五、發明說明（1) 發明領域 本發明係關於一種感光樹脂組成物，其可用來製備無表 面黏著及可抗紫外輻射老化之凸版印刷板；及由此製造之 印刷板。 發明背景 膠版印刷用之光聚合物印刷板可從液體感光樹脂組成物 或從固體感光薄板組成物來製造。液體感光樹脂組成物典 型地包括一預聚物，其於分子的每個終端具有乙烯系不飽 合基（如丙烯酸酯或甲基丙烯酸酯）；一種或多種乙烯系不 飽合化合物（例如單體類或寡聚物類）；及一光聚合反應起 始劑。膠版印刷板可藉由將液體感光樹脂曝露在光化輻射 下而製成，首先先於一邊形成印刷板之基底或底層、然後 透過照相底片或其它遮罩形成影像、接著利用顯影製程移 除未硬化的樹脂、再進行後曝光製程及乾燥製程以產生凸 版影像。 除非採用特定的方法來減低該光聚合物印刷板的表面黏 著性，否則該印刷板之印刷凸版表面會相當地黏。過黏的 印刷表面會使得在板子的表面上快速地累積乾掉的墨水及 紙纖維，及亦會塡滿板子之相反區域和沈積在印刷符號的 邊緣上。這些事件全部會產生熟知的骯髒印刷（d i r t y P r i n t i n g )，而需要中止印刷機及淸潔印刷板。此外，板 子過黏實際上會造成起皺片或印上紙的網狀組織黏附在板 子的表面而需中斷印刷操作。 五、發明說明（2) 於技藝中已熟知數種方法可以減低該液體光聚合物印刷 板之表面黏著。美國專利4, 7 1 6, 094揭示可將減黏添加劑 (諸如脂肪酸類、脂肪酸醯胺類、脂肪醇類及硫酯類）摻入 液體感光樹脂以減低印刷板的表面黏著。表面黏著可利用 於硬化的光聚合物樹脂中，減黏添加劑其低溶解度且可漂 移至板子的表面而提供滑的表面而減低。然而，這些添加 劑可能會被沖洗掉、或是溶解在印刷墨水中、或於印刷製 程期間使用的淸潔劑中而減少板子的不黏性本質。除了在 顯影後的後硬化光聚合物印刷板外，並不需要其它化學反 應或由這些添加劑誘導出其它化學反應。 美國專利4,202, 696揭示該硬化的感光樹脂之表面黏著 可利用將該物體的表面浸漬至特定的有機羰基化合物（諸 如二苯甲酮）中，然後以波長從200至300奈米之光化輻 射輻照該組成物而減低。典型地，該表面以該有機羰基化 合物來浸漬，可將其浸泡在含適當的揮發性溶劑（諸如異 丙醇或乙醇）之羰基化合物溶液中。典型的有機羰基化合 物包括二苯甲酮、經取代的二苯甲酮類及經取代的蒽醌類 。不幸地，此合適的溶劑類經常是極易燃且不易在沒有非 常好的通風系統下使用，同時所有的電子設備都需改變成 抗爆型。 美國專利4,806,506揭示一種脫黏凸版印刷板之方法， 其利用在該板子顯影及乾燥後，及在將該板子表面曝露至 波長範圍200至300奈米的輻射前，將非質子有機溶劑塗 五、發明說明（3) 佈至該板子表面。 歐洲專利申請EP 674，229及EP 691，3 5 7描述出使用的 感光樹脂包括二者，第一光起始劑系統，其可在曝露至波 長至少300奈米的輻射後有效地硬化感光樹脂；及第二光 起始劑系統，其包含一羰基化合物（諸如二苯甲酮與相關 之經胺改質的聚胺甲酸酯預聚物），其可在曝露至波長範 圍2 00至3 00奈米的輻射後有效地脫黏該印刷板表面。於 此實例中，可藉由將該有機羰基化合物倂入液體感光樹脂 本身而消除將其浸漬至硬化的物體表面之需求，而避免使 用揮發性溶劑。 亦熟知該有機羰基化合物類（諸如二苯甲酮）爲三元感光 劑類而可大大地加速聚胺甲酸酯在波長3 50奈米及較高處 的光降解。因此，當將印刷板浸在二苯甲酮溶液中（或從 含二苯甲酮的樹脂製造）然後接受殺菌燈輻照後，可於初 起時製備成完全沒有黏性，但該聚合物會快速老化。確實 地，當將其貯存在日光、螢光或金屬-鹵化物型的燈光（在 其輸出中會放射出一小部分低於400奈米的波長）下時’ 任何此印刷板類之機械特性將會快速地衰退，諸如張力強 度、延伸度及抗碎裂性或其它物理損害。 如於本發明中使用之減低表面黏著或獲得不黏性表面之 槪念提到更多的描述，其中該硬化的光聚合物印刷板之黏 著量將減低或避免。在光聚合物印刷板中，已顯影或經 '淸 洗以移除未硬化的樹脂、在水下後曝光及乾燥之板子’初 588216 五、 發明說明 ( 4； ) 始 地 可 視 爲 在 表 面上僅具有些微黏性或並不黏 性 〇但 是 ’ 經 發 現 在 將 板 子 表面與墨水類、墨水淸潔劑類 或 醇接 觸 後 ’ 該 表 面 因 此 會 變得非常黏而難以接觸。因此 > 根據 本 發 明 之 製 備 一 種 不 黏性表面的觀念，其包括永久 地 減低 或 消 除 黏 著 狀 態 〇 至 今 並 沒 有 方法能夠克服光聚合物印刷板 之 加速 老 化 ， 此 老 化 由 於 用 做UV光穩定劑或吸收劑的二 苯 甲酮 之 存 在而 發 生 因 此 無法阻止感光樹脂自身硬化。 現 在已 驚 人 地 發 現 可 使 用 含 芳香族或多不飽合羧酸或酯之 感 光樹 脂 及 將 該 印 刷 板 子 接受波長範圍在200至300奈 米 的輻 射而 製 備 永 久 不 黏 性 之抗UV光老化的凸版印刷板。 