CN1735838A - Incorporation of markings in optical media - Google Patents

Abstract

Optical media having markings that are non-interfering, or substantially non-interfering with readout of data from the optical media are disclosed. The optical media make use of certain formulations of color forming coatings described herein. Protective coatings used to enhance the color forming coatings are also presented. Methods for incorporating the coatings into the optical media are included. In preferred embodiments, the marking is formed in a photosensitive coating that is applied to the optical media, and then cured with a first light. A second light, having a substantially separate band of wavelengths from the first light, is used to image a marking into the coating. The coating is robust to many external influences, such as ambient environmental conditions, and physical wear.

Description

Incorporation of markings in optical medium

Invention field

The present invention relates in the various components of optical medium, produce fast the method and apparatus of high quality image.

Background of invention

The typical optical medium that uses comprises the various supplementarys the record data in optical medium at present.Supplementary often exists with the form of exquisiteness, with fabricator's sale, advertisement or other congruence.Supplementary can be included in the various forms, as passing through to use bar, the printing ink on the label or passing through other technology.

Label or tag generally is applied to " non-reading " face of CD such as CD (CD) or multi-usage optical digital disk (DVD), is used for the tabulation of recorded information on descriptive information such as source optical disc and its.Non-reading at optical medium placed the various labelling techniques of mark permission use from simple to complexity on the face.To place mark be bigger challenge in the zone of record data of reading on the face especially of optical medium, because mark can influence the use of optical medium.

Consider annual about 1,000,000,000 DVD of production and surpass 4,000,000,000 CD (InternationalRecording Media Association estimation), potential advertising space is equal to 1,000,000,000 magazine advertising pages or leaves, 30,000 ten thousand newspaper advertisement pages or leaves or 300 ten thousand billboards.Therefore, incorporation of markings is very high to the especially present unmarked value of reading face of optical medium.

The exercise question of announcing on Dec 23rd, 1999 is for disclosing an example of mark optical media technology among the international application published WO99/65696 of " Permanent Image Formation ".This application discloses at substrate and has comprised the method and apparatus that forms permanent image on CD, DVD and the packing (especially those that are formed by circulation polycarbonate and/or cycle P ET).This application discloses printing process wherein and has been different from prior art, because printing ink is applied to the quite most of of substrate surface, rather than only in image region.Those of skill in the art can recognize that when being optical medium, non-the reading that printing ink is limited in optical medium provides image on the zone.For example, because the pigment that uses in the printing ink generally comprises particle, printing ink may cause the scattering of reading light (laser), thereby suppress reading of data characteristics.In addition, disclosed use infrared (IR) laser transfer image hint printing ink will influence normal data readout, because CD and dvd media use nearly IR laser in the mechanism of reading.

Previous having carried out in the trial of reading placement mark on the face.But reference pin is to the United States Patent (USP) of optical memory system.For example, the exercise question of the LiLi that published on August 27th, 1996 has the technology that the membrane structure of the optically-variable security performance and the optical data of encoding prevents to forge various substrates for the U.S. Patent No. 5549953 of " OpticalRecording Media Having Optically-Variable Security Properties " discloses by introducing.Another United States Patent (USP) is that the people's such as Sullivan of publication on April 23rd, 1996 exercise question is the No.5510160 of " Optical Storage MediaHaving Visible Logos ".This patent also discloses especially and has prevented to forge optical storage medium by producing visual sign on the face reading of substrate.Although these patents provide the mark combination that may have some advantage, limited any advantage.That is to say that for example, mark is visible under given conditions only, and require complicated or expensive fabrication process finished product.In addition, control degree or mark complicacy may not reach effective advertisement or out of Memory carrying scheme is desired.

Other example that relates to the coating that is applied to optical medium can find in U.S. Patent No. 6051298 " Optical Disc Having Protective Films ".This patent disclosure have a CD of protective film; film has good transmissivity and anti abrasive high rigidity; in U.S. Patent No. 6322868B1 " Use and Manufacturing Applications ofPolymer/Dye-Based Thin Layer Coatings for Enhancement of theQuality of Recording On and Readout From the Optical StorageMedia ", disclose and used the thin layer coating to be used to improve the quality of encoded digital information.Another example comprises U.S. Patent No. 6338933 " Methods and Apparatus forRendering an Optically Encoded Medium Unreadable ".This patent disclosure comprise that the optical activation material reduces the reflectivity on surface.

But above-mentioned patent is not utilized some progress of material.For example, have to mention the international patent publications WO02/101462A1 " Laser Marking Method " that publishes in 19 days Dec in 2002 of CibaSpecialty Chemicals Holding Inc. application.This announcement discloses the polymeric material method of colouring that comprises the acid of diving, colour coupler and optional other composition by with the UV rayed being.Another international patent publications WO02/100914A2 exercise question of Ciba Specialty Chemicals Holding Inc. application is " Polymeric Material, Containing aLatent Acid ".This announcement discloses the polymeric material that comprises dive acid and optional other composition, and the acid of wherein diving is by being converted into acid with laser radiation.Another example is disclosed in the U.S. Patent No. 5028792 " System for the Visualization ofExposure to Ultraviolet Radiation " of the publication in 2 days July in 1991 of Mullis.This patent disclosure be exposed to the photochemical systems that UV-irradiation directly shows, wherein when with UV-irradiation, form light acid and make dyestuff experience visual change color.

More patent disclosure be used to apply compound and the technology of quality material as coating.Referring to the U.S. Patent No. 6013601 of for example publishing January 11 in 2000, " LaserPrinting Method and Substrate "; With its continuous application, the U.S. Patent No. 6140267 that on October 31st, 2000 published.These patent disclosures the method and the substrate of printing information, wherein at least a coating is coated onto on the substrate, coating comprises photosensitive quality component.When using laser beam heats, the variation of chromium takes place at least one coating, the printing of information is provided whereby.

The patent of open quality coating comprises that the exercise question published people's such as Reardon 12 days November in 1985 is the exercise question published the August 10 nineteen eighty-two of the U.S. Patent No. 4552830 of " Carbonylic Halides as Activators for PhototropicCompositions " and the Reardon U.S. Patent No. 4343885 for " Phototropic Photosensitive CompositionsContaining Fluoran Colorformer ".These two pieces of patents all disclose the composition that is used to produce the used in electronic industry photo-induced corrosion resistant film.These compositions are disclosed and comprise with light trigger polymerizable, crosslinkable or curable component, colour coupler and activator; Wherein composition becomes soluble and variable color under influence of actinic radiation.

Known applying when radiation-sensitive coating is used to be exposed to radiation to object shows.The exercise question of publishing with reference to July 25 nineteen ninety-five is the U.S. Patent No. 5436115 of " Systems for the Visualization ofExposure to Ultraviolet Radiation ".Equally, can use similar techniques and the acid-sensitiveization fluorescent dye invisible fluorescent image that develops, as HeTian, Jiaan Gan, Kongchang Chen, Jun He, Qun Liang Songb and Xiao Yuan Houb at " Positive and Negative Fluorescent ImagingInduced by Naphthalimide Polymers ", Journal of Material Chemistry2002,12, those that report among the 1262-1267.

The U.S. Patent No. 5885746 " Photosensitive Resin Composition, PhotosensitivePrinting Plate Using the Same and Method of Manufacturing PrintingMaster Plate " that publish the 23 days March in 1999 that also has an example to be disclosed in people such as Iwai.This patent disclosure photosensitive resin composition, comprise superpolymer adhesive, monomer, produce the photopolymer initiating agent and the optical excitation acid producing agent of free radical when being exposed to visible light, acid producing agent produces acid when being exposed to the 200nm-380nm wavelength, and colour coupler colour developing when acid exists.This patent especially discloses the use spreading agent, and this shows unevenness, a kind of character that will cause laser scattering in the optical medium read-out system.In addition, disclosed initiating agent and need to use oxidation prevention layer to realize fully solidifying to the visible light sensitivity in this patent.The use of oxidation prevention layer is huge obstacle to applying these materials to a large amount of CDs, because manufacturing environment does not generally provide the environment of dark and/or anaerobic.More this additional step is brought economical and is produced burden, and this is with the use of limit markers system.

The non-limitative example of the existing embodiment of optical medium (prior art) is provided among Fig. 1-8.In Fig. 1, the optical medium 8 of prior art is described to CD (CD).CD 8 comprises substrate 17 (generally being formed by polycarbonate), coating metal layer 14 (being also referred to as reflection horizon 14) and protective seam 12.Label is placed on the label surface 7, and on protective seam 12, it is generally formed by the curable acrylic acid of UV.Reading light (shown in tip arrow upwards) sees through and reads the data characteristics that face 2 provides read output signal to be used to explain to be called recessed district 5 and convex region 6.The situation of optical medium 8 other embodiments is provided among Fig. 2-8.

Other form that optical medium 8 is provided is so that the variation on the description architecture.Fig. 2 has described the optical medium 8 as multi-usage optical digital disk (DVD) single face/individual layer embodiment.Usually, DVD 8 comprises substrate layer 17, reflection horizon 14, adhesive linkage 15.Structure shown in Figure 2 is corresponding to the situation of the optical medium 8 that is commonly referred to " DVD-5 ".Fig. 3 has described another embodiment of prior art optical medium 8, has wherein shown single face/double-deck embodiment of DVD.In this embodiment, reflection horizon 14 comprises semi-reflective layer 14-1 and complete reflection horizon 14-2.Substrate layer 17 comprises the first substrate layer 17-1 and the second substrate layer 17-2.This structure is corresponding to the situation of the optical medium 8 that is commonly referred to " DVD-9 ".In this embodiment, on the one side of DVD8, provide two data characteristic layers.Other example of prior art optical medium 8 comprises two-sided/individual layer DVD, as shown in Figure 4.This structure is corresponding to the optical medium 8 that is commonly referred to " DVD-10 ".Two-sided/double-deck embodiment of DVD 8 is shown in Fig. 5.This structure is corresponding to the situation of the optical medium 8 that is commonly referred to " DVD-18 ".This embodiment of DVD comprises the two sides, has dual layer format separately.On single polycarbonate substrate layer 17, make two layers of each face, bond to together at adhesive linkage 15 places subsequently.DVD-18 has capacity maximum in the series, but makes the most difficult and complicated.Need each in unique four substrate layers 17 of pressing mold formation.DVD-14 is that to have only half be the related pattern of double-layer CD 8 to CD 8.This form comprises the data of about 14GB.DVD-14 is easy to make than DVD-18 a little, because one side is DVD-5.More many cases of optical medium 8 comprises mixing SACD, as shown in Figure 6; Mix DVD, as shown in Figure 7; And DVD+, as shown in Figure 8.

The associating disk format is known, for example the DVD-RAM on the associating of the DVD-ROM on the one side another side.This CD 8 is a both-sided optical disc, and can read from the two sides.Mixing SACD is the form of Philips and Sony development, and associating SACD (i.e. DVD layer physically) and CD layer.Two layers this means the necessary reflection Red laser of SACD layer but the infrared CD laser of transmission all from reading with one side.This CD not only can but also can have been play on the SACD player in CD Player (it will read the CD layer).

Mixing DVD is to be similar to the form that mixes SACD, has conventional DVD data Layer on the CD data Layer.DVD+ is meant and comprises the CD that bonds to the CD on the DVD substrate.The CD that obtains allows DVD and CD data all to read from a CD, resemble and mix DVD, but this CD is to read from the two sides.So far, these two kinds of forms are not used always.

The optical medium 8 of every kind of form is all used specific specification statement.For example, for CD shown in Figure 1, the gauge thickness of substrate layer 17 is 1.2mm, and recessed district 5 separates about 125nm with convex region 6.In DVD, shown in Fig. 2-5, it is thick that substrate layer 17 is generally 0.6mm.

This rough close examination to optical medium 8 these popular (just minority) embodiments is used to point out exist various layers in the different-format of optical medium 8.The selected material of each self-contained specific quantity of these layers is used to the character that provides specific, as the transparency and rigidity.Those skilled in the art can infer that different layers can be made of a batch of material, provides the function of optical medium 8 simultaneously.

Transmittance when this batch of material generally is subjected to standard such as setted wavelength, the viscosity when applying and other optical property limit.Be appreciated that material always in development to improve the performance of optical medium 8.

The example of the CD moulding material of latest developments comprises Elf Atochem of NorthAmerica Inc., Philadelphia, and the PLEXIGLAS VOD-100 that PA produces, it is that specialized designs is used for the one-level acrylic acid thermoplasticity that CD is made; Similar material is CYROIndustries, Rockaway, the ACRYLITE DQ501 of NJ; Another product is DowPlastics, Midland, the poly-hexamethylene ethene (PCHE) of MI, its saturated cyclic hydrocarbons for deriving by styrene monomer, allegedly have the superior optical purity and the transparency, refractive index is 1.51, comprises high transmission rate in indigo plant-green scope at full spectrum.Other non-limitative example of CD moulding material is General Electric of Pittsfield, the LEXAN product of MA, and it comprises model OQ1040L, OQ1050 and OQ1030L.

The widespread use of optical medium 8 requires advanced tagging scheme.Along with the demand of the variation and the growth of optical media technology, this needs increase just fast.For example, the appearance of two-sided optical medium 8 makes development can or can not influence the tagging scheme of reading laser substantially to necessitate.

This scheme should be optical medium provides the mark of enhancing, identification, authentication and code capacity.Scheme should provide the quick production of image, text or other optical encoding information on the label of optical medium and/or reading face.In addition, scheme should also provide can be in the environment that may use optical medium robust mark.

Summary of the invention

Solve above-mentioned and other problem by method and apparatus disclosed herein and according to embodiment of the present invention.

Reading and/or the non-method and apparatus that image is provided on the face of reading at optical medium such as CD and DVD disclosed.Aspect of the present invention includes but not limited to: specific material is applied on the optical medium as coating or laminated coating; Solidified coating is preferably used first kind of light, as long wave ultraviolet (UV) light; Second kind of light such as shortwave UV with specific wavelength handle each coating; Be exposed to recording picture in the overall appearance of coating with the selectivity of utilizing coating to second kind of light of specific wavelength.Preferred use separately the UV light of wave band to be used to solidify to guarantee with the imaging step that this technology can provide do not influence the mark that data are read, because most of present and following disk formats utilize IR, NIR or visible wavelength lasers to read, and owing in these forms of great majority, use the UV curable materials.Therefore, preferred consolidation and imaging wavelength utilize the wavelength in the spectrum UV zone.

Aspect of the present invention is included on the reading face of optical medium or the non-reading face and applies coating or laminated coating.Many-sided gray scale, monochrome or multicolor image (being called " mark ") that forms in the overall appearance that is applied to coating that comprise of the present invention.Coating and mark can or can not influence the use of optical medium substantially.For example, the wavelength that coating and mark transmissive or basic transmission are concerned about is read the wavelength that laser uses as optical medium.

Aspect of the present invention can also include but not limited to use coating, use compound token and the usage flag that can absorb or reflect the light of predetermined wavelength as safety practice.Consider to use the reading face of optical medium to be used for mark advertisement, code and non-other relevant mark of face of reading common and medium many-sided comprising of the present invention.

Herein disclosed is a kind of optical medium, have at least one layer that comprises the prescription that is formed by at least one group of photosensitive quality material, wherein at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, at least one is marked at reading at least in the zone of optical medium is significantly, and substantially not the interferometric optical medium read light.

Also disclose a kind of optical medium, had by the response flag rayed and form the ground floor that the photosensitive quality material of mark forms and be arranged on the ground floor and comprise the second layer of the material that absorbs mark light; Wherein, be marked at reading at least in the zone of optical medium and be significantly, and substantially not the interferometric optical medium read light.

In addition, optical medium with at least one layer is disclosed, and comprise at least one group of photosensitive quality material, wherein at least one group of photosensitive quality material shows at least one mark reading of optical medium in the zone, this mark substantially not the interferometric optical medium read light.

A kind of method of making optical medium is disclosed, comprise the prescription of selecting to have at least one group of photosensitive quality material, wherein at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source, wherein, when forming, at least one is marked at reading in the zone at least of optical medium and occurs, and substantially not the interferometric optical medium read light; With at least a portion of at least one layer of optical medium, apply prescription.

Also disclose a kind of optical medium with at least one ground floor, ground floor is formed by following material: the polyether-modified dimethyl silicone polymer of about 0.3wt%; The stable liquid potpourri of trimethylbenzene formyl oxidation diphenyl phosphine, alpha-alcohol ketone and the benzophenone derivates of about 10wt%; The 1,6 hexanediol diacrylate of about 10wt%; The tetrahydrofurfuryl acrylate of about 15wt%; The ethoxylation of about 32.35wt% (4) tetramethylol methane tetraacrylate; Height propoxylation (5.5) glycerol tri-acrylate of about 32.35wt%; The triphenylsulfonium fluoroform sulphonate of about 3wt% and wavelength absorption peak are the colour coupler of about 540nm.

Another kind of optical medium disclosed herein has the protective seam that is formed by the prescription with at least one group of photosensitive quality material, and wherein at least one component color material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, at least one is marked in the optical medium is tangible.

Another kind of optical medium disclosed herein has the adhesive linkage that is formed by the prescription with at least one group of photosensitive quality material, and wherein at least one component color material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, at least one is marked in the optical medium is tangible.

The accompanying drawing summary

When read in conjunction with the accompanying drawings, above-mentioned and further feature of the present invention will be more obvious in detailed description of the Invention subsequently, wherein:

Fig. 1 has described the prior art optical medium that is called CD;

Fig. 2-5 has described the prior art optical medium that is called DVD;

Fig. 6 has described and has been called the prior art optical medium that mixes SACD;

Fig. 7 has described and has been called the prior art optical medium that mixes DVD;

Fig. 8 has described the prior art optical medium that is called DVD+;

Fig. 9 has described the optical medium with coating;

Figure 10 A-E that is called Figure 10 has jointly described the exemplary of destination layer among the DVD;

Figure 11 has described the absorption curve of colour coupler in the coating formula;

The background color that Figure 12 has compared in the various compositions forms;

Figure 13 has described the absorption spectrum of two kinds of light acid producing agents;

Figure 14 has described the UV absorption spectrum of first kind of light trigger;

Figure 15 has described the UV absorption spectrum of second kind of light trigger;

Figure 16 has described the line spectrum of the lamp of middle foundary weight doping;

Figure 17 has described the line spectrum of gallium iodide lamp;

Figure 18 has described the line spectrum of xenon filling lamp;

Figure 19 has described the transmission curve of various optical filters;

Figure 20 has described the absorption peak of various concentration colour couplers at the 540nm place;

Figure 21 has described the absorption peak of various concentration triphenylsulfonium fluoroform sulphonates at the 540nm place;

The average color that Figure 22 has described in the first environment research lowers;

Figure 23 has described the relation of capillary reduction and various concentration of wetting agent;

Figure 24 has described the average absorption rate of various prescriptions after the environmental test;

Figure 25 has described the decreased average amount of various prescription optical density (OD)s after the environmental test;

Figure 26 has described the storage condition of fully loaded filter paper;

Figure 27 has described TEA and has exposed the color fading that causes;

Figure 28 has described colour developing and the relation that exposes wavelength;

Figure 29 has described the colour developing in the sample that comprises the UV absorbing agent;

Figure 30 has described and has added the influence that the UV absorbing agent produces color;

The color that Figure 31 has described in the stable prescription of UV forms;

The color that Figure 32 has described in the stable prescription concrete sample of UV forms;

Figure 33 has described the result of study that is adjusted to toner and light acid producing agent ratio;

Figure 34 has described the relation of color levels and susceptibility and light acid producing agent concentration and film thickness;

Figure 35 has described the absorptivity of CN-120 based formulas;

Figure 36 has compared the absorption spectrum of various UV absorbing agents;

Figure 37 has described the color formation time of the combination with various smooth acid producing agents;

Figure 38 has described the relation of color generation aspect and light acid producing agent;

Figure 39 has described the relation of color formation with illumination type;

Figure 40 has described the relation of color formation with the UV absorbing agent;

Figure 41 has described color and has formed the relation that can flow with irradiation;

Figure 42 has described the relation of color formation with enhancement additive;

Figure 43 has described the color in the buffer system and has formed;

Figure 44 has described the relation of film thickness and rotational speed;

Figure 45 has described the relation of film thickness and optical density (OD) and rotational speed;

Figure 46 has described the relation of film thickness and optical density (OD) and rotational speed;

The color that Figure 47 has described light acid producing agent and colour coupler different proportion forms;

Figure 48 has described the optical density (OD) of two kinds of coatings;

Figure 49 has described color formation and the relation of time once how much (one geometry);

Figure 50 has described the absorption spectrum of three kinds of embodiments of external coating;

Figure 51 has described the remaining susceptibility in two coat systems;

Figure 52 has described the fastness to light in the exposed region;

Figure 53 has described the colour developing of environmental test;

Figure 54 has described the environment color retention;

Figure 55 has described fading of amine research;

Figure 56 has described the relation of film thickness and rotational speed;

Figure 57 has described the relation of viscosity and temperature;

Figure 58 has described shear rate curve;

Figure 59 has described shear stress and shear rate curve;

Figure 60 has described the viscosity of constant shear rate;

The color that Figure 61 has described one group of light acid producing agent and colour coupler forms;

The color that Figure 62 has described one group of light acid producing agent and colour coupler forms;

The color that Figure 63 has described one group of light acid producing agent and colour coupler forms;

The color that Figure 64 has described one group of light acid producing agent and colour coupler forms;

Figure 65 has described the comparison of light source;

Figure 66 has described the comparison of light source;

Figure 67 has described color and has formed and the relation that can flow;

Figure 68 has described the remaining susceptibility of the coating with various UV absorbing agents;

Figure 69 has described the optical density (OD) of exposed region and the relation of UV absorbing agent;

Figure 70 is the xsect that scribbles the optical medium of multilayer on the reflection horizon;

Figure 71 is the xsect that scribbles the optical medium of multilayer on the reflection horizon;

Figure 72 is the xsect that scribbles the optical medium of multilayer on the reflection horizon;

Figure 73 is for describing the figure that orange and redness becomes the absorption curve of chromatograph;

Figure 74 is the figure of the absorption curve of description polychrome embodiment;

The figure of absorptivity when Figure 75 has only the top to become chromatograph to be exposed for describing;

Figure 76 is for describing the figure of absorptivity in the multi-color systems with UV restraining barrier;

Figure 77 has described the system of solidified coating;

Figure 78 has described the mark on the optical medium that forms with the mark light irradiation;

Figure 79 has described the test figure of the dish that does not have coating;

Figure 80 has described the test figure of cated dish;

Figure 81 has described the test figure of the cated dish that has at least one recording picture on it;

Figure 82 has described the test figure of the optical medium of making in manufacturing system; With

Figure 83 has described the spectrum of the various prescriptions that are applied to the optical medium label surface.

