System for applying markings to optical media

The present invention relates to a method and an apparatus for rapidly producing a high quality image on the reading side of an optical medium.

Optical media, as is commonly used today, contain a variety of complementary information in addition to the data recorded on the optical media. The complementary information is often displayed in complex form and is suitable for marketing, advertising, or other purposes of the manufacturer. The complementary information may be included in various forms, such as with the use of sticking labels, inks, and other techniques.

Considering that about 1 billion DVDs and more than 4 billion CDs are produced annually (according to estimates by the International Recording Media Association), the potential advertising space is 1 billion pages when converted to magazine ads, newspapers. When converted to advertisements, it is equivalent to 300 million pages, and when converted to advertising versions, it is equivalent to 3 million pages. Therefore, it is very valuable to incorporate the marking on the read side of the optical medium.

Labels or markings are typically affixed to the "non-read" side of a disc, such as a CDROM or DVD, to indicate information such as the origin of the disc or a list of information recorded therein. Placing the markings on the non-read side of the optical media makes it possible to use a wide variety of marking techniques, from simple markings to complex markings. Placing the markings on the read side of the optical media is very difficult, especially in the data recording area, as the markings can interfere with the use of the optical media.

There is a need for more advanced marking methods. This need is growing rapidly with changes in optical media technology. For example, in DVD-10 and DVD-18, which are examples of embodiments of DVD optical media, recording and presentation of magnetic data are required on both sides of the optical media. As a result, manufacturers are therefore unable to incorporate conventional durable labels or markings on optical media.

Attempts have been made to achieve this challenge. Citing a US patent made for an optical storage system. For example, Li published on August 27, 1996. US Pat. No. 5,549,953 by Mr. Li, the title of the invention "Optical recording media with optical variable safety characteristics", is a printed matter by introducing a thin film structure with optically changing safety characteristics and coded optical data. Discloses a variety of anti-counterfeiting techniques. Another US patent is Patent No. 5,510,160 by Sullivan et al., Issued August 23, 1996, entitled "Optical Recording Media with a Visible Logo". This patent also discloses anti-counterfeiting technology for optical storage media, especially by creating a visible logo on the read side of the printed matter. These patents provide for the inclusion of markings with certain advantages, but all advantages are limited. That is, for example, markings are visible only under certain conditions, requiring a complex or costly manufacturing process to produce the final product. Moreover, the degree of control, or marking complexity, may be less than desired for effective advertising or other communication methods.

Other examples of coatings on optical media can be found in US Pat. No. 6,051,298, "Optical discs with protective film." This patent discloses an optical disc having a protective film, which has high transmittance and high hardness against abrasion. In addition, U.S. Pat. No. 6,322,868 B1 "Use and Manufacture of Application of Polymer / Dye Thin Film Coatings to Improve the Quality of Recording and Reading of Optical Storage Media" aims to improve the quality of encoded magnetic information. The use of thin film coatings is open to the public. Another example includes US Pat. No. 6,338,933, "Rendering Methods and Devices for Non-Readable Optically Coded Media." The patent discloses that it includes an optically activated material to reduce the reflectance of the surface.

However, the aforementioned patents do not take advantage of certain advantages of the material. For example, the international patent gazette WO 02/101462 A1 Laser Marking Method published on December 19, 2002 and filed by Ciba Specialty Chemicals Holding Inc is cited. This publication discloses a method for coloring a polymer material containing a latent oxide which is a coloring agent, and a constituent substance which can be further selected by irradiation with ultraviolet rays. Another international patent gazette WO 02/100914 A2 is an invention "polymer material containing latent oxides" filed by Ciba Specialty Chemical Holding Inc. This publication further discloses polymeric materials containing latent oxides that can be converted to acids by laser irradiation and any constituents.

Another example is disclosed in US Pat. No. 5,028,792, "Exposure Visualization System for Ultraviolet Radiation," issued by Mullis on July 2, 1991. The patent discloses a photochemical system for direct visualization of exposure to UV radiation, where photoacids are formed by irradiation with UV light and pigments are generated by visible color change. However, their use is not suitable for optical media as these materials polymerize with later added color formers. Therefore, these materials do not reach the cured state required for manufacturing optical media.

Yet another example is disclosed in US Pat. No. 5,885,746, issued by Iwai et al. On March 23, 1999, "Photosensitive resin composition, photosensitive printing board using the same composition and printing original plate manufacturing method". Has been done. In this patent, high polymers, monomers, photopolymerization initiators that form atomic bonds upon exposure to visible light, color formers that develop colors in the presence of acids, and exposure to wavelengths from 200 nm to 380 nm A photosensitive resin composition composed of an optically activated acid-producing agent that produces an acid is disclosed. In particular, this patent discloses the use of non-uniform dispersion agents, a property that causes laser scattering in optical media readout systems. Also, the initiator disclosed in this patent reacts to visible light, requiring the use of an oxygen barrier layer that affects proper curing. The use of oxygen barrier layers is a major obstacle to the application of these materials to large numbers of optical discs, as the manufacturing environment generally does not provide a dark and / or anoxic environment. In addition, such additional steps pose an economic and manufacturing burden that affects restrictions on the use of marking systems.

Therefore, enhanced marking, identification, authentication, and coding capabilities need to be provided to media containing optically readable information. That is, there is a need to quickly create images, text, or other optically coded information on the label and / or read side of the optical media. Furthermore, this method must not interfere with the execution of data reading from the optical media. Systems that provide these capabilities also need to provide robust and durable markings in the environment in which the optical media is used.

There is also a need to provide an optical media or disk manufacturing system to meet the aforementioned needs, such as enhanced marking, identification, authentication, and coding capabilities.<patcit num="1"><text>U.S. Pat. No. 5,549,953</text></patcit><patcit num="2"><text>U.S. Pat. No. 5,510,160</text></patcit><patcit num="3"><text>U.S. Pat. No. 6,051,298</text></patcit><patcit num="4"><text>U.S. Pat. No. 6,322,868B1</text></patcit><patcit num="5"><text>Publicly owned U.S. Pat. No. 6,338,933</text></patcit><patcit num="6"><text>U.S. Pat. No. 6,338,933</text></patcit><patcit num="7"><text>International Publication WO 02/101462A No. 1 Gazette</text></patcit><patcit num="8"><text>International Publication WO02 / 100914A No. 2</text></patcit><patcit num="9"><text>U.S. Pat. No. 5,028,792</text></patcit><patcit num="10"><text>U.S. Pat. No. 5,885,746</text></patcit>

The aforementioned and other problems are overcome by the methods and devices disclosed herein, and by the methods and devices according to the embodiments of the present invention.

Disclosed is an image transfer method and apparatus for reading and / or non-reading an optical medium such as a CD or DVD. Aspects of the invention include, but are not limited to: Applying a material on an optical medium as a coating (s), curing the coating with the first light, such as UV, or treating each coating with a second light of a certain wavelength, such as UV, infrared, or near infrared. , Selectively expose the coating to a second light of constant wavelength and record an image on the bonding surface of the coating.

Aspects of the present invention include coating and marking on the read or non-read side of the optical media without impairing or substantially impairing the functionality of the medium.

Aspects of the invention further include monochromatic or multicolor images or markings formed on the bonding surfaces of the coating, in which case the markings are transmissive or substantially transmissive to the wavelength of interest. Created in form. For example, the marking is transparent to the read wavelength used when reading the optical media marked by the color image.

Aspects of the present invention further include, but are not limited to, the use of coatings that absorb or reflect light of a predetermined wavelength, the use of multiple markings, and the use of markings as a security measure.

A further feature of the present invention includes provisions for marking other markings on the non-read side of advertisements, brands, and ordinary media on the read side of optical media.

As disclosed herein, equipment associated with the production of coated optical media suitable for marking applications includes, but is not limited to, optical media integrated manufacturing equipment. In this case, the integrated device will be modified appropriately to accommodate the embodiments described herein. Alternatively, the device may include the use of manual or semi-automated techniques for the generation of coated optical media and its marking.

Another aspect of the present invention also includes the use of test and inspection techniques for determining conformity and / or controlling the manufacture of optical media from various aspects. For example, the manufacturing process may include the process of evaluating the optical quality of the coating prior to marking. Alternatively, the manufacturing process may include a step of quality inspection of the statistical majority of the final product. For example, a CCD camera or processor, or similar device, may be employed to image the various appearances of product markings and compare them with data records that describe the target display quality of each appearance.

The above description of the invention and other functions will be further clarified by reading the following detailed description of the invention in conjunction with the accompanying drawings.

The teachings of the present invention describe a coating, or series of coatings, for applying at least one grayscale, monochromatic or multicolor marking to an optical medium such as a CD (compact disc) or DVD (digital versatile disc). .. It also discloses the components of the optical media manufacturing system characterized by these markings. Aspects of the invention include, but are not limited to: Apply certain materials on the optical media as coatings (including multiple); cure the coating with a first light such as UV; treat each coating with a second light of a certain wavelength such as UV , The coating is selectively exposed to a second light of a constant wavelength and an image is recorded on the bonding surface of the coating. Layers may be added to the coating and the procedure is repeated as default. Further aspects of this teaching include inspection of coated optical media and techniques for its manufacture.

The optical media marked according to the teachings of the present invention should be manufactured in a mass production environment. Therefore, the disclosures herein are made according to the demands of the mass production environment. For example, a mass production environment generally requires a minimum production time, which requires quick curing and image formation. Some of the embodiments disclosed herein may be further enhanced to accommodate other production models, such as stand-alone production, and to take advantage of longer cure times or alternative imaging techniques. You should be aware of that. Such enhanced examples are considered part of the teachings herein and are described in the appended claims.

The disclosure contents of the present invention are shown in the following sections. I.

II. <u style="single">Optical media coating</u>A. Development of single layer coating 1. General preparation 2. Photoacid generator screening 3. Curing considerations Four. Oxygen suppression Five. Color and image formation 6. Environmental impact 7. Triethylamine fading studies 8. 8. Light resistance accelerated test 9. Retesting photoacid generators Ten. Absorption spectrum of photoacid generator and membrane 11. 11. Screening of photoacid generators required for imaging speed 12. Color enhancement additive 13. Spin coating, film thickness and light density B. Development of multi-layer coating 1. Development of color coating and protective film 2. Initial test 3. Environmental testing Four. Adjustment of 2-layer coating formulation Five. Amine test 6. Qualitative research 7. Physical properties of the coating 8. 8. Viscosity vs. temperature 9. Viscosity vs. displacement Ten. Color formation with various lamps 11. 11. Ratio of photoacid generator and color former 12. Lamp effect 13. Protective film: Light resistance of protective film with various UV absorbers C. Optical media coating example 1. 2-layer coating 2. Multi-layer coating 3. Multicolor disc<u style="single">II. Marking formation</u>A. Marking forming equipment B. Marking type<u style="single">III. Coating inspection</u>A. General inspection equipment B. Study of coating conditions and radial noise C. Inspection technique<u style="single">IV. Manufacturing system</u>A. General manufacturing equipment B. General offline manufacturing equipment C. Singulus SKYLINE DUPLEX coating conditions and radial noise D. Curing action of Singulus SKYLINE DUPLEX and lamp<u style="single">I. Optical media coating</u> The coatings disclosed herein are suitable for incorporation into various components of optical media. It is recognized that there are many types of optical media, many of which, at least in part, have a structure that differs from other optical media. Accordingly, the present disclosure teaches what is considered an embodiment (but not limiting) of incorporating a coating into an optical medium. That is, this disclosure does not provide a comprehensive disclosure that incorporates coatings into optical media.

FIG. 1 shows an aspect of a typical optical medium. FIG. 1 shows the prior art optical media 8. The optical media 8 includes various layers referred to herein as "components" of the optical media 8. The substrate layer 16 is formed by pits 5 and lands 6 (data feature) and is generally made of polycarbonate or similar permeable plastic material. The reflective layer 14 is placed on a data portion that allows reading by a query laser. The protective film layer 12 is one of the commonly included components to ensure the integration of the reflective film 14, and is generally formed of UV curable acrylate or similar material. The disc may be read through the substrate layer 16 as indicated by the direction of the arrow in FIG. Generally, printing or other pasting is placed on the protective film layer 12.

FIG. 2 provides a cross-sectional view of the optical media 10 and is the first installation example to which the coating 100 is applied. In this figure, the optical media 10 includes a reflective (reflective) layer 14 and a base layer 16. In a typical embodiment, the base layer 16 is made of polycarbonate and the reflective layer 14 is metallized (where reflective metal is attached). Since it is recognized that the sides of the reflective layer 14 and the substrate layer 16 are generally determined by the specifications of the optical media 10, details are generally not discussed here. Disc 10 generally contains pits 5 and lands 6 as data parts. As disclosed herein, the coating 100 is preferably applied to the substrate layer 16 of the optical media 8. In some embodiments, the sides of the substrate layer 16 are adjusted for subsequent formation of the coating 100. For example, the base layer 16 may be installed with a reduced thickness so as to be determined by referring to the specifications of the manufacturer according to the type of the optical media 8. After that, by installing the coating 100, the thickness of the optical media 10 is increased, and the specification of the preferable thickness is satisfied.

Coating 100 contains a coloring material necessary for producing a color image. Coloring materials are constructed in a variety of ways, as discussed in detail here. Coloring materials are used to develop grayscale, monochromatic, or multicolored markings. The coating 100 does not interfere with, or substantially does not interfere with, the reading of the optical media 10. That is, the coating 100 and any markings recorded on the coating 100 do not absorb or scatter light to the extent that it can be perceived at the readout wavelength of the optical media readout laser. Similarly, the thickness of the coating 100 and other aspects do not substantially interfere with the readout mechanism. Therefore, the coating 100 can be applied to the "regenerated" side 16 or the "non-regenerated" side 12 of the optical media 10 shown in FIG.

Coating 100 includes what can be referred to as two "sets" of photosensitive materials. One set of photosensitive materials accelerates the curing of the coating 100 when the coating 100 is placed. That is, exposure at one set of wavelengths causes curing of the first set of photosensitive materials. The second set of photosensitive materials in coating 100 will show optical changes upon proper exposure at another set of wavelengths. As such, the coating 100 may include a photoinitiator that initiates cross-bonding. The coating 100 may include, but is not limited to, a complex such as a photoacid or a photobase-forming agent, an acid or base-reactive dye, a leuco dye, a metal chelate, a fluorescent dye, or a laser dye. Coating 100 may appear colored or colorless to the eye and may fluoresce under certain electromagnetic radiation. The wavelength of fluorescence emission includes, but is not limited to, the wavelength in the visible region.

The wavelengths of the readout light commonly used in the optical media 10 are 408 nm, 440 nm, 630 nm, 650 nm and 780 nm, but other readout wavelengths are also possible.

Although a photosensitive material that reacts to ultraviolet (UV) wavelengths is disclosed here, the coating 100 may include a material that is sensitive to any wavelength band (also referred to as a "series of wavelengths"). For example, photosensitive materials react to UV-A, UV-B, UV-C, VIS (visible wavelength), shortwave infrared (IR), IR or longwave IR. As inferred, having two sets of wavelength materials allows the use of two sets of wavelengths to initiate a change in the coating 100, as described herein. In other formation processes not discussed here, wavelengths other than the spectrum of wavelengths used may be favorably used. Therefore, the teaching here is merely an example of a marking coating system on an optical medium, and is not limited to a typical embodiment here.

"Optical media" here refers to general terms such as "CD" or "DVD". However, optical media 8 is known to include a number of different media formats. For example, many formats for optical media 8 include: DVD5, DVD9, DVD10, DVD14, DVD18, DVD-R, DVD-RW, CD-Audio, CD-Video, CD-R, CD-RW, CD-ROM, CD-ROM / XA, CD-i, CD- Extra, CD-Photo, Super-Audio CD, Mini Disc composite format including one or more of the above, Blu-Ray, etc. It is well known that this is not a complete list and is therefore only considered as an example of the various optical media formats that may benefit from the use of the present invention. <u style="single">A. Development of single layer coating</u> The mode of development of the coating material is shown below. Some of the embodiments disclosed herein include experimental results. One of ordinary skill in the art will recognize that in certain settings, one embodiment has certain advantages over other embodiments. Further embodiments may also be developed. Therefore, it should be recognized that the formation of coatings and the formation of applications and the process thereof are exemplary and do not limit the invention.

1. General preparation Initially, attempts were made to create photosensitive color paints by combining acrylates, photoinitiators, photoacid generators (PAGs), and color formers. One of the first formulations to be preferred was composed of about 3% photoacid generator (PAG), about 3% color former, and about 94% mixture called "coating base". The coating base is formed of a mixture containing an acrylate and a photoinitiator. Currently, preferred examples of coating bases are typically a mixture of monomeric acrylates and oligomers, wetting agents, and photoinitiators. Color formers and photoacid generators are called "imaging components" and are added to the coating base.

Early experiments on the development of suitable coating-based materials included a mixture of acrylates in which SR-494 and SR-238 were mixed in approximately equal amounts. The photoinitiator ESACURE KTO-46 was added to the acrylate mixture to make up about 10% of the initial coating base.