發 明 槪 述 本 發 明 之 的 爲提供一種用來製造永久不黏 性 之凸 版 印 刷 板 的 感 光 樹 脂 組成物，其在長時間曝露至低 程 度波 長 小 於約 400 奈 ί米 :的 1光下不會老化。本發明之進一 步 的目 的 爲 提 供 一 種 製 造 該 永久不黏性的印刷板之方法。 本 發 明 提 供 一 種感光樹脂組成物，其包括（ i ) 聚胺 甲 酸 酯 寡 聚 物 、 (1 1 ) 一具有至少一個乙烯系不飽合 基 之單 體 (i ϋ )- -光聚合反應起始劑及Π V ) —減黏添加 劑 。以 此 樹 脂 製 造 的 膠 版 印 刷板可藉由於200奈米至300 奈 米的 輻 射 波 長 下 後 曝 光 κ±^ 7G 全地製造且永久不黏性，同時 可在長 時 間 曝 露 至 低 程 度 的 3 0 0奈米及更長的波長之光化 車虽 射後 抗老 化 〇 -6 -V. Description of the invention (1) Field of the invention The present invention relates to a photosensitive resin composition which can be used to prepare a relief printing plate having no surface adhesion and resistance to UV radiation aging; and a printing plate manufactured therefrom. BACKGROUND OF THE INVENTION Photopolymer printing plates for offset printing can be manufactured from a liquid photosensitive resin composition or from a solid photosensitive sheet composition. The liquid photosensitive resin composition typically includes a prepolymer having an ethylenically unsaturated group (such as acrylate or methacrylate) at each terminal of the molecule; one or more ethylenically unsaturated compounds (such as mono Or oligomers); and a photopolymerization initiator. Offset printing plates can be made by exposing liquid photosensitive resin to actinic radiation. First, the substrate or bottom layer of the printing plate is formed on one side, and then an image is formed through a photographic film or other mask. Then, the undeveloped film is removed by a developing process. The hardened resin is subjected to a post-exposure process and a drying process to produce a relief image. Unless a specific method is used to reduce the surface adhesion of the photopolymer printing plate, the printing relief surface of the printing plate will be quite sticky. An over-adhesive printing surface will cause the dry ink and paper fibers to quickly accumulate on the surface of the board, and will also fill the opposite area of the board and deposit on the edges of the printed symbols. All of these events will produce the well-known dirty printing (d i r t y Pr n t i n g), and the need to suspend the printing press and clean the printing plate. In addition, over-adhesion of the board can actually cause wrinkled sheets or paper-printed nets to stick to the surface of the board and interrupt printing operations. 