TW200846405A - Photopolymer resins for photo replication of information layers - Google Patents

Abstract

Photopolymer resins are disclosed which includes metal and/or ceramic surface chelating agents to provide strong bonding of the photopolymer resin to the inorganic surface of the first information layer of an optical disc. The resins also include a fast surface cure and glass transition temperature controlling monomers that provides easy stamper separation. The disclosed photopolymer resins also include short wavelength (< 405 nm) surface cure initiators. The resins may also optionally include shrinkage control oligomers and/or polymer fillers or a combination of both. Use of the disclosed resins eliminates two steps from the manufacture of a multiple information layer optical disc as the formation of spacer layers and the curing of spacer layers is no longer necessary.

Description

200846405 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The invention relates generally to optical discs, and more particularly to photopolymer resins useful for optical duplication and other applications of optical disc layers. Therefore, the present invention relates to optical disc applications such as Blu-ray (BD_Rw, BD-RE) and High-Density DVD (HD-DVD) discs. [Prior Art]

One of the optical storage devices is exemplified as a disc (CD). A CD can store a large amount of digital information (783 MB) on a very small surface, which is not expensive to manufacture. The CD surface is basically a mirror surface covered by countless tiny pits arranged in a long, tight loop or groove. The CD player reads the pit with precise laser and interprets the information with data bits. The upper pit circle starts at the center of the disc. The €0 track is about 5.5 microns wide and divides the two tracks by 1.6 microns. The extended pits are about 0. 5 microns wide, at least 0.83 microns long and 125 nm. The main part of the CD is a transparent polycarbonate plastic that is molded into a variable piece, which is about 1.2 mm thick. During the manufacturing process, the plastic is pressed to have a small pit, which is composed of long and round windings. - A thin, reflective aluminum layer is then applied over the top of the disc to cover the pit. When a CD is played or read, a CD of a CD player or driver passes through the carbonate layer of the CD, reflected back and struck by the aluminum layer. The optoelectronic device of the debt metering change. The light reflected by the pit is different from the flat part of the aluminum layer, which is called land. The photoinductor measures these changes in reflectivity, and in the CD-player. The electronic components in the drive interpret these changes as data 200846405 bits. For detachable storage applications, CD-recordable (CD-R) and CD-rewritable (CD-RW) devices can be used. CD-R operates as a normal (: The aluminum layer of tantalum is replaced by an organic dye compound. This compound is usually reflective, but when the laser is focused on a point and heated to a specific temperature, it "burns" the dye, causing it to blacken. Take the data written to the CD-R, the laser is moved back over the disc and the burning point is regarded as a pit. The data can only be written to CD_R once; when the dye has been burned to a point, it cannot be changed back. CD- RW and DVD discs use this change to cope with this problem, relying on a very special ', mixed mixture of indium, silver and antimony. .... Provides more information on the summer CD and DVD discs to meet high paintings The need for quality recording, video and τν recording, interactive DVD movies and gaming applications. To increase data capacity, use shorter wavelength lasers. For example, 'First CD 使用 uses 78 〇 nm laser, then format 650 nm laser, while current Blu-ray (BD RW, BD re) or high density dvd The (hd-dvd) format uses a 405 nm laser. With the acquisition of shorter wavelength lasers, smaller pits and narrower, more closely packed trenches can be created on the disc and more data can be found on the disc. The chip is packaged into a specific area. In order to further increase the data density of the optical disc, a multi-layer data information layer can be constructed on the disc. In short, the data density of the high-density optical disc can be increased in two ways. (1) Encapsulation on the surface of the optical disc More pits and trenches, due to the shorter wavelength laser and higher NA lens acquisition, and (2) vertical multi-information layer to provide more data layers in the disc. ^ An example of a DVD-type disc having a single, double, and four data layer is 200846405, which is shown in Figures 1A-1C. Displayed in the first

Part of the illustration is shown as having a single information layer 12. The discs 10B and lcc shown in the figure 1 of the DVD disc 1A1C are used to create a multi-layer information layer, such as the layers 1B and 22, photopolymer trees and Μ, U, 2〇 For use in pit and trench applications. As shown in Fig. 1B', % is "2P resin", as shown in Fig. 1C, the information households are separated from each other by the transparent spacer layers indicated by 24, 26, 28, 30: 曰 There are many ways to manufacture multiple data on the optical disc. Shellfish layer. A method of manufacturing this data layer is called 2P process because it is prepared by people.