The chemical substances corresponding to these materials are as follows. SR-494 is pentaerythritol ethoxylate (4) tetraacrylate. SR-238 is hexanediol 1,6 diacrylate having a low viscosity, fast curing monomer with a low volatility, hydrophobic backbone and good solubility in the use of free radical polymerization. And ESACURE KTO-46 is a stabilized liquid mixture of trimethylbenzoyldiphenylphosphinic acid, α-hydroxyketone, and benzophenone derivatives. ESACURE KTO-46 is a liquid photoinitiator that can be incorporated by simply mixing it with a resin system, is insoluble in water, and is soluble in most common organic solvents and monomers. KTO-46 is sometimes called ESACURE KIP-150 or ESACURE TXT. ESACURE KIP-150 is an oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], and ESACURE TZT is 2,4,6-trimethylbenzophenone and 4-methylbenzophenone. Is a liquid eutectic mixture of.

ESACURE KTO-46, ESACURE KIP-150 and ESACURE TXT are manufactured by Lamberti Spa in Gallarate-Va, Italy. SR-494 and SR-238 are manufactured by Sartmer Corporation in Exton, Pennsylvania. KTO-46, like SARCURE-1135, is also sold by Sartomer Corporatio (hence, KTO-46 and SR-1135 are used interchangeably here).

A study of the properties of Coating 100 using the first coating base revealed certain disadvantages. That is, it has been acknowledged that the final product formed from the first coating base does not exhibit the desired surface hardness and can irritate the skin. Therefore, other components were also evaluated for use on a coating base. Table 1 shows the mode of the components selected for the coating base and includes their performance characteristics.

<tables num="1"><img file="JP4530273B2_D0001.tif" /></tables> SR-285 is a tetrahydrofurfurylacrylic acid, a low-viscosity, polar monotube group monomer containing cyclic groups that promotes adhesion to multiple substrates. SR-9021 is also a highly propoxylated (5.5) glyceryl triacrylate, which provides low viscosity, good flexibility, fast curing, excellent hardness, less skin irritation, and trifunctionality. It is a monomer of. SR-285 and SR-9021 are products of Sartmer Corporation of Exton, PA.

SR-494 and SR-9021 were selected for use in coating bases due to their high functionality, low surface tension, fast surface and cure result reaction, tackiness, and hardness. These components are also considered an advantage as they are less prone to skin irritation due to alkoxylation. In contrast, SR-238 and SR-285 irritate the skin but provide the additive with the desired solvent and cause the polycarbonate to swell upon good adhesion. SR-238 and SR-285 also show low viscosity, giving them the opportunity to adjust the viscosity of the coating base. KTO-46 was selected for use as a photoinitiator because it is considered to be substantially sensitive to long waves of ultraviolet light (ie, above about 320 nm to 400 nm).

Experiments have further revealed that applying the coating 100 to the optical media 10 is feasible with a variety of techniques. The coating 100 is preferably applied by spin coating. However, during the initial application of Coating 100 by the use of spin coating, the edges of the optical media 10 were often less than intended. It was determined that this was due to the high surface tension of the paint (coating base). Therefore, a wetting agent was added to the coating base to improve the wetting of the substrate and reduce the surface tension.

Typical systems for forming spin coatings on substrate 16 include Headway Research, Inc.'s system in Garland, Texas. The systems used here to perform the formation by spin coating include: Formation temperature control controller, a controller that has a maximum rotational speed of at least 10,000 (10K) rpm and increases or decreases the rotational speed in certain increments. The system also has components such as an environmental control device that controls the environmental gas and a formulation recovery device that recycles unused formulations. Other systems are used for spin coating and may be further integrated into mass production equipment. One of the models suitable for application of the formulation here is at least a small quantity batch production, and as described here, the model of the PWM32-PS-R790 rotation system used in the test. Since spin coating systems are well known, these systems will only be described here in general with respect to the application of coating 100 and its requirements.

To see how it affects the performance of Coating 100, all of the new components (Table 1) were added to create a formulation. Wetting agents were included in the new formulation to allow the formulation to be more widely distributed on Disc 10. The wetting agents tested were BYK-307 and BYK-333, both of which are polyether-treated poly-dimethyl-siloxanes and exhibit properties similar to reduced surface tension. BYK-307 and BYK-333 are products of BYK-Chemie of West Germany and are sold in the United States by BYK-Chemie USA of Wallingford, Connecticut. Table 2 shows the formulations and results.

<tables num="2"><img file="JP4530273B2_D0002.tif" /></tables> Table 2 shows a total of 10 formulation components. The first coating base is shown for experimental use and the other formulations are shown as mixtures 1-9. The amount of each component of the 10 formulations is expressed as a weight percent of the total mixture.

This result indicates that the preparation containing the wetting agent has a reduced surface tension as compared with the preparation containing no wetting agent. This is considered to be an advantage because the coating of the base 16 is superior to the preparation having a high surface tension in the preparation having a low surface tension. However, after adding 0.3% BYK-333 and 0.05% BYK-307, the surface tension of the formulation does not change substantially. Thus, formulations 3 and 7 were physically tested by spin-coating a coating base onto a variety of discs 10 and inspecting the edges of the base 10. This test revealed that Formulation 3 had the best coating on Disc 10 while substantially improving surface smoothness. However, the viscosities of the various formulations did not change substantially between Samples 1-9. As a result, Formulation 3 was selected as the preferred coating base.

Immediately after this experiment, it was found that SR-9021 and SR-9020 can be used synonymously because SR-9021 and SR-9020 have similar properties. This is considered an advantage as the SR-9020 provides better thermal stability than the SR-9021. Therefore, SR-9020 is used as an alternative to Formulation 3. SR-9020 is a 3-molar propoxylate glyceryl triacrylate, a trifunctional monomer that provides low viscosity, high flexibility, fast curing and excellent hardness. SR-9020 is a product of Sartmer Corporation. The new components and performance of the formulations are shown in Table 3, and the formulation and viscosity results are shown in Table 4.

At about the same time, several formulations with different acrylates were created to find paints that achieved a harder coating. Table 3 shows the new components for the formulations and aspects of their performance, while Table 4 shows the formulations and viscosities.

<tables num="3"><img file="JP4530273B2_D0003.tif" /></tables> The components shown in Table 3 are trade names of Sartmer Corporation and are used for: Propoxylate (3) glyceryl triacrylate (SR-9020), ethoxylate (3) trimethylolpropane triacrylate (SR-454), tris (2-hydroxyethyl) isocyanurate triacrylate (SR-368), dimethylolpropane Tetra acrylate (SR-355) and urethane acrylate (CN-983).

<tables num="4"><img file="JP4530273B2_D0004.tif" /></tables> Inspection of the rotating coating and cured sample revealed that formulations 10 and 14 had similar viscosities but were significantly superior in hardness to the subject (formulation 3). Formulations 10 and 14 were subsequently subject to several trials consisting of the new formulation screening trials shown in Table 5. In a preferred embodiment, each formulation must pass the screening in order to be considered a candidate for a coating 100 base. Table 5 shows not only the conditions but also the related tests.

<tables num="5"><img file="JP4530273B2_D0005.tif" /></tables> As shown in Table 6, two new formulations passed the new formulation screening trial. Formulation samples 10 and 14 were considered for future use and more detailed studies.

<tables num="6"><img file="JP4530273B2_D0006.tif" /></tables> 2. Screening for photoacid generators A photoacid generator (PAG) is added so that the coating 100 develops color when exposed at a wavelength of light. This process involves the production of acids by PAG during exposure at light wavelengths. The acid-reactive color former (CF) interacts with the acid one after another to form a color. It is desirable for PAG to react to UV light.

Several photoacid generators were tested to find a photoacid generator that worked well with Coating 100. Each formulation is prepared in the same way to compare different PAGs. The performance required of PAG includes proper acid production for the desired color formation and stability in the post-color formation environment.

Coating-based samples were prepared by mixing the first target formulation (45% SR-494, 45% SR-238, and 10% KTO / 46). A concentration of 3% of COPIKEM 16 Red (color former) and a concentration of 3% of each photoacid generator to be tested were added to 94% of the mixture. The paint was spin-coated on a blank, non-metalized, polycarbonate base 16 at 4K rpm for 15 seconds. Each disc 10 was then placed under a double-framed pulsed Zenon lamp with a windowpane filter for 5 seconds. The resulting disc 10 has a clear, dry, hard coating. Then, a part of the disc 10 is exposed for 5 seconds. Another part of the disc 10 is exposed for 10 seconds. As a result, the transparent disc 10 was produced in red with different intensities in each part. To quantitatively measure the color intensity formed on the exposed disc 10, the absorbance curve was recorded with a spectrum measuring instrument. The spectrum measuring instrument used was LAMBDA manufactured by Perkin Elmer Corporation in Boston, Massachusetts. It is a UV / VIS model called 2. The prepared data revealed that the peak absorbance of the formulation containing COPIKEM 16 Red occurs at about 540 nm. A typical absorbance curve is shown in FIG. The results are shown in Table 7. However, in Table 7, the intensity of the background color was measured in zero seconds.

<tables num="7"><img file="JP4530273B2_D0007.tif" /></tables> As a result, (tert-butoxycarbonylmethoxynaphthyl) diphenylsulfonium triflate, (4-phenoxyphenyl) diphenylsulfonium triflate, triphenylsulfonium triflate and (4-tert-butylphenyl) diphenylsulfonium triflate are strong. Gradually decreased. However, 0.5 AU is considered to be sufficient for visibility, so other factors such as cost were taken into account when selecting the desired photoacid reactant. Triphenylsulfonium triflate was chosen as the preferred choice for Coating 100. However, all photoacid generators were soluble at 3%, except for bis (4-tert-butylphenyl) iodonium p-toluenesulfonic acid and diphenyliodonium triflate. Bis (4-tert-butylphenyl) iodonium p-toluenesulfonic acid required a filter to remove most of the insoluble photoacids.

Table 8 shows the results of the three photoacid generators (PAGs). The three PAGs are Reinforced Coating Base Formulation 10 (32.35% for SR-494, 32.35% for SR-9020, 15% for SR-285, 10% for SR-238, 10% for KTO / 46 and BYK-333. It was included in 94% of 0.3%). Each photoacid generator at a concentration of 3% was mixed with the color former PERGASCRIPT RED I-6B. Comparing the three photoacid generators, (4-tert-butylphenyl) diphenylsulfonium triflate is more soluble than (4-methylphenyl) diphenylsulfonium triflate and triphenylsulfonium triflate. The formulation of PERGASCRIPT RED I-6B is monopolized and is not shown here. However, from now on, various color formers suitable for use with this teaching will be shown.

<tables num="8"><img file="JP4530273B2_D0008.tif" /></tables> 3. Curing considerations Further investigation into curing at this point led to the study of other photoacid generators, which were replaced by KTO / 46 at a concentration of 10%. Table 9 shows the experimental results of the first set with varying amounts of photoinitiator. Each sample was prepared by spin coating and then cured by irradiation with a Zenon lamp with a window glass filter for 5 seconds. Each data in Table 9 is expressed as a weight percent of photoinitiator as part of the 94% coating base. The degree of cure is established by attempting physical blurring of the coating, and the degree of cure is indicated by the following grades. E (excellent)&gt; G (good)&gt; D (normal)&gt; P (poor).

<tables num="9"><img file="JP4530273B2_D0009.tif" /></tables> The results show that the curing of samples 20, 21, and 24 is good. However, Sample 24, which contains 5% Irgacure 369, does not emit any color when exposed to UV light. Also, samples 20 and 21 containing 5% and 7% Irgacure 369 cure slightly pink. However, in addition to being insoluble, formulations 22 and 23 turned red with paint and were discarded.

DAROCUR4265 is a mixture of 50% 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 50% 2-hydroxy-2-methyl-1-phenyl-propan-1-one. Irgacure 369 is 2-benzyl-2-dimethylamino-1- (4-phenylmorpholin) -butanone-1 and is chemically prepolymerized (eg, acrylate) in combination with a single or multifunctional monomer. It is a very effective UV curing agent used to initiate photopolymerization. Irgacure 819 is a bis (2,4,6-trimethylbenzoyl) -phenylphosphinic acid, a versatile photoinitiator for radical polymerization of unsaturated resins by exposure to ultraviolet light. In particular, it is suitable for curing white pigments, polyester / styrene tempered glass fibers, and transparent coatings for outdoor use in combination with light stabilizers. Further, the thick portion can be cured by the photoinitiator. All of these are products of Ciba Specialty Chemicals, located in Basel, Switzerland and Talitown, New York.

To further improve Samples 20 and 21, CN-384 and amine synergizers were added at 0.5% and 1%, respectively. With this new addition, a very transparent cured coating could be produced. However, at 1%, the density is not sufficient in the exposed area. Unfortunately, with the addition of CN-384, it was found that the exposed part of Disc 10 showed considerable fading after about 24 hours at room temperature. (CN-384 is a dual-function amine common initiator that, when used with photosensitizers such as benzophenones, promotes rapid curing under UV light, as well as both the press side and the cured film. It has the advantages of reduced odor and reduced coating. CN-384 is a product of Sartmer Corporation in Exton, Pennsylvania.) Another experiment was performed with different combinations of the above experiments, in addition to additional photoinitiators. Again, the coating base is generally the same as Formulation 10 except when replaced with photoinitiator KTO / 46, as shown in Table 10.

<tables num="10"><img file="JP4530273B2_D0010.tif" /></tables> Irgacure 2959 is 1- [4- (2-hydroxyethoxy) -phenyl] -2-Hydroxy-2-methyl-1-propan-1-one, a highly effective non-yellow color radical photoinitiator for UV curing systems composed of unsaturated monomers and prepolymers. In particular, it is suitable for cases where it is required to suppress bad odors and for the use of water-based systems based on acrylate or unsaturated polyester resin. Activated hydroxy groups are capable of reacting with optimally functional unsaturated resins. SARCURE1124 is isopropylthioxanthone, a photoinitiator used in combination with a suitable common initiator (eg, ethyl 4- (dimethylamino) benzoate (SARCURE SR1125)) to initiate UV-free radical polymerization. .. SARCURE SR1124 is used for inks, varnishes and decorative coatings. ESACURE KIP 100F contains about 70% oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone and about 2-hydroxy-2-methyl-1-phenylpropan-1-one. It is a 30% liquid mixture.

The experimental data in Table 10 show that samples 27, 31, 32 and 37 are well cured and further research is underway. Samples 20 and 21 cured slightly pink, so spectra were collected by selecting formulations using Irgacure 819 in the cured portion immediately after curing and 24 hours after curing, as shown in FIG.

This experiment shows that as the amount of Irgacure 819 in the formulation increases, the color intensity of the cured coating increases and continues to increase. It is theorized that Irgacure 819 may act as a photosensitizer, increasing sensitivity to longer wavelengths of light and causing unwanted color development. Therefore, formulations 27 and 31 are removed due to the intensity of the cured background color.

Sample 37 cured quickly, but was considered to have an unfavorable amount of color development after curing. Therefore, another formulation was made at low concentrations of SR-1124. Other formulations were made with the addition of SR-1124, as SR-1124 appears to promote rapid curing. The experimental combinations of the third photoinitiator are shown in Table 11.

<tables num="11"><img file="JP4530273B2_D0011.tif" /></tables> Experiment III shows that samples 41 and 43 are poorly cured. Sample 43 also turned pink very quickly. Certain formulations containing SR-1124 were as expected, but the sensitizing effect of the photoacid generator SR-224 was considered negative for other properties such as UV stability of the image. It was. However, from these experiments shown in Table 9-11, potential combinations of photoinitiators were developed and if the preferred use of KTO-46 (formulation 10) showed impaired future studies. It can be used.

It is important to note further aspects of the curing of Coating 100 disclosed herein. These aspects include the filter spectrum, the curing environment, and the aspects of the curing lamp to be considered.

An important aspect in achieving both curing and imaging is the spectral region resolution capability available at each stage. As mentioned here, it is preferred that both curing and imaging be completed using the wavelength of ultraviolet light. Formulations other than those disclosed herein are found to exhibit excellent reactions at other wavelengths, and therefore the use of wavelengths specified herein is merely an example. In a preferred embodiment, a photoacid generator operating in this range can be used, and deep UV light generally does not show high density under natural irradiation (sunlight, fluorescent, or incandescent light). , Deep UV light (wavelengths less than about 320 nm) is used for imaging. It tends to provide images that are durable in environmental conditions during use. For example, the absorption spectra of two commercially available photoacid generators with a slight absorption of about 290 nm are shown in FIG.

Many photoinitiators with a major absorption band above 300 nm are commercially available. Most notably, phosphine oxide is a photoinitiator such as BASF Corporation's LUCIRINTPO (a key component of KTO46) or Irgacure 819 in Charlotte, NC, whose spectra are shown in Figures 6 and 7, respectively. Is to promote the function of. In addition, photoinitiators that exhibit absorption at wavelengths above about 300 nm are also used. Also note that these initiators are a direct split type of single molecule initiator.

