JP4530273B2 - System for marking optical media - Google Patents

Description

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

  Optical media includes a variety of complementary information in addition to data recorded on optical media, as is commonly used today. The complementary information is often displayed in a complex manner and fits for marketing, advertising, or other purposes of the manufacturer. The complementary information may be included in various forms, such as by use of sticky labels, ink, or other techniques.

  Considering that about 1 billion DVDs and over 4 billion CDs are produced annually (according to International Recording Media Association estimates), the potential advertising space is 1 billion pages in terms of magazine advertisements, newspapers This is equivalent to 300 million pages when converted to advertisements and 3 million pages when converted to advertisements. Therefore, the value of incorporating the marking on the reading side of the optical media is very high.

  The label or marking is generally attached to the “non-read” side of a disc such as a CDROM or DVD in order to indicate information such as a source of the disc and a list of information recorded therein. By placing the marking on the non-read side of the optical media, it is possible to use a variety of marking techniques, from simple marking to complex marking. Placing the marking on the read side of the optical medium is very difficult, especially in the data recording area, because the marking may interfere with the use of the optical medium.

  There is a need for more advanced marking methods. This need is growing rapidly with changes in optical media technology. For example, DVD-10 and DVD-18, which are examples of embodiments of DVD optical media, require recording and presentation of magnetic data 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 task. Reference is made to a US patent issued to an optical storage system. For example, US Pat. No. 5,549,953 issued by Li Li issued on August 27, 1996, entitled “Optical Recording Medium with Optically Variable Safety Characteristics”, describes optically changing safety characteristics. And various anti-counterfeiting techniques for printed materials by introducing a thin film structure with coded optical data. Another US patent is Sullivan et al., Patent No. 5,510,160, issued August 23, 1996, entitled “Optical Recording Media with Visible Logo”. This patent also discloses anti-counterfeiting technology for optical storage media, in particular by creating a visible logo on the read side of the substrate. Although these patents provide for the incorporation of markings with certain advantages, any advantages are limited. That is, for example, the marking is only visible under certain conditions, and a complex or expensive manufacturing process is required to produce the final product. Further, the degree of control, or marking complexity, may be less than what is desired for effective advertising or other information delivery methods.

  Another example in which a coating is applied to optical media can be found in US Pat. No. 6,051,298 “Optical Disc with Protective Film”. In this patent, an optical disk having a protective film is disclosed, which film has high transmittance and high hardness against abrasion. Also, US Pat. No. 6,322,868 B1, “Use and manufacture of polymer / dye thin film coating for the purpose of enhancing the quality of recording and reading of optical storage media” describes the quality of encoded magnetic information. The use of thin film coatings is disclosed for the purpose of improvement. Another example includes Public US Pat. No. 6,338,933 “Rendering method and apparatus for non-readable optically encoded media”. This patent discloses the inclusion of optically activated materials to reduce surface reflectivity.

  However, the aforementioned patents do not take advantage of certain advantages of the material. For example, reference is made to International Patent Publication WO 02/101462 A1 “Laser Marking Method” issued on December 19, 2002 and applied for by Ciba Specialty Chemicals Inc. This publication discloses a method for coloring a polymer material containing a latent oxide that is a color former and a further selectable constituent by ultraviolet irradiation. Another international patent publication WO 02/100914 A2 is an invention “polymeric material containing latent oxide” filed by Ciba Specialty Chemical Inc. This publication further discloses a polymer material containing a latent oxide that can be converted to an acid by laser irradiation and an optional constituent.

  Another example is disclosed in US Pat. No. 5,028,792, “Exposure Visualization System to Ultraviolet Radiation” issued by Mullis on July 2, 1991. This patent discloses a photochemical action system to directly visualize exposure to ultraviolet radiation, in which photoacid is formed upon irradiation with ultraviolet light, and a dye is generated by visible color change. However, their use is not suitable for optical media because these materials polymerize with later added color formers. Therefore, these materials are not in a cured state necessary for the production of optical media.

  Further, another example is US Pat. No. 5,885,746 issued March 23, 1999 by Iwai et al. “Photosensitive resin composition, photosensitive composition using the same composition and printing original plate manufacturing method” Disc ". In this patent, the action of a high polymer, a monomer, a photopolymerization initiator that generates an atomic bond by exposure to visible light, a color former that develops color in the presence of an acid, and exposure to wavelengths from 200 nm to 380 nm. A photosensitive resin composition composed of an optically activated acid-generating agent that generates an acid is disclosed. In particular, this patent discloses the use of a dispersive agent that exhibits non-uniformity, a property that causes laser scattering in an optical media readout system. The initiator disclosed in this patent also reacts to visible light and requires the use of an oxygen barrier layer that affects proper curing. The use of an oxygen barrier layer is a major obstacle to applying these materials to large numbers of optical discs, as the manufacturing environment generally does not provide darkness and / or an oxygen-free environment. Further, such additional steps are an economic and manufacturing burden that affects the use restrictions of the marking system.

  Accordingly, there is a need to provide enhanced marking, identification, authentication, and encoding capabilities to media that contains optically readable information. That is, there is a need to quickly create images, text, or other optically encoded information on the label and / or readout side of optical media. Furthermore, this method must not interfere with the execution of data reading from optical media. A system that provides these functions further needs to provide a robust and durable marking in the environment where the optical media is used.

There is also a need to provide an optical media or disc manufacturing system that addresses the aforementioned needs, such as enhanced marking, identification, authentication, and encoding capabilities.
US Pat. No. 5,549,953 US Pat. No. 5,510,160 US Pat. No. 6,051,298 US Pat. No. 6,322,868B1 Public US Pat. No. 6,338,933 US Pat. No. 6,338,933 International Publication WO02 / 101462A1 International Publication WO02 / 100914A2 US Pat. No. 5,028,792 US Pat. No. 5,885,746

  The foregoing and other problems are overcome by the method and apparatus disclosed herein and by the method and apparatus according to embodiments of the present invention.

  An image transfer method and apparatus for reading and / or non-reading optical media such as CDs and DVDs are disclosed. Aspects of the present invention include, but are not limited to: Apply a material in optical media as a coating (s), cure the coating with the first light such as UV, treatment for each coating with a second light of a certain wavelength such as UV, infrared or near infrared The coating is selectively exposed to a second light having a constant wavelength, and an image is recorded on the bonding surface of the coating.

  Aspects of the invention include the application of coatings and marking on the read side or non-read side of the optical media that do not impair or substantially impair the functionality of the media.

  Aspects of the present invention further include monochromatic or multicolor images or markings formed on the bonding surface of the coating, in which case the markings are transparent or substantially transparent to the wavelength of interest. Created in shape. For example, the marking is transparent to the readout wavelength used when reading optical media marked with a 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 security measures.

  Further features of the invention include provisions for marking the read side of optical media with advertisements, brands, and other markings on the non-read side of normal media.

  As disclosed herein, devices associated with the production of coated optical media suitable for marking applications include, but are not limited to, integrated manufacturing equipment for optical media. In this case, the integrated device is modified appropriately and corresponds to the embodiment described herein. Alternatively, the apparatus may involve the use of manual or semi-automated techniques for the production of coated optical media and their marking.

  Another aspect of the present invention also includes the use of testing and inspection techniques to determine and / or control suitability of optical media manufacturing from various aspects. For example, the manufacturing process may include a process of evaluating the optical quality of the coating before marking. Alternatively, the manufacturing process may include quality inspection of a statistically large portion of the final product. For example, a CCD camera, processor, or similar device may be employed to image various appearances of product markings and compare to data records that describe the target display quality of each appearance.

  The foregoing description and other features of the invention will become more apparent from the following detailed description of the invention when read 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 multicolored marking to optical media such as CD (compact disc) or DVD (digital versatile disc). . Also disclosed are components of an optical media manufacturing system characterized by these markings. Aspects of the invention include, but are not limited to: Apply a certain material on the optical media as a coating (s); cure the coating with a first light such as UV; treat each coating with a second light of a constant wavelength such as UV The coating is selectively exposed with a second light of a certain 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 prescribed. Further aspects of the present teachings include inspection of coated optical media and techniques for its manufacture.

  Optical media marked in accordance with the teachings of the present invention is preferably manufactured in a mass production environment. Accordingly, the disclosure herein is described in response to the demands of mass production environments. For example, mass production environments generally require a minimum production time and therefore require rapid curing and image formation. Some 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. It should be recognized. Such enhanced embodiments are considered part of the teaching herein and are described by the appended claims.

The disclosure of the present invention is shown in the following section.
I.

II.
Optical media coating
A.
Development of single layer coating
1.
General preparation
2.
Screening for photoacid generators
3.
Curing considerations
Four.
Oxygen suppression
Five.
Color and image formation
6.
Environmental impact
7.
Study on fading of triethylamine
8.
Light resistance acceleration test
9.
Retest of photoacid generator
Ten.
Absorption spectrum of photoacid generator and membrane
11.
Screening for 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 two-layer coating formulation
Five.
Amine testing
6.
Quantitative study
7.
Physical properties of the coating
8.
Viscosity vs. temperature
9.
Viscosity versus shear rate
Ten.
Color formation by various lamps
11.
Ratio of photoacid generator and color former
12.
Lamp effect
13.
Protective film: Light resistance of protective film with various UV absorbers
C.
Example of optical media coating
1.
2-layer coating
2.
Multi-layer coating
3.
Multicolor disc
II. Marking formation
A.
Marking forming equipment
B.
Marking type
III. Coating inspection
A.
General inspection equipment
B.
Study of coating conditions and radial noise
C.
Inspection technique
IV. Manufacturing system
A.
General manufacturing equipment
B.
General offline manufacturing equipment
C.
Coating conditions and radial noise of Singulus SKYLINE DUPLEX
D.
Singulus SKYLINE DUPLEX and lamp curing action
I. Optical Media Coatings 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 have structures that are at least partially different from other optical media. Thus, the present disclosure teaches what is considered an example (but not a limitation) of incorporating a coating into an optical media. That is, the present disclosure does not provide a comprehensive disclosure for incorporating a coating into optical media.

  FIG. 1 illustrates a typical optical media aspect. In FIG. 1, a prior art optical media 8 is shown. The optical media 8 includes various layers, referred to herein as “components” of the optical media 8. The base layer 16 is formed by pits 5 and lands 6 (data function) and is generally formed of polycarbonate or similar transparent plastic material. The reflective layer 14 is placed on a data portion that allows readout by an interrogation laser. The protective film layer 12 is one of the components generally included to ensure integration of the reflective film 14 and is typically formed of an acrylate or similar material that is curable by ultraviolet light. The disc may be read through the base layer 16 as indicated by the arrow direction 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 implementation example in which the coating 100 is applied. In this figure, the optical medium 10 includes a reflective (reflective) layer 14 and a base layer 16. In a typical embodiment, the base layer 16 is formed of polycarbonate and the reflective layer 14 is metalized (with a reflective metal attached thereto). Since it is recognized that the sides of the reflective layer 14 and the base layer 16 are generally determined by the specifications of the optical media 10, details are not generally discussed here. The disk 10 generally includes pits 5 and lands 6 as data portions. 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 base layer 16 may be adjusted for subsequent generation of the coating 100. For example, the base layer 16 may be installed with a reduced thickness as determined with reference to the manufacturer's specifications according to the type of the optical media 8. Thereafter, by installing the coating 100, the thickness of the optical media 10 is increased to meet the preferred thickness specification.

  The coating 100 includes a coloring material necessary for generating a color image. The coloring material is constructed in various ways, as will be discussed in detail here. Chromogenic materials are used to develop gray scale, single color, or multicolor markings. The coating 100 does not disturb 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 appreciably at the readout wavelength of the readout laser of the optical media. Similarly, the thickness and other aspects of the coating 100 do not substantially interfere with the readout mechanism. Accordingly, the coating 100 can be applied to the “reproduction” side 16 or the “non-reproduction” side 12 of the optical media 10 shown in FIG.

  The coating 100 includes what can be referred to as two “sets” of photosensitive material. One set of photosensitive material promotes curing of the coating 100 when the coating 100 is disposed. That is, when exposed at one set of wavelengths, curing of the first set of photosensitive material occurs. The second set of photosensitive materials in coating 100 is optically altered upon proper exposure at another set of wavelengths. Thus, the coating 100 may include a photoinitiator that initiates cross-linking. Coating 100 may include, but is not limited to, a complex such as a photoacid or photobase generator, an acid or base reactive dye, a leuco dye, a metal chelate, a fluorescent dye, or a laser dye. The 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, a wavelength in the visible range.

  Readout light wavelengths commonly used in optical media 10 are 408 nm, 440 nm, 630 nm, 650 nm, and 780 nm, although other readout wavelengths are possible.

  Although a photosensitive material is disclosed herein that is sensitive to ultraviolet (UV) wavelengths, the coating 100 may include a material that is sensitive to any wavelength band (also referred to as a “series of wavelengths”). For example, the photosensitive material responds to UV-A, UV-B, UV-C, VIS (visible wavelength), shortwave infrared (IR), IR or longwave IR. As may be inferred, having two sets of wavelength materials allows the use of two sets of wavelengths to initiate the coating 100 change as described herein. Other formation processes not considered here may advantageously use wavelengths other than the spectrum of wavelengths utilized. Accordingly, the teachings herein only provide one example of a marking application system for optical media and are not limited to the exemplary embodiments herein.

“Optical media” here refers to general terms such as “CD” or “DVD”. However, it is known that the optical media 8 includes a number of different media formats. For example, many formats of the optical media 8 include the following. 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 foregoing, Blu-Ray, etc. It is well known that this is not a complete list and is therefore only considered as an illustration of a variety of optical media formats that may benefit from the use of the present invention.
A. Single-layer coating development The following describes the development of coating materials. Some of the embodiments disclosed herein are experimental results. One skilled in the art will recognize that certain embodiments have certain advantages over other embodiments in certain settings. Further embodiments may also be developed. Thus, it should be recognized that the creation of the coating and the formation of the application and process are exemplary and not limiting of the invention.

1. General Formulation At first, an attempt was made to create a photosensitive color coating by combining an acrylate, a photoinitiator, a photoacid generator (PAG), and a color former. One of the first formulations that became favorable was composed of about 3% photoacid generator (PAG), about 3% color former, and about 94% of a mixture called “coating base”. The coating base is formed of a mixture including an acrylate and a photoinitiator. Currently, preferred examples of coating bases are typically monomeric acrylate and oligomer mixtures, 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 a suitable coating base material included a mixture of acrylates in which about the same amount of SR-494 and SR-238 were mixed. The photoinitiator ESACURE KTO-46 was added to the acrylate mixture so that it was about 10% of the initial coating base.

  Chemical substances corresponding to these materials are as follows. SR-494 is ethoxyl (4) pentaerythritol tetraacrylate. SR-238 is 1,6-diacrylate hexanediol with a low viscosity, fast cure monomer with low volatility, hydrophobic backbone and good solubility in the use of free radical polymerization. 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 simply by mixing into a resin system, is insoluble in water, and is soluble in most common organic solvents and monomers. KTO-46 may be called ESACURE KIP-150 or ESACURE TXT. ESACURE KIP-150 is oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], and ESACURE TZT is 2,4,6-trimethylbenzophenone and 4 methylbenzophenone. This is a liquid eutectic mixture.

  ESACURE KTO-46, ESACURE KIP-150 and ESACURE TXT are manufactured by Lamberti Spa, Gallate-Va, Italy. SR-494 and SR-238 are manufactured by Sartomer Corporation, Exton, Pennsylvania. KTO-46 is also sold by Sartomer Corporation, as is SARCURE-1135 (thus KTO-46 and SR-1135 are used interchangeably herein).

  A study of the properties of the coating 100 using the initial coating base has revealed certain disadvantages. That is, it is recognized that the final product formed from the initial coating base does not exhibit the desired surface hardness and may irritate the skin. Accordingly, other components were also evaluated for use on the coating base. Table 1 shows the aspects of the components selected for the coating base and includes their performance characteristics.

ＳＲ−２８５は、テトラヒドロフルフリルアクリル酸で、環状基を含む、粘度の低い、極性の単管能基のモノマーであり、多数の基盤への接着を促進する。また、ＳＲ−９０２１は、高度にプロポキシレート化された（５．５）グリセリルトリアクリレートで、低粘性、良好な柔軟性、高速硬化、優れた硬度を提供する、皮膚への炎症が少ない、三官能性のモノマーである。ＳＲ−２８５とＳＲ−９０２１は、ペンシルバニア州エクストンのサートマーコーポレイション社製品である。

SR-285 is tetrahydrofurfurylacrylic acid, a low viscosity, polar, monofunctional monomer containing a cyclic group that promotes adhesion to multiple substrates. SR-9021 is a highly propoxylated (5.5) glyceryl triacrylate that provides low viscosity, good flexibility, fast cure, excellent hardness, low skin irritation, It is a functional monomer. SR-285 and SR-9021 are products of Sartomer Corporation, Exton, PA.

  SR-494 and SR-9021 were chosen 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 advantageous because they are less prone to irritation to the skin due to alkoxylation. In contrast, SR-238 and SR-285 irritate the skin, but provide the target solvent for the additive and cause the polycarbonate to swell upon good adhesion. SR-238 and SR-285 also exhibit low viscosity, thus providing an 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 ultraviolet longwaves (ie, greater than about 320 nm to 400 nm).

  Experiments have further shown that applying the coating 100 to the optical media 10 can be accomplished by a variety of techniques. The coating 100 is preferably applied by spin coating. However, during the initial application of the coating 100 by using spin coating, the edge of the optical media 10 was often less than intended. This was judged to be due to the high surface tension of the paint (coating base). Accordingly, wetting agents were added to the coating base to improve the wetting of the substrate and lower the surface tension.

