounds suitable for use has DETX congener, acyloxylation phosphine and congener, corresponding polymer and amine and Aminobenzoate.

Adding under the situation of pigment coating, for given pigment concentration, can regulate the concentration of light trigger, to reduce the laser energy that makes needed every square centimeter of coating completely solidified to greatest extent.In practical application of the present invention, the bandwidth of used laser apparatus under operation wavelength is generally about 5 nanometers, or narrower.For the combination of each pigment and light trigger, has only a narrow optimal wavelength scope.Double wavelength and disperse, or, all will increase required energy to either direction skew optimal wavelength 5 nanometers.

Have been found that with the acyloxylation phosphine to have special advantage as light trigger, use it can obtain one hard, solidify well, beautiful pure white coating.Because rutile TiO ₂In the 400-450 nano waveband, do not have strong the absorption, the application of ultraviolet laser in this wave band succeeded.As previously mentioned, produce the pigment that absorbs in spectrographic ultraviolet region shortwave direction for other, or thinner coating, as printing ink, finishing the energy that solidifies required unit surface will be still less.Hence one can see that, and absorbing the light trigger that produces absorption under the minimum wavelength at used pigment should preferentially adopt.

Use benefit of the present invention and superiority, be illustrated with reference to the accompanying drawings, wherein:

Curve among Fig. 1 is for a specific light trigger, and the curing that will be undertaken by the method for the invention is compared with the curing that the possible traditional mercury lamp of usefulness carries out.

Fig. 2 is under two kinds of different coat-thicknesses, and the curing of Clear paint can be with the variation of photoinitiator concentration.

Fig. 3 can be with the variation of finishing the used monopulse flux of this curing for the curing of Clear paint, and pulse-repetition is per second 250 times.

When Fig. 4 was two kinds of different pulse repetition, the curing of Clear paint can be with the variation of monopulse flux.

Fig. 5 is for adding two kinds of different Ti O in the pigment coating ₂During concentration, TiO ₂Transmitted spectrum.

Fig. 6 be add the curing of pigment coating can be with finishing the variation that this solidifies used optical maser wavelength.

Fig. 7 be add the curing of pigment coating can be with the variation of optical maser wavelength.Light trigger wherein is different with the light trigger among Fig. 6.

Fig. 8 has provided the variation how change in concentration of two kinds of solvents in the dye laser causes optical maser wavelength.

Fig. 9 be add the curing of pigment coating under two kinds of different pigment concentrations can be with the variation of coat-thickness.

Figure 10 be add the curing of pigment coating can be with the variation of simple venation flux, pulse-repetition is per second 250 times.

Figure 11 is under the fixed wave length, and the curing that adds pigment coating can be with the variation of laser pulse repetition frequency.

Figure 12 adds the variation of the exposure intensity of the used laser of pigment coating with curing for the optimum concn of light trigger.

Usually be applicable to that laser instrument of the present invention is the rare gas halogen excimer laser. Since occurring in 1976, these laser instruments are improved on reliability and mean power. Can consider that the laser instrument of selecting also comprises and draw record at those of " the solvent dependency characteristic of the ultraviolet dye laser of chlorination xenon excitation ", Cassard, Corkum and Alcock, Appl. The phys.25 volume, 17-22 page or leaf, (1981).

According to the present invention, the basic principle of the laser curing of coating and printing ink is based on such fact, and namely laser is monochromatic light substantially, thereby all luminous energy all can be used to finish useful work. The selection of light trigger is to make it have maximum activity under optical maser wavelength. Light trigger three parts (Trigonal) 12 the absorption curve that drawn among Fig. 1,100% output of the 308 nanometers laser that also drawn. By contrast, the present mercury lamp that generally is used for curing transparent coating has many spectral lines, wherein only has sub-fraction to do useful work. For example, among Fig. 1, the radiation of wavelength more than 350 nanometers seldom absorbed by light trigger, and the following radiation of 270 nanometers can not penetrate the main body of coating, and near the radiation the 300 remaining nanometers only has 10% of ultra-violet (UV) band lamp output light.