Detailed Description Of The Invention

Optical medium has been described in the instruction of this paper, comprises a coating or a series of coating, and coating is combined to be used to keep at least one gray scale, monochrome or multi-color marking to the reading in the zone of optical medium, can not influence or can not influence substantially the function of optical medium.Aspect of the present invention includes but not limited to: specific material is applied on the optical medium as coating or laminated coating; Solidified coating is preferably used first kind of light, as ultraviolet (UV) light; Handle each coating and utilize coating the selectivity of second kind of light of specific wavelength to be exposed to recording picture in the overall appearance of coating with second kind of light of specific wavelength such as UV.

The disclosure of this paper is provided in the part below:

I. foreword

II. the coating of optical medium

A. single coating research

1. general prescription

2. light acid producing agent screening

3. curing Consideration

4. oxygen suppresses

5. color and image

6. environmental impact

7. the triethylamine research of fading

8. acceleration phototesting

9. the light acid producing agent reexamines

10. the absorption spectrum of light acid producing agent and film

11. be imaging speed screening light acid producing agent

12. color enhancement additive

13. spin coating, film thickness and optical density (OD)

B. overbrushing layer research

1. coloured coating and external coating research

2. initial trial

3. environmental test

4. to the adjustment of two coating formulas

5. amine test

6. quantitative examination

7. the physical property of coating

8. viscosity temperature

9. viscosity is to shear rate

10. the color of various lamps forms

11. light acid producing agent and colour coupler ratio

12. lamp shadow rings

13. external coating: photostability with external coating of various UV absorbing agents

C. the embodiment of coating on the optical medium

1. two layers of coatings

2. laminated coating

3. polychrome CD

4. in existing form, use the Consideration of coating

III. form mark

A. solidified coating

B. form the equipment of mark

C. type

IV. coating inspection

A. exemplary checkout facility

B. coating parameters and radially noise research

C. check technology

V. other embodiment

A. direct combined formulation in destination layer

I. foreword

Although under present embodiment preferred situation, promptly under the situation of specific optical media exemplary, described the instruction of text, will be appreciated that these instructions can relate to any support prescription disclosed herein and be exposed to the optical medium of the energy source that suits subsequently.The character of at least one mark or image is relevant with various factors, includes but not limited to the material composition in the user's request, every layer, the functional requirement of optical medium, and other factors.

Generic term herein " optical medium " is meant " CD " or " DVD ", and still, the existing form of considering optical medium 8 exists or at present in development.For example, the multiple form of optical medium 8 comprises: DVD 5, DVD 9, DVD 10, DVD 14, DVD 18, DVD-R, DVD-RW, audio frequency CD, CD-Video, CD-R, CD-RW, CD-ROM, CD-ROM/XA, CD-i, CD-Extra, CD-Photo, supersonic frequency (s.f.) CD, Blu-Ray, Mini Disk and aforesaid mixed form, and some other.Other form of optical medium or example of structure comprise that United States Patent (USP) 5452282 and its part continuation application, exercise question are those disclosed in the United States Patent (USP) 6160789 of " Optical Data StorageDisc with a Visible Holographic Image and Method for itsManufacture " for the United States Patent (USP) 6011767 and the exercise question of " Optical DataStorage Disc ".Therefore above-mentioned tabulation should only be considered to illustrate can be supported or instruct the variant of the optical medium 8 of being benefited the application from this paper, therefore neither exhaustively also nonrestrictive.

In addition, also can realize some modification, but not be considered to special " form " these forms.For example, in the embodiment of Fig. 9, coating 100 is applied to prior art optical medium 8 and goes up the cated optical medium 10 of generation as CD.Optical medium 10 comprises the layer as comprising in the prior art optical medium 8.For example, in this embodiment, optical medium 10 comprises CD substrate layer 17 (being also referred to as " layer of polycarbonate "), coating metal layer 14 and protective seam 12.The increase of coating 100 provides the modification to manufacturer's specification of optical medium 8 forms.More particularly, for example, the coating 100 of increase has realized improving the thickness of optical medium 8.But,, do not influence or do not influence substantially the function of optical medium 10 although the thickness of increase has changed form (being CD in this case) specification.Thereby, think that the increase of coating 100 is modification that allows or the structure that does not depart from form substantially.Thickness in coating 100 causes departing under the situation of optical medium 10 thickness specifications, can use various compensation techniques.In one embodiment, in forming process, reduce of the increase of the thickness of CD substrate layer 17, and produce the CD 10 that keeps specification with solution coating 100.

Recognize that also special form may be characterised in that the structure (physical Design) total with other form.The instruction of this paper is not restricted to the particular design of optical medium 8.Therefore, the layer or the component of given format are mentioned with generic term sometimes at this paper.These terms comprise that title is as " layer ", " structure " and " component ".In addition, in some cases, the special available more special term of layer mentioned.

Term used herein " prescription " means usually to forming visual contrast and therefore form the composition that mark is applied to the material of optical medium in the optical medium zone.Prescription can comprise the material that is called " quality ", although some embodiments may use the method that loses lustre to form image.Other embodiment only produces gray scale image.Therefore, these materials also can be called as " in pairs than ".Term " quality " and " in pairs than " so be interchangeable in this article, and the ability of the square one-tenth visable indicia of assignment.

Preferably, at least a prescription with at least a energy-sensitive quality material is applied on the optical medium 10.Apply the intact part of prescription as optical medium 10 inner structures.In preferred embodiments, the substrate layer 17 (it is generally formed by polycarbonate) that generally occurs in optical medium is for adding the target of prescription.According to aspect disclosed herein, other layer can be used as the target of replacing or increasing with prescription.Consider the variation of optical medium 8 forms, term " destination layer " is generally used for referring to any layer in the optical medium 8, that is to say, destination layer is by in conjunction with prescription quilt disclosed herein or may be replaced or increase.

Therefore, consider that herein the mentioning of conventional title to the layer (for example substrate layer 17 and acrylate layer 12) in the optical medium 8 may be chaotic, and in some cases, explanation is inadequate.Therefore, the discussion of this paper may provide some strict embodiments with " destination layer " words and phrases, rather than utilizes conventional title.

Although prescription be considered to destination layer " in " use, prescription in fact can be in destination layer stratification, replace that the conventional material that uses uses in the destination layer, or combine with the conventional material that uses in the destination layer.Or rather, in this back one example, but prescription instead of part destination layer, or mix with the material that uses in the destination layer.

The composition and/or the use of filling a prescription in a large amount of any given destination layers of factor may command.For example, the design standards of optical medium 8 ad hoc structures can be stipulated specific thickness, transparency or hardness requirement.Other factors can comprise the operation wavelength of reading laser.The optical wavelength of reading commonly used of optical medium 8 comprises 408nm, 440nm, 630nm, 650nm and 780nm, and simultaneously other is read wavelength and also is fine.

Term " optical wavelength " and " wavelength " are meant the appropriate wavelength that is used for the realization technology or is effective.For example, can use long wave or short wave ultraviolet light (UV) to solidify destination layer, in destination layer, form mark, or observe mark.Usually, optical wavelength comprises wave band or set of wavelengths, and they can refer to: a kind of in UV-A, UV-B, UV-C, UV, visible (VIS), near infrared (NIR), infrared (IR) and the LONG WAVE INFRARED (LIR).Can use other classification.Term used herein " wavelength ", " optical wavelength ", " wave band of wavelength ", " set of wavelengths " and " energy source " can comprise any suitable form of actinic radiation, and this form is used to obtain required influence.For the wavelength that specific purposes are selected relevant with various factors, for example and the composition that is not limited to fill a prescription and the laser that do not influence optical medium read.Although it should be understood that to herein disclosed is some optimization formula that utilizes special wavelength UV, the wavelength that can select to suit reaches predetermined purpose, remains on simultaneously in the instruction of this paper.

The general curing of using first group of optical wavelength to realize destination layer.But the use of first kind of light does not limit.For example, apply prescription by hybrid technology and can require fully to cool off destination layer simply to consider to solidify the formula materials in the destination layer.Preferably, in this embodiment, prescription is cooled to environment temperature.

The energy source that is used to form mark can comprise any optical wavelength or optical wavelength combination that forms image in destination layer that be considered suitable for.In some embodiments, can use the particle beams (as electron beam) as energy source.

Being exposed to optical wavelength by selective control does not preferably influence the UV wavelength that laser reads cause optical change (for example color formation) in destination layer.Can in the single target layer, use prescription, maybe can use a plurality of destination layers.When using a plurality of destination layer, each can be to identical or different energy source sensitivity.Each target coupler layer comprises at least a prescription.The known technology of general use realizes selectivity or control exposure.Example comprises use positivity or negativity photomask, direct writing laser or electronic light mask (as LCD display).

In some embodiments, at least one destination layer of optical medium, use the quality prescription, become chromatograph to be used for showing primary colors or dissipation primary colors.In using the embodiment of a plurality of destination layers, a kind of color that each in the multilayer is preferably relevant with at least a and additive color or the scheme that loses lustre is correlated with.For example, every layer can provide red, green or blue (RGB) outward appearance; Perhaps, every layer can provide losing lustre of cyan, magenta, yellow or black (CMYK).In some embodiments, determine that according to the factor except that the colorimetric design layer outward appearance may be useful.For example, obtaining complexity and may needing to depart from Color Scheme of some quality material in some cases, uses the layer of varying number more to be necessary than color designing requirement.

In some embodiments, become chromatograph to be coated onto on the optical medium and in conjunction with external coating.In these embodiments, " two coating systems " provides some multifunctionality that can not obtain in " the single coating system " that only uses quality prescription layer.For example, in an embodiment of two coatings applications, applied the external coating that comprises light absorbing material.In this embodiment, external coating provides protection to becoming chromatograph, makes it to avoid the influence of UV in the surround lighting, improves the appearance of indicia appearance whereby.For example, use the UV absorbing agent to limit owing to be exposed to background color growth and the mark life-span therefore that surround lighting causes.

Term " mark " and " image " are meant the optical change that forms owing to be exposed to energy source in destination layer.Mark can be used as " label ".Image can comprise any type of mark in the people's limit of consideration that forms image.For example, mark can comprise bar code, literal, figure, alphabetic character and symbol ad lib.Equally, " content " of mark can comprise any content in people's limit of consideration of making mark.For example, content can comprise the information of command information, promotion message, advertising message, trademark information, authentication information, identifying information, seriation information and/or other type ad lib.

In some embodiments, mark preferably from reading face as seen.In the other embodiment, as seen mark preferably reads face from non-.Some mark may be from the two sides on an equal basis as seen.

With reference to figure 3, the prior art form of single-surface double-layer optical medium 8 has been described.Using an example of the optical medium 8 of this structure is the form that is called " DVD-9 ", and as shown in Figure 3.Promptly read face 2 from the bottom surface, optical medium 8 shown in Figure 3 is that DVD-9 comprises the first substrate layer 17-1, semi-reflective layer 14-1, adhesive linkage 15, reflection horizon 14-2, the second substrate layer 17-2 and label surface 7.Figure 10 A-E that is called Figure 10 jointly provides use the introduction of coating as shown in Figure 3 in the single-surface double-layer optical medium 8 at optical medium 10.

With reference to figure 10A, shown that thickness is the optical medium 10 of T.The others of thickness T and optical medium 10 are corresponding to the DVD-9 form.Substrate layer 17-1 is designated as the destination layer in conjunction with coating 100.Coating 100 comprises two layers, single one-tenth chromatograph 101 and external coating 102.In one embodiment, make the first substrate layer 17-1, with the production of the optical medium 10 of the increase that solves coating 100 and band coating to the thickness 111 that reduces.

In the embodiment shown in Figure 10 B, whole adhesive linkage 15 is by being replaced in conjunction with single one-tenth chromatograph 101.In the illustrated embodiment, be combined into chromatograph 101 and do not have external coating 102.The remainder of optical medium 10 is according to the specification structure of prior art.

In Figure 10 C, adhesive linkage 15 provides in conjunction with external coating 102 and the destination layer that becomes chromatograph 101, and wherein the remainder of adhesive linkage 15 uses prior art material (as the UV curable acrylates).Figure 10 D has described the variation of embodiment shown in Figure 10 C.

Another embodiment is provided among Figure 10 E.Figure 10 E further discusses in this article.Those skilled in the art can recognize that the above-mentioned embodiment of destination layer introduced the combined aspects that can comprise a large amount of variations.Therefore, these above-mentioned embodiments are illustrative, and do not limit the present invention.

In preferred embodiments, prescription can effectively keep the color of selecting and showing in the manufacture process, and meets the physics requirement of application fully.That is to say that color is strong basically under normal operation for every kind of prescription, and anti-basically normal wear.In some embodiments, prescription comprises the material that is distributed in polymer substrate or other the suitable equivalent.In some embodiments, distribution of material is in ultraviolet light (UV) curable polymer.

Can apply prescription by any technology of optical medium 10 that is applicable to.For example, in one embodiment, apply prescription by spin coating.The step that spin coating is filled a prescription on the optical medium 10 appears in the large-scale production of optical medium 10, and preferably after the conventional procedures of making optical medium 8.

Device disclosed herein and technology are combined also in the instruction of this paper with other technology of mark optical medium 10.For example, can in a destination layer, comprise prescription, and the concave-convex surface pattern that has continuous variation and limit hologram image is incorporated into another layer.In some embodiments, fill a prescription and concave-convex surface combinations of patterns use with continuous variation and qualification hologram image, or as its external coating.In these embodiments, be combined into non-reading on the face now.Therefore, the instruction that is appreciated that this paper can be used with the various manufacturing technologies of optical medium 10.

The prescription that research is used as into chromatograph 101 and external coating 102 is discussed now.

II. optical medium coating

Preferably, coating 100 comprises and can be described as the two " group " materials of photochromics.One group of photochromics is used for coating 100 in case solidified coating 100 afterwards in position.That is to say, be exposed to one group of wavelength and be used to solidify first group of photochromics.Second group of photochromics in the coating 100 shows optical change when fully being exposed to other one group of wavelength.Therefore, coating 100 can comprise the crosslinked light trigger of initiation.Coating 100 can include but not limited to that compound such as light acid or light alkali produce agent, acid or alkali sensitive dye, leuco dye, metallo-chelate, fluorescent dye or laser dye.Coating 100 seems can be coloured or colourless, and fluoresce under specific electromagnetic radiation.The fluorescent emission wavelength can include but not limited to the wavelength in the visibility region.

Although herein disclosed is the photochromics of response ultraviolet light (UV) wavelength, coating 100 can comprise the light activated material of any wave band wavelength (being also referred to as " set of wavelengths ").For example, photochromics can respond UV-A, UV-B or UV-C wavelength.Can infer to have two groups of photochromicss and will consider to use two groups of wavelength to cause variation in the coating 100 as herein described equally.Can think that other prescription that this paper does not discuss can advantageously utilize the interior wavelength separation of useful wave spectrum.Therefore, the instruction of this paper is not limited to the exemplary of this paper, and it only provides and applies the example of mark to the system of optical medium.

It should be noted that adopting term " coating " to mean applies prescription disclosed herein.That is to say that although technology can be used for applying prescription as coating, as by spin coating, combined formulation does not mean and is limited to coating technology.Other non-limitative example that applies one or more prescriptions comprises the use hybrid technology, and at this moment prescription is incorporated in other material that puts on optical medium.Usually, think that term " coating " is applicable to the material that comprises in the optical medium that meets this paper instruction.

A. single coating research

Summed up the research aspect of coating material, these aspects are provided now.Embodiments more disclosed herein are test findings.Those skilled in the art can recognize that the part embodiment can provide some advantage above other embodiment in specific settings.Also can study more embodiment.Therefore, will be appreciated that prescription and manufacturing that provides and the method that applies coating are exemplary, do not limit the present invention.

1. general prescription

Make the combination of making great efforts to start from acrylate, light trigger, light acid producing agent (PAG) and colour coupler in early days of photosensitive one-tenth colored paint.One of first kind of prescription that is considered to show desired properties comprises about 3% light acid producing agent (PAG), about 3% colour coupler and about 94% the potpourri that is called " coating base-material ".The coating base-material is formed by the potpourri that comprises acrylate and light trigger.At present preferred coating base-material embodiment is generally the potpourri of acroleic acid esterification monomer and oligomer, wetting agent and light trigger.The colour coupler and the light acid producing agent that are called " imaging component " are added in the coating base-material.Term used herein " coating base-material " also can be expressed as " base material ".

The initial test of research suitable coating base material relates to acrylic acid composition, and wherein SR-494 and SR-238 mix with the amount that approximately equates.Light trigger ESACURE KTO-46 is added in the acrylate composition, is about 10% of the first coating base-material.

The chemical equivalence thing of these materials is: SR-494 is ethoxylation (4) tetramethylol methane tetraacrylate; SR-238 is quick curing monomer, hydrophobic framework with low viscosity, low volatility and the 1,6 hexanediol diacrylate that is suitable for the excellent dissolution ability of free radical polymerization; ESACURE KTO-46 is the stable liquid potpourri of trimethylbenzene formyl oxidation diphenyl phosphine, alpha-alcohol ketone and benzophenone derivates.ESACURE KTO-46 is for can just being attached to Liquid photoinitiators in the resin system by simple agitation, and is water insoluble, is dissolved in great majority organic solvents commonly used and monomers.KTO-46 also can refer to comprise ESACURE KIP-150 and ESACURE TZT.The equivalent of ESACURE KIP-150 is: low [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone]; ESACURE TZT is 2,4, the eutectic liquid mixture of 6-tri-methyl benzophenone and 4-methyldiphenyl ketone.

ESACURE KTO-46, ESACURE KIP-150 and ESACURE TZT be by Lamberti Spa, Gallarate-Va, and Italy produces.SR-494 and SR-238 are SartomerCorporation of Exton, the product of PA.KTO-46 also is that Sartomer Corporation sells (therefore, the replaceable in this article use of KTO-46 and SR-1135) with SARCURE-1135.

Use the performance of first coating base-material investigation coating 100, demonstrate some defective.That is to say, think that the final products that formed by the first coating base-material do not show the skin hardness of required degree, and have skin irritation.Therefore, estimate the other component that is used for the coating base-material.Table 1 has shown the component of selecting for the coating base-material, and comprises its some performance characteristics.

Table 1

The coating base ingredient

Component	Performance characteristic
		SR-494	Quick curing reaction/good hardness
SR-238	Quick curing reaction/excellent bonds
		SR-285	Low viscosity/enhancing color
SR-9021	Quick curing reaction/fabulous hardness
		KTO-46	Excellent surface solidifies/good integrally curing

SR-285 is a tetrahydrofurfuryl acrylate, and it is low viscosity, polarity, monofunctional monomer, comprises cyclic group, and promotion and numerous substrates is bonding; SR-9021 is height propoxylation (a 5.5) glycerol tri-acrylate, and it be the trifunctional monomer of low skin irritability, low viscosity, good flexibility is provided, solidifies and the hardness of excellence fast.SR-285 and SR-9021 are SartomerCorporation of Exton, the product of PA.

SR-494 and SR-9021 are owing to high functionality, low surface tension, colour-fast surface and curing reaction, cohesive and hardness are selected for the coating base-material completely.Think that also these components are because alkoxylate can advantageously reduce the tendency of chafe.On the contrary, SR-238 and SR-285 have skin irritation, but desirable adjuvant solvation are provided really and make the polycarbonate swelling to possess good adhesive property.SR-238 and SR-285 also show low viscosity, and they provide the chance of customization coating base-material viscosity.KTO-46 is selected as light trigger, because the long wavelength (the about 400nm of promptly about 320nm-) that KTO-46 is considered to ultraviolet light is fully responsive.

Test also shows, can realize coating 100 is applied on the optical medium 10 by various technology.Preferably, apply coating 100 by spin coating.But, utilizing spin coating to begin to apply in coating 100 processes, the edge of optical medium 10 shows the covering of not enough needs sometimes.Can determine that this is because the high surface tension of lacquer (coating base-material) causes.Therefore, in the coating base-material, add wetting agent, to improve the substrate wetting state and to reduce surface tension.

Spin coating fills a prescription that example system on the substrate 17 comprises can be from HeadwayResearch, Inc.of Garland, those that TX obtains.The system that is used to utilize spin coating method to apply prescription used herein comprises: adjust the prescription temperature controlling, incrementally change the control of rotational speed, maximum rotative speed is at least 10000 (10K) rpm.System can also comprise the prescription retracting device that prescription is not used as the environment control and the circulation of control ambient gas in these aspects.Also can use other system to be used for spin coating, and also can be integrated in the large-scale device.Be suitable for applying a model of this paper prescription, on small batch, be model PWM32-PS-R790Spinner System at least, it is used for test described herein aspect.Because the spin coating system is known, thus these systems in this article usually only coating 100 apply and require aspect further describe.

Make prescription with all new component (table 1), observe the performance how they influence coating 100.Comprise that in new prescription wetting agent is to improve the distribution of prescription on dish 10.The wetting agent of test is BYK-307 and BYK-333, and two kinds of wetting agents are polyether-modified dimethyl silicone polymer all, and shows the capillary similarity of reduction.BYK-307 and BYK-333 are BYK-Chemie, the product of of West Germany, and by BYK-Chemie USA, of Wallingford, Conneticut sells in the U.S..Table 2 has shown prescription and result.

Table 2

Improved coating base material formulation

Component	Control

	1	2	3	4	5	6	7	8	9
										SR-494	45.00	32.50	32.45	32.35	32.25	32.00	31.50	32.48	32.45	32.43
SR-9021		32.50	32.45	32.35	32.25	32.00	31.50	32.48	32.45												32.43
										SR-238	45.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00
SR-285		15.00	15.00	15.00	15.00	15.00	15.00	15.00	15.00												15.00
										KTO-46	10.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00	10.00
BYK-333			0.10	0.30	0.50	1.00	2.00
										BYK-307								0.05	0.10	0.15
Surface Tension (dynes/cm)	42.67	42.83	30.67	28.33	27.00	26.67	26.67	31.50	30.33												30.67
										Viscosity(cP)	36.50	51.50	46.40	48.00	49.80	53.80	53.80	47.70	48.30	49.60

In table 2, shown the composition that amounts to 10 prescriptions.The first coating base-material shows that in contrast the prescription of back is shown as potpourri 1-9.10 kinds of amounts of forming every kind of component in each are represented with the percent by weight of whole potpourris.