Two-molecule initiators are generally composed of photosensitive molecules that are capable of absorbing light and transferring it to synergist molecules that can form radicals after energy transfer. The most common sensitizers that absorb visible light are ITX or isopropylthioxanthone. ITX is commonly used with amine synergists such as ethyl-p-dimethylaminobenzonate (EDAB) and octyl-p-dimethylaminobenzonate (ODAB). Both EDAB and ODAB can form radicals by receiving energy transfer from ITX. These components are not considered suitable for use with coatings for two reasons. The first reason is that ITX sensitizers also expose photoacids to visible light, thus limiting the spectral decomposition of curing and writing. (This occurs to some extent when using certain monomolecular photoacid generators, such as Irgacure 819, which causes the photoacid generator to be slightly sensitive to long waves of UV light). The second reason is that common covalent agents such as amines (and to a lesser extent alkoxylated monomers such as SR-494, SR-9020, SR-9021) are produced by photoacid generators. Neutralizing the acid may significantly reduce or even eliminate color formation and image stability.

See below for a study of photoinitiator types and processes. "Chemistry and Technology of UV and EB Formulations for Coatings, Inks, and Coatings, Photoinitiators for Free Radical Cation and Anion Photopolymerization, Volume 3" (2nd Edition, by JV Crivello and K. Dietliker Eds) , WILEY / SITA Series, Surface Coatings Technology Magazine, John Wiley and Sons, 1998), Chapters 1 and 2.

In addition to the requirement to have the absorption spectra of the photoacid generator and the decomposed photoinitiator (very separated from each other), for mass production, sufficient light density of each band is sufficient for curing in the minimum time. It is required that it must be dark enough for imaging. Commonly used light sources for curing UV curable coatings are metal and metal halogen arc lamps (Honle UV America, Inc., Marlboro, Mass.) Continuous wave (CW) light sources and Zenon gas arc lamps (Massachusetts). There are pulse arc lamps like the state, Woburn's Zenon).

One advantage of using optical filters or other techniques is that narrow wavelengths are created, or unwanted wavelengths are effectively eliminated. Such techniques result in better decomposition (wavelength separation of curing and imaging) and thus open up the possibilities and choices of photoinitiators, photoacid generators and their composites.

A typical mercury gas lamp produces a spectrum that is largely a line spectrum. For example, the spectrum of FIG. 8 shows the output of a medium pressure iron-doped mercury lamp commonly used in UV curable paints for paints applied to optical media 10. It can be seen that most of the output comes from the individual rays associated with the electronic transitions of the lamp additive. A similar spectrum of another metal halogen lamp of gallium iodide with different transition lines is shown in Figure 9.

These lamps generally work well with UV curing, as most of the wires are compatible with the photoinitiators used in UV curing systems. Another frequently used lamp is the Pulse Zeno gas-filled lamp, such as the Zeno lamp in Woburn, Massachusetts. The spectra of these lamps are effectively "blackbody" -like, and the spectra are derived from the color temperature of the plasma formed on the lamps during the pulse. The general spectrum of the Zenon RC-747 gas-filled lamp is shown in Figure 10.

In addition to a suitable UV light source, it must be possible to separate the long-wave UV portion from the short-wave UV portion of the spectrum in order for the coating 100 to cure first without early color formation. This is preferably achieved by using an absorption filter with the transition curve shown in FIG. During the development of Coating 100, a series of experiments were carried out to find the right combination of lamps, filters and photoinitiators to properly provide a short cure time without premature color formation. As shown in FIG. 11, the L37 filter is substantially transparent above about 370 nm.

A preferred method of coating curing consists of a combination of Zenon bulbs and L37 filter glass and the use of KTO-46 photoinitiator. Typical mercury line lamps do not produce adequate light densities when both are equipped with L37 filters, compared to Zenon lamps. Zenon lamps were chosen to cure coating 100 because the light density of Zenon pulsed lamps creates excellent properties for cured coatings.

In actual work, curing wavelength filtering is performed using cold mirror technology, where the mirror selectively reflects some part of the UV spectrum and transmits visible and infrared parts to provide only the wavelength of interest. Will be done. The technique provides the advantage of thermal control in which the absorption filter needs to be cooled while reducing the thermal buildup of the coating 100. Another approach that is considered beneficial for curing is to use different types of glasses for different UV transitions as the bulb material preserves the heat buildup of the lamp housing. This is a known approach used by most bulb manufacturers, including Zenon, which offers five bulbs based solely on the type of glass used.

4. Oxygen suppression During UV curing of free radical systems, the presence of oxygen has a detrimental effect on the curing reaction, especially in thin film coatings. Therefore, it is considered preferable to suppress environmental oxygen (air) in the curing environment. Oxygen suppression is known and described by Crivello and K. Dietliker (see Chapter 2, page 83). When the coating 100 is cured in air, oxygen reacts with free radicals and reacts with photoinitiators, monomers, or growth chain radicals to form peroxide radicals. The reactivity of the radical peroxide is insufficient to continue the polymerization process of the free radical, leading to the termination of the chain, resulting in an inadequate curing system. Methods of overcoming oxygen suppression include (1) increasing the amount of photoinitiator added, or (2) increasing the curing time. Option (2) is considered preferred over option (1) because the selected photoinitiator is relatively expensive.

A further solution to the oxygen suppression problem is to replace the atmospheric environment with an inert gas such as nitrogen. This makes all the free radicals created by UV exposure used in the polymerization process effective. Unfortunately, the use of purge gases such as nitrogen has an economic correlation due to the large amount of nitrogen required. Therefore, the cost of using purge gas must be weighed against a variety of other requirements, such as curing time and the final product of interest.

A further way to overcome oxygen suppression is to use photoinitiators that are less reactive with oxygen. These initiators tend to require short-wave UV light (&lt;320 nm) to function. Instead, the photoinitiator has a sensitizing molecule or the synergist described above. As mentioned above, the sensitizer makes the photoacid generator sensitive to visible light. This tends to reduce the spectral resolution between the curing and writing wavelength widths. Common synergists such as amines (and to a lesser extent alkoxylated monomers such as SR-494, SR-9020, SR-9021) neutralize the acid produced by the photoacid generator. This can even significantly reduce or even eliminate color formation or image stability. Therefore, this technique is not preferred for use with Coating 100.

A preferred method of overcoming oxygen suppression is to increase the intensity of the cured light, such as by using a high intensity pulsed light source such as the model RC-747 lamp sold by Zenon in Woburn, Massachusetts. In a preferred embodiment of the pulsed UV effect, the energy of each flash of light is so strong that very high concentrations of free radicals are created. This approach creates enough free radicals so that the oxygen on the surface of the coating 100 is depleted and additional free radicals can be used for curing. In this approach, energy strength is an important factor in achieving instant curing. More information on the effects of light intensity on hardening and overcoming oxygen suppression can be obtained by referring to the technical document "The Secret of Darkness" produced by Fusion UV Systems, Inc. of Gaithersburg, Massachusetts.

The use of pulsed light has demonstrated an advantage in curing the coating 100 disclosed herein because it provides high intensity light in a spectral region compatible with the color formation process. In addition, the use of pulsed light has greatly reduced the problem of oxygen suppression so that no more than necessary amount of nitrogen environment or photoinitiator is needed while keeping the cure time as short as possible.

5. Color and image formation Several different color formers have been tested with the use of Coating 100. Formulated by mixing with the base coating of the original comparative formulation (45% SR494, 5% SR238, and 10% KTO / 46) to perform a comparison of the color formers and their respective strengths. did. To 94% of the coating base mixture was added a concentration of 3% of triphenylsulfonium triflate and a concentration of 3% of the color former to be tested. Due to the wide range of colors, absorption peaks occurred at various wavelengths. Figure 3 shows a typical curve recorded with a LAMBDA 2 UV-VIS spectrum instrument. Table 12 shows remarkable results.

<tables num="12"><img file="JP4530273B2_D0012.tif" /></tables> With reference to the COPIKEM materials in Table 12, it is considered to be a specific example of the materials introduced into the formulation according to the embodiment of the present invention. In practice, these materials are no longer commercially available and are not preferred. BK-305Black, S-205Black, BK-400, Red520 are coloring materials sold by Yamada Chemical Co., Ltd. in Japan and Arlington, Virginia. Preferred examples include the use of a wide variety of PERGASCRIPT color formers, but the structures and formulations of these color formers are monopolized. However, an example of the most suitable coloring material for practicing the present invention is, on July 25, 1978, Garner et al., US Pat. No. 4,102,893, "Manufacturing a coloring agent for indole and aromatic anhydrides or heterocyclic aromatic compounds. Process, Proximity Dicarboxylic Acids, New Coloring Agents of the Class and Their Uses . By reference, the disclosure of US Pat. No. 4,102,893 is incorporated herein. For example, one color former disclosed in U.S. Pat. No. 4,102,893, which is the sixth from the top of the formulations in Table 1, has been tested according to some of the experiments shown here and for at least some purposes. It has been shown to be a color former with properties.

As a result, it was shown that the red color-developing preparations, COPIKEM 16 Red and PERGAS CRIPT Red I-6B, gave the highest color intensity. Therefore, in a preferred embodiment of Coating 100, the above color formers, and other color formers not considered herein, should be considered to be usable in the production of suitable color formations, but reddish formulations are used.

Further experiments mainly used the PERGASCRIPT Red I-6B color former. However, in some cases, the solubility of some color formers became a problem when added at 3%. The black and green color formers showed some dissolution problems on the coating base used, so these formulations were filtered to reduce the concentration to just below 3%. However, further testing of green and black color formers will probably produce improved results with a wide variety of coating-based formulations. In addition to the colorants in Table 12, PERGAS CRIPT Yellow I-3R was also tested. However, this color former showed some color formation when cured, and the effective use of PERGASCRIPT Yellow I-3R requires further research.

Formulation 3 (BYK-333 0.3%, KTO / 46 10%, SR-238 10%, SR-285 15%, SR-494 32.35% and SR-9020 32.35%) ). A well-functioning color former was then tested again to ensure that the color formation was the same. Table 13 shows the color formation with slightly different results.

<tables num="13"><img file="JP4530273B2_D0013.tif" /></tables> Tables 14 and 15 show that in 3% color formers, 3% photoacid generators, and 94% base coatings (Comparison of Formulation Control or Formulation 3 respectively), the intensity of one color is higher than the others. However, the color intensity was not modified. It may be possible to increase the color intensity in a variety of ways, including increasing the concentration of photoacid generators and / or color formers, and adding color promoters.

Later, improvements in color intensity were studied. First, the amount of the color former, COPIKE M16Red, was increased from 3% to 6% and 9%. This was done with a coating base of the remaining control comparative formulation of the mixture, leaving the amount of photoacid generator fixed at 3%. Absorption curves were obtained using a UV-VIS LAMBDA 2 spectral instrument. The results shown in FIG. 12 represent the absorption peak at 540 nm.

From Figure 12, it can be concluded that exposure to 9% COPIKEM16Red, 3% triphenylsulfonium triflate, and 88% coating base for 10 seconds gives the highest light density (OD). However, only up to 9% of COPIKE M16 Red was tested for 10 seconds. This result showed that it is possible to increase the color intensity by increasing the color former, at least to some extent. Since different color formers work differently in the same amount, specific experiments with other color formers are underway and further research is being conducted on changes in color intensity. However, as long as the color former used is soluble, it is believed that similar changes in color intensity will be achieved.

In another experiment, the amount of photoacid generator was increased as in the color former experiment. FIG. 13 shows the effect of color intensity after increasing the amount of photoacid generator (triphenylsulfonium triflate was used in this experiment) at coating 100. In FIG. 13, the combination of 6% photoacid generator, 3% color former and 91% coating-based formulation produced the most color with an exposure time of 10 seconds. It is also possible to increase the light density (OD), in which case a photoacid generator was added at 6% or more. However, when the photoacid generator was 9%, the color intensity showed a noticeable decrease. For this reason, it has been demonstrated that it is preferable to test triphenylsulfonium triflate (TPST) at concentrations between 6% and 9%. Overall, adding more color formers than photoacid generators gives favorable results and is more economical.

In further experiments, the photoacid generator and color former increased simultaneously to 6% and 9%, respectively, when the coating base was 88% and 82%. However, these formulations were not soluble and no further studies were conducted.

6. Environmental impact Early studies conducted showed that Coating 100 was environmentally sensitive. That is, the imaged or colored region of the disc 10 fades due to substantial exposure to humidity and temperature. Therefore, another study was conducted to quantitatively measure the color reduction affected by environmental influences.

Eight different formulations have been tested for color reduction and these formulations are shown in Table 14. (However, formulations are generally specified and referenced herein according to the constituents of the base coating formulation). Samples of each formulation were spin-coated on three discs 10 at 4000 rpm for 15 seconds. Disc 10 was then cured in nitrogen for 2 seconds under an L37 filter. After that, half of each disc 10 was exposed for 10 seconds. The absorption curve of each disc 10 was measured before and after the test to determine the average color reduction. In the humidity and temperature test, the disc was placed in an environmental furnace at 90% humidity and 70 ° C for 96 hours.

<tables num="14"><img file="JP4530273B2_D0014.tif" /></tables> The test results shown in FIG. 14 showed that in the presence of temperature and humidity, some formulations retained better color than others. In particular, the addition of non-alkoxylated monomers such as SR-355 (formulation 14), CN-983 (formulation 45), SR-368 (formulation 46), etc. all improved performance. This is considered to be the result of a decrease in alkoxy content (decrease in hydrophilicity) and an increase in Tg or crosslink density. The use of a triphenyl butyl derivative of triphenylsulfonium triflate (TPST) or a high concentration of photoacid generator does not substantially affect performance.

The second group of formulations was designed and prepared based on the results of previous studies. The second group is listed in Table 15. Prior to the addition of the photoacid generator and color former, all basic components were added and mixed. The components, SR-368, CN-983, CN-120, were liquefied on a hot plate prior to addition. Once the basic components were mixed and homogenized, 3% photoacid generator was added to the individual batches. Formulations 53, 55 and 57 did not dissolve and these batches were discarded. The components of the base coating formulation 10-based formulation did not dissolve as easily as the others, but eventually did. When all the photoacid generators were dissolved, the color former was added in an amount of 3% of the total weight of each batch. All formulations dissolved without problems and no mixing problems occurred with the addition of color formers. Each formulation was then filtered with a 5 micron nylon syringe filter. The colors of all formulations were initially pale to pale pink or yellow.

SR-506 is isobornyl acrylate, which is an excellent reactive diluent for oligomers. CN-120 is a bifunctional bisphenol A-based epoxy acrylic. Both are products of Sartmer Corporation.

Each formulation is manually coated on 5 polycarbonate discs 10. Each disc 10 is then cured under a Zenon pulsed lamp at a distance of approximately 5 inches using a nitrogen environment and an L-37 filter. Formulation 56 was very thick but well coated. Formulation 10 cured in 2 seconds. The remaining samples of the formulation cured in 4 seconds as they only contained 5% photoinitiator. Then half of each disc is exposed to the lamp for 10 seconds to form a red color. All discs 10 were sequentially scanned using an ultraviolet spectrum instrument to measure light density at 540 nm (both cured and exposed).

<tables num="15"><img file="JP4530273B2_D0015.tif" /></tables> The study also evaluated changing the wetting agent from BYK-333 to a crosslinkable siloxane. Several reactive wetting agents were tested, including three RAD products from TEGO (RAD2250, RAD2200N, RAD2100). The performance of these products was tested using Formulation 48. As a result, TEGO RAD2200N, which had the lowest surface tension and was transparent, was selected. The results of the test are shown in Figure 15. TEGO RAD2250 and RAD2200N are crosslinkable silicone acrylic acid polyethers, respectively, and TEGO RAD2100 is a crosslinkable silicone acrylate. TEGO products are available from Tego Chemie Service GmbH and are sold in the United States by Degussa Tego Coating &amp; Ink Additives in Hopewell, Virginia.

The three discs 10 of each formulation were placed in an environmental oven at a temperature of 70 ° C. and 100% relative humidity for 96 hours. Disc 10 containing formulations 4 and 5 was stored in a translucent disc container for comparison. When the disc 10 was removed from the container, all discs 10 of each formulation (10, 48-51) were again scanned at 540 nm to measure the difference in light density. Comparative data are provided in Figures 16 and 17.

From the data, it is clear that the difference in viscosity affects the thickness of the film and the color produced by constant exposure. Therefore, the thick, that is, the dark coating 100 has more severe fading, but retains the color more than the lightly applied coating 100, so that the color reduction is not necessarily a clear guideline for the performance. However, in the first estimate, the rate of color reduction is an indicator of the relative stability of a particular underlying imaging chemical.

Formulation 59, based on bisphenol A diacrylate and SR-355 (Di-TMPTA), was considered to have the best performance in the group tested. Once applied, the coating 100 formed from formulation 59 is a highly crosslinkable, high Tg, non-alkoxylated film. All other coatings contained large amounts of alkoxylated monomers, which were low in Tg, hydrophilic, and provided a basic environment. Therefore, the third group of formulations was devised to test the CN-120 formulation and the effect of alkoxylation on image stability.

The best formulation without CN-120 was tested in parallel with a series of CN-120 formulations. The state of preparation of these preparations and the performance of each are shown in Table 16. Also tested was CN-132, a low-viscosity aliphatic compound diacrylate manufactured by Sartmer Corporation. Finally, tests were conducted to determine if the aliphatic urethane acrylate CN-983 could be used like CN-120. The results showed that only the CN-120 formulation provided excellent image retention. Of particular interest was formulation CN-120-R, the only formulation using the alkoxylated monomer SR-454. The performance of this formulation was poor, again showing that alkoxylation was negative for image retention. CN-132 generally failed, and the CN-983 formulation did not produce results similar to CN-120. CN-132 is a diacrylate oligomer of a low-viscosity aliphatic compound and is a product of Sartmer Corporation.