Fig. 2 shows that very thick (50-150 micron) clear coat also can be cured with the method for laser. Light trigger when the concentration of DETX reaches certain value, solidifies required total laser energy and reaches minimum. Ben Tu and below figure in, coating be in nitrogen with the expansion laser beam irradiation, until reach (commercial approval) curing of high-quality.

Fig. 3 shows, lower flux (laser beam that broadening is bigger) causes lower curing energy demand. With the actual irradiated area of maximum, the lowest flux that can obtain allowing. And this has determined possible minimum total flux conversely, and thereby has determined the fastest " belt speed " that can make material cured. Use the free radical composite theory, can well explain figure in slope of a curve.

Fig. 4 shows, to given pulse flux, increases pulse recurrence frequency, then reduces its usefulness. Reduce the pulse flux, then can refill partial loss. To the belt speed of maximum, laser instrument is worked under its maximum repetition rate.

Fig. 5 shows, to containing Tio₂Coating (being opaque paint), must be greater than Tio₂Carry out ultra-violet curing under the wavelength of absorption edge (being 400 to 410 nanometers among the figure). Under shorter wavelength, light was just all absorbed before reaching the coating bottom.

Theoretical curing rate can think that the light intensity bottom arriving coating is directly proportional.

Solidifying among Fig. 6 can be to the empirical curve of wavelength, and Best Point is clearly arranged when having shown take DETX as light trigger: best radiation wavelength is 422 ± 5 nanometers. In the coating of 20 micron thickness, contain 50% rutile, the commercially available paint that can obtain having enough covering powers.

Fig. 7 shows that to another light trigger, the acyloxylation phosphine also can find similar best solidification range: 413 ± 3 nanometers. These add the required arrowband adjustable radiation of pigment coating to only have now dye laser can produce curing. The Isosorbide-5-Nitrae-two (2-(5-Ben Ji oxazolyl) of the output of dye laser in the cyclohexane/diox) benzene (Popop) dyestuff is measured.

Use various solvents, can make dyestuff Popop send the laser (see figure 8) at many wavelength, comprising solidifying the Tio that adds that makes light trigger with DETX and acyloxylation phosphine (APO)₂The optimal wavelength that pigment coating is required.

Use different dyes, dye laser can be luminous in 300 to 1000 nanometer range, about 25 watts of power (supposing that 308 nanometer incident lights are 100 watts).

Fig. 9 shows that the dye laser method can be used to solidify different Ti o₂The thick-skinned material coating of content (thickness can reach 60 microns).

The same with the situation of clear dope, with lower illumination pigment coating is carried out irradiation, can obtain higher solidification rate (less curing total energy and more efficient light-use). The curve of Figure 10 laser of two kinds of wavelength, 308 and 415 nanometers. The light of 308 nanometers can increase surface cure speed.

As shown in figure 11, high laser repetition rate causes adding the curing efficiency reduction (identical with the situation of clear dope) of pigment coating.

Light trigger changes with irradiation intensity such as the optium concentration of acyloxylation phosphine, as shown in figure 12. Fortunately, small throughput is mutually auxiliary with high curing rate and low photoinitiator concentration, this means and can reduce cost.

To and add pigment coating at printing ink, Clear paint below, for some examples that is cured with method of the present invention.

Printing ink

The trade(brand)name of using when used printing ink is all sold with the Australian special-purpose company limited of Olds brother of section in these examples (Viodri).The definite composition of these printing ink is maintained secrecy.Yet the article states of section's Olds contained multifunctional acrylic ester and light trigger, as benzophenone in the printing ink.