  A typical system for forming a spin coating on the substrate 16 is a system from Headway Research, Inc. of Garland, Texas. The systems used here for forming by spin coating process include: A forming temperature adjustment control device, a control device having a maximum rotation speed of at least 10,000 (10K) rpm and increasing or decreasing the rotation speed in increments. The system further includes components such as an environmental control device that controls environmental gases and a preparation collection device that recycles unused preparations. Other systems are used for spin coating and may be further integrated into mass production equipment. One model suitable for application of the formulation here is at least small batch production and, as described herein, the model of the PWM32-PS-R790 rotating system used in the test. Since spin coating systems are well known, these systems will only be described generally with respect to the application of the coating 100 and its requirements.

  To see how it affects the performance of the coating 100, everything in the new component (Table 1) was added to create a formulation. In order to distribute the formulation more widely on the disk 10, wetting agents were included in the new formulation. The wetting agents tested were BYK-307 and BYK-333, both polyether-processed poly-dimethyl-siloxanes, which exhibit properties similar to surface tension reduction. BYK-307 and BYK-333 are products of BYK-Chemie, West Germany, and are sold in the United States by BYK-Chemie USA, Wallingford, Connecticut. Table 2 shows the formulations and results.

表２では、全部で１０の製剤の構成要素が示されている。最初のコーティングベースは、実験対象として示されており、その他の製剤は混合物１−９として示されている。１０個の製剤の各構成要素の量は、混合物全体の重量パーセントで表されている。

In Table 2, a total of 10 formulation components are shown. The initial coating base is shown as the experimental subject 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 formulation containing the wetting agent has a reduced surface tension compared to the formulation containing no wetting agent. This is considered to be an advantage of the preparation having a low surface tension because the coating on the substrate 16 is superior to the preparation having a high surface tension. However, after adding BYK-333 0.3% and BYK-307 0.05%, the surface tension of the formulation remains substantially unchanged. Therefore, formulations 3 and 7 were physically tested by spin coating the coating base onto various disks 10 and inspecting the edges of the substrate 10. This test revealed that Formulation 3 substantially improved the surface smoothness while the disk 10 coating was the best. However, the viscosities of the various formulations were not substantially changed 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 have similar properties, so that SR-9021 and SR-9020 can be used interchangeably. This is believed to be an advantage because SR-9020 provides superior thermal stability compared to SR-9021. SR-9020 is therefore 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 cure, and excellent hardness. SR-9020 is a product of Sartomer Corporation. The new components and performance of the formulation are shown in Table 3, and the formulation and viscosity results are shown in Table 4.

  Around the same time, several formulations with different acrylates were created to find paints that achieve a harder coating. New components for those performance formulations and aspects are shown in Table 3, while formulations and viscosities are shown in Table 4.

表３に示された構成要素は、サートマーコーポレイション社の商標名であり、以下のものに使用される。プロポキシレート（３）グリセリルトリアクリレート（ＳＲ−９０２０）、エトキシレート（３）トリメチロールプロパントリアクリレート（ＳＲ−４５４）、トリス（２−ヒドロキシエチル）イソシアヌレートトリアクリレート（ＳＲ−３６８）、ジトリメチロールプロパンテトラアクリレート（ＳＲ−３５５）、及びウレタンアクリレート（ＣＮ−９８３）。

The components shown in Table 3 are trade names of Sartomer Corporation and are used for: Propoxylate (3) Glyceryl triacrylate (SR-9020), Ethoxylate (3) Trimethylolpropane triacrylate (SR-454), Tris (2-hydroxyethyl) isocyanurate triacrylate (SR-368), Ditrimethylolpropane Tetraacrylate (SR-355) and urethane acrylate (CN-983).

回転コーティング、硬化サンプルの検査により、製剤１０と１４は、同様な粘度を示しながらも、対象（製剤３）より硬度が大幅に優れていることがわかった。その後、製剤１０と１４は、表５に示されている新しい製剤のスクリーニング試験から構成されるいくつかの試験の対象となった。好ましい実施例において、各製剤が、コーティング１００用ベースの候補と見なされるためには、前記スクリーニングに合格しなければならない。表５では、条件だけでなく関連試験も示す。

Examination of the spin coating and cured samples showed that formulations 10 and 14 were significantly better in hardness than the target (formulation 3), while exhibiting similar viscosities. Formulations 10 and 14 were then subject to several tests consisting of new formulation screening tests shown in Table 5. In a preferred embodiment, each formulation must pass the screening in order to be considered a base candidate for coating 100. Table 5 shows not only the conditions but also the related tests.

表６に示されるように、２つの新しい製剤が、新しい製剤スクリーニング試験に合格した。製剤サンプル１０と１４には、今後の使用およびより詳細な試験が検討された。

As shown in Table 6, two new formulations passed the new formulation screening test. Formulation samples 10 and 14 were considered for future use and more detailed testing.

２．光酸発生剤のスクリーニング
光酸発生剤（ＰＡＧ）は、コーティング１００が光の波長で露光されると発色するように加えられる。本過程は、光の波長での露光時の、ＰＡＧによる酸の生成に関係する。酸反応性の発色剤（ＣＦ）が、次々に酸と相互作用を起こし、色を形成する。ＰＡＧは紫外線に反応することが望ましい。

2. Photoacid Generator Screening A photoacid generator (PAG) is added to develop color when the coating 100 is exposed at the wavelength of light. This process relates to acid generation by the PAG during exposure at the wavelength of light. Acid-reactive color formers (CF) in turn interact with the acid to form a color. It is desirable that the PAG reacts to ultraviolet light.

  In order to find photoacid generators that function properly in coating 100, several photoacid generators were tested. Each formulation is prepared in the same way to compare various PAGs. The performance required for PAG includes proper acid generation for the desired color formation and stability in the environment after color formation.

  A coating-based sample was made by mixing the original target formulation (45% SR-494, 45% SR-238, and 10% KTO / 46). 94% of the mixture was added with a concentration of 3% of COPIKEM 16 Red (color former) and 3% of each photoacid generator tested. The paint was spin coated at 4K rpm on a blank, non-metallized, polycarbonate substrate 16 for 15 seconds. Thereafter, each disk 10 was placed under a pulsed Zenon lamp with a double-glazed window glass filter for 5 seconds. The disc 10 thus obtained has a transparent, dry and hard coating. Thereafter, a part of the disk 10 is exposed for 5 seconds. Another portion of the disk 10 is exposed for 10 seconds. As a result, red colors having different intensities were created on the transparent disc 10. In order to quantitatively measure the intensity of the color formed on the exposed disc 10, an absorbance curve was recorded with a spectrophotometer. The spectrometer used was a UV / VIS model called LAMBDA 2 manufactured by Perkin Elmer Corporation of Boston, Massachusetts. The generated data revealed that the absorbance peak 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 at zero seconds.

結果として、（ｔｅｒｔ−ブトキシカルボニルメトキシナフチル）ジフェニルスルホニウムトリフレート、（４−フェノキシフェニル）ジフェニルスルホニウムトリフレート、トリフェニルサルフォニウムトリフレート及び（４−ｔｅｒｔ−ブチルフェニル）ジフェニルスルホニウムトリフレートは強さが次第に減少した。しかしながら、０．５ＡＵは、可視には充分であると考えられるので、目的の光酸反応剤を選択する際には、費用などその他の要素が考慮された。トリフェニルスルホニウムトリフレートが、コーティング１００の好ましい選択として選ばれた。ただし、光酸発生剤は、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウム ｐ−トルエンスルホン酸とジフェニルヨードニウムトリフレートを除き、全て、３％で溶解性であった。ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムｐ−トルエンスルホン酸は、不溶解性の光酸の大部分を除去するためにフィルタが必要であった。

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 sufficient for visibility, so other factors such as cost were considered when selecting the desired photoacid reactant. Triphenylsulfonium triflate was chosen as the preferred choice for coating 100. However, the photoacid generators were all 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 photoacid.

  Table 8 shows the results for three photoacid generators (PAG). The three PAGs were reinforced coating base formulation 10 (SR-494 32.35%, SR-9020 32.35%, SR-285 15%, SR-238 10%, KTO / 46 10% and BYK-333 was incorporated in 0.3% (94%). 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 has higher solubility than (4-methylphenyl) diphenylsulfonium triflate and triphenylsulfonium triflate. The PERGASCRIPT RED I-6B formulation is exclusive and is not shown here. However, a wide variety of color formers suitable for use with the present teachings will now be presented.

３．硬化における考慮事項
この時点での硬化に関しては更に調査が進められるので、その他の光酸発生剤が研究され、濃度１０％のＫＴＯ／４６に代えられた。表９は、光開始剤の量を変えた最初のセットの実験結果を示す。各サンプルは、スピンコーティングにより準備され、その後、５秒間、窓ガラスフィルタの付いたゼノン社製ランプによる照射で硬化された。表９の各データは、９４％のコーティングベースの一部として、光開始剤の重量パーセントで表されている。硬化度は、コーティングに物理的ぼかしを試行することにより確立され、硬化度は以下の等級で示される。Ｅ（優）＞Ｇ（良）＞Ｄ（普通）＞Ｐ（劣）。

3. Curing Considerations As further investigations are ongoing regarding curing at this point, other photoacid generators have been studied and replaced with a 10% concentration of KTO / 46. Table 9 shows the results of the first set of experiments 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 in weight percent of photoinitiator as part of a 94% coating base. The degree of cure is established by attempting a physical blur on the coating, and the degree of cure is indicated by the following grade: E (excellent)> G (good)> D (normal)> P (poor).

結果は、サンプル２０、２１、及び２４の硬化は良好であることを示している。しかしながら、５％のイルガキュア３６９を含むサンプル２４は、紫外線の露光により色を全く発しない。また、５％と７％のイルガキュア３６９を含むサンプル２０と２１はわずかにピンク色に硬化する。ただし、不溶性であることに加えて、製剤２２と２３は塗料で赤に変化したので、廃棄した。

The results show that samples 20, 21, and 24 are cured well. However, sample 24 containing 5% Irgacure 369 does not emit any color upon UV exposure. Samples 20 and 21 containing 5% and 7% Irgacure 369 also cure slightly pink. However, in addition to being insoluble, formulations 22 and 23 turned red with paint and were discarded.

  DAROCUR 4265 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-phenylmorpholine) -butanone-1, which is chemically combined with a single or multifunctional monomer in a prepolymer (eg acrylate). It is a very effective UV curing agent used to initiate photopolymerization. Irgacure 819 is bis (2,4,6-trimethylbenzoyl) -phenylphosphinic acid and is a versatile photoinitiator for radical polymerization of unsaturated resins by exposure to ultraviolet light. In particular, it is suitable for transparent coatings intended for outdoor use by combining white pigment preparations, polyester / styrene-based reinforced glass fibers, and light stabilizers. Further, the thick portion can be cured by the photoinitiator. These are all products of Ciba Specialty Chemicals in Basel, Switzerland and Tarrytown, New York.

To further improve samples 20 and 21, CN-384 and amine synergist were added at 0.5% and 1%, respectively. With this new addition, a very clear cured coating could be produced. However, at 1%, the density is not sufficient in the exposed portion. Unfortunately, with the addition of CN-384, it has been found that the exposed portion of the disk 10 shows significant fading after about 24 hours at room temperature. (CN-384 is a dual-functional amine common initiator that, when used with photosensitizers such as benzophenone, promotes rapid curing under ultraviolet light. In addition, both the press side and cured film. CN-384 is a product of Sartomer Corporation, 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.

イルガキュア２９５９は、１−［４−（２−ヒドロキシエトキシ）−フェニル］
−２−ヒドロキシ−２−メチル−１‐プロパン−１−オンであり、不飽和モノマーとプリポリマーから構成される紫外線硬化システムに対する、非常に効果的な非黄色発色のラジカル光開始剤である。特に、悪臭を抑えることが要求される場合や、アクリレートあるいは不飽和ポリエステル樹脂を基剤とする水系システムの使用に適する。活性化されたヒドロキシグループは最適の機能性の不飽和樹脂と反応が可能である。ＳＡＲＣＵＲＥ１１２４は、イソプロピルチオキサンテンであり、紫外線不要のラジカル重合を開始するために適当な共通開始剤（例えばエチル４−（ジメチルアミノ）ベンゾエート（ＳＡＲＣＵＲＥＳＲ１１２５））との組み合わせで使用される光開始剤である。ＳＡＲＣＵＲＥ ＳＲ１１２４は、インク、ニス、装飾的コーティングに用いられる。ＥＳＡＣＵＲＥ ＫＩＰ １００Ｆは、オリゴ［２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンを約７０％と２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンを約３０％の液体混合物である。

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 use in cases where it is required to suppress malodors or in aqueous systems based on acrylates or unsaturated polyester resins. Activated hydroxy groups can react with unsaturated resins of optimal functionality. SARCURE 1124 is isopropylthioxanthene, a photoinitiator used in combination with a suitable common initiator (eg, ethyl 4- (dimethylamino) benzoate (SARCURESR 1125)) to initiate UV-free radical polymerization. . SARCURE SR1124 is used for inks, varnishes and decorative coatings. ESACURE KIP 100F is about 70% oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone and 2-hydroxy-2-methyl-1-phenylpropan-1-one Is a liquid mixture of about 30%.

  The experimental data in Table 10 shows 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 selecting formulations using Irgacure 819 in the cured portion immediately after curing and after 24 hours, as shown in FIG.

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

  Sample 37 cured rapidly but was deemed to have an undesirable amount of color development after curing. Therefore, another formulation was made with a low concentration of SR-1124. Other formulations were made with SR-1124 as SR-1124 appears to promote rapid cure. The experimental combinations of the third photoinitiator are shown in Table 11.

実験ＩＩＩは、サンプル４１と４３の硬化が良くないことを示す。サンプル４３も非常に速くピンクに変わった。ＳＲ−１１２４を含む一定の製剤は、予想通りであったが、光酸発生剤のＳＲ−２２４の増感作用は、イメージの紫外線安定性などのその他の特性に対してマイナスであると見なされた。しかしながら、表９−１１に示されたこれらの実験から、光開始剤の可能性のある組み合わせが開発され、ＫＴＯ−４６（製剤１０）の好ましい使用が今後の試験で障害を示した場合に、使用可能である。

Experiment III shows that samples 41 and 43 are not well cured. Sample 43 also turned pink very quickly. While certain formulations containing SR-1124 were as expected, the sensitizing action of the photoacid generator SR-224 was considered negative for other properties such as the UV stability of the image. It was. However, from these experiments shown in Tables 9-11, if possible combinations of photoinitiators were developed and the preferred use of KTO-46 (Formulation 10) showed obstacles in future studies, It can be used.

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

  An important aspect in achieving both curing and imaging is the spectral domain resolution capability available at each stage. As has been described herein, it is preferred that both curing and imaging be completed using ultraviolet wavelengths. Formulations other than those disclosed herein are found to show excellent response at other wavelengths, and therefore the use of the wavelengths specified herein is only an example. In the preferred embodiment, photoacid generators operating in this range can be used, and deep UV radiation generally does not show high density with natural irradiation (sunlight, fluorescent or incandescent light). Deep UV (wavelength less than about 320 nm) is used for imaging. This tends to realize an image having excellent durability under environmental conditions during use. For example, the absorption spectra of two commercially available photoacid generators with a slight absorbance at about 290 nm are shown in FIG.

  Many photoinitiators with a major absorption band at wavelengths above 300 nm are commercially available. Most notably, the phosphine oxide is a photoinitiator such as LUCIRINTPO (a major component of KTO46) and Irgacure 819 from BASF Corporation in Charlotte, NC, whose spectra are shown in FIGS. 6 and 7, respectively. Is to promote the function of In addition, photoinitiators that exhibit absorption at wavelengths greater than about 300 nm are also used. Note also that these initiators are direct split types of unimolecular initiators.

  Bimolecular initiators are generally composed of photosensitive molecules capable of absorbing light and transmitting to a synergist molecule that can form radicals after energy transfer. The most common sensitizer that absorbs visible light is ITX or isopropylthioxanthene. ITX is commonly used with amine synergists such as ethyl-p-dimethylaminobenzoate (EDAB) and octyl-p-dimethylaminobenzoate (ODAB). Both EDAB and ODB can form radicals upon receiving energy transfer from ITX. These components are not considered suitable for use in the coating for two reasons. The first reason is that ITX sensitizers also sensitize photoacids to visible light, thus limiting the spectral resolution of curing and writing. (This occurs to some extent when using certain monomolecular photoacid generators, such as Irgacure 819, which cause the photoacid generator to be slightly sensitive to long wave ultraviolet radiation). The second reason is that common synergists 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 discussion of photoinitiator types and processes. "UV and EB Formulation Chemistry and Technology for Coatings, Inks, and Paints, Photoinitiators for Free Radical Cation and Anion Photopolymerization, Volume 3" (2nd Edition, JV Crivello and K. Dieticker) Eds, WILEY / SITA series, Surface Coatings Technology, John Wiley and Sons, 1998).

  In addition to the requirement of having an absorption spectrum of photoacid generator and decomposed photoinitiator (which are very separate from each other), for mass production, sufficient light density in each band is required to cure in a minimum amount of time. It must be dark enough for imaging. Commonly used light sources for curing UV curable coatings include 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 such as the Zenon Company of Woburn, Oregon.

  One advantage of using an optical filter or other technique is that narrow wavelength wavelengths are created, or unnecessary wavelengths are substantially eliminated. Such a technique results in better resolution (separation of curing and imaging wavelengths) and thus opens up the possibility and choice of use of photoinitiators, photoacid generators and their composites.

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

  These lamps generally work well with UV curing because most lines are compatible with the photoinitiators used in UV curing systems. Another frequently used lamp is a pulsed Zenon gas-filled lamp, such as a Zenon lamp in Woburn, Massachusetts. The spectra of these lamps are essentially “black bodies” and the spectrum is derived from the color temperature of the plasma formed in the lamp during the pulse. A typical spectrum of a Zenon RC-747 gas-filled lamp is shown in FIG.

  In addition to a suitable UV light source, in order to first cure the coating 100 without premature color formation, it must be possible to separate the long wave UV portion from the short UV portion of the spectrum. This is preferably achieved through the use of an absorption filter having the transition curve shown in FIG. During the development of coating 100, a series of experiments were conducted to find the right combination of lamp, filter, and photoinitiator to adequately provide a short cure time without the occurrence of premature color formation. As shown in FIG. 11, the L37 filter is substantially transparent when it exceeds about 370 nm.