5. Description of the invention (2) Several methods are well known in the art to reduce the surface adhesion of the liquid photopolymer printing plate. U.S. Patent No. 4, 7 1 6, 094 discloses that viscosity-reducing additives (such as fatty acids, fatty acid amines, fatty alcohols, and thioesters) can be incorporated into liquid photosensitive resins to reduce surface adhesion of printing plates. Surface adhesion can be used in hardened photopolymer resins. The viscosity-reducing additive has low solubility and can drift to the surface of the board to provide a slippery surface to reduce it. However, these additives may be washed away, or dissolved in printing inks, or detergents used during the printing process, reducing the non-stick nature of the board. With the exception of post-cured photopolymer printing plates after development, no other chemical reactions or other chemical reactions induced by these additives are required. U.S. Patent No. 4,202,696 discloses that the surface adhesion of the hardened photosensitive resin can be obtained by dipping the surface of the object into a specific organic carbonyl compound such as benzophenone and then actinic radiation at a wavelength from 200 to 300 nm Reduced by irradiating the composition. Typically, the surface is impregnated with the organic carbonyl compound, which can be immersed in a carbonyl compound solution containing a suitable volatile solvent such as isopropanol or ethanol. Typical organic carbonyl compounds include benzophenones, substituted benzophenones, and substituted anthraquinones. Unfortunately, this suitable solvent is often extremely flammable and difficult to use without a very good ventilation system, and all electronic equipment needs to be changed to an explosion-proof type. U.S. Patent No. 4,806,506 discloses a method for debonding letterpress printing plates by applying an aprotic organic solvent to the substrate after it is developed and dried, and before the surface of the