201009032 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種利用紫外線而硬化之紫外線硬化型塗 劑及塗佈有該紫外線硬化型塗劑之成形品。 ‘ 【先前技術】 、 先前，於貧訊處理等領域中，電性地記錄資訊且可進行 再生或記錄之資訊記錄媒體普及使用。作為此種資訊記錄 媒體，例如眾所周知有作為光資訊記錄媒體之光碟（CD， Compact Disc)或數位化多功能光碟（DVD，⑷[Technical Field] The present invention relates to an ultraviolet curable coating material which is cured by ultraviolet rays and a molded article coated with the ultraviolet curable coating material. ‘ 【Prior Art】 Previously, in the field of poor processing, information recording media that can record information electronically and can be reproduced or recorded are widely used. As such an information recording medium, for example, a compact disc (CD, Compact Disc) or a digital versatile disc (DVD) (4) is known as an optical information recording medium.
Versatile Disc)等對樹脂基材設置資訊記錄層而形成為資訊 記錄媒體者，或者軟性磁碟（FD，FlexiMe忉吐）、磁光 (MO，Magnet-Optical)碟、迷你磁碟（MD，Mini Disc)、卡 式磁帶等將資訊記錄部用g等之樹脂基材收納而形成為資 訊記錄媒體之形態者。 上述資訊記錄媒體具有資訊記錄性能，並且多將表示所 φ °己錄之内谷的索引或各種裝飾設計印刷於資訊記錄媒體之 表面等上。而且作為印刷，係藉由噴墨印刷或絲網印刷等 先前公知之印刷方法來實施。 另一方面，由於構成資訊記錄媒體之樹脂基材的表面不 具有油墨吸收性’因此係於樹脂基材之表面形成油墨接受 層，對該油墨接受層實施印刷。 並且，作為用以形成油墨接受層之塗劑係使用紫外線硬 化型塗齊J，業界不斷謀求使其具有優#之油墨吸收性（例 如參照文獻1 ·曰本專利特開2〇〇3_123323號公報、文獻 141843.doc 201009032 2 :曰本專利特開2003-257 10號公報、文獻3 :曰本專利特 開2006-97015號公報、文獻4 :日本專利特開2006-213844 號公報）。 於文獻1中，揭示有藉由在聚碳酸酯等透明合成樹脂之 基板上依序積層凹凸資訊（訊坑，pit)、記錄層、反射層、 保護層、印刷層、油墨吸收層而構成之光碟。 於文獻2中’揭示有如下放射線硬化型接受性油墨，其 包含液狀之水溶性單體、可溶解於該單體之聚合物及染料 固色劑’於此，所謂液狀之水溶性單體，係指常溫下可以 任意比率與水溶合之放射線聚合性單體，且可溶解於水溶 性單雜之聚合物之添加量係相對於每1〇〇重量份之液狀之 水溶性單體添加〇.5〜3〇重量份。 於文獻3中，揭示有如下活性能量線硬化型網印油墨組 合物，其包含：含有丙烯醯嗎啉與…乙烯基甲醯胺之混合 物之水溶性單體；含有羥丙基甲基纖維素之水溶性聚合 物；含有陽離子聚胺樹脂之染料固色劑；以及選自矽土、 石夕灰石及矽珠中之一種以上之填料。 於文獻4中，揭示有如下活性能量線硬化型網印油墨組 合物’其包含：具有經基之水溶性單官能單體；水溶性聚 合物；染料固色劑；以及矽土，其平均粒徑為6〜i8 且 最大粒杈為3〇 μπ1以下，於1〇〇份油墨組合物中係含有 10 〜25 份。 ’、 且說，作為油墨接受層之印刷適應性，要求優異之油墨 及收性’並且亦同時要求印刷圖像之乾燥性、渗透性及对 H1843.doc 201009032 水吐。但是’上述專利文獻1〜專利文獻4中所揭示之先前 之塗劑，在充分維持作為油墨接受層之印刷適應性而要求 的印刷圖像之乾燥性及滲透性’並且獲得在浸潰於水中之 嚴酶環境下亦優異之耐水性方面尚有進一步改善之餘地。 【發明内容】 本發明係考慮上述方面研究而成者，其目的在於提供一 種可充分維持作為油墨#受層t印刷適應性而要求的印刷 • 冑像之乾燥性及滲透性’並且獲得在嚴酷之環境下亦優異 之耐水性的紫外線硬化型塗劑及成形品。 本發明之紫外線硬化型塗劑之特徵在於：包含聚合反應 性低聚物、水溶性單體、光聚合起始劑及染料固色劑，且 作為上述染料固色劑，係包含選自烯丙胺聚合物、烯丙胺 鹽酸鹽聚合物、稀丙胺鹽酸鹽與二稀丙胺鹽酸鹽之共聚 物、稀丙胺鹽酸鹽與二曱基烯丙基胺鹽酸鹽之共聚物、二 氰二胺與二乙三胺之共聚物之鹽酸鹽、及二曱基胺與表氣 φ 醇之共聚物中的至少任一種之水溶液。 本發明中，於包含聚合反應性低聚物、水溶性單體、光 聚合起始劑及染料固色劑之紫外線硬化塑塗劑中，係使用 含有選自埽丙胺聚合物、烯丙胺鹽酸鹽聚合物、浠丙胺鹽 酸鹽與二烯丙胺鹽酸鹽之共聚物、烯丙胺鹽酸鹽與二甲基 烯丙基胺鹽酸鹽之共聚物、二氰二胺與二乙三胺之共聚物 之鹽酸鹽、及二甲基胺與表氣醇之共聚物中的至少任一種 之水溶液的染料固色劑。 藉此，可獲得印刷圖像之乾燥性及滲透性良好，尤其是 I4IS43.doc 201009032 耐水性優異之印㈣應性。因此，藉由使用本發明所記載 之紫外線硬化型塗劑，可充分維持作為油墨接受層之印刷 適應性而要求的印刷圖像之乾燥性及滲透性，並且可獲得 在浸潰於水中之嚴酷環境下亦優異之耐水性。 又’藉由包含上述之至少一種之水溶液作為染料固色 劑，可均勻地塗佈成膜。 本發明之紫外線硬化型塗劑較好的是含有〇5質量％以 上、8質量％以下之上述染料固色劑之構成。 於本發明中，若染料固色劑之含量少於〇5質量％，則耐 水性有可能會降低。另—方面，#染料固色劑之含量多於 8質量％，則耐水性達到飽和狀態，並且耐光性有可能會 降低。 據此，將染料固色劑之含量設為〇5質量％以上、8質量 %以下，較好的是〇.7質量％以上、6質量％以下較佳。 本發明之紫外線硬化型塗劑較好的是包含選自丙烯酸胺 基曱酸醋低聚物、環氧丙烯酸酯低聚物、聚酯低聚物、及 丙烯酸酯低聚物中之至少一種，作為上述聚合反應性低聚 物的構成。 於本發明中’係使用選自丙烯酸胺基甲酸酯低聚物、環 氧丙稀酸酯低聚物、聚酯低聚物、及丙稀酸酯低聚物中之 至少一種作為上述聚合反應性低聚物，因此藉由添加低聚 物’尤其是可提高耐水性’可容易地獲得作為用以提供優 異之印刷適應性之材料的聚合反應性低聚物。 本發明之紫外線硬化型塗劑較好的是包含50質量％以上 141843.doc 201009032 之丙烯酿嗎琳作為上述水溶性單體之構成。 於本發明中，係使用含有50質量％以上之丙烯醯嗎啉者 作為水溶性單體’因此藉由添加單體，尤其是可提高印刷 圖像之乾燥性及滲透性，使例如藉由製膜而形成之油墨接 受層獲得優異之印刷適應性。 於此，若丙烯醢嗎啉之含量少於5〇質量％，則有例如藉 由製膜而形成的油墨接受層之印刷適應性、尤其是印刷圖 像之乾燥性及滲透性降低之虞。據此，較好的是將丙烯醯 嗎啉之含量設為50質量％以上。 本發明之紫外線硬化型塗劑較好的是包含5質量％以 上、30質量％以下之上述聚合反應性低聚物之構成。 於本發明中’若聚合反應性低聚物之含量少於5質量 %，則有例如藉由製膜而形成之油墨接受層之印刷適應性 中、尤其是耐水性降低之虞。 另一方面，若聚合反應性低聚物之含量多於3〇質量0/〇， 則有例如藉由製膜而形成之油墨接受層之印刷適應性、尤 其是印刷圖像之乾燥性及滲透性降低之虞。 據此’將聚合反應性低聚物之含量設為5質量。/。以上、 30質量％以下，較好的是8質量％以上、25質量％以下較 佳。 本發明之紫外線硬化型塗劑較好的是包含40質量。/〇以 上、85質量％以下之上述水溶性單體之構成。 於本發明中，若水溶性單體之含量少於4〇質量％，則有 例如藉由製膜而形成之油墨接受層之印刷適應性中、尤其 141843.doc 201009032 是印刷圖像之乾燥性及滲透性降低之虞。 ^ 另一方面’若水溶性單體之含量多於85質量％，則有例 如藉由製膜而形成之油墨接受層之印刷適應性中、尤其是 印刷圖像之耐水性降低之虞。據此，將水溶性單體之含量 設為40質量。以上、85質量。/。以下，較好的是4〇質量。/〇以 上、7 5質量％以下較佳。 本發明之紫外線硬化型塗劑較好的是包含〗質量％以 上、10質量❶/〇以下之上述光聚合起始劑之構成。 於本發明中，若光聚合起始劑之含量少於1質量％，則 有硬化不充分之虞。另一方面，若光聚合起始劑之含量多 於10質量％，則有耐光性降低之虞。 據此’將光聚合起始劑之含量設為1質量％以上、1〇質 量〇/❶以下，較好的是2質量％以上、6質量％以下。 本發明之紫外線硬化型塗劑較好的是包含5質量。/〇以 上、50質量％以下之吸水性填料之構成。 於本發明中，藉由除聚合反應性低聚物、水溶性單體、 光聚合起始劑及染料固色劑以外，亦包含5質量％以上、 5〇質量％以下之吸水性填料，可使例如藉由製膜而形成之 油墨接受層獲得更優異之印刷適應性。 於此，若吸水性填料之含量少於5質量％，則有例如藉 由製膜而形成之油墨接受層之印刷適應性中、尤其是印刷 圖像之乾燥性及滲透性降低之虞。另一方面，若吸水性填 料之含量多於50質量％，則有塗劑增稠而無法獲得均勻之 製膜之虞。 141843.doc 201009032 設為5質量％以上、50質量0/〇 、40質量％以下較佳。 據此，將吸水性填料之含量 以下，較好的是10質量。Λ以上 本發明之成形品之特徵在於：係將上述本發明之紫外線 硬化型塗劑塗佈於基材表面。 於本發明中，係將可使例如藉由製膜*形成之油墨接受 層獲得優異之印刷適應性的紫外線硬化型塗劑塗佈於基材 表面。Versatile Disc), etc., which is formed as an information recording medium by setting an information recording layer on a resin substrate, or a flexible disk (FD, FlexiMe 忉), a magneto-optical (MO, Magnet-Optical) disk, a mini disk (MD, Mini) The information recording unit is stored in a resin substrate such as g to form an information recording medium. The information recording medium described above has information recording performance, and an index or a variety of decorative designs indicating the inner valley of the recorded medium are printed on the surface of the information recording medium or the like. Further, as printing, it is carried out by a conventionally known printing method such as inkjet printing or screen printing. On the other hand, since the surface of the resin substrate constituting the information recording medium does not have ink absorbability, an ink receiving layer is formed on the surface of the resin substrate, and the ink receiving layer is printed. In addition, as a coating agent for forming an ink receiving layer, an ultraviolet curing type coating is used, and the industry is constantly seeking to make it excellent in ink absorption (for example, refer to Document 1) Patent Publication