1324171 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種吸墨塗層，更特別有關於一種紫 外光硬化型吸墨塗層及此吸墨塗層之組成物。 【先前技術】 喷墨紀錄方式是一種非接觸式的印刷過程，係以壓電 或加熱等方式將含有色料（顏料或染料）之墨水產生小墨 滴，再以高速由噴嘴喷射至吸墨塗層上。因其具有高速紀 錄、低噪音、低成本、及易於彩化等優點，近來已普及應 用於各種印表機上。 此種喷墨方式所需之吸墨塗層，包括於基材（如紙張、 金屬、木材、或塑膠板等等）上塗佈含矽石、碳酸鈣、氧化 鋁等填充劑之樹脂以組成多孔性吸墨塗層，可快速吸收大 量墨水。或是利用可溶解或膨潤之親水性高分子樹脂等基 材，作為可直接吸收墨水之吸墨塗層。 吸墨塗層需能快速吸收大量墨水，因此當帶有色料之 墨水喷印至基材表面時，可被吸墨塗層快速吸收並乾燥。 吸墨塗層吸收墨水後不會有墨點向外擴散、墨點之間不會 互滲而均勻、色塊界面鮮明且高光澤。此外，喷墨後還須 能長時間的保存，特別是在高濕度環境下喷墨圖案亦不會 發生變質。 關於具有吸墨塗層之紀錄片，大多於基材上塗佈一層 0954-A21612TWF(N2)；P54950011 TWihsuhuche 5 明 41711324171 IX. Description of the Invention: [Technical Field] The present invention relates to an ink absorbing coating, and more particularly to an ultraviolet light-curing ink absorbing coating and a composition of the ink absorbing coating. [Prior Art] The inkjet recording method is a non-contact printing process in which a small ink droplet is produced by a toner (pigment or dye) by piezoelectric or heating, and then ejected at a high speed from a nozzle to an ink absorbing ink. On the coating. Due to its high speed recording, low noise, low cost, and easy coloring, it has recently become popular in a variety of printers. The ink-receiving coating required for such an ink-jet method comprises coating a resin containing a filler such as vermiculite, calcium carbonate, alumina, etc. on a substrate (such as paper, metal, wood, or plastic plate, etc.). A porous ink-absorbing coating that quickly absorbs large amounts of ink. Alternatively, a base material such as a hydrophilic polymer resin which can be dissolved or swelled can be used as an ink absorbing coating which can directly absorb ink. The ink absorbing coating needs to be able to absorb a large amount of ink quickly, so that when the ink with the color material is printed onto the surface of the substrate, it can be quickly absorbed and dried by the ink absorbing coating. After the ink absorbing coating absorbs the ink, there is no ink dot diffusion, the ink dots are not mutually permeable and uniform, and the color patch interface is bright and high gloss. In addition, it must be stored for a long time after inkjetting, especially in high-humidity environments. For the documentary film with ink-absorbing coating, most of the substrate is coated with a layer of 0954-A21612TWF (N2); P54950011 TWihsuhuche 5 Ming 4171
- 或多層含親水性樹脂之組成物，如聚乙稀醇(poly vinyl alcohol，ργΑ)、聚乙稀皮略酮（poly vinyl pyrrolidone)、明 • 膠（Gelation)、纖維素（cellulose)、或上述之衍生物。上述含 • 親水性樹脂之組成物可添加二氧化矽、碳酸鈣、氧化鋁、 氧化鋅等無機填充劑’以形成多孔性吸墨塗層。但噴印使 用水性墨水時，吸墨塗層之親水性樹脂因高濕或遇水產生 膨潤甚至溶解的現象’從而使吸墨塗層吸附之染料滲出而 降低解析度。 噴墨專用墨水之染料以酸性染料或直接型染料為主， 為了使噴墨圖樣遇水時能固定於吸墨塗層内部，可添加陽 離子型染料固定劑於吸墨塗層内。固定劑一般為水溶性樹 月曰，當與染料接觸後形成非水溶性鹽類，使染料不因水而 备解。但此種吸墨塗層仍以親水性樹脂為主，因此噴黑 案仍缺乏防水性。 土回 為解決吸墨塗層防水性的問題，已研發多種技術。、， 國專利U. S. Pat. No 5,984,467在親水性高分子吸墨=屏杲 加入熱硬化架橋劑，使塗層内的高分子樹脂架橋形：：内 立體網狀結構。雖然此習知技藝具有較佳防水性，佝「度 塗層與基材_附著力不足，特料疏水性基材。:及， 高與基材間的附著力’需要複雜且多道的額外程序=提 一層底漆(Pdmer)作為底層。此外，硬化處理需要高=增加 時間烘烤使熱硬化架橋劑作用。 门地及長 為克服熱硬化之缺點，可利用紫外線硬化級成物 〇954-A2l6l2TWF(N2)；P5495001 1TW:hsuhuche 6 1324171 吸墨塗層’紫外線硬化組成物係經紫外線等輻射線照射產 生硬化父聯樹脂，並附著固定於基材表面，此種製程可塗 佈於非親水的基材表面，由於是直接照光硬化成臈不須繁 瑣的加熱烘烤製程’可節省能源並大幅縮短製程時間。 