plate is exposed to radiation in the wavelength range of 200 to 300 nm DESCRIPTION OF THE INVENTION (3) It is distributed on the surface of the board. European patent applications EP 674,229 and EP 691,3 5 7 describe the use of photosensitive resins including both, a first photoinitiator system that effectively hardens the photosensitive resin after exposure to radiation having a wavelength of at least 300 nm ; And a second photoinitiator system comprising a carbonyl compound (such as benzophenone and related amine-modified polyurethane prepolymers), which can be exposed to a wavelength range of 200 to 3 The surface of the printing plate was effectively de-bonded after radiation of 00 nm. In this example, the need to impregnate the organic carbonyl compound into the surface of the liquid photosensitive resin itself eliminates the need to impregnate it to the surface of a hardened object and avoids the use of volatile solvents. It is also well known that the organic carbonyl compounds (such as benzophenone) are ternary photosensitizers, which can greatly accelerate the photodegradation of polyurethanes at a wavelength of 350 nm and higher. Therefore, when the printing plate is immersed in a benzophenone solution (or made from a benzophenone-containing resin) and then irradiated with a germicidal lamp, it can be prepared at the beginning to be completely non-sticky, but the polymer Will age quickly. Indeed, when stored under daylight, fluorescent, or metal-halide type lights (which emit a small portion of wavelengths below 400 nm in their output) 'any of the mechanical properties of this printed board Will decay rapidly, such as tensile strength, elongation, and resistance to chipping or other physical damage. The idea of reducing the surface adhesion or obtaining a non-adhesive surface as used in the present invention mentions more descriptions, in which the amount of adhesion of the hardened photopolymer printing plate will be reduced or avoided. In photopolymer printing boards, boards that have been developed or 'washed to remove unhardened resin, exposed and dried after exposure to water', etc. Initially 