The result shows, comprises that the formula table of wetting agent reveals the surface tension that reduces than the prescription that does not have wetting agent.This is considered to favourable, because the prescription that has than low surface tension should be better than those prescription coated substrate 17 with high surfaces tension force.Notice that the surface tension of prescription does not have marked change after adding 0.3%BYK-333 and 0.05%BYK-307.Therefore, by the edge that the coating base-material is spun on the various dishes 10 and checks substrate 10 test recipe 3 and 7 physically.During inspection, find that prescription 3 coating disks 10 are best, significantly increased surperficial smooth simultaneously.The viscosity of noticing various prescriptions does not have acute variation between sample 1 to 9.Therefore, select prescription 3 as preferred coating base-material.

After this test, soon, find that SR-9021 can exchange use with SR-9020, because both have similar character.This is considered to favourable, because SR-9020 provides the thermal stability higher than SR-9021.Therefore, SR-9020 replaces in the prescription 3.SR-9020 is 3 moles a propoxylated glycerol triacrylate, and it is for providing low viscosity, good flexibility, solidifying and the trifunctional monomer of excellent hardness fast.SR-9020 is the product of Sartomer Corporation.

Approximately at the same time, preparation has the prescription of different acrylate in a large number to find producing the more lacquer of hard conating.The new component of prescription and their aspect of performance are shown in table 3, and prescription and viscosity results are shown in table 4.

Table 3

Possible new recipe ingredient

Component	Performance characteristic
		SR-9020	The higher Tg form of SR-9021
SR-454	Quick curing reaction/good hardness, high Tg
		SR-368	Adhesion promotor/wear-resisting
SR-355	High Tg replaces SR-494
		CN-983	Hard urethane acrylate

The component that provides in the table 3 is the trade name that is used for the Sartomer Corporation of following material: propoxylation (3) glycerol tri-acrylate (SR-9020); Ethoxylation (3) trimethylolpropane triacrylate (SR-454); Three (2-hydroxyethyl) isocyanuric acid ester triacrylates (SR-368); Two trimethylolpropane tetra-acrylate (SR-355); And urethane acrylate (CN-983).

Table 4

Improve may filling a prescription and viscosity results of hardness

Component	Control(3)	10	11	12	13	14	15	16
									BYK-333	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
KTO/46	10	10	10	10	10	10	10	10
									SR-238	10	10	10			10	10
SR-285	15	15	15	10	10	15	15	15
									SR-494	32.35	32.35	32.35	34.85	34.85			25
SR-9021	32.35
									SR-9020		32.35			34.85		32.35
SR-454			32.35	34.85		32.35		29.7
									SR-368				10	10
SR-355						32.35	32.35
									CN-983								20
Viscosity(cP)	42.65	41.61	37.92	76.85	82.95	45.36	57.33	96.95

When checking the sample of spin coating, curing, obviously comparison is hard according to (prescription 3) to find prescription 10 and 14, still shows similar viscosity simultaneously.10 and 14 test in a large number filling a prescription then, form the new formulation screening test shown in the table 5.In preferred embodiments, every kind of prescription all must be by this screening to be regarded as the possible base-material of coating 100.Table 5 has shown test and the standard that relates to.

Table 5

New formulation screening test

Test	Describe	Uncured	Solidify	Explanation
					UV-VIS	190-800nm, quartz	×	×	Background color (during peak value＜0.05AU)
Viscosity	ASTM	×		＜100cP@25C
					Surface tension	Tensiometer	×		＜33 dyne/cm
Pencil hardness	ASTM		×	＞＝2B
					Set time	Xenon lamp-1 " far away, optical filter is arranged	×		Fully sclerosis is＜3 seconds
The quality time	Xenon lamp-10 " far away, free of light filter		×	0.5AU＜10 second when the peak value, 3%CF/PAG

Two kinds of new prescriptions are by new formulation screening test, and are as shown in table 6, consider that prescription sample 10 and 14 is used for following the use and more deep test.

Table 6

Two prescriptions by new formulation screening test

Test

	10	14
			UV-VIS	0.0315AU in the time of 3 seconds	0.0189AU in the time of 2 seconds
Viscosity	41.61cP	45.36cP
			Surface tension	28.83 dyne/cm	28.33 dyne/cm
Pencil hardness	2B	2B
			Set time	3 seconds	2 seconds
The quality time	0.5501AU in the time of 10 seconds	In the time of 10 seconds 0.5579

2. light acid producing agent screening

In a single day add light inlet acid producing agent (PAG) with colour developing in coating 100 when being exposed to optical wavelength.This process comprises when being exposed to optical wavelength by PAG generation acid.Then, acid-sensitive sense colour coupler (CF) interacts with acid, and forms color.Preferably, PAG is to the ultraviolet light sensitivity.

Checked the sort of that a large amount of light acid producing agents work in coating 100 to find to suit.For more various PAG, prepare every kind of prescription by identical mode.Seek the aspect of performance of PAG, comprise that sufficient acid generation is used for required quality and the stability in the environment after quality.

By mixing initial control formula (45%SR-494,45%SR-238 and 10%KTO/46) preparation coating base-material sample.This potpourri joins the COPIKEM 16RED (a kind of colour coupler) of 3% concentration and every kind of light acid producing agent that will be studied of 3% concentration with 94% concentration.Lacquer is spun to 17 last 15 seconds of polycarbonate substrate of blank not coating metal layer with 4K rpm.Then each dish 10 is placed on following 5 seconds of pulse XENON lamp with two lattice glass pane optical filters.Transparent, dry and hard coating that the dish 10 that obtains has.Make the part of dish 10 expose 5 seconds then.Make another part of dish 10 expose 10 seconds.This is producing the redness that intensity changes between dish 10 different pieces on transparent plate 10.In order to form the intensity of color in the quantitative measurment exposure dish 10, on spectrometer, write down absorption curve.The UV/VIS model that is called LAMBDA 2 is counted in the beam split of using, Perkin ElmerCorporation, and of Boston, MA produces.The data presentation that produces, the absorption peak that comprises the prescription of COPIKEM16Red appears at about 540nm place.Typical absorption curve is shown in Figure 11.The results are shown in table 7.Attention was measured the intensity of background color in 0 second in table 7.

Table 7

Use the light acid producing agent result of control formula

3% smooth acid producing agent	AU，540nm	AU，540nm	AU，540nm
					0 second	5 seconds	10 seconds
Two (4-tert-butyl-phenyl) iodine tosilate	-	0.0834	0.0864
				(tert-butoxycarbonyl methoxyl naphthyl) hexichol sulfonium fluoroform sulphonate	0.0151	0.4896	0.6639
(4-Phenoxyphenyl) hexichol sulfonium fluoroform sulphonate	0.0037	0.4826	0.5899
				(4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate	0.0047	0.3759	0.5262
The diphenyl iodonium hexafluorophosphate		Redden immediately
				The diphenyl iodonium fluoroform sulphonate	-	Redden and insoluble
The triphenyl sulfonium fluoroform sulphonate		0.5496	0.5989
				2-methyl-4, two (the trichloromethyl)-s-triazines of 6-		Color fading in 24 hours
Three (2,4, the 6-trichloromethyl)-s-triazines		Color fading in 24 hours
				2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-		Color fading in 24 hours
2-(4-chlorphenyl)-4, two (the trichloromethyl)-s-triazines of 6-		Color fading in 24 hours

The result shows that (tert-butoxycarbonyl methoxyl naphthyl) hexichol sulfonium fluoroform sulphonate, (4-Phenoxyphenyl) hexichol sulfonium fluoroform sulphonate, triphenyl sulfonium fluoroform sulphonate and (4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate intensity are decrescence.But,, therefore when selecting the preferred light acid producing agent, consider other factors such as cost because fully as seen 0.5AU is considered to.Select of the preferred selection of triphenyl sulfonium fluoroform sulphonate as coating 100.Notice that all light acid producing agents are all dissolving in 3% o'clock except two (4-tert-butyl-phenyl) iodine tosilate and diphenyl iodonium fluoroform sulphonate.Two (4-tert-butyl-phenyl) iodine tosilate need remove by filter most of insoluble light acid.

Table 8 has shown the result of three kinds of light acid producing agents (PAG).Three kinds of PAG are incorporated in the improved coating base material formulation 10 (account for 94%, be 32.35%SR-494,32.35%SR-9020,15%SR-285,10%SR-238,10%KTO/46 and 0.3%BYK-333).Every kind of light acid producing agent of 3% concentration is mixed with colour coupler PERGASCRIPT RED I-6B.The dissolubility that compares three kinds of light acid producing agents, (4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate is better than (4-aminomethyl phenyl) hexichol sulfonium fluoroform sulphonate dissolubility, and (4-aminomethyl phenyl) hexichol sulfonium fluoroform sulphonate is better than triphenyl sulfonium fluoroform sulphonate dissolubility.Because the prescription of PERGASCRIPT RED I-6B has patent right, so this paper does not provide.But, the various colour couplers that are applicable to that this paper instructs are provided herein in addition.

Table 8

Light acid producing agent result in the prescription 10

3% smooth acid producing agent	AU，540nm	AU，540nm	AU，540nm
					0 second	5 seconds	10 seconds
The triphenyl sulfonium fluoroform sulphonate	0.0176	0.4027	0.5829
				(4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate	0.0093	0.3893	0.4908
(4-aminomethyl phenyl) hexichol sulfonium fluoroform sulphonate	0.0138	0.3921	0.4741

3. curing Consideration

The curing here makes further research with good grounds, has therefore studied other light trigger, and has replaced the KTO/46 of 10% concentration.Table 9 has shown the first group of test findings that changes light trigger quantity.Prepare each sample by spin coating, the XENON light irradiation by the fenestrate glass filter of apparatus solidified in 5 seconds then.10 seconds kinds of exposed sample under the XENON lamp then.In the table 9 every percentage by weight that accounts for 94% coating base-material part with light trigger provides.Obliterate coating and determine state of cure by attempt physics, the state of cure level is as follows: E (fabulous)＞G (well)＞D (still can)＞P (poor).

Table 9

Light trigger test I

	Formulation No.
										Photoinitiator	10	17	18	19	20	21	22	23	24
ESACURE KTO-46	10	5
										DAROCUR 4265			10
IRGACURE 819				5	5	7	9	10
										IRGACURE 369									5
ESACURE TZT				5
										Degree of cure	G	P	P	D	G	G	-	-	G

It is good that the result shows that sample 20,21 and 24 solidifies.But the sample 24 with 5%IRGACURE369 can not produce any color being exposed to the UV light time.In addition, the sample 20 and 21 with IRGACURE 819 of 5% and 7% solidifies and shows pink a little.Attention prescription 22 and 23 is abandoned, because they also redden in the lacquer form except insoluble.

DAROCUR 4265 be 50% 2,4, the potpourri of 6-trimethylbenzoyl-oxidation diphenyl phosphine and 2-hydroxy-2-methyl-1-phenyl-the third-1 ketone of 50%.IRGACURE 369 is 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, and it is for being used to cause chemical prepolymer such as acrylate and list or the photopolymerisable efficient UV hardening agent of polyfunctional monomer.IRGACURE 819 is two (2,4, the 6-trimethylbenzoyl)-oxidation phosphnilines, and it is the multifunctional light initiating agent of unsaturated polyester free radical polymerization when being used for the exposure of UV light.It is particularly useful for the curing of polyester/styrene system that Chinese white prescription, glass fibre strengthen and the clear coat of the outdoor use of combined light stabilizing agent.Utilize this light trigger, thickness portion curing also is fine.These three kinds all is Ciba Specialty Chemicals of Basle, Switzerland, andTarrytown, the product of NY.

In order further to improve sample 20 and 21, add 0.5% and 1% CN-384 respectively, a kind of amine synergistic agent.These new interpolations have successfully produced very transparent solidified coating.But, at 1% o'clock, the exposure area insufficient strength.Unfortunately, owing to add CN-384, the exposure area of discovery dish 10 shows sizable fading after at room temperature about 24 hours.(CN-384 is for the auxiliary initiating agent of bifunctional amine, and when being used in combination with photosensitizer such as benzophenone, it can promote to solidify fast under UV light.Auxiliary benefit comprises the smell that has reduced in squeeze side and the cured film, and has reduced blooming.CN-384 is SartomerCorporation of Exton, the product of PA).

Utilize the various combination and the more light trigger of above-mentioned test to carry out another group test.Equally, the coating base-material is equal to prescription 10 usually, except replacement light trigger KTO/46 as shown in table 10.

Table 10

Light trigger test II

	Formulation No.
																Photolnitiator	25	26	27	28	29	30	31	32	33	34	35	36	37	38	39
ESACURE KTO-46	7.5												10
																IRGACURE 819		3	6	2.25	1.5	0.75	4.5	3	1.5
IRGACURE 2959				0.75	1.5	2.25	1.5	3	4.5
																DAROCUR 4265										5	7	10
SARCURE SR-1124													2
																ESACURE TZT															10
ESACURE KIP100F														10
																Degree of cure	D	D	G	P	Prefe rably	P	G	G	P	P	P	D	E	P	D

IRGACURE 2959 is 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone, it is the efficient non-yellowing free radical photo-initiation that is used to comprise that the system UV of unsaturated monomer and prepolymer solidifies.It especially is fit to few occasion of needs smell and the water-based system that is used for based on acrylate or unsaturated polyester resin.The activity hydroxy group can react with suitable functionalized unsaturated polyester; SARCURE 1124 is an isopropyl thioxanthone, and a kind of and suitable auxiliary initiating agent such as ethyl-4-(dimethylamino) benzoic ether (SARCURE SR1125) are used in combination the light trigger that causes UV free radical polymerization.SARCURE SR1124 uses in printing ink, varnish and decorative coveringn.ESACURE KIP100F is the liquid mixture of 2-hydroxy-2-methyl-1-phenyl the third-1 ketone of about 70% low [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone and about 30%.

This test findings in the table 10 shows that sample 27,31,32 and 37 solidifies good, and the reason of further research is arranged.Because sample 20 and 21 is cured to pink a little outward appearance, after the curing soon with 24 hours after, the selected prescription that uses IRGACURE 819 is collected the spectrum of consolidation zone, as shown in figure 12.

This test shows that when the amount of IRGACURE 819 in the prescription increased, the color intensity of solidified coating increased and will continue to increase.IRGACURE 819 may cause the susceptibility of longer wavelength light is improved as the sensitizer of light acid in theory, causes unwanted quality.Therefore, prescription 27 and 31 is owing to the intensity of solidifying background color is abandoned.

Sample 37 solidifies rapidly, but is considered to have after curing the quality of undesirable quantity.Therefore, preparation has another prescription of low concentration SR-1124.As if prepare other prescription by adding SR-1124, because SR-1124 can promote to solidify fast.The combination of the 3rd light trigger test is shown in table 11.

Table 11

Light trigger test III

	Formulation No.
					Photolnitiator	40	41	42	43
ESACURE KTO/46	5
					IRGACURE 819			3
IRGACURE 2959		5
					SARCURE SR-1124	1	2	1	5
Degree of cure	D	P	G	P

Test III shows that sample 41 and 43 can not finely solidify.Sample 43 is pulverize redness very fast also.Look and show hope that SR-1124 is considered to obstacle to other character to the sensibilization of light acid producing agent, as the UV stability of image although comprise some prescription of SR-1124.But, from by listed these tests carried out of table 9-11, develop the potential combination of light trigger, and can be used for preferably using KTO-46 (prescription 10) in testing future, to demonstrate the situation of defective.

Be important to note that the others that coating 100 disclosed herein is solidified.These aspects comprise considers to filter spectrum, curing environment and cure lamp aspect, and wherein some are discussed now.

Think and not only realize solidifying but also realize that importance that imaging is used is to split the ability of the spectral range that each step can use.As described in other place of this paper, preferably use ultraviolet wavelength to finish and solidify and imaging.Recognize that other prescription except that this paper discloses those may show better response at other wavelength place, it is exemplary therefore using the wavelength of this paper appointment.In preferred embodiments, use dark UV light (wavelength is below about 320nm) imaging, because it is feasible that the light acid producing agent is operated, and because in natural irradiation (daylight, fluorescence or incandescence), generally there is not high-intensity dark UV light in this scope.When this often can provide and use under environmental baseline more durable image.For example, described more than 290nm, to have the absorption spectrum of two kinds of commercially available smooth acid producing agents that seldom absorb among Figure 13.

A large amount of main absorption bands are arranged at the commercially available light trigger that exists greater than the 300nm wavelength.That the most famous is LUCIRIN TPO (key component among the KTO46) and the IRGACURE 819 of functionalized light trigger of phosphine oxide such as BASF Corporation of Charlotte NC, and their spectrum is shown in Figure 14 and 15 respectively.Can use other light trigger that the wavelength more than about 300nm is also shown absorption.It shall yet further be noted that these initiating agents are direct cracking type unimolecule initiating agent.

The bimolecular initiating agent generally comprises the energy absorbing light and converts the sensitization molecule of synergistic agent molecule to, and the synergistic agent molecule can form free radical when energy conversion.The most frequently used a kind of sensitizer that absorbs visible light is ITX or isopropyl thioxanthone.ITX is often with amine synergistic agent such as ethyl-right-dimethylaminobenzoic acid ester (EDAB) or octyl group-right-dimethylaminobenzoic acid ester (ODAB) use.EDAB and ODAB can both form free radical from the ITX energy conversion time.These components are considered to be not suitable for being used for coating two reasons.First be the ITX sensitizer also to visible light photoactivated light acid, thereby eliminated solidify and write between spectral resolution.(to a certain extent, this also can take place when using some unimolecular initiators such as IRGACURE 819, and it also causes the slight sensitization of light acid to produce long wave UV light).Second reason is that acid that typical synergistic agent such as amine (being alkoxylate monomer such as SR-494, SR-9020, SR-9021 on lesser extent) produce by neutralization light acid producing agent significantly reduces or even eliminated color and form or image stabilization.

For the discussion of light trigger type and method, can reference: " Chemistry ﹠amp; Technology of UV ﹠amp; EB Formulation for Coatings, Inks ， ﹠amp; Paints, Volume III Photointiators for Free Radical Cationic ﹠amp; AnionincPhotopolymerization " I and II chapter in the 2nd edition, J.V.Crivello and K.Dietliker Eds, WILEY/SITA Series in Surface Coatings Technology, John Wiley and Sons, 1998.

Except requiring to have the light acid producing agent of decomposition and the absorption spectrum of light trigger (separated from one another basically), large-scale production also needs in each wave band fully light intensity must be high enough to provide in the minimum time to solidify and imaging.The light source commonly used that is used for the UV curing curable coating comprises that continuous wave (CW) light source such as metal and metal halide arc lamps are (from HonleUV America, Inc of Marlboro, MA), and pulsed arc light modulation such as XENON gas arc lamp (Xenon Corporation, of Woburn MA).

Make the wavelength that is to produce narrow wave band with an advantage of light optical filter or other technology, or can eliminate undesired wavelength substantially.This technology provides better resolution (separately solidifying and the imaging wavelength), thereby has increased the availability and the selectivity of light trigger and light acid producing agent and their combinations.

Typical mercury vapor light produces the spectrum that is mainly line spectrum.For example, the spectrum among Figure 16 has shown the output of middle foundary weight doped mercury lamp, and this mercury lamp generally is used to be applied to the UV solidified paint of optical medium 10.How relevantly can observe from the major part output of line of discontinuity with the electronic transition of lamp adulterant.Similar spectrum with different metal halide lamp gallium iodide of different transition lines is shown in Figure 17.

These lamps generally can perform well in UV and solidify, because the light trigger that uses in main line and the UV curing system is compatible.Another primary light is that pulse XENON gas is filled lamp, those that make as XENON Corporation of Woburn MA.The spectrum of these lamps more is " black matrix " in nature, and the plasma colour temperature that spectrum forms in lamp from pulse process obtains.Described the exemplary spectrum of XENON RC-747 gas filling lamp among Figure 18.

Except having suitable UV light source, must realize separate of long UV and short UV spectra part, so that solidified coating 100 at first, and can not cause color formation too early.Preferably, this realizes by using as shown in figure 19 those of absorption filter such as transmission curve.In the development process of coating 100, carry out the combination accepted that lamp, optical filter and light trigger are sought in a series of tests, so that to be provided the set time of abundant weak point, not have too early color and form generation.As shown in figure 19, the L37 optical filter is abundant transmission more than about 370nm.

The method for optimizing of solidified coating comprises use KTO-46 light trigger and XENON bulb and L37 glass of color filter.Compare with the XENON lamp, typical mercury line lamp can not produce sufficient light intensity, and the both is equipped with the L37 optical filter.Because the high strength of XENON flashlight produces more performance in solidified coating, therefore select the XENON lamp to be used for solidified coating 100.

In practical operation, also can wherein optionally reflect the UV spectra part and allow catoptron visible and that infrared part is passed through that therefore required wavelength will only be provided by the filtration of using the cold light reflector technology to realize solidifying wavelength.This technology will provide the benefit that reduces the required heat management of thermal load in the coating 100 and cooling and absorbing optical filter.The other method that is considered to be used to solidify is to use the dissimilar glass with different UV transmissivities as bulb material, thereby keeps the thermal load in the lampshade.This is comprised the technology of knowing that XenonCorporation uses by most of bulbmakers, and only five kinds of different bulb types on the type of glass of use can be provided.

4. oxygen suppresses

In the UV of free radical system solidification process, the existence of oxygen can have adverse effect to curing reaction, especially for film coating.Therefore, pay the utmost attention to the ambient oxygen (air) that suppresses in the curing environment.It is known that oxygen suppresses, and describes (referring to the 83rd page in the 2nd chapter) by Crivello and K.Dietliker.When solidified coating 100 in surrounding air, oxygen and free radical reaction and by with light trigger, monomer or increase the chain radical reaction and form peroxy.The reactivity of peroxy is not enough to continue radical polymerization process, causes chain termination and produce solidifying not enough system.The method that overcomes the oxygen inhibition comprises that (1) adds more light trigger or (2) increase set time.Because the light trigger of selecting is relatively costly, so option (2) is considered to be better than option (1).

Another solution that oxygen suppresses problem is to replace surrounding air environment with inert gas such as nitrogen.This can make all free radicals that produce by the UV exposure use in polymerization process.Unfortunately, use the meeting of pure gas such as nitrogen owing to needing a large amount of nitrogen have relevant economic impact.Therefore, use the expense of purge gas to require quite, as set time and required final products with various other.