The catastrophic light embossing embosses the pits and grooves on the data layer of the optical disc. The communication secret pits and trenches represent pre-recorded digital information in the case of pre-recorded media or represent tracking or header information in the example of recordable media w—typical or binary 2p process is shown in Figure 2 flow chart. In Fig. 2, an injection molded first information layer is shown at 4, which has a half reflective layer (not shown). The first information layer 4 1 is coated with a light transparent resin to substantially harden it to form the first spacer layer 42. The first spacer layer 42 is then coated with a photopolymer resin 43, followed by a template 44. The template is preferably optically transparent so that UV energy is allowed to penetrate the template 44 and the embossed material from the stencil 44 to the hardened photopolymer layer 43 置于 template 44 placed on top of the spacer layer 42 is then removed. In a conventional 2P process, two types of UV resins are required. First, the spacer layer 42 is made of a UV resin which can adhere well to the semi-reflective layer 41, which is made of metal or ceramic. The resin of the spacer layer 42 must be low-retracted so that the radial and tangential tilt of the disc is low, which facilitates tracking of the disc at high speeds. The second resin is a UV-curable resin for layer 43, which has good adhesion to the hardened spacer layer 42 and can be easily separated by the transparent plastic template 44 after the UV exposure step 200846405. In this technique, a plastic template 44 is used for each data layer. The template can be made of different materials including polycarbonate (pc), polymethylmethacrylate (PMMA), and polyolefin (P0). Only polyolefins were successfully used without any help of the outer release layer on the surface of the mold. However, polyolefins are expensive because they can be an alternative to additional release layers on the stencil. The lower cost plastic materials such as PC and PMMA are polar, and their adhesion to 2p resin is so great that it is difficult to be cleanly separated from the plastic template after the UV hardening step. SUMMARY OF THE INVENTION The present invention discloses an improved photopolymer (2p) resin comprising a surface chelating agent, a monomer, and a surface hardening initiator. Conveniently, the resin also includes a shrinkage control component in the form of an oligomer or polymeric filler. More specifically, the resin of the present invention comprises a gold-plated and/or ceramic surface chelating agent, a fast surface hardening and glass transition temperature control monomer, a surface hardening initiator, and a shrink-controlled oligomerization selectively added. And / or polymer filler. In one embodiment, the chelating agent is selected from the group consisting of a combination of a toxic acid, a phosphoric acid, a metal hybrid acrylates, an anthracycline coupling agent, an amine phthalic acid ester, a guanamine acrylate, and the like. In the group. In one embodiment, the chelating agent is selected from the group consisting of amine acrylate, decylaminoethyl methacrylate, polycaprolactone modified 2-hydroxyethyl methacrylate phosphate S Phosphate of 2-hydroxyethyl methacrylate, 2-methylpropenyl oxyacetate phosphate, 2-methyl propylene fluorenyl 200846405

Oxyethyl succinic acid, 2-methacry Ioyloxyethyl hexahydrophthalate, 2-propenyloxyethyl succinate, 2-propenyl phthalate Oxyethyl ester, 2-acryloyloxy ethyl phosphate, 2-acryloyloxy ethyl phosphate diaerylate, hexahydrophthalic acid 2-acry〇ly〇xyethyl hexahydro phthalate, γ-hydrothiopropyltrimethoxy decane, gamma-glycidoxypropyltrimethoxysilane, Ν- (β-Aminoethyl hydrazine-aminopropyltrimethoxy-decane, γ-methylpropenyloxypropyltrimethoxy oxane, a mixture thereof, etc., in an embodiment, The hardened 2 Ρ resin has a glass transition temperature (Tg) of at least 45 〇 C. In another embodiment, the monomer is at least a tetra-, penta-, or hexafunctional monomer. In yet another embodiment The monomer is at least one of mono-, di- or tri-propyl benzoate. In one embodiment, the monomer is selected Groups of the following composition: diacetone diacetate, isobornyl acrylate, dimethyl trimethyl acetaldehyde modified trimethyl oxypropane diacrylate, hydroxy trimethyl acetic acid neopentyl glycol diacrylate , tricyclodecane dimethanol dipropionate, cyclohexane didecyl didecyl acrylate, ethoxylated A type bisphenol diacrylate, tripropylene glycol diacrylate, triethylene glycol Dipropionate, 1,3-butanediol dimethacrylate, trimethoxypropane tris(decyl) acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylate Trimethyl propylene oxide triacrylate vinegar,