Printing ink spreads on the cardboard with the rubber printing cylinder, and thickness is roughly the 3-5 micron.Curing inks is to reduce its soaking in paper as early as possible.Be solidificated in the nitrogen and carry out with excimer laser, red and Yellow ink is with the light of 308 nanometers, and black and blue printing ink is with the light of 415 nanometers, per second 250 subpulses, monopulse flux be 1 in the least Jiao/centimetre ²Whether complete with streak test check curing, write down minimum curing total energy.

Example:

(section's Olds ink types is solidified total energy, milli Jiao/centimetre ²)

1) LUV 308 red 18

2) LUV 307 Huangs 25

3) LUV 309 indigo plants 160

4) LUV 311 black 350

Clear paint or varnish

Transparent varnish in the example contains epoxy acrylate and HDDA(vinylformic acid hexylene glycol ester), ratio is 60/40.Add the light trigger of 0.5-3% and the amine (N methyldiethanol amine) identical on this basis with photoinitiator concentration.Coating spreads on the cardboard with the handful of wire-wound, and thickness is less than 50 microns; Or spread in the layer of paper, thickness is 150 microns.In nitrogen, with 308 nanometers of directly sending from excimer laser (Lambda physik EMG 203) or the light of 351 nanometers (Lambda physik 150 ETS), with small throughput radiation irradiation coating, make its curing.Whether complete with streak test check curing, write down minimum curing total energy.

1) utmost point thick-layer

Light trigger-0.5%DETX; Thickness-150 micron; Monopulse flux-1.3 milli Jiao/centimetre ²; Optical maser wavelength-351 nanometer; Repetition rate-per second 1 subpulse; Minimum curing total energy-20 milli Jiao/centimetre ²

2) thick-layer

Light trigger-5% Ai Jia solidifies 651(Irgacare 651); Thickness-35 micron; Monopulse flux-0.008 milli Jiao/centimetre ²; Optical maser wavelength-308 nanometer; Repetition rate-per second 250 subpulses; Minimum curing total energy-4 milli Jiao/centimetre ²

3) thin layer

Light trigger-3% three parts 12; Thickness-7 micron; Monopulse flux-0.0023 milli Jiao/centimetre ²; Optical maser wavelength-308 nanometer; Repetition rate-per second 250 subpulses; Minimum curing total energy-0.41 milli Jiao/centimetre ²To 100 watts laser, the belt speed that can be extrapolated to transparent lamina is 1460 square metres/minute.

4) thick-layer

Light trigger-0.75% three parts 12; Thickness-35 micron; Monopulse flux-0.0008 milli Jiao/centimetre ²; Optical maser wavelength-308 nanometer; Repetition rate-per second 250 times; Minimum curing total energy-2 milli Jiao/centimetre ²; For 100 watts laser, the belt speed that this result can be extrapolated to transparent thickness is 300 square metres/minute.

The white oil lacquer

Paint in the example contains the composition identical with transparent varnish (on seeing), adds a kind of pigment or covering agent in addition (usually with rutile Tio ₂Grind into varnish), these paint use the situation of varnish the same with the front, are coated onto on cardboard or the high-quality zinkosite metal sheet, and solidify in nitrogen.For making Tio ₂Absorption reduce to minimum, the light stimulus dye laser with excimer laser 308 nanometers makes it luminous in the 410-430 nanometer range.Whether complete with streak test check curing, write down minimum curing total energy.

1) utmost point thick-layer on the paper

Light trigger-3% acyloxylation phosphine; Thickness-60 micron; Pigment loading level-32%(weight) Tio ₂; Monopulse flux-0.023 milli Jiao/centimetre ²; Optical maser wavelength-414.5 nanometer; Repetition rate-per second 250 subpulses; Minimum curing total energy-35 milli Jiao/centimetre ²

2) thick-layer on the paper

Light trigger-2%DETX; Thickness-20 micron; Pigment loading level-50% weight ratio Tio ₂; Monopulse flux-0.05 milli Jiao/centimetre ²; Optical maser wavelength-422 nanometer; Repetition rate-per second 250 subpulses; Minimum curing total energy-27 milli Jiao/centimetre ²