Overcome the light trigger that another method is to use and the oxygen reaction is less of oxygen inhibition.These initiating agents often need short UV light come work (＜320nm).Perhaps, light trigger can comprise above-described sensitization molecule and synergistic agent.As mentioned above, sensitizer also makes the light acid producing agent to the visible light sensitivity.This has the tendency that reduces the curing wavelength range and write spectral resolution between the wavelength range.The acid that typical synergistic agent such as amine (being alkoxylate monomer such as SR-494, SR-9020, SR-9021 on lesser extent) produce by neutralization light acid producing agent significantly reduces or even has eliminated color and form or image stabilization.Therefore, for being used for coating 100, this technology is not preferred.

Overcoming the method for optimizing that oxygen suppresses is to improve to solidify light intensity, as using the high intensity pulses source, as the RC-747 model lamp that can obtain from Xenon Corporation of Woburn MA.In the preferred embodiment that pulse UV solidifies, the energy of each flash of light is by force to forming the very free radical of high concentration.This method produces enough free radicals, thereby the oxygen on coating 100 surfaces is depleted, and other free radical just is used for solidifying.In this method, energy intensity provides the key factor of instant curing.Can be by with reference to Fusion UV Systems about light intensity to the more information of the influence solidifying and overcome oxygen and suppress, the technical papers that Inc.of Gaithersburg, MD go out " Secrets of the Dark " obtains.

The curing that the use of pulsed light has been proved to coating 100 disclosed herein is favourable because it can with the matched spectral range of color forming process in high-intensity light is provided.In addition, use pulsed light to significantly reduce oxygen and suppress problem, thereby do not need nitrogen environment or excessive light trigger, keep short as far as possible set time simultaneously.

5. color and image

A large amount of different colour couplers are studied and are used for coating 100.For being provided as toner and the comparison of brightness separately thereof, by mixing the coating base-material preparation prescription of initial control formula (45%SR494,45%SR238 and 10%KTO/46).This coating base material mixture is added to the triphenyl sulfonium fluoroform sulphonate of 3% concentration and the colour coupler that will study of 3% concentration with 94%.Because have the color of wide region, absorption peak appears at various wavelength place.Figure 11 has shown the typical curve of LAMBDA 2 UV-VIS spectrometers records.Table 12 has shown effective result.

Table 12

Colour coupler test findings among the SR494/SR238

3％Colorformer	nm peak	AU，nm peak	AU，nm peak
						5sec	10sec
Copikem
	16 Red	540	0.3600	0.4607
Copikem 6 Green					440，600	0.2069，0.1722	0.2211，0.1807
	Copikem 34 Black	464，586	0.2551，0.2267	0.2757，0.2448
Pergascript Red I-6B					540	0.4846	0.5729
	Pergascript Crange I-G	493	0.1580	0.1600
Pergascript Green I-2GN					440，602	0.1956，0.1628	0.2290，0.1862
	Pergascript Blue I-2RN	613	0.0577	0.0677
Pergascript Black I-2R					460，586	0.2871，0.2553	0.2830，0.2476
	BK-305 Black	464，586	0.2757，0.2439	0.2730，0.2350
S-205 Black					464，586	0.3049，0.2704	0.2975，0.2623
	BK-400	464，586	0.2605，0.2314	0.2684，0.2598
Red 520					525	0.3070	0.4031

The COPIKEM material quotes to be considered to be illustrated as and implements these instructions and can be incorporated into material in the prescription in the table 12.In fact, owing to these materials are no longer sold, so these materials are not preferred.BK-305 Black, S-205 Black, BK-400 and Red 520 are can be from Yamada Chemical Co., the colour coupler material that Ltd.Of Japan and Arlington, VA obtain.Embodiment preferred comprises uses various PERGASCRIPT colour couplers, and the structure of these colour couplers and prescription are patented.But, be applicable to that the quality examples of material of implementing these instructions is separately in people's such as Garner United States Patent (USP) 4102893, " Process for Manufacture of Color Formers of Indoles andAnhydrides of Aromatic or Heteroaromatic; Vicinal DicarboxylicAcids; New Color Formers of These Classes of Substance and TheirUse ", on July 25th, 1978.Whole disclosures that this paper introduces United States Patent (USP) 4102893 as a reference.For example, according to disclosed a kind of quality material in the part test described herein test United States Patent (USP) 4102893, i.e. downward the 6th compound of prescription in the table 1, show have the quality material to the required character of small part.

These results show that red colour coupler COPIKEM 16 Red and PERGASCRIPTRed I-6B produce best color intensity.Therefore, the preferred embodiment of coating 100 is used red colour coupler, but will be appreciated that other colour coupler that above-mentioned colour coupler and this paper do not discuss can be used for producing sufficient color formation.

The main PERGASCRIPT Red I-6B colour coupler that uses of remaining test.Notice that in some cases, when adding 3%, the dissolubility of some colour couplers becomes problem.Black and green colour coupler show some solubility problem in the coating base-material that uses, therefore, filter these prescriptions, reduce their concentration and arrive a shade below 3%.But, recognize that the green that perhaps has various coating base material formulations and the further test of black colour coupler may produce improved result.Except the colour coupler in the table 12, also tested PERGASCRIPT Yellow I-3R.But this colour coupler shows the part quality when solidifying, therefore think that effective use of PERGASCRIPT Yellow I-3R also requires further study.

The base material formulation that changes coating 100 then is prescription 3 (0.3%BYK-333,10%KTO/46,10%SR-238,15%SR-285,32.25%SR-494 and 32.35%SR-9020).And then the good colour coupler of experiment work, identical to guarantee that color forms.Color forms has only difference slightly, the results are shown in table 13.

Table 13

Colour coupler test findings in the prescription 3

3％Colorformer	Nm peak	AU，nm peak	AU，nm peak
						5sec	10sec
Pergascript Red I-6B	540	0.4027	0.5289
				Pergascript Orange I-G	493	0.1937	0.2186
Pergascript Green I-2GN	440，602	0.2046，0.1716	0.2126，0.1704
				Pergascript Blue I-2RN	613	0.0814	0.0899
Pergascript Black I-2R	460，586	0.2636，0.2404	0.3016，0.2696
				Red 520	525	0.4044	0.4888

Table 14 and 15 demonstrations, in 3% colour coupler, 3% smooth acid producing agent and 94% coating base-material (be respectively formulations reference or fill a prescription 3), some other height of the strength ratio of part color.But the intensity of color is not fixed.Recognize and to improve color intensity by the whole bag of tricks, as the concentration of raising light acid producing agent and/or colour coupler with by adding the color reinforcing agent.

So research is to the improvement of color intensity.At first, the quantity of colour coupler COPIKEM 16 Red is increased to 6% from 3%, again to 9%.When doing like this, the fixed amount that keeps the light acid producing agent simultaneously is 3%, the remainder of the coating base-material composition mixture of control formula.Use the UV-VIS LAMBDA 2 spectrometers curve that is absorbed.Result shown in Figure 20 has described the absorption peak at 540nm place.

9%COPIKEM 16 Red, 3% triphenyl sulfonium fluoroform sulphonate and 88% coating base-material show the highest optical density (OD) (OD) in exposure after 10 seconds as can be determined from Figure 20.But, only tested in the time of 10 seconds that to be up to 9% COPIKEM 16 red.The result shows, can improve color intensity by adding more colour coupler at least to a certain extent.Because different colour couplers shows different under identical heap(ed) capacity, therefore the concrete test that has reasonable ground to carry out other colour coupler changes with further inspection color intensity.But,, just can think the similar variation that should be able to realize color intensity as long as the colour coupler that uses is soluble.

In another test, increase the quantity of light acid producing agent by the mode identical with the colour coupler test.Figure 21 has described the effect that increase coating 100 photolytically acids produce color intensity after agent (in this test, the using the triphenyl sulfonium fluoroform sulphonate) quantity.Figure 21 shows, uses the exposure that is combined in of 6% smooth acid producing agent, 3% colour coupler and 91% coating base material formulation to produce maximum colors after 10 seconds.In this case, also can improve optical density (OD) (OD) by the light acid producing agent that adds above 6%.But for 9% light acid producing agent, color intensity shows remarkable reduction.For this reason, the experimental concentration of susceptible of proof triphenyl sulfonium fluoroform sulphonate (TPST) is favourable between 6% and 9%.In a word, as if add the colour coupler of Duoing and can produce preferred result than the light acid producing agent, and more economical.

In further testing, light acid producing agent and colour coupler are increased to 6% and 9% simultaneously, the coating base-material is respectively 88% and 82%.But these prescriptions are soluble, do not finish further research.

6. environmental impact

The original research of carrying out shows, 100 pairs of environmental impact sensitivities of coating.More particularly, the imaging or the painted areas of dish 10 are faded when obviously being exposed to humidity and temperature.Therefore, carrying out the color that other research quantitative measurment environmental impact causes goes down.

Go down for color, tested 8 different formulations, their prescription is shown in table 14.(prescription of noting is generally discerned according to the composition of coating base material formulation in this article and is mentioned).Under 4000rpm, the sample of every kind of prescription is spun to three 10 last 15 seconds of dish.Under the L37 optical filter, will coil 10 curing 2 seconds in the presence of the nitrogen then.Then half of each dish 10 exposed 10 seconds.Before test and after obtain each dish absorption curve of 10, go down with the reflection average color.Humidity and humid test comprise dish is put in 70 ℃, the environment baking oven of humidity 90% and kept 96 hours.

Table 14

The prescription that is used for Environmental Studies I

	Base Coat Formulation No.
									3	10	14	44	45	46	47
Formulation Name：	9021	9020	3％4TB	454/355	5％KTO	983	368
								COMPONENT
Wetting Agent BYK-333	0.3 0.3 0.3 0.3 0.3 0.3 0.3
								Photolnitiator KTO/46	10 10 10 10 5 10 10
Diluents SR-238 SR-285 SR-506	10 10 10 10 10 10 10 15 15 15 15 15 15 15
								Main Components SR-494 SR-9021 SR-9020 SR-454 SR-368 SR-355 CN-983 CN-120	32.35 32.35 32.35 32.35 32.35 32.35 32.35 34.85 27.35 27.35 10 32.35 34.85 27.35 27.35 10
TOTAL	100	100	100	100	100	100	100
								Photoacld generator TPST t-butylphenyl DPST	3 3 3 3 3 3 3
Color former Pergascript Red 6B	3 3 3 3 3 3 3
								Fading％ Viscosity(cP)	66.74 64.5 65.0 52.3 51.8 47.6 45 58.5 58.7 72.0 67.8 109.9 90.7

Test findings shown in Figure 22 shows that in the presence of temperature and humidity, the part prescription can keep their color better than other those.Specifically, add non-alkoxylate monomer such as SR-355 (prescription 14), CN-983 (prescription 45) and SR-368 (prescription 46) and all improved performance.This may be that alkoxy group content reduces the result that (water wettability reduction) and Tg or cross-linking density improve.Use the tert-butyl group derivant of triphenyl sulfonium fluoroform sulphonate (TPST) or the light acid producing agent of higher concentration to have no significant effect performance.

Design also prepares the second assembly side so that the observation of front to be described in detail in detail.Second group is described in the table 15.Before adding light inlet acid producing agent and colour coupler, add and mix all base ingredient.Component S R-368, CN-983 and CN-120 liquefy on heating plate before adding.In case base ingredient is added 3% smooth acid producing agent by mixed and even in every batch of material.Prescription 53,55 and 57 can not enter solution, abandon these batch of materials.Recipe ingredient based on coating base material formulation 10 can not easily dissolve as other, but they finally enter solution.In case the dissolving of all light acid producing agents then adds the colour coupler that quantity is every batch of material general assembly (TW) 3%.All prescription enters solution with having no problem, does not also have mixed problem because of adding colour coupler.Filter every kind of prescription by 5 micrometer nylon syringe filter then.During beginning, all prescriptions have canescence to bright rose-colored or yellow.

SR-506 is an isobornyl acrylate, and it is the sound response thinning agent of oligomer.CN-120 is a difunctionality bisphenol-A basic ring oxypropylene acid esters.Both are the product of Sartomer Corporation.

With hand is that 5 clear polycarbonate dishes 10 are coated with every kind of prescription.Under the Xenon flashlight, use nitrogen environment and L-37 optical filter to solidify each dish 10 then in about 5 inches distances.Prescription 56 is extremely thick, but is coated with finely.Prescription 10 solidified in 2 seconds.All the other samples of prescription solidified in the time of 4 seconds, because they only comprise 5% light trigger.Then with each the dish 10 half under lamp, expose 10 seconds with formation red color.Use the UV-spectrometer to scan all dishes 10 (solidifying and two sides of exposing) subsequently to measure the optical density (OD) at 540nm place.

Table 15

The prescription that is used for Environmental Studies II

	Base Coating Fomulation No.
															10	48	49	50	51	52	53 *	54	55 *	56 **	57 *	58	59
	9020	355-5％	355-Tego	983	368-1	368-2	368-3	368-4	506-1	506-2	506-3	120-1	120-2
														Component
Wetting Agent BYK-333 TEGO RAD 2200N Photolnltiator KTO/46 Diluents SR-238 SR-285 SR-506 Main Components SR-494 SR-9021 SR-9020 SR-454 SR-368 SR-355 CN-983 CN-120 TOTAL	0.3 0.3 1 1 1 1 1 1 1 1 1 1 1
														10 5 5 5 5 5 5 5 5 5 5 5 5
	10 10 10 15 15 24 10 50 10 10 10 15 20 15 15 14 15 15 15 50 24 24 24 14
														32.35 22 32.35 22 34.85 35 22 22 40 35 25 25 20 30 44 44 20 34.85 35 22 22 35 25 25 30 20 40 20 30
	100 100 100 100 100 100 110 100 110 130 110 100 100
														Photoacld TPST t-butylphenyl DPST	3 3 3 3 3 3 3 3 3 3 3 3 3
Colorformer Pergascript Red 6B	3 3 3 3 3 3 3 3 3 3 3 3 3
														Fading％	56.95	43.22	49.42	48.19	45.85	41.92		44.04		44.46		54.25	21.01
Viscosity(cP)	56.7	65	68	113.4	82.8	108.7		728		38.5		116.5	370.9
														Optical Dansity	0.42	0.49	0.50	0.62	0.56	0.61		0.61		0.75		0.65	0.79
Fllm Thickness(um)	3.6	3.9	3.7	4.6	4.6	4.5		4.8		8.9		5.0	8.9

^*Even also keep insoluble after adding 238

^*Be not cured

This research has also been estimated wetting agent has been become crosslinkable silicon from BYK-333.Checked several candidates' active wetting agent, comprise TEGO three kinds of RAD products (RAD 2250, RAD 2200N, RAD2100).Use prescription 48 to check the performance of three kinds of products.Select the RAD 2200N of TEGO, reduce and properties of transparency because it has provided best surface tension.Check result is shown in Figure 23.The RAD 2250 of TEGO and the RAD 2200N crosslinkable silicone polyether acrylate of respectively doing for oneself, and the RAD 2100 of TEGO is crosslinkable silicone acrylate.The TEGO product can obtain from Tego Chemie Service GmbH, and in the U.S. by Degussa Tego Coating ﹠amp; Ink Additives of Hopewell, VA sells.

Three of every kind of prescription dishes 10 are placed down in the environmental chamber 96 hours 70 ℃ and 100% relative humidity.Comprising prescription 4 and 5 dish 10 is stored in the opaque Sheng dish container in contrast.Take out from the chamber in case will coil 10, scan every kind of prescription once more (10, all dishes 10 48-51) are to measure any difference of optical density (OD) at the 540nm place.Correlation data is provided in Figure 24 and 25.

Can know from data and to find out that viscosity change plays an important role to the color that film thickness and constant exposure produce.Therefore, think that it must not be the clear and definite index of performance that color goes down because thicker and therefore darker coating 100 may fade manyly, but still kept more color than the thin application of coating 100.But for first approximation, the color percent that goes down is the index of imaging chemistry relative stability in the particular substrate.

Prescription 59 based on bisphenol a diacrylate and SR-355 (Di-TMPTA) is considered to show best performance in test group.In case be applied with, should be highly cross-linked by prescription 59 coatings that form 100, have high Tg, film does not have alkoxylate.All all the other prescriptions comprise the alkoxylate monomer of effective dose, and it causes lower Tg, water wettability and possible alkaline environment.Therefore, design the influence of the 3rd assembly side discussion CN-120 prescription and alkoxylate to image stabilization.

Test the best prescription that does not comprise CN-120 with a series of CN-120 prescriptions.The composition aspect of these prescriptions and their performance specifications separately are in table 16.Also tested CN-132, a kind of low viscosity aliphatics diacrylate that Sartomer Corporation produces.At last, tested CN-983, whether a kind of aliphatic urethane acrylate can use as CN-120 to determine it.The result shows to have only the CN-120 prescription to provide outstanding visual retention.That especially be concerned about is prescription CN-120-4, uses unique prescription of alkoxylate monomer SR-454.This prescription performance is bad, shows that once more alkoxylate is the negative factor of visual retention.CN-132 is unsuccessful usually, and the CN-983 prescription does not obtain resembling the result of CN-120 yet.CN-132 is low viscous aliphatics diacrylate ester oligomer, is the product of Sartomer Corporation.

According to this research, select prescription 61 to be used for further research, because it has provided the good combination of curing rate, film hardness and outstanding image stabilization.CN-120 and SR-368 monomer are difficult to cooperation, so liquid form CN-120-B60 (60%CN-120 in SR-238) and SR-368D (among the TMPTA approximately 85%SR-368) be substituted, to be easy to handle and subsequently manufacturing.

Table 16

The prescription that is used for Environmental Studies III

	Base Coating Fomulation No．
														49	60	58	59	61	62	63	64	65	66	67	68	69
	Fomulation Name	355/454	355/454-2	120-1	120-2	120-3	120-4	120-5	132-1	132-2	132-3	132-4	132-5														963-1
Component
	Watting Agent TEGO RAD 2200N Photoinitiator KTO/46 Dlluents SR-238 SR-285 SR-506 Main Components SR-454 SR-368 SR-355 CN-983 CN-120 CN-132	1 1 1 1 1 1 1 1 1 1 1 1 1
5 5 5 5 5 5 5 5 5 5 5 5 5
													10 24 20 34 34 34 44 24 30 30 40 40 44 14 14
35 20 30 20 30 20 35 50 30 30 35 14 50 50 30 30 30 30 50 35 50 14 34 34
													TOTAL	100	100	100	100	100	100	100	100	100	100	100	100	100
Photoacid TPST 1-butylphenyl DPST Colorformer Pargascript Red 6B	3 3 3 3 3 3 3 3 3 3 3 3
														3 3 3 3 3 3 3 3 3 3 3 3
	Fading ％	57	56	30	36	22	52	31	57	69	53	69	68														51
Vlacosity(cP)														66	96	375	315	504	177	330	197	162	112	67	116	260
	Optical Density	0.45	0.50	0.63	0.59	0.60	0.58	0.55	0.58	0.60	0.50	0.42	0.54														0.68
Film Thickness(um)														3.7	4.3	7.8	6.9	9.3	5.3	6.9	5.7	4.3	4.0			6.5

Can not remove film from 67,68

Optical density (OD) is all measured behind identical exposure interval

The last research of CN-120 prescription with begin that to reduce coating consistent to the effort of sight and fluorescence radiation susceptibility by optimizing light acid producing agent concentration and interpolation UV absorbing agent (other place also further describes the interpolation of UV absorbing agent) herein.Therefore, the 4th secondary environment research is included as light exposure test subsequently and changes several prescriptions of light acid producing agent concentration and UV concentration of absorbing.The composition aspect of these prescriptions is provided in the table 17.

In addition, use two kinds of rotational speeies (4k and 6K) inspection to change of the influence of coating 100 thickness to image stabilization.Except darker, the more thick film of expectation coating 100 can provide color retention preferably in environmental test.Do not have the prescription of UV absorbing agent by preamble preparation, be included in the nitrogen environment, utilize in about 1 inch distance that the L37 glass of color filter was cured 2 seconds under XENON " C " bulb.By shine imaging on dish 10 in about 10 seconds in about 5 inches distance.Prescription imaging with UV blocking agent amounts to about 30 seconds (15 seconds * 2 imaging time), also is from lamp about 5 " distance.Give these prescriptions the long time shutter, because their quality time is slower.

The result shows that when 2% or 3% light acid producing agent charging capacity, liquid component replaces (CN-120-B60 and SR-368D) to be influenced very little to image stabilization or quality basically.Noticing that lower light acid producing agent concentration looks provides color percent retention preferably really, but higher charging capacity always produces higher color intensity.As if the adding of UV stabilizing agent cause the substantially seldom reduction of environmental stability (5% charging capacity) to change to the medium reduction of environmental stability (10% charging capacity).But the final color of these prescriptions is not too strong.

SR-368D is three (2-hydroxyethyl) isocyanuric acid ester triacrylate, for the transparent liquid triaizine compounds, uses in free radical polymerization.CN120B60 is mixed with the difunctionality bisphenol-A basic ring oxypropylene acid esters that 40%SR-238 is a hexanediyl ester.CN120B60 provides the well balanced of aqueous nature and high response.The both is the product of Sartomer Corporation.

Table 17

The prescription that is used for the research of the 4th secondary environment

	Base Coating Fomulation No.
											70	71	72	73	74	75	76	77	78	79
	Formulation Name：	Base-2 Base-3 368D3 368D2 368D1.5 UV1 UV2 UV3 UV4 UV5
Component
	Wetting Agent TEGO RAD 2200N	1 1 1 1 1 1 1 1 1 1
Photoinitiator KTO/46												5 5 5 5 5 5 5 5 5 5
	UV Blockers UV-24 MC80	5 2.5 5 10 5 2.5 5
Dlluents SR-238												18 18 18 18 18 13 13 13 14 14
	Maln Components SR-368 SR-368D CN-120 CN120B60	10 10 10 10 10 10 10 10 10 10 66 66 66 66 66 66 66 66 60 60
TOTAL												100	100	100	100	100	100	100	100	100	100
	Photoacid TPST	2 3 3 2 1.5 2 2 2 2 2
Colorformer Pergasoript Red 6B												3 3 3 3 3 3 3 3 3 3
	Absorbance
4K												0.38	0.5	0.5	0.38	0.25	0.33	0.55	0.43	0.26	0.23
	6K	0.32	0.47	0.43	0.31	0.22	0.33	0.43	0.38	0.25	0.23
Fadlng％
	4K	19.3	25.5	25	26	16.3	22.3	27.2	24.1	30.5	38.6
6K												27	40	40	30	29	28	36	34	39	35

Under L37 Xenon " C " lamp 2 seconds, nitrogen environment was located imaging 10 seconds at 5 inches, UV blocking agent 30 seconds (15 * 2)

7. the triethylamine research of fading

Notice based on the color that exposes of the prescription of SR-9021 (prescription 3) and fade in alkaline environment the time.This is to be put back in their original packaging at the commerce dish with band coating to find first.Because the alkaline characteristic of paper and/or printing ink, the acid of opening color in the coating 100 is neutralized, thereby color is sharply faded.When being placed on the label-side of dish 10 of band coating and putting into storage box, the label of producing is also noted that another problem in ink-jet printer.Equally, image fades.Therefore, for the quantitative measurment amount of fading, the test in the alkaline environment of triethylamine (TEA) simulation is put into the dish 10 of band coating in design.But measuring disk 10 shows the amount of fading then.