由於以親水性高分子樹脂配合熱架橋硬化的製程方式 並不適用於疏水性基材如可紀錄式光碟片（c〇mpact disk， CD)、可紀錄式多媒體光碟（Digital Versatile Disk，DVD)、 φ 或投影片（overhead projector film，OHP film)等基材，為了 使吸墨塗層能有效固定於疏水性基材上，必須使用輻射線 知、射硬化架橋樹脂。US5573831、US5599649、US5683855、 US5616447、US6437017、US6254958、WO0216518 等專利 使用光可硬化交聯樹脂作為吸墨塗層。第丨圖係習知技藝 中，一吸墨塗層12形成於基材13上經光硬化後之結果。 由於吸墨塗層12之填充劑為微米等級，粗糙的表面將使光 線Π無法均勻反射而呈霧面狀態。 _ 【發明内容】 為解決習知熱硬化吸墨塗層及霧面光硬化吸墨塗層等 問題，本發明提供一種紫外線硬化型吸墨塗層組成物，包 括奈米級無機填充劑，其平均粒徑小於4〇奈米；含乙烯不 飽合官能基之四級銨鹽；光起始劑；以及紫外光可硬化單 體、寡聚物 '樹脂、或上述之組合。 本發明更提供一種紫外線硬化型吸墨塗層，形成於基 材上，係由上述紫外線硬化型吸墨塗層組成物經紫外線硬 0954-A21612TWF(N2)：P54950011TW;hsuhuche 7 1324171 化而成。 【實施方式】 本發明之紫外線硬化型吸墨塗層組成物，主要包括· 奈米級無機填充劑，其平均粒徑小於40奈米；含乙稀不飽 合官能基之四級銨鹽；光起始劑；以及紫外光可硬化單體、 寡聚物、樹脂、或上述之組合。本發明較佳實施例中，紫 外光可硬化單體、寡聚物、樹脂、或上述之組合物，其具 有碳碳雙鍵、碳碳三鍵、碳氮雙鍵、或其他不飽和官能基， 如 SartomerSR344、丙烯酸(acrylic acid)、丙烯基_ι,4_氧氮 陸圜（acrylmorpholine)、羥基乙基丙烯酯（hydroxyethyl acrylate)或經基丙基丙烯酯（hydroxypropyl acrylate)。本發 明之吸墨塗層組合物需要光起始劑使紫外光可硬化單體、 寡聚物、樹脂、或上述之組合物聚合硬化。較佳實施例中， 光起始劑可為苯乙酮類、安息香類、二苯基酮類、噻吨酮 類、蒽醌類、或上述物質之組合，如2-羥基-2-甲基-1苯基 -卜丙基酮（2-hydroxy-2-methyl-l~phenyl-propan-l-one)、4-苯偶因-4-曱基二笨基硫化物、2-苯甲基-2二甲胺基-1-[4-(曱硫基）苯基]-2-嗎磷丙烷小酮、2,2 -二乙氧基-2-苯基 苯乙酮、2-曱基蒽醌' 2-乙基蒽醌、2-三級丁基蒽醌或2,4-二曱基噻吨酮。 為使喷墨硬化後之圖形具有防水性，本發明組成物更 包括陽離子性染料固定劑如含乙烯不飽合官能基之四級鍵 鹽’以防止染料受水時而溶解滲出造成喷墨圖案損傷。上 0954-A21612TWF(N2)：P549500l1TW；hsuhuche 8 1324171 . 述之四級銨鹽可為中日化學所售之QD-100、（曱基）丙稀酿 基氧乙基三甲基銨曱基硫酸鹽、或（甲基）丙烯醯基氧丙基 - 三曱基銨甲基硫酸鹽，由於其具有乙烯不飽合官能基，在 照光硬化後可與其他紫外光可硬化物交聯，使吸收之色料 更固定於塗層中。 填充劑會影響吸墨塗層的表面平整度、孔洞性，進而 影響塗層表面光澤度及吸墨性，透過篩選與實驗驗證，本 _ 發明選用奈米級無機填充劑，其平均粒徑小於40奈米，較 佳介於5至30奈米，硬化後之塗層具有光面、較佳吸墨性、 及防水性。本發明較佳實施例中，奈米級無機填充劑（平均 粒徑小於40奈米）可為炭黑、矽膠、矽酸鹽、沸石、高嶺 土、矽藻土、硫酸鋇、氧化鋁、氧化鋅、氫氧化鋁、碳酸 1弓、或上述之組合。如第2圖所示，由於本發明中，基板 13上之吸墨塗層22其奈米級無機填充劑之平均粒徑小於 40奈米，平勻的表面將使光線11均勻反射，將使製得之 • 喷墨圖案呈光面狀態。 在某些情況中，若不經適當的分散程序，奈米級無機 填充劑極易凝聚成較大的粒子，使吸墨塗層失去光面的效 果。因此較佳實施例中，可以分散劑搭配溼式研磨分散、 ' 滾輪式、或超音波振盪將奈米級無機填充劑均勻分散於吸 墨塗層組成物中，以避免奈米級無機填充劑凝聚。分散劑 可為AD Products所售之ADO 1、TG或BASF所售的 cermoplior®RH40、cermophor®RH60。奈米級無機填充劑 在分散後須具備良好之分散安定性，以避免在塗佈前又重 0954-A21612TWF(N2)：P54950011TW；hsuhuche 9 1324171 新嘁集，造成黏度過大而無法塗佈。此外，可視情況決定 疋否加入界面活性劑如BYK-333或BYK-344,以提高對疏 ' 水性基材表面的附著力。 ； 上述之紫外線硬化型吸墨塗層組合物，奈米級無機填 '•充劑較佳介於5_50重量份；含乙烯不飽合官能基之四級銨 鹽較佳介於1-30重量份；光起始劑較佳介於u重量份； 紫外光可硬化單體、寡聚物、樹脂、或上述之組合較佳介 _ 於30-90重量份。 本發明亦提供一種吸墨塗層，係由上述之紫外線硬化 型及墨塗層組合物經照光硬化而成。較佳實施例中，塗層 厚度一般介於5-250 μιη，其60度之反射率約大於50%， 較佳介於65-95%之間。由於本發明之吸墨塗層為疏水性， 因此可有效固定於疏水性基材上，如可紀錄式光碟片 (CD)、可紀錄式多媒體光碟(DvD)、或投影片（〇HPfilm)， 而不需額外的底漆，這將節省製程及材料成本。投影片的 馨材質一般可為聚乙稀（polyethylene，PE)、聚氯乙烯 (polyvinyl chloride，PVC)、聚乙烯對苯二甲酸酉旨 (polyethylene terephthalate，PET)、丙烯腈/丁二烯/丙烯酸 酯共聚物（acrylonitrile-butadiene-styrene，ABS)、聚碳酸醋 • (Polycarbonate ’ PC)、或其他合適之有機高分子或無機材 - 料。 為了讓本發明之上述和其他目的、特徵、和優點能更 明顯易懂，下文特舉數較佳·實施例，並配合所附圖示，作 詳細說明如下： 0954-A216i2TWF(W2);P54950011TW；hsuhuche 10 1324171 【較佳實施例】 實施例1:使用15nmDegussaAersoilMOXl7〇作為填充 劑 將紫外光可硬化物SartomerSR344 (5重量份）、丙稀 酸(acrylic acid ’ 40重量份）、及丙烯基-κ氧氮陸圜 (acrylmorpholine ’ 20重量份）；含乙烯不飽合官能基之四 級銨鹽（中日化學QD-100 ’ 15重量份）、乙醇（ethan〇1，2〇 重量份）’混合後用機械攪拌機攪拌15分鐘，加入imm研 磨锆珠’隨後再分批逐批加入奈米級無機填充劑（Degussa AersoilMOX 170 ’ 20重量份）’潤濕後研磨8小時，過濾 分離研磨珠後’加入光起始劑2-經基-2-曱基-1苯基_ι_丙 基酮（2-1^(11"〇\)^2-11^1:11>4-1-?1^11>4-1)1*〇卩&11-1-〇116，5份重） 和界面活性劑（BYK-333，1份重）。