588216 V. Description of the invention (4;) Originally considered to be on the surface Only slightly sticky or non-sticky, but 'the surface of the board was found to be in contact with inks, ink cleaners or alcohols' and the surface became very sticky and difficult to contact. Therefore > The concept of preparing a non-stick surface according to the present invention includes permanently reducing or eliminating the state of adhesion. So far, there is no way to overcome the accelerated aging of photopolymer printing plates, which is used as a UV light stabilizer Or the presence of benzophenone in the absorbent and therefore cannot prevent the photosensitive resin from hardening itself. It has now been surprisingly found that a permanent non-stick UV-aging resistant photoresist can be prepared using a photosensitive resin containing aromatic or polyunsaturated carboxylic acids or esters and receiving the printing plate with radiation in a wavelength range of 200 to 300 nm. Letterpress printing plate. SUMMARY OF THE INVENTION The present invention is to provide a photosensitive resin composition for manufacturing a permanently non-stick letterpress printing plate, which does not deteriorate under long-term exposure to a low degree of wavelength of less than about 400 nanometers: 1 light. . It is a further object of the present invention to provide a method for manufacturing the permanently non-stick printing plate. The present invention provides a photosensitive resin composition comprising (i) a polyurethane oligomer, (1 1) a monomer (iϋ) having at least one ethylenically unsaturated group, and a photopolymerization reaction. Initiator and Π V) — viscosity reducing additive. Offset printing plates made with this resin can be made post-exposure κ ± ^ 7G due to radiation wavelengths from 200 nm to 300 nm. It is entirely manufactured and permanently non-sticky, and at the same time can be exposed to a low level of 3 0 0 Nano- and longer-wavelength actinic vehicles are resistant to aging after shooting. 0-6-