5 dishes 10 with coating base-material of comprising SR-9021 are by spin coating, solidify and utilize L37 optical filter and nitrogen exposure 10 seconds.Gather the absorption curve of each dish 10.To coil 10 then is put into filter paper 181 and is placed in the storage box 180 at angular aperture and center, as shown in figure 26.

Figure 26 has described the typical storage box 180 of optical medium, wherein the position of gray area representative placement filter paper 181.100 μ l triethylamines are sunk on each cross section of filter paper 181.Airtight then each box 180, and being put in the dark drawer 2 hours, the fade amount of acquisition time absorption curve then to determine to have taken place.

The result shows that the on average amount of fading in the test recipe is 36.0%.Because this is considered to be less than and is wanted, check that therefore other prescription is determining whether obtaining better result.Test recipe based on 9020,355/454,5%4TB, 5%KTO, 368 and 983, the results are shown in Figure 27.Notice that all prescriptions also exist 3% triphenyl sulfonium fluoroform sulphonate, 5%4TB to have 5% (4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate except 5%4TB.Figure 27 shows, some prescriptions more anti-fading in alkaline environment, and they usually and environmental performance reach unanimity.

8. acceleration phototesting

Notice that the background color with the dish 10 that comprises 9020 coating 100 slightly reddens along with time lapse when the fluorescence indoor lamp exists.Therefore, design another group test to estimate the influence of ambient lighting to image in the coating 100.

At first, make the test stand of forming by four feet long pair bulb fluorescence lamp bracket.The lamp that uses is 37 watts of the Philips ECON-O-WATT F40-CW of Philips Lighting Co.of NJ.The amount that produces in the UV-A wave band is about 250mw/m ², use commercially available device measuring.

Have the greatest impact in order to check which kind of optical wavelength forms background color, use one group of dish 10 of prescription 10 preparations based on SR-9020.To coil 10 curing and keep unexposed in the imaging wavelength.To coil 10 then and be fixed under the fluorescence lamp bracket, each dish part of 10 is by 2 " * 2 " glass of color filter covers, and causes maximum color to form to determine which kind of optical wavelength.To coil 10 exposures then not cover the about 0.2AU of zone colour developing.As if as shown in figure 28, the most disruptive wavelength is lower than about 370nm, the wavelength that is lower than about 320nm is the most problematic.As if this show that the UVB of spectrum partly is the most useful wave band of UV protection.Figure 28 has described the illumination result, and wherein UV-30, L-37, L-38, L-39, L-40 and L-42 represent the model name of the commercially available UV optical filter of Tokyo HOYACorporation.

Usually, name WD 50% transmission point of cutoff filter.For example, the UV-30 optical filter, its grade is for the 300nm wavelength, has 50% transmission point at the 300nm place.Recognize that 50% transmission point is similar to, and can slightly move that therefore a thin slice L-37 optical filter may look and be very similar to a sheet UV-36 etc. with thickness.Therefore, although herein usually during the thick L-37 of advantageous applications 1mm, (having about 50% transmission point at the 370nm place), thicker UV-36 optical filter also can be worked well, and the UV-34 optical filter except that some other optical filters.UV-32 is considered at about lower limit place, and more than UV-39, solidifies slack-off.Therefore, preferred cutoff filter provides 50% transmission point between about 320nm and about 380nm, most preferably between about 340nm and about 370nm.

Whether in the trial that forms by the bias light constant color, it is slack-off or stop observing when sample is subjected to the environmental chamber intraoral illumination color formation to add light absorbing material in the prescription sample.For the prescription of research, the light absorbing material of selecting to be used to test is the UV absorbing agent.The UV absorbing agent that uses is TINUVIN 327, TINUVIN 171, TINUVIN 213 and TINUVIN571.TINUVIN 327 is 2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) phenol; TINUVIN 171 is (2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methyl-phenol); TINUVIN 213 is the potpourri of 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) methyl propionate/PEG 300 reaction product; With TINUVIN 571 be side chain and straight chain 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol.The TINUVIN product is produced by CibaSpecialty Chemicals.

Each TINUVIN sample all is a liquid form, except being the TINUVIN 327 of powder.Test by in prescription 10, adding every kind of UV absorbing agent of 1%, except a sample carries out with 5% TINUVIN 171.But,, therefore carry out another step and still can produce enough colors when the imaging to guarantee each sample because the point of UV absorbing agent has slowed down color formation.Figure 29 shows that sample has produced sufficient color.In fact, the sample that combines the UV absorbing agent produces more color than the sample that does not have the UV absorbing agent (representing with MC9020 among Figure 29).Comprise color in the sample of 5%TINUVIN 171 and form and be not identified, but carry out quick check after 10 seconds, and the absorptivity that is presented at the 540nm place is 0.40OD in exposure.

Coil 10 with three curing (background color) of every kind of prescription of fluorescent light test stand irradiation then.Before light on, in the whole test, normally every day collected specimens absorption curve form with the monitoring background color.That simplifies the results are shown in Figure 30, and it has described the influence of the adding UV absorbing agent of measuring in quickening fluorescent light research.

Figure 30 shows that the TINUVIN of some types is better than some other work, but the comparing difference minimum during 1% concentration.The sample that comprises 5% concentration TINUVIN 171 forms and shows preferable performance reducing color, but difference to be considered to be medium influence.The write time that the concentration of use 5% also causes producing the image needs significantly increases.Attempt the prescription that preparation comprises 10%TINUVIN 171, still, material becomes flower (be not exposed to image light and just show color formation) after curing.The sample that comprises the TINUVIN 171 of 5% concentration shows same effect after the long period.Therefore, TINUVIN 171 is excluded to not being the good candidates for high as the UV absorbing agent probably.

The result of combining environmental test, become optimization formula a kind of based on the prescription of CN-120 and SR-368 in test UV absorbing agent.A series of three kinds of UV absorbing agents use with 5% charging capacity, and are shown in table 18.Be coated with prescription 80-82 by under 6K rpm speed, being spin-coated as dish 10, in nitrogen environment, solidified 2 seconds from the about l inch of lamp.Dish 10 is by L37 optical filter exposure 10 seconds, also is be about 1 inch away from lamp.With these the dish 10 with do not have stable base-material 9020 recipe ratios.

Table 18

The test of UV absorbing agent is with filling a prescription

	Formulation No./Name
				80	81	82
	COMPONENT	MC80	UV-24				UV-531
TEGO RAD
	2200N KTO/46 SR-238 SR-368 CN-120	1 1 1 5 5 5 44 44 44 10 10 10 40 40 40
TOTAL					100	100	100
	MC80 UV24 UV-531	5 5 5
TPST					2	2	2
	Perg I-6B	3	3	3

UV-24 is the abbreviation of CYASORB UV-24, is 2,2 '-dihydroxy-4-methoxy benzophenone.UV-531 is the abbreviation of CYASORB UV-531 FLAKE, is Octabenzone.Both are Cytec Corporation of Stamford, the product of CT.MC80 is the abbreviation of UVINUL MC80, is octyl methoxycinnamate, is the product of BASFCorporation of Japan.

Compare with unstabilized prescription, the formula table that UV is stable reveals slower color formation time, and the more weak final color that is equal to UV dosage.The results are depicted among Figure 31.But long color formation time (or higher flowing) was considered to outside the cycling time of manufacturing specification request.In addition, the high flow capacity rate that writing these coatings needs causes some undesirable physical deformation (as shrinking and crooked), and the difference of coating performance between exposure and the unexposed area.For example, the color formation time of prescription 81 is shown in Figure 32.Even from the about 1 inch place of XENON lamp, the time shutter that still needs to surpass 10 seconds forms greater than the color of 0.5AU obtaining.

9. the light acid producing agent reexamines

In coating 100, cause the long write time owing to directly add the UV absorbing agent, and light stability has only minimum increase, therefore various smooth acid producing agents and their concentration is reexamined.Notice that higher light acid producing agent concentration often produces the write time faster for fixing colour coupler concentration.Think may be able to control the light acid producing agent with in the generation that can accept to provide in cycling time the required color level.But, (comprise economical) for various reasons, wish to use the light acid producing agent of minimum.One in the beginning step is to optimize color to form ratio and coating 100 thickness of light acid producing agent with colour coupler.Result of study is shown in Figure 33, and shows colour coupler: TPST is the ratio that 3: 2 ratio was better than 1: 1.

Result of study (being shown in Figure 34) shows that the thickness of coating 100 is working aspect color formation and the lightsensitivity.Under study for action, be coated onto on the dish 10 by the sample of will filling a prescription in spin coating under 4K rpm and the 6K rpm.This generation has the coating 100 of different-thickness.In nitrogen environment, coiled 10 two seconds from the about 1 inch curing of lamp.Make 10 seconds kinds of exposure area imaging, also from the about 1 inch place of XENON lamp.Utilization spin coating under 4K rpm produces the control sample based on the prescription that comprises SR-9020.At the control sample 10 seconds (fading) that exposes from 5 inches distances of lamp because definite higher energy conductance causes in the prescription that comprises SR-9020.

The result shows that color forms and occurs on the whole thickness of coating 100, rather than seriously is partial to coupler surface.Therefore, think that needs are optimized viscosity and rotational speed thinks that required optical density (OD) provides minimum film thickness.This research provides indirect benefit, is exactly the colour coupler that also confirms for 3%, and 2% produces identical final color with the light acid producing agent of 3% concentration, but formation speed difference.

10. the absorption spectrum of light acid producing agent and film

In this, think and use fully stablize triphenyl sulfonium fluoroform sulphonate (TPST) based formulas possibility being impracticable owing to be difficult to obtain of UV absorbing agent.As if the UV absorbing agent absorbs the identical wavelength that is used for imaging simply, and non preference ground absorbs the UVA-UVB from daylight to the fluorescent illumination.Therefore, check the absorption spectrum of light acid producing agent and coating formula so that dwindle the critical wavelength region may of possibility in these processes.

TPST is considered to simple and the shortest available UV and absorbs sulfonium base light acid producing agent.Diphenyl iodonium hexafluorophosphate (DPI HXFP) also is considered to simply short UV absorbing light acid producing agent.The absorption spectrum of two kinds of light acid producing agents of shown in Figure 13 this has maximal value at about 200nm place, UV in the middle of afterbody enters.

The spectrum of CN-120 based formulas is shown in Figure 35.Do not resemble the early stage complete aliphatic prescription that is, these prescriptions promptly have sizable UV from the about 300nm of about 250nm-at middle UV and absorb.Obviously, the high absorption region of the major part of the sensitive wave length scope of light acid producing agent and acrylate matrix is total.Therefore, think the wavelength that the degree of depth quality that sees through coating 100 is played a major role be not probably the short wavelength (＜250nm), but middle to the long wavelength, this moment, the matrix optical density (OD) was low.

Because it is invalid that the short wavelength forms image in the stable prescription of UV, the ability that therefore produces short wavelength UV in the laboratory is as than seeming impracticable to the prescription of test with bigger speed imaging advantage with daylight or fluorescence.Therefore, for these prescriptions, the higher intensity of preferred use provides imaging faster.The adding of deducibility UV absorbing agent slow down imaging to form the identical degree of background color by fluorescence or daylight.Therefore, think that then can carry out imaging in 3 seconds, this will be equivalent to colorific daylight in 30000 seconds or about 8 hours if can to produce be the UV amount of 10000 times of environment daylight.Suppose that unacceptable background color level can be low to moderate 5% of maximum color, the effective daylight exposure that then forms unacceptable background color level may only be had an appointment 30 minutes.Therefore, though think use 10000 times to or greater than the amount (from the material settling out viewpoint, being unacceptable high dose) of environment daylight, then light stability will only extend to about 5 hours.

When observing the UV absorption spectrum of matrix and UV absorbing agent, as shown in figure 36, overcoming one of the light stability problem may approach not be the light acid producing agent of seeking the shortest absorption, but may seek the light acid producing agent of maximum absorption wavelength near middle UV, this moment, coating 100 showed transmission behavior to a certain degree.Wish that this can provide the UV blocking-up protection to UV-A and UV-B zone, and by effectively utilizing the UV-C radiation to guarantee certain imaging speed.Under this idea, screened a series of smooth acid producing agent with longer UV transition.As used herein, think UV-A wavelength usually at about 320nm between about 400nm; The UV-B wavelength usually at about 270nm between about 320nm, the UV-C wavelength is usually below about 270nm.These wave band wavelength and other wave band wavelength also can be described as " set of wavelengths ".

11. be imaging speed screening light acid producing agent

The prescription of 10%UV-24 as the UV absorbing agent used in preparation.The concentration of adjusting every kind of light acid producing agent is equivalent to the 2.5%TPST in mole.Figure 37 has shown that the color of every kind of prescription of preparation forms curve.Sample shown in Figure 37 is in the distance exposure from 1 inch on XENON lamp.Part light acid producing agent show than TPST faster color form (writing) time, the most significant is the 4-derivatives containing phenoxy group.

Although these different light acid producing agents provide different writing speed and color densities, prior performance parameter is considered to whether the light acid producing agent can provide raising when the susceptibility to fluorescence and daylight exposure does not increase writing speed or color density.In order to check this, prepare the dish 10 of every kind of light acid producing agent prescription and about 65 hours of exposure under the fluorescence lamp bracket.Figure 38 shows, although every kind of light acid producing agent provides different writing speeds and final color, and the remarkable TPST that surpasses aspect the ratio of neither one between color formation time and fluorescent stability subsequently.In fact, as if data support that the write time with the XENON lamp is the direct prediction of light stability subsequently.Therefore, obviously the most of light that is used for imaging from the XENON lamp is not short UV (wavelength is below about 250nm), but the UVB of spectrum (the about 320nm of about 270nm-) part.This conclusion also obtains the support that XENON " D " bulb does not improve the observation of write time, as shown in figure 39.Although " D " bulb produces than the more UV-C radiation of " C " bulb, not observing the color formation time increases.

The UV-24 of higher concentration and the use of UV-24 and another absorbing agent MC80 associating have been checked.Result shown in Figure 40 shows that the UV absorbing agent of higher concentration has reduced susceptibility, and independent UV-24 is better than the associating with MC80 under the identical weight charging capacity.

Carried out another test to measure the color formation time of 10%UV-24 prescription.Measuring the UV-B power level from the different distance of lampshade by the plastics mask.Also have, at about 1 inch minimum distance place, use quartz mask to improve UV-B power, main short end place at spectrum.Result shown in Figure 41 shows that for the 10%UV absorbent formula, the XENON lamp can not form sufficient rate of discharge to produce acceptable optical density (OD) near 3 seconds required cycling time.In fact, most of coating 100 samples obviously break or are crooked.In addition, notice that removing the plastics mask causes about UV-B more than 40%, but writing speed has only a small amount of increase, supported coating once more in the short UV (＜300nm) theory of optics densification down.

12. color enhancement additive

Tested several adjuvants and attempted to reduce the write time of the coating that is loaded with the UV absorbing agent, and a fluorescence and a day lightsensitivity can not increase pro rata.First kind of trial comprises and reexamines the color enhancement additive so that acid produces more effectively.These effort focus on uses acid to make " priming paint " of color formation with coating.The matrix of using is for filling a prescription 10, and it comprises the alkoxylate monomer.As shown in figure 42, the concentration of used acid and composition all do not have sharply to influence the final color of writing speed or coating.Use 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid to carry out other test, it is a crosslinkable sulfonic acid.But even when 1% charging capacity, this acid is strong too and need not under any UV exposure status coating become redness.Therefore, mix that to help color to form seemingly impossible for the acid of various intensity or concentration.

Estimate the other method that reduces photosensitivity, used buffer system this moment.When using buffer system, think that the UV of low dosage will produce a small amount of additional acid that can be cushioned the liquid absorption.In this case, because trifluoromethanesulfonic acid is extremely strong acid, almost any alkali can both be removed the acid that (neutralization) produces.Acrylated amine is used in initial test, as the CN-384 of Sartomer Corporation.These amine are proved to be too strong alkali, and color forms and suppressed fully.In test subsequently, when using a small amount of CN-384, it is shallow that background color is held, but image stabilization is no good, and color under environmental baseline 24 hours or shorter in fade.Therefore, check the use of weak base.The example of weak base comprises acetate and sodium salt.Unfortunately, these compounds dissolubility in acrylate is not fine, can only obtain 0.1% charging capacity.But, even under this low charging capacity, also observed influence.Salt is really as damping fluid, but it has also reduced the speed of color formation and the integral color of coating.Use the aspect of damping fluid to be described among Figure 43.

13. spin coating, film thickness and optical density (OD)

The purpose of this test is related rotational speed (rpm), optical density (OD) (absorptivity at the 540nm place) and film (coating 100) thickness (micron) of applying.On the spin coater that is called Headway SpinCoater, apply clear polycarbonate dish 10.Use prescription 3, it has the viscosity of about 60cps.Coating and rotating disc are 100 seconds under 4000-10000rpm (1.0K) increment.In nitrogen environment, used XENON flashlight and L-37UV optical filter curing dish 2 seconds.Half that each is coiled 10 exposed 10 seconds under lamp then.Curing and exposure side to each dish are carried out UV scanning, and MEASUREMENTS OF THIN thickness.

Measurement result shows, film thickness from distribute the district come out to plate edge by thin change to thicker.For various rotational speeies, the optical density (OD) of dish 10 is also directly proportional with thickness.Obviously, when top speed (greater than about 8K rpm), film thickness there are minimum influence, according to expectation.The results are shown in Figure 44.In Figure 44, shown to separate the film thickness of joining selected distance place, district.The optical density (OD) of various spin speed and film thickness estimate to be shown in Figure 45.

Apply prescription 58 (375cps) and 61 (504cps) with cumulative rotational speed 5-10K.Carry out optical density (OD) and film thickness and measure, the results are shown in Figure 46.According to expectation, sticking prescription produces thicker film.Interesting in addition is these two kinds sticking prescriptions produce film thicknesses to rotational speed than linear response.In finished product, the method for control color can comprise the control time shutter or change prescription, still, thinks to be generally this few of attractive force preferably and change film thickness.That is to say that the change film thickness has the final user of permission and distributes minimum given color density material requested, thereby the cost of reduction is provided and reduces photosensitivity.

Carry out the further optimization of light acid producing agent concentration, and be shown in Figure 47.Figure 47 has shown the relation between constant film thickness time acid producing agent (TPST) and colour coupler (PERGASCRIPT I-6B) concentration and the optical density (OD).In nitrogen environment, about 1 inch away from lamp locating to solidify on 2 seconds the dish 10 and measuring optical density (OD) be.Then in the time of 1 inch away from lamp locating to expose these samples indications be.

B. overbrushing layer research

Obviously, the balance accepted between cycling time, UV flow and the photosensitivity subsequently can not reach in single coating formula.Think that replacement scheme can use two coatings, one is designed to provide quick color to form and image stabilization, and second external coating provides required UV stability.Second external coating can provide more beneficial effect, as the environmental stability to humidity and alkali of resistance to marring and increase.

1. coloured coating and external coating research

The first step of research quality coating 100 is to estimate to become the performance of distributing between chromatograph 101 and the external coating 102 to simplify prescription to provide.For becoming chromatograph 101, need be to the cohesive of polycarbonate, good color formation, light acid producing agent and colour coupler dissolubility.For external coating 102, need be cured to well hard anti scuffing surface, the high optical density (OD) among the UV with to the following cohesive that becomes chromatograph 101.Two layers 101,102 can both not have nitrogen ground to solidify fast ideally, and low contraction and acting in conjunction improve the environmental stability (promptly heat, humidity or additional chemicals being introduced the resistibility that influences) of image.

Consider existing research, the CN-120 based formulas produces best environment result, but to show higher quality wavelength optical more intensive as filling a prescription 1 and 9 than all aliphatics prescriptions.But, add the stability that external coating 102 improves in heat/humid test owing to can utilize, so check that once more non-CN-120 prescription, target are to reduce wetting time and reduce contraction.

Initial trial shows, removes to write agent to making second coating 102 wetting and to be adhered to into chromatograph 101 be essential from become chromatograph 101.Screened the prescription of core series.These prescriptions are provided in the table 19.

Table 19

The initial coloured coating prescription of two layer system

	Color Forming Layer			Overcoat
						C1	C2	C3	O1	O2
	Wetting Agent TEGO RAO 2200N	0 0 0 2 2
Photoinitiator KTO/48							5 5 5 5 5
	Diluents SR-238	10 35 35 20 30
Maln Components SR-9021 SR-368D CN-120B60							30 20 30 30 73 30 65 30 33
	TOTAL	100	100	100	100	100
UV-24										10	10
	TPST	2.5	2.5	2.5
Pergascript Red 6B							3.5	3.5	3.5

Prescription C1 and C2 comprise the CN-120 content of minimizing and the SR-368 content of increase, are used for improving the transparency of UV and reduce bonding contraction.Prescription C3 comprise SR-9021 and SR-368 shrink to provide low, high bonding, solidify and UV transmission coating fast.Prescription O1 and O2 comprise SR-238 and SR-368 makes up so that good bonding and curing to be provided, and the CN-120 among the prescription O2 is used for extra hardness and UV impermeability.In prescription O1 and O2, use the UV absorbing agent UV-24 of 10% charging capacity.As previously mentioned, Direct observation is that light acid producing agent minimally is dissolved among the alkoxylate monomer SR-9021.(obviously, the prescription of using " C " to name is indicated into the prescription of chromatograph 101, and the prescription of " O " name indication external coating 102.)