No. 2〇〇3_123323 Document 141843. doc 201009032 2: Japanese Laid-Open Patent Publication No. 2003-25710, No. 3, Japanese Patent Application Laid-Open No. Hei. No. 2006-97015, No. Hei. No. 2006-213844. In Document 1, it is disclosed that a layer of concave and convex information (pit), a recording layer, a reflective layer, a protective layer, a printed layer, and an ink absorbing layer are sequentially laminated on a substrate of a transparent synthetic resin such as polycarbonate. CD. In Document 2, the following radiation-curable inks are disclosed, which comprise a liquid water-soluble monomer, a polymer soluble in the monomer, and a dye fixing agent. Here, the so-called liquid water-soluble single The body refers to a radiation polymerizable monomer which can be dissolved in water at any ratio at normal temperature, and the amount of the polymer which can be dissolved in the water-soluble mono-hybrid is relative to the liquid water-soluble monomer per 1 part by weight. Add 〇.5~3〇 parts by weight. In Document 3, there is disclosed an active energy ray-curable screen printing ink composition comprising: a water-soluble monomer comprising a mixture of acryloquinone morpholine and vinyl carbamide; containing hydroxypropyl methylcellulose a water-soluble polymer; a dye fixing agent containing a cationic polyamine resin; and a filler selected from the group consisting of alumina, sphagnum and beryllium. In Document 4, there is disclosed an active energy ray-curable screen printing ink composition comprising: a water-soluble monofunctional monomer having a warp group; a water-soluble polymer; a dye fixing agent; and alumina, an average particle thereof The diameter is 6 to i8 and the maximum particle size is 3 〇μπ1 or less, and is 10 to 25 parts in one ink composition. In addition, as the printing suitability of the ink receiving layer, excellent ink and retractability are required, and the dryness and permeability of the printed image and the water spouting of H1843.doc 201009032 are also required. However, the prior coating agents disclosed in the above Patent Documents 1 to 4 sufficiently maintain the dryness and permeability of the printed image required as the printing suitability of the ink receiving layer and are obtained by being immersed in water. There is still room for further improvement in water resistance in the environment of strict enzymes. SUMMARY OF THE INVENTION The present invention has been made in view of the above-described aspects, and an object of the present invention is to provide a printing and squeegee which is required to sufficiently maintain the printing adaptability of the ink layer. An ultraviolet curable coating agent and a molded article which are excellent in water resistance under the environment. The ultraviolet curable coating agent of the present invention is characterized by comprising a polymerizable reactive oligomer, a water-soluble monomer, a photopolymerization initiator, and a dye fixing agent, and as the dye fixing agent, which comprises an allylamine selected from the group consisting of allylamines Polymer, allylamine hydrochloride polymer, copolymer of dilute propylamine hydrochloride and dilute propylamine hydrochloride, copolymer of dilute propylamine hydrochloride and dimercaptopropylamine hydrochloride, dicyanoquinone An aqueous solution of a hydrochloride of a copolymer of an amine and diethylenetriamine, and a copolymer of at least one of a copolymer of a dinonylamine and an epigas φ alcohol. In the present invention, in the ultraviolet curable plastic coating agent containing a polymerizable reactive oligomer, a water-soluble monomer, a photopolymerization initiator, and a dye fixing agent, a polymer selected from the group consisting of a propylamine polymer and an allylamine hydrochloride is used. a salt polymer, a copolymer of propylamine hydrochloride and diallylamine hydrochloride, a copolymer of allylamine hydrochloride and dimethylallylamine hydrochloride, dicyandiamide and diethylenetriamine A dye fixing agent for an aqueous solution of a copolymer of a copolymer and at least one of a copolymer of dimethylamine and a gas of a gas. Thereby, the dryness and permeability of the printed image can be obtained, and in particular, I4IS43.doc 201009032 is excellent in water resistance (iv). Therefore, by using the ultraviolet curable coating agent of the present invention, the dryness and permeability of a printed image which is required as the printing suitability of the ink receiving layer can be sufficiently maintained, and the harshness of being immersed in water can be obtained. Excellent water resistance in the environment. Further, the film can be uniformly applied by using an aqueous solution containing at least one of the above as a dye fixing agent. The ultraviolet curable coating agent of the present invention preferably contains 5% by mass or more and 8% by mass or less of the above dye fixing agent. In the present invention, if the content of the dye fixing agent is less than 5% by mass, the water resistance may be lowered. On the other hand, when the content of the dye fixing agent is more than 8% by mass, the water resistance is saturated, and the light resistance may be lowered. Accordingly, the content of the dye fixing agent is preferably 5% by mass or more and 8% by mass or less, more preferably 7% by mass or more and 6% by mass or less. The ultraviolet curable coating agent of the present invention preferably comprises at least one