From this experiment, Formulation 61 was selected for further development because of the excellent combination of cure rate, film strength and excellent image stability. CN-120 and SR-368 monomers were difficult to work with, so liquefied CN-120-B60 (60% CN-120 for SR-238) and SR-368D (SR-368 for TMPTA) 85%) will be substituted for future manufacturing due to its ease of handling.

<tables num="16"><img file="JP4530273B2_D0016.tif" /></tables> The final development of the CN-120 formulation was a coating against sunlight and fluorescent light by optimizing the concentration of photoacid generators and adding UV absorbers (addition of UV absorbers will be further explained elsewhere). It started with the start of an attempt to reduce the sensitivity of the. That is, the fourth environmental experiment included preparations in which the concentration of the photoacid generator and the concentration of the UV absorber in the subsequent exposure test were changed. The composition of these preparations is shown in Table 17.

In addition, two rotation speeds (4K and 6K) were used to test the effect of changes in the thickness of the coating 100 on image stability. In addition to thickening, the thickened coating 100 film was expected to give good results in environmental tests. Preparations without UV absorbers are prepared as before, including curing for 2 seconds in a nitrogen environment using L37 filter glass under a Zenon "C" bulb about 1 inch away. Was done. Disc 10 was imaged by irradiation at a distance of about 5 inches for about 10 seconds. Formulations containing UV blockers were also imaged at a distance of approximately 5 inches from the lamp for a total of 30 seconds (15 seconds x 2 imaging sessions). Due to the long color formation time of these formulations, a long exposure time was given.

The results, even when replaced with liquid components (CN-120-B60 and SR-368D), with the use of 2% or 3% photoinitiator, are practically almost inferior to image stability and color formation. Indicates that it has no effect. However, the color of the photoacid generator always became stronger when used in a large amount, but the lower the concentration, the better the ratio of color retention. With the addition of UV stabilizers, there is virtually no deterioration in environmental stability (5% addition) to moderate deterioration in environmental stability (10% addition). However, the final color of these formulations became weaker.

SR-368D is a tri (2-hydroxyethyl) triacrylic acid isocyanurate, a clear liquid triazine compound used in free radical polymerization. CN120B60 is a hexanediol diacrylate in which a bifunctional bisphenol A-based epoxy acrylate is mixed with 40% SR-238. CN120B60 provides a good balance of water properties and high reactivity. Both are products of Sartmer Corporation.

<tables num="17"><img file="JP4530273B2_D0017.tif" /></tables> 7. Triethylamine fading research Note that the exposed color of the SR-9021 based formulation (formulation 3) faded in the basic environment. It was initially understood that the coated off-the-shelf discs were returned to their original packaging. Due to the basic properties of paper and / or ink, the acid in Coating 100 neutralized the color and thus significantly faded. Another problem is when a label created by an inkjet printer is placed on the label side of a coated disc 10 and placed in a storage case. Again, the image fades. Therefore, in order to quantitatively measure the amount of fading, the test assumed that the coated disc 10 was placed under triethylamine (TEA), which stimulates the basal environment. Disc 10 is then measured to reveal the amount of fading.

A coating base containing SR-9021 was spin coated and cured on 5 discs 10 and exposed for 10 seconds with an L37 filter and nitrogen. The absorption curve of each disc 10 was measured. The disc 10 was then placed in a storage case 180 containing filter paper 181 in the empty corners and center, as shown in FIG.

FIG. 18 represents a typical storage case 180 for optical media. Here, the place where the filter paper 181 is packed is indicated by a gray part. 100 μL of triethylamine is placed in each portion of filter paper 181. Each case 180 is then closed and placed in a dark drawer for 2 hours before measuring the absorption curve to determine the amount of fading.

As a result, it was shown that the average amount of fading of the tested preparation was 36.0%. This was considered to be less than the desired amount and was tested to see if other formulations gave better results. Formulations were tested based on 9020, 355/455, 5% 4TB, 5% KTO, 368, and 983, the results of which are shown in Figure 19. Note that all formulations have 3% triphenylsulfonium triflate, except for 5% 4TB, which has 5% (4-tert-butylphenyl) diphenylsulfonium triflate. FIG. 19 shows that certain formulations are resistant to fading in the basal environment and generally tended to have environmental capacity.

8. Light resistance accelerated test It was noted that the background color of the disc 10 with the coating 100 containing 9020 turned slightly red over time in the presence of fluorescent room light. Therefore, another set of experiments was devised to assess the effect of ambient light on the image of coating 100.

First, a test fixture was created consisting of a fluorescent lamp fixture with two bulbs that were 4 feet long. The lamp used was a Philips ECON-O-WATT F40-CW 37 watt from Philips Lighting Co, NJ. The formed fluence is about 250 mw / m in the UV-A band when created with commercially available equipment.²Met.

A set of discs 10 was prepared utilizing SR-9020-based formulation 10 to determine which wavelength of light had the greatest effect on background color formation. After curing, the disc 10 was stored without exposure at the wavelength of imaging. Then, to determine which wavelength of light has the greatest effect on color formation, place the disc 10 under a fluorescent fixture, along with a portion of each disc 10 covered with a 2 "x 2" filter glass. set. Subsequently, the disc 10 was exposed and about 2.0 AU was developed on the uncovered portion. As shown in FIG. 20, the most damaging wavelengths are less than about 370 nm, and wavelengths less than about 320 nm cause the most problems. This seems to indicate that the UVB portion of the spectrum is the most beneficial bandwidth for UV protection. FIG. 20 shows the result of irradiation. Here, UV-30, L-37, L-38, L-39, L-40 and L-42 indicate model names of UV filters commercially available from HOYA Corporation in Tokyo, Japan.

Generally, the name of the cutoff filter indicates 50% transmittance. For example, UV-30 filters are valued for wavelengths at 300 nm and have a transmittance of 50% at 300 nm. It has been found that the thinner L-37 filter is very similar to the thicker UV-36, as the 50% transmission is an approximation and fluctuates slightly with thickness. Therefore, in general, a 1 mm thick L-37 is preferred here (about 50% transmission at 370 nm), but not only UV-34 filters with other filters, but also thicker UV-36 filters. It works well. UV-32 is considered to be the lower limit, above UV-39, curing slows. Therefore, preferred cutoff filters provide 50% transmission between about 320 nm and about 380 nm, most preferably between about 340 nm and about 370 nm.

In an attempt to correct color formation with background light, a UV absorber was added to the sample of the formulation to see if the color formation of the sample was slowed or interrupted by ambient room light. The absorbents used were chinubin 327, chinubin 171, chinubin 213, and chinubin 571. Tinubin 327 is 2,4-di-t-butyl l-6- (5-chlorobenzotriazol-2-yl) phenol, and Tinubin 171 is (2- (2H-benzotriazol-2-yl) phenol. )-6-Dodecyl-4-methyl-phenol), tinuvin 213, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) proplionate / It is a mixture of PEG300 reactants. Tinubin 571 is a branched linear type 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol). Chinubin products are manufactured by Ciba Specialty Chemicals.

Each sample of chinubin is liquid except for the powder chinubin 327. The test was performed by adding 1 percent of each UV absorber to Formulation 10, except for one sample made with 5 percent tinubin 171. However, since the important point of UV absorbers is to slow down the rate of color formation, another step was performed so that each sample could still form sufficient color when imaged. FIG. 21 shows a sample that created the appropriate colors. In fact, the samples with UV absorbers formed more color than the samples without UV absorbers (shown as MC9020 in Figure 21). No color formation was observed in the sample containing 5% tinuvin 171 but a brief examination after 10 seconds of exposure showed an absorbance at 540 nm of 0.40 OD.

Three cured (background color) discs 10 of each formulation were then irradiated by a fluorescence test instrument. Absorption curves of the sample were collected before the start of irradiation and usually daily during the test to observe the formation of background color. The aggregated results are shown in FIG. 22 and represent the effect of the addition of UV absorbers, as determined by accelerated X-ray fluorescence experiments.

Figure 22 shows that some types of tinubin are superior to others, but the comparison difference at a concentration of 1% is very small. Samples containing 5% tinuvin 171 showed excellent performance in reducing color formation, but the difference is believed to be only moderate effect. Also, the use of 5% density substantially increased the write time required to create the image. Attempts were made to prepare a formulation containing 10% tinuvin 171 but the material changed after curing (showing color formation without exposure to imaging rays). Samples containing 5% tinuvin 171 showed the same effect after a long period of time. Therefore, it was determined that tinubin 171 would not be an excellent candidate for use as a UV absorber.

Together with the results of environmental tests, UV absorbers were tested with CN-120 and SR-368-based formulations, which are becoming the preferred formulations. As shown in Table 18, a series of three UV absorbers were used at 5% uptake. Disc 10 was spin coated with formulation 80-82 at a rate of 6 K rpm and cured in a nitrogen environment at a distance of approximately 1 inch from the lamp for 2 seconds. Disc 10 was also exposed through an L37 filter for 10 seconds at a distance of about 1 inch from the lamp. These discs 10 were compared to the base 9020 formulation without stabilizers.

<tables num="18"><img file="JP4530273B2_D0018.tif" /></tables> UV-24 is an abbreviation for CYASORB UV-24, which is 2,2'-dihydroxy-4-methoxybenzophenone. UV-531 is an abbreviation for CYASORB UV-531FLAKE, which is 2-hydroxy-4-n-octoxybenzophenone. Both are products of Cytec Corporation in Stamford, Connecticut. MC80 is an abbreviation for UVINUL MC80, which is octyl methoxycinnamate and is a product of BASF Japan Ltd. of Japan.

UV-stabilized preparations had a weaker final color for comparable UVs and took longer to form than non-stabilized preparations. The results are shown in Figure 23. However, if the color formation takes a long time (or high fluence), it is considered that the cycle time required for the manufacturing specifications is exceeded. Moreover, the high fluence required for writing these coatings resulted in some unfavorable physical deformations (shrinkage and distortion) in addition to the difference in coating properties between exposed and unexposed areas. As an example, the color formation time of the preparation 81 is shown in FIG. Even at a distance of about 1 inch from the Zenon lamp, an exposure time of more than 10 seconds was required to obtain color formation exceeding 0.5 AU.

9. Retesting photoacid generator Retesting of various photoacid generators and their concentrations was performed because the addition of UV absorbers directly to Coating 100 required a long write time to obtain very slight light stability. It was noted that when the concentration of the photoacid generator was increased, the writing time tended to be shortened when the concentration of the color former was constant. Photoacid generators are believed to be potentially controllable to produce favorable color levels at appropriate cycle times. However, for a variety of reasons (including economic reasons), the use of minimal photogenic agents is preferred. As one of the first steps, in color formation, the ratio of the photogenic agent to the thickness of the color former or coating 100 was optimized. The results of the experiment are shown in Figure 25, showing that 3: 2 (color formation: TPST) is preferred over the 1: 1 ratio.

Experimental results (shown in FIG. 5) show that the thickness of coating 100 plays a role in color formation and photoreactivity. In the experiment, a sample of the formulation was spin-coated on the disc at 4K rpm and 6K rpm. As a result, the thickness of the coating 100 is different. Disc 10 was cured in a nitrogen environment at a distance of approximately 1 inch from the lamp for 2 seconds. The exposed area was also imaged for 10 seconds at a distance of 1 inch from the Zenon lamp. Comparative control samples based on formulations containing SR-9020 were prepared by spin coating at 4K rpm. This control sample was exposed for 10 seconds at a distance of 5 inches from the lamp (because high fluence was determined to cause fading in formulations containing SR-9020).

This result indicates that the color formation is not due to a large bias towards the surface, but over the entire thickness of the coating 100. Therefore, it may be desirable to optimize the viscosity and rotation speed to provide the preferred light density with the lowest film thickness. This experiment also provided the added benefit of confirming that 3% of the color former and 2% and 3% of the photoacid generators would eventually be the same color with different formation rates.

10. Absorption spectrum of photoacid generator and membrane At this point, moderately stable triphenylsulfonium triflate (TPST) -based formulations using UV absorbers were considered impractical due to their difficulty in activation. It was found that UV absorbers simply absorb the same wavelengths used for imaging, but do not selectively absorb UVB-UVB from sunlight or fluorescent light. Therefore, the absorption spectrum of photoacid generators and coating formulations were tested to adjust the wavelength range that could be important for these treatments.

TPST was considered to be the simplest and shortest UV-absorbing sulfonium-based photoacid generator available. Diphenyliodonium hexafluorophosphate (DPI HXFP) was also considered a simple and short UV-absorbing photoacid generator. The absorption spectra of these two photoacid generators are shown in FIG. 5, but the last is in the mid-range UV, which is highest at about 200 nm.

The spectrum of the CN-120 based formulation is shown in Figure 27. Unlike previous formulations, which were all fatty compounds, these formulations have significant UV absorption in the mid-UV range from about 250 nm to about 300 nm. It is also clear that most of the wavelength reaction range of the photoacid generator shares a high absorption range with the acrylate substrate. Therefore, the wavelengths that play a major role in color formation across the thickness of the coating 100 are likely to be medium to long waves rather than short wavelengths (&lt;250 nm) when the substrate light density is low. it was thought.

Shortwave wavelengths have the advantage of imaging much faster than sun and fluorescent rays because they are inefficient in image formation in UV-stable formulations, but they do not take advantage of the ability to generate shortwave UVs in the laboratory. Therefore, the high intensity must be utilized to make the imaging faster than the development of the background color. It is concluded that the addition of UV absorbers slows imaging as much as the formation of background colors from fluorescent or sun rays. Therefore, if UV fluence is 10,000 times greater than that produced by the sun's rays and imaging is performed in 3 seconds, it is considered that sunlight produces color in 30,000 seconds, or about 8 hours. Be done. Given that unacceptable levels of background color are as low as 5% of the highest colors, effective sunlight exposure to form unacceptable levels of background color is about 30 minutes. Therefore, it was thought that the use of fluence of 10,000 times or more of the environmental sun rays (an unacceptable amount in terms of material stability) would only extend the light stability by about 5 hours. ..

Looking at the UV absorption spectra of the substrate and UV absorbers, as shown in Figure 28, the potential approach to the problem of overcoming light stability is to look at the shortest absorbing photoacid generator. Instead, if possible, look for a photoacid generator with the highest absorption wavelengths close to mid-UV. In this case, the coating 100 exhibits some transmissive features. It was hoped that this would provide UV blocking protection for the UV-A and UV-B regions while increasing the speed of imaging to some extent through the effective use of UV-C radiation. A series of photoacid generators with longer UV transitions were chosen for this. As used here, the wavelength of UV-A was generally considered to be from about 320 nm to about 400 nm. UV-B wavelengths are generally from about 270 nm to about 320 nm, and UV-C wavelengths are generally less than about 270 nm. These wavelength bands and other wavelength bands are also referred to as "a series of wavelengths".

11. Screening of photoacid generators required for imaging speed A preparation using 10% UV-24 as a UV absorber was prepared. The concentration of each photoacid generator was adjusted to be comparable to 2.5% TPST on a molar basis. FIG. 29 shows the color formation curve of each prepared preparation. The sample shown in FIG. 29 was exposed at a distance of 1 inch from the Zenon lamp. Some photoacid generators, especially 4-phenoxy derivatives, showed shorter color formation (writing) times than TPST.

These different photoacid generators produce different write speeds and color densities, but a more important performance condition is that the photoacid generators produce different write speeds and color densities without increasing their sensitivity to fluorescence and exposure to sunlight. It was wondered if it could provide an increase in. To experiment with this, a disc 10 of each photoacid generator formulation was prepared and exposed under a fluorescent instrument for about 65 hours. Figure 30 shows that while each photoacid generator determines its own write rate and final color, nothing substantially exceeds TPST in terms of the ratio of color formation time to subsequent fluorescence stability. Is shown. In fact, the data suggest that the write time with a Zenon lamp is a direct predictor of subsequent light stability. Therefore, it was revealed that most of the light used for imaging from Zenon lamps is UVB (about 270 nm to about 320 nm) rather than shortwave UV (wavelengths less than about 250 nm) in the spectrum. It was. This result is supported by the observation that the Zenon "D" bulb does not improve write time, as shown in FIG. The "D" bulb produced more UV-C emission than the "C" bulb, but no increase in color formation time was observed.

Higher concentrations of UV-24 were tested, as well as a combination of UV-24 and another absorber, MC80. The results are shown in FIG. 32, where higher concentrations of UV absorbers reduce sensitivity, and with the same weight, UV-24 alone is superior to the mixture of MC80.

Further experiments were performed to measure the color formation time of the 10% UV-24 formulation. UV-B capability levels were measured at various distances from the lamp housing through a plastic mask. Quartz masks were also used to increase the UV-B capability, which is mostly shortest in the spectrum, at the closest distance of about 1 inch. The results are shown in Figure 33, where for 10% UV absorbers, Zenon lamps develop an appropriate fluence rate and an acceptable light density within a favorable cycle time of close to 3 seconds. Could not be generated. In fact, most coating 100 samples were substantially cracked or distorted. Also noteworthy is that the removal of the plastic mask results in about 40% more UV-B, but with only a slight increase in writing speed, again the coating is optical at shortwave UV (&lt;300 nm). It supported the theory that the density is high.