Become chromatograph 101 to substrate 17 by what have prescription C1, C2 and a C3 with 4K rpm spin coating, and in nitrogen environment, prepared sample disc 10 by L37 UV optical filter in 3 seconds with the curing of " D " bulb in about 1 inch distance.Carrying out imaging 10 seconds by quartz mask from the about 5 inches distances of lamp.Apply external coating 102 (prescription O1 and O2) on the chromatograph 101 by being spin-coated on into 2.5K rpm.In nitrogen environment, about 1 inch away from lamp locating to use L37 UV optical filter to use " D " bulb curable overcoat 102 3 seconds be.Become chromatograph 101 wetting good by what prescription C2 and C3 made, and prescription C1 performance is not fine with spin coating.Two prescription O1 of external coating 102 all become chromatograph 101 good with wetting good also coating of O2.All finished disk 10 nibs of anti-plastics scratches.

Use the SCOTCH band to utilize the band tension test of 2.5mm spaced blade as the light adhesive strip.(PERMACEL#99 is not adhered on the coating of use well enough).One-tenth chromatograph 101 failures that the C1 that fills a prescription forms, and the chromatograph 101 that becomes that prescription C2 and C3 form passes through test.Two external coatings 102 (O1 and O2) all are adhered on the chromatograph 101 without any problem.When external coating 102 be bonded with problem the time, notice at substrate layer 17 and become the appearance at the interface of chromatograph 101 to damage (according to expectation).

From these initial trial, design candidate's two layers of coatings 100.These prescriptions are provided in the table 20.Be modified into chromatograph 101 with the concentration that reduces CN-120 with enhance the transparency and cohesive.The light acid producing agent is increased to 3: 4.5 to the ratio of colour coupler, to improve writing speed and color intensity.External coating 102 is the prescription of SR-368 and SR-238.

Table 20

Two initial coat systems

Component	Formula number
				C4	O1
Wetting agent
			TEGO RAD 2200N
	0	2
			Light trigger
KTO/46	5	5
			Thinning agent
SR-238	20	20
			Key component
SR-368D	40	73
			CN-120B60	35
Amount to	100	100
			UV-24		10
TPST	4
			Pergascript Red 6B	3.5

2. initial trial

Test the test of two layers of coatings 100.Under 3K and 4K rpm, apply into chromatograph 101, as shown in figure 48 by being spin-coated as dish 10.From lamp about 5 " locate to make the different time of dish 10 imaging to check color intensity.Apply external coating 102 by being coated with then at 3K rpm backspin.In this research, also checked the use of nitrogen and optical filter.Do not need nitrogen to be solidified into chromatograph 101, to consider to apply external coating 102 to acceptable level.Think that aforesaid use nitrogen is solidified into chromatograph 101 and can has the added benefit that forms seamless adhesion between color layers 101 and external coating 102.About 1 inch away from lamp locating curable overcoat 102 totally 1.5 seconds, do not have nitrogen and do not use optical filter then, thereby provide the full spectrum of light irradiation to strengthen surface cure be.Below one-tenth chromatograph 101 do not look not since top coat 102 be solidified to form any can observable color.

3: 4.5 light acid producing agent and colour coupler ratio are proved height, and cause very strong color.On XENON " D " bulb, locate to obtain in the short time about 0.8 optical density (OD) for 5.25 inches.

More importantly, use the qualitative light exposure test (63 hours) of fluorescence frame to show that the external coating performance in the phototesting is far superior to single coating schemes.Also pay close attention to be beginning the time look that the image of too dark (crossing high-contrast) is now because part background color reduction contrast seems turns better.

More importantly, the UV resistant strata with become chromatograph 101 separately make shorter UV wavelength (＜320nm) can be effective to color form.This makes into chromatograph 101 and uses these wavelength effectively to expose, and is not subjected to these wavelength and the wavelength affects of typical case's illumination as existing in daylight and the fluorescent illumination thereby shielded layer 101.

But, notice that this combination of using layer 101,102 needs further research bond property.Become chromatograph 101 can not be adhered on the polycarbonate following in the following substrate layer 17, make band tension test failure with the light adhesive strip.Adhesion failure only polycarbonate substrate 17 with become running at the interface of chromatograph 101, thereby can not estimate into the bonding of 101 pairs of external coatings 102 of chromatograph.

3. environmental test

In this, the knowledge that obtains from basic two coating tests is concentrated, and the basis of another series prescription of research is provided.Check the quantitative environmental test of these prescriptions, and in table 21, list.

Prescription C5 is the SR-9021 based formulas 3 (table 14) of front, and it has excellent performance but fails in environmental test.Think that external coating 102 may improve the environmental stability of the one-tenth chromatograph 101 that uses prescription C3, and the enough CN-120 of protection to avoid using high contraction, UV to absorb are provided.Prescription C6 is the improvement to prescription C5, wherein uses SR-368 to replace SR-494.This in theory replacement will reduce extent of alkoxylation and cause film 101 or one-tenth chromatograph 101 harder but still low contraction.Prescription C7 is the improvement prescription that comprises CN-120, SR-368, SR-238 that bonding requirement is satisfied in design.Think that the one-tenth chromatograph 101 that comprises the C7 that fills a prescription should easily pass through environmental test, though with the write time be punctured into cost.Expectation prescription O3 can produce external coating hard, that UV absorbs, and it is because CN-120 has the contraction problem.Prescription O4 mainly is made of SR-368, uses SR-399 as strengthening the thinning agent that UV absorbs.Prescription O5 is the SR-9021 based overcoat, for hardness adds CN-120.Component design O5 wishes that SR-9021 can control contraction and not sacrifice hardness and anti-zoned property.Use 10% and 20% UV-24 preparation external coating 102.20% charging capacity appreciable impact viscosity.

Table 21

The prescription of basic two coating tests

Component	Formulation No.
							C5	C6	C7	O3	O4	O5
	Wetting Agent TEGO RAD 2200N	0 0 0 1 1 1
Photoinitiator KTO/46								5 5 5 5 5 5
	Diluents SR-238 SR-339	25 20 35 14 34 10
Maln Components SR-9021 SR-494 SR-368D CN-120B60 CN-132								35 35 50 35 40 30 10 84 30 50 30
	TOTAL	100	100	100	100	100	100
UV-24											10-20	10-20	10-20
	TPST	2	2	2
Pergascript Red 6B								3	3	3
	Viscosity	61	83	68	134	200	162
20％UV 24								102	404	236

Aspect the dissolubility of light acid producing agent and colour coupler, not heating and when ultrasonic comprises the prescription C5 of alkoxylate SR-9021 and the problem that C7 has dissolved solid.C5 and C7 need to filter.The UV-24 that prescription O4 and O5 dissolve 20% concentration has any problem, and prescription O4 and O5 also are filtered.

By applying the coloured coating prescription with 4K rpm spin coating, then in surrounding air under lamp about 1 inch locate to use the L37 optical filter to solidify 2 seconds.Notice that dish 10 solidifies " pink " with different amounts.The very slight color of pink from the no color of C5 to C6 is to the slight color of C7.Suppose the optical density (OD) of this most probable tracking coating, because C7 has the highest aromatic content, C6 comprises the SR-368 of absorption portion UV, and C5 is the coating that can see through UV.

From lamp about 4 " locate to carry out imaging 10 seconds by chromium-quartz mask with " D " bulb.Apply top coat 102 by being coated with, and about 1 inch away from lamp locating to use " D " bulb of full spectrum to solidify be at 4K rpm backspin.Solidify and continue 1.5 seconds (for the 10%UVA group) or 2.0 seconds (for the 20%UVA group).

Under about 70 ℃ and 90% relative humidity, carried out environmental test 78 hours.Comprise the external coating 102 part or all of delaminations of 20%UV absorbing agent.Mechanism is the contraction or the swelling of external coating 102 seemingly, and it causes coloured coating 101 to break away from from coiling 10 substrate layer 17 then.The composition that second observation is color layer 101 is the main driving factors of decision image stabilization.Filling a prescription, C7 is better than form A 6 and C5 is a lot.As previously mentioned, coating C5 falls flat, and is irrelevant with the coating 102 that uses.Coating C6 is better than C5, but still can not be near C7, and same and outer covering layer 102 has nothing to do.Prescription C7 is better than other coating 101, even without external coating 102.The result is described among Figure 49.

For the external coating 102 of 10% charging capacity applies, as if it is stable that each sample keeps aspect cohesive and hardness.In addition, the sample of undercoat is arranged, notice the trend of following image stabilization about 1c.That is to say that prescription O3 does very well than O4, O4 is more much better than the O5 performance, and the O5 ratio does not have external coating 102 to do very well.This is harmonious with glass transition temperature and the hydrophobicity that alkoxylate lacks with potential coating 100 once more.

Visual examination determines that whole samples are existing very good in fluorescence lamp bracket following table.Be exposed to fluorescence after one week, forming the part background color, be exposed to fluorescent light after several weeks, image still can distinguish, but owing to background color intensity fails.The sample of 20% charging capacity forms and does very well at the restriction background color, is considered to because above-mentioned environmental problem and purposes is limited.Have that the CN-120 based formulas O3 of high aromatic content obtains the highest optical density (OD) in coating 100, and best light fastness also is provided.The absorption spectrum of external coating prescription O3, O4, O5 is shown in Figure 50.

4. to the adjustment of two coating formulas

Also tested the serial acrylated polyurethane of Sartomer Corporation, so that check their applicabilities in coating 100.This series is shown in table 22.The coating deliquescing that all use the acrylated polyurethane is easy to damage final coat, thereby seems that they can not do very well.Further do not test.

Table 22

The evaluation of acrylated polyurethane in the external coating

Component	Formulation No.
					O6	O7	O8	O9
	Wetting Agent TEGO RAD 2200N	0 0 0 1
Photoinitiator KTO/46						5 5 5 5
	Diluents SR-238 SR-339	20 20 20 20
Maln Components CN963B80 CN965 CN968B85 CN981B88 SR368D						50 50 50 75 25 25 20
	TOTAL	100	100	100	96
UV-24									10
	TPST	2	2	2
Pergascript Red 6B						3	3	3

CN965 is an aliphatic polyester based polyurethanes diacrylate ester oligomer.It is for providing the elasticity oligomer of good weather resisteant.CN966885 is mixed with the aliphatic polyester based polyurethanes diacrylate ester oligomer that 15%SR238 is a hexanediyl ester.CN981888 is mixed with the aliphatic polyester that 12%SR238 is the hexanediyl ester monomer/polyether based polyurethanes diacrylate ester oligomer.These three kinds all is the product of Sartomer Corporation.

Because as if the CN-120 prescription can not be replaced by any other monomer class, therefore more test to adjust other component and to improve performance.Prescription and each explanation note of adjusting the back reason are provided in the table 23.

Table 23

Adjustment to the CN-120 prescription

	Formulation No.
										Component	C8	C9	C10	C11	C12	O10	O11	O12	O13
Wettina Agent TEGO RAD 2200N	1 1 1 1
										Photoinitiator KTO/46 CN-384	5 5 5 5 5 7.5 7.5 7.5 8 10
Dlluents SR-606 SR-238 SR-339	15 35 35 20 35 35 30 39 30 26
										Main Components SR-368D CN-120B60 CN-120M50 SB520M35	30 30 30 30 30 10 10 18 20 30 30 30 30 30 41.5 22.5 25 20 43.5 20
TOTAL	100	100	100	100	100	100	100	100	100
										PIGMENTS
UV-24						10	10	10	10
										TPST	2	2	2	2	2
Pergascrlpt Red 6B	3	3	3	3	3
										Viscoslty	93.19	93.54				128	88	217	187
Adheslon	Terrible	Terrible	moderate	Terrible	Terrible	GOOD	GOOD	GOOO	GOOD
										Cure/hardness	good	good				good	soft	soft	good

Synergistic agent causes color heavy losses in the environmental test, may be because acid migration and quenching

The indicative explaination of his-and-hers watches 23:

C8	Reduce SR-238 content with SR-339, reduce and shrink, the write time may rise
		C9	Replace SR-238 with SR-339, reduce and shrink, the write time increases
C10	Reduce SR-238 with SR-339, reduce and shrink, the write time may rise
		C11	Reduce SR-238 with SR-506, reduce and shrink, writing speed does not increase
C12	Replace SR-238 with SR-506, reduce and shrink, improve Tg, keep writing speed
		O10	Remove SR-238, improve optical density (OD) and reduce contraction, also use cure boosters
O11	Add the acid functionality, improve anti-printing ink, do not have synergistic agent
		O12	Complete sour top coat, the low contraction, hard, UV absorbs
O13	The hard form of O11

This research causes recognizing that the moderate reduction of SR-238 concentration causes the adhesion loss to polycarbonate in the coloured coating.But external coating 102 can be based on SR-339 as thinning agent, and this will provide excellent UV absorptive character, reduces and shrinks and the reduction skin irritatin.As few environmental test result to 24 hours, this research also provides such observation, promptly comprises the loss fully that the amine synergistic agent still causes image in top coat 102.This is considered to unfortunate, and synergistic agent can produce under the 7.5%KTO-46 charging capacity fast and curing completely because add in top coat 102.

SR-339 is that the 2-phenoxyethyl acrylate is low volatilization simple function aromatic monomer, and it can provide good bond property.CN120M50 is mixed with the difunctionality bisphenol-A basic ring oxypropylene acid esters that 50%SR-339 is a phenoxyethyl acrylate.CN120M50 provides the well balanced of aqueous nature and high response.SB520M35 be appropriate official can the SR-339 that is blended in contain the carboxylic acid acrylates oligomer in the phenoxyethyl acrylate monomer.SB520M35 provides curing rate fast, to excellent bonding and the good wetting and flow performance of metal and plastics.SB520M35 also comprises carboxylic acid functional, and this causes the anti-amine fadedness that improves.These three kinds of products that acrylate is Sartomer Corporation.

After carrying out various screening studies, on preferred coloured coating prescription, utilize two kinds of preferred external coating prescriptions to finish test.Selecting selected external coating prescription, is because there is not test to comprise acidic oligomer such as SB-520 in Environmental Studies, also confirms the purposes of acid in oil resistant China ink fadedness is provided.End formulation is shown in table 24.

Table 24

The end formulation of two coat systems

Component	Formulstion No.
					C13	C14	O14	O13
	Wetting Agent TEGO RAD 2200N	1 1
Photoinitiator KTO/46 CN-384						5 5 8 8
	Diluents SR-506 SR-238 SR-339	35 35 26 26
Main Components SR-368D CN-120B60 CN-120M60 SB520M35						30 30 20 20 30 30 45 25 20
	TOTAL	100	100	100	100
PIGMENTS
	UV-24			10	10
TPST						2	2.5
	PergascrlptRed 6B	3	4
Viscosity						68			187

The light acid producing agent and the colour coupler of two kinds of concentration have been studied, because also there be not accurately to determine final light acid producing agent and colour coupler ratio so far.For these two kinds of coatings, all use two kinds of rotational speeies, be 3K and 4K rpm.By L37 optical filter cured base coating 3 seconds, there is not nitrogen.From Xenon " D " bulb about 4 " locate to expose 10 seconds.Solidify top coat 3 seconds, and do not have optical filter or nitrogen.

The remaining susceptibility of coating 100 is shown in Figure 51.Sample is divided into two according to light acid producing agent concentration and organizes greatly.Notice that in both cases as if external coating (O13) provide better UV protection than external coating (O14).As if as if prescription C13 have minimum remaining susceptibility and the best unexposed area optical density ratio to the exposure area be provided.But, be further noted that the possibility of result of this ratio comprises some deviation.This deviation may be due to unexposed C14 and fills a prescription the sufficiently long time with more abundant apparent final color, and thereby effectively reduced the colour developing of C14 prescription.Also have, can reckon with, the coating 101 with maximum amount light acid producing agent and colour coupler has kept a large amount of their colors when prolonging exposure.This influence is shown in Figure 52.

Environmental test under 70 ℃ and 90% relative humidity shows that acid can be moved to undercoat from top coat.The result is provided among Figure 53.At the prescription (external coating O14) that does not comprise acid with comprise and see in the sour coating (external coating O13) that the clear of background color level cut apart.Therefore, in prescription, comprise SB-520 or equivalent before, will have to determine the purposes of acid in amine/printing ink test.If desired, can be used alternatingly/optimization study, form this top coat 102, ink resistance still is provided simultaneously to minimize colour developing.

At last, the color level that environment exposure back keeps is controlled by light acid producing agent and colour coupler concentration basically, rather than the composition that uses in the thickness of film 101 or the external coating 102.The result is provided among Figure 54.The result shows, in order to obtain required color density and to write cycling time and optimize light acid producing agent and colour coupler ratio and concentration and will influence photostability and environmental stability greatly.

5. amine test

Use new prescription to repeat amine test.At first, as if the new prescription that is applied to chromatograph 101 does not have external coating 102 just can support that amine test does not have any fading.But the DVD10 that is marked with first picture pattern shows obviously fading to a certain degree after comprising a DVD Storage Box 180 medium-term and long-term storages of insert material.The Storage Box 180 that uses be actually from the retailer buy a kind of, and think the commercially available DVD Storage Box 180 of representative.This provides some enlightenment, and the test of perhaps before having carried out based on triethylamine (TEA) is inadequate to the prescription that designs.Therefore, use relatively large TEA in the standard plastic DVD case 180 that is similar to a DVD Storage Box 180, to carry out new test.Use large stretch of filter paper 181 to replace insert, 1ml TEA is distributed in around the filter paper 181.This test fails to cause that any of picture pattern faded in the coating 101.So thinking perhaps needs more to have volatility and mobile alkali, as ammoniacal liquor.

First trial of this test is included in that the dense ammonium hydroxide drop of 200 μ l is placed at filter paper 181 middle parts and sealing pad 10 in Storage Box 180.This image that causes being with or without on whole dishes 10 of any external coating destroys fully.It is excessive that the ammonium hydroxide amount of using is proved, and substantially exceed the amount that runs in the packing in fact probably.Therefore, use 25 μ l ammonium hydroxide to carry out second test.In 2 hours, do not have the dish 10 of external coating 102 and do not have the external coating 102 all fade fully (external coating may be better a little) of acid, and the external coating 102 that comprises acid has kept most of original look really, except near the zone (base ring) near ammonium hydroxide point.In ensuing several hrs, these dishes 10 also radially outward obviously degenerate from interior ring.Equally, with the environmental facies ratio of typical optics media package 180 as CD or DVD, the ammonium hydroxide amount of use may be also excessive.

With the dense ammonium hydroxide revision test of 10 μ l.As previously mentioned, there is not the dish 10 of external coating 102 in 1 hour, to degenerate.But the dish 10 that has the external coating 102 of O14 prescription formation specifically postpones to fade several hrs.Have the dish 10 basic not variations of the external coating 102 of O13 prescription formation, and only after 1 day, showing the sign that fades near the middle part of coiling 10.

Packing be closed leave standstill several days after, the sample more than three is placed in the initial 200 μ l packing.After 24 hours, not protected dish 10 shows moderate and fades, and it is all still intact to have a dish 10 of external coating 102.In order to finish further test, obtain other DVD Storage Box 180.Be with the sample of the dish 10 of external coating to put in the new packing whether cause more progressive fading into each to observe.External coating sample neither one after 3 days shows any sign that fades.

6. quantitative examination

Use and comprise the light acid producing agent the coloured coating prescription coating metallization substrate 17 of colour coupler ratio as 2.0%TPST:3.5%CF.The composition of every kind of test recipe is provided in the table 25 in the quantitative examination.By prescription being applied on the substrate 17 with 4K rpm spin coating 10 seconds.The dish that under the L-37UV optical filter, in nitrogen environment, in about 1 inch distance, uses XENON D-bulb to solidify to produce 10 2 seconds.Under the D-bulb, produced color totally in 10 seconds then at 4 inches distances each dish 10 that exposes.At last, using the manual top coat 102 that applies of various prescriptions on the HEADWAY to each dish 10.Under the D-bulb, solidified this top coat 102 3 seconds 1 inch distance.

Table 25

The fade prescription of quantitative examination of amine

Component	Formulation No.
								O14	O13	O15	O16	O17	O18	O19
	Welting Agent TEGO RAD 2200N Photoinitiator KTO/46 CN-384 Diluents SR-339 Main Components SR-368D CN-120M50 SB520M35 Acrylic acld	1 1 1 1 1 1 1
8 8 8 8 8 8 8
							26 26 26 26 23.5 21 16
20 20 18 20 20 20 20 45 25 17 35 45 45 45 20 30 10 2.5 5 10
							TOTAL	100	100	100	100	100	100	100
PIGMENTS
								UV-24	10	10	10	10	10	10	10

Use Ocean Optics Spectrometer to measure the optical density (OD) of each dish 10.Measure the absorptivity at 540nm place.Dish 10 is put in the independent DVD box 180 and is exposed to 10 μ l ammonium hydroxide.Ammonium hydroxide is placed on the center of a slice filter paper 181 that is fixed to each box 180 inner cap.Shut box 180, and keep leaving standstill.Regularly from each box 180, take out each dish 10, and carry out the optical density (OD) measurement and lose with evaluate color.The data that obtain are provided among Figure 55.

7. the physical property of coating

By in the SR-238 thinning agent, preparing one-tenth chromatograph 101 prescriptions of improved form with the 5%KTO-46 diluted formulations of 30wt%.The film thickness that produces two kinds of prescriptions is to the rotational speed curve.Then every kind of prescription is spun on the borosilicate glass dish with the interval of 1K rpm from 2K-10K rpm.Then under L37 with Xenon D bulb one-tenth chromatograph on the curing dish 10 101 two seconds in nitrogen atmosphere.Apply then adhesive tape to the dish 10 to remove coating, then on WYKO test with the thickness of film 101 in two zoness of different on the mensuration dish.Figure 56 has shown the result of every kind of average film thickness of rotational speed.This test shows that primary colors coating C6 is when using the rotational speed (S.S.) from about 2K-5K rpm to have bigger film thickness when applying.But after this, two samples are proved very similar.

8. viscosity and temperature

In typical copy machine, coloured coating can be in different temperature distribution with lacquer.Therefore, determine the relation of viscosity and temperature.Carry out viscosity measurement at about 25 ℃-Yue 50 ℃ with about 5 ℃ interval.Utilize Brookfield LVDV-III+CP flow graph and rotor CPE-40 under 4.75rpm, to measure.Viscosity and the temperature curve of coloured coating C6 are shown in Figure 57.According to expectation, the viscosity with temperature of lacquer raises and reduces.