  A preferred method of coating curing consists of the use of a KTO-46 photoinitiator with a combination of Zenon bulbs and L37 filter glass. A typical mercury line lamp does not produce an appropriate light density when both are equipped with L37 filters, compared to a Zenon lamp. Since the light density of the Zenon pulse lamp creates excellent properties for the cured coating, a Zenon lamp was chosen to cure the coating 100.

  In practice, curing wavelength filtering is performed by using cold mirror technology, where the mirror selectively reflects a portion of the ultraviolet spectrum and transmits only the visible and infrared portions to provide only the desired wavelength. Is done. The present technique reduces the heat buildup of the coating 100 and provides the benefits of thermal management that requires cooling the absorption filter. Another approach that is considered beneficial for curing is to use different types of glasses for different UV transitions, since the bulb material keeps the heat buildup of the lamp housing. This is a known approach used by most bulb manufacturers, including Zenon, which provides five bulbs with only the type of glass used.

4). Oxygen suppression During the 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 a curing environment. Oxygen suppression is known and Crivello and K.C. By Dietricker (see Chapter 2, page 83). When coating 100 is cured in air, oxygen reacts with free radicals and forms peroxide radicals by reaction with photoinitiators, monomers, or growth chain radicals. The reactivity of the peroxide radical is insufficient to allow the free radical polymerization process to continue, leading to chain termination and resulting in an insufficient curing system. Methods for overcoming oxygen suppression include (1) adding more photoinitiator or (2) increasing cure time. Since the selected photoinitiator is relatively expensive, option (2) is considered preferred over option (1).

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

  A further way to overcome oxygen suppression is to use a photoinitiator that is less reactive towards oxygen. These initiators tend to require short wave ultraviolet light (<320 nm) to function. Instead, the photoinitiator has a sensitizing molecule or synergist as described above. As described above, the sensitizer makes the photoacid generator sensitive to visible light. This tends to reduce spectral resolution between 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 significantly reduce or even eliminate color formation or image stability. Therefore, this technique is not preferred for use with the coating 100.

  A preferred method of overcoming oxygen suppression is to increase the intensity of the curing light, such as by using a high intensity pulsed light source such as the Model RC-747 lamp sold by Zenon, Woburn, Massachusetts. In the preferred embodiment of the pulsed ultraviolet 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 are available for curing. In this approach, energy intensity is an important factor in achieving instantaneous curing. Detailed information on the effects of light intensity on curing 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, as 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 a nitrogen environment or an unnecessary amount of photoinitiator is not necessary while keeping the cure time as short as possible.

5). Color and imaging Several different color formers were tried using the coating 100. Formulations are made by mixing the base coating with the original control formulation (45% SR494, 5% SR238, and 10% KTO / 46) to perform a comparison of strength with each color former. did. 94% of the coating base mixture was added with a concentration of 3% of triphenylsulfonium triflate and a concentration of 3% of the color former to be tested. Absorption peaks occurred at various wavelengths due to the wide range of colors. FIG. 3 shows a typical curve recorded with a LAMBDA 2UV-VIS spectrometer. Table 12 shows significant results.

表１２のＣＯＰＩＫＥＭ材料を参照すると、本発明の実施の製剤に導入される材料の具体例と考えられる。実際には、これらの材料はもう市販されていないので、好ましくない。ＢＫ−３０５Ｂｌａｃｋ，Ｓ−２０５Ｂｌａｃｋ，ＢＫ−４００，Ｒｅｄ５２０は、日本とバージニア州アーリントンの山田化学工業株式会社から販売されている発色材料である。好ましい実施例には、多種のＰＥＲＧＡＳＣＲＩＰＴ発色剤の使用が含まれるが、これらの発色剤の構造と製剤は独占されている。しかしながら、本発明の実施に最適な発色材料の例は、１９７８年７月２５日にＧａｒｎｅｒ氏らの米国特許第４，１０２，８９３号「インドールおよび芳香族の無水物または複素環式芳香族化合物の発色剤製造工程、近接ジカルボン酸、同クラス物質の新規発色剤およびその使用」に開示されている。参照により米国特許第４，１０２，８９３号の開示がここに組み入れられる。例えば、米国特許第４，１０２，８９３号で開示された１つの発色剤は、表１の製剤の上から６番目であるが、ここに示した実験のいくつかに応じて試験され、少なくともいくつかの目的の特性を持つ色形成剤であることが示された。

Referring to the COPIKEM material in Table 12, it is considered a specific example of the material that is introduced into the formulation of the practice of the present invention. In practice, these materials are not preferred because they are no longer commercially available. BK-305Black, S-205Black, BK-400, and Red520 are color materials sold by Yamada Chemical Co., Ltd. in Japan and Arlington, Virginia. Preferred examples include the use of a variety of PERGASCRIPT color formers, but the structure and formulation of these color formers are exclusive. However, examples of chromophoric materials that are suitable for the practice of the present invention include those disclosed in Garner et al., U.S. Pat. No. 4,102,893, Jul. 25, 1978 "Indole and aromatic anhydrides or heterocyclic aromatic compounds. The color former production process, proximity dicarboxylic acid, novel color former of the same class and use thereof ”. The disclosure of US Pat. No. 4,102,893 is hereby incorporated by reference. For example, one color former disclosed in US Pat. No. 4,102,893 is the sixth from the top of the formulations in Table 1, but has been tested according to some of the experiments presented here, and at least some It was shown to be a color former having the desired properties.

  As a result, it was shown that the red coloring preparations, COPIKEM 16 Red and PERGASCRIPT Red I-6B exhibited the highest color intensity. Thus, in a preferred embodiment of the coating 100, the above color formers, and other color formers not discussed here, should be considered usable to create a suitable color formation, but a red-based formulation is used.

  In further experiments, a color former of PERGASCRIPT Red I-6B was mainly used. However, in some cases, the solubility of certain color formers became a problem when added at 3%. Since the black and green color formers showed some dissolution problems with the coating base used, these formulations were filtered and the concentration was reduced to slightly below 3%. However, further testing of green and black color formers probably produces improved results with a variety of coating-based formulations. In addition to the color former of Table 12, PERGASCRIPT Yellow I-3R was also tested. However, since this color former showed some color formation upon curing, the effective use of PERGASCRIPT Yellow I-3R requires further research.

  The basic formulation for coating 100 is formulation 3 (BYK-333 0.3%, KTO / 46 10%, SR-238 10%, SR-285 15%, SR-494 32.35% and SR- 9020 was changed to 32.35%). The well-functioning color former was then tested once more to make sure that the color formation was the same. The color formation with slightly different results is shown in Table 13.

表１４と１５は、３％発色剤、３％光酸発生剤、と９４％のベースコーティング（それぞれ、製剤対照比較、あるいは製剤３）において、ある色の強さがほかより高いことを示す。しかしながら、色の強さは、修正されなかった。光酸発生剤及び／又は発色剤の濃度を増加する、および色促進剤を追加するなど、さまざまな方法で、色の強さを増やすことは可能であると考えられる。

Tables 14 and 15 show that the intensity of one color is higher than the other in the 3% color former, 3% photoacid generator, and 94% base coating (formulation control comparison, or formulation 3, respectively). However, the color intensity was not corrected. It may be possible to increase the color intensity in various ways, such as increasing the concentration of the photoacid generator and / or color former and adding a color accelerator.

  Later, improvements in color strength were studied. First, the amount of color former, COPIKEM16Red, was increased from 3% to 6% and 9%. This was done with the coating base of the remaining control comparison formulation in the mixture, keeping the amount of photoacid generator fixed at 3%. Absorption curves were obtained using a UV-VIS LAMBDA 2 spectrometer. The results shown in FIG. 12 represent the absorbance peak at 540 nm.

  From FIG. 12, it can be concluded that exposure to 9% COPIKE 16Red, 3% triphenylsulfonium triflate, and 88% coating base for 10 seconds gives the highest light density (OD). However, only up to 9% COPIKEM 16Red was tested for 10 seconds. This result indicated that the color intensity could be increased by increasing the color former, at least to some extent. Since different color formers work differently at the same amount, specific experiments with other color formers are underway, and further studies are underway on changes in color intensity. However, as long as the color former used is soluble, it is believed that a similar change in color intensity will be realized.

  In another experiment, the amount of photoacid generator was increased as in the color former experiment. FIG. 13 represents the effect of color intensity after increasing the amount of photoacid generator (in this experiment, triphenylsulfonium triflate was used) in coating 100. FIG. 13 shows that the combination using 6% of the photoacid generator, 3% of the color former, and 91% of the coating base preparation generated the most color with an exposure time of 10 seconds. Moreover, although it is also possible to increase optical density (OD), 6% or more of photo-acid generators were added in this case. However, when the photoacid generator was 9%, the color intensity showed a noticeable decrease. For this reason, it has proved preferable to test triphenylsulfonium triflate (TPST) at concentrations between 6% and 9%. Overall, the addition of more color former than the photoacid generator 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 performed.

6). Environmental Effects Early studies conducted showed that the coating 100 is susceptible to environmental influences. That is, the imaged or colored area of the disk 10 fades due to substantial exposure to humidity and temperature. Therefore, another study was conducted to quantitatively measure the subtractive color affected by environmental effects.

  Eight different formulations were tested for color reduction and these formulations are shown in Table 14. (However, formulations are generally identified and referenced herein according to the constituents of the base coating formulation). Samples of each formulation were spin coated on 3 disks 10 for 15 seconds at 4000 rpm. The disk 10 was then cured under an L37 filter for 2 seconds in nitrogen. Thereafter, half of each disk 10 was exposed for 10 seconds. The extinction curve for each disk 10 was measured before and after the test to determine the average color reduction. In the humidity and temperature test, the disk was placed in an environmental furnace for 96 hours at 90% humidity and 70 ° C.

図１４に示された試験結果は、温度と湿度の存在下で、ある製剤はその他の製剤より色をよく保持していることを示した。特に、ＳＲ−３５５（製剤１４）、ＣＮ−９８３（製剤４５）、ＳＲ−３６８（製剤４６）などのようなアルコキシレート化されていないモノマーを追加すると、性能がすべて向上した。これは、アルコキシ含有の減少（親水性の低下）、及び、Ｔｇあるいは架橋密度の増加の結果と考えられる。トリフェニルサルフォニウムトリフレート（ＴＰＳＴ）の３基ブチル誘導体の使用、あるいは、光酸発生剤の高い濃度は、実質的に性能に影響を与えない。

The test results shown in FIG. 14 showed that certain formulations retained color better than others in the presence of temperature and humidity. 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 thought 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 tri-butyl derivative of triphenylsulfonium triflate (TPST) or a high concentration of photoacid generator does not substantially affect performance.

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

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

  Five polycarbonate discs 10 are manually coated with each formulation. Each disk 10 is then cured under a Zenon pulse lamp at a distance of about 5 inches using a nitrogen environment and an L-37 filter. Formulation 56 was very dark but well coated. Formulation 10 cured in 2 seconds. The remaining sample of the formulation cured in 4 seconds because it contained only 5% photoinitiator. Thereafter, half of each disk is exposed to a lamp for 10 seconds to form a red color. All discs 10 were scanned sequentially to measure light density at 540 nm (both cured and exposed) using a UV spectrometer.

この研究では、湿潤剤をＢＹＫ−３３３から架橋可能なシロキサンに変更することも評価した。ＴＥＧＯからの３つのＲＡＤ製品（ＲＡＤ２２５０、ＲＡＤ２２００Ｎ、ＲＡＤ２１００）を含めて、いくつかの反応性湿潤剤を試験した。これらの製品の性能は、製剤４８を使用して試験された。その結果、最も表面張力を減少させ、透明であったＴＥＧＯ ＲＡＤ２２００Ｎが選択された。試験の結果は図１５に示されている。ＴＥＧＯ ＲＡＤ２２５０とＲＡＤ２２００Ｎは、それぞれ、架橋可能なシリコンのアクリル酸ポリエーテルで、ＴＥＧＯ ＲＡＤ２１００は、架橋可能なシリコンのアクリレートである。ＴＥＧＯ製品は、Ｔｅｇｏ Ｃｈｅｍｉｅ Ｓｅｒｖｉｃｅ ＧｍｂＨ社から入手可能であり、米国では、バージニア州ホープウェルのＤｅｇｕｓｓａ Ｔｅｇｏ Ｃｏａｔｉｎｇ ＆ Ｉｎｋ Ａｄｄｉｔｉｖｅｓ社により販売されている。

This 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 selected the most transparent surface tension and was transparent was selected. The results of the test are shown in FIG. TEGO RAD2250 and RAD2200N are each a crosslinkable silicone acrylic polyether, and TEGO RAD2100 is a crosslinkable silicon acrylate. The TEGO product is available from Tego Chemie Service GmbH and is sold in the United States by Degussa Tego Coating & Ink Additives, Hopewell, Virginia.

  Three disks 10 of each formulation were placed in an environmental furnace for 96 hours at a temperature of 70 ° C. and a relative humidity of 100%. Disc 10 containing formulations 4 and 5 was stored in a translucent disc container as a control. When the disc 10 was removed from the container, all discs 10 of each formulation (10, 48-51) were again scanned at 540 nm and the difference in light density was measured. Comparison data is provided in FIGS.

  From the data, it is clear that the difference in viscosity affects the film thickness and the color produced by constant exposure. Thus, although the thick or dark coating 100 is severely faded, it is believed that color reduction is not necessarily a clear indicator of performance because it retains more color than the thinly coated coating 100. However, in the first estimate, the rate of color reduction is an indicator of the relative stability of a particular base imaging chemical.

  Formulation 59, based on bisphenol A diacrylate and SR-355 (Di-TMPTA), was considered to have performed the best in the group tested. Once applied, the coating 100 formed from the formulation 59 is a highly cross-linkable, high Tg, non-alkoxylated film. All other coatings contained high amounts of alkoxylated monomers that had low Tg, hydrophilicity, and basic environment. Therefore, a third group of formulations was devised to test the effect of alkoxylation on CN-120 formulations and 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, manufactured by Sartomer Corporation, which is a diacrylate of a low viscosity fatty compound. Finally, a test was conducted to determine if CN-983, a fatty urethane acrylate, could be used like CN-120. The results showed that only the CN-120 formulation provides excellent image retention. Of particular interest was the formulation CN-120-R, the only formulation using the alkoxylated monomer, SR-454. The performance of this formulation was not excellent, again indicating that alkoxylation was negative for image retention. CN-132 was generally unacceptable and the CN-983 formulation did not give results as CN-120. CN-132 is a diacrylate oligomer of a low viscosity fatty compound and is a product of Sartomer Corporation.

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

ＣＮ−１２０製剤の最終開発は、光酸発生剤の濃度の最適化とＵＶ吸光剤の追加（ＵＶ吸光剤の追加は、他の箇所でさらに説明される）により、太陽光と蛍光光線に対するコーティングの感度を下げる試みの開始と共に開始した。すなわち、４番目の環境実験には、光酸発生剤の濃度と、後の露光試験でのＵＶ吸光剤の濃度を変えた製剤を含めた。これらの製剤の構成の様子は、表１７に示された。

The final development of the CN-120 formulation is to coat sunlight and fluorescent light by optimizing the concentration of photoacid generator and adding UV absorbers (addition of UV absorbers will be further explained elsewhere) Started with the start of an attempt to reduce the sensitivity of. That is, the fourth environmental experiment included a preparation in which the concentration of the photoacid generator and the concentration of the UV light absorber in the subsequent exposure test were changed. The state of the composition of these preparations is shown in Table 17.

  In addition, two rotational speeds (4K and 6K) were used to test the effect of changes in coating 100 thickness on image stability. In addition to thickening, the thickened coating 100 film was expected to perform well in environmental tests. The formulation without UV absorber is prepared as before, including curing for 2 seconds in a nitrogen environment using an L37 filter glass under a “C” bulb from Zenon with a distance of about 1 inch. It was done. The disc 10 was imaged by irradiation for about 10 seconds at a distance of about 5 inches. The formulation containing the UV blocking agent was also imaged at a distance of about 5 inches from the lamp for a total of 30 seconds (15 seconds × 2 imaging session). These formulations were given long exposure times due to the long color formation time.

  The results show that even with the replacement of liquid components (CN-120-B60 and SR-368D), the use of 2% or 3% photoinitiator has substantially reduced image stability and color formation. Indicates no effect. However, the photoacid generator always has strong color when used in a large amount, but the lower the concentration, the better the color retention. With the addition of UV stabilizers, there is virtually no degradation of environmental stability (addition of 5%) to moderate degradation of environmental stability (addition of 10%). However, the final color of these formulations was weakened.

  SR-368D is tri (2-hydroxyethyl) triacrylic acid isocyanurate, a transparent 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 between water properties and high reactivity. Both are products of Sartomer Corporation.

７．トリエチルアミンの退色研究
基本環境で、ＳＲ−９０２１基剤の製剤（製剤３）の露光された色が退色したことに注目する。これは、当初、コーティングされた市販のディスクが本来のパッケージに戻されたと理解された。紙及び／又はインクの基本的性質により、コーティング１００の酸は、色を中和し、従って、大幅に退色した。別の問題は、インクジェットプリンタで作成されたラベルがコーティングされたディスク１０のラベル側に張られて、保管ケースに入れられた時を考える。ここでも、画像は退色する。従って、退色の量を数量的に測定するために、試験では、コーティングされたディスク１０が、基本環境を刺激するトリエチルアミン（ＴＥＡ）下に置かれた場合を想定した。ディスク１０は、その後、退色の量を明らかにするために測定される。

7). Triethylamine Fading Study Note that the exposed color of the SR-9021 base formulation (Formulation 3) faded in the basic environment. This was initially understood as a coated commercial disc was returned to its original package. Due to the basic nature of the paper and / or ink, the acid of the coating 100 neutralized the color and therefore faded significantly. Another problem is considered when a label produced by an inkjet printer is stretched on the label side of the coated disc 10 and placed in a storage case. Again, the image fades. Therefore, to quantitatively measure the amount of fading, the test assumed that the coated disc 10 was placed under triethylamine (TEA), which stimulates the basic environment. The 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 L37 filter and nitrogen. The absorbance curve of each disk 10 was measured. Thereafter, as shown in FIG. 18, the disk 10 was placed in a storage case 180 in which filter paper 181 was placed in the empty corners and the center.