上述之混合物於室溫下 攪拌2小時，即得紫外線硬化型吸墨塗層組合物，為透明 外觀狀的樹脂。藉由旋轉塗佈法或篩網模板印刷方式將上 述吸墨塗層組成物塗佈於CD或DVD基材上，再經紫外線 照射硬化，即可製得膜厚約為20〜60 μιη之吸墨塗層。 實施例2:使用7 nm Cabot TS 610作為填充劑 實施例2配方組成、製備方法與實施例1相同，除了 以填充劑 Cabot TS 610 取代 Degussa Aersoil MOX 170 〇 實施例3:使用7nmDegussaAersoil30Q作為填充劑 〇954-A21612TWF(N2);P54950011TW；hsuhuche 1324171 實施例3配方組成、製備方法與實施例1皆相同，除 了以填充劑 Degussa Aersoil 300 取代 Degussa Aersoil MOX-170。 實施例4:使用15nmDegussaAersoiIMOX170作為填充 ^'劑，並使用分散劑- or a plurality of compositions containing a hydrophilic resin, such as polyvinyl alcohol (ργΑ), polyvinyl pyrrolidone, gelation, cellulose, or The above derivatives. The composition containing the hydrophilic resin may be added with an inorganic filler such as cerium oxide, calcium carbonate, aluminum oxide or zinc oxide to form a porous ink absorbing coating layer. However, when aqueous ink is used for printing, the hydrophilic resin of the ink-absorbing coating is swollen or even dissolved by high humidity or water, and the dye adsorbed by the ink-absorbing coating is oozing out to lower the resolution. The dye for the inkjet ink is mainly an acid dye or a direct dye. In order to fix the inkjet pattern inside the ink-absorbent coating when it is in contact with water, a cationic dye fixing agent may be added to the ink-absorbing coating. The fixative is generally a water-soluble tree, which forms a water-insoluble salt upon contact with the dye so that the dye is not prepared by water. However, such an ink-absorbing coating is still mainly a hydrophilic resin, so the blackout case still lacks water repellency. Soil Back In order to solve the problem of water repellency of ink absorbing coatings, various techniques have been developed. , U.S. Pat. No 5,984,467 in the hydrophilic polymer ink absorption = screen 杲 Adding a heat-hardening bridging agent to make the polymer resin bridge in the coating:: internal three-dimensional network structure. Although this prior art has better water repellency, the "degree of coating and substrate _ adhesion is insufficient, the special hydrophobic substrate.: and, the adhesion between the substrate and the substrate" requires complex and multi-channel extra Procedure = Add a primer (Pdmer) as the bottom layer. In addition, the hardening treatment requires high = increased time to bake the thermosetting bridging agent. Door and length to overcome the shortcomings of thermal hardening, UV-curable grades can be used 〇954 -A2l6l2TWF(N2);P5495001 1TW:hsuhuche 6 1324171 The ink-absorbing coating 'ultraviolet hardening composition is irradiated with ultraviolet rays and other radiation to produce a hardened parent resin, which is attached to the surface of the substrate. This process can be applied to non- Hydrophilic substrate surface, because it is directly photo-hardened into a crucible, does not require a tedious heating and baking process, which saves energy and greatly shortens the process time. The process of curing with hydrophilic polymer