200846405 Ethylene oxide modified A-type double aged dimethacrylate, methyl third-butyl ester, polyethylene glycol diacrylate, 3-methyl-1,5-pentaacrylate, 2 a mixture of -butyl-2-ethyl-1,3-propanediol diacrylate, -1,8-octanediol-diacrylate-1,9-nonanediol diacrylate. In one embodiment, the activation agent has an activation wavelength in the range of 3 to 10 nm. In one embodiment, the initiator is selected from the group consisting of benzophenone-2-methyl-1-phenyl-propan-1 - fluorene, .1 - thio-per hexyl-pan- a group consisting of a mixture of ketones, and the like. In one embodiment, the polymer filler is selected from the group consisting of methyl methacrylate propylene based polymers, η methacrylate methacrylate, decyl acrylate, η-butyl methacrylate. A polymer or copolymer of a copolymer, an ene or a polybutadiene or a mixture thereof, etc. In one embodiment, the oligomer is selected from the group consisting of histides, polyethers, polyesters, acrylics Mixing of esters, and the like, in one embodiment, discloses a method of making a disc. The method comprises: forming a first information layer by using a half reflective material; rotating and coating the photopolymer resin on the first information layer; printing the photopolymer resin layer by an optically clear stamper; and printing the light The polymer resin layer is exposed to UV energy to be embossed from the template: In one embodiment of the invention, a separate spacer is not deposited to harden the separation spacer layer, thereby reducing the number of steps required to form a light manufacturing step. In general, the composition of the uncured 2P resin comprises: a group consisting of about 0· acrylic acid diol di-2-methyl group and the like to 40 5 , 2′ hydroxy benzophenone. Poly-liquid. The method package will be as poor as the template. 0001 to 10 200846405 of the layer and the disc, about 10% by weight (wt%) of the chelating agent; from about 10 to about 90% by weight of the high Tg monomer; from about 〇5 to about 40% by weight of the oligomer and / or polymer filler; from about 0,5 to about 15% by weight of short-wavelength surface hardening initiator: 0 · 5 -1 5 % 〇 unmultiplied 2P resin preferably contains: by about 〇 · 〇〇 〇2 to about 5% by weight of a chelating agent; from about 20 to about 90% by weight of a monomer; from about 5% to about 5% by weight of a polymeric and/or polymeric filler; 3 to about 15% by weight of short-wavelength surface hardening initiator: 0.5 - 1 5%.

More preferably, the uncured 2 P resin comprises: from about 〇6 to about 2% by weight of a chelating agent; from about 35 to about 90% by weight of a high τ g monomer; from about '·5 Up to about 15% by weight of oligomer and/or polymeric filler; from about 3 to about 12% by weight of a short wavelength surface hardening initiator. Other advantages and features of the present invention will become apparent from the Detailed Description and the accompanying drawings. In order to more fully understand the resin, method and optical disk of the present invention, reference is made to the detailed explanation of the drawings. [Embodiment] It is to be understood that the drawings are not necessarily to In a particular example, details of the method and apparatus of the present invention that are not necessary or that may cause other details to be difficult to understand will be omitted. Of course, it is to be understood that the disclosure of the invention is not limited to the specific embodiments described herein. The photopolymer UP) resin disclosed in the present invention has good adhesion to the metal/ceramic surface of the semi-reflective layer and can be easily separated (displaced or demolded) from all types of plastic stencils used in the current optical disc manufacturing 11 200846405. Plastic templates include, but are not limited to, PC, PMMA, acrylic, PMMA-PS copolymer, polyene smoke or other types of plastic. The resin of the present invention provides ()) clear separation from the plastic template, (2) good adhesion of the semi-reflective layer, and (3) low shrinkage upon hardening. Low shrinkage, strong adhesion to metal or semi-reflective surfaces, and complete separation from the plastic template allow the 2P resin of the present invention to be used in both the spacer layer and the replication layer or relief layer. The low shrinkage ensures that the desired disc of the disc such as the Blu-ray (BD-RW 'BD_RE) double layer and the HD-DVD double layer can be tilted. The low disc tilt provided by the 2P resin of the present invention results in a high-capacity manufacturing process with high throughput, less steps, and increased throughput. The 2P resin of the present invention can be used at one time. A low-cost, conventional plastic template, such as a PC or PMMA template, is used to fabricate both the spacer layer and the knee layer of the optical disc. The 2P resin of the present invention allows for reduced process steps and eliminates the need for more expensive templating materials. Therefore, the resin of the present invention can reduce the cost of manufacturing an optical disk. Fig. 3 is a flow chart of the 2 p process of the present invention using the 2 P resin of the present invention, wherein at least two process steps in the conventional manufacturing technique are omitted. The 2P resin of the present invention may comprise: a chelating agent such as a metal/ceramic surface chelating agent, a monomer such as a rapid surface hardening and a Tg controlling monomer; and an initiator such as a surface hardening initiator. Conveniently, a shrinkage control polymer or a polymeric filler may be included as needed when low shrinkage is desired. Metal/ceramic surface chelating agent 12 200846405 Metal/ceramic surface chelating agent promotes the adhesion of 2P resin to the inorganic surface of the first information lip such as metal or ceramic surface. Chelating agents also provide differential bonding strength to metal and plastic surfaces. The use of a chelating agent provides a relatively high bonding strength of the 2P resin to the metal or ceramic surface compared to the plastic template. The following types of chelating agents have been found to be effective: carboxylic acid, phosphoric acid, metal mixed acrylic acid, decane coupling Agents, alkaline chelating agents include amine or guanamine based adhesion promoters, including amine acetophenone esters.