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

  As a result, it was shown that the average color fading amount of the tested preparation was 36.0%. This was considered less than the desired amount and was tested to see if other formulations showed better results. The formulation was tested based on 9020, 355/455, 5% 4TB, 5% KTO, 368, and 983, and the results are shown in FIG. Note that all formulations have 3% triphenylsulfonium triflate except 5% 4TB with 5% (4-tert-butylphenyl) diphenylsulfonium triflate. FIG. 19 shows that certain formulations are resistant to fading in the basic environment and generally tended to have environmental capabilities.

8). It was noted that the background color of the disk 10 with the coating 100 containing the accelerated light fastness test 9020 turns slightly red over time when there is fluorescent room light. Accordingly, another set of experiments was devised to evaluate the effect of ambient light on the image of the coating 100.

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

  In order to determine which wavelength of light has the most influence on the formation of the background color, a set of discs 10 was prepared utilizing formulation 10 based on SR-9020. Disc 10 was stored without being exposed at the imaging wavelength after curing. Thereafter, to determine which wavelengths of light have the greatest effect on color formation, the disc 10 is placed under the fluorescent fixture with a portion of each disc 10 covered with a 2 inch × 2 inch 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 damaged wavelength is less than about 370 nm, and wavelengths less than about 320 nm cause the most problems. This appears to indicate that the UVB portion of the spectrum is the most useful 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.

  In general, the name of the cutoff filter indicates 50% transmittance. For example, a UV-30 filter is evaluated for its wavelength at 300 nm and has a transmittance of 50% at 300 nm. The 50% transmission is an approximation, and it has been found that the thin L-37 filter is very similar to the thick UV-36, as it varies slightly with thickness. Thus, in general, a 1 mm thick L-37 is desirable here (approximately 50% transmission at 370 nm), but not only UV-34 filters with other filters but also thicker UV-36 filters. Works well. UV-32 is considered the lower limit, and beyond UV-39, curing is slowed. Accordingly, preferred cut-off filters provide 50% transmission between about 320 nm and about 380 nm, and most preferred is between about 340 nm and about 370 nm.

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

  Each sample of tinuvin is liquid except for the powder of tinuvin 327. The test was performed by adding 1 percent of each UV absorber to formulation 10 except for one sample made with 5% tinuvin 171. However, an important step with UV absorbers is to slow down the color formation, so another step was performed so that each sample could still produce sufficient color when imaged. FIG. 21 shows a sample that created the appropriate color. In fact, the sample incorporating the UV absorber formed more color than the sample without the UV absorber (shown as MC9020 in FIG. 21). The color formation of the sample containing 5% tinuvin 171 was not confirmed, but when examined briefly after 10 seconds of exposure, the absorbance at 540 nm was 0.40 OD.

  Three cured (background color) discs 10 of each formulation were then irradiated by a fluorescent light testing instrument. Sample absorption curves were collected before the start of irradiation and usually daily during the study to observe the formation of background color. The aggregated results are shown in FIG. 22 and represent the effect of adding UV absorbers as determined in accelerated fluorescence experiments.

  FIG. 22 shows that one type of tinuvin is superior to the others, but the comparative difference at 1% concentration is very small. Samples containing 5% tinuvin 171 showed excellent performance in reducing color formation, but the difference is considered to be only moderate. Also, the use of 5% density substantially increased the writing time required for image creation. An attempt was made to prepare a formulation containing 10% tinuvin 171, but the material changed after curing (showing color formation without exposure to imaging light). The sample containing 5% tinuvin 171 showed the same effect after a long time. Therefore, it was determined that tinuvin 171 would not be an excellent candidate for use as a UV absorber.

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

ＵＶ−２４は、ＣＹＡＳＯＲＢ ＵＶ−２４の短縮名で、２，２’−ジヒドロキシ−４−メトキシベンゾフェノンである。ＵＶ−５３１は、ＣＹＡＳＯＲＢ ＵＶ−５３１ＦＬＡＫＥの短縮名で、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンである。どちらも、コネチカット州スタンフォードのＣｙｔｅｃ Ｃｏｒｐｏｒａｔｉｏｎ社の製品である。ＭＣ８０は、ＵＶＩＮＵＬ ＭＣ８０の短縮名で、メトキシケイ皮酸オクチルであり、日本のＢＡＳＦジャパン株式会社の製品である。

UV-24 is the abbreviated name of CYASORB UV-24 and is 2,2′-dihydroxy-4-methoxybenzophenone. UV-531 is a short name for CYASORB UV-531FLAKE and is 2-hydroxy-4-n-octoxybenzophenone. Both are products of Cytec Corporation of Stamford, Connecticut. MC80 is an abbreviated name of UVINUL MC80, octyl methoxycinnamate, and a product of BASF Japan Ltd. in Japan.

  The UV stable formulation had a weaker final color for comparable UV compared to the unstabilized formulation and took longer to color. The result is shown in FIG. However, it took a long time (or high fluence) for color formation to exceed the cycle time required for manufacturing specifications. Furthermore, the high fluence rate required for writing these coatings resulted in some undesirable physical deformation (shrinkage and distortion) in addition to the difference in coating properties between the exposed and unexposed areas. As an example, the color formation time of the preparation 81 is shown in FIG. An exposure time of more than 10 seconds was required to achieve color formation in excess of 0.5 AU even at a distance of about 1 inch from a Zenon lamp.

9. Retesting of photoacid generators Adding UV absorbers directly to coating 100 requires a long writing time to obtain very little light stability, so retesting various photoacid generators and their concentrations Was implemented. It was noted that increasing the concentration of the photoacid generator tended to shorten the writing time when the concentration of the color former was constant. It is believed that the photoacid generator is potentially controllable to produce the desired color level with an appropriate cycle time. However, for a variety of reasons (including economic reasons), the use of minimal photogenerators is preferred. As one of the first steps, the ratio of photogenerator and photogenerator to the thickness of coating 100 was optimized in color formation. The results of the experiment are shown in FIG. 25 and show that 3: 2 (color formation: TPST) is preferred over a ratio of 1: 1.

  Experimental results (shown in FIG. 5) show that the thickness of the 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. The disk 10 was cured for 2 seconds at a distance of about 1 inch from the lamp in a nitrogen environment. The exposed portion was again imaged for 10 seconds at a distance of 1 inch from a Zenon lamp. A control sample based on a formulation containing SR-9020 was made by spin coating at 4K rpm. This control sample was exposed for 10 seconds at a distance of 5 inches from the lamp (because the high fluence was judged to cause fading with formulations containing SR-9020).

  This result indicates that the color formation is not performed by a large bias towards the surface but is performed throughout the thickness of the coating 100. Therefore, it may be desirable to optimize viscosity and rotational speed in order to provide the desired light density at the lowest film thickness. This experiment has the attendant advantage of confirming that the color former 3%, the photoacid generator concentrations 2% and 3% will eventually become the same color with different formation rates.

10. Absorption spectrum of photoacid generator and membrane At this point, a moderately stable triphenylsulfonium triflate (TPST) -based formulation using a UV absorber is impractical because it is difficult to activate It was considered. It has been found that the UV absorber simply absorbs the same wavelength used for imaging and does not selectively absorb UVB-UVB from sunlight or fluorescent light. Therefore, to adjust the wavelength range that can be important for these treatments, the absorption spectrum of photoacid generators and coating formulations were tested.

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

  The spectrum of the CN-120 base formulation is shown in FIG. Unlike previous formulations that 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 the majority of the photoacid generator wavelength response range shares a high absorbance range with the acrylate substrate. Therefore, the wavelength that plays a major role in color formation throughout the thickness of the coating 100 is likely to be medium to long, rather than short (<250 nm), if the substrate light density is low. it was thought.

  Since short wavelengths are inefficient for image formation of UV stable formulations, there is the advantage of imaging much faster than sunlight or fluorescent light, but the ability to generate short wave UV in the laboratory cannot be utilized. Therefore, high intensity must be used to make imaging faster than background color development. It can be concluded that the addition of UV absorbers slows down imaging as much as the formation of background colors from fluorescent or sunlight. Thus, if the UV fluence is 10,000 times greater than the sun creates, and if the imaging is performed in 3 seconds, the sunlight will produce a color in 30,000 seconds, or about 8 hours. Is considered to be equal to Considering an unacceptable level of background color as low as 5% of the highest color, an effective sunlight exposure that forms an unacceptable level of background color is about 30 minutes. Therefore, even if using a fluence 10,000 times or more than that of environmental sunlight (a large amount that is unacceptable in terms of material stability), the light stability will only be extended by about 5 hours. It was.

  As shown in FIG. 28, looking at the UV absorption spectra of the substrate and UV absorber, a 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 wavelength close to mid-range UV. In this case, the coating 100 exhibits some degree of transparency. It was desired to provide UV blocking protection for the UV-A and UV-B regions while increasing the imaging speed to some extent by the effective use of UV-C radiation. A series of photoacid generators with longer UV transitions were chosen for this purpose. As utilized herein, the wavelength of UV-A was generally considered to be 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 for photoacid generators required for imaging speed A formulation utilizing 10% UV-24 as UV absorber was prepared. The concentration of each photoacid generator was adjusted to be equivalent to 2.5% TPST on a molar basis. FIG. 29 shows the color formation curve of each prepared formulation. The sample shown in FIG. 29 was exposed at a distance of 1 inch from a Zenon lamp. Some photoacid generators, particularly 4-phenoxy derivatives, showed shorter color formation (writing) times than TPST.

  These different photoacid generators produce different writing speeds and color densities, but a more important performance condition is that the photoacid generator does not increase the sensitivity to fluorescence and sunlight exposure, and the photoacid generators write speed and color density. Was thought to be able to provide an increase in. To experiment with this, a disc 10 of each photoacid generator formulation was prepared and exposed for about 65 hours under a fluorescent instrument. FIG. 30 shows that each photoacid generator determines its respective writing speed and final color, while nothing substantially exceeds TPST in terms of color formation time and subsequent fluorescence stability ratio. Indicates. In fact, the data suggests that the writing time with a Zenon lamp is a direct predictive measure of subsequent light stability. Thus, it is clear that most of the light used for imaging from Zenon lamps is the UVB (about 270 nm to about 320 nm) portion of the spectrum, not the shortwave UV (wavelength less than about 250 nm). It was. This result is supported by the observation that the writing time is not improved by the “D” bulb manufactured by Zenon, as shown in FIG. The “D” bulb produced a greater amount of UV-C radiation than the “C” bulb, but no increase in color formation time was observed.

  A higher concentration of UV-24 was tested, as well as a combination of UV-24 and another absorber, MC80. The results are shown in FIG. 32, but the sensitivity decreases as the concentration of the UV absorber increases, and UV-24 alone is superior to the MC80 mixture when the same weight is added.

  Further experiments were performed to determine the color formation time of the 10% UV-24 formulation. The UV-B capability level was measured at various distances from the lamp housing through a plastic mask. Also, a quartz mask was utilized to increase the shortest spectral UV-B capability at the closest distance of about 1 inch. The results are shown in FIG. 33, but for a 10% UV absorber, a Zenon lamp develops an appropriate fluence rate within a preferred cycle time of nearly 3 seconds and produces an acceptable light density. Could not be generated. In fact, most coating 100 samples were substantially cracked or distorted. Also noteworthy is that removal of the plastic mask results in about 40% more UV-B, but only a slight increase in writing speed, and again the coating is optical at shortwave UV (<300 nm). Supported the theory of high density.

12 Color Enhancement Additives For some additives, attempts have been made to reduce the writing time of coatings with UV absorbers without proportionally increasing the sensitivity of fluorescence and sunlight. The first attempt was a re-experiment of color enhancement additives to make the acid produced more effectively. This attempt focused on the use of an acid that “primes” the coating for color formation. The substrate used is formulation 10 containing an alkoxylated monomer. As shown in FIG. 34, the acid concentration and components used had no significant effect on writing time or the final color of the coating. Furthermore, an experiment was attempted using 2-acrylamido-2-methyl-1-propanesulfonic acid, a crosslinkable sulfonic acid. However, even at 1% contamination, the acid was too strong and turned the coating red without UV exposure. Therefore, it was thought that the addition of impurities with acids of various strengths and concentrations would not aid in color formation.

  Additional approaches to reducing light sensitivity when a buffer system is used were evaluated. Using a buffer system, low doses of UV were thought to produce small amounts of additional acid that was absorbed by the buffer. In this case, triflic acid is a very strong acid, so almost any substrate is capable of eliminating (neutralizing) the acid created. In the first experiment, an amic acid acrylate such as CN-384 from Sartomer Corporation was used. These amine acids proved too strong for the base and color formation was completely prevented. In the next experiment, since a small amount of CN-384 was used, the background color was kept low, but the stability of the image was poor and the color faded under environmental conditions within 24 hours. Therefore, the use of weak bases was experimented. Examples of weak bases include acetic acid and sodium salts. Unfortunately, these composites were not very soluble in acrylate and only 0.1% contamination was achieved. However, the effect was observed with this low contamination. The salt functioned as a buffer but also reduced the color formation rate and the overall color of the coating. The state of use of the buffer is shown in FIG.

  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). A transparent polycarbonate disk 10 was coated with a spin coater called a spin coaster manufactured by HEADWAY. Formulation 3 having a viscosity of about 60 cps was used. The disk 10 was coated and rotated from 4,000 to 10,000 rpm (1.0 K) for 10 seconds. The disk was cured for 2 seconds in a nitrogen environment using an L-37 UV filter and a Zenon pulse lamp. Half of each disk 10 was then exposed for 10 seconds under the lamp. UV scans were measured for both curing and exposure of each disc, and the film thickness was also measured.

  Measurements showed that the thickness of the film varied from thin to thick, from the prescription portion to the end portion of the disk. The optical density of the disk 10 was also measured directly for the thickness at various rotational speeds. It was clear that at the highest speed (above about 8K rpm), the effect was reduced on the film thickness, as expected. The result is shown in FIG. In FIG. 36, the thickness of the film at a selected distance from the prescription portion is shown. Evaluation of light density and film thickness at various spin coating speeds is shown in FIG.

  Formulations 58 (375 cps) and 61 (504 cps) were coated at respective rotational speeds of 5-10K. The light density and film thickness were measured, and the results are shown in FIG. As expected, the thicker formulation produced a thicker film. Also interesting is that these high viscosity formulations show a more linear response of film thickness to rotational speed. In the final product, color management methods include exposure time management and formulation changes, but these are not very attractive and it is generally considered preferable to change the thickness of the film. That is, changing the thickness of the film has the advantage that the end user can dispense the minimum amount of material required for a given color depth, thus realizing a reduction in cost and a reduction in light sensitivity.

  Further optimization of the concentration of photoacid generator was performed. This is illustrated in FIG. FIG. 39 shows the relationship between the photoacid generator (TPST) and color former (PERGASCRIPT I-6B) concentration and light density when the film thickness is constant. The light density was measured with 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 indicated times.

B. It has been found that an acceptable balance between development cycle time, UV fluence, and subsequent photosensitivity of a multilayer coating is not achieved with a single layer coating formulation. An alternative approach was thought to be to use two coatings, one designed for fast color formation and image stability, and a second overcoat that provides the desired UV stability. The second protective film can provide further advantageous effects such as scratch resistance and the addition of environmental stability to humidity and base.

  FIG. 40 shows a cross-sectional view of an embodiment of the optical medium 10. In FIG. 40, the disk 10 includes pits 5 and lands 6 as data functions. In this embodiment, the disk 10 is formed of a base 16 and includes a reflective layer 14. As described above, the color forming coating 100 is shown to be formed from two components. The first component of the color forming coating 100 is a color forming layer 101. The second component of the color forming coating 100 is a 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. The color forming layer 101 was required to have adhesion to polycarbonate, excellent color formation, and solubility of a photoacid generator and a color former. The protective film 102 was required to have a hard scratch resistant surface with good curing, a high UV light density, and adhesion to the underlying color forming layer 101. Ideally, both layers 101 and 102 cure quickly without nitrogen and work together to increase low shrinkage and environmental stability of the image (ie heat, humidity). Or against the impact of the introduction of additional chemicals).

In view of previous developments, CN-120 formulation produced the best environmental results, but higher light density for color-forming wavelength than all fatty compound formulations such as formulation 1 and formulation 9. Indicated. However, the addition of protective film 102 may be used to enhance the stability of the heat / humidity test, so that formulations other than CN-120 can be used to reduce writing time and shrinkage. Tested again.