resin and thermal bridging is not suitable for hydrophobic Substrate such as recordable optical disc (CD), recordable multimedia disc (DVD), φ or slide (overhead projector film, OH For the substrate such as P film), in order to enable the ink-absorbing coating to be effectively fixed on the hydrophobic substrate, it is necessary to use radiation to cure and cure the bridging resin. US5573831, US5599649, US5683855, US5616447, US6437017, US6254958, WO0216518, etc. The photohardenable crosslinked resin is used as an ink absorbing coating. In the prior art, an ink absorbing coating 12 is formed on the substrate 13 by photohardening. Since the filler of the ink absorbing coating 12 is The micron-scale, rough surface will make the light ray unable to be uniformly reflected and be in a matte state. _ SUMMARY OF THE INVENTION In order to solve the problems of the conventional heat-hardening ink-absorbing coating and the matte-light hardening ink-absorbing coating, the present invention provides a The ultraviolet curable ink-absorbing coating composition comprises a nano-scale inorganic filler having an average particle diameter of less than 4 nanometers; a quaternary ammonium salt containing an ethylene unsaturated functional group; a photoinitiator; and ultraviolet light The hardening monomer, the oligomer 'resin, or a combination thereof. The present invention further provides an ultraviolet curing type ink absorbing coating formed on the substrate by the ultraviolet ray-curable ink absorbing coating composition. Hard 0954-A21612TWF (N2): P54950011TW; hsuhuche 7 1324171. [Embodiment] The ultraviolet curable ink-absorbing coating composition of the present invention mainly comprises a nano-scale inorganic filler having an average particle diameter of less than 40 Nano; a quaternary ammonium salt containing an ethylenically unsaturated functional group; a photoinitiator; and an ultraviolet light curable monomer, oligomer, resin, or a combination thereof. In a preferred embodiment of the invention, UV A photohardenable monomer, oligomer, resin, or combination thereof having a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, or other unsaturated functional group, such as Sartomer SR344, acrylic acid , propylene-based, acrylmorpholine, hydroxyethyl acrylate or hydroxypropyl acrylate. The ink receptive coating composition of the present invention requires a photoinitiator to cure the ultraviolet curable monomer, oligomer, resin, or a combination thereof. In a preferred embodiment, the photoinitiator may be acetophenone, benzoin, diphenyl ketone, thioxanthone, anthraquinone, or a combination thereof, such as 2-hydroxy-2-methyl. -1 hydroxy-2-methyl-l~phenyl-propan-l-one, 4-phenylene-4-pyridyl diphenyl sulfide, 2-benzyl-2 Dimethylamino-1-[4-(indolyl)phenyl]-2-phosphopropane ketone, 2,2-diethoxy-2-phenylacetophenone, 2-mercaptopurine '2-Ethyl hydrazine, 2-tris-butyl hydrazine or 2,4-dimercaptothioxanthone. In order to make the pattern after inkjet hardening water-repellent, the composition of the present invention further includes a cationic dye fixing agent such as a quaternary bonding salt containing an ethylene unsaturated functional group to prevent the dye from being dissolved and oozing when the dye is subjected to water to cause an ink jet pattern. damage. 