12. Color enhancement additives Attempts have been made to reduce the write time of coatings with UV absorbers without proportionally increasing the sensitivity of fluorescence and sunlight for some additives. The first attempt was to re-experiment the color-enhancing additives to more effectively produce the acid produced. This attempt focused on the use of acids that "prime" the coating for color formation. The substrate used was formulation 10 containing an alkoxylated monomer. As shown in FIG. 34, the acid concentration and components used had no significant effect on write time or the final color of the coating. In addition, experiments were attempted using 2-acrylamide-2-methyl-1-propanesulfonic acid, which is a crosslinkable sulfonic acid. However, even with 1% contamination, the acid was too strong and turned the coating red without UV exposure. Therefore, it was considered that the addition of impurities by acids of various intensities and concentrations would not assist in color formation.

Additional approaches to reducing photosensitivity when buffer systems were used were evaluated. Utilizing a buffer system, low doses of UV were thought to produce small amounts of additional acid absorbed by the buffer. In this case, trifric acid is a very strong acid, so almost any substrate has the ability to eliminate (neutralize) the acid produced. In the first experiment, amine acid acrylates such as Sartmer Corporation's CN-384 were used. These amine acids proved to be too strong for the base and color formation was completely inhibited. In the next experiment, a small amount of CN-384 was used, so the background color was kept low, but the image was not stable and faded under environmental conditions within 24 hours. Therefore, the use of weak bases was tested. Examples of weak bases include acetic acid and sodium salts. Unfortunately, these compounds were poorly soluble in acrylates and only 0.1% contamination was achieved. However, even with this low contamination, an effect was observed. The salt acted as a buffer, but also reduced the color formation rate and the overall color of the coating. The state of using the buffer is shown in Fig. 35.

13. Spin coating, film thickness and light density.

The purpose of this experiment is to correlate rotational speed (rpm), light density (absorption at 540 nm), and film (coating 100) thickness (microns). The transparent polycarbonate disc 10 was coated with a spin coating machine called a HEADWAY spin coaster. Formulation 3 with a viscosity of about 60 cps was used. Disc 10 was coated and rotated from 4,000 to 10,000 rpm (1.0 K) for 10 seconds. The disc was cured in a nitrogen environment for 2 seconds using an L-37 UV filter and a Zenon pulse lamp. Half of each disc 10 was then exposed under a lamp for 10 seconds. UV scans were measured for both curing and exposure of each disc, and film thickness was also measured.

Measurements showed that the thickness of the membrane varied from the prescription portion to the edge portion of the disc and from the thin portion to the thick portion. The light density of the disc 10 was also directly measured in both thickness at various rotational speeds. At maximum speeds (above about 8 K rpm), it was clear that the effect on film thickness was reduced, as expected. The results are shown in Figure 36. FIG. 36 shows the thickness of the membrane at a selected distance from the formulation. Evaluations of light density and film thickness at various spin coating rates are shown in Figure 37.

Formulations 58 (375 cps) and 61 (504 cps) were coated at their respective rotation speeds of 5-10 K. The light density and film thickness were measured, and the results are shown in Fig. 38. As expected, the more viscous formulations produced thicker films. Interestingly, these highly viscous formulations also show a more linear response to film thickness with respect to rotational speed. In the final product, color control methods include exposure time control and formulation changes, which are less attractive and it is generally considered preferable to change the film thickness. That is, changing the film thickness has the advantage that the end user can dispense the minimum amount of material required for a given color intensity, thus reducing costs and photosensitivity.

Further optimization of the concentration of photoacid generator was made. This is shown in FIG. FIG. 39 shows the relationship between the photoacid generator (TPST) and color former (PERGASCRIPT I-6B) concentrations and the light density when the film thickness is constant. Light density was measured on a disk 10 cured for 2 seconds at a distance of about 1 inch from the lamp in a nitrogen environment. These samples were then exposed 1 inch from the lamp for the time shown.

<u style="single">B. Development of multi-layer coating</u> It has been found that an acceptable balance between cycle time, UV fluence, and subsequent photosensitivity is not achieved with a single layer coating formulation. An alternative method was considered to be the use of two coatings, one designed for fast color formation and image stability, and a second protective film that provides favorable UV stability. The second protective film can provide additional beneficial effects such as scratch resistance and added environmental stability to humidity and bases.

FIG. 40 shows a cross-sectional view of an embodiment of the optical media 10. In FIG. 40, disk 10 includes pits 5 and lands 6 as data functions. In this embodiment, the disk 10 is formed of a substrate 16 and includes a reflective layer 14. As mentioned above, the color forming coating 100 indicates that it is formed from two components. The first component of the color-forming coating 100 is the color-forming layer 101. The second component of the color forming coating 100 is the protective film 102.

1. Development of color coating and protective film The first step in the development of the color-forming coating 100 is to evaluate the distinguishing properties between the color-forming layer 101 and the protective film 102 in order to simplify the formulation. In the color forming layer 101, adhesion to polycarbonate, excellent color formation, and solubility of a photoacid generator and a color former were required. The protective film 102 was required to have a hard scratch resistant surface due to good curing, a high UV density, and adhesion to the underlying color forming layer 101. Ideally, both layers 101 and 102 cure quickly in the absence of nitrogen, have low shrinkage, and work together to increase the environmental stability of the image (ie, heat, humidity). Or, against the effects of the introduction of additional chemicals).

Considering the previous development, the CN-120 based formulation produced the best environmental results,<u style="single">Formulation 1 and Formulation 9 etc.</u>It showed higher light density with respect to the color formation wavelength than all of the preparations of the aliphatic compounds of. However, since the addition of protective film 102 may be used to enhance the stability of heat / humidity tests, formulations other than CN-120 were used to reduce write time and shrinkage. Tested again.

Initial experiments have shown that removing the wetting agent from the cambium 101 is necessary to moisten the second coating 102 and adhere it to the cambium 101. A series of formulations was easily selected. These are shown in Table 19.

<tables num="19"><img file="JP4530273B2_D0019.tif" /></tables> In formulations C1 and C2, CN-120 content was reduced and SR-386 content was increased in order to increase UV clarity and reduce sticky shrinkage. Formulation C3 contains SR-9021 and SR-368 to achieve low shrinkage, high adhesion, fast curing, and UV transmission coating. Formulations O1 and O2 contained a mixture of SR-238 and SR-368 to achieve good adhesion and cure, and Formulation O2 CN-120 was included for strength and UV permeability. In formulations O1 and O2, the UV absorber UV-24 was used with a contamination rate of 10%. Immediate observations showed that, as before, the photoacid generator had minimal dissolution in the alkoxylated monomer SR-9021. (As is clear, the preparations starting with "C" indicate the preparations of the color-forming layer 101, and the "O" indicates the preparations of the protective film 102.) Sample disk 10 is 4K The cambium 101 was spin-coated on substrate 16 with formulations C1, C2, and C31 at rpm and prepared by curing in a nitrogen environment for 3 seconds at a distance of approximately 1 inch through an L37 UV filter with a "D" bulb. Imaging through a crystal mask was performed for 10 seconds at a distance of approximately 5 inches from the lamp. The protective film layers 102 (formulations O1 and O2) were applied onto the cambium 101 by spin coating at 2.5 Krpm. The protective film layer 102 was cured in a nitrogen environment for about 3 seconds, about 1 inch from the lamp, using an L37 UV filter with a "D" bulb. The cambium 101 made by formulations C2 and C3 was well moistened and rotated, but formulation C1 was not performed as well. The formulations of both O1 and O2 of the protective film layer 102 were well moistened and well coated throughout the color-forming layer 10. All final discs 10 had damage resistance to the plastic pen tip.

Using SCOTCH tape as a light adhesive tape, a tape tensile test was conducted using blades at 2.5 mm intervals. (PERMACEL # 99 did not adhere well to the coating used). The color-forming layer 101 formed from formulation C1 failed, while the color-forming layer 101 formed from formulations C2 and C3 passed the test. Both protective film layers 102 (O1 and O2) adhered to the cambium 101 without problems. When there was a problem with the adhesion of the protective film layer 102, the problem occurred at the contact surface between the polycarbonate layer 16 and the color forming layer 101 (as expected).

From these first experiments, candidates for a two-layer coating 100 were devised. These formulations are shown in Table 20. The cambium 101 was modified to reduce the density of CD-120 and increase its transparency and stickiness. The ratio of color former to photoacid generator was increased to 3: 4.5 to increase writing speed and color depth. The protective film layer 102 is a preparation of SR-368 and SR-238.

<tables num="20"><img file="JP4530273B2_D0020.tif" /></tables> 2. Initial test Experiments for testing the two-layer coating 100 were underway. Disc 10 was spin coated at 3K and 4K rpm and coated with cambium 101, as shown in FIG. The disc 10 was imaged at a distance of about 5 inches from the lamp at varying times to test the color density. The protective film 102 was then applied by spin coating at 3 K rpm. The use of nitrogen and filters was also tested in this experiment. Nitrogen was not required to cure the cambium 101 to acceptable levels that provided the application of protective film 102. Future use of nitrogen for the curing of the color-forming layer 101 will add the advantage of forming a perfect bond between the color-forming layer 101 and the protective film 102. The protective film 102 then cures at a distance of about 1 inch from the lamp for 1.5 seconds without the use of nitrogen and a filter, thereby giving a complete spectrum of lamp irradiation to enhance surface curing. No significant color due to curing of the topcoat 102 appeared in the base color cambium 101.

A 3: 4.5 ratio of photoacid generator to color former has been shown to provide a high degree of very strong color. A light density of about 0.8 was achieved in a short time with the 5.25-inch Zenon "D" bulb.

More importantly, a qualitative exposure test (63 hours) using a fluorescent instrument showed that the protective film performance of the optical test was far superior to that of the single layer coating solution. Also interesting is that an image that initially looks very dark (the contrast is too large) looks good with a background color that has less contrast.

Most importantly, the separation of the UV stable layer and the color cambium 101 allows the effective use of short UV wavelengths (&lt;320 nm) for color formation. This enables effective exposure of the color forming layer 101 utilizing these wavelengths, and blocks the layer 101 from such wavelengths found in general irradiation such as sunlight and fluorescent lamps.

However, it should be noted that the use of a combination of 101 and 102 layers requires further investigation of the adhesive properties. The color-forming layer 101 did not adhere to the underlying polycarbonate 16 and failed the tape tensile test using a weak adhesive tape. Since the failure of adhesion occurred only on the contact surface between the polycarbonate 16 and the color forming layer 101, it was impossible to evaluate the adhesion of the color forming layer 101 with respect to the protective film layer 102.

3. Environmental test At this point, the knowledge gained from the two coating experiments to date was combined to lay the foundation for further development of the series of formulations. These formulations have undergone qualitative environmental testing experiments and the results are shown in Table 21.

Formulation C5 is the previous SR-9021 based Formulation 3 (Table 14), which has excellent properties but failed environmental studies. The protective film 102 may improve the environmental safety of the cambium 101 with formulation C3 and was thought to provide sufficient protection to avoid the use of the UV absorber CN-120, which exhibits high shrinkage. .. Formulation C6 was modified from Formulation C5 to use SR-368 instead of SR-494. It was theorized that this substitution reduced the content of alkoxylation, resulting in a hard but low shrinkage film 101 or cambium 101. Formulation C7 is a modified formulation containing CN-120, SR-368, SR-238 to meet the adhesive requirements. The color-forming layer 101 containing formulation 7 was considered to easily pass environmental tests, despite the cost of writing time and shrinkage. Formulation O3 is expected to provide a hard protective film that absorbs UV, although CN-120 may have shrinkage problems. Formulation O4 is made primarily from SR-368 and uses SR-339 as an additional UV absorption diluent. Formulation O5 is a protective film based on SR-9021 to which CD-120, which is necessary for hardness, is added. Formulation O5 was devised with the expectation that SR-9021 would solve the contraction problem without sacrificing stiffness and scratch resistance. Protective film 102 was dispensed using both 10% and 20% UV-24. Adding 20% has a significant effect on viscosity.

<tables num="21"><img file="JP4530273B2_D0021.tif" /></tables> In terms of photoacid generator and color former solubility, both C5 and C7 formulations contain alkoxylated SR-9021, which is problematic when dissolving solids without heat and ultrasound. It was. Both C5 and C7 required filtration. The formulations O4 and O5 had difficulty dissolving UV-24 at a concentration of 20%. Formulations O4 and O5 were also filtered.

The color film formulation was applied by spin coating at 4 K rpm and then cured in the air about 1 inch below the lamp using an L37 filter for 2 seconds. However, Disc 10 was "pinkish" hardened to varying strengths. The degree of this pink ranged from colorless in C5 to a very slight color in C6 and a slight color in C7. This was presumed to detect the light density of the coating, as C7 contained the most aromatics, C6 contained SR-368, which absorbed some UV, and C5 transmitted the most UV in the coating. ..

Imaging was performed with a D-bulb for 10 seconds through a chrome-on-quartz mask, approximately 4 inches from the lamp. Topcoat 102 was applied by spin coating at 4K rpm and cured approximately 1 inch from the lamp using a full spectrum D-bulb. Curing was 1.5 seconds (10% UVA set) or 2.0 seconds (20% UVA set).

The environmental test was conducted for 78 hours at a temperature of about 70 ° C and a relative humidity of 90%. The protective film 102 containing the 20% UV absorber was torn into a partially or completely thin film. As the mechanism, shrinkage or distortion of the protective film 102 appeared, and then the thin film of the color coating 101 was torn from the polycarbonate layer 16 of the disk 10. The second observation was that the composition of color layer 101 was a major determinant in image safety determination. Formulation C7 far exceeded C6 and C5. Coating C5, as before, was completely rejected regardless of the use of protective film 102. Coating C6 was superior to C5, but not as good as C7, and again the protective film 102 was irrelevant. Formulation C7 outperformed the other coatings 101 even without protective film 102. The results are shown in Figure 42.

With respect to the 10% addition of protective film 102, each sample appears to remain stable in terms of adhesion and strength. In addition, we noticed a tendency for basal image stability for the 1c primed sample. That is, formulation O3 performed better than O4, O4 performed much better than O5, and O5 performed better than without protective film 102. Again, the lack of alkoxylation, the potential glass transition temperature and the hydrophobicity of the coating 100 were tracked.

All samples were judged by visual inspection to be very good performance under fluorescent lighting. After a week of exposure to fluorescent light, some background colors were developed, and then several weeks of exposure to fluorescent light, the image was still recognizable, but worsened by the darkness of the background color. The sample with 20% added showed good performance in terms of background color development, but its use was considered to be limited due to the above environmental problems. The CN-120-based formulation O3 contained the highest amount of aromatics, but with coating 100, it had the highest light density and the best light resistance. The absorption spectra of O3, O4 and O5 of the protective membrane preparation are shown in FIG.

4.2 Adjustment of layer coating formulation A series of acrylate urethanes from Sartmer Corporation was also tested to confirm their suitability for use with Coating 100. These are shown in Table 22. All coatings that use acrylate urethane do not appear to perform well as they are soft and impair the final product. No further testing was conducted.

<tables num="22"><img file="JP4530273B2_D0022.tif" /></tables> CN965 is a urethane diacrylate oligomer based on an aliphatic polyester. It is an oligomer that provides excellent light resistance and is flexible. CN966B85 is a mixture of an aliphatic polyester-based urethane diacrylate oligomer with 15% SR238, diacrylate and hexanediol. CN981B88 is a mixture of an aliphatic polyester / polyether-based urethane diacrylate oligomer with 12% SR238 and a diacrylate hexanediol monomer. All three are products of Sartmer Corporation.

Since it is clear that the formulation of CN-230 cannot be replaced by any other monomer class, further experiments were carried out to adjust other components and improve performance aspects. A description of the formulations and the rationale for each adjustment is given in Table 23.

<tables num="23"><img file="JP4530273B2_D0023.tif" /></tables>

<tables num="23a"><img file="JP4530273B2_D0024.tif" /></tables> Studies have shown that a mild reduction in SR-238 content in the color coating results in a lack of adhesion of the polycarbonate. However, in the protective film 102, SR-339 can be used as a base because the diluent providing excellent UV absorption properties reduces shrinkage and reduces skin irritation. The study also observed that the inclusion of amine synergizers in protective film 102 also resulted in complete image loss as a result of environmental testing within just 24 hours. This was considered unfortunate, as the addition of a covalent agent to the protective film 102 resulted in a rapid and complete cure with the addition of 7.5% of KTO-46.

SR-339, 2-phenoxyethyl acrylate is a low-viscosity monotube-based aromatic monomer, but provides good adhesive properties. CN120M50 is a mixture of a bifunctional bisphenol A-based epoxy acrylate and 50% SR-339, a phenoxyethyl acrylate. CN120M50 provides a good balance of water properties and high reactivity. SB520M35 functions mildly and SR-339 is a carboxylic acid containing an acrylate oligomer mixed with a phenoxyethyl acrylate monomer. The reaction solid is 100%. The SB520M35 offers fast cure rates, excellent adhesion to metals and plastics, and good wettability and flow characteristics. SB520M35 also contains the functionality of a carboxylic acid, resulting in improved amine fading resistance. These three acrylates are products of Sartmer Corporation.