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

製剤Ｃ１とＣ２では、ＵＶの透明度を増加させて、粘着の収縮率を減少させるために、ＣＮ−１２０含有を減少させて、ＳＲ−３８６含有を増加した。製剤Ｃ３は、低収縮率、高い粘着、高速硬化、及び、ＵＶ透過コーティングを実現するように、ＳＲ−９０２１とＳＲ−３６８を含む。製剤Ｏ１とＯ２は、良好な粘着と硬化を実現するようにＳＲ−２３８とＳＲ−３６８の混合物を含み、製剤Ｏ２のＣＮ−１２０は強さとＵＶ不透過率のために含まれた。製剤Ｏ１とＯ２では、ＵＶ吸光剤のＵＶ−２４が１０％の混入率で使用された。直後の観察では、以前と同様に、光酸発生剤は、アルコキシレート化されたモノマーＳＲ−９０２１で最小の溶解であった。（明らかなように、「Ｃ」で始まる製剤は色形成層１０１の製剤を示し、「O」は保護膜１０２の製剤を示す。）
サンプルディスク１０は、４Ｋ ｒｐｍで色形成層１０１を製剤Ｃ１、Ｃ２、Ｃ３１と共に基盤１６上にスピンコーティングし、３秒間、約１インチの距離で、「Ｄ」バルブによりＬ３７ＵＶフィルタを通して、窒素環境で硬化させて準備した。水晶マスクを通しての画像化は、１０秒間、ランプから約５インチの距離で実施された。保護膜層１０２（製剤Ｏ１とＯ２）は、色形成層１０１の上に、２．５Ｋ ｒｐｍでスピンコーティングすることにより、塗布された。保護膜層１０２は、窒素環境で、約３秒間、ランプから約１インチで「Ｄ」バルブによりＬ３７ＵＶフィルタを使用しながら、硬化された。製剤Ｃ２とＣ３により作られた色形成層１０１は良好に湿潤しかつ回転したが、製剤Ｃ１は同様には実行されなかった。保護膜層１０２の製剤Ｏ１とＯ２両方の製剤は、良好に湿潤して、色形成層１０の全体に良好にコーティングされた。全ての最終ディスク１０は、プラスチックのペンチップに対する損傷抵抗があった。

In formulations C1 and C2, the content of SR-386 was increased and the content of SR-386 was increased in order to increase the UV transparency and reduce the shrinkage rate of adhesion. Formulation C3 includes SR-9021 and SR-368 to achieve low shrinkage, high adhesion, fast cure, and UV transmissive coating. Formulations O1 and O2 included a mixture of SR-238 and SR-368 to achieve good tack and cure, and CN-120 of Formulation O2 was included for strength and UV opacity. In formulations O1 and O2, UV absorber UV-24 was used at a contamination rate of 10%. In the observation immediately after, as before, the photoacid generator was minimally soluble in the alkoxylated monomer SR-9021. (As is clear, the formulation starting with “C” indicates the formulation of the color forming layer 101, and “O” indicates the formulation of the protective film 102.)
Sample disk 10 is spin coated with color forming layer 101 at 4K rpm on substrate 16 with formulations C1, C2, C31 and passed through an L37UV filter with a “D” bulb at a distance of about 1 inch for 3 seconds in a nitrogen environment. Prepared by curing. Imaging through a quartz mask was performed at a distance of about 5 inches from the lamp for 10 seconds. The protective film layer 102 (formulations O1 and O2) was applied on the color forming layer 101 by spin coating at 2.5 K rpm. The overcoat layer 102 was cured using a L37 UV filter with a “D” bulb at about 1 inch from the lamp for about 3 seconds in a nitrogen environment. Color forming layer 101 made with formulations C2 and C3 wetted well and rotated, but formulation C1 was not performed as well. Both the preparations O1 and O2 of the protective film layer 102 were wetted well, and the entire color forming layer 10 was well coated. All final discs 10 were resistant to damage to plastic pen tips.

  Using SCOTCH tape as a light adhesive tape, a tape pull test utilizing a 2.5 mm spacing blade was performed. (PERMACEL # 99 did not stick well to the coating used). The color forming layer 101 formed from formulation C1 failed, but 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 color forming layer 101 without any problem. 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 initial experiments, two-layer coating 100 candidates were devised. These formulations are shown in Table 20. The color forming layer 101 was modified to reduce the concentration of CD-120 and increase transparency and tackiness. 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 formulation of SR-368 and SR-238.

２．初期試験
２層コーティング１００の試験用の実験が進められた。ディスク１０は、図４１に示されているように、３Ｋと４Ｋ ｒｐｍでスピンコーティングされ、色形成層１０１でコーティングされた。このディスク１０は、色密度を試験するために、時間を変えて、ランプから約５インチの距離で画像化された。その後、保護膜１０２が、３Ｋ ｒｐｍでスピンコーティングにより適用された。また、窒素とフィルタの使用もこの実験で試験された。窒素は、保護膜１０２の適用を提供する許容レベルまで色形成層１０１を硬化するためには必要ではなかった。色形成層１０１の硬化のために、窒素を今後使用することで、色形成層１０１と保護膜１０２の完全な接着を形成する利点が追加されると考えられる。その後、保護膜１０２は、窒素とフィルタを使用しない状態で、１．５秒間、ランプから約１インチの距離で硬化し、これにより表面の硬化を強化するために、ランプ照射の完全なスペクトルを与える。基底の色形成層１０１には、トップコート１０２の硬化による顕著な色は現れなかった。

2. Initial test An experiment for testing the two-layer coating 100 was undertaken. The disk 10 was spin coated at 3K and 4K rpm and coated with a color forming layer 101 as shown in FIG. This disk 10 was imaged at a distance of about 5 inches from the lamp at varying times to test the color density. A protective film 102 was then applied by spin coating at 3K rpm. The use of nitrogen and filters was also tested in this experiment. Nitrogen was not necessary to cure the color forming layer 101 to an acceptable level that provided application of the protective film 102. It is considered that the use of nitrogen in the future for curing the color forming layer 101 adds an advantage of forming complete adhesion between the color forming layer 101 and the protective film 102. The protective film 102 is then cured at a distance of about 1 inch from the lamp for 1.5 seconds without using nitrogen and a filter, thereby increasing the complete spectrum of lamp irradiation to enhance surface hardening. give. In the base color forming layer 101, no noticeable color due to the curing of the top coat 102 appeared.

  A ratio of 3: 4.5 of photoacid generator to color former has proven to be high and produce very strong colors. A light density of about 0.8 was achieved in a short time with 5.25 inches of Zenon "D" bulb.

  More importantly, the qualitative exposure test (63 hours) using a fluorescent instrument showed that the overcoat performance of the light test was much better than the single layer coating solution. Also interesting is that images that initially looked very dark (contrast too large) looked better with background colors with fewer contrasts.

  Most importantly, the separation of the UV stable layer and the color forming layer 101 allows effective use of short UV wavelengths (<320 nm) for color formation. This allows for effective exposure of the color forming layer 101 using these wavelengths, and blocks this layer 101 from such wavelengths found in general illumination such as sunlight or fluorescent lamps.

  However, it should be noted that using a combined layer of 101 and 102 requires further investigation on the properties of adhesion. The color forming layer 101 did not adhere to the base polycarbonate 16 and failed the tape tensile test using a weak adhesive tape. Since the adhesion failure 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 to the protective film layer 102.

3. Environmental testing At this point, the knowledge gained from the previous two coating experiments was put together and laid the foundation for further development of a series of formulations. These formulations were subjected to qualitative environmental testing experiments and the results are shown in Table 21.

  Formulation C5 is formulation 3 (Table 14) of the previous SR-9021 base and has excellent properties but failed the environmental test. The protective film 102 may improve the environmental safety of the color forming layer 101 using Formulation C3 and was thought to provide sufficient protection to avoid the use of UV absorber CN-120 exhibiting high shrinkage. . Formulation C6 used SR-368 instead of SR-494 with modifications to formulation C5. It has been theorized that this substitution reduces the alkoxylation content, resulting in a hard but low shrinkage film 101 or color forming layer 101. Formulation C7 is a formulation that has been modified to include CN-120, SR-368, SR-238 to meet adhesion requirements. The color forming layer 101 containing formulation 7 was considered to pass the environmental test easily 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, using SR-339 as an added UV absorbing diluent. Formulation O5 is an SR-9021 base protective film to which CD-120 necessary for hardness is added. Formulation O5 was devised in the hope that SR-9021 would solve the shrinkage problem without sacrificing stiffness and scratch resistance. The overcoat 102 was formulated using both 10% and 20% UV-24. Adding 20% has a significant effect on viscosity.

光酸発生剤と発色剤の溶解度という点では、Ｃ５とＣ７の両方の製剤は、アルコキシル化されたＳＲ−９０２１を含んでおり、熱と超音波なしで、固体を溶解する場合に問題があった。Ｃ５とＣ７は両方共ろ過が必要であった。製剤Ｏ４とＯ５は、濃度２０％のＵＶ−２４の溶解に困難があった。また製剤Ｏ４とＯ５もろ過した。

In terms of the solubility of the photoacid generator and color former, both C5 and C7 formulations contain SR-9021, which is alkoxylated, which presents problems when dissolving solids without heat and ultrasound. It was. Both C5 and C7 required filtration. Formulations O4 and O5 had difficulty dissolving 20% concentration of UV-24. Formulations O4 and O5 were also filtered.

  The color film formulation was applied by spin coating at 4K rpm and then cured in air for about 2 inches under the lamp using an L37 filter for 2 seconds. However, the disk 10 hardened “pinkish” to various strengths. The degree of pink ranged from C5 colorless to C6 very faint, C7 faint. This was supposed to detect the light density of the coating, probably because C7 contains the most aromatics, C6 contains SR-368 which absorbs some UV, and C5 is the most transmitted UV of the coating. .

  Imaging was performed approximately 4 inches from the lamp through a chrome on quartz mask for 10 seconds with a D bulb. Topcoat 102 was applied by spin coating at 4K rpm and cured about 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 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 a thin film of the color coating 101 occurred from the polycarbonate layer 16 of the disk 10. The second observation was that the construction of the color layer 101 was a major determinant in determining image safety. Formulation C7 greatly exceeded C6 and C5. Coating C5 was completely unacceptable regardless of the use of protective film 102, as before. The coating C6 was superior to C5, but did not reach C7, and again the protective film 102 was not relevant. Formulation C7 exceeded other coatings 101 without protective film 102. The results are shown in FIG.

  With respect to the addition of 10% of the protective film 102, each sample appears to maintain stability in terms of adhesion and strength. In addition, we noticed a trend of underlying image stability for the undercoated sample of 1c. That is, the formulation O3 showed performance superior to O4, O4 showed much better performance than O5, and O5 showed performance superior to the case without the protective film 102. Again, the lack of alkoxylation, the potential glass transition temperature and the hydrophobicity of the coating 100 were followed.

  All samples were judged to be very good under fluorescent light by visual inspection. After exposure to a fluorescent lamp for a week, several background colors were developed, and after exposure to a fluorescent lamp for several weeks, the image was still recognizable, but deteriorated due to the intensity of the background color. The sample with 20% added showed good performance in terms of development of the background color, but its use was thought to be limited due to the environmental problems described above. CN-120 base formulation O3 contained the most aromatics, but with the highest light density in coating 100 and the highest performance in light resistance. The absorption spectra of O3, O4, and O5 of the protective film preparation are shown in FIG.

4.2 Preparation of the two-layer coating formulation A series of acrylate urethanes from Sartomer Corporation was also tested to verify its suitability for use in coating 100. These are shown in Table 22. All coatings that use acrylate urethanes are not likely to perform well because they are soft and detract from the final product. No further testing was performed.

ＣＮ９６５は、脂肪族ポリエステル基剤のウレタンジアクリレートオリゴマーである。これは、優れた耐光性を提供し、柔軟性を持つオリゴマーである。ＣＮ９６６Ｂ８５は、脂肪族ポリエステル基剤のウレタンジアクリレートオリゴマーを１５％のＳＲ２３８、ジアクリレート・ヘキサンジオールと混合している。ＣＮ９８１Ｂ８８は、脂肪族ポリエステル／ポリエーテル基剤のウレタンジアクリレートオリゴマーを１２％のＳＲ２３８、ジアクリレートへキサンジオールモノマーと混合している。これら３つは、全てサートマーコーポレイション社の製品である。

CN965 is an aliphatic polyester-based urethane diacrylate oligomer. This is an oligomer that provides excellent lightfastness and flexibility. CN966B85 mixes an aliphatic polyester-based urethane diacrylate oligomer with 15% SR238, diacrylate hexanediol. CN981B88 is an aliphatic polyester / polyether based urethane diacrylate oligomer mixed with 12% SR238, diacrylate hexanediol monomer. All three are products of Sartomer Corporation.

  Since it was clear that the CN-230 formulation could not be replaced by any other monomer class, further experiments were conducted to adjust other components and improve performance aspects. A description of the formulation and the rationale for each adjustment is shown in Table 23.

研究により、色コーティングのＳＲ−２３８含有の穏やかな減少は、ポリカーボネートの粘着の欠如をもたらすことが認識された。しかしながら、保護膜１０２では、優れたＵＶ吸収特性を提供する希釈液が収縮を減少させ、皮膚の刺激が低くなることから、ＳＲ−３３９を基剤にすることができる。また、この研究では、保護膜１０２にアミン共力剤を含めると、やはり、わずか２４時間以内の環境試験の結果として、画像が完全に失われることが観察された。これは、保護膜１０２に共力剤を追加すると、ＫＴＯ−４６の７．５％の追加で、高速で完全に硬化することから、残念なことと考えられた。

Studies have recognized that a modest reduction in SR-238 content of the color coating results in a lack of polycarbonate adhesion. However, in the protective film 102, SR-339 can be used as a base because a diluent that provides excellent UV absorption properties reduces shrinkage and reduces skin irritation. In this study, it was also observed that when an amine synergist was included in the protective film 102, the image was completely lost as a result of an environmental test within only 24 hours. This was considered unfortunate because when the synergist was added to the protective film 102, it was cured completely at a high speed with an addition of 7.5% of KTO-46.

  SR-339, 2-phenoxyethyl acrylate, is a low viscosity, single-pipe group aromatic monomer, but provides good adhesive properties. CN120M50 is a mixture of bifunctional bisphenol A-based epoxy acrylate and 50% SR-339, phenoxyethyl acrylate. CN120M50 provides a good balance between water properties and high reactivity. SB520M35 functions gently and SR-339 is a carboxylic acid containing an acrylate oligomer mixed with a phenoxyethyl acrylate monomer. The reaction solid is 100%. SB520M35 provides fast cure rate, excellent adhesion to metals and plastics, and good wetting and flow characteristics. SB520M35 also includes the functionality of a carboxylic acid, thereby improving amine fading resistance. These three acrylates are products of Sartomer Corporation.

  After various screening studies were completed, a final test was conducted using two preferred overcoat formulations and a preferred color coating formulation. The selected protective film formulation has not been tested in environmental experiments and has not been confirmed to be practical in terms of protection resistance against ink fading, but has been selected because it contains an acidic oligomer such as SB-250. It was. The final formulation is shown in Table 24.

最終的な光酸発生剤と発色剤の割合と濃度はまだ正確に決定されていないため、光酸発生剤と発色剤の２つの濃度が研究された。両方のコーティングには、３Ｋと４Ｋ ｒｐｍの２つの回転速度が使用された。基盤のコーティングは窒素なしでＬ３７フィルタを通して３秒間で硬化した。露光は、ゼノン社製「Ｄ」バルブから約４インチで１０秒間であった。保護膜はフィルタや窒素のない状態で３秒間で硬化した。

Since the final photoacid generator and color former ratios and concentrations have not yet been accurately determined, two concentrations of photo acid generator and color former were studied. Two rotation speeds of 3K and 4K rpm were used for both coatings. The base coating was cured in 3 seconds through an L37 filter without nitrogen. Exposure was about 4 inches from a Zenon “D” bulb for 10 seconds. The protective film was cured in 3 seconds without a filter or nitrogen.

  The residual sensitivity of the coating 100 is shown in FIG. Samples are divided into two main groups depending on 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 seen that Formulation C13 had the lowest residual sensitivity and achieved the highest light density ratio in the non-exposed part relative to the exposed part. Furthermore, it was noted that this percentage result included some bias. This bias may have arisen from the fact that the C14 formulation was not exposed for an appropriate length of time to fully develop the final color, thus effectively developing the developed color of the C14 formulation. Will be reduced. Also, as expected, the coating 101 containing the highest amount of photoacid generator and color former retained the maximum amount of color upon prolonged exposure. This effect is shown in FIG.

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

  Ultimately, the level of color retained after exposure to the environment is largely determined by the concentration of the photoacid generator and color former, and not by the thickness of the film 101 or the constituent materials used for the protective film 102. . The results are shown in FIG. The results show that optimizing the ratio and concentration of photoacid generator and color former to reach the preferred color density and writing cycle time 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 color forming layer 101 appeared to withstand the amine test without protective film 102 and without degradation. However, the DVD 10 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 commercially available DVD storage container 180. This probably suggested that previously conducted triethylamine (TFA) based tests were inappropriate for the modified formulation. Therefore, a new test was conducted using a large amount of TEA in a typical plastic DVD container 180 similar to the original DVD storage container 180. A large filter paper 181 was used in place of the insert, and 1 ml of TEA was dispersed around the filter paper 181. In this test, the image pattern on the coating 101 did not fade. Later, it was probably considered necessary to have a 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 the filter paper 181 and seal the disk 10 in the storage container 180. This resulted in complete destruction of the images on all discs 10 with or without a protective film. It has been demonstrated that too much ammonium hydroxide has been used, and in practice it appears that it will be much more than occurs in the package. Therefore, the second test was performed using 25 microliters of ammonium hydroxide. Within two hours, both the disk without the protective film 102 and the protective film 102 without the acid faded completely (the protective film was slightly better), but the protective film 102 containing the acid was part of the ammonium hydroxide. Most of the original color was maintained except for the area close to (around the stacking ring). After several hours, these disks 10 also deteriorated substantially from the inside to the outside of the ring. Again, the amount of ammonium hydroxide used may have been too much 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 disk 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 for several hours. The disk 10 with the protective film 102 formed from the O13 preparation basically did not change, and only showed signs of fading in a portion near the center of the disk 10 a day later.

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

6). Quantitative study The metalworked substrate 16 was coated using a color coating formulation containing a photoacid generator and a color former in a ratio of TPST 2.0%: CF3.5%. The components of each formulation tested in the quantitative experiment are shown in Table 25. The formulation was applied to substrate 16 by spin coating at 4K rpm for 10 seconds. The prepared disk 10 was placed at a distance of about 1 inch from the Zenon D bulb, and cured by irradiation for 2 seconds through an L-37 UV filter in a nitrogen environment. Thereafter, each disk 10 was placed at a distance of 4 inches from the D bulb and exposed for 10 seconds to develop color. Finally, the protective film 102 was manually applied to each disk 10 using various formulations on the HEADWAY product. This protective film 102 was placed at a distance of 1 inch from the D bulb, and cured by irradiation for 3 seconds.