0954-A21612TWF(N2): P549500l1TW; hsuhuche 8 1324171. The quaternary ammonium salt described above can be QD-100, (mercapto) propylene ethoxyethyl trimethyl ammonium sulfhydryl sulfate sold by Sino-Japanese Chemical Co., Ltd. Salt, or (meth) propylene decyl oxypropyl-trimethyl ammonium methyl sulfate, due to its ethylene unsaturated functional group, can be cross-linked with other ultraviolet light-curable materials after light hardening, so as to absorb The colorant is more fixed in the coating. The filler affects the surface flatness and porosity of the ink-absorbing coating, which in turn affects the surface gloss and ink absorption of the coating. Through screening and experimental verification, the invention uses a nano-scale inorganic filler with an average particle size smaller than 40 nm, preferably between 5 and 30 nm, the cured coating has a glossy finish, better ink absorption, and water repellency. In a preferred embodiment of the present invention, the nano-scale inorganic filler (having an average particle diameter of less than 40 nm) may be carbon black, tannin, silicate, zeolite, kaolin, diatomaceous earth, barium sulfate, aluminum oxide, zinc oxide. , aluminum hydroxide, carbonic acid 1 bow, or a combination thereof. As shown in Fig. 2, in the present invention, the ink-repellent coating layer 22 on the substrate 13 has an average particle diameter of the nano-sized inorganic filler of less than 40 nm, and the evenly-surfaced surface will uniformly reflect the light 11 and will cause Made • The inkjet pattern is glossy. In some cases, the nano-scale inorganic filler is easily condensed into larger particles without proper dispersing procedures, so that the ink-absorbing coating loses its smooth surface. Therefore, in a preferred embodiment, the dispersant may be uniformly dispersed in the ink-absorbing coating composition by wet-grinding dispersion, 'roller type, or ultrasonic wave oscillation to avoid the nano-scale inorganic filler. Condensed. The dispersant can be cermoplior® RH40 or cermophor® RH60 sold by ADO 1, TG or BASF sold by AD Products. Nano-grade inorganic fillers must have good dispersion stability after dispersion to avoid heavy weights before application. 0954-A21612TWF(N2): P54950011TW; hsuhuche 9 1324171 new enthalpy, resulting in too much viscosity to coat. In addition, it may be determined whether or not to add a surfactant such as BYK-333 or BYK-344 to improve the adhesion to the surface of the water-repellent substrate. The above ultraviolet curing type ink absorbing coating composition, the nano inorganic filling agent is preferably 5 to 50 parts by weight; the quaternary ammonium salt containing the ethylene unsaturated functional group is preferably 1 to 30 parts by