After various screening studies were completed, a final test was conducted with two preferred protective film formulations and preferred color coating formulations. The selected protective membrane formulation has not been tested in environmental experiments and has not been confirmed to be practical in protective resistance against ink fading, but was selected due to its inclusion of acidic oligomers such as SB-250. It was. The final formulation is shown in Table 24.

<tables num="24"><img file="JP4530273B2_D0025.tif" /></tables> Two concentrations of photoacid generator and color former were studied because the final proportions and concentrations of photoacid generator and color former have not yet been determined accurately. Two rotation speeds of 3K and 4K rpm were used for both coatings. The substrate coating was cured in 3 seconds through an L37 filter without nitrogen. The exposure was about 4 inches from a Zenon "D" bulb for 10 seconds. The protective film cured in 3 seconds without a filter or nitrogen.

The residual sensitivity of coating 100 is shown in FIG. Samples are divided into two main groups according to the concentration of photoacid generator. Note that in both cases, the protective film (O13) appeared to provide better UV protection than the protective film (O14). It was found that formulation C13 had the lowest residual sensitivity and achieved the highest light density ratio of the unexposed portion with respect to the exposed portion. Furthermore, it was noted that the results of this percentage included some bias. This bias may have arisen from the failure of the C14 formulation to be exposed for an appropriate length of time to fully develop the final color, thus effectively utilizing the developed color of the C14 formulation. It was decided to reduce it. Also, as expected, the coating 101 containing the maximum amount of photoacid generator and color former retained the maximum amount of color for long exposures. This effect is shown in FIG.

Environmental tests at a temperature of 70 ° C and a relative humidity of 90% showed that acid transition from the protective membrane to the basement membrane was possible. The results are shown in Figure 46. A clear division of background color levels was found in acid formulations that did not contain acid (protective film 14) and contained a coating (protective film O13). Therefore, the usefulness of acids in amine / ink tests must be confirmed before SB-520 or similar substances are included in the formulation. If necessary, offset / optimization experiments may be performed to provide ink resistance while minimizing color development from the protective film 102.

Ultimately, the level of color retained after environmental exposure was largely determined by the concentration of photoacid generator and color former, not by the thickness of film 101 or the constituents used in protective film 102. .. The results are shown in Figure 47. The results show that optimizing the proportions and concentrations of photoacid generators and color formers to reach favorable color densities and write cycle times will have a significant impact on light resistance and environmental stability.

5. Amine test The amine test was repeated using the new formulation. Initially, the application of a new formulation of cambium 101 appeared to withstand the amine test, without protective film 102 and without deterioration. However, the DVD10 marked with the image of the first pattern showed a substantial degree of fading after long-term storage of the first DVD storage container 180 containing the added material. The storage container 180 used was actually purchased from a retailer and was considered representative of the DVD storage container 180 on the market. This probably suggested that previous triethylamine (TFA) -based trials were unsuitable for modified formulations. Therefore, a new test was conducted using a large amount of TEA in a common plastic DVD container 180 similar to the first DVD storage container 180. A large filter sheet 181 was used in place of the insert and 1 ml of TEA was dispersed around the filter sheet 181. In this test, the pattern of the image on the coating 101 did not fade. Later, it was probably necessary to have a highly volatile and mobile base, such as ammonia.

The first trial of this test was to drop 200 microliter drops of concentrated ammonium hydroxide into the center of filter paper 181 and seal the disc 10 in storage container 180. This led to the complete destruction of the images on all discs 10 with or without protective film. It has been proven that too much ammonium hydroxide was used, and in practice it is likely that it will be much higher than it would occur in the package. Therefore, the second test was performed using 25 microliters of ammonium hydroxide. Within 2 hours, both the disc without protective film 102 and the protective film 102 without acid completely faded (the protective film was slightly better), but the protective film 102 containing acid was a portion of ammonium hydroxide. Most of the original color was maintained except for the area close to (around the stacking ring). After a few hours, these discs 10 also substantially deteriorated from the inside to the outside of the ring. Again, the amount of ammonium hydroxide used may have been too high compared to the environment of a typical optical media package 180 such as a CD or DVD.

The test was repeated with 10 microliters of concentrated ammonium hydroxide. The disc 10 without the protective film 102 deteriorated within one hour as before. However, this time, the disc 10 with the protective film 102 formed from the O14 formulation delayed fading by several hours. The disc 10 with the protective film 102 formed from the O13 formulation was essentially unchanged, showing only signs of fading near the center of the disc 10 one day later.

After the package was sealed for several days, three samples were added to the first 200 microliter container. After 24 hours, the unprotected disc 10 showed a mild fading, but both discs 10 with the protective film layer 102 were still robust. An additional DVD storage container 180 was obtained to complete further testing. A sample of each disc 10 coated with a protective film was placed in a new container to see if further fading progressed. Neither protective membrane sample showed any signs of fading after 3 days.

6. Quantitative research The metalworked substrate 16 was coated with a color coating formulation containing a photoacid generator and a color former at a ratio of TPST 2.0%: CF 3.5%. Table 25 shows the components of each formulation tested in the quantitative experiment. The formulation was spin-coated on substrate 16 at 4 K rpm for 10 seconds. The prepared disc 10 was placed at a distance of about 1 inch from the Zenon D-bulb and cured by irradiating it in a nitrogen environment for 2 seconds through an L-37 UV filter. Each disc 10 was then placed at a distance of 4 inches from the D bulb and exposed for 10 seconds for color development. Finally, protective film 102 was manually applied to each disc 10 using various formulations on HEADWAY products. The protective film 102 was placed at a distance of 1 inch from the D bulb and irradiated for 3 seconds to cure.

<tables num="25"><img file="JP4530273B2_D0026.tif" /></tables> The light density of each disk 10 was measured using a spectrum meter manufactured by Ocean Optics. Absorption was measured at 540 nm. Disc 10 was placed in individual DVD containers 180 and exposed to 10 microliters of ammonium hydroxide. Ammonia hydroxide was added dropwise to the center of a sheet of filter paper 181 fixed inside each container 180. After closing the container 180, it was left to stand. Each disc 10 was periodically removed from each container 180 and light density measurements were performed to assess color loss. The result data is shown in Figure 48.

7. Physical properties of the coating Modified formulations for color cambium 101 were prepared by diluting into formulations at 30% by weight of 5% KTO-46 in SR-238 diluent. Membrane thickness vs. rotational speed curves were generated for both formulations. Each formulation was then spin coated on a borosilicate glass disc from 2K to 10K rpm at 1K rpm intervals. The color-forming layer 101 of the disc 10 was then cured under L37 by a Zenon D-bulb in a nitrogen environment for 2 seconds. A tape was then applied to the disc 10 to remove the coating and tested on WYKO to determine the thickness of the membrane 101 in two different regions of the disc. This experiment showed that when the original color coating C6 was applied using a rotation speed (SS) of about 2K to 5K rpm, the film thickened. However, the two samples have since proved to be very similar.

8. Viscosity vs. temperature In a typical replicating machine, color-coated paints can be dispensed at different temperatures. Therefore, the viscosity as a function of temperature was determined. Viscosity measurements were performed at intervals of about 5 ° C in the temperature range of about 25 ° C to about 50 ° C. Measurements were performed with a Brookfield LVDV-III + CP rheometer and a spindle CPE-40 at 4.75 rpm. The viscosity and temperature profiles for the color coating C6 are shown in Figure 50. As expected, the viscosity of the paint decreases with increasing temperature.

9. Viscosity vs. shear rate The spin coating process causes variations in the shear rate on the paint. Since it is a function of the viscosity deviation rate, it is also desirable to obtain this property. Certain practical limitations prevent the determination of accurate values of shear rate during spin coating. However, in order to evaluate the properties of the paint, a range of viscosity and shear ratio measurements were made. Measurements were performed using Brookfield LVDV-III + CP and spindle CPE-40 in the range of low to maximum speed shear rates. The highest shear rate reached with this particular paint was 45 / sec. If a high shear rate is desired, it may be feasible to replace some of the hardware configurations of the spin coating system. For example, the use of spindles CPE-51 and CPE52 should achieve higher shear rates than CPE-40 spindles. These spindles are compatible with rheometers and have the ability to generate high shear rates.

Therefore, a program has been devised to obtain high and low shear rates by changing the speed of the spindle. Speeds from 1K to 6K at 1K rpm intervals were used to increase the shear rate. This speed was then returned from 6K rpm to 1K rpm. The flow curve graph of FIG. 51 shows the relationship between viscosity and shear rate.

FIG. 51 shows that the viscosity of the basal lamina 101 (containing formulation c6) is substantially constant with the increase in shear rate. However, the increasing time of the shear increases the viscosity. The increasing shear curve implied that the formulation was Newtonian fluid. However, the decreasing curve implies that the fluid dynamics of the liquid is time-dependent. Another type of graph shows that the behavior of the fluid is characteristic of the shear stress and shear rate shown in FIG. In FIG. 52, the primary relationship between shear stress and shear rate confirms that this liquid is a Newtonian fluid in both shear directions.

Another experiment was performed to see if the fluidism of the color coating was time dependent, that is, the phenomenon of viscosity and the shear rate curve shown were possible. To study this, the viscosity was measured while the shear rate and temperature were constant over a period of time. Again, LVDV-III + CP and spindle CPE-40 were used. The spindle speed was set to 2K rpm. It was concluded that formulation C6 exhibits Newtonian fluid behavior, confirming that the time characteristics shown in FIG. 53 remain constant with time.

10. Color formation with various lamps Color formation experiments were performed with 9 samples and 3 different light sources shown in Table 26. Each of the photoacid generator and color former combinations shown was included in the coating base of formulation C7 (KTO 5%, SR-238 35%, SR-368D 30% and CN-120B60 30). % Included). Three sets of discs 10 containing the above formulation were prepared and exposed separately using a Zenon D bulb, a Zenon C bulb and a HONLE lamp. The exposure time is from 1 to 10 seconds at 1 second intervals. A metalworked base 16 was placed just below each disc 10 to provide a reflective tergum. All samples were prepared by spin coating the formulation onto a clear polycarbonate substrate 16 at a rate of 4K rpm on a HEADWAY product. The formulation was cured with a Zenon D-bulb and L37 UV filter for 2 seconds in a nitrogen environment.

<tables num="26"><img file="JP4530273B2_D0027.tif" /></tables> This experiment was devised to test several variables. The first is the effect of changing the ratio of the photoacid generator to the color former. Generally, a ratio of 2: 3 has been used, but it is not known as a preferred ratio. Second, the preferred concentrations of photoacid generator and color former are evaluated. This includes assessing the effect of density changes on color formation time. In addition, the use of different bulbs for color formation time is appreciated. Zenon's "D" and "C" bulbs provide different amounts of shortwave UV. The effect of shortwave UV on color formation was considered to be poorly understood. In addition, the HONLE "H" bulb is a continuous wavelength mercury gas solution with a linear spectrum very different from that of Zenon lamps, and testing this lamp was considered beneficial. HONLE lamps are sold by Honle UV America, Inc. in Marlboro, Manachusetts.

11. Ratio of photoacid generator and color former FIGS. 54 to 57 show the effect of the ratio of the photoacid generator to the color former on the color formation. Looking at the concentrations of each different photoacid generator as a set, we can see that there is a general tendency. This trend is shown in Figure 54, showing that sample color formation at a ratio of 2: 3.5 (or equivalent) performed better than 2: 3, which is better than 2: 4. It is thought that it is.

The apparent recession of color formation due to the high proportion of color formers was thought to result from the inactivity of the color formers in the formulation due to the high absorption of UV light. It was noted that while this tendency appears to be similar at each concentration of photoacid generator, higher concentrations of color former may be better for the environment or light resistance. It was also noted that the performance difference between these proportions is small, so the benefits obtained from the high proportions of color formers are probably valued correctly.

Assuming that the optimal ratio of photoacid generator to color former is close to 2: 3.5, it is possible to directly compare the effect of photoacid generator concentration on color level. The increase in color roughly follows the increase in the concentration of the photoacid generator relative to the color former.

12. Lamp effect The writing efficiency of the three lamps was tested using both 2: 3 and 2: 4 concentrations of the photoacid generator relative to the color former. For simplicity, the lamps were compared with 2.5% photoacid generator: 5% color former and used the combined intensity of UVA and UVB measured by the GIGAHERTZ OPTIK power meter to fluence the time. Converted to a value. The power levels are shown in Table 27.

<tables num="27"><img file="JP4530273B2_D0028.tif" /></tables> In general, HONLE "H" bulbs performed best on a fluence basis for UVA / UVB mixed levels, as shown in Figure 58. However, it should be noted that HONLE's emits more UVB than any of the Zenon bulbs. When only UVB levels were used to draw the curve, HONLE lamps were found to have less advantages, but still superior to Zenon bulbs, as shown in Figure 59. At all levels, HONLE's and "C" valves are superior to "D" valves. Finally, a HONLE "H" bulb was used to perform long exposures to test the maximum useful fluence required to image the coating. As can be seen in Figure 60, a typical formulation has a UVB exposure of approximately 5 kJ / m.²Later it begins to reach its maximum. In one example, the entire spectrum of UV was used to cure the protective film 102.

13. Protective film: Light resistance of protective film with various UV absorbers The protective membrane (O1) formulation was made with the addition of various UV absorbers at a concentration of 10%. The various absorbents used are shown in Table 28. Tinubin-327 was insoluble and formulations using Tinubin-R796 crystallized after 24 hours. Tinubin-R796 is a 2- (2'hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazol, a reactive UV absorber that provides a cross-linking function for the coating.

<tables num="28"><img file="JP4530273B2_D0029.tif" /></tables> The clear polycarbonate disc 10 was coated with formulation C6 and cured in a nitrogen environment for 2 seconds using an L-37 UV filter at a distance of 1 inch from the Zenon C-bulb. Disc 10 was then imaged for 10 seconds at a distance of 4 inches from the lamp. Each protective film 102 was applied on three discs 10 containing images. Disc 10 was then cured under Zenon's product for 3 seconds at a distance of 1 inch. Each disc 10 cured well and showed good surface quality. With the exception of the UV-24 formulation, each tip of the cured formulation was cured. The formulation containing MC80 developed a pink color after curing.

Viscosity was measured for each formulation and light density was measured for both curing and exposure range of disc 10. Disc 10 was placed in a bright container, removed regularly and measured at a light density of 540 nm. The results are shown in Figure 61. It was noted that the UVA composition had little light-resistant effect on the exposed portion of the disc 10, as shown in FIG.

As a result of the development work described above, techniques for the development of various formulations and further formulations have been developed. These formulations and techniques for the development of formulations are color-forming that can be cured at wavelengths of light and are stimulated by the wavelengths of light to create and retain images, patterns, and other markings of interest. The material was provided. These formulations are advantageous because they can be applied over the data features that appear in the optical media. Very advantageously, the appearance of the image can be controlled, thus avoiding interference with the reading device used to interpret the data stored in the data function. It should be recognized that the above are specific examples of formulations and do not limit practical examples. The introduction of other constituents, such as the functionality of an acid that acts as a basic supplement for protective film 102, is believed to further support the stability of image preservation.

Since we have examined aspects of the development of such formulations and formulations, we will now consider further aspects of the application and use of these formulations.

<u style="single">C. Examples of coating of optical media 10</u> It will be apparent to those skilled in the art that formulations having the efficacy of use as described herein are not limited to the examples described above. Therefore, further studies and properties of the coating 100 are not limited by the particular aspects of the aforementioned examples.

1.2 layer coating 2 and 40 show a review of the two embodiments of Coating 100 so far. FIG. 2 shows a single layer coating, where the color forming material is included along with the other constituents that make up the coating 100. In this example, the coating 100 provides color-forming attributes as well as environmental stability (such as UV absorbers) to provide the stability of the coating 100 during normal use. FIG. 40 shows the second embodiment, where the components are separated into two layers 101 and 102. In FIG. 40, the coating 100 is formed by the color forming layer 101 and the protective film 102. In this second embodiment, the components of the color-forming layer 101 are advantageously distinguished from the components of the protective film 102, thus providing improved performance with respect to some properties of the coating 100. To do.

2. Multi-layer coating Further, unlimited examples are shown in FIGS. 63-65. In a further embodiment, multiple layers are employed, as shown in FIG. In one embodiment represented by FIG. 63, the first layer 301 and the second layer 302 are the color forming layer 101, and the color forming layer 101 is the red of the first 301 and the green of the second 302. Produces a clear color such as. The third layer 303 is adopted as a protective film 102 devised as protection against environmental elements. In another embodiment, the optical media 10 shown in FIG. 63 is formed, so that the first layer 301, the second layer 302, and the third layer 303 are applications of the formulation of the single layer example. .. In these other embodiments, the layers 301, 302, 303 produce distinct colors such as red, green, and blue.