selected from the group consisting of amino phthalic acid acrylate oligomers, epoxy acrylate oligomers, polyester oligomers, and acrylate oligomers. It is a structure of the said polymeric reactive oligomer. In the present invention, at least one selected from the group consisting of urethane acrylate oligomers, epoxy acrylate oligomers, polyester oligomers, and acrylate oligomers is used as the above polymerization. Since a reactive oligomer is used, a polymerizable reactive oligomer which is a material for providing excellent printing suitability can be easily obtained by adding an oligomer 'in particular, it can improve water resistance'. The ultraviolet curable coating agent of the present invention preferably comprises, as a water-soluble monomer, 50% by mass or more of 141843.doc 201009032. In the present invention, a propylene morphomorph containing 50% by mass or more is used as a water-soluble monomer. Therefore, by adding a monomer, in particular, the dryness and permeability of a printed image can be improved, for example, by The ink receiving layer formed by the film achieves excellent printing suitability. Here, when the content of the acrylose morpholine is less than 5% by mass, for example, the printing suitability of the ink receiving layer formed by film formation, in particular, the drying property and the permeability of the printed image are lowered. Accordingly, it is preferred to set the content of propylene morphomorph to 50% by mass or more. The ultraviolet curable coating agent of the present invention preferably contains 5% by mass or more and 30% by mass or less of the above polymerizable reactive oligomer. In the present invention, when the content of the polymerization-reactive oligomer is less than 5% by mass, for example, the printing suitability of the ink-receiving layer formed by film formation, in particular, the water resistance is lowered. On the other hand, if the content of the polymerizable reactive oligomer is more than 3 Å by mass / 〇, there is, for example, printing suitability of the ink receiving layer formed by film formation, especially drying and penetration of printed images. The reduction in sexuality. Accordingly, the content of the polymerization-reactive oligomer was set to 5 mass. /. The above is 30% by mass or less, preferably 8% by mass or more and 25% by mass or less. The ultraviolet curable coating agent of the present invention preferably contains 40 mass. The composition of the above water-soluble monomer of 85% by mass or less. In the present invention, if the content of the water-soluble monomer is less than 4,000% by mass, there is, for example, the printing suitability of the ink receiving layer formed by film formation, in particular, 141843.doc 201009032 is the dryness of the printed image and Reduced permeability. On the other hand, when the content of the water-soluble monomer is more than 85% by mass, for example, the printing suitability of the ink receiving layer formed by film formation, in particular, the water resistance of the printed image is lowered. Accordingly, the content of the water-soluble monomer was set to 40 mass. Above, 85 quality. /. Hereinafter, it is preferably 4 〇 mass. / 〇 or more, preferably 7.5 mass% or less. The ultraviolet curable coating agent of the present invention preferably comprises a composition of the above photopolymerization initiator in an amount of not more than 5% by mass or more. In the present invention, when the content of the photopolymerization initiator is less than 1% by mass, the curing is insufficient. On the other hand, when the content of the photopolymerization initiator is more than 10% by mass, the light resistance is lowered. In this case, the content of the photopolymerization initiator is 1% by mass or more and 1 〇 〇/❶ or less, preferably 2% by mass or more and 6% by mass or less. The ultraviolet curable coating agent of the present invention preferably contains 5 masses. / The composition of the water-absorbing filler of 50% by mass or less. In the present invention, in addition to the polymerization-reactive oligomer, the water-soluble monomer, the photopolymerization initiator, and the dye fixing agent, the water-absorbing filler of 5% by mass or more and 5% by mass or less is also contained. More excellent printability is obtained by, for example, an ink receiving layer formed by film formation. When the content of the water-absorptive filler is less than 5% by mass, for example, the printing suitability of the ink-receiving layer formed by film formation, in particular, the drying property and the permeability of the printed image are lowered. On the other hand, if the content of the water-absorbent filler is more than 50% by mass, the coating agent may be thickened to obtain a uniform film formation. 141843.doc 201009032 It is preferably 5 mass% or more, 50 masses 0/〇, and 40 mass% or less. Accordingly, the content of the water-absorbent filler is preferably 10 or less. The molded article of the present invention is characterized in that the ultraviolet curable coating agent of the present invention is applied onto the surface of a substrate. In the present invention, an ultraviolet curable coating agent which can obtain excellent printing suitability by, for example, an ink receiving layer formed by film formation* can be applied to the surface of a substrate.