五、發明說明（5 ) 發明揭示 本發明提供一種可用來製備凸版印刷板之光可聚合的樹 脂組成物，其包括： (A) 50重量％至98重量％的聚胺甲酸酯預聚物， (B) l .0%至50%的乙烯基系不飽合單體或該些單體之混合 物， (C) 0.2%至5.0%的光起始劑，及 (D) 0.5%至5.0%的減黏添加劑。 於本發明中用做組分（A)之預聚物爲具有一個或多個末 端乙烯系不飽合基（諸如甲基丙烯酸酯或丙烯酸酯類）之聚 胺甲酸酯預聚物。該胺基甲酸乙酯預聚物可藉由反應聚醚 二醇（或聚醚二醇類之混合物）、具有至少二個異氰酸酯基 (較佳地爲二異氰酸酯）之分子、具有至少一個羥基及至少 一個（甲基）丙烯酸酯（亦熟知爲羥基-官能化的（甲基）丙烯 酸酯）之分子而形成。合適的聚醚二醇類包括亞克克蘭 (Acclaim) 3 20 1、亞克克蘭 3 20 5、亞克克蘭 4220及亞 克克蘭 2220，其可從 Arco Chemical of Newtowne Square，PA購得。其它的聚醚二醇類亦同樣地合適。 使用來製備本發明之聚胺甲酸酯預聚物的二異氰酸酯較 佳地爲芳香族二異氰酸酯，雖然亦可同樣地使用脂肪族二 異氰酸酯。典型的芳香族二異氰酸酯包括亞甲基二苯基二 異氰酸酯（又稱爲二苯基甲烷_ 4，4 ’ -二異氰酸酯）、二異氰 酸間-及對-亞二甲苯酯、甲苯-2 , 4 -二異氰酸酯、甲苯- 588216 五、發明說明（6) 2 , 6 -二異氰酸酯、或後二者之異構物類（又稱爲2 , 4 -及 2，6 -甲苯二異氰酸酯）的混合物類、萘-1，5 -二異氰酸酯、 苯基苄基醚4，4 '-二異氰酸酯及其類似物。 可使用脂肪族及/或環脂族二異氰酸酯類做爲二異氰酸 酯組分。例如，合適的脂肪族二異氰酸酯類包括在脂肪族 基中具有2至1 2個碳原子的那些，例如，二異氰酸六亞 甲酯、二異氰酸2 , 2，4 -三甲基六亞甲酯及其類似物。例如 ，合適的環脂族二異氰酸酯類包括1，4 -二異氰酸酯-環己 烷、二環己基甲烷-4，4 1 _二異氰酸酯（又稱爲二異氰酸雙-環己基亞甲酯）、異佛爾酮二異氰酸酯及其類似物。 較佳地將過量的二異氰酸酯與二醇反應以產生異氰酸酯 爲終端的聚胺甲酸酯寡聚物。二醇組分與二異氰酸酯組分 之莫耳比率較佳地在約1 . 〇 : 1 · 〇 8及1 . 0 : 1 . 5之間，更 佳地在約1 . 0 : 1 · 1 2及1 . 〇 : 1 . 3之間。聚胺甲酸酯寡聚 物的數量平均分子量較佳地在約6,000及40,000之間， 更佳地在約8,000及30, 000之間及最佳地在約1 2,000及 20,000 之間。 較佳地，在二醇及二異氰酸酯間的反應藉由於有效濃度 (較佳地從約50至約1 OOppm )的催化劑（較佳地爲二丁基錫 二月桂酸酯或此烷基錫的其它催化劑）存在下，將反應物 相互接觸而進行。反應溫度約6 0 °C，於此溫度下反應時間 約4小時。 在將聚醚二醇與過量的二異氰酸酯反應以獲得異氰酸酯 588216 五、發明說明（7) 爲終端的聚胺甲酸酯寡聚物之後，將該寡聚物與羥基丙烯 酸酯或羥基甲基丙烯酸酯反應以將不飽合的烯基導入寡聚 物，而獲得胺基甲酸乙酯預聚物。合適的羥基丙烯酸酯類 或羥基甲基丙烯酸酯類包括（非爲限制）（甲基）丙烯酸2 -羥 丙酯、多丙二醇單甲基丙烯酸酯、多丙二醇單丙烯酸酯或 丙烯酸酯化的己內酯寡聚物。這些當中，多丙二醇單甲基 丙烯酸酯及丙烯酸酯化的己內酯寡聚物對製造需要用來在 起皺片或其它具有不規則表面的纖維基材上印刷的軟光聚 合物來說較佳。 使用爲本發明之感光樹脂組成物的組分（B)之單體爲一 種具有至少一個丙烯酸酯基之單體，亦熟知爲一種反應性 單體，或簡單的說一種單體。本發明之反應性單體可爲任 何通常可獲得的具有一個或多個光可聚合的官能基之分子 。較佳的反應性單體爲一種單-或多丙烯酸酯或甲基丙烯 酸酯的化合物（包括其酯類）。於此將使用特定的（甲基）丙 烯酸酯以同時地指爲甲基丙烯酸酯類及丙烯酸酯類之一或 二者。 使用於分子中具有二個或多個乙嫌系不飽合基之化合物 會增加印刷板的硬度。因此，應該控制此化合物的使用量 以獲得具有想要的硬度之印刷板。爲此理由，較佳的反應 性單體爲單-(甲基）丙烯酸酯及多（甲基）丙烯酸酯之混合 物。 典型的反應性單體類爲丙烯酸及/或甲基丙烯酸與單羥 588216 五、發明說明（8) 或多羥基的醇類之酯類，其包括（例如及非爲限制）（甲基） 丙嫌酸丁酯；（甲基）丙烯酸2 -乙基己酯；（甲基）丙烯酸異 癸酉曰’（甲基）丙烯酸月桂酯；（甲基）丙烯酸啡乙氧酯；乙 一醇單乙基醚單（甲基）丙烯酸酯；二乙二醇單乙基醚單（ 甲基）丙烯酸酯；三乙二醇單乙基醚單（甲基）丙烯酸酯； 乙二醇二（甲基）丙烯酸酯；（甲基）丙烯酸2 _羥乙酯、丨，6 _ 己二醇二（甲基）丙烯酸酯；丨，丨，丨_三羥甲基丙烷三（甲基） 丙烯酸酯；二、三、及四乙二醇二（甲基）丙烯酸酯；三丙 二醇二（甲基）丙烯酸酯；季戊四醇四（曱基）丙烯酸酯；丙 氧基化的二經甲基丙院單-、二-及三-(甲基）丙嫌酸酯； 乙氧基化的三羥甲基丙烷三（甲基）丙烯酸酯及含（甲基）丙 烯酸之寡聚聚丁二烯類，即，擁有活化的、光可聚合的烯 雙鍵之寡聚聚丁二烯類。 較佳的單體爲甲基丙烯酸月桂酯、多丙二醇單甲基丙烯 酸酯、二乙二醇單乙基醚單丙烯酸酯、三羥甲基丙烷三甲 基丙烯酸酯及四乙二醇二甲基丙烯酸酯。 