FIG. 64 shows a coating 100 containing four layers. In one embodiment, the first layer 101 is the cambium 101 and the second layer 402 is the protective film 102. The third layer is also the color-forming layer 101, and the fourth layer 404 is another protective film 102. Alternatively, each of the first layer 401, the second layer 402, and the third layer 403 is the color forming layer 101, and the fourth layer 404 is the protective film 102. In this alternative embodiment, the colors formed in each of the first three layers are the primary colors, and upon completion of imaging, a multicolored image appears.

FIG. 65 shows a further embodiment of coating 100. In some cases, the alternative layers 501, 503, 505 are the color forming layers 101, and the protective film is included as layers 502, 504, 506. In this embodiment, each of the alternate layers 501, 503, 505 corresponds to a particular color, such as one of the primary colors. The imaging of layers 501, 503, and 505 respectively provides a comprehensive multicolored image.

3. Multicolor disc To create a multicolored image on the disc, the multicolored cambium 101 is applied. A study was conducted to create red and orange multicolor discs. The formulations used throughout the study are shown in Table 29.

<tables num="29"><img file="JP4530273B2_D0030.tif" /></tables> First, a metal-worked disc was spin-coated with an orange formulation at 4000 rpm for 10 seconds. The orange formulation was then cured with a Zenon "C" bulb for 3 seconds at a distance of 1 inch below the windowpane. A crystal mask was then placed on the disc 10 and exposed for 10 seconds at a distance of 4 inches with the same Zenon "C" bulb. The resulting disc 10 had an orange image on a transparent background. Disc 10 was then once again spin coated with a red formulation onto the HEADWAY product at 4000 rpm for 10 seconds. The red formulation was then cured with a Zenon "C" bulb for 3 seconds at a distance of 1 inch below the windowpane. Finally, Mask 925 was exposed on Disc 10 for 10 seconds with a Zenon "C" bulb at a distance of 4 inches. The final product was Disc 10 with red and orange images on a transparent background.

Samples of orange and red formulations were taken. These samples were spin coated, cured and exposed at 4000 rpm on a clear polycarbonate disc as described above. Also, a spectrum of colors in layers of different combinations was taken. Disc 10 was first coated with orange or red, followed by other colors.

FIG. 66 shows the spectra of the red disc 10 and the orange disc 10 when each color is evaluated separately. FIG. 67 shows that when the red and orange layers are exposed together, the resulting color spectra are essentially the same. This does not matter in the order in which the coatings are applied. Further, FIG. 68 shows that the layer 101 above the series of layers 101 can be selectively exposed without completely developing the substrate layer. It may be noted that most of the developed colors are developed in the upper layer 101 and the base layer 101 is relatively unexposed.

If desired, the selective development of the upper color layer 101 can be enhanced by adding a UV blocking layer 102 between the color forming layers 101. Table 30 shows the formulation of the UV blocking layer. The formulation was spin coated between the orange and red cambium 101. In this example, the UV blocking layer could further improve the reproduction of the top color alone. Again, exposure to both cambium 101 results in the same overall color, regardless of the order in which the layers 101 were applied. The results are shown in Figure 69.

<tables num="30"><img file="JP4530273B2_D0031.tif" /></tables> The aforementioned examples make use of coatings that include the cambium 101, the protective film layer 102, the monolayer 100, and various combinations thereof, as will be apparent. As expected, many combinations can be developed. These can provide a variety of effects, such as monochromatic or multicolor images.

Furthermore, as expected, the stepwise application of the imaging layer of Coating 100 provides certain advantages. For example, the first layer 401 is applied and then the image is recorded there. Next, the protective film layer 102 is applied as the second layer 402, and the third layer 403 is applied as the second color forming layer 101. The second layer 402 is used to limit the exposure of the first layer 401 by using a material that absorbs the image wavelength during the imaging of the second color cambium 403. In this method, one image is recorded on the first layer 401 and the second image is recorded on the third layer 403. Recording of the second image proceeds without interfering with the sides of the first image. Similar techniques can be used for monolayer formulations where the color-forming material is mixed with UV (or other wavelength) absorbers. Multiple wavelengths can be used for curing and imaging. In summary, various coating techniques, formulations, cures, and imaging techniques are used to achieve multiple cures in the overall appearance of the image.

<u style="single">II. Marking formation</u><u style="single">A. Marking forming equipment</u> Selective irradiation of the color-forming material of the coating 100 with a second light is used to record the image or marking on the optical medium 10. In a preferred embodiment, the wavelength of UV was used and a second light was prepared. Selective irradiation can be used to provide various contrasts with the unexposed or underexposed areas of the optical media 10. That is, different shades can be created in the image. For example, an increase in UV exposure in one part of the coating 100 results in greater absorption than shown in another part of the coating 100. Therefore, shading effects, or other marking techniques, can be achieved using image creation units such as positive, negative, or electrical photomasks, direct writing lasers (laser galvanizing systems), or by other techniques. May be done. FIG. 70 shows an enlarged view of a part of an example of the photomask 925 suitable for developing the shading effect. Marking as a single marking (eg, marking of the monochromatic cambium 101) is achieved by a comprehensive display of a series of markings (eg, a series of markings of the various color cambium 101). In one embodiment of the electrical photomask 925, it is preferable to utilize a programmable liquid crystal display to exhibit high light density at a wavelength of about 355 nm. In one embodiment of the electrical photomask 925, each of the series of optical media 10 is provided with a unique marking as it is reconstructed during the marking procedure.

One convention used here relates to "images" and "markings." When these terms are used together, the image means the production of the marking, and the marking means the manifestation (ie, recording) of the image within the coating 100. The two terms are closely related and, where appropriate, are considered interchangeable.

<u style="single">B. Types of markings</u> Markings include textual information such as alphanumeric characters and symbols, graphic information such as logos and barcodes, or any other information or symbols that may be appropriate to be included in the markings. Formed according to unrestricted specifications. In addition, the marking may include built-in information or an authentication signature, which may include at least one digital watermark, or other type of hidden marking. For example, the markings may not be visible to the naked human eye.

In some embodiments, the markings are self-defeating. For example, markings disappear when entering atmospheric conditions such as ambient light. The use of self-defeating markings is particularly beneficial in some applications, such as examples of approval schemes.

An example of the marked optical media is shown in FIG. FIG. 71 represents an optical medium 10 in which a series of layers together form a coating 100 on top of each other. In the embodiment shown, the optical media 10 is being manufactured on production line 2000, where the production direction is represented by a dashed arrow. The imaging wavelength source 920 is represented as a lamp with the photomask 925 attached above and is used to generate markings on the coating 100. In the embodiment shown, the marking 620 is made on the first color cambium 401 of the coating 100. Additional lamps 921,922 (at least shown in FIG. 78) may be used to create marking 620 on additional cambium 402, 403. In some embodiments, the imaging wavelength source 920 is a laser. In this embodiment, the lamp 920 is controlled in writing direction on the optical media by an external device not shown here. In other embodiments, the imaging wavelength source 920 can include directional writing lasers, pulsed UV lamps, other light sources, and any combination thereof.

The marking 620 can carry any desired information. For example, the marking 620 may represent content that includes identification information (such as a serial number), approval information, and / or instructional information. In addition, the content includes advertisement, brand, and promotion information, which are collectively referred to as "promotion information" here. The information contained in the marking 620 may include, but is not limited to, the types of information or combinations described above. For convenience, the term "content" as used herein refers to the content of the marking 620, which can be images, alphanumeric text, and other symbols, graphics, and combinations of images and symbols. The marking 620 may include at least one digital watermark.

An example of a technique for changing the contrast of a transferred image includes the contact technique used in grayscale printing. It uses a group of colored shapes or patterns of appropriate size on a colorless background, or instead uses a colorless shape or pattern on a colored background. By constantizing the size and density of shapes and patterns, it is possible to control the visual perception of color depth in any particular area of marking.

FIG. 70 shows an example of a technique when contrast is established by using a photomask. FIG. 70 represents a portion of a stretched cross section of a corner of the photomask 925, where shadow recognition is established by controlling the size and orientation of the rectangle in the photomask 925. In another embodiment, shading is achieved by controlling the exposure by the UV laser 920 used to write directly onto the optical media 10 by controlling time, intensity level, or other factors. In some cases.

In one embodiment, photomask 925 is used to expose the optical media 10. The photomask 925 is placed directly on the optical media 10 or used at some fixed distance from the optical media 10, such as on the lens of a lamp. The second light source 920 is adjusted and focused to achieve a favorable effect on the marking 620. The duplication device appropriately moves the coated optical media 10 so as to line up with the fixed position of the photomask 925 or the fixed position of the marking in order to realize a high processing amount. The cycle time for marking generation by this method is preferably within about 3 seconds.

In other embodiments, an electrical photomask 925, such as a liquid crystal display (LCD) device, is used. In these examples, the electrical photomask 925 is remotely programmed and controlled. The use of the electrical photomask 925 has certain advantages, including, but not limited to, increasing processing power by rapidly changing images, and reducing maintenance costs due to the small number of moving parts. Brought to you.

<u style="single">III Coating inspection</u><u style="single">A. General inspection equipment</u> When the coating 100 is applied to the optical media 10, it may be inspected for conformity with the preferred specifications. In some embodiments, the test is optional or omitted. In one embodiment, in the aspect shown in FIG. 73, a non-destructive inspection is performed on the optical inspection table 700. The optical inspection table 700 can include, but is not limited to, components such as a laser 710, a detection device 715, and an optimally configured processor 720. In the above embodiment, the laser beam is directed at the coating 100 of the optical media 10. The detection device 715 detects the reflected light and sends a signal to the processor 720. The processor 720 makes a determination about the characteristics of the coating, or a series of determinations. These properties can include, but are not limited to, thickness and uniformity. Other properties apply to unlimited transmission and target defects, as well as coating defects such as porosity, dye fog, dye stains, irradiation deflection, dye density, or dye edge range defects, or the like. It includes, but is not limited to, deviations from industry standards.

The determination is used to determine the pass / fail of the coated optical media 10. Processor 720 sends a signal to production line controller 730. The rejected optical media 10 is properly removed from the production line 2000 by the production line controller 730 for the next disposal, while the accepted optical media 10 proceeds through the manufacturing process. In this example, the optical media product is 100% inspected. However, in other examples, a certain number of manufactured quantities may be inspected. For example, a statistically significant quantity, every other, or a new batch of optical media 10 may be inspected. These optical media 10 may be removed from the production line for inspection routines or inspections of the manufacturing process.

Further inspection routines involve an electronic imaging system that assesses the quality of markings. Again, each optical media 10, or some pair, may be inspected. In these examples, devices such as properly illuminated CCD arrays and well-configured microprocessors are used as detection devices 715, but not limited to. Examples of suitable equipment include VERICAN from Spectra Systems, Rhode Island.

In this embodiment, the determination device 715 may be located above the optical media 10 as a way to clearly capture the marking 620 in order to minimize reflections or other interference. In this embodiment, the detection device 715 includes several components working together, as depicted in FIG. 73. In Figure 73, a typical marking detector 715 incorporates components such as a display 840, keyboard 850, and network link 860 (which may use one or more available communication protocols and designs). In addition to the user interface 845, it also includes a lighting 830, a lens / CCD system 820, a memory 815, and a storage device 818. These various components are controlled by the centralized integrated processing unit 800 on the board of the detection device 715. The detection device 715 in this case can be carried or fixed. In one embodiment, the detection device 715 includes a microscope laser scanner.

When used, the illumination 830 is used to provide standard light conditions, whereby the CCD array 820 images the markings on the optical media 10. The quality of certain properties of marking 620 is determined. For example, the color of the marking, the alignment of the text on the inner or outer edge of the optical media marking, the appearance of the digital watermark, or the placement of one marking 620 related to another marking 620 is evaluated. Processor 800 compares the observed characteristics with known or preferred characteristics and indicates the pass / fail criteria for the optical media 10. A pass or fail signal can be sent from network link 860 to a separate production line controller. Again, the rejected optical media is properly removed for the next disposal, while the accepted optical media 10 goes through the production line.

Another inspection system suitable for quality auditing of Optical Media 10 and Marking 620 on it is commercially available from Zyris Automation, Burlington, Ontario, Canada. The XIRIS PI-1500 includes three CCD chip camera modules, an integrated light source mounted on top, an arrangement structure, a flat panel computer screen, a visual processor device, eight digital inputs, eight digital outputs, and included software. Is included.

As another alternative, some parts of the optical media 10 manufacturing process may be inspected by destructive methods. In these embodiments, the operator may cut the portion of the optical media 10 or damage the optical media 10 in order to determine the final system performance information.

Another system that analyzes the quality of optical media 10 manufactured according to the teachings here is the CATS SA3 system sold by AudioDev USA in Woodland Hills, California. The system tests the reading and playback capabilities of optical media by measuring various signals and parameters. The levels of these parameters can then be analyzed to draw conclusions about the stability of the disc manufacturing process and possible playback function problems.

<u style="single">B. Study of coating conditions and radial noise</u> Another study was conducted to evaluate the performance of optical media manufactured according to the teachings here. Disc 10 is coated on a HEADWAY PWM32-PS-R790 spinner system with an HDP98 liquid dispenser and a MA24WEA dispensing arm. Formulation 3 (9021) was used (see Table 14). Changes in rotational speed and various coating parameters were adopted to test the effect of the spin coating parameters on the electrical specifications of the disc 10. Programs using two or more, or programs that increase the speed of rotation, were tested. A preferred coating was determined using a single rotation at 4K rpm for 10 seconds. The spin coating programs used in the HEADWAY system are shown in Table 31.

<tables num="31"><img file="JP4530273B2_D0032.tif" /></tables> As the distribution time to maintain a 2.0 ml distribution increased (depending on viscosity), the rotational speed (rpm) used in steps 1 and 2 decreased. The distribution amount of the HEADWAY spin coating system is a function of distribution time and distribution pressure. Therefore, when the distribution time was set to 3.5 seconds at a constant pressure of 50 psi, the distribution amount was 1.9 to 2.0 ml. This amount of paint is provided for the desired coating 100. To test the effectiveness of the performance parameter imaging process, the disc 10 was coated, cured and then tested in a CATS system. The disk 10 is then imaged and a second test is performed on the CATS system. There was no difference in the CATS test results. The data produced by the CATS system is shown in Figure 74, but here the data for uncoated disk 10 is shown. Note that the final surge at the end of each test is due to the end of the data and is not an inherent error in Disc 10 or Coating 100. FIG. 75 shows the data of the coating disc 10 which has been cured but not imaged. FIG. 76 shows the coated disc 10 that has been cured and imaged.

Further research on radial noise was carried out as part of the evaluation of the manufacturing system for Optical Media 10. This study will be reviewed in the "Manufacturing Systems" section.

<u style="single">C. Inspection technique</u> Inspection techniques include completing inspections at various stages of optical media 10 manufacturing. For example, the cambium 101 is applied, cured on the reflective layer 14 treated on the substrate 16, and then sent to the inspection table 700. Upon passing the inspection, in some embodiments, the substrate 16 is then sent to the marking. In some other embodiments, the substrate 16 proceeds to another platform for applying the protective film 102.

<u style="single">IV manufacturing system</u><u style="single">A. General manufacturing equipment</u> In the first embodiment, a manufacturing system similar to the Singlas Skyline system sold by Singlas Technology, Windsor, Connecticut, is used to manufacture the optical media 10. Appropriate changes and enhancements have been incorporated into the system for the examples described herein and for the examples to take effect. The appearance of the device is described here, or is considered common to those skilled in the art and will not be described in further detail.

In this typical embodiment, a newly replicated disk 10 comes out of the replication line on the spindle. Coating 100 is applied using a spin coating process and then cured by exposure to first light with wavelengths in the ultraviolet (UV) range. After proper coating and curing, at least one image 620 transitions to coating 100 using exposure to a second light 920. In one embodiment, the second light 920 employs a UV wavelength and a photomask 925. In another embodiment, the second light 920 is directed at the coating 100 as a controlled directional writing laser. It is preferred that an inspection step be included before or after exposure to the second light 920 to ensure that the coating 100 meets the light or other standards of the optical media 10 type. The manufacturing time may vary depending on factors such as the components of the coating 100, spin coating time, curing time, imaging time, inspection time and the like.

The appearance of the above-described embodiment, which is preferable for producing the marked optical media 10, includes, but is not limited to, the following typical conditions. 1. The rotary coating table has the following. Manual adjustment function by using micrometer screw and automatic adjustment function of radial position of distribution nozzle of coating material, for example, use of viscous formulation of about 35 cps, filtration system to eliminate particles up to about 0.2 micrometer, rotation Recycling function of the paint that flew in, distribution amount up to about 30 ml, distribution speed from about 30 to 100 RPM, speed increase up to about 2,000 RPSS, rotation speed up to about 5,000 RPM, and stepwise speed increase. 2. Approximately 300 mW / cm at a wavelength of approximately 365 nm²Gives a UV curing table. 3. An optical inspection table that has the function of detecting surface defects in the form of a height change of about 100 nm and a side change of about 200 microns. 4. Approximately 2 W / cm at a wavelength of approximately 350 nm²Give a photomask stand (0.5 seconds required for handling is added, about 2.5 seconds, about 5 J / cm²If is realized). 5. Total about 4J / cm²A characteristic laser that provides the fluence of, operated at a wavelength of 355 nm, approximately 0.15 J / cm per pulse.²It has a pulse energy limit of less than and has an average power of about 4 watts. In this unrestricted embodiment, the coating cycle time of the markings described herein is less than about 7.5 seconds from start to finish, but does not exceed 3 seconds at each stage.