對㈣Μ具有油墨吸收性之基材或油墨吸收性 較低之基材等，亦可施以良好之印刷。 【實施方式】 以下詳述用以實施本發明之最佳形態。 再者，於本實施形態中，作為本發明中之成形品，例如 係例示 CD-R(C〇mpact Disc_Rec〇rdaMe，可燒錄光碟）' DVD-R(Digital Versatile以“如⑽咖，可燒錄一次式 數位化多功能光碟）等一面具有資訊記錄面、另一面具有 標記面的圓盤狀之資訊記錄媒體，但並不限定於此。例如 可以下述各種基材作.為對象：軟性磁碟（FD，Flexibie Disk)、磁光（MO，Magnet-Optical)碟、迷你磁碟（MD， Mini Disc)、卡式磁帶等收容資訊記錄部之匣；各種資訊 記錄媒體所使用之印刷用標記紙等印刷用紙；進而合成樹 脂成形品、玻璃、木材、鋼板、皮革品、織布或不織布 等。 [成形品之構成] 圖1係表示本實施形態中之資訊記錄媒體之概略構成的 141843.doc •9- 201009032 剖面圖。 作為圖1之成形品之資訊記錄媒體1例如為CD_R4 dvd R等圖盤狀之記錄媒體，於其一面設置有記錄資訊之未圖 示之資訊記錄面，另一面設置有可進行印刷之標記面。 該資訊記錄媒體1係於圓盤狀之碟片即基材3之表面具備 藉由紫外線照射而硬化之油墨接受層2而構成。再者，資 訊記錄媒體1之記錄資訊之層（資訊記錄層）係包含於圖 基材3之層構成中。而且，作為基材3,可例示通常用於資 訊圮錄媒體1的由以聚碳酸酯樹脂所形成之圓盤狀之碟片 基板所構成者。 另外，油墨接受層2係藉由各種方法將下文中詳述之紫 外線硬化型塗劑塗佈於基材3之表面，形成為例如水性之 被膜狀。作為塗膜方法，可適當採用棒塗、刮刀式塗佈、 刀塗、模塗、旋塗、絲網印刷、凹板印刷、軟板印刷、移 印、喷墨印刷等先前公知之塗佈或印刷方法。再者，尤其 疋棒塗、旋塗、絲網印刷之方法係作為資訊記錄媒體之塗 膜方法而普遍使用者’因而較好。又，對於塗膜之硬化， 考慮到照射裝置之構成、塗膜步驟中之作業性或裝置構成 等方面，以及作業性容易且可利用通用之簡單構成之方 面，係使用紫外線。 (紫外線硬化型塗劑之組成） 於本實施形態中，構成油墨接受層2之紫外線硬化型塗 劑包含聚合反應性低聚物、水溶性單體、光聚合起始劑、 染料固色劑及吸水性填料。 141843.doc •10- 201009032 ' 2者，可於不妨礙本發明之效果之範圍内，根據需要而 適田調配消/包劑、分散劑、保濕劑、增稠劑、脫模劑、防 腐劑、著色顏料、濕潤劑、螢光塗料及紫外線吸收劑等添 加劑。又，紫外線硬化型塗劑亦可不含吸水性填料。 對於聚合反應性低聚物，例如只要為末端具有反應性雙 鍵之低聚物，且為可溶解於水溶性單體中之聚合反應性低 聚物則無特別限制。 • 此外，作為聚合反應性低聚物，尤其是就提高耐水性之 方面而言，較好的是選自丙烯酸胺基甲酸酯低聚物、環氧 丙稀酸醋低聚物、聚醋低聚物'及丙稀酸醋低聚物中之至 少-種者。此外’例如可使用「光硬化技術資料冊材料 篇」（TECHNONET公司發行（2_年12月5日發行））之第84 頁〜第118頁所記載的水溶性之低聚物。 水溶性單體例如可使用常溫下可以任意比率與水溶解之 各種單體。 • 具體而言可例示：丙稀醯嗎琳、丁二醇單丙烯酸S旨、丙 烯酸2-羥基乙酯、丙烯酸'^^二甲胺乙酯、N，N_二甲基丙 稀醯胺及2-經乙基乙稀醚等。此外，例如可使用「光硬化 技術資料冊材料篇」（TECHN0NET公司發行（2〇〇〇年以月 5曰發行））之第6頁〜第81頁所記載之水溶性單體。尤其是 以丙烯醯嗎料為线之系統巾印刷適應性優異，故較 好。 作為該水溶性單體，尤其是就乾燥性及滲透性方面而 言，較好的是使用含有50質量％以上之丙_嗎你者。 141843.doc 11 201009032 於此’若丙烯醯嗎啉之含量少 士制“〜 ”於50質ι%，則有例如藉 由製膜而形成之油墨接受層2之印刷適應性、尤其 圖像之乾㈣及滲透性降低之虞。據此，較好的是將丙歸 醯嗎啉之含量設為50質量％以上。 再者，水溶性單體中亦可以5()質量％以下之比例而含有 其他可共聚之水溶性單體。進而，亦可於不妨礙本發明之 效果之範圍内，以相對於水溶性單體為3〇質量％以下之比 例而含有非水溶性單體。 吸水性填料可使用無機填料、有機填料中之任一種。 作為無機填料，例如可列舉：矽土、滑石、碳酸鈣、硫 酸鋇、沸石等。又，作為有機填料，例如可列舉：天然有 機物細粉末（膠原蛋白、蠢絲（silk)、纖維素、澱粉、;^'殼 素、殼聚糖、殼膜等）、吸水性樹脂粉末（例如吸水性丙烯 酸系樹脂、吸水性聚酯樹脂等之粉末）等。該等無機填料 及有機填料可單獨使用1種，亦可將2種以上組合使用。 作為光聚合起始劑，可使用藉由利用紫外線而產生之自 由基’而與水溶性單體或聚合反應性胺基甲酸酯低聚物中 之雙鍵反應’從而引起聚合反應的各種聚合起始劑。 具體而言，可例示：作為羥基酮之2_羥基_2_甲基-丨·笨 基丙烧·1·酮、安息香乙醚、羥基環己基苯基曱酮，作為 胺酮之2-曱基-i_[4-(甲硫基）苯基]_2_嗎啉基丙烷-1-酮等。 此外’例如可使用「光硬化技術資料冊材料篇」 (TECHNONET公司發行（2000年12月5日發行））之第122頁〜 第133頁所記載之光聚合起始劑。尤其是就乾燥性方面而 141843.doc 12 201009032 言，較好的是使用2_經基甲基小苯基丙烷+酮、安息 香乙醚。又，光聚合起始劑亦可將上述各種光聚合起始劑 之2種以上組合使用。 作為染料固色劑，係使用含有選自烯丙胺聚合物、烯丙 胺鹽酸鹽聚合物、稀丙胺鹽酸鹽與二烤丙胺鹽酸鹽之共聚 物、烯丙胺鹽酸鹽與二曱基烯丙基胺鹽酸鹽之共聚物、二 氰二胺與二乙三胺之共聚物之鹽酸鹽、及二甲基胺與表氣 φ 醇之共聚物中的至少一種之水溶液的染料固色劑。再者， 作為染料固色劑，可使用將上述水溶液直接調配而成者’ 但並不限定於此，亦可使用將吸水性填料以高濃度混合於 上述水溶液中而形成為糊狀者。 [實施形態之作用效果] 如上所述，本實施形態之紫外線硬化型塗劑係包含聚合 反應性低聚物、水溶性單體、光聚合起始劑及染料固色 劑，因此作為添加低聚物之特徵之耐水性、與作為添加單 鲁 體之特徵之乾燥性及滲透性的平衡性良好，例如於基材3 之表面塗佈形成之油墨接受層2具有優異之油墨吸收性， 並且印刷圖像之乾燥性、印刷圖像之滲透性、对水性亦良 好，可獲得優異之印刷適應性。進而，根據本實施形態， 與藉由熱而硬化之情形相比，不會對塗佈之基材3賦予多 餘之能量，因此可防止例如由於熱變形等而引起之損傷等 基材3之劣化》因此’對於不可進行加熱等之塗佈對象亦 可適用，可提高通用性。 又’於本實施形態中’作為染料固色劑，係使用含有選 141843.doc •13- 201009032 自烯丙胺眾合物、烯丙胺鹽酸鹽聚合物、烯丙胺鹽酸鹽與 一烯丙胺鹽酸鹽之共聚物、烯丙胺鹽酸鹽與二甲基烯丙基 胺鹽酸鹽之共聚物、二氰二胺與二乙三胺之共聚物之鹽酸 鹽、及二甲基胺與表氯醇之共聚物中的至少任一種之水溶 液的染料m色劑’因此可獲得印刷圖像之乾燥性、印刷圖 像之滲透性良#，且在浸潰於水中之嚴酷環&下耐水性亦 優異之印刷適應性。 進而’於本實施形態中，較好的是包含〇5質量。以上、 8質量％以下之染料固色劑。因此，可充分維持耐水性與 耐光性兩者’使例如藉由製膜而形成之油墨接受層2獲得 優異之印刷適應性。 另外，於本實施形態中，作為聚合反應性低聚物，可較 好地使用選自丙烯酸胺基甲酸酯低聚物、環氧丙烯酸酯低 聚物、聚醋低聚物、丙稀酸醋低聚物中之至少1種。 因此，藉由添加低聚物，尤其可提高耐水性，可使例如 藉由製膜而形成之油墨接受層2獲得優異之印刷適應性。 又’於本實施形態中’作為水溶性單體，可較好地使用 含有50質量％以上之丙烯醯嗎啉者。 因此，藉由添加單體’尤其可提高乾燥性及滲透性，可 使例如藉由製膜而形成之油墨接受層2獲得優異之印刷適 應性。 進而，於本實施形態中，較好的是包含5質量。/。以上、 30質量。/。以下之聚合反應性低聚物，4〇質量％以上' 85質 量％以下之水溶性單體’ 1質量％以上、1 〇質量。/。以下之光 141843.doc •14 201009032 聚合起始劑。 因此’作為添加低聚物之拉外_ — &, 之特徵之耐水.!生、與料添加單 體之特徵之乾燥性及滲透性的平衡性良好，可使例如藉由 製膜而形成之油墨接受層2獲得優異之印刷適應性。 又，於本實施形態中，較好的是除聚合反應性低聚物、 水溶性單體及光聚合起始劑以外，亦包…質量⑽^ 50質量％以下之吸水性填料。 因此，可獲得因添加填料而帶來之尤其是乾燥性及財水 性之提高’可使例如藉由製膜而形成之油墨接受層2獲得 更優異之印刷適應性。 [實施形態之變形例] 再者以上所說a月之態樣係表示本發明之一態樣者，本 發明並不限定於上述實施形態，勿庸置疑，於可達成本發 明之目的及效果之範圍内之變形或改良係包含於本發明之 内谷中X ’於可達成本發明之目的及效果之範圍内，實 施本發明時之具體之結構及形狀等亦可為其他結構或形狀 等。 亦即’於本實施形態中’作為基材3係例示由材質為聚 碳酸醋樹脂之圓盤狀基板所構成之例，但並不限定於此， 例如基材3亦可為收納DVD_RAM(DVD Rand〇m AccessFor (4) substrates having ink absorbability or substrates having low ink absorbability, good printing can be applied. [Embodiment] The best mode for carrying out the invention will be described in detail below. In the present embodiment, the molded article of the present invention is, for example, a CD-R (C〇mpact Disc_Rec〇rdaMe, recordable disc) DVD-R (Digital Versatile is "(10) coffee, A disk-shaped information recording medium having a information recording surface and a marking surface on the other surface, such as a one-time digital versatile disc, is not limited thereto. For example, the following various substrates can be used: Soft disk (FD, Flexibie Disk), magneto-optical (MO, Magnet-Optical) disc, mini-disc (MD, Mini Disc), cassette tape, etc., which are used for information recording and recording; printing of various information recording media Printing paper such as a label paper; synthetic resin molded article, glass, wood, steel plate, leather product, woven fabric, non-woven fabric, etc. [Configuration of molded article] Fig. 1 shows a schematic configuration of the information recording medium in the present embodiment. 