各ディスク１０の光密度は、オーシャンオプティクス社製スペクトル計を使用して測定した。５４０ｎｍに吸光が測定された。ディスク１０を個々のＤＶＤ容器１８０に入れ、１０マイクロリットルの水酸化アンモニウムにさらした。水酸化アンモニウムは、各容器１８０の内側に固定された一枚のフィルタ用紙１８１の中央に滴下した。容器１８０を閉じた後放置した。定期的に各ディスク１０を各容器１８０から取り出し、光密度の測定を実施して色の損失を評価した。結果データを図４８に示す。

The optical density of each disk 10 was measured using a spectrum meter manufactured by Ocean Optics. Absorbance was measured at 540 nm. Disc 10 was placed in an individual DVD container 180 and exposed to 10 microliters of ammonium hydroxide. Ammonium hydroxide was dropped on the center of one filter paper 181 fixed inside each container 180. The container 180 was closed and left standing. Each disk 10 was periodically removed from each container 180 and light density was measured to evaluate color loss. The result data is shown in FIG.

7). Physical properties of the coating A modified formulation for color forming layer 101 was prepared by diluting the formulation at 30% per weight of 5% KTO-46 in SR-238 diluent. Membrane thickness versus rotational speed curves were generated for both formulations. Each formulation was then spin coated onto borosilicate glass disks from 2K-10K rpm at 1K rpm intervals. Thereafter, the color forming layer 101 of the disk 10 was cured for 2 seconds under L37 using a Zenon D valve in a nitrogen environment. A tape was then applied to the disk 10 to remove the coating and tested on WYKO to determine the thickness of the film 101 in two different areas of the disk. This experiment showed that when the original color coating C6 was applied using a rotational speed (SS) of about 2K-5K rpm, the film became thicker. However, the two samples have since proven to be very similar.

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

9. Viscosity vs. shear rate The spin coating process varies the shear rate on the paint. It is also desirable to obtain this property because it is a function of the shear rate. Certain practical limitations prevent determining an accurate value for the shear rate during spin coating. However, a range of viscosities and shear rates were measured to evaluate the properties of the paint. The measurement was carried out using a Brookfield LVDV-III + CP and a spindle CPE-40 in the range from low speed to maximum speed shear rate. The highest shear rate achieved with this particular paint was 45 / sec. If a high shear rate is desired, it may be possible to replace some of the hardware configuration 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 are capable of producing high shear rates.

  Therefore, a program has been devised to obtain high and low shear rates by changing the spindle speed. A speed of rpm from 1K to 6K at intervals of 1K rpm was 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 layer 101 (containing formulation c6) is almost constant with increasing shear rate. However, the viscosity increases with increasing shear time. An increasing shear curve implied that the formulation was a Newtonian fluid. However, the decreasing curve implies that the fluid rheology is time dependent. Another type of graph shows that the fluid behavior is a shear stress and shear rate characteristic 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 conducted to confirm whether the color coating rheology is time-dependent, that is, the indicated viscosity phenomenon and shear rate curve are 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 at 2K rpm. It was concluded that formulation C6 exhibits Newtonian fluid behavior, confirming that the time characteristics shown in FIG. 53 remain consistent with time.

10. Color Formation with Various Lamps Color formation experiments were performed with the nine samples shown in Table 26 and three different light sources. Each photoacid generator and color former combination shown was included in the coating base of Formulation C7 (KTO 5%, SR-238 35%, SR-368D 30% and CN-120B60 30 % Content). Three sets of disks 10 containing the formulation were made and exposed separately using a Zenon D bulb, a Zenon C bulb, and a HONLE lamp. The exposure time is 1 to 10 seconds at 1 second intervals. A metalworked substrate 16 was placed directly under each disk 10 to provide a reflective backplate. All samples were prepared by spin coating the formulation onto a clear polycarbonate substrate 16 on a HEADWAY product at a speed of 4K rpm. The formulation was cured with a Zenon D bulb and L37 UV filter for 2 seconds in a nitrogen environment.

本実験は、いくつかの変数を試験するために考案された。最初は、光酸発生剤の発色剤に対する割合を変更させる効果についてである。一般的に、２：３の割合が使用されてきたが、好ましい割合としては知られていない。２番目に、光酸発生剤と発色剤の好ましい濃度が評価される。これには、色形成時間に対する濃度変更の影響を評価することが含まれる。さらに、色形成時間に対する異なるバルブの使用が評価される。ゼノン社製「Ｄ」と「Ｃ」バルブは、短波ＵＶの異なる量を与える。色形成に対する短波のＵＶの効果は、よく理解されていないと考えられた。さらに、ＨＯＮＬＥ社製「Ｈ」バルブは、ゼノン社製ランプからとは極めて異なる直線スペクトルによる、連続波長の水銀気体溶液であり、このランプを試験することは、有益であると考えられた。ＨＯＮＬＥ社製ランプは、マナチューセッツ州、ＭａｒｌｂｏｒｏのＨｏｎｌｅ ＵＶ Ａｍｅｒｉｃａ， Ｉｎｃ社から販売されている。

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. In general, a 2: 3 ratio has been used, but the preferred ratio is not known. Second, the preferred concentrations of photoacid generator and color former are evaluated. This includes evaluating the effect of density changes on color formation time. In addition, the use of different valves for color formation time is evaluated. Zenon "D" and "C" bulbs provide different amounts of shortwave UV. The effect of shortwave UV on color formation was considered poorly understood. Furthermore, the HONLE “H” bulb is a continuous wavelength mercury gas solution with a linear spectrum that is very different from that of a Zenon lamp, and it was considered beneficial to test this lamp. HONLE lamps are available from Honle UV America, Inc. of Marlboro, MA.

11. Ratio of Photoacid Generator to Coloring Agent FIGS. 54-57 show the effect of the ratio of photoacid generator to color former on color formation. Looking at the concentration of each different photoacid generator as a set, it can be seen that there is a general trend. This trend is shown in FIG. 54, where the color formation of the sample at a ratio of 2: 3.5 (or equivalent) is better than 2: 3, which is better than 2: 4. It is thought that it shows.

  The apparent inferiority of color formation due to the high proportion of color former was thought to arise from the inactivity of the color former in the formulation due to the high absorption of UV light. While this trend appears to be similar at each concentration of photoacid generator, it has been noted that a high concentration of color former may be superior in environment or light resistance. It was also noted that the performance difference between these proportions is small so that the benefits obtained from the higher proportions of color former are probably evaluated 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 concentration of photoacid generator to color former.

12 Lamp Effect The writing efficiency of three lamps was tested using both 2: 3 and 2: 4 concentrations of photoacid generator to color former. For simplicity, the lamps were compared using 2.5% photoacid generator: 5% color former and using the combined intensity of UVA and UVB measured with a GIGAHERTZOPTIK wattmeter, time Was converted to a fluence value. The power levels are shown in Table 27.

一般的に、ＨＯＮＬＥ社製「Ｈ」バルブは、図５８に示すように、ＵＶＡ／ＵＶＢ混合レベルに対するフルエンスベースで性能が最も優れていた。しかしながら、ＨＯＮＬＥ社のものはゼノン社製バルブのいずれよりも多くのＵＶＢを出すことに注目すべきである。ＵＶＢレベルだけが、曲線を書くために使用されると、図５９に示すように、ＨＯＮＬＥ社製ランプは、利点が少ないが、ゼノン社製バルブよりもやはり優れていることが分かった。どのレベルでも、ＨＯＮＬＥ社のものと「Ｃ」バルブは「Ｄ」バルブよりも優れている。最後に、ＨＯＮＬＥ社製「Ｈ」バルブが、コーティングの画像化に必要な最大有用フルエンスを試験するために長時間の露光の実施に使用された。図６０に見られるように、一般的な製剤は、ＵＶＢの露光が約５ｋＪ／ｍ^２後に最大に到達し始める。ある実施例においては、保護膜１０２の硬化にＵＶの全スペクトルが使用された。

In general, the HONLE “H” bulb had the best performance on a fluence basis for UVA / UVB blend levels, as shown in FIG. However, it should be noted that HONLE's produces more UVB than any of the Zenon valves. When only the UVB level was used to write the curve, as shown in FIG. 59, the HONLE lamp was found to be superior to the Zenon bulb, albeit with fewer advantages. At any level, the HONLE and “C” valves are superior to the “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 seen in FIG. 60, the typical formulation begins to reach a maximum after UVB exposure of about 5 kJ / m ² . In one embodiment, the entire UV spectrum was used to cure the overcoat 102.

13. Protective film: Light resistance of protective film with various UV absorbers The formulation of protective film (O1) was made with various UV absorbers added at 10% concentration. The various absorbents used are shown in Table 28. Tinuvin-327 did not dissolve and the formulation using tinuvin-R796 crystallized after 24 hours. Tinuvin-R796 is 2- (2′hydroxy-5′methacryloxyethylphenyl) -2H-benzotriazole, a reactive UV absorber that provides a crosslinking function for the coating.

透明なポリカーボネートのディスク１０は、製剤Ｃ６でコーティングされ、２秒間、窒素環境で、Ｌ−３７ＵＶフィルタを使用して、ゼノン社製Ｃバルブから１インチの距離で硬化した。その後、ディスク１０はランプから４インチの距離で１０秒間画像化された。各保護膜１０２は、画像を含む３つのディスク１０上に塗布された。その後、ディスク１０はゼノン社製品の下で３秒間、１インチの距離で硬化した。各ディスク１０は良好に硬化して、良い表面品質を示した。ＵＶ−２４製剤を除いて、硬化した製剤の各先端は硬化した。ＭＣ８０を含有する製剤は、硬化後、ピンクの色が現われた。

A clear polycarbonate disc 10 was coated with Formulation C6 and cured at a distance of 1 inch from a Zenon C bulb using an L-37 UV filter in a nitrogen environment for 2 seconds. The disk 10 was then imaged for 10 seconds at a distance of 4 inches from the lamp. Each protective film 102 was applied on three disks 10 containing images. The disk 10 was then cured at a distance of 1 inch under a Zenon product for 3 seconds. Each disk 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 appeared a pink color after curing.

  Viscosity was measured for each formulation, and light density was measured for both the curing of the disk 10 and the exposure range. The disc 10 was placed in a bright container, removed periodically and measured at a light density of 540 nm. The results are shown in FIG. As shown in FIG. 62, it was noted that the UVA composition had little lightfastness effect on the exposed portion of the disk 10.

  As a result of the aforementioned development work, techniques for the development of various formulations and further formulations have been developed. These formulations, as well as techniques for formulation development, can be cured at the wavelength of light and stimulated by the wavelength of light to create and retain markings for images, patterns, and other purposes. Provided material. These formulations are advantageous because they can be applied over the data functions that appear on optical media. Very advantageously, the aspect of the image can be controlled, so that interference with the readout device used to interpret the data stored in the data function is avoided. It should be appreciated that the foregoing are specific examples of formulations and are not intended to limit the practical examples. For example, the introduction of other constituents, such as the functionality of an acid that functions as a basic supplement for the protective film 102, is believed to further support the stability of image storage.

  Since the development aspects of such formulations and formulations have been studied, further aspects of the application and use of these formulations will now be examined.

C. Examples of Coatings for Optical Media 10 It will be apparent to those skilled in the art that formulations with efficacy for use as described herein are not limited to the examples described above. Accordingly, further consideration and properties of the coating 100 are not limited by the specific aspects of the foregoing embodiments.

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

2. Multilayer Coating Further unlimited examples are shown in FIGS. 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 first 301 red or the second 302 green. Produces a clear color. The third layer 303 is employed as a protective film 102 designed as a protection against environmental elements. In another embodiment, the optical media 10 shown in FIG. 63 is formed, so the first layer 301, the second layer 302, and the third layer 303 are application of the formulation of the single layer embodiment. . In these other embodiments, each layer 301, 302, 303 produces distinct colors such as red, green, blue.

  In FIG. 64, a coating 100 comprising four layers is shown. In one embodiment, the first layer 101 is the color forming layer 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 by the first three layers are the primary colors, and upon completion of imaging, a multicolor image appears.

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

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

最初に、金属加工されたディスクがオレンジの製剤を１０秒間４０００ｒｐｍでスピンコーティングされた。その後、オレンジの製剤はゼノン社製「Ｃ」バルブで３秒間、窓ガラスの下１インチの距離で硬化された。その後、水晶マスクがディスク１０の上に置かれて、１０秒間、４インチの距離で、同じゼノン社製「Ｃ」バルブで露光された。これにより得られたディスク１０は、透明な背景にオレンジの画像を持っていた。次に、ディスク１０はもう一度、赤い製剤を１０秒間４０００ｒｐｍでＨＥＡＤＷＡＹ製品上にスピンコーティングされた。その後、赤い製剤は、ゼノン社製「Ｃ」バルブで３秒間、窓ガラスの下１インチの距離で硬化された。最後にマスク９２５をディスク１０の上において、１０秒間、ゼノン社製「Ｃ」バルブで４インチの距離で露光した。最終製品は、透明な背景に赤とオレンジの画像のあるディスク１０であった。

Initially, a metallized disc was spin coated with an orange formulation for 10 seconds at 4000 rpm. The orange formulation was then cured with a Zenon “C” bulb for 3 seconds at a distance of 1 inch under the window glass. A quartz mask was then placed on the disk 10 and exposed with the same Zenon “C” bulb for 10 seconds at a distance of 4 inches. The resulting disc 10 had an orange image on a transparent background. Next, the disc 10 was once again spin coated with the red formulation on the HEADWAY product for 10 seconds at 4000 rpm. The red formulation was then cured with a Zenon "C" bulb for 3 seconds at a distance of 1 inch under the window glass. Finally, the mask 925 was exposed on the disk 10 for 10 seconds with a Zenon “C” bulb at a distance of 4 inches. The final product was a disk 10 with red and orange images on a transparent background.

  Samples of orange and red formulations were taken. These samples were spin-coated at 4000 rpm, cured and exposed on transparent polycarbonate discs as described above. A spectrum of colors in different combinations of layers was also taken. Disc 10 was overlaid with an initial orange or red coating, followed by other colors.

  FIG. 66 represents the spectrum of the red disk 10 and the orange disk 10 when each color is evaluated separately. FIG. 67 shows that when the red and orange layers are exposed together, the resulting spectrum of colors is essentially the same. This is not related to the order in which the coatings were applied. Furthermore, FIG. 68 shows that layer 101 over a series of layers 101 can be selectively exposed without fully developing the substrate layer. It may be noted that most of the developed color is 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. This formulation was spin coated between orange and red color forming layer 101. In this example, the reproduction of the top color alone could be further improved by the UV blocking layer. Again, exposure to both color forming layers 101 results in the same overall color regardless of the order in which layers 101 were applied. The results are shown in FIG.

前述の実施例は、明らかであるように、色形成層１０１、保護膜層１０２、単層１００、及びこれらの様々な組み合わせを含むコーティングを利用する。予想されるように、多くの組み合わせが開発される可能性がある。これらは、単色あるいは多色画像のような、様々な効果をもたらすことができる。

The foregoing embodiments utilize a coating that includes the color forming layer 101, the overcoat layer 102, the single layer 100, and various combinations thereof, as will be apparent. As expected, many combinations can be developed. These can bring about various effects such as single color or multicolor images.

  Furthermore, as can be expected, the stepwise application of the imaging layer of coating 100 provides certain advantages. For example, the first layer 401 is applied and the image is subsequently 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 imaging of the second color forming layer 403. In this method, one image is recorded on the first layer 401 and the second image is recorded on the third layer 403. The recording of the second image proceeds without disturbing the side of the first image. Similar techniques can be used for single layer formulations where the color forming material is mixed with a UV (or other wavelength) absorber. Multiple wavelengths can be used for curing and imaging. In summary, various application techniques, formulations, curing, and imaging techniques are used to achieve multiple curing in the overall appearance of the image.

II. Marking formation
A. The selective irradiation of the color forming material of the coating 100 with the second light of the marking forming device is used to record the image or marking on the optical media 10. In the preferred embodiment, the wavelength of UV was used and a second light was prepared. Selective illumination can be used to provide various contrasts with areas of the optical media 10 that are unexposed or less exposed. That is, different shadows can be created in the image. For example, increasing the UV exposure of one part of the coating 100 results in a greater absorbance than shown in another part of the coating 100. Thus, shadow effects or other marking techniques can be realized using positive, negative or electrical photomasks, imaging units such as direct writing lasers (laser galvanizing systems) or by other techniques. May be. FIG. 70 shows an enlarged view of a portion of an example of a photomask 925 suitable for developing shadow effects. Marking as a single marking (for example, marking of the single color forming layer 101) is realized by a comprehensive display of a series of markings (for example, a series of markings of various color forming layers 101). One embodiment of the electrical photomask 925 preferably utilizes a programmable liquid crystal display to exhibit high light density at a wavelength of about 355 nm. One embodiment of the electrical photomask 925 is reconfigured during the marking procedure, thus providing each of the series of optical media 10 with a unique marking.

  One convention used here relates to “image” and “marking”. When these terms are used together, an image means the production of a marking, and the marking means the manifestation (ie recording) of the image in the coating 100. The two terms are closely related and, when appropriate, are considered interchangeable.

B. Types of markings Markings may include textual information such as alphanumeric characters, symbols, graphic information such as logos, barcodes, or any other information or symbols that may be appropriate for inclusion in the marking. , Formed according to a specification not limited thereto. In addition, the marking may include embedded information or an authentication signature, and may include at least one digital watermark or other type of hidden marking. For example, the marking may not be visible to the human naked eye.

  In some embodiments, the marking is self-destructing. For example, the marking disappears when it enters an atmospheric environment such as ambient light. The use of self-destructive marking is particularly beneficial in some applications, such as an example of an approval scheme.