3) thick-layer on the paper

Light trigger-4% acyloxylation phosphine and 3% three parts 12; Thickness-35 micron; Pigment loading level-32% weight ratio Tio ₂; Dual wavelength solidifies: 308 nanometer flux be 0.0015 milli burnt/centimetre ²With 415 nanometer flux be 0.003 milli burnt/centimetre ²; Repetition rate-per second 250 subpulses; Total dye laser energy-2.6 milli of minimum curing Jiao/centimetre ²Suppose that this efficiency of dye is 25%, this belt speed that is equivalent to thick-skinned material coating is 50 square metres/minute.

4) thick-layer on the metal sheet

Light trigger-2% acyloxylation phosphine and 2% three parts 12; Thickness-28 micron; Pigment loading level-32%(weight) Tio ₂; Dual wavelength solidifies: 308 nanometer flux be 1.39 millis burnt/centimetre ²With 414.5 nanometer flux be 0.03 milli burnt/centimetre ²; Repetition rate-per second 250 times; Total dye laser energy-30 milli of minimum curing Jiao/centimetre ²Suppose that this dye laser efficiency is 25%, the belt speed that is equivalent to thick-skinned material coating is 50 square metres/minute.

To illustrate prescription and their application and the curing of coating below.

The embodiment I

According to the method described in the present invention, Clear paint generally comprises following component, by weight: 56.4% epoxy acrylate oligomer (A.C. breathes out to hang down and digests the 51-650 that learns the special-purpose company limited of reagent); 37.6%H.D.O.D.A. hexanediol diacrylate (A.C.H.); 3% tripartite 12 phenyl benzophenone (Ai Kezuo chemical reagent) and 3%MDEOA methyldiethanolamine (Union Carbide Corporation).

This mixture is held in both hands wet being coated with rolling, and making thickness is 7 microns, and with the monopulse flux be 0.0065 milli Jiao/centimetre ²Light in nitrogen, solidify.Curing can be burnt for 0.9 milli/centimetre ², and measure the hardness of coating by streak test, thus the degree of evaluate cure.

With the matrix of high-quality low hole blank sheet of paper as coating.With width is the wet coating sample of 5 centimetres of laser beam irradiation 10 cm x of 15 centimetres of 15 cm x.When the result of this static test is extrapolated to dynamic condition, be equivalent to the belt speed operation with 667 meters/minute, bandwidth is 1 meter, and radiation exposed area is 1 * 3 meter ²

The embodiment II

This example also relates to a Clear paint, and it is mixed by following weight percent by following component: epoxy acrylate oligomer (Seris affiliated company) 56.4% Sai Er Rider 3700(Celrad 3700); 37.6%HDODA(A.C.H.); 3% tripartite 12(AK20 Chemicals) and 3%MDEOA(Union Carbide Corporation).Coating is applied to thickness is 5 microns with rolling handful, used matrix and embodiment I with, but that the monopulse flux that applies is 0.00015 milli is burnt/centimetre ², curing can be burnt for 0.29 milli/centimetre ²Under this condition, corresponding belt speed is 2069 meters/minute, and irradiated area and embodiment I are together.

The embodiment III

Following component is mixed by following weight percent, and with its mixture solidified, can obtain one add pigment coated: 61% epoxy acrylate oligomer (A.C。H.51-650) and H.D.O.D.A.(A.C.H.) mixture, the two ratio are 60/40; 32%Tio ₂.RHD ₂(I.C.I.); 3% three parts 12; With 4% acyloxylation phosphine (BASF).

Be used for embodiment I the be coated with method identical with II, the wet thickness that makes coating is 35 microns.With two irradiation wavelength, one in 308 nanometers, the monopulse flux be 0.0015 milli burnt/centimetre ²; Another is in 415 nanometers, the monopulse flux be 0.0025 milli burnt/centimetre ²Curing can to 308 nm radiations be 1.4 millis burnt/centimetre ², to 415 nm radiations be 2.6 millis burnt/centimetre ²

Under this condition, with 1 * 3 meter ²Irradiated area, corresponding belt speed is 50 meters/minute.