141843.doc •9- 201009032. The information recording medium 1 as a molded article of Fig. 1 is, for example, a disk-shaped recording medium such as CD_R4 dvd R, and an information recording surface (not shown) on which information is recorded is provided. The other surface is provided with a mark surface that can be printed. The information recording medium 1 is formed on the surface of the substrate 3 which is a disk-shaped disk, and is provided with an ink receiving layer 2 which is cured by ultraviolet irradiation. The layer (information recording layer) of the recording information of the medium 1 is included in the layer structure of the drawing substrate 3. Further, as the substrate 3, a polycarbonate resin is generally used for the information recording medium 1. Further, the ink receiving layer 2 is applied to the surface of the substrate 3 by various methods by various methods, and is formed into, for example, an aqueous film. As the coating method, previously known coatings such as bar coating, blade coating, knife coating, die coating, spin coating, screen printing, gravure printing, flexographic printing, pad printing, ink jet printing, and the like can be suitably employed. Or a printing method. Further, in particular, the method of bar coating, spin coating, and screen printing is generally used as a coating method for an information recording medium. Therefore, for the hardening of the coating film, the irradiation device is considered. Composition, Ultraviolet rays are used in terms of workability, device configuration, and workability in the film step, and workability is easy, and a general configuration can be used. (Composition of ultraviolet curable paint) In the present embodiment, the ink receiving layer 2 is constituted. The ultraviolet curable coating agent comprises a polymerizable reactive oligomer, a water-soluble monomer, a photopolymerization initiator, a dye fixing agent, and a water-absorbent filler. 141843.doc •10- 201009032 ' 2, can not interfere with this Within the scope of the effects of the invention, an additive such as a decontaminating agent, a dispersing agent, a moisturizing agent, a thickening agent, a releasing agent, a preservative, a coloring pigment, a wetting agent, a fluorescent coating, and an ultraviolet absorber may be formulated as needed. . Further, the ultraviolet curable coating agent may also contain no water-absorbent filler. The polymerization-reactive oligomer is not particularly limited as long as it is an oligomer having a reactive double bond at the terminal and is a polymerizable reactive oligomer which is soluble in a water-soluble monomer. • In addition, as the polymerization-reactive oligomer, in particular, in terms of improving water resistance, it is preferably selected from the group consisting of urethane acrylate oligomers, propylene acrylate oligopolymers, and polyester vinegar. At least one of the oligomer' and the acetoacetate oligomer. Further, for example, a water-soluble oligomer described in pages 84 to 118 of the "Photohardening Technology Information Booklet" (published by TECHNONET Co., Ltd. (issued on December 5, 2)) can be used. As the water-soluble monomer, for example, various monomers which can be dissolved in water at an arbitrary ratio in an ordinary temperature can be used. • Specifically, it can be exemplified by acrylonitrile, butanediol monoacrylic acid, 2-hydroxyethyl acrylate, acrylic acid dimethylamine ethyl ester, N,N-dimethyl propyl amide and 2-Ethyl ethyl ether and the like. Further, for example, a water-soluble monomer described on pages 6 to 81 of the "Photohardening Technology Information Book Material" (published by TECHN0NET Co., Ltd. (issued 5 years later)) can be used. In particular, it is preferable that the system towel which is made of acrylonitrile is excellent in printing compatibility. As the water-soluble monomer, in particular, in terms of drying property and permeability, it is preferred to use a content of 50% by mass or more. 141843.doc 11 201009032 Here, if the content of acryloline morpholine is less than 50% by weight, there is a printing suitability of the ink receiving layer 2 formed by, for example, film formation, especially an image. Dry (four) and the reduction of permeability. Accordingly, it is preferred to set the content of the ruthenium morpholine to 50% by mass or more. Further, the water-soluble monomer may contain other copolymerizable water-soluble monomers in a ratio of 5 (% by mass or less). Further, a water-insoluble monomer may be contained in a ratio of not less than 3% by mass based on the water-soluble monomer, within a range that does not impair the effects of the present invention. As the water-absorbing filler, any of an inorganic filler and an organic filler can be used. Examples of the inorganic filler include alumina, talc, calcium carbonate, barium sulfate, zeolite, and the like. In addition, examples of the organic filler include natural organic fine powder (collagen, silk, cellulose, starch, chitin, chitosan, shell film, etc.), and water-absorbent resin powder (for example). A powder such as a water-absorbent acrylic resin or a water-absorbent polyester resin). These inorganic fillers and organic fillers may be used alone or in combination of two or more. As the photopolymerization initiator, various polymerizations which cause a polymerization reaction by reacting with a double bond in a water-soluble monomer or a polymerizable reactive urethane oligomer by using a radical generated by ultraviolet rays can be used. Starting agent. Specifically, it can be exemplified as 2-hydroxyl-2-methyl-hydrazino-phenylidene-1-ketone, benzoin ethyl ether, hydroxycyclohexylphenyl fluorenone as a hydroxyketone, and 2-mercapto group as an amine ketone. -i_[4-(methylthio)phenyl]_2_morpholinylpropan-1-one or the like. In addition, for example, a photopolymerization initiator described in pages 122 to 133 of the "Photohardening Technology Information Book Material" (published by TECHNONET Co., Ltd. (issued on December 5, 2000)) can be used. In particular, in terms