9. viscosity and shear rate

The spin coating process applies the shear rate of variation to lacquer.Because viscosity is the function of shear rate, so also wish to obtain this curve.Some physical constraints hinders the explicit value of measuring shear rate in the spin coating process.But, the performance of getting the scope evaluation lacquer of viscosity and shear rate measured value.Use Brookfield LVDV-III+CP flow graph and rotor CPE-40 in available maximum shear speed range, measuring from low rate.The maximum shear speed of utilizing this concrete lacquer to obtain is 45/ second.Think higher if desired shear rate, then can carry out the replacing of part hardware component in the spin coating system.For example, use rotor CPE-51 and CPE-52 that the shear rate higher than CPE-40 rotor should be able to be provided.These rotors are compatible with this flow graph, and can produce higher shear rate.

Therefore, program of design is to obtain low and high shear rate by the speed that changes rotor.Use improves shear rate from the speed of 1K-6K rpm with the interval of 1K rpm.Then, speed turns back to 1K rpm from 6K rpm.Rheological diagram among Figure 58 has shown the relation of viscosity and shear rate.

Figure 58 shows that along with shear rate increases, bottom 101 (comprising prescription c6) viscosity is almost constant.But along with shear time increases, viscosity increases.Cumulative shearing curve shows that prescription is Newtonian fluid.But curve table free flow body rheology decrescence is relevant with the time.The another kind of figure that shows the fluid behavior is that shear stress and shear rate distribute, and is provided among Figure 59.In Figure 59, the linear relationship between shear stress and the shear rate confirms that fluid is a Newtonian fluid, on two shear directions.

Whether to observe coloured coating rheology with time relevant, can show decrescence viscosity and shear rate curve if carrying out another test.For studying this, in a period of time, keep shear rate and temperature-resistant, carry out viscosity measurement simultaneously.Equally, use LVDV-III+CP and rotor CPE-40.Spinner velocity is set in 2K rpm.The time curve that Figure 60 shows confirms that viscosity remains unchanged in time, infers that prescription C6 shows the Newtonian fluid behavior.

10. the color of various lamps forms

Utilize 9 samples shown in the table 26 to carry out color and form test with three kinds of different light sources.Every kind of light acid producing agent that shows and colour coupler combination all are included in the coating base-material of prescription C7 (comprising 5%KTO, 35%SR-238,30%SR-368D and 30%CN-120860).Prepare three groups of dishes 10 that comprise prescription, and use XENON D bulb, XENON C bulb and the exposure of HONLE lamp respectively.Time shutter is 1-10 second, is spaced apart 1 second.Metallization substrate 17 is placed in each dish 10 following cremasteric reflex background.By prescription being spun to all samples of preparation on the clear polycarbonate substrate 17 in the speed with 4K rpm on the HEADWAY.In nitrogen environment, used XENON D bulb and L37 UV optical filter curing formula 2 seconds.

Table 26

The one-tenth colour test of different lamps is with filling a prescription

											1	2	3	4	5	6	7	8	9
TPST	2	2	2	2.25	2.25	2.25	2.5	2.5	2.5
										PERG I-6B	3	3.5	4	3.38	3.94	4.5	3.75	4.38	5

Design this research to test several variablees.First is to change the influence of light acid producing agent to the ratio of colour coupler.Typically, use 2: 3 ratio, but think that this is not preferred ratio.Secondly, estimate preferred light acid producing agent and colour coupler concentration.This comprises estimates the influence of change concentration to the color formation time.Once more, estimate the influence of the use of different bulbs to the color formation time.XENON " D " and " C " bulb discharge the short UV of different amounts.Think that short UV is not obvious to the effect characteristics that color forms.In addition, HONLE " H " bulb is a continuous wave mercuryvapour scheme, and line spectrum and xenon lamp have a great difference, thinks that this lamp of test can prove benefit gained from others' wisdom.The HONLE lamp can be from H nle UV America, Inc., and of Marlboro, MA obtains.

11. light acid producing agent and colour coupler ratio

Figure 61-64 illustrates the influence of the ratio of light acid producing agent and colour coupler to color formation.Every kind of different light acid producing agent concentration is seen as one group, as if follows general trend.Figure 61-64 shows, ratio be in the sample of 2: 3.5 (or its equivalence) color to form than ratio be that 2: 3 sample does very well, ratio is that 2: 3 sample is that 2: 4 sample does very well than ratio.

Think that it may be owing to do not activate the UV light higher absorption that colour coupler causes in the prescription that the obvious relatively poor color of higher colour coupler ratio forms.Although as if this trend support every kind of light acid producing agent concentration, notice that higher colour coupler concentration can cause environment or photostability preferably.In addition, notice that the performance difference between these ratios is little, therefore any because the additional benefits that higher colour coupler ratio causes all is proved to be justified probably.

The optimal proportion of supposing light acid producing agent and colour coupler then can directly compare the influence of light acid producing agent concentration to color level near 2: 3.5.The increase of color is consistent to the increase of colour coupler concentration ratio with the light acid producing agent substantially.

12. lamp shadow rings

Use the efficient that writes of the light acid producing agent of 2: 3 and 2: 4 and three kinds of lamps of colour coupler ratio inspection.For concisely, at 2.5% smooth acid producing agent: lamp relatively during 5% colour coupler charging capacity, using the combination UVA that measures on GIGAHERTZ OPTIK power meter and UVA intensity to be converted into the time can flow valuve.Power level is shown in table 27.

Table 27

The lamp power level

	C@4”	D@4”	H@5”
					kW/m 2
UVA	0.73	0.62	0.40
				UVB	0.40	0.44	0.57
UVA+B	1.13	1.06	0.97

Usually, HONLE " H " bulb behaves oneself best flowing on the basis of combination UVA/UVB level, shown in Figure 65.But, it should be noted that HONLE discharges more UVB than any XENON bulb really.As if when only using the horizontal curve plotting of UVB, shown in Figure 66, the HONLE lamp shows less advantage, but still be better than the XENON bulb.On any level, HONLE and " C " bulb all are better than " D " bulb.At last, use HONLE " H " bulb to carry out longer exposure is used to make the coating imaging with inspection maximum available energy stream.Shown in Figure 67, typically fill a prescription at about 5kJ/m ²Begin to reach maximum after the UVB exposure.In some embodiments, use the full spectrum curable overcoat 102 of UV.

13. external coating: photostability with external coating of various UV absorbing agents

Preparation has external coating (O1) prescription of the various UV absorbing agents of 10% concentration.The various absorbing agents that use are shown in table 28.TINUVIN-327 can not enter solution, and the prescription that uses TINUVIN-R796 was at 24 hours post crystallizations.TINUVIN-R796 is 2-(2 ' hydroxyl-5 ' methacryloxyethyl phenyl)-2H-benzotriazole, and for being linked to the active UV absorbing agent in the coating.

Table 28

The UV absorbing agent that uses in the external coating

The UV absorbing agent	Dispensing viscosity (cps)	Physical form	Edge cure
				UV
24	145	Powder	Not
				MC80	99	Liquid	Be
T-171	110	Liquid	Be
				T-213	141	Liquid	Be
T-327	Not dissolving	Powder	Be
				T-571	119	Liquid	Be
T-R796	Crystallization	Powder	Be

C6 is coated with clear polycarbonate dish 10 with prescription, and is using the L-37UV optical filter to solidify in nitrogen environment 2 seconds from 1 inch distance of XENON C bulb.Make dish 10 imaging 10 seconds from 4 inches on lamp then.Three comprise the image dish 10 on apply every kind of top coat 102.Under XENON, coiled 10 3 seconds 1 inch distance curing.Each dish 10 solidifies good, and shows favorable surface quality.Every kind of prescription edge cure is except the UV-24 prescription.The prescription that comprises MC80 has pink painted after curing.

Measure the viscosity of every kind of prescription, and the optical density (OD) on measuring disk 10 curing and the exposure area.To coil 10 and be placed in the light chamber, regularly take out and measure the optical density (OD) at 540nm place.The results are shown in Figure 68.Notice of the photostability almost not influence of UVA composition, shown in Figure 69 to coiling 10 exposure areas.

The result of aforementioned research work is to work out various prescriptions and develops the more technology of polygamy side.The quality material that these prescriptions and its development technique provide the available light wavelength to solidify, this material and available light wavelength excite to produce and reservation image, pattern and other required mark.These prescriptions can advantageously be applied on the data characteristics that occurs in the optical medium.More advantageously, the may command image content is so that the readout device of avoiding influencing use is translated the data that are stored in the data characteristics.It should be understood that above-mentioned is the explanation prescription, rather than limits feasible embodiment.For example, think that other composition of introducing such as acid functional group can further help the stability of image reservation as the alkali scavenger in the external coating 120.

Although all this work supports exploitation can provide the set of diagrams of long-term lively image to resemble, produce interim image and also be in some applications be concerned about, as safety label, prescribe a time limit promotion message or novelty effect.In this case, heat, humidity, surround lighting or other environmental baseline all may cause image to fade.Prescription described herein especially do not protect external coating 102 those can produce this fade relevant with the time.In preferred embodiments in case from packing provide control environment the taking-up optical medium 10, this will take place.

The aspect has been discussed as prescription and its exploitation, the many-sided of the application of these prescriptions and use will be discussed now.

C. the embodiment of coating on the optical medium 10

Obviously, for those skilled in the art, as described herein having uses the prescription of effect to be not restricted to above-mentioned embodiment.Therefore, more discussion of coating 100 and its character are not subjected to the restriction of the concrete aspect of above-mentioned embodiment.

1. two layers of coatings

With reference to figure 9 and Figure 10, two kinds of embodiments of the coating 100 that provides have so far been looked back.In Fig. 9, shown signal layer coating, comprising other component of quality material and generation coating 100.In this embodiment, coating 100 provides the quality attribute, and ambient stable agent (as the UV absorbing agent).Figure 10 provides second kind of embodiment, and wherein component is divided into two-layer 101,102.In Figure 10, coating 100 is by becoming chromatograph 101 and external coating 102 to form (Figure 10 B exception).In two layer system, the component that becomes chromatograph 101 advantageously with external coating 102 in component separate, thereby can provide improved performance in some properties of coating 100.For example, from become chromatograph 101, remove the UV absorbing agent and in external coating 102 collateral use UV absorbing agent can provide selection the stronger UV absorbing agent that can not influence imaging procedures.

The UV absorbing agent only is an example of the image enhancement agent that can use in external coating 102.Other non-limitative example comprises the material (as described in other place of this paper) that can limit humidity effect or strengthen color.

2. laminated coating

In addition, provide nonrestrictive embodiment among Figure 70-72.In another embodiment shown in Figure 70, three layers 301,302,303 have been used.In a kind of embodiment shown in Figure 70, ground floor 301 and the second layer 302 are for becoming chromatograph 101, and wherein each becomes chromatograph 101 to produce different colors, as be red in ground floor 301, is green in the second layer 302.Be configured to external coating 102 for the 3rd layer 303, it is designed to protection and is not subjected to such environmental effects.In another embodiment, the optical medium 10 of formation Figure 70 demonstration makes ground floor 301, the second layer 302 and the 3rd layer of 303 prescription for the individual layer embodiment use.In these other embodiments, each layer 301,302,303 produces different colors, as one of red, green and blue.

In Figure 71, shown the coating 100 that comprises four layers 401,402,403,404.In one embodiment, ground floor 401 is for becoming chromatograph 101, and the second layer 402 is protection external coating 102.The 3rd layer 403 also for becoming chromatograph 101, and the 4th layer 404 be another protection external coating 102.Perhaps, ground floor 401, the second layer 402 with the 3rd layer 403 in each all for becoming chromatograph 101, and the 4th layer 404 be protection external coating 102.In this alternate embodiment, the color that forms in each in initial 401,402,403 layers can be corresponding to primary colours, thereby when finishing imaging, show multicolor image.

In Figure 72, shown the another embodiment of coating 100, six layers of embodiment.In one case, the layer 501,503,505 that replaces is for becoming chromatograph 101, and external coating 102 comprises layer 502,504,506.In this embodiment, in the layer 501,503,505 that replaces each corresponding to a kind of special color, a kind of as in the primary colours.The imaging of each provides the overall appearance of multicolor image in the layer 501,503,505.

In some embodiments, those use to small part destination layer material as shown in Figure 70-72.That is to say that in Figure 70-72, part substrate layer 17 comprises polycarbonate, without any the quality material.This embodiment is preferred, the component used in the chromatograph 301,401,501 have the material that character may make following coating metal layer 14 fade.For example, at least a portion polycarbonate is left the restraining barrier is not subjected to may to cause in the quality material acid of coating metal layer 14 oxidations (reflectance varies) with protection coating metal layer 14 influence.

3. polychrome CD

Dish 10 in order to have multicolor image above preparing applies polychrome cambium layer 101.Study to prepare red and orange polychrome dish 10.The prescription that uses in the whole research is shown in table 29.

Table 29

One-tenth chromatograph in the polychrome dish

Colorant	Red	Orange
			Perg Red
	4
			Perg Orange		3
TPST	2	3
			Base-material	1b	1b
KTO
		5	5
SR-239				35	35
	SR-368D	30	30
CN-120B60				30	30

At first, with orange prescription on 4000rpm backspin plating dish 10 seconds.Then under glass pane 1 " solidified orange prescription 3 seconds with Xenon " C " bulb at a distance.Then quartz mask is placed on dish 10 tops, and 4 " at a distance with identical Xenon " C " bulb exposure 10 seconds.The dish 10 that obtains has orange image in the above and has transparent background.Then, get dish 10, and fill a prescription on Headway with 4000rpm spin coating 10 seconds with red again.Then under glass pane 1 " solidified red prescription 3 seconds with Xenon " C " bulb at a distance.At last, photomask is placed on dish 10 tops, and 4 " at a distance with Xenon " C " bulb exposure 10 seconds.Final product have above being red with become color picture and have the dish 10 of transparent background.

Obtain the spectrum of orange and red prescription.With 4000rpm these samples of spin coating on the clear polycarbonate dish, and by solidifying as mentioned above and exposing.In addition, obtaining the spectrum of stacked color various combination, no matter coil 10 and be laminated with first orange coating or the red coatings, then is other color above.

Figure 73 has described the spectrum of red dish 10 and orange dish 10, wherein separately estimates every kind of color.Figure 74 shows, when red color layer and orange layer exposed together, the color spectrum that obtains was identical substantially.This does not consider the order that coating is placed.In addition, Figure 75 has shown that the top layer 101 in the series of layers 101 can optionally be exposed rather than the apparent fully color of surface layer down.Can notice to show most of color in the top layer 101, and following layer 101 keeps unexposed relatively.

If desired, can be by becoming to add the selective coloration that UV restraining barrier 102 strengthens top color layers 101 between the chromatograph 101.Table 30 provides the prescription on UV restraining barrier.This prescription is spin-coated between the orange and red one-tenth chromatograph 101.In this example, UV restraining barrier 102 allows even only reproduces single the top color better.Equally, two become the exposure of chromatograph 101 to cause identical total color, with the sequence independence of applied layer 101.The results are shown in Figure 76.

Table 30

The UV restraining barrier of using in the research of polychrome dish

Wetting agent
		TEGO RAD 220N	1
Light trigger
		KTO/46	8
Thinning agent
		SR-339	26
Key component
		SR-368D	20
CN-120M50	45
		Amount to	100
Pigment
		UV-24	10

Obviously, above-mentioned embodiment utilization comprises into the coating of chromatograph 101, external coating 102, individual layer 100 and its various combinations.Therefore can infer, can develop multiple combination.These can provide various effects, as monochrome or multicolor image.

In addition, also can infer, apply stage by stage and the imaging in coating 100 middle levels can provide some advantage.For example, in one embodiment, apply ground floor 401, then recording picture therein.Subsequently, apply protection external coating 102, apply the 3rd layer 403 as the second one-tenth chromatograph 101 as the second layer 402.Use the second layer 402 to utilize the material that absorbs the imaging wavelength in the imaging procedures of the second one-tenth chromatograph 403, to limit the exposure of ground floor 401.In this manner, image of record in ground floor 401, record second image in the 3rd layer 403.Substantially do not influencing the record that carries out second image under first situation aspect visual.The individual layer prescription also can use similar techniques, and wherein the quality material mixes with UV (or other wavelength) absorbing agent.Can use and solidify and the imaging multi-wavelength.In a word, can use various applying in technology, prescription, curing and imaging technique the overall appearance to obtain pleiotropism with coating 100 on optical medium 10.

4. in existing form, use the Consideration of coating

Can in the optical medium 8 of the prior art shown in Fig. 1-8, advantageously use coating 100.For example, in Fig. 1, a kind of embodiment requires to use the acrylic acid protective seam 12 among coating 100 replacements or the covering CD 8.The optimization formula of this application will comprise C13 or C14.In this application, influence laser and read and be not problem, therefore can use other colour coupler.Therefore, the use of PERGASCRIPT Red 6B can be replaced by a large amount of other colorants among C13 and the C14.Spectrum in the C13/C14 coating base-material and colour coupler are illustrated in Figure 83 with the ratio of TPST.

In DVD-5, as shown in Figure 2, become chromatograph 101 can be placed in the adhesive linkage 15.Substrate layer 17-2 can increase external coating 102.Related embodiment will be that reflection horizon 14 is replaced by semi-reflective layer 14-1, and mark 620 reads by semi-reflective layer 14-1, and this observes from reading face 2.This embodiment has the advantage for conventional tags slot milling on label surface 7.In another embodiment, use the adhesive linkage 15 of coating 100 replacement DVD-9, as shown in Figure 3.For these embodiments, laser is read and is still main Consideration, and prescription C13 and C14 will be preferred.

With reference to figure 4, recognize that this double-sided disc 8 can not be printed, except the center in introducing the zone.Therefore label is problems for this dish 8.This can solve by using translucent reflective layer.Become chromatograph 101 to be disposed in the adhesive linkage, imaging is finished in this layer.Also can be two-sided inner label imaging, use into chromatograph 101 this moment on each semi-reflective layer 14, uses the 3rd to become chromatograph 101 in adhesive linkage 15.In yet another embodiment, one side is total reflection, thereby image can only be seen from one side.

With reference to figure 5, can between semi-reflective layer and reflection horizon, use coating 100.With reference to figure 6-8, in preferred embodiments, in bonding (bonding) layer 15, use coating 100.

In some embodiments, directly contacting use coating 100 with metal or other reflection horizon 14 needs to use protection part (shown in Figure 70-72, the part destination layer among the CD is mixed with polycarbonate at this moment), or improves reflecting material.For example, can in reflection horizon 14, use silver or gold with fading that the acid of protection light causes.Therefore, recognize in some embodiments, must consider material compatibility.Again for example, in DVD-18, bonding relating to used resin cation (it makes and uses up acid as initiating agent).Before bonding, use the UV cured acrylate to be coated with reflection horizon 14.In using the embodiment of constructing like this,, just may need intermediate steps so that the final products 10 that can suitably show required mark 620 to be provided as DVD-18.

II. form mark

A. solidified coating

Before in coating 100, forming mark, coating 100 suitably must be attached in the optical medium 10.As previously mentioned, can use hybrid technology or other technology such as spin coating to apply coating.When using spin coating, preferably use first kind of light solidifying coating 100.Figure 77 has described the first kind of light 910 that is used to solidify coating 100 on the optical medium 10.In this example, optical medium 10 is the part of production line 7800.

B. form the equipment of mark

Figure 78 has described the device that forms mark in coating 100.In Figure 78, utilize image 620 (mark) to be recorded in the optical medium 10 by the quality material in second kind of light, the 920 elective irradiation coatings 100.In preferred embodiments, use the UV wavelength that second kind of light 920 is provided.In this diagram, optical medium 10 produces in production line 2000.

Can utilize the elective irradiation of optical medium 10 that the contrast of variation is provided for the unexposed or less exposure area of optical medium 10.That is to say, can in image 620, form the shade that changes.For example, the increase of a part of UV exposure will cause the bigger absorption that shown than coating 100 another part in the coating 100.Therefore can utilize image to form unit such as positive and negative or electric light mask, direct recording laser (laser current meter systems) or realize hatching effect or any other labelling technique by other technology.Mark 620 should be as single labelled realization (mark in for example monochromatic cambium layer 101), or realizes (a series of marks in for example various one-tenth chromatographs 101) by the overall appearance of series of markings.The example that provides among Figure 78 comprises two types.That is to say that a mark 620 comprises monochromatic star.Another mark 620 comprises the bar with two kinds of different colours.

In the example of Figure 78, four layers of coating 100 are applied on the optical medium.Ground floor 401 provides support for the color generation of star 620, and the second layer 402 and the 3rd layer of 403 color generation of supporting bar.Apply the 4th layer 404 with the stable mark 620 that is applied on the optical medium 10.

A kind of embodiment-electronic light the mask of photomask 925 utilizes LCD able to programme, and it preferably shows high optical density (OD) at about 355nm wavelength place.In some embodiments, the electronic light mask is readjusted between the mark program, thereby provides unique mark 620 on each of continuous optical medium 10.

It should be noted that a convention used herein is about term " image " and " mark ".When using these terms together, obtain image and mean the generation mark, this tense marker 620 is the demonstration (i.e. record) of image in the coating 100.Will be appreciated that two terms are closely related, and think interchangeable in due course.

C. type

Mark 620 can transmit any required information with any required form.For example, mark 620 can provide the content that comprises identifying information (as sequence number), authentication information and/or command information.Content also can comprise advertisement, trade mark or promotion message, is called " promotion message " herein jointly.Content can comprise the decryption key that is used for decipher optics medium 10 storage data.Other embodiments can relate to other arrangement of enciphered message.The information that comprises in the mark 620 can include but not limited to the information of any the above-mentioned type or their combination.For convenience, the content of term used herein " content " digit synbol 620.The combination that content can be used as image, alphanumeric and other symbol, figure and image and symbol provides, and these all are non-limitative example.Content can be provided as data code symbols system (as bar code) and provide and can provide with at least a digital watermarking.

Mark 620 can manifest at the wavelength place that is higher or lower than the visible wavelength wave band.For example, 620 couples of naked eyes people of mark observer is sightless.

In some embodiments, mark 620 is a self destruction.For example, when being incorporated into ambient environmental conditions such as 620 disappearances of ambient illumination tense marker.The mark 620 of use self destruction may be used particularly useful to some, as in some embodiments of certification scheme.