Examples of specific chelating agents include, but are not limited to, the following: amine acrylates 'included under the trademarks CN 373, CN 984, CN 384, CN 386, and CN 371, SR 368 by Sartomer Co., Ltd. (www.sartomer .com) The seller, monomethylaminoethyl methacrylate H·, sold by —Kyoeis-ha Chemical Co. (www.kyoeisha.co.jp); acid chelating agent such as polycaprolactone Modified acid-based propyl ketone 2-ethyl acetal acid-filled vinegar, methyl propyl ketone 2-ethyl vinegar vinegar, which is supplied by Nippon Kayaku Co. Ltd. (·www.nipponkayaku.co_jp Seller; 2-methacryloyloxyethyl acid phosphate, hexahydrophthalic acid g-methyl 2-methylpropanyloxyethyl ester, 2-acrylonitrile succinate Oxyethyl acetoacetate, hexahydrophthalic acid 2-propenyl oxyethyl ester, 2-propenyl methoxy oxyethyl acid, dipropionate 2- propylene oxy ethoxylate, Hexahydro-o-co-dimethyl hydrazine complex 2-propenyl decyl oxyethyl ester, which is sold by Kyoeisha Co., Ltd.; simmering chelating agent includes γ-hydrothiopropyltrimethoxy sulphur, γ-glycidoxypropyltrimethoxy Base arson -(β-Aminoethyl)-γ-aminopropyltrimethoxy_ Mengzhuo, γ-methacryloxypropyltrimethoxymethane, sold by OSi Specialties, now GE Specialty Materials A division of the department (http://gespecialtymaterials.com), and so on. 13 200846405 Fast surface hardening and Tg control monomer The surface hardening of 2P resin is important for overall performance. If the surface hardening is poor, the 2P tree will behave as a binder and will not behave as a protective coating for good plastic plate separation. If the surface of the resin is poorly hardened, the surface energy of the tree will be greater than 70 dynes/cm. Therefore, the hardened, soft surface and not cleaned by the plastic template. The final surface hardening of the 2P resin can be designed using suitable monomers to provide a suitable surface for the separation process step. The surface energy of the hardened resin should be between 25 and 70 dynes/cm with a hardening dose of less than mJ/cm2 to allow for a good semi-reflective layer of the disc, while providing a good plastic template. The final glass transition temperature (Tg) of the hardened 2P resin should exceed 45 ° C. The high Tg of the hardened 2P resin is necessary for two main reasons. First, the uv_ 'chemical step generates heat; therefore, if the 2P resin is hardened If the Tg is too low, the shape of the pit will be distorted during the separation or stripping process. Second, the high Tg hardened 2P resin can reduce the penetration of moisture during the life of the disc, so it provides '2G resin to Tg. Highly reliable discs. It is known that tetra-, penta- or hexa-functional monomers provide high Tg and fast surface hardening. However, these monomers have too high shrinkage when hardened. Therefore, only Specific examples of mono-, mono- or tri-acrylate monomers using mono-, di- or tri-glycolic acid high Tg, fast surface hardening, but not limited to the following: diamyl diacrylate, acrylic acid Borneol vinegar, hydroxytrimethylacetaldehyde modified trimethyl oxypropane Diacrylate, hydroxytrimethylacetic acid neopentyl glycol diacrylate, tricyclodecane didecyl diacrylate, cyclohexane 14 200846405 dimethanol dimethacrylate, ethoxylated A_ Type bisphenol diacrylate vinegar, tripropylene glycol diacrylate vinegar 'triethylene glycol diacrylic acid vinegar, hydrazine, 3 - butanediol dimethyl acrylate vinegar, trimethoprim tris (meth) acrylate vinegar, Tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated tridecyloxypropane triacrylic acid, 氡 氡 烧 改 之 之 A _ _ _ _ _ _ _ _ _ _ _ _ Vinegar, methacrylic acid, third-butyl, polyethylene glycol diacrylate, 3_methyl-1,5-pentanediol diacrylate, 2 butyl-2-ethyl-^3-propanediol Diacrylate, 2-methyl-18-octanediol-diacrylate vinegar + 9-decanediol diacrylate, and mixtures thereof, etc. • Shrinkage control oligomer or polymer filler...