of drying properties, 141843.doc 12 201009032 It is preferred to use 2- mercaptomethyl small phenylpropane + ketone and benzoin ethyl ether. Further, the photopolymerization initiator may be used in combination of two or more kinds of the above various photopolymerization initiators. As a dye fixing agent, a copolymer containing an allylamine polymer, an allylamine hydrochloride polymer, a mild propylamine hydrochloride and a di-alanine hydrochloride, an allylamine hydrochloride and a didecylene is used. Dye fixing of an aqueous solution of a copolymer of propylamine hydrochloride, a hydrochloride of a copolymer of dicyandiamide and diethylenetriamine, and a copolymer of at least one of a copolymer of dimethylamine and epoxide Agent. In addition, as the dye fixing agent, those obtained by directly mixing the above aqueous solution can be used. However, the present invention is not limited thereto, and a water-absorbent filler may be mixed in the aqueous solution at a high concentration to form a paste. [Effects of the Embodiments] As described above, the ultraviolet curable coating agent of the present embodiment contains a polymerization-reactive oligomer, a water-soluble monomer, a photopolymerization initiator, and a dye fixing agent, and thus is added as an oligomerization. The water resistance characteristic of the article is good in balance with the dryness and permeability of the feature as the added single-rubber. For example, the ink-receiving layer 2 formed by coating the surface of the substrate 3 has excellent ink absorbability, and is printed. The dryness of the image, the permeability of the printed image, and the water resistance are also good, and excellent printing suitability can be obtained. Further, according to the present embodiment, since the excess energy is not applied to the applied substrate 3 as compared with the case where it is cured by heat, deterioration of the substrate 3 such as damage due to thermal deformation or the like can be prevented. Therefore, it is also applicable to a coating object that cannot be heated, and the versatility can be improved. Further, in the present embodiment, as a dye fixing agent, it is used to contain 141843.doc •13-201009032 from allylamine complex, allylamine hydrochloride polymer, allylamine hydrochloride and monoallylamine salt. Copolymer of acid salt, copolymer of allylamine hydrochloride and dimethylallylamine hydrochloride, hydrochloride of copolymer of dicyandiamide and diethylenetriamine, and dimethylamine and The dye m toner of the aqueous solution of at least one of the copolymers of chlorohydrin can thus obtain the dryness of the printed image, the permeability of the printed image, and the water resistance under the harsh ring & Excellent printability. Further, in the present embodiment, it is preferable to contain 〇5 mass. Above, 8 mass% or less of the dye fixing agent. Therefore, both the water resistance and the light resistance can be sufficiently maintained. For example, the ink receiving layer 2 formed by film formation is excellent in printability. Further, in the present embodiment, as the polymerization-reactive oligomer, a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, or an acrylic acid can be preferably used. At least one of vinegar oligomers. Therefore, by adding an oligomer, in particular, water resistance can be improved, and excellent printing suitability can be obtained, for example, by the ink receiving layer 2 formed by film formation. Further, in the present embodiment, as the water-soluble monomer, those containing 50% by mass or more of acryloquinone morpholine can be preferably used. Therefore, the drying property and the permeability can be particularly improved by adding the monomer ', and the ink receiving layer 2 formed by, for example, film formation can obtain excellent printing suitability. Further, in the present embodiment, it is preferable to contain 5 masses. /. Above, 30 quality. /. The following polymerization-reactive oligomers have a water-soluble monomer of 1% by mass or more and 875% by mass or less by 1% by mass or more and 1% by mass. /. The following light 141843.doc •14 201009032 Polymerization initiator. Therefore, 'the characteristics of the water-repellent and the added monomer of the additive are good as the addition of the oligomer, and the balance between the dryness and the permeability of the monomer to be added is good, and can be formed, for example, by film formation. The ink receiving layer 2 achieves excellent printability. Further, in the present embodiment, it is preferred to contain, in addition to the polymerization reactive oligomer, the water-soluble monomer, and the photopolymerization initiator, a water-absorbent filler having a mass (10) of 50% by mass or less. Therefore, it is possible to obtain an improvement in drying property and water-saving property by the addition of the filler. The ink-receiving layer 2 formed by, for example, film formation can obtain more excellent printability. [Modification of the embodiment] The above-mentioned aspect of the a month indicates one aspect of the present invention, and the present invention is not limited to the above embodiment, and it is needless to say that the object and effect of the invention can be achieved. The modifications and improvements within the scope of the present invention are included in the inner valley of the present invention. The specific structure and shape of the present invention may be other structures or shapes. In the present embodiment, the substrate 3 is exemplified by a disk-shaped substrate made of a polycarbonate resin. However, the substrate 3 is not limited thereto. For example, the substrate 3 may be a DVD-RAM (DVD). Rand〇m Access