weight; The photoinitiator is preferably present in an amount by weight by weight; the ultraviolet light curable monomer, oligomer, resin, or a combination thereof is preferably present in an amount of from 30 to 90 parts by weight. The present invention also provides an ink receptive coating which is obtained by photohardening of the above ultraviolet curing type and ink coating composition. In a preferred embodiment, the thickness of the coating is typically between 5 and 250 μm, and the reflectance at 60 degrees is greater than about 50%, preferably between 65 and 95%. Since the ink-receiving coating of the present invention is hydrophobic, it can be effectively fixed on a hydrophobic substrate such as a recordable compact disc (CD), a recordable multimedia disc (DvD), or a transparencies (〇HPfilm). This eliminates the need for additional primers, which saves on process and material costs. The fragrant material of the film can generally be polyethylene (PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile/butadiene/acrylic acid. Acrylonitrile-butadiene-styrene (ABS), polycarbonate (Polycarbonate 'PC), or other suitable organic polymer or inorganic material. The above and other objects, features, and advantages of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Hsuhuche 10 1324171 [Preferred Example] Example 1: Ultraviolet hardenable Sartomer SR344 (5 parts by weight), acrylic acid (40 parts by weight), and propylene-κ using 15 nm Degussa Aersoil MOXl7® as a filler. Oxygen nitrogen hydrazine (acrylicoline '20 parts by weight); quaternary ammonium salt containing ethylene unsaturated functional group (Zhongri Chemical QD-100 '15 parts by weight), ethanol (ethan 〇 1, 2 parts by weight) 'mixed After stirring for 15 minutes with a mechanical stirrer, adding imm-milled zirconium beads' followed by batchwise addition of nano-scale inorganic filler (Degussa Aersoil MOX 170 '20 parts by weight) in batches, followed by grinding for 8 hours, and separating the beads after filtration. Addition of photoinitiator 2-yl-2-mercapto-1phenyl-ι-propyl ketone (2-1^(11"〇\)^2-11^1:11>4-1-?1 ^11>4-1)1*〇卩&11-1-〇116, 5 parts by weight) and surfactant (BYK-333, 1 part) weight). The above mixture was stirred at room temperature for 2 hours to obtain an ultraviolet curable ink-receptive coating composition, which was a resin having a transparent appearance. The ink-absorbing coating composition is applied onto a CD or DVD substrate by spin coating or screen stencil printing, and then cured by ultraviolet irradiation to obtain a film thickness of about 20 to 60 μm. Ink coating. Example 2: Using 7 nm Cabot TS 610 as a filler Example 2 Formulation composition, preparation method is the same as in Example 1, except that Degussa Aersoil MOX 170 is replaced by filler Cabot TS 610. Example 3: Using 7 nm Degussa Aersoil 30Q as a filler 〇 954-A21612TWF(N2); P54950011TW; hsuhuche 1324171 The formulation of Example 3 was prepared in the same manner as in Example 1, except that Degussa Aersoil MOX-170 was replaced with the filler Degussa Aersoil 300. Example 4: Using 15 nm Degussa Aersoi IMOX 170 as a filling agent and using a dispersing agent