For some Southcomer disc formats, including BD and hd-DVD, the radial tilt specification is less than one. . In order to ensure reliability and high productivity processes, a low shrinkage nut and/or filler may be suitably used in combination with the 2p resin of the present invention. An oligomer having a shrinkage of less than 7% and a filler having a shrinkage of about 〇% can be used to compensate for the high shrinkage (&gt; 8%) of the UV-hardenable monomer. A 2 Ρ resin having a hardening shrinkage of less than 8% provides a disc having a radial tilt of less than 1 °. The choice of oligomer or polymer filler is also based on the desired viscosity of the process. An example of a polymer filler includes a methyl methacrylate acrylic polymer (Elvacite 2008-C, available from Lucite Ιηΐβηια1: ίοηα1(λνντ^_1ιιοίί 63〇1ιιΗοη5·οοιη), methyl propyl butyl acrylate polymer, A a polymer or copolymer of acrylate (Elvacite 205 1, from Lucite) and η-butyl methacrylate (Elvacite 2767, available from Lucite), polystyrene # or polybutadiene or The similarity. Examples of low shrinkage propionate oligomers include polyurethanes, poly 15 200846405 ethers or polyesters, acrylates, or the like, or mixtures thereof. Surface hardening initiator The initiator of the 2P resin of the present invention is a short wavelength initiator. The a-ketone initiators include dibenzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173, available from Ciba-Geigy Co.

(www.cibasc.com/darocur-I173.htm)), 1-hydroxy-cyclohexyl-phenol ketone (Irgacure 184 from Ciba), benzophenone (from Aldrich Chemicals), or similar material. A shorter wavelength initiator with an activation wavelength in the range of 31 〇 4 〇 5 nm provides a higher cross-linked micro-surface, which helps to harden the 2P resin from the plastic template. Furthermore, the laser wavelength for high-density optical discs is 40 5 nm. The initiator for the 2P composition of the BD or HD-DVD format disc should have an absorbance of less than 405 nm. In general, the composition of the uncured 2P resin may comprise from about 〇 to about 10% by weight of a chelating agent; from about 10 to about 90% by weight of high butyl &amp; monomer · from about 0.5 to about 40% by weight of oligo Polymer and/or polymer filler; from about 0.5 to about 15% by weight of short-wavelength surface hardening initiator · 〇5 _〗 5 0/. . The uncured 2 eucalyptus deer preferably comprises: from about 2 to about 5 weight percent of the auxiliaries; from about 20 to about 9% by weight of the high Tg monomer; from about 〇·5 to about 25% by weight. Oligomer and/or polymeric filler; from about 3 to about 15 5 denier % short wavelength surface hardening initiator: 0.5 - 15%. Most preferably, the uncured 2 Ρ resin comprises: from about 0 〇〇〇 6 to about 2 重量% chelating agent; from about 35 to about 90% by weight of high Tg monomer; from about 〇5 to about 15% by weight oligomerization And/or polymeric filler; from about 3 to about 12 weights 16 200846405 % by volume short-wave surface hardening initiator. Example