Memory，數位化多功能光碟隨機存取記憶體卜卡式磁 帶、MO等資訊記錄媒體等形狀，於成為減之基材 3之表面形成油墨接受層2即可。此外，如上所述，可將資 訊-己錄媒體所使用之印刷用標記紙等印刷用紙，合成樹脂 141843.doc •15- 201009032 成形品、玻璃、木材、鋼板、皮革品、織布或不織布等各 種基材作為對象。 又’對於紫外線硬化型塗劑两言，作為紫外線硬化型塗 劑之形態’例如可應用包含聚合反應性低聚物、水溶性單 體及光聚合起始劑之單液型者，以及於塗佈形成油墨接受 層2時再將光聚合起始劑混合而使用之多液型者等之任一 種構成。 又’於本實施形態中係使用包含聚合反應性低聚物、水 溶性單體、光聚合起始劑、染料固色劑及吸收性填料之紫 外線硬化型塗劑，但並不限定於此，例如亦可根據需要而 適當調配消泡劑、分散劑、保濕劑、增稠劑、脫模劑、防 腐劑、著色顏料、濕潤劑、螢光塗料及紫外線吸收劑等之 添加劑。 [實施例] 以下，列舉實施例及比較例來進一步詳細說明本發明， 但本發明不受該等實施例等之記載内容之任何制約。 (試樣之製作） 以下述表1及表2中所示之調配比例來計量特定量之原 料，用混合機（THINKY股份有限公司製造商品名：A_ 250)加以混合。再者，表1及表2中所示之「水」係為了將 染料固著劑製成水溶液而使用者。 141843.doc 16 201009032The memory, the digital versatile optical disk random access memory, the magnetic tape, the MO, and the like are recorded in a shape such as an information recording medium, and the ink receiving layer 2 can be formed on the surface of the substrate 3 to be reduced. Further, as described above, it is possible to use a printing paper such as a printing paper for printing on a medium-recorded medium, synthetic resin 141843.doc •15-201009032 A molded article, glass, wood, steel, leather, woven or non-woven fabric, etc. Various substrates are targeted. In addition, as for the ultraviolet curable coating agent, as a form of the ultraviolet curable coating agent, for example, a single liquid type containing a polymerizable reactive oligomer, a water-soluble monomer, and a photopolymerization initiator can be used, and When the cloth is formed into the ink receiving layer 2, the photopolymerization initiator is mixed and used in any of the liquid type. Further, in the present embodiment, an ultraviolet curable coating agent containing a polymerization reactive oligomer, a water-soluble monomer, a photopolymerization initiator, a dye fixing agent, and an absorbing filler is used, but the invention is not limited thereto. For example, an antifoaming agent, a dispersing agent, a moisturizing agent, a thickener, a releasing agent, a preservative, a coloring pigment, a wetting agent, a fluorescent coating, and an ultraviolet absorber may be appropriately added as needed. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the description of the examples and the like. (Preparation of sample) A specific amount of the raw material was measured by the mixing ratio shown in the following Tables 1 and 2, and mixed by a mixer (trade name: A_250, manufactured by THINKY Co., Ltd.). Further, the "water" shown in Tables 1 and 2 is intended to be used as an aqueous solution for the dye fixing agent. 141843.doc 16 201009032
【1<】 實施 例-13 Ό CN 00 s - 寸 < < C0 實施 例-12 >n 'sO ο (N CM (S 00 cs CQ CQ < 實施 例-11 W~J CN 00 Ό n 对 < < < 實施 例-10 V) cs '«Ο ir> V) CN *n CN o 寸 CQ < < Ο - fS CO o 寸 < < < W"i - S Vi wS »Ti <M < < < 私¥ ν~> Ό 对 v> CN| < < < 駟军 l〇 V» »〇 v~> (M -τΤ < < < V) V-1 v> 00 in fM < < < 碧Ί· *Τί *Ti jn ο *n (N — »n ΓΊ 寸 < < cn Ό 寸 \D *n (N 寸 < < CQ m Ό Ό (N < < < νΊ CS 00 »〇 cs < < < s终 質量％ 質量％ 質量％ 1 質量％ 1 質量％ 質量％ 乾燥性 滲透性 耐水性(浸溃試驗） EBECRYL2000(*1) IRR569(*2) JJO «3 ΡΓ ο 竽墩 Ψ A 装衆 颤粜；^ 窗硪老 〇 ® « 5 r 1| ϊ ϊ | /—N -4^ 1 | \\\ *!. '.' 丨.1 〇 ® 蓉頷韻 辋 ,1 « ♦缠银 ^ So i, f 鉍頷讕 銪乞淫 甾 锲缕缕 甾者Μ 硪 载*:寰涑M P-SF(*li) K-SF(*12) AEROSIL300(*I3) —U嘱 低聚物 單體 染料固 色刺 Si 評價 結果 141843.doc -17- 201009032 【ΓΝΙΐ 比較 例·9 〇〇 ΓΟ CN (N 〇〇 «τ> 寸 塗膜 不均 勻 比較 例-8 00 ν〇 CS 00 m 寸 D U U 比較 例-7 in m 1—Η (N 00 Ο 寸 Q Q U 比較 例-6 m 00 <N 00 »Ti (Ν U < D 比較 例-5 m V) 〇 CN yri CS 寸 < < Ο 比較 例-4 IT) yr> CN 寸 < < Ο 比較 例-3 yn (N V-l m CN < < Ο 比較 例-2 00 Η <Ν Ι> (N 寸 < < Q 粲7 »Τ) 00 (N 寸 < < Q sef 1質量％ |質量％ 質量％ 質量％ 質量％ 質量％ 乾燥性 滲透性 耐水性(浸潰試驗） EBECRYL2000(*1) 丙烯醯嗎琳(*3) 0? ϊ 賴；^ 镏Γ G 蒯茗Γ 2 «壤蓉S ®7 J 龚颤虢卜键；f Φ ^ Ί «1 T 鉍颤《?砩绪鍥 辑绪®-叱《 Μ 肊肊Φ装爱祐 爱装命>1 »1 <1 P-SF(*11) DAROCUR1173(*14) 低聚物 單體 染料固色劑 吸水性填料 光聚合起始劑 評價結果 -18- 141843.doc 201009032 . 表1、2中之註釋*係如下所述。 (*1) Daicel-Cytec股份有限公司製造 (*2) Daicel-Cytec股份有限公司製造 (*3) Kohjin股份有限公司製造 (*4)大阪有機化學股份有限公司製造 ， （*5)日東紡股份有限公司製造，製品名：paa-03 (*6)曰東紡股份有限公司製造，製品名：Paa-HCL-03 鲁 （*7)日東紡股份有限公司製造，製品名：PAA-D11-HCL (*8)曰東紡股份有限公司製造，製品名：paa_1112Cl (*9)曰華化學股份有限公司製造，製品名：Neofix IJ-117 (* 10)曰華化學股份有限公司製造，製品名：Neofix IJ-450 (11)出光精禮·科技股份有限公司（Idemitsu Technofine Co.,Ltd.)製造 (* 12)出光精密科技股份有限公司製造 (*13)日本Aerosil股份有限公司製造 鲁 （14)、/飞巴精化股份有限公司（Ciba Specialty Chemicals Co.,Ltd)製造 (*15)曰東紡股份有限公司製造，製品名：pAA_u5〇〇〇 (* 16)日東紡股份有限公司製造，製品名：pas_h_5l (* 17)曰東紡股份有限公司製造，製品名：PAS-21 CL (*18)三洋化成股份有限公司製造，製品名：Sunfix7〇 (油墨接受層之形成） 用棒塗佈機（RK Print Coat lnstruments公司商品名：κ_ 202) ’將上述所製作之試樣以膜厚為15〜25 μηι之方式而塗 141843.doc •19- 201009032 * 佈於 100 μηι厚之PET(polyethylene terephthalate，聚對苯二 甲酸乙二酯）膜（Toray股份有限公司製造商品名： Lumirror 丁1〇〇)上。 繼而’使用紫外線照射裝置（GS Yuasa Lighting公司商 品名：CSOT-40)以200 mJ/cm2之累計放射量使塗膜硬化， 形成油墨接受層。 (印刷適應性之評價） 使用喷墨方式之於色列印機（Seiko Epson股份有限公司 製造商品名：PM-G850)，於上述油墨接受層之表面鄰接 印刷黑色、藍色、黃色、紅色之實體圖像（s〇lid image)。 繼而，對印刷狀況進行比較評價。作為印刷狀況，係以4 個階段對以下所示之乾燥性、滲透性、耐水性進行評價。 即，非常良好者為「A」、良好者為「b」、精差者為 「C」、非常差者為「D」。將該評價結果歸納表示於表1及 表2中。 •乾燥性 於印刷5分鐘後，將紙（Askul公司製造，商品名： Multipaper Super Economy)按壓於印刷面上，評價油墨轉 印至紙上之程度。 •滲透性 評價塗膜之印刷圖像之滲透程度。 •对水性 將塗膜之印刷圖像於水中浸潰3分鐘。取出之後直接乾 燥，評價油墨之滲透程度。 141843.doc -20- 201009032 (結果） 由表1及表2所示之結果可確認，以特定之範圍而調配聚 合反應性低聚物、水溶性單體、光聚合起始劑及染料固色 劑之實施例1〜實施例13中，可獲得使用同質之材料但調配 比例不同之比較例1~比較例9無法獲得的综合而言較為良 好之印刷特性。