FIG. 77 shows a diagram of an industrial manufacturing environment referred to as an "in-line" system. In FIG. 77, the sides of the optical media duplicator 2100 are characterized by at least one marking 620 of the single layer coating 100 and used to create the coated optical media 10 like a skyline system or similar system. To. In this embodiment, the optical media duplicator 2100 properly receives the material at production line 2000 and manufactures the final optical media 11 with markings as disclosed herein. In one embodiment, the system 2100 completes the first step, such as attaching the reflective layer 14 to the base 16 if the prepared base 16 was created using the preparation base 2110. The preparation table 2110 may be subject to other manufacturing steps, such as the formation of base 16. The preparation platform 2110 may scan for defects in board 16 and may include additional equipment needed to complete this task. Therefore, the depiction of the preparation table 2110 should be understood as an indication that the system 2100 may incorporate the additional equipment required to manufacture the prior art optical media 8. The optical media 8 proceeds to the spin coating table 2120 to apply a single layer of formulation forming the coating 100. The optical media 8 proceeds to a curing table 2130, where the coating 100 is exposed to the first light 910 to cure, as described herein. When the coating 100 of the optical media 8 is cured, the cured optical media proceeds to the marking table 2140. At the marking table 2140, the optical media 10 is exposed at the wavelength of light from the second light 920. In the example shown, the second light 920 utilizes a photomask 925 to create a marking 620 on the coating 100 of the optical media 10. The final stage will be completed on the final platform 2150 if necessary. The final stage may include, without limitation, the use of a pass or fail detection device 700 for each of the marked optical media 11. Manufacturing system 2 The operation of 100 and other aspects may be suppressed by a system controller 2101 such as processor 2101 running an instruction set (software), or by other techniques such as manual operation. An example of the system controller 2101 is an external personal computer 2101 connected to control various components of the manufacturing system 2100. In other embodiments, the first and last inspection aspects are mixed with the other manufacturing stages. For example, the optical media 10 may be inspected after each of spin coating, curing, and marking. Systems such as those in the embodiments described above are preferably automated, but are otherwise equipped to achieve high speed mass production.

FIG. 78 represents an aspect of one embodiment of manufacturing system 2100 equipped with markings of optical media 10 with coating 100 along with a plurality of color forming layers 401, 402, 403. In FIG. 78, the marking table 2140 includes a series of light sources such as the second light 9210, which is referred to by "marking source", "marking light" or other similar terminology. In this embodiment, the first marking lamp 921 is used with the first photomask 925 to give the first color forming layer 401 the marking 620. The second marking lamp 921 is used in conjunction with the second photomask 926 to give the second color cambium 402 the marking 620. The third marking lamp 922 is used in conjunction with the third photomask 927 to give the third color cambium 403 the marking 620.

A further embodiment of manufacturing system 2100 is shown in FIG. In FIG. 79, the manufacturing system 2100 was devised for the manufacture of optical media 10 using a two-layer coating 100. In this embodiment, the first spin coating table 2120 is coated with the color forming layer 101. The cambium 101 is cured on the first curing table 2130. The cured color cambium 101 is marked with a marking 620 on the imaging table, as described elsewhere here. The marked optical media 11 then proceeds to a second spin coating table 2160 to coat the protective film layer 102. The protective film 102 described above is cured on the second curing table 2170 using the second curing ray 975. The final inspection or other final stage will be done on the final platform 2150.

As you can imagine, the appearance of the manufacturing system 2100, such as the components incorporated herein, depends on the design of the optical media 10 and the desired appearance of the optical media 11 to be marked. Further examples of the manufacturing system 2100 shown in FIG. 80 include the use of a series of manufacturing systems 2100 as shown in FIGS. 77 and 79. In this embodiment, the first manufacturing system 2100 is used to apply the first color forming layer 401, cure the layer 401, and then give an image to the layer 401. The second manufacturing system 2100 applies a second color forming layer 402, cures the layer 402, and then gives an image to the layer 402. The third manufacturing system 2100 applies a third color forming layer 403, cures the layer 403, and then gives an image to the layer 403. The operation and other aspects of the manufacturing system 7700 are controlled by the system controller 7701, which executes the instruction set (software), or by other techniques such as manual operation. One example is an external personal computer 7701 connected to various other control systems 210.

<u style="single">B. General offline manufacturing equipment</u> In a further embodiment that does not provide unlimited, a manual or semi-automated system is used offline for the production of coated optical media 10 and / or marked optical media 11. As one example of this example, a previously manufactured or commercially available optical media 8 was selected and coated. As described herein, the coating 100 is applied to the optical media 8. The treatment of Coating 100 is carried out in an environment where factors such as environmental dust and air are properly controlled to limit contamination of Coating 100.

Examples of offline systems include systems such as those shown in Figures 77-79, although the preparation table 2110 is omitted. In the offline system, the steps described in the above discussion are performed to create the marked optical media from the coated optical media 10 and / or the existing optical media 8.

A manual or automated technique is then used to align the coated optical media with the curing ray 910 to cure the coating 100. FIG. 81 illustrates an example of a curing table 7800 for manual curing. The coating 100 is then cured. The cured optical media is subsequently cooled or otherwise placed in the required situation. The coated optical media 10 may enter the distribution chain and be directed to a marking stand or removed for the next marking by the manufacturer. Marking is performed in the manner described herein and may be associated with the use of photomask 925 and / or the use of direct writing laser 920. Thus, the coated optical media 10 is ready for the next marking by the manufacturer or others such as a third party.

FIG. 82 shows a diagram of an offline marking technique when used to create a marked optical media 11 from a coated optical media 10. In this embodiment, an unmarked or "blank" coated optical media 10 is introduced into production line 7900. The production line 7900 and its equivalents are also called "optical media receivers". Optical media 10 goes through production line 7900 when an offline marking system 7901 containing at least a second optical 920 is used to provide marking 620 on optical media 10. Other components of the offline marking system 7901 include, but are not limited to, photomasks, equipment, aligners, spin coating and curing tables for protective film 102, and other supplementary equipment. The direct writing laser 920 and supporting equipment may be incorporated into the offline marking system 7901 in combination with a photomask or in placement. In some embodiments, the optical media receiver 7900 may only be a tray in a fixed position with respect to the marking light 920.

Offline marking can occur at various points in the distribution chain. For example, offline marking may be performed by the manufacturer of Optical Media 10, a second manufacturing plant, a distributor, or an end user. For example, the prepared (coated) optical media 10 may be marked at a video rental store equipped with suitable equipment. In this way, the store may incorporate its own content, such as promotional information, owner information, or other information such as duration of use. Similarly, end users can be involved in marking their optical media 10 with the use of appropriate equipment. This feature may be attractive as a novelty for small manufacturers or individual users. Therefore, the additional devices of these further embodiments may be used for marking the optical media 10 and are within the scope of the intent of the present invention disclosed herein. For example, the end user can use software, several suitable substrates used in a laser printer to create a photomask 925 from software, and a suitable light source (diode,) used in a laser printer that created a photomask 925. Inexpensive kits may be provided that include (such as an array of black lights).

<u style="single">C. Thingrass Skyline Duplex coating conditions and radial noise</u> The use of off-the-shelf disc duplication equipment such as Singulus Technology's Skyline Duplex should allow disc coating within specifications that include radial noise. To test this, Disc 10 was coated and cured with Formulation 9021 using a Singlas Skyline Duplex machine. Subsequent evaluations showed that the coating was within the radial noise specification below 30 nm. Measurements showed that the difference in radial noise between uncoated and coated discs using the Singlas Skyline Duplex machine was minimal. Figure 83 shows the test results of the CATS SA3 system on a disk 10 coated on a Singlas Skyline Duplex machine.

Analysis shows that the best coatings were obtained using single rotation and speed. The coating conditions used for the Singlas Skyline Duplex machine are shown in Table 32. These settings can be applied to any coating of coatings 101, 102, or coating temperature, which has a thickness of coating 100 determined by the viscosity of the paint.

<tables num="32"><img file="JP4530273B2_D0033.tif" /></tables><u style="single">D. Thingrass Skyline Duplex and Lamp Curing Action</u> Research has been completed to test the curing of the coating on the Singlas Skyline Duplex machine. In this study, a formulation protective film O1 was placed in a Skyline duplex machine and various lamps were tested for top and edge curing. A Zenon C-bulb was used and the exposure power was set to 1.0kW. The exposed disc was completely cured at the top and edges for 2.0 seconds. Time intervals of 1.0 and 1.5 seconds were also evaluated, but Disc 10 did not cure sufficiently. The reflector on the paddle of the machine was obstructed using a felt tip marker. Again, disk 10 was evaluated, but no difference appeared and it was in the same state. Disc 10 was completely cured at the top and edges.

An F-bulb with a metallized reflector was also evaluated. For the F-bulb control, the maximum exposure power was set to 5.0 kW and the maximum exposure time was set to 5.0 seconds. The exposed disc 10 did not cure at the top or edges. Next, a V-bulb (gallium iodide) with a metal-worked reflector was evaluated. For the V-bulb control, the maximum exposure power was set to 5.0 kW and the maximum exposure time was set to 5.0 seconds. Disc 10 did not cure sufficiently at the top or edges.

Changes in the formulation of protective film O1 were evaluated. In these studies, the protective membrane O1 formulation was prepared to replace the photoinitiator KTO / 46 ratio with Irgacure 819. Four formulations were made as shown in Table 33.

<tables num="33"><img file="JP4530273B2_D0034.tif" /></tables> The formulations in Table 33 were manually coated onto Disc 10 using a HEADWAY spin coating machine. These were tested for curing at various time intervals on Skyline Duplex machines using V-valves (gallium iodide). The results are as shown in Table 34 (NG indicates bad). All discs were completely hardened at the edges, with the reflector obstructed.

<tables num="34"><img file="JP4530273B2_D0035.tif" /></tables> Tables 35 and 36 disclose preferred embodiments of the protective film layer 102 and the color forming layer 101, respectively.

<tables num="35"><img file="JP4530273B2_D0036.tif" /></tables>

<tables num="36"><img file="JP4530273B2_D0037.tif" /></tables> Thus, while the present invention is specifically shown and described with respect to preferred embodiments, changes in form and detail may be made without departing from the scope and intent of the invention. I hope the vendor will understand. For example, many changes may be made in coating application, curing, marking, and marking quality control methods and equipment. Such examples include performing various steps in an order other than those disclosed herein, or performing specific steps, such as bulk spin coating or curing. As mentioned herein, techniques for developing protective films and cambium will produce many other formulations suitable for the practice of the present invention. Accordingly, the present invention has been generally described with the examples described herein and their modifications, but the present disclosure is not disclosed or merely presented herein with those examples. Including others.

<figref num="1">It is sectional drawing of the optical medium in the prior art.</figref><figref num="2">FIG. 5 is a cross-sectional view of an optical medium having a coating according to the teachings of the present invention.</figref><figref num="3">It represents the absorbance curve of the color former at the time of coating formation.</figref><figref num="4">Compare the background color formation of various components.</figref><figref num="5">The absorption spectra of the two photoacid generators are shown.</figref><figref num="6">Represents the ultraviolet absorption spectrum of the first photogenerator.</figref><figref num="7">Represents the ultraviolet absorption spectrum of the second photogenerator.</figref><figref num="8">Represents the linear spectrum of a medium pressure iron dope lamp.</figref><figref num="9">Represents the linear spectrum of a gallium iodide lamp.</figref><figref num="10">Represents the linear spectrum of a gas-filled lamp manufactured by Zenon.</figref><figref num="11">Represents the transmission curves of various filters.</figref><figref num="12">It represents an absorption peak at 540 nm for various concentrations of color former.</figref><figref num="13">It represents an absorption peak at 540 nm for various concentrations of triphenylsulfonium triflate.</figref><figref num="14">Average color loss in the first environmental survey.</figref><figref num="15">Represents a decrease in surface tension as a concentration function of various wetting agents.</figref><figref num="16">Represents the average absorbance of various formations after environmental testing.</figref><figref num="17">Represents the average decrease in light density of various formations after environmental testing.</figref><figref num="18">Represents a storage case containing filter paper.</figref><figref num="19">Represents fading due to TEA exposure.</figref><figref num="20">Represents color development with the exposure wavelength as a function.</figref><figref num="21">Represents color development on a sample containing an ultraviolet absorber.</figref><figref num="22">Represents the effect of adding UV absorbers to color production.</figref><figref num="23">Represents the color formation of the UV stabilizing agent.</figref><figref num="24">Represents color formation in a particular sample of UV stabilizers.</figref><figref num="25">It shows the result of the adjustment study of the ratio of the color former and the photoacid generator.</figref><figref num="26">The color level and sensitivity are expressed using the concentration of the photoacid generator and the film thickness as functions.</figref><figref num="27">Indicates the absorbance of the CN-120 basal agent.</figref><figref num="28">Compare the absorption spectra of various UV absorbers.</figref><figref num="29">Represents the color development time for a mixture containing various photoacid generators.</figref><figref num="30">As a function of the photoacid generator, it represents the aspect of color generation.</figref><figref num="31">Represents color formation as a function of the type of illumination.</figref><figref num="32">It represents color formation as a function of UV absorbers.</figref><figref num="33">It represents color formation as a function of the amount of illumination.</figref><figref num="34">Represents color formation as a function of fortifying additives.</figref><figref num="35">Represents color formation in a buffering system.</figref><figref num="36">The film thickness is expressed as a velocity function of the intrinsic angular momentum.</figref><figref num="37">It expresses the film thickness and light density as a velocity function of the intrinsic angular momentum.</figref><figref num="38">The film thickness is expressed as a velocity function of the intrinsic angular momentum.</figref><figref num="39">Represents color formation with respect to changes in the ratio of photoacid generator to color former.</figref><figref num="40">A cross-sectional view of an optical medium having a color forming layer and a protective film layer is shown.</figref><figref num="41">Represents the light density of the two coatings.</figref><figref num="42">Represents color formation as a function of shape start time.</figref><figref num="43">The absorption spectra in the three examples of the protective film layer are shown.</figref><figref num="44">Represents residual sensitivity in two coating systems.</figref><figref num="45">Represents the light resistance of the exposed area.</figref><figref num="46">Represents color development by environmental test.</figref><figref num="47">Represents the color retention of the environment.</figref><figref num="48">Represents fading due to the study of amines.</figref><figref num="49">The film thickness is expressed as a function of the intrinsic angular momentum velocity.</figref><figref num="50">Viscosity is expressed as a temperature function.</figref><figref num="51">Represents the characteristics of the shear rate.</figref><figref num="52">It represents the characteristics of shear pressure and shear rate.</figref><figref num="53">Represents the viscosity of a constant shear rate.</figref><figref num="54">Represents the color formation of a series of photoacid generators and luminescent agents.</figref><figref num="55">Represents the color formation of a series of photoacid generators and luminescent agents.</figref><figref num="56">Represents the color formation of a series of photoacid generators and luminescent agents.</figref><figref num="57">Represents the color formation of a series of photoacid generators and luminescent agents.</figref><figref num="58">Represents a comparison of light sources.</figref><figref num="59">Represents a comparison of light sources.</figref><figref num="60">Represents color formation as a function of the amount of sunshine.</figref><figref num="61">Shows the residual sensitivity of the coating with various UV absorbers.</figref><figref num="62">As a function of the ultraviolet absorber, it represents the light density in the exposure range.</figref><figref num="63">It is sectional drawing of the optical medium in which a plurality of layers are applied on the reflective layer.</figref><figref num="64">It is sectional drawing of the optical medium in which a plurality of layers are applied on the reflective layer.</figref><figref num="65">It is sectional drawing of the optical medium in which a plurality of layers are applied on the reflective layer.</figref><figref num="66">It is a graph which shows the absorbance curve in the orange and red cambium.</figref><figref num="67">It is a graph which shows the absorbance curve in the example of multicolor.</figref><figref num="68">It is a graph which shows the absorbance when only the upper color cambium is exposed.</figref><figref num="69">It is a graph which shows the absorbance in the multicolor system which has an ultraviolet ray blocking layer.</figref><figref num="70">It is a partial view of the photomask which shows the shading technique.</figref><figref num="71">Marking Represents a marking formed on an optical medium by illumination with a lamp.</figref><figref num="72">Represents an inspection device that evaluates markings.</figref><figref num="73">Represents a component of an inspection device.</figref><figref num="74">Represents test data for uncoated discs.</figref><figref num="75">Represents test data for coated discs.</figref><figref num="76">Represents test data on a coated disc on which at least one image is recorded.</figref><figref num="77">Represents a component of one embodiment of an applied manufacturing system for monochromatic cambium.</figref><figref num="78">Represents a component of another embodiment of optical media creation.</figref><figref num="79">Represents a component of a manufacturing system for applying two coating systems.</figref><figref num="80">Represents a device that applies multiple coatings.</figref><figref num="81">Represents a manual curing device for coatings of optical media.</figref><figref num="82">Represents an offline marking system that marks optical media.</figref><figref num="83">Represents test data of optical media manufactured by the manufacturing system.</figref>