Handler will see apparently and use the resulting benefit of the present invention, and for adding pigment coating, let alone Clear paint, can apply it to paper, timber, furniture, can, metal plate, steel and aluminium foil, the inside and outside portion of automobile, assembly, plastic components, or the like.

Claims (21)

1, a kind of coating material solidified method, comprise that the coating that will contain liquid or solid polymkeric substance and/or oligopolymer and/or monomer and at least a light trigger is coated on the surface, this coating of pulsed ultraviolet laser irradiation with at least one predetermined wavelength, select the luminous energy of above-mentioned predetermined wavelength, make it by other component preferential absorption in described at least a light trigger rather than the coating, under the fixed pulse-repetition, reduce the monopulse flux, reduce to minimum so that will solidify the required total energy of described coating.

2, a kind of coating material solidified method, comprise that the coating that will contain liquid or solid polymkeric substance and/or oligopolymer and/or monomer and at least a light trigger is coated on the surface, the described coating of pulsed ultraviolet laser irradiation with at least one predetermined wavelength, select the luminous energy of described predetermined wavelength, make it by other component preferential absorption in described at least a light trigger rather than the coating, in fixing monopulse flux decline low pulse frequency, reduce to minimum so that will solidify the required total energy of described coating.

3, according to claim 1 or 2 described methods, wherein at least one presetted wavelength is a peak wavelength.

4, according to claim 1 or 2 described methods, wherein finishing curing needs 25 pulses at least.

5, in accordance with the method for claim 4, wherein finish curing and need 50 pulses at least.

6, according to claim 1 or 2 described methods, wherein the monopulse flux less than 3 millis burnt/centimetre ²

7, in accordance with the method for claim 6, wherein the monopulse flux less than 1 milli burnt/centimetre ²

8, in accordance with the method for claim 7, wherein the monopulse flux less than 0.5 milli burnt/centimetre ²

9, according to claim 1 or 2 described methods, wherein pulse-repetition frequency is equal to or less than 250 hertz.

10, according to claim 1 or 2 described methods, wherein coating comprises a kind of pigment; Select for use at least one predetermined described Wavelength of Laser to make it be reduced to minimum by the absorption of pigment.

11, in accordance with the method for claim 10, wherein coating is a kind of printing ink of thickness≤20 micron.

12, in accordance with the method for claim 10, the thickness of its floating coat 〉=0.5 micron.

13, according to claim 1 or 2 described methods, coating wherein is a Clear coating, its thickness 〉=2 micron.

14, in accordance with the method for claim 12, coat-thickness wherein 〉=20 micron.

15, according to claim 1 or 2 described methods, wherein the monopulse flux less than 8 millis burnt/centimetre ²

16, according to preceding claim 1 or 2 described methods, wherein coating comprises at least two kinds of light triggers.

17, in accordance with the method for claim 16, wherein first kind of light trigger optionally absorbs the laser of first wavelength, and second kind of light trigger optionally absorbs the laser of second wavelength, thereby make the selected curing that is used for finishing whole coating of described first kind of light trigger, second kind of then selected curing that is used for finishing coatingsurface of light trigger.

18, in accordance with the method for claim 10, wherein pigment is TiO ₂

19,, wherein solidify and in nitrogen, carry out according to claim 1 or 2 described methods.

20, in accordance with the method for claim 13, wherein said coating comprises (by weight) 56.4% epoxy acrylate oligomer, 37.6% hexanediol diacrylate, 3% phenyl benzophenone and 3% methyldiethanolamine.

21, in accordance with the method for claim 10, wherein said coating comprises 60/40 mixture of (by weight) 61% epoxy acrylate oligomer and hexanediol diacrylate, 32%TiO ₂, 3% tripartite 12 and 4% acyloxylation phosphine.

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