  An example of the marked optical media is shown in FIG. FIG. 71 represents the optical media 10 when a series of layers collectively form a coating 100 on each. In the illustrated embodiment, the optical media 10 is being manufactured on a manufacturing line 2000, where the manufacturing direction is represented by a dashed arrow. An imaging wavelength source 920 is represented as a lamp with a photomask 925 attached thereon and is used to generate markings on the coating 100. In the illustrated embodiment, the marking 620 is created on the first color forming layer 401 of the coating 100. Additional lamps 921, 922 (shown at least in FIG. 78) may be used to create markings 620 on the additional color forming layers 402, 403. In some embodiments, imaging wavelength source 920 is a laser. In this embodiment, the lamp 920 controls the writing direction on the optical media by an external device not shown here. In other embodiments, the imaging wavelength source 920 can include a direction writing laser, a pulsed UV lamp, 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 instruction information. The contents include advertisement, brand, and promotion information, and are collectively referred to as “promotion information” here. The information included in the marking 620 can include, but is not limited to, the aforementioned types of information or combinations. For convenience, “content” as used herein refers to the contents of the marking 620 and 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 the transferred image includes the contact technique used in grayscale printing. This uses a group of appropriately sized colored shapes or patterns on a colorless background, or uses a colorless shape or pattern on a colored background instead. By making the size and density of the shape and pattern constant, it is possible to control the visual recognition of the color intensity in any specific region of the marking.

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

  In one embodiment, photomask 925 is used for exposure of optical media 10. The photomask 925 is placed directly on the optical media 10 or is used at some fixed distance from the optical media 10, such as on a lamp lens. The second light source 920 is adjusted and focused to achieve a favorable effect on the marking 620. In order to realize a high throughput, the duplicating apparatus appropriately moves the coated optical medium 10 so that it is aligned with the fixed position of the photomask 925 or the fixed position of the marking. The cycle time for producing the marking in this way 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 embodiments, electrical photomask 925 is remotely programmed and controlled. The use of an electrical photomask 925 provides certain advantages, including but not limited to, increased throughput by changing images quickly and reduced maintenance costs due to fewer moving parts. Brought about.

III Coating inspection
A. When the general inspection equipment coating 100 is applied to the optical media 10, it may be inspected for compliance with preferred specifications. In some embodiments, testing is optional or omitted. In one embodiment, in the situation shown in FIG. 73, a non-destructive inspection is performed on the optical inspection table 700. The optical inspection table 700 may include, but is not limited to, components such as a laser 710, a detection device 715, and an optimally configured processor 720. In the embodiment, the laser beam is directed to 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 regarding the properties of the coating or a series of determinations. These properties can include, but are not limited to, thickness and uniformity. Other properties apply, including unlimited transmission and target defects, as well as coating defects such as porosity, dye coverage, dye smudges, irradiation deflection, dye density, or dye edge range defects, or others Including but not limited to deviations from industry standards.

  The determination is used to determine whether the coated optical medium 10 is acceptable. The processor 720 sends a signal to the production line controller 730. The rejected optical media 10 is appropriately removed from the production line 2000 for the next disposal by the production line control device 730, while the accepted optical media 10 proceeds through the manufacturing process. In this example, the optical media product is 100% inspected. However, in other embodiments, a certain number of manufacturing 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 manufacturing line for inspection routines or inspection of manufacturing processes.

  Further inspection routines involve an electronic imaging system that evaluates the quality of the marking. Again, each optical media 10 or several sets may be inspected. In these embodiments, a device such as, but not limited to, a CCD array with proper illumination or a suitably configured microprocessor is used as the sensing device 715. Examples of suitable equipment include VERICA from Spectra Systems, Inc. of Rhode Island.

  In this embodiment, the determination device 715 may be positioned on the optical medium 10 as a method of clearly capturing the marking 620 in order to minimize reflection or other interference. In this example, the sensing device 715 includes several components that work together, as depicted in FIG. In FIG. 73, a typical marking detection device 715 incorporates components such as a display 840, a keyboard 850, and a network link 860 (which may use one or more available communication protocols and designs). In addition to including a user interface 845, an illumination 830, a lens / CCD system 820, a memory 815, and a storage device 818 are also included. These various components are controlled by a centralized integrated processing unit 800 on the detection device 715 board. In this case, the detection device 715 can be carried or fixed. In one embodiment, the sensing device 715 includes a microscope laser scanner.

  When used, the illumination 830 is used to provide standard light conditions so that the CCD array 820 images the marking on the optical media 10. The quality of certain characteristics of the marking 620 is determined. For example, the color of the marking, the alignment of text on the inner or outer edge of the optical media marking, the appearance of a digital watermark, or the placement of one marking 620 relative to another marking 620 is evaluated. The processor 800 compares the observed characteristics with known or preferred characteristics and indicates a pass / fail criterion for the optical media 10. A signal indicating pass or fail may be sent from the network link 860 to a separate production line controller. Again, the failed optical media is properly removed for subsequent disposal, while the passed optical media 10 proceeds through the production line.

  Another inspection system suitable for quality auditing of optical media 10 and markings 620 thereon is commercially available from Xelis Automation, Inc., Burlington, Ontario, Canada. XIRIS PI-1500 includes 3 CCD chip camera modules, integrated light source mounted on top, arrangement structure, flat panel computer screen, visual processor device, 8 digital inputs, 8 digital outputs, and accompanying software Is included.

  As another alternative, part of the manufacturing process of the optical media 10 may be inspected by a destructive method. In these embodiments, the operator may cut portions of the optical media 10 or damage the optical media 10 to determine final system performance information.

  Another system for analyzing the quality of optical media 10 manufactured in accordance with the teachings herein is the CATS SA3 system sold by AudioDev USA, Inc., Woodland Hills, California. This system tests the read and playback capabilities of optical media by measuring various signals and parameters. The levels of these parameters can then be analyzed to obtain conclusions regarding the stability of the disc manufacturing process and possible playback function issues.

B. Coating conditions and radial noise studies Another study was conducted to evaluate the performance of optical media produced according to the teachings herein. The disk 10 is coated with a HDP98 liquid dispenser and MA24WEA dispensing arm on a HEADWAY PWM32-PS-R790 spinner system. Formulation 3 (9021) was used (see Table 14). In order to test the effect of spin coating parameters on the electrical specifications of the disk 10, changes in rotational speed and various coating parameters were employed. Programs that used more than one or increased rotational speed were tested. The preferred coating was determined using single rotation for 10 seconds at 4K rpm. The spin coating program used for the HEADWAY system is shown in Table 31.

２．０ｍｌの分配量を維持する分配時間が増加すると（粘度に依存）、段階１と２で使用される回転速度（ｒｐｍ）が減少した。ＨＥＡＤＷＡＹ社製スピンコーティングシステムの分配量は、分配時間と分配圧の関数である。従って、５０ｐｓｉの一定圧で分配時間が３．５秒に設定されると、１．９〜２．０ｍｌの分配量になった。この量の塗料が目的のコーティング１００に提供される。
性能パラメータの画像化処理の効果を試験するため、ディスク１０は、コーティングされ、硬化され、その後、ＣＡＴＳシステムで試験された。その後、前記同ディスク１０は画像化され、ＣＡＴＳシステム上で２回目の試験が実施される。ＣＡＴＳ試験結果に差はなかった。ＣＡＴＳシステムにより作成されたデータは図７４に示してあるが、ここでは、コーティングされていないディスク１０のデータが示されている。各試験の最後の急上昇は、データの終了によるもので、ディスク１０あるいはコーティング１００の固有のエラーではないことに注意する。図７５は、硬化が終了しているが、画像化が終了していないコーティングディスク１０のデータを示す。図７６は、硬化と、画像化が終了したコーティングディスク１０を示す。

Increasing the dispensing time to maintain a 2.0 ml dispensing volume (depending on viscosity) decreased the rotational speed (rpm) used in stages 1 and 2. The dispensing volume of the HEADWAY spin coating system is a function of dispensing time and dispensing pressure. Therefore, when the dispensing time was set to 3.5 seconds with a constant pressure of 50 psi, the dispensing volume was 1.9 to 2.0 ml. This amount of paint is provided to the target coating 100.
To test the performance of the performance parameter imaging process, the disk 10 was coated, cured, and then tested with the CATS system. Thereafter, the disk 10 is imaged and a second test is performed on the CATS system. There was no difference in CATS test results. The data created by the CATS system is shown in FIG. 74, but here the data for the uncoated disk 10 is shown. Note that the last spike in each test is due to the end of the data and not an inherent error in the disk 10 or coating 100. FIG. 75 shows data of the coating disk 10 that has been cured but has not been imaged. FIG. 76 shows the coating disk 10 after curing and imaging.

  Further studies of radial noise were conducted as part of the evaluation of the optical media 10 manufacturing system. This study will be discussed in the “Manufacturing System” section.

C. Inspection Techniques Inspection techniques include completing inspections at various stages of optical media 10 manufacture. For example, the color forming layer 101 is applied, cured on the reflective layer 14 processed on the substrate 16, and then sent to the inspection table 700. If the inspection passes, in some embodiments, the substrate 16 is then sent for marking. In some other embodiments, the substrate 16 is advanced to another platform for applying the protective film 102.

IV manufacturing system
A. GENERAL MANUFACTURING EQUIPMENT In the first embodiment, a manufacturing system similar to the Singrass Skyline system sold by Singlass Technology, Inc., Windsor, Connecticut, is used to manufacture the optical media 10. Appropriate changes and enhancements have been incorporated into the system for the embodiments described herein and to enable the embodiments. The appearance of the instrument is described here, or is considered general to those skilled in the art and will not be described in further detail.

  In this exemplary embodiment, a newly duplicated disk 10 on the spindle emerges from the duplicate line. The coating 100 is applied using a spin coating process and then cured by exposure to initial light having a wavelength in the ultraviolet (UV) range. After proper application and curing, at least one image 620 transitions to the coating 100 using a second light 920 exposure. In one embodiment, the second light 920 employs a UV wavelength and a photomask 925. In other embodiments, the second light 920 is directed to the coating 100 as a controlled direction writing laser. An inspection step is preferably included before or after exposure to the second light 920 to confirm that the coating 100 has reached the type of light of the optical media 10 or other standards. Manufacturing time may vary depending on factors such as coating 100 components, spin coating time, curing time, imaging time, inspection time, and the like.

The preferred embodiment described above for manufacturing the marked optical media 10 includes, but is not limited to, the following typical conditions. 1. The rotating coating table has the following: Manual adjustment function by using micrometer screw and automatic adjustment function of radius position of dispensing nozzle of coating material, for example, use of formulation with viscosity of about 35 cps, filtration system to eliminate particles up to about 0.2 micrometer , Recycle function of paint flew by rotation, dispensing volume up to about 30 ml, dispensing speed from about 30 to 100 RPM, speed increase up to about 2,000 RPSS, rotation speed up to about 5,000 RPM, and stepped speed increase . 2. UV curing stage that provides about 300 mW / cm ² at a wavelength of about 365 nm. 3. An optical inspection table with the function of detecting surface defects in the form of a change in height of about 100 nm and a side change of about 200 microns. 4). A photomask stage that provides approximately 2 W / cm ² at a wavelength of approximately 350 nm (if 0.5 seconds required for handling are added, and approximately 5 J / cm ² is achieved in approximately 2.5 seconds). 5). Characterized laser providing a total fluence of about 4 J / cm ² , operated at a wavelength of 355 nm, with a pulse energy limit of less than about 0.15 J / cm ² per pulse, and an average power of about 4 watts . In this non-limiting example, the marking application cycle time 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 side of the optical media duplicator 2100 is characterized by at least one marking 620 of the single layer coating 100 and used to create the coated optical media 10, such as a skyline system or similar system. The In this embodiment, the optical media duplicator 2100 properly receives the material on the production line 2000 and produces the final optical media 11 with the marking as disclosed herein. In one embodiment, the system 2100 completes the initial steps such as attaching the reflective layer 14 to the substrate 16 when the prepared substrate 16 was created using the preparation platform 2110. The preparation platform 2110 may be subject to other manufacturing steps such as the formation of the substrate 16. The preparation platform 2110 may scan for defects in the substrate 16 and may include additional equipment necessary to complete this task. Accordingly, the depiction of the preparation platform 2110 should be understood as an indication that the system 2100 may incorporate additional equipment necessary 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 the formulation that forms the coating 100. The optical media 8 proceeds to the curing platform 2130 where it is exposed to the initial light 910 that cures the coating 100 as described herein. When the coating 100 of the optical media 8 is cured, the cured optical media proceeds to the marking table 2140. In the marking table 2140, the optical medium 10 is exposed with the wavelength of light from the second light 920. In the illustrated embodiment, 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 is completed on the final platform 2150 as needed. 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. Operation and other aspects of the manufacturing system 2100 may be suppressed by a system controller 2101 such as a processor 2101 that executes an instruction set (software) or other techniques such as manual operation. An example of the system control apparatus 2101 is an external personal computer 2101 connected for controlling various components of the manufacturing system 2100. In other embodiments, the first and last inspection aspects are intermingled with other manufacturing stages. For example, the optical media 10 may be inspected after each of spin coating, curing, and marking. Systems such as the previous embodiments are preferably automated, but are otherwise equipped to achieve high speed mass production.

  FIG. 78 represents an aspect of one embodiment of a manufacturing system 2100 equipped with a marking of optical media 10 having a coating 100 with a plurality of color forming layers 401, 402, 403. In FIG. 78, the marking stage 2140 includes a series of light sources, such as a second light 9210, referred to by “marking source”, “marking light” or other similar terminology. In this example, an initial marking lamp 921 is used with an initial photomask 925 to provide a marking 620 on the initial color forming layer 401. A second marking lamp 921 is used with a second photomask 926 to provide a marking 620 on the second color forming layer 402. A third marking lamp 922 is used with a third photomask 927 to provide a marking 620 on the third color forming layer 403.

  One further embodiment of the manufacturing system 2100 is depicted in FIG. In FIG. 79, a manufacturing system 2100 was devised for manufacturing optical media 10 using a two-layer coating 100. In this embodiment, the first spin coating table 2120 applies the color forming layer 101. The color forming layer 101 is cured on the first curing table 2130. The cured color forming layer 101 is marked with a marking 620 on the image stage as described elsewhere herein. Thereafter, the marked optical medium 11 proceeds to the second spin coating table 2160 in order to apply the protective film layer 102. The protective film 102 is cured on the second curing table 2170 using the second curing light beam 975. The final inspection or other final stage is performed on the final stage 2150.

  As expected, the appearance of the manufacturing system 2100, such as the components incorporated herein, depends on the design of the optical media 10 and the intended appearance of the optical media 11 to be marked. A further example of the manufacturing system 2100 shown in FIG. 80 includes the use of a series of manufacturing systems 2100 as shown in FIGS. 77 and 79. In this example, the initial manufacturing system 2100 is used to apply the initial color forming layer 401, cure the layer 401, and then provide an image on the layer 401. The second manufacturing system 2100 applies a second color forming layer 402, cures the layer 402, and then provides an image to the layer 402. The third manufacturing system 2100 applies a third color forming layer 403, cures the layer 403, and then provides an image to the layer 403. Operation and other aspects of the manufacturing system 7700 are controlled by a system controller 7701 executing an 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.

B. In a further embodiment that does not provide general off-line production equipment unlimited, a manual or semi-automated system is used off-line for the production of coated optical media 10 and / or marked optical media 11. The As an example of this example, an optical media 8 manufactured so far or commercially available was selected and received a coating. As described herein, the coating 100 is applied to the optical media 8. Processing of the coating 100 is performed in an environment where elements such as environmental dust and air are appropriately controlled to limit contamination of the coating 100.

  In the example of the offline system, the preparation base 2110 is omitted, but a system as shown in FIGS. 77 to 79 is included. In an off-line system, steps as described in the previous discussion are performed to create a marked optical media from the coated optical media 10 and / or the existing optical media 8.

  Thereafter, manual or automated techniques are used to align the coated optical media with the curing light beam 910 to cure the coating 100. FIG. 81 represents an example of a curing platform 7800 for manual curing. Thereafter, the coating 100 is cured. The cured optical media is then cooled or otherwise placed in a situation as required. The coated optical media 10 may enter the distribution chain and be directed to a marking table or removed for subsequent marking by the manufacturer. The marking is performed in the manner described herein and may be related to the use of a photomask 925 and / or the use of a direct writing laser 920. Thus, the coated optical media 10 is ready for the next marking by the manufacturer or others such as third parties.

  FIG. 82 shows a diagram of an off-line marking technique when used to create a marked optical media 11 from a coated optical media 10. In this example, an unmarked or “blank” coated optical media 10 is introduced into the production line 7900. The production line 7900 and its equivalent are also called “optical media receiver”. The optical media 10 goes through the production line 7900 when an off-line marking system 7901 that includes at least a second light 920 is used to provide a marking 620 on the optical media 10. Other components of the offline marking system 7901 include, but are not limited to, photomasks, equipment, alignment devices, spin coating and curing tables for the protective film 102, and other supplemental devices. The direct writing laser 920 and the support device may be incorporated into the off-line marking system 7901 in combination or placement with a photomask. In some embodiments, the optical media cradle 7900 may only be a tray in a fixed position relative to the marking light 920.

  Offline marking can occur in various places in the distribution chain. For example, off-line marking may be performed by a manufacturer of the optical media 10, a second manufacturing factory, a distributor, or an end user. For example, the prepared (coated) optical media 10 may be marked at a video rental store with appropriate equipment. In this way, the store may incorporate unique content such as, for example, promotional information, owner information, or other information such as a usage period. Similarly, end users can also be involved in marking their optical media 10 through the use of appropriate equipment. This feature may be attractive as a novelty for small manufacturers or individual users. Accordingly, these additional embodiments of additional devices may be used for marking the optical media 10 and are within the spirit of the invention disclosed herein. For example, the end user may use software, several suitable substrates used in a laser printer to create a photomask 925 from the software, and an appropriate light source (diode, used in the laser printer that created the photomask 925). In some cases, an inexpensive kit including a black light array is provided.