於本發明之感光樹脂配方中反應性單體的比例至少部分 地支配了產生的液體感光樹脂所想要的黏度。對已付予分 子量的聚胺甲酸酯預聚物來說，摻入感光樹脂的單體量越 多，產生的樹脂黏度越低。於使用的溫度下感光樹脂的黏 度較佳地在1 0,000cps及1 00,000cps之間，更佳地在 20,000 cps 及 5 0,000cps 之間。最佳地，約 25,000cps 至 約40，OOOcps。對已付予分子量的聚胺甲酸酯預聚物來說 -10- 五、發明說明（9) ，所需用來達成已付予黏度的感光樹脂之不飽合反應性單 體的量，可容易地由熟知此技藝之人士不需過度的實驗即 可測得。 典型地，該反應性單體的量爲光可聚合的混合物之約1 0 至約3 5重量百分比，更佳地爲混合物的約1 5至約3 0重 量百分比。 使用爲本發明之感光樹脂組成物的組分（C)之光起始劑 可爲任何習慣上使用於凸版印刷板之光起始劑。典型的光 起始劑類包括醯基氧化磷、苯偶姻甲基醚、苯偶姻異丙基 醚、苯偶姻正丁基醚、苯偶姻異丁基醚、二苯甲酮、2，2 -二甲氧基-2-苯基乙醯苯（即，号加昆爾（Irgacure)®651 (Ciba-Geigy))、苯偶醯1-甲基1-乙基縮酮、2-氯噻蒽酮 、二苯並環庚酮、2,2-二乙氧基-2-苯基乙醯苯、2,2-二 乙氧基乙醯苯、2 -二甲氧基苯甲醯基二苯基氧化磷、 4，4 '-雙（二甲基胺基）二苯甲酮、2 , 4 , 6 -三甲基苯甲醯基 苯基亞磷酸乙酯、1 -羥基環己基苯基酮、4 ’ -嗎啉去氧苯 偶姻及2，4，6 -三甲基苯甲醯二苯基氧化磷。 光聚合反應起始劑的量可爲任何有效濃度，而可藉由背 面曝光一段合理的時間而對膠版印刷板形成一底層，及形 成具所需的影像解析度之凸版影像。此時間與欲形成的影 像型式及想要的膠版印刷板之厚度相關。該光聚合反應起 始劑的有效量依所選擇的起始劑之型式而定。 建議使用0 . 1 - 1 0重量％的光起始劑濃度範圍。當光起始 -1 1 - 588216 五、發明說明（1〇) 劑的量少於0 . 1 %時，紫外光定型的密度會降低及光聚合物 板的物理特性會極度地降低。當光起始劑的量超過5重量 %時，並無觀察到對任何特性有增益的效應，而使得該配 方的成本變成商業上不想要的。較高的光起始劑濃度亦會 使得產生的印刷板更容易於低程度的光化輻射存在下老化 〇 對2，2 -二甲氧基-2-苯基乙醯苯來說，於光可聚合的混 合物中使用的光起始劑量從約0 . 1 %至約5 %，較佳地約 0 · 2%至約1 · 5%，更佳地從約〇 . 25%至約0 . 75%。 使用爲本發明之感光樹脂組成物的組分（D)之減黏添加 劑可爲芳香族羧酸或芳香族羧酸酯、多不飽合羧酸或多不 飽合羧酸酯類或其混合物，該添加劑可吸收波長從200奈 米至3 0 0奈米的光化輻射，較佳地從約2 4 5奈米至約2 6 5 奈米，更佳地約2 5 4奈米，及該添加劑實質上並不吸收在 波長3 0 0奈米或較高時的光化輻射，更佳地爲3 3 0奈米或 較高。合適之減黏添加劑包括4 -羥基苯甲酸、4 -甲氧基苯 甲酸、4 -烷氧基苯甲酸類、4 -羥基苯甲酸甲酯、4 -甲氧基 苯甲酸甲酯、2 -噻吩羧酸、肉桂酸、2 , 4 -己二烯酸及其混 合物。較佳之減黏添加劑包括4 -羥基苯甲酸及4 -甲氧基 苯甲酸。減黏添加劑量可從約0 . 5重量％至約5重量％。更 佳地，其量從約Q.7 5重量％至約3重量％。最佳地，其量 從約1重量％至約2重量％。 除此上述描述之組分A、B、C及D外，本發明之光可聚 -1 2- 588216 五、發明說明（11 ) 合的樹脂亦可包含其它額外的添加劑，諸如熱抗氧化劑、 紫外光吸收劑、位阻胺光安定劑、染料、色素或塑化劑。 例如，典型的抗氧化劑包括空間位阻的單酚類（諸如2，6 -二-第三丁基·對-甲酚（BHT))、烷基化的硫雙酚類及亞烷 基雙酚類（諸如2,2 -亞甲基雙- (4 -甲基-6-第三丁基酚）或 2，2 -雙（1 ·羥基-4 -甲基-6 -第三丁基苯基）硫醚）。BHT爲較 佳的抗氧化劑。 可利用任何常用於其它感光樹脂之方法使用本發明之感 光樹脂來製備印刷板。亦即，此感光樹脂可在基材背板及 面對照相底片的遮板間提供厚度均勻的一層，及使該層接 受光化輻射的背面曝光及影像曝光，接著顯影該板。 基材背板（亦熟知爲支持物）可爲任何傳統上用來製備膠 版印刷板且具彈性之感光元件材料。合適的基材材料之實 例包括聚合薄膜，諸如由加成聚合物及線性縮合聚合物、 透明的泡沬塑料及織物形成的那些。較佳的基材爲聚酯薄 膜；特別佳的爲聚苯二酸-乙二醇。典型的基材厚度從2 至10密耳（ 0.005 1至0.025公分），較佳的厚度爲4至7 密耳（〇 . 0 1 0至0 . 0 1 8公分）。 合適的光化輻射源之實例爲日光及商業UV螢光管；中 壓、高壓及低壓汞燈；超光化螢光管；脈衝的氙燈；摻雜 金屬碘化物的燈及碳電弧燈。