[1<] Example-13 Ό CN 00 s - inch << C0 Example -12 > n 'sO ο (N CM (S 00 cs CQ CQ < Example-11 W~J CN 00 Ό n Pairs <<<<<<<> Example-10 V) cs '«Ο ir> V) CN *n CN o 寸 CQ << Ο - fS CO o 寸<<<<<<<> Vi wS »Ti <M <<< Private ¥ ν~> Ό For v> CN| <<< 驷军 l〇V» »〇v~> (M -τΤ <<< V) V-1 v> 00 in fM <<< 碧Ί· *Τί *Ti jn ο *n (N — »n ΓΊ &<< cn Ό inch \D *n (N Inch << CQ m Ό Ό (N <<<< νΊ CS 00 »〇cs <<< s final mass % mass % mass % 1 mass % 1 mass % mass % dry permeability water resistant Sex (impregnation test) EBECRYL2000(*1) IRR569(*2) JJO «3 ΡΓ ο 竽 Ψ A A 众 粜 粜; ^ 硪 硪 « « « « « « « « « « « « « « « « « / / / / / / / / / / / / / / / / / / / / / / 1 | \\\ *!. '.' 丨.1 〇® 蓉颔韵辋, 1 « ♦ 缠银^ So i, f 铋颔谰铕乞淫铋颔谰铕乞 Μ **:寰涑M P-SF(*li) K- SF(*12) AEROSIL300(*I3) —U嘱 oligomer monomer dye fixing color Si evaluation result 141843.doc -17- 201009032 【ΓΝΙΐComparative example·9 〇〇ΓΟ CN (N 〇〇«τ> 寸Film unevenness Comparative Example-8 00 ν〇CS 00 m inch DUU Comparative Example-7 in m 1—Η (N 00 Ο inch QQU Comparative Example -6 m 00 <N 00 »Ti (Ν U < D Comparison Example-5 m V) 〇CN yri CS inch << Ο Comparative Example-4 IT) yr> CN inch<<< Ο Comparative Example-3 yn (N Vl m CN << Ο Comparative Example-2 00 Η <Ν Ι> (N inch << Q 粲7 »Τ) 00 (N inch << Q sef 1% by mass | mass % mass % mass % mass % mass % dry permeable water resistance (Immersion test) EBECRYL2000(*1) 醯 醯 醯 ( (*3) 0? ϊ 赖;^ 镏Γ G 蒯茗Γ 2 «土蓉 S ®7 J Gong 虢 虢 ; key; f Φ ^ Ί «1 T 铋 《 "? 砩 锲 锲 锲 ® 叱 叱 叱 叱 叱 ® Μ 肊肊 装 装 爱 爱 & & & & & & & & & & & & 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Fixing agent water-absorbing filler photopolymerization initiator evaluation results -18- 14 1843.doc 201009032 . The notes * in Tables 1 and 2 are as follows. (*1) Manufactured by Daicel-Cytec Co., Ltd. (*2) Manufactured by Daicel-Cytec Co., Ltd. (*3) Manufactured by Kohjin Co., Ltd. (*4) Manufactured by Osaka Organic Chemical Co., Ltd., (*5) Nisshinbo Co., Ltd. Made by the company, the product name: paa-03 (*6) manufactured by Jidong Textile Co., Ltd., product name: Paa-HCL-03 Lu (*7) manufactured by Nitto Spinning Co., Ltd., product name: PAA-D11-HCL (*8) Manufactured by Jidong Textile Co., Ltd., product name: paa_1112Cl (*9) manufactured by Yuhua Chemical Co., Ltd., product name: Neofix IJ-117 (* 10) manufactured by Yuhua Chemical Co., Ltd., product name: Neofix IJ-450 (11) Manufactured by Idemitsu Technofine Co., Ltd. (* 12) manufactured by Idemitsu Precision Technology Co., Ltd. (*13) manufactured by Japan Aerosil Co., Ltd. (14) , manufactured by Ciba Specialty Chemicals Co., Ltd. (*15) manufactured by Toho Textile Co., Ltd., product name: pAA_u5〇〇〇 (* 16) manufactured by Nitto Spinning Co., Ltd. Name: pas_h_5l (* 17) manufactured by Jidong Textile Co., Ltd. Product name: PAS-21 CL (*18) Sanyo Chemical Co., Ltd. manufactured, product name: Sunfix7〇 (formation of ink receiving layer) with bar coater (RK Print Coat Instruments, trade name: κ_ 202) The prepared sample was coated with a film thickness of 15 to 25 μηι. 141843.doc •19- 201009032 * PET (polyethylene terephthalate) film coated with 100 μηι thick (Toray Co., Ltd.) The company manufactures the trade name: Lumirror Ding 1〇〇). Then, the coating film was cured by an ultraviolet irradiation device (GS Yuasa Lighting Co., Ltd., trade name: CSOT-40) at a cumulative emission amount of 200 mJ/cm 2 to form an ink receiving layer. (Evaluation of Printing Adaptability) An ink jet printing method (manufactured by Seiko Epson Co., Ltd., trade name: PM-G850) was used, and black, blue, yellow, and red were adjacently printed on the surface of the ink receiving layer. Entity image (s〇lid image). Then, the printing status was compared and evaluated. As the printing condition, the drying property, the permeability, and the water resistance shown below were evaluated in four stages. That is, those who are very good are "A", those who are good are "b", those who are very poor are "C", and those who are very poor are "D". The results of this evaluation are summarized in Tables 1 and 2. • Dryness After 5 minutes of printing, paper (manufactured by Askul, trade name: Multipaper Super Economy) was pressed against the printing surface to evaluate the extent to which the ink was transferred onto the paper. • Permeability The degree of penetration of the printed image of the film was evaluated. • Water-based The printed image of the film was dipped in water for 3 minutes. After taking out, it was directly dried to evaluate the degree of penetration of the ink. 141843.doc -20- 201009032 (Results) From the results shown in Tables 1 and 2, it was confirmed that a polymerizable reactive oligomer, a water-soluble monomer, a photopolymerization initiator, and a dye fixing were prepared in a specific range. In Examples 1 to 13 of the present invention, it was possible to obtain printing characteristics which were excellent in combination which were not obtained in Comparative Example 1 to Comparative Example 9 in which the materials of the same quality were used.
尤其可確認’實施例1〜實施例13中，可充分維持作為油 墨接受層之印刷適應性而要求的印刷圖像之乾燥性及唆透 性’並且可獲得在浸潰於水中之嚴酷環境下亦優異之^ 【圖式簡單說明】 圖1係表示本發明之一實施形態資 圖 貫訊s己錄媒體的 〇 【主要元件符號說明】 資訊記錄媒體 油墨接受層 基材 141843.doc -21-In particular, it can be confirmed that in the first to third embodiments, the dryness and the permeability of the printed image which is required as the printing suitability of the ink receiving layer can be sufficiently maintained, and it is possible to obtain a severe environment which is immersed in water. It is also excellent. [Simplified description of the drawings] Fig. 1 is a diagram showing an embodiment of the present invention. [Main component symbol description] Information recording medium ink receiving layer substrate 141843.doc -21-