Example 1 Ingredients Functional amount of isobornyl acrylate monomer, rapid hardening, control of Tg 0.25 dipentyl diacrylate monomer, rapid hardening, control of Tg 0.5 ethylene oxide modified A-type bisphenol dimercapto Acrylate monomer, fast hardening, control of Tg 0.2 2 -methacryl fluorenyl oxyacetate phosphate metal / ceramic chelating agent 0.01 Irgacure 184 Surface hardening starter 0.04 Composition shrinkage (%) 6 Excellent peeling from PC template Adhesion of the reflective layer Excellent Example 2: Ingredients Functional weight of isobornyl isocyanate monomer, rapid hardening, control of Tg 0.25 dipentyl diacrylate monomer, rapid hardening, control of Tg 0.5 ethylene oxide modification A-type bisphenol dimercapto acrylate monomer, fast hardening, control Tg 0.15 Elvacite 2008-C polymer filler 0.05 2_mercapto propylene fluorenyl oxyacetate metal / ceramic chelating agent 0.01 Irgacure 184 surface hardening Starting agent 0.04 composition result 17 200846405

Shrinkage (%) 3 Adhesion of excellent semi-reflective layer by PC template Excellent Example 3: Component Functionality Part of hydroxytrimethylacetaldehyde-modified trimethyl oxypropane diacrylate monomer, fast hardening, control Tg 0.4 Dipentyl diacrylate monomer, fast hardening, control of Tg 0.4 Ethylene oxide modified A-type bisphenol dimethacrylate monomer, fast hardening, control Tg 0.1 Elvacite 2008-C polymer filling Agent 0.05 2-mercapto acrylonitrile oxyacetic acid phosphate vinegar 1. Metal V ceramic chelating agent 0.01 Irgacure 184 Surface hardening starter 0.04 Composition shrinkage (%) 3 Good adhesion of excellent semi-reflective layer by PC template peeling Example 4: Ingredients Functionality Part of hydroxytrimethylacetaldehyde modified trimethyl oxypropene propylene diacetate monomer, fast hardening, control Tg 0.4 dipentyl acrylate monomer, fast hardening, control Tg 0.43 Ethylene oxide modified A-type bisphenol dimethacrylate monomer, fast hardening, control Tg 0.05 Elvacite 2008-C polymer filler 0.05 Amine propylene Vinegar CN 373 metal / ceramic surface hardening chelator 0.03 Irgacure 184 initiator 0.04 18 200 846 405

Composition shrinkage (%) 2 Adhesion of excellent semi-reflective layer by PC template Excellent Example 5: Component Functionality Part of hydroxytrimethylacetaldehyde-modified trisyloxypropane diacrylate monomer, rapid hardening , control Tg 0.4 dipentyl diacrylate monomer, fast hardening, control Tg 0.33 methyl propionate third-butyl ester monomer, fast hardening, control Tg 0.15 polystyrene polymer (from Bimax) polymer Filler 0.05 Amine acrylate CN 373 ·--------- -Metal/ceramic chelating agent 0.03 Daro cure 1173 Surface hardening starter 0.04 Composition shrinkage (%) 5 Excellent peeling from PC template Adhesion of the reflective layer Excellent Example 6: Ingredients Functional hydroxytrimercaptoacetaldehyde modified trimethyl oxypropane diacrylate monomer, fast hardening, control Tg 0.4 dipentyl acrylate monomer, fast Hardening, control Tg 0.43 tridecyloxypropane trimethacrylate monomer, fast hardening, control Tg 0.05 polystyrene polymer (from Bimax) polymer filler 0.0 5 Amine acrylate CN 373 Metal/ceramic chelating agent 0.03 Darocure 1173 Surface hardening starter 0.04 19 200846405 Composition shrinkage (%) 4 Adhesion of excellent semi-reflective layer by PC template Excellent Example 7: Component Functionality Partial hydroxyl group Trimethyl acetaldehyde modified trimethyl oxypropane diacrylate monomer, fast hardening, control Tg 0.4 dipentyl methacrylate monomer, fast hardening, control Tg 0.48 trimethyl oxypropane tridecyl acrylate Ester monomer, fast hardening, control Tg 0.05 Amine acrylate CN 373 Metal/ceramic chelating agent 0.03 Darocure 1173 Surface hardening starter 0.04 Composition shrinkage (%) 7 Good adhesion of excellent semi-reflective layer by PC template peeling