C. Singrass Skyline Duplex Coating Conditions and Radial Noise We believe that the use of commercial disk duplication equipment such as Singularus Technology Skyline Duplex should allow for coating of disks within specifications that include radial noise. It is done. To test this, disk 10 was coated and cured with formulation 9021 using a Singlass Skyline Duplex machine. Subsequent evaluations showed that the coating was within radial noise specifications of less than 30 nm. Measurements showed that the difference in radial noise between uncoated and coated discs using a thin glass skyline duplex machine was minimal. FIG. 83 represents the test results of the CATS SA3 system of disk 10 coated on a Singlass Skyline Duplex machine.

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

Ｄ．シングラススカイラインデュープレックスとランプの硬化作用
シングラススカイラインデュープレックス機械でコーティングの硬化を試験するための研究が完了した。この研究では、スカイラインデュープレックス機械に製剤保護膜Ｏ１を入れ、多種のランプで、上部と端の硬化における試験が行われた。ゼノン社製Ｃバルブが使用され、露光電力を１．０ｋＷに設定した。露光されたディスクは、２．０秒間、上部と端を完全に硬化した。１．０秒と１．５秒の時間間隔も評価されたが、ディスク１０は充分に硬化しなかった。機械のパドル上の反射板は、フェルトチップマーカーを使用して妨害された。ここでも、ディスク１０が評価されたが、差は現われず同じ状態であった。ディスク１０は、上部と端が完全に硬化した。

D. Curing action of Singrass Skyline Duplex and Lamps A study to test the curing of coatings on the Singrass Skyline Duplex machine was completed. In this study, the formulation protective film O1 was placed in a skyline duplex machine, and various types of lamps were tested for top and end curing. A Zenon C bulb was used and the exposure power was set to 1.0 kW. The exposed disc was fully cured at the top and edges for 2.0 seconds. A time interval between 1.0 and 1.5 seconds was also evaluated, but the disk 10 did not cure sufficiently. The reflector on the machine paddle was blocked using felt tip markers. Again, the disk 10 was evaluated, but no difference appeared and was in the same state. The disk 10 was completely cured at the top and end.

  An F bulb with a metallized reflector was also evaluated. The F bulb control was set to a maximum exposure power of 5.0 kW and a maximum exposure time of 5.0 seconds. The exposed disk 10 did not harden at the top or end. Next, a V-valve (gallium iodide) with a metal-worked reflector was evaluated. For the control of the V bulb, the maximum exposure power was set to 5.0 kW and the maximum exposure time was set to 5.0 seconds. The disk 10 was not fully cured at the top or end.

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

表３３の製剤はＨＥＡＤＷＡＹ社製スピンコーティング機を使用して、ディスク１０の上に手動でコーティングされた。これらは、Ｖバルブ（ヨウ化ガリウム）を使用して、スカイラインデュープレックス機械上で様々な時間間隔の硬化の試験が行われた。結果は、表３４に示されている通りである（「ＮＧ」は「不良」を示す）。全てのディスクは、反射板が妨害された状態で、完全に端が硬化した。

The formulations in Table 33 were manually coated onto disk 10 using a HEADWAY spin coater. These were tested for cure at various time intervals on a skyline duplex machine using a V-bulb (gallium iodide). The results are as shown in Table 34 (“NG” indicates “bad”). All discs were fully cured at the edges with the reflector obstructed.

表３５と表３６は、保護膜層１０２と色形成層１０１それぞれの好ましい実施例を開示する。

Tables 35 and 36 disclose preferred embodiments of the protective film layer 102 and the color forming layer 101, respectively.

このように、本発明が、好ましい実施例に関して特別に示され、説明される一方で、形式や詳細の変更は、本発明の範囲と意図から離れることなく、実施される場合があることを当業者が理解することを願う。例えば、コーティングの塗布、硬化、マーキング、及びマーキングの品質管理の方法や装置で、多くの変更が実施される場合がある。このような例には、ここに開示された以外の順番で様々な段階を実施すること、あるいは、一括スピンコーティングや硬化のような、特定の段階の実施が含まれる。ここに述べたように、保護膜や色形成層の開発の技術は、本発明の実施に適したその他の多くの製剤を作成することになる。従って、本発明はここに述べた実施例、及びそれらの変更に伴い、一般的に説明されたが、本開示は、それらの実施例と、ここで開示されていない、あるいは提示されただけのその他のものを含む。

Thus, while the invention has been particularly shown and described with reference to preferred embodiments, it is to be understood that changes in form and detail may be practiced without departing from the scope and spirit of the invention. I hope the contractor understands. For example, many changes may be made in coating application, curing, marking, and marking quality control methods and apparatus. Such examples include performing the various stages in an order other than those disclosed herein, or performing certain stages, such as bulk spin coating and curing. As described herein, the technology for developing protective films and color forming layers will produce many other formulations suitable for the practice of the present invention. Thus, although the invention has been generally described with the embodiments described herein and variations thereof, the present disclosure is not limited to those embodiments or has been presented here. Including others.

It is sectional drawing of the optical media in a prior art. 1 is a cross-sectional view of an optical media having a coating in accordance with the teachings of the present invention. It represents the absorbance curve of the color former during the formation of the coating. Compare the background color formation of various components. 2 represents the absorption spectra of two photoacid generators. 1 represents the ultraviolet absorption spectrum of the first photogenerator. The ultraviolet absorption spectrum of the 2nd photogenerator is represented. The linear spectrum of a medium pressure iron dope lamp is represented. 1 represents a linear spectrum of a gallium iodide lamp. The linear spectrum of the gas filling lamp by Zenon Co. is shown. Represents the transmission curves of various filters. Absorption peaks at 540 nm are represented for various concentrations of color former. Absorption peaks at 540 nm are represented for various concentrations of triphenylsulfonium triflate. Average color reduction in the first environmental survey. It represents surface tension reduction as a function of concentration of various wetting agents. Represents the average absorbance of various formations after environmental testing. Represents the average decrease in light density of various formations after environmental testing. Represents a storage case containing filter paper. Represents fading due to TEA exposure. Expresses color development as a function of exposure wavelength. Represents color development with samples containing UV absorbers. Represents the effect of adding UV absorbers to color generation. It represents the color formation of the UV stabilizer. Represents color formation in specific samples of UV stabilizers. The result of the adjustment study of the ratio of color former and photoacid generator is shown. Expresses color level and sensitivity as a function of photoacid generator concentration and membrane thickness. Represents the absorbance of CN-120 base agent. Compare the absorption spectra of various UV absorbers. It represents the color development time for a mixture containing various photoacid generators. Represents aspects of color generation as a function of photoacid generator. It represents color formation as a function of the type of illumination. It represents color formation as a function of UV absorber. Represents color formation as a function of illumination. It represents the color formation as a function of the reinforcing additive. Represents color formation in a buffered system. The film thickness is expressed as a speed function of the intrinsic angular momentum. The film thickness and light density are expressed as a speed function of the intrinsic angular momentum. The film thickness is expressed as a speed function of the intrinsic angular momentum. It represents the color formation with respect to the change in the ratio of the photoacid generator to the color former. FIG. 3 is a cross-sectional view of an optical medium having a color forming layer and a protective film layer. Represents the light density of the two coatings. Represents color formation as a function of shape start time. The absorption spectrum in three Examples of a protective film layer is represented. It represents the residual sensitivity in the two coating systems. Represents the light resistance of the exposed area. Represents color development by environmental testing. Represents the color retention of the environment. Represents fading due to amine studies. It represents the film thickness as a function of the intrinsic angular momentum velocity. Viscosity is expressed as a function of temperature. Represents the characteristics of shear rate. It represents the characteristics of shear pressure and shear rate. Represents a constant shear rate viscosity. Represents the color formation of a series of photoacid generators and luminescent agents. Represents the color formation of a series of photoacid generators and luminescent agents. Represents the color formation of a series of photoacid generators and luminescent agents. Represents the color formation of a series of photoacid generators and luminescent agents. Represents a comparison of light sources. Represents a comparison of light sources. Represents color formation as a function of sunshine. The remaining sensitivity of the coating with various UV absorbers is shown. Expresses the light density in the exposed area as a function of the UV absorber. It is sectional drawing of the optical media with which the several layer is applied on the reflection layer. It is sectional drawing of the optical media with which the several layer is applied on the reflection layer. It is sectional drawing of the optical media with which the several layer is applied on the reflection layer. It is a graph showing the light absorbency curve in an orange and red color formation layer. It is a graph showing the absorbance curve in a multicolor Example. It is a graph showing the absorbance when only the upper color forming layer is exposed. It is a graph showing the light absorbency in the multicolor system which has a ultraviolet shielding layer. It is a fragmentary figure of the photomask which shows the shading technique. The marking formed on the optical media by illumination with a marking lamp is represented. Represents an inspection device that evaluates markings. Represents the components of the inspection device. Represents test data for uncoated discs. Represents test data for coated discs. Represents test data of a coated disc on which at least one image is recorded. 1 represents the components of one embodiment of a monochromatic forming layer application manufacturing system. Fig. 4 represents components of another embodiment of optical media creation. 1 represents the components of a manufacturing system for applying two coating systems. Represents an apparatus that applies multiple coatings. 1 represents a manual curing device for coating optical media. Represents an off-line marking system for marking optical media. Represents test data of optical media manufactured by the manufacturing system.

Claims (47)

A system for marking optical media,
A unit for forming a coating having at least one photosensitive material in at least one readout region of the optical media;
A first light source for exposing the coating at a wavelength of light, wherein the light wavelength cures the coating on the at least one readout region;
A unit for generating an image of the marking;
A second light source for exposing at least a portion of the coating to the image to record the marking on the coating ;
Wherein the coating is Ru with a color former, system.   The system of claim 1, wherein the wavelength generated by the first light source comprises a wavelength substantially away from the wavelength of the second light source.   The system of claim 1, wherein at least one of the first light source and the second light source comprises a wavelength filter.   The system of claim 3, wherein the wavelength filter comprises a wavelength blocking filter that cuts out wavelengths between about 340 nm and about 370 nm. The system of claim 1, wherein the coating further comprises a photoinitiator . The system of claim 1, wherein the coating further comprises a photoacid generator.   The photoinitiator is a stable mixed solution of trimethylbenzoyldiphenylphosphine oxide and α-hydroxyketone and a benzophenone derivative, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone eutectic mixture, 50% 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 50% 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Isopropylthioxanthone, 70% oligo [2-hydroxy-2- 6. At least one of a mixture of til-1- [4- (1-methylvinyl) phenyl] propanone and 30% 2-hydroxy-2-methyl-1-phenylpropan-1-one. The system described in. The photoacid generator is bis (4-t-butylphenyl) iodonium p-toluenesulfonic acid, (t-butoxycarbonylmethoxynaphthyl) diphenylsulfonium triflate, (4-phenoxyphenyl) diphenylsulfonia triflate, (4 -T-butylphenyl) diphenylsulfonia triflate, diphenyliodonium hexafluorophosphate, diphenyliodonium triflate, triphenylsulfonia triflate, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, (4-me Butylphenyl) diphenyl sulfonium near triflate, and among hexafluorophosphate diphenyliodonium system of claim 6 comprising at least one. The system of claim 5 or 6 , wherein the coating further comprises a wetting agent.   The system of claim 9, wherein the wetting agent comprises at least one of a polyether-modified polydimethylsiloxane, a crosslinkable acrylate silicone polyether, and a crosslinkable acrylate silicone.   The system of claim 1, wherein the coating comprises a mixture of at least one acrylate.   The acrylate is ethoxylated pentaerythritol tetraacrylate, 1,6 hexanediol diacrylate, tetrahydrofurfuryl acrylate, highly propoxylated (5,5) glyceryl triacrylate, 3 mol propoxylated glyceryl triacrylate, 3 mol ethoxylated Trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, urethane diacrylate oligomer, isobornyl acrylate, bifunctional bisphenol A-based epoxy acrylate, low viscosity aliphatic diacrylate oligo Mail, tris (2-hydroxyethyl) isocyanurate triacrylate, 2-phenoxyethyl acrylate, 40% At least one of bifunctional bisphenol A-based epoxy acrylate mixed with 1,6 hexanediol diacrylate, bifunctional bisphenol A-based epoxy acrylate mixed with 50% 2-phenoxyethyl acrylate, and acrylic acid is provided. The system of claim 11.   The system of claim 11, wherein the acrylic acid comprises at least one non-alkoxylated monomer. The system of claim 1, further comprising a unit that applies a light-absorbing substance to the coating.   The coating comprises 2,4-di-t-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl- Mixtures of phenol, methyl 3 (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionic acid and PEG300 reaction product, branched and straight chain 2- (2H- Benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2′hydroxy-5′methacryloyloxyethylphenyl) -2H-benzotriazole, 2,2′-dihydroxy-4-methoxybenzophenone, 2 At least one of -hydroxy-4-n-octoxybenzophenone and octyl methoxycinnamate The system of claim 1.   The system of claim 1, wherein the system comprises an optical media replication system.   The optical media format is DVD5, DVD9, DVD10, DVD18, DVD-R, DVD-RW, Audio CD, Video CD, CD-R, CD-RW, CD-ROM, CD-ROM / XA, CD-I. The system of claim 1, comprising one of: CD-Extra, Photo CD, Super Audio CD, Blu-Ray, MD, and hybrid formats.   The system of claim 1, wherein the application unit comprises at least one spin coating station.   The system of claim 1, wherein the image generation unit comprises a photomask comprising an image of the marking.   The system of claim 1, wherein the image generating unit comprises a drawing laser for forming an image of the marking.   The system of claim 1, wherein the image generating unit comprises an electrically writable photomask for forming an image of the marking.   The system of claim 1, further comprising an inspection station for inspecting for at least one quality of the substrate, the coating, the curing of the coating, and the marking in the coating. The system of claim 1, wherein the coating is formed on one of a substrate layer, a reflective layer, and a protective layer of optical media.   The system of claim 1, further comprising a system controller for operating the system.   The system of claim 1, wherein the marking comprises at least one of text information, alphanumeric characters, symbols, graphic information, embedded information, digital watermarks, and hidden markings.   The system according to claim 1, wherein the marking includes at least one of ID information, authentication information, operation information, advertisement, brand, and promotion information. A system for forming a colored coating in the readout area of an optical medium,
A unit for forming the color coating in the readout region of the optical media, wherein the color coating is substantially remote from the first set of wavelengths and the photocurable component sensitive to the first set of wavelengths; A unit having a sensitive color developing component sensitive to the second set of
A light source for exposing the colored coating to the first set of wavelengths ;
Wherein the color coating Ru comprising a color former system. A system for marking a read area of an optical medium,
A station for receiving the optical media, the optical media having at least a color-developing coating thereon, the coating being substantially separated from the first set of wavelengths and the photocurable component sensitive to the first set of wavelengths; A station having a sensitive color component sensitive to a second set of different wavelengths;
A unit for generating marking images;
A light source for forming a second set of wavelengths and exposing at least a portion of the coating to the image to record the marking on the coating;
Wherein the coating is Ru with a color former system.   30. The system of claim 28, further comprising a unit for coating a protective film on the color coating. A method for marking a read area of an optical medium,
Forming a coating with at least one color former in the readout area of the optical media;
Exposing the coating with a first set of wavelengths;
Curing the coating formed on the at least one readout region;
Selectively exposing a portion of the coating in a pattern that records the marking on the coating by using a second set of wavelengths that are substantially away from the first set of wavelengths;
A method comprising: 31. The method of claim 30, wherein forming the coating on the optical media includes forming the coating by spin coating. 32. The method of claim 30, wherein the forming step includes temperature control of the color former. 32. The method of claim 30, wherein the forming step includes viscosity control of the coating. 32. The method of claim 30, wherein the forming step includes thickness control of the coating. 32. The method of claim 30, wherein the forming step comprises replacing a component layer of the optical media.   32. The method of claim 30, wherein the curing step includes providing an environment having an inert gas.   32. The method of claim 30, wherein the first set of wavelengths has a wavelength greater than about 370 nm.   32. The method of claim 30, wherein the second set of wavelengths has a wavelength between about 270 nm and 320 nm.   32. The method of claim 30, wherein the selective exposure step includes using at least one of a photomask and a writing laser. The method of claim 30 wherein said forming step comprises forming at least one light absorbent substances. A computer program stored on a computer readable medium comprising an instruction set for operating a system for producing an optical media comprising at least one marking applied to a read side of the optical media, the computer program comprising: The instruction is
Forming a coating with at least one color former in the readout area of the optical media;
Exposing the coating with a first set of wavelengths;
Curing the coating formed on the at least one readout region;
Selectively exposing portions of the coating in a pattern that records the marking on the coating by using a second set of wavelengths that are substantially away from the first set of wavelengths;
Computer program.   42. The computer program according to claim 41, wherein the operation instruction is executed by a system controller adapted to operation control of a system.   42. The computer program according to claim 41, wherein the operation instruction comprises at least one operation instruction of an inspection station, a spin coating station, a curing processing station, and a marking station. A system for marking optical media, the system comprising:
A unit for forming at least one color- developing layer comprising a color former in at least one readout region of the optical medium;
A first light source for exposing the at least one color developing layer in a first band of wavelengths and performing a curing process on the at least one color developing layer;
A second light source for selectively exposing at least a portion of the at least one color developing layer in a second band of wavelengths to record the marking on the at least one color developing layer;
A unit for forming at least one protective film layer on the at least one coloring layer;
A third light source that exposes the at least one protective film in a third band of wavelengths to cure the at least one protective film layer;
A system comprising:   45. The system of claim 44, wherein the protective layer comprises at least one of a light absorbing material and an acid removal agent.   45. The system of claim 44, wherein the at least one overcoat layer exhibits a high optical density in a second band of wavelengths. A method of marking on optical media,
- at least one color development layer comprising a color former, and forming at least one reading area of the optical medium,
Exposing the at least one color forming layer in a first band of wavelengths and performing a curing process on the at least one color developing layer;
Selectively exposing at least a portion of the at least one color developing layer in a second band of wavelengths to record the marking on the at least one color developing layer;
Forming the at least one protective film layer on the at least one coloring layer;
Exposing the at least one protective film layer in a third band of wavelengths and performing a curing treatment of the protective film layer;
A method comprising:

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