將紫外光可硬化物Sartomer SR344 (20重量份）、經基 乙基丙烯酯（hydroxyethyl acrylate，40重量份）、含乙烯不 飽合官能基之四級銨鹽（中日化學QD-100，25重量份）、分 散劑（Air Products所售之AD01，5重量份）、乙醇（ethanop 2 0重jc份）混合俊用機械授摔機擾摔15分鐘，加入1 πππ 研磨錯珠’再後逐批加入奈米級無機填充劑（Degussa Aersoil MOX 170 ’ 20重量份），經潤濕後研磨8小時，過 濾分離研磨珠後，加入光起始劑2-經基-2-甲基-1苯基-1- 丙基酮(2-hydroxy-2-methyl-l-plienyl-propan小one，5 份重) 和界面活性劑BYK-333 (1份重）於室溫下攪拌2個小時， 即可得紫外線硬化型吸墨塗層組成物，為透明外觀狀的樹 脂。藉由旋轉塗佈法或篩網模板印刷方式將上述吸墨塗層 組成物塗佈於CD或DVD基材上，再經紫外線照射硬化， 即可製得膜厚約為20 ~ 60 μιη之吸墨塗層。 對比例1:使用40nmDegussaAersoilOX50作為較大粒 徑之無機填充劑 0954-A21612TWF(N2);P54950011 TW;hsuhuche 1324171 . 對比例1配方組成、製備方法與實施例1相同’除了 以較大粒徑之填充劑Degussa Aersoil 0X50取代DeSussa - Aersoil ΜΟΧ 170。 墨水乾燥速度測試 以商用喷墨印表機（EPSON STYLUS R310)噴印2.5 cm x2.5 cm 之黃色（Yellow，Y)、紫色(Magenta，Μ)、青 色（Cyan，C)及黑色（Black，Κ)四原色色塊於上述之喷墨塗 馨層上，列印完成後以硫酸紙覆蓋列印色塊，並使用40g/cm2 缺碼負重，紀錄墨水乾燥的時間，如表一所示。 ◎:三十秒以内乾燥 三十秒至一分鐘乾燥 △: 一分鐘以上 防水性測試 以同樣印表機，列印相同四原色色塊於吸墨塗層上， 之後將色塊浸在20〜30 °C水中三分鐘，以自動影像分析系 統(QEAIAS-1000)量測浸水前後四原色色塊濃度，再由色 濃度儀軟體計算其四原色色差ΔΕ，如表一所示。 表面光澤度 以同樣印表機，列印相同四原色色塊於吸墨塗層上， 以光澤度計量測60度之入射光/反射光之反射率，如表一 所示。 表一 編號 實施例1 實施例2 實施例3 實施例4 對比例1 0954-A2l612TWF(N2)；P54950011TW;hsuhuche 1324171 表面光澤度 60° 92 74 78 67 5 墨水乾燥速度 ◎ ◎ △ ◎ △ 防水性 ΔΕ Y 2.2 1.9 0.3 2.2 0.7 Μ 6.2 1.6 1.2 1.9 2.0 C 2.3 2.5 1.2 2.8 1.2 Κ 19.3 9.5 18.3 1.9 10.4 - 如表一所示，對比例1之奈米級無機填充劑為40 nm 時，表面光澤度遠小於其他粒徑小於40 nm之實施例1 -4。 • 墨水乾燥度的表現上，大部份的實施例也優於對比例1。 色塊防水性相差不大，但使用分散劑的實施例4在黑色色 塊的防水性上具有特別優異的表現。綜上所述，光面的吸 墨塗層必需使用平均粒徑小於40 nm之奈米級無機填充 劑。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， Φ 在不脫離本發明之精神和範圍内，當可作任意之更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。 0954-A21612TWF(N2)；P54950011TW；hsuhuche 1324171 【圖式簡單說明】 第1圖係習知技藝之吸墨塗層示意圖； 第2圖係本發明較佳實施例之吸墨塗層示意圖。 【主要元件符號說明】 11〜光線； 12、22~吸墨塗層；Ultraviolet hardenable Sartomer SR344 (20 parts by weight), hydroxyethyl acrylate (40 parts by weight), quaternary ammonium salt containing ethylene unsaturated functional group (Zhongri Chemical QD-100, 25 (parts by weight), dispersant (AD01 sold by Air Products, 5 parts by weight), ethanol (ethanop 2 0 weight jc) mixed with mechanical mechanical weight loss machine for 15 minutes, adding 1 πππ grinding wrong beads 'and then Add nano-grade inorganic filler (Degussa Aersoil MOX 170 '20 parts by weight), grind and grind for 8 hours, filter and separate the beads, and add photoinitiator 2-yl-2-methyl-1benzene. 2-Hydroxy-2-methyl-l-plienyl-propanone (5 parts by weight) and surfactant BYK-333 (1 part by weight) were stirred at room temperature for 2 hours, ie A UV-curable ink-absorbing coating composition is obtained, which is a resin having a transparent appearance. The ink-absorbing coating composition is applied onto a CD or DVD substrate by spin coating or screen stencil printing, and then cured by ultraviolet irradiation to obtain a film thickness of about 20 to 60 μm. Ink coating. Comparative Example 1: 40 nm Degussa Aersoil OX50 was used as the inorganic filler of larger particle size 0954-A21612TWF (N2); P54950011 TW; hsuhuche 