Change the example of technology that shifts contrast in the image and be included in the joining technique that uses in the gray scale printing.That is to say, use suitably the band look shape of size or the set of pattern on not with the background of look, perhaps on panchromatic background, use not set with look shape or pattern.The size of adjustment shape or pattern and density provide the control to color intensity vision in the arbitrarily concrete zone in the mark.

In some embodiments, after " trigger event ", mark 620 begins to fade, and may finally disappear, mix, or the basic distortion that becomes.For example, after optical medium was put into environmental conditions such as ambient light, mark 620 began to fade, and final the disappearance.This embodiment can advantageously be used with other technology, uses as the optical medium (as in case be exposed to the optical medium of environmental baseline with regard to self destruction) with limited broadcast.For example, optical medium 10 can comprise the symbol 620 that indication is readable.The example of limited broadcast optical medium is disclosed in the United States Patent (USP) of publishing in 13 days Augusts in 2002 of people such as Rollhaus 6434109 " Machine-Readable Optical Disc with Reading-Inhibit Agent ".

As described in other place of this paper, mark 620 is transmissible under interested wavelength, or basic transmission.For example, mark 620 is (the non-substantially interference) of basic transmission reading under the optical maser wavelength of optical medium 10.For example, mark 620 is not interfered the wavelength of about 400nm, about 440nm, about 630nm, about 650nm and about 780nm basically.

III. coating inspection

A. exemplary checkout facility

In case coating 100 is applied on the optical medium 10, can checks the compatibility of it and required specification.Equally, check mark 620.In some embodiments, inspection be choose wantonly or the abridged.An example of suitable equipment comprises Spectra Systems, Inc.OfProvidence, the VERICAM of Rhode Island.Another exemplary check system is XirisAutomation, of Burlington Ontario, the XIRIS PI-1500 that Canada sells.Another system that is used to analyze optical medium 10 quality is a CATS SA3 system, can be from AudioDev USA of Woodland Hills, and CA obtains.This system is by measuring the readability and the playability of a large amount of signals and parameter verification optical medium.The level that can analyze these parameters then is to draw a conclusion to the stability of dish manufacture process and possible playability problem.

B. coating parameters and radially noise research

Carry out the performance of the optical medium 10 of research evaluation band coating.Has coating disk 10 on the HEADWAY PWM32-PS-R790 SpinnerSystem of HDP98 flow distributor and MA24WEA dispense arm.Use prescription 3 (9021) (seeing Table 14).Use different rotational speeies and various coating parameters to check that the spin coating parameter is to coiling the influence of 10 electrical specification.The program that surpasses a kind of or cumulative rotational speed is used in test.Determine preferred coating parameters, under 4Krpm, use single spin coating 10 seconds.The spin coating program that is used for the HEADWAY system is provided at table 31.

Table 31

The Headway System program that is used for final test

		Speed (RPM)	Even become (RPM/S)	F6 (24V)	The arm direction	Speed (%)	Time (S)
								Step	Purpose
		1	Start program	90	1000	N	Just		40	3
2	Distribute lacquer										90	1000	Y’＝ON	Do not have		3.5
		3	Be the thickness spin coating	4000	2000	N	Original position		40	10
4	Finish										0	2000	N	Original position		0.5

The increase distribution time needs to reduce used rotational speed (rpm) in the step 1 and 2 with the dispensed volume (viscosity is relevant) that keeps 2.0ml.Dispensed volume on the HEADWAY Spin Coating Systems is the function of distribution time and dispense pressure.Therefore, under the constant pressure of 50psi, set the dispensed volume of distribution time to 3.5 second generation 1.9-2.0ml.This lacquer volume production is given birth to required coating 100.

In order to check the influence of imaging procedures to performance parameter, apply single disc 10, solidify, in the CATS system, test then.Make same dish 10 imaging then, and test for the second time in the CATS system.Difference in the CATS test result is very little.The data that the CATS system produces are included among Figure 79, have wherein shown the data of uncoated dish 10.Big peak value when noting each end of test (EOT) is because data stop causing, is not the inherent error of dish 10 or coating 100.Figure 80 provides and has been cured and the data of the dish 10 of the band coating of imaging not.Figure 81 provides and has been cured and the data of the dish 10 of the band coating of imaging.Figure 82 has described the test result of dish 10 on CATS SA3 that applies on SingulusSKYLINE DUPLEX machine.

The analysis showed that, use single spraying and speed to obtain preferred coating.For the used coating parameters of SingulusSKYLINE DUPLEX machine is shown in table 32.These settings can be applicable to any apply of coating 101,102, and coating 100 thickness are coated with lacquer viscosity or apply the restriction of temperature.

Table 32

Be used to coil the Singulus set point of production

Set point

1
		Minimum	Maximum
Temperature				20.00	40.00
	The lacquer radius	24.00	24.00
Dosage				1.20	1.20
	The batching time	0.50	0.50
Time				0.75	0.75
	Speed	120	120
Even speed change degree				0.45	0.3
	Time	0.90	0.90
Speed				4500	4000
	Even reduction of speed degree	0.25	0.25

D.Singulus SKYLINE DUOLEX and lamp solidify

Finish research to check the curing of Singulus SKYLINE DUPLEX machine floating coat.In this research, SKYLINE DUPLEX machine is mounted with prescription external coating O1, tests the curing of various lamps at top and edge.Use XENON C bulb, exposure power is set at 1.0kW.The dish 10 of exposure is in 2.0 seconds inner tops and edge full solidification.Also estimate the time interval of 1.0 seconds and 1.5 seconds, do not had abundant curing dish 10.Use the reflecting plate on the felt-tip pen blacking robot blade.Evaluating disc 10 once more, do not have notable difference under identical in addition condition.Dish 10 is along top and edge full solidification.

Also estimated and used F-bulb with metallization reflecting body.Control F-bulb, setting maximum exposure power is 5.0kW, the maximum exposure time is 5.0 seconds.Dish 10 tops of exposure or edge do not solidify.Then, estimate V-bulb (gallium iodide) with metallization reflecting body.Control V-bulb, setting maximum exposure power is 5.0kW, the maximum exposure time is 5.0 seconds.Dish 10 along the top or the edge fully do not solidify.

Estimated the change of external coating O1 prescription.In these trials, the light trigger KTO/46 that external coating O1 prescription is replaced certain percentage with Irgacure 819.Prepared four kinds of prescriptions, shown in table 33.

Table 33

The variation of light trigger combination among the external coating O1

Formula number	The light trigger combination
		1	5%KTO/46 and 3%Irgacure 819
2	3%KTO/46 and 5%Irgacure 819
		3	2%KTO/46 and 6%Irgacure 819
4	1%KTO/46 and 7%Irgacure 819

Use the HEADWAY spin coater that the prescription of table 33 is coated onto on the dish 10 with hand.Use V-bulb (gallium iodide) on SKYLINE DUPLEX machine, to test them in different time curing at interval.The result is provided at (" NG " representative " bad ") in the table 34.All dishes are in the edge full solidification, and reflecting body keeps blackening.

Table 34

The set time that external coating O1 changes

External coating-1 light prescription	Solidify V-bulb (gallium iodide)
						1 second	2 seconds	3 seconds	4 seconds	5 seconds
	5％KTO/3％819		NG								Can
3％KTO/5％819							NG	Good	Fabulous
	2％KTO/6％819	NG	Can	Fabulous
1％KTO/7％819						NG	Good	Fabulous

Table 35 discloses external coating 102 and the preferred embodiment that becomes chromatograph 101 respectively with table 36.Select these preferred embodiments to reach all types of target best, as supporting the high yield manufacturing.They do not limit the present invention.

Table 35

The preferred embodiment of external coating

External coating prescription 14	Wt％
		Component
TEGO RAD 2200N
		1
KTO/46			8
	SR-339	26
SR-368D			20
	CN-120M50	45
Amount to			100
	Pigment UV-24	10

Table 36

Become the preferred embodiment of chromatograph

Quality layer formula C15	Wt％
		BYK-333	0.3
KTO/46	10
		SR-238	10
SR-285	15
		SR-494	32.35
SR-9021	32.35
		Amount to	100
Pigment
		TPST
	3
		Pergascript Red 6B	3

V. other embodiment

A. direct combined formulation in destination layer

In yet another embodiment, produce potpourri, this potpourri comprises the prescription that is attached to the material that is used for constructing substrate 17-1.The exemplary of describing the potpourri use is shown in Figure 10 E.In this embodiment, 10g bisphenol-a polycarbonate (Aldrich Chemical produces, and molecular weight is about 64000) is dissolved in about 200g methylene chloride.(Aldrich Chemical Corp.ofSt.Louis MO) with 300mg PERGASCRIPT Red 6B, forms transparent homogeneous solution to add 300mg triphenyl sulfonium fluoroform sulphonate in this potpourri.Then with solution-cast to the polycarbonate slide glass and in hot blast dry about 1 minute.The film that obtains is transparent and colourless, is illustrated as uniform solid film.When being exposed to XenonRC747C (at about 1.5kW/m ²Following operation, and be created in wavelength in the about 400nm scope of about 270nm-) film shows strong redness the time.It is transparent and colourless that the unexposed area of film keeps.

Discovery can directly be attached to TPST (or similar derivative thing such as tert-butyl-phenyl hexichol sulfonium fluoroform sulphonate) and PERGASCRIPT (or other colour coupler) in the base material by fusion, as be used to construct the makrolon material of optical medium 8.This is suitable for coiling injection molding polycarbonate by standard polymers hybrid technology (nonrestrictive example is extruded) formation and light acid producing agent/colour coupler potpourri is realized.This technology can be described as " directly mixing " or " mixing " technology.When hybrid technology is used when the use of others of instructing with this paper such as external coating 102 with special formulation disclosed herein, provide coating 100 and mark 620 to the interior effective combination of destination layer.Other technology of noting the photosensitive polycarbonate of formation is known.But therefore this class prior art is not suitable for coating 100 and mark 620 effectively are attached in the destination layer of optical medium 10 not in conjunction with disclosed these aspects.

Also refer in conjunction with coating 100 in the inherent scope provided herein of destination layer by mixing direct combined formulation.More specifically, as mentioned above, recognize that destination layer can increase coating 100 or coated 100 and replace.Like this, according to the instruction of this paper, using hybrid technology only is that a nonrestrictive coating 100 applies technology.

Can use various material structure substrate 17-1.These materials are called as " disc molding material " in this article.The non-limitative example of disc molding material comprises Elf Atochem of NorthAmerica Inc., Philadelphia, the PLEXIGLAS VOD-100 that PA produces; Materials similar is CYRO Industries, Rockaway, the ACRYLITE DQ501 of NJ; Dow plastics, Midland, the poly-hexamethylene ethene (PCHE) of MI; General Electricof Pittsfield, the LEXAN product of MA comprises OQ1040L, OQ1050 and OQ1030L; Except all these, also have many other products.

Therefore can recognize that although specifically represent in conjunction with preferred embodiment and described the present invention, ability those technician can recognize, under the situation that does not break away from the scope of the invention and spirit, wherein can carry out the variation on form and the details.For example, can and apply in the quality control of device, curing, mark and mark of coating in research coating composition, method and take multiple variation.Recognize that formation external coating as described herein and the technology that becomes chromatograph can make them produce and be suitable for implementing many other prescriptions of the present invention.Therefore, although usually described the present invention with regard to embodiment described herein and variation thereof, the disclosure has contained not open or that just advise in this article those embodiments.

Claims (51)

1. an optical medium has at least one layer, and described layer comprises the prescription that contains at least one group of photosensitive quality material, and wherein this described at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, described at least one zone of reading at least that is marked at optical medium is significantly, and substantially not the interferometric optical medium read light.

2. optical medium as claimed in claim 1, wherein said layer comprises at least one in substrate layer, adhesive linkage and the protective seam.

3. optical medium as claimed in claim 1, wherein the form of optical medium comprises at least one in substrate layer, adhesive linkage, semi-reflective layer, reflection horizon and the protective seam.

4. optical medium as claimed in claim 1, wherein at least one group of photosensitive quality material be to forming second group of wavelength sensitive of mark, and second group of wavelength separates with the used first group of wavelength of curing formula substantially.

5. optical medium as claimed in claim 4, wherein first group of wavelength comprises the wavelength that about 370nm is above.

6. optical medium as claimed in claim 4, wherein second group of wavelength comprises the wavelength of the about 320nm of about 270nm-.

7. optical medium as claimed in claim 1, wherein prescription comprises the potpourri of light acid producing agent, colour coupler and base material.

8. optical medium as claimed in claim 7, wherein the light acid producing agent comprises two (4-tert-butyl-phenyl) iodine tosilate, (tert-butoxycarbonyl methoxyl naphthyl) hexichol sulfonium fluoroform sulphonate, (4-Phenoxyphenyl) hexichol sulfonium fluoroform sulphonate, (4-tert-butyl-phenyl) hexichol sulfonium fluoroform sulphonate, the diphenyl iodonium hexafluorophosphate, the diphenyl iodonium fluoroform sulphonate, the triphenyl sulfonium fluoroform sulphonate, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, three (2,4, the 6-trichloromethyl)-the s-triazine, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-chlorphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, at least a in (4-aminomethyl phenyl) hexichol sulfonium fluoroform sulphonate and the diphenyl iodonium hexafluorophosphate.

9. optical medium as claimed in claim 7, wherein colour coupler wavelength place of one in comprising about 540nm, about 440nm and about 600nm, about 464nm and about 586nm, about 493nm, about 440nm and about 602nm, about 613nm, about 460nm and about 586nm, about 525nm shows at least one absorption peak.

10. optical medium as claimed in claim 7, wherein base material comprises at least a disc molding material.

11. optical medium as claimed in claim 7, wherein base material comprises at least a acrylate.

12. optical medium as claim 11, wherein at least a acrylate comprises the ethoxylation tetramethylol methane tetraacrylate, 1, the 6-hexanediyl ester, tetrahydrofurfuryl acrylate, height propoxylation (5.5) glycerol tri-acrylate, 3mol propoxylated glycerol triacrylate, the 3mol ethoxylated trimethylolpropane triacrylate, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, two trimethylolpropane tetra-acrylate, the urethane diacrylate oligomer, isobornyl acrylate, difunctionality bisphenol-A basic ring oxypropylene acid esters, aliphatics diacrylate ester oligomer, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, the 2-phenoxyethyl acrylate, be mixed with about 40%1, the difunctionality bisphenol-A basic ring oxypropylene acid esters of 6-hexanediyl ester, be mixed with at least a in the difunctionality bisphenol-A basic ring oxypropylene acid esters of about 50%2-phenoxyethyl acrylate and the acrylic acid.

13. as the optical medium of claim 11, wherein at least a acrylate comprises at least a non-alkoxylate monomer.

14. optical medium as claimed in claim 7, wherein base material comprises at least a light trigger.

15. optical medium as claim 14; wherein light trigger comprises trimethylbenzene formyl oxidation diphenyl phosphine; the stable liquid potpourri of alpha-alcohol ketone and benzophenone derivates; 2-benzyl-2-dimethylamino-1-(4-morpholine and phenyl)-butanone-1; two (2; 4; the 6-trimethylbenzoyl)-the oxidation phosphniline; 2; 4; the eutectic liquid mixture of 6-tri-methyl benzophenone and 4-methyldiphenyl ketone; about 50% 2; 4, the potpourri of 6-trimethylbenzoyl-oxidation diphenyl phosphine and 2-hydroxy-2-methyl-1-phenyl-the third-1 ketone of about 50%; 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone; isopropyl thioxanthone; at least a in the liquid mixture of about 70% low [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone and 2-hydroxy-2-methyl-1-phenyl the third-1 ketone of about 30%.

16. optical medium as claimed in claim 7, wherein base material comprises wetting agent.

17. as the optical medium of claim 16, wherein wetting agent comprises at least a in polyether-modified dimethyl silicone polymer, crosslinkable silicone polyether acrylate and the crosslinkable silicone acrylate.

18. as the optical medium of claim 16, wherein prescription comprises the wetting agent of the about 1wt% of about 0.3wt%-.

19. optical medium as claimed in claim 7, wherein prescription comprises the light acid producing agent of the about 9wt% of about 1.5wt%-.

20. optical medium as claimed in claim 7, wherein prescription comprises the colour coupler of the about 9wt% of about 3wt%-.

21. optical medium as claimed in claim 7, wherein prescription comprises the base material of the about 95.5wt% of about 82wt%-.

22. optical medium as claimed in claim 7, wherein base material comprises light absorbing material.

23. optical medium as claimed in claim 7, wherein base material comprises the color reinforcing material.

24. optical medium as claimed in claim 7, wherein base material comprises height propoxylation (5.5) glycerol tri-acrylate of ethoxylation (4) tetramethylol methane tetraacrylate He the about 32.35wt% of trimethylbenzene formyl oxidation diphenyl phosphine, alpha-alcohol ketone and the stable liquid potpourri of benzophenone derivates of the polyether-modified dimethyl silicone polymer of about 0.3wt%, about 10wt%, the 1,6 hexanediol diacrylate of about 10wt%, the tetrahydrofurfuryl acrylate of about 15wt%, about 32.35wt%.

25. an optical medium comprises:

Comprise be used for the response flag rayed form mark photosensitive quality material ground floor and be arranged on the ground floor and comprise the second layer of the material that absorbs mark light; Wherein, the zone of reading at least that is marked at optical medium is significantly, and substantially not the interferometric optical medium read light.

26. as the optical medium of claim 25, wherein the second layer comprises at least a UV light absorbing material.

27. optical medium as claim 26, wherein at least a UV light absorbing material comprises 2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-yl) phenol, 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methyl-phenol, the potpourri of 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) methyl propionate and PEG30 reaction product, side chain and straight chain 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, 2-(2 ' hydroxyl-5 ' methylacryoyloxyethyl phenyl)-2H-benzotriazole, 2,2 '-dihydroxy-4-methoxy benzophenone, a kind of in Octabenzone and the octyl methoxycinnamate.

28. as the optical medium of claim 26, wherein the second layer comprises at least a UV light absorbing material of the about 20wt% of about 5wt%-.

29. an optical medium has at least one layer that comprises at least one group of photosensitive quality material, wherein said at least one group of photosensitive quality material optical medium read in the zone formation at least one substantially not the interferometric optical medium read the mark of light.

30. as the optical medium of claim 29, wherein the form of optical medium comprises at least one in substrate layer, adhesive linkage, semi-reflective layer, reflection horizon and the protective seam.

31. as the optical medium of claim 29, wherein at least one is marked at and forms when comprising in UV-A, UV-B, the UV-C wavelength at least one the photosensitive quality material of wavelength illumination group.

32. as the optical medium of claim 29, wherein mark is illustrated in a plurality of layers the overall appearance.

33. as the optical medium of claim 29, wherein mark is passed in time and is faded.

34. as the optical medium of claim 29, wherein mark comprises at least a in identifying information, authentication information, command information, enciphered message and the promotion message.

35. as the optical medium of claim 29, wherein mark comprises at least a in image, alphabetic character, symbol, figure, data code symbols system and the digital watermarking.

36. as the optical medium of claim 29, wherein mark is not interfered the wavelength of about 400nm, about 440nm, about 630nm, about 650nm and about 780nm substantially.

37., also comprise the color enhancement additive as the optical medium of claim 29.

38. as the optical medium of claim 29, wherein mark comprises at least a in colourless mark, monochromatic mark and the multi-color marking.

39. a method of making optical medium comprises:

Selection comprises the prescription of at least one group of photosensitive quality material, wherein said at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source, wherein, when forming, described at least one mark reading on the zone at least of present optical medium, and do not interfere the light of reading of described optical medium substantially; With

In at least a portion of at least one layer of optical medium, apply prescription.

40., wherein apply and comprise the spin coating prescription as the method for claim 39.

41. as the method for claim 39, wherein apply and comprise by the exposure first kind of photocurable formulation of filling a prescription, described first kind of light comprise basic with comprise one group of wavelength that mark light wavelength component is opened.

42., wherein apply and comprise by forming potpourri with the base material mixing formula and applying potpourri to optical medium as the method for claim 39.

43., wherein apply potpourri and comprise injection moulding as the method for claim 42.

44., comprise that also at least a portion by exposing at least one layer forms image to the mark light that forms pattern as the method for claim 39.

45. as the method for claim 44, wherein exposure comprises the use photomask and a kind of of laser instrument that write direct.

46. as the method for claim 39, also be included at least a portion of at least one layer and apply the another one layer, wherein said another one layer comprises the material that absorbs mark light.

47. optical medium, has at least one ground floor, described ground floor comprises the polyether-modified dimethyl silicone polymer of about 0.3wt%, the trimethylbenzene formyl oxidation diphenyl phosphine of about 10wt%, the stable liquid potpourri of alpha-alcohol ketone and benzophenone derivates, the 1,6 hexanediol diacrylate of about 10wt%, the tetrahydrofurfuryl acrylate of about 15wt%, the ethoxylation of about 32.35wt% (4) tetramethylol methane tetraacrylate, height propoxylation (5.5) glycerol tri-acrylate of about 32.35wt%, the triphenyl sulfonium fluoroform sulphonate of about 3wt% and wavelength absorption peak are the colour coupler of about 540nm.

48. the optical medium as claim 47 also comprises:

Be arranged at least one second layer at least one ground floor, the second layer comprises 2 of about 10wt% in base-material, 2 '-dihydroxy-4-methoxy benzophenone, described base-material comprise the crosslinkable silicone polyether acrylate of about 1wt%, the trimethylbenzene formyl oxidation diphenyl phosphine of about 8wt%, the stable liquid potpourri of alpha-alcohol ketone and benzophenone derivates, the 2-phenoxyethyl acrylate of about 26wt%, the difunctionality bisphenol-A basic ring oxypropylene acid esters that is mixed with about 50%2-phenoxyethyl acrylate of three (2-hydroxyethyl) isocyanuric acid ester triacrylate of about 20wt% and about 45wt%.

49. an optical medium has protective seam, described protective seam comprises the prescription that contains at least one group of photosensitive quality material, and wherein said at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, described at least one to be marked in the optical medium be tangible.

50. an optical medium has adhesive linkage, described adhesive linkage comprises the prescription that contains at least one group of photosensitive quality material, and wherein said at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, described at least one to be marked in the optical medium be tangible.

51. an optical medium has substrate layer, described substrate layer comprises the prescription that contains at least one group of photosensitive quality material, and wherein said at least one group of photosensitive quality material is suitable for forming at least one mark when being exposed to the mark light source; Wherein, when forming, described at least one to be marked in the optical medium be tangible.

Images