較佳地，於本發明中使用的 光聚合物板以具有波長1 50 - 500奈米（特別是3 00 - 400奈 米）的紫外線硬化，此波長可由低壓汞燈、高壓汞燈、碳 -1 3- 五、發明說明（12) 電弧燈、紫外螢光燈、化學燈、氙燈或鍩燈產生。 實際上已有數種型式的裝置用來顯影光聚合物板。其中 一種利用將沖洗溶液加壓噴灑在板子上以形成凸版。另一 種利用壓縮空氣吹掉未曝光的部分而形成凸版。而另一種 則利用刷子摩擦固定在平坦表面或圓柱體的板子，因此將 未曝光的部分溶解在溶液中以形成凸版。較佳的是該光聚 合物板在曝露至上述提及的光源而硬化之後，利用顯影劑 (亦熟知爲沖洗溶液）顯影以移除未曝光的非影像部分。此 製程會於光聚合物板上形成凸版影像。已利用沖洗溶液移 除的未曝光部分在沖洗浴槽的沖洗溶液中以乳化或懸浮的 形式存在。 較佳地使用水性顯影劑。最合意的顯影劑爲具有pH5 . 0 -9 . 0的水（自來水），其可視需要地包括鹼性金屬化合物及 表面活性劑。對光聚合物來說需要加入表面活性劑以容易 地分散進入水及在水中維持分散態。較佳的表面活性劑爲 烷基-萘磺酸鈉及烷基苯磺酸鈉。其它表面活性劑的實例 包括陰離子表面活性劑類，包括羧酸鹽、硫酸鹽-酯、磺 酸鹽或磷酸鹽-酯；非離子表面活性劑類，諸如聚乙二醇 衍生物、多羥基醇衍生物及山梨聚糖衍生物；陽離子表面 活性劑類，包括一級、二級、三級胺鹽或四級銨鹽；及含 胺基酸親水基或甜菜鹼親水基的兩性表面活性劑類。較佳 的鹼金屬化合物類有六聚偏磷:酸鈉、三聚磷酸鈉、氫氧化 鈉及碳酸鈉。該沖洗溶液應該於2 5。- 5 0 °C下使用，較佳地 -14- 588216 五、發明說明（13 ) 爲30°-40&c。水中的表面活性劑濃度並無限制，但是通常 白勺IS圍約0 · 5%至約4%。雖然皮子最常使用水性顯影劑溶 令夜噴_、冲洗顯影’同樣地可使用上述提及的其它技術顯影 °視需要’可將除泡劑（諸如矽酮抗發泡劑）加入水性顯影 劑溶液。 在顯影步驟後，在板子的基底及數邊中部分聚合的感光 樹脂可利用在氧吸收化合物（諸如重亞硫酸鈉）溶液中，將 其曝露在光化輻射下而完成硬化，以防止氧抑制聚合反應 。然後利用將該2板子的表面曝露在波長從約200奈米至 約300奈米的光化輻射下而可獲得永久的不黏性。較佳的 光化輻射波長爲2 54奈米而可由殺菌燈產生，諸如由伏塔 克科技公司（Voltarc Technologies)製造的伏塔克 (Voltarc) GRFX 5058燈。該脫黏反應較佳地在溫度從約 100°F至約]40°F下進行。更佳地，該脫黏反應在溫度從約 1 25°F至約1 40卞下進行。 下列實例提供更好的揭示及教導製備本發明之感光樹脂 組成物及印刷板。這些實例僅用於闡明的目的，需了解可 在實質上沒有影響本發明如在下列敘述的申請專利範圍中 之精神及範圍下製得變化及改變。 一般程序 以分離已強加到樣品板表面上之鋼腳所需的應力値來測 量印刷板之表面黏著’該測量使用歐美加（Omega)工程有 限公司出品的型號DFU - 2之歐美加力量計量器。下列描述 588216 五、發明說明（14 ) 用來測量如上述提及的表面黏著之詳細方法。以將板子的 凸版面直接向上的方式將印刷板與水平的支持物接合。將 接有數位力量計量器且半徑爲0 . 25 "的鋼腳與板子的凸版 面之平面部分接觸。施加由歐美加力量計量器測量之500 克負載至鋼腳上及保持1 〇秒。接著，將該腳以固定的提 昇速度0 . 5英吋/分鐘向上舉起直到板子與腳部分離。應 力値僅在板子與腳分離之前使用歐美加力量計量器測量。 根據本發明製備之印刷板的黏性値利用上述程序測量爲50 克或較少，較佳地爲2 5克或較少。 每個下列實例之光可聚合的組成物根據下列程序形成光 共聚物印刷板。使用瑪俐葛來芙（Merigiraph)®型式3048 曝光單位，在塗佈著黏著劑的聚酯背板及聚丙烯薄膜的遮 板間形成一層0.2 50 "厚的感光樹脂組成物層，其將光樹脂 與照相底片分離，如在闡明中顯示。光聚合物接受2 : 30 的背面曝光，接著透過底片影像曝光6 : 00。在曝光之後 ，移除遮板及未硬化的樹脂於35-4(TC下利用噴灑水性溶 液沖洗十分鐘來移除以獲得凸版，該水性溶液包括2重量 %的瑪俐葛來芙⑧沖洗去垢劑W64 1 0L及2重量％的三磷酸鈉 。然後將該板子浸入重亞硫酸鈉水溶液中，及接受具有最 小強度8毫瓦/平方公分之光化輻射後曝光以完全地硬化 板子的凸版部分。然後於40°C下乾燥板子30至45分鐘。 然後將該板子在殺菌燈下接受乾燥後曝光步驟約10至20 分鐘，其中該殺菌燈爲伏塔克GRFX 505 8殺菌燈列而放置 -1 6 - 588216 五、發明說明（15) 在離光聚合物印刷板的表面約15公分處。如上所述測量 每個板子的表面黏著。藉由在0 . 0 0 4 ”未塗佈的聚酯薄板及 聚丙烯薄膜間鑄塑〇 . 040”厚的感光樹脂組成物層’硬化該 感光樹脂組成物以測量張力強度及延伸度。該光聚合物接 受背面曝光3 0秒接著前面曝光400秒。剝離聚酯及聚丙 烯薄膜，及根據ASTM之D- 4 1 2方法對樣品沖切以測試張 力。 藉由將該硬化的樣品曝露至從古柏（Coope r)照光型號Μ -59的金屬-鹵化