1324171. Comparative Example 1 Formulation, preparation method was the same as in Example 1 except for filling with a larger particle size Degussa Aersoil 0X50 replaces DeSussa - Aersoil ΜΟΧ 170. The ink drying speed test was printed with a commercial inkjet printer (EPSON STYLUS R310) of 2.5 cm x 2.5 cm yellow (Yellow, Y), purple (Magenta, Μ), cyan (Cyan, C) and black (Black, Κ) The four primary color blocks are on the above-mentioned inkjet coating layer. After the printing is completed, the printing color block is covered with sulfuric acid paper, and the weight of the ink is recorded by using 40 g/cm2 of the missing code, as shown in Table 1. ◎: Drying within 30 seconds to dry for 30 seconds to one minute △: Water resistance test for more than one minute. Print the same four primary color blocks on the ink absorbing coating with the same printer, and then immerse the color swatch in 20~ Three minutes in 30 °C water, the automatic image analysis system (QEAIAS-1000) was used to measure the concentration of the four primary color blocks before and after immersion, and then the four primary color difference ΔΕ was calculated by the color concentration meter software, as shown in Table 1. Surface Gloss With the same printer, the same four primary color blocks were printed on the ink-receiving coating, and the reflectance of incident light/reflected light of 60 degrees was measured by gloss, as shown in Table 1. Table 1 No. Example 1 Example 2 Example 3 Example 4 Comparative Example 1 0954-A2l612TWF (N2); P54950011TW; hsuhuche 1324171 Surface gloss 60° 92 74 78 67 5 Ink drying speed ◎ ◎ △ ◎ △ Water repellency ΔΕ Y 2.2 1.9 0.3 2.2 0.7 Μ 6.2 1.6 1.2 1.9 2.0 C 2.3 2.5 1.2 2.8 1.2 Κ 19.3 9.5 18.3 1.9 10.4 - As shown in Table 1, when the nano-scale inorganic filler of Comparative Example 1 is 40 nm, the surface gloss is far. Example 1-4 is smaller than other particle sizes less than 40 nm. • Most of the examples are superior to Comparative Example 1 in the performance of ink dryness. The water repellency of the color patches was not much different, but Example 4 using a dispersing agent exhibited particularly excellent water repellency in the black color block. In summary, the smooth ink-absorbing coating must use a nano-scale inorganic filler with an average particle size of less than 40 nm. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and the invention may be arbitrarily carried out without departing from the spirit and scope of the invention. The scope of protection of the present invention is defined by the scope of the appended claims. 0954-A21612TWF(N2); P54950011TW; hsuhuche 1324171 [Simplified Schematic] Fig. 1 is a schematic view of an ink absorbing coating of a conventional technique; Fig. 2 is a schematic view of an ink absorbing coating of a preferred embodiment of the present invention. [Main component symbol description] 11~ light; 12, 22~ ink-absorbing coating;
13〜基板。13 ~ substrate.
0954-A21612TWF(N2);P54950011TW；hsuhuche 150954-A21612TWF(N2); P54950011TW; hsuhuche 15