In the foregoing embodiments, the main component is always a monomer or a combination of monomers. In order to maintain a high monomer content, the resulting uncured resin will have a low viscosity of less than or equal to 300 cp, which makes the uncured resin suitable for spin coating. However, uncured resins with substantially higher viscosities, in the range of more than 300 cp and even up to 5,000 - 6,000 cp, can be used in spin coating applications, which are only slow. Therefore, in order to keep the viscosity low, a solid monomer is used and the monomer is the main component. Although only a fast hardening, Tg control monomer is required, the composition is used in the foregoing examples and the specific monomer composition is based on its viscosity, hardening time, and glass transition temperature. The method of increasing the viscosity in the cost of the monomer content is to add an oligomer or a polymer filler. Any of the shrinkage control oligomers exemplified in the examples can be added to the examples to increase the shrinkage control problem.曰 As shown in Figure f3, the use of the photopolymerization disclosed herein can reduce the number of steps of the two-layer information layer disc by at least two process steps and the information layer can reduce the number of additional process steps. In particular, the present polymer resin is free from depositing and hardening a transparent spacer layer 42. The photopolymer resin layer 43a is directly deposited on the upper first information layer 43a and then printed and hardened by the mold 44. The second information layer, shown on the right side of Figure 3. Resins enhance manufacturing efficiency, increase throughput, and increase manufacturing capacity by eliminating process steps for discs with only two information layers and eliminating additional steps for a four-layer disc. Although only specific embodiments are set forth, those skilled in the art will recognize and modify the foregoing. These and other changes and refinements are considered to be equivalent to the spirit and scope of the patent application scope described below. [Simple description of the drawings] Figures 1A to 1C are single information layer DVD, one or two DVD and A side view of a four-layer information layer DVD; FIG. 2 is a flow chart showing the process of forming a conventional photopolymer resin and a conventional optical disc; and FIG. 3 is another illustration of the use of the present invention. A flow chart of a photopolymer optical disc forming process in which at least two different shrinkage controls are dispensed with. The above-mentioned viscosity-increasing resin is more than two bright light I. Only 4 1 〇 layer As in the at least 2 invention, the invention can be seen. Information Layer Spacer Resin Manufacturing 21 200846405 Steps. [Main component symbol description] 10A DVD disc 10B disc 10C disc 12, 14, 16, 18, 20, 22 24, 26, 28, 30 Light transparent room

Information layer compartment 41 First information layer 42 First spacer layer 43, 43a · ··... Light-polymer-tree·Moon purpose 44 Template 22

Claims (1)

200846405 X. Patent Application Range: 1. A photopolymer resin comprising: a surface chelating agent; a monomer; and a surface hardening initiator. 2. The resin of claim 1, wherein the surface chelating agent is a metal surface and a ceramic surface chelating agent. 3. The resin according to claim 1, wherein the chelating agent is selected from the group consisting of: carboxylic acid, phosphoric acid, metal mixed acrylates, A mixture of Shi Xi stalk mixture, amine acrylate, guanamine acrylate and the like. 4. The resin according to claim 1, wherein the chelating agent is selected from the group consisting of amine acrylate, dimethyl propyl acetoacetate, and polycaprolactone. 2-Hydroxyethyl acid phosphate, 2-methacryl〇yloxyethyl acid phosphate, succinic acid 2-Mercaptopropenyloxyethyl ester, hexahydrophthalic acid 2-methylpropenyloxyethoxyethyl, 2-propenyloxyethyl succinate, 2-propenyloxy phthalate Vinegar, 2-propenyloxyethyl phosphate, 2-propenyl oxyethyl phosphate diacrylate, 2-propenyl decyl hexahydrophthalate, γ-hydrothiopropyltrimethoxy Decane, γ-glycidoxypropyltrimethoxydecane, Ν-(β-aminoethyl)_γ-aminopropyltrimethoxy-decane, γ- 23 200846405 Mercaptopropenyloxypropyltrimethoxy a mixture of decane, and the like. 5. The resin of claim 1, wherein the hardened 2P resin has a glass transition temperature (Tg) of at least 45 °C. 6. The resin of claim 1, wherein the monomer is at least one of: a tetra-, penta-, or hexafunctional monomer. 7. The resin according to claim 1, wherein the monomer is at least one of the following: a mono-, di- or tri-acrylate. 8. The resin according to claim 1, wherein the monomer is selected from the group consisting of neopentyl diacrylate, isobornyl acrylate, and hydroxytrimethyl acetaldehyde. Trimethoxypropane diacrylate, hydroxytrimethylacetic acid neopentyl glycol diacrylate, tricycloanthracene dimethanol diacrylate, cyclohexane dimethanol dimercapto acrylate, ethoxylated A type bisphenol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol dimercapto acrylate, trimethyl oxypropane tri (meth) acrylate, three (2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, ethylene oxide modified A-type bisphenol dimercapto acrylate, A Third-butyl acrylate, polyethylene glycol diacrylate, 3-mercapto-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate , 2-mercapto-1,8-octanediol-diacrylate-1,9-nonanediol diacrylate, and mixtures thereof. 24 200846405 9. The resin as claimed in claim i wherein the initiator has an activation wavelength in the range of from 3 1 Torr to 4 5 5 n m. The resin according to claim i, wherein the initiator is selected from the group consisting of: &gt; benzophenone, 2-cyso-2-methyl-1-benzene A mixture of benzyl-propan-1-indole, trans-cyclohexyl-branched-S, and the like. 11. The resin of claim 1, further comprising at least one of: a low shrinkage oligomer and a polymeric filler. 1 2 ·If the resin of the first item of the patent application scope is mentioned, the polymer filler is in the group consisting of: methyl propyl succinate A S gamma: base polymer, methacrylic acid η a butyl ester polymer, a mercapto acrylate, a η-butyl methacrylate copolymer, a polymer or copolymer of polystyrene or polybutadiene or a mixture thereof. The resin according to claim 1, wherein the oligomer is selected from the group consisting of polyamino carboxylic acid vinegar, polyether, polyester, propylene warm ester, and the like. a mixture. 14. A photopolymer resin comprising: from about 0.10 to about 1% by weight of a metal and a ceramic surface chelating agent; from about 10 to about 90% by weight of a fast hardening glass transition temperature (Tg) Controlling the monomer; 25 200846405 About 0.5 to about 15% by weight of the surface hardening initiator and at least one of about 0.5 to about 40% by weight of the low shrinkage oligomer and a polymeric filler. The resin according to claim 14, wherein the chelating agent is selected from the group consisting of amine acrylate, dimethylaminoethyl methacrylate, and polycaprolactone. Phosphate of 2-hydroxyethyl methacrylate, 2-ethyl ester of methacrylic acid, 2-mercaptopropenyl oxyacetate, 2-methylpropenyl oxyethyl amber Acid, 2-mercaptopropenyloxyethyl hexahydrophthalate, 2-propenyloxyethyl succinate, 2-aceticyloxyethyl phthalate, phosphoric acid. 2 - propyl Ionyl oxyethyl ester, 2-propenyl methoxyethyl phosphate diacrylate, 2-propenyl decyl hexahydrophthalate, γ-decyl propyl trimethoxy decane, γ·glycidol Oxypropyl tridecyloxydecane, fluorene-(β-aminoethyl)-γ-aminopropyltrimethoxy-decane, γ-mercaptopropoxypropyltrimethoxydecane, and the like mixture. 16. The resin of claim 14, wherein the monomer is selected from the group consisting of neopentyl diacrylate, isobornyl acrylate, and hydroxytrimethyl acetic acid. Dioxyacrylate, hydroxytrimethylacetic acid neopentyl glycol diacrylate, tricycloanthracene dimethanol diacrylate, cyclohexanedimethanol dimethacrylate, ethoxylated Α-type bisphenol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, 1,3 · butanediol dimethacrylate, tridecyloxypropane tri (meth) acrylate, three (2-hydroxyethyl)isocyanurate tripropylene 26 200846405 acid ester, ethoxylated trimethylolpropane triacrylate, ethylene oxide modified A-type bisphenol dimercapto acrylic acid Ester, third-butyl methacrylate, polyethylene glycol dipropionate, 3-methyl-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3 -propylene glycol diacrylate, 2-methyl-1,8-octanediol-diacrylate vinegar-1,9-nonanediol diacrylate, and the like 0 substance 17. The resin of claim 14, wherein the starter is selected from the group consisting of benzophenone, 2-hydroxy-2-indolyl-1-phenyl-propane a mixture of -1 - ketone, 1-hydroxy-cyclohexyl-phenol-ketone, benzophenone, and the like. The resin according to claim 14, wherein the filler is in a group selected from the group consisting of methyl methacrylate propylene-based polymers and η-butyl methacrylate. a polymer, a methacrylate, a η-butyl bottle copolymer of methacrylate, a polymer or copolymer of polystyrene or polybutadiene or a mixture thereof, and wherein the oligomer is selected from the following materials In the group: polycarbamic acid S, a mixture of polyether, polyester, acrylate, and the like. 27 200846405 9 The printed photopolymer resin layer is exposed to uv energy to emboss the tribute from the template. 20. The method of claim 19, wherein the deposition of a different spacer layer is not performed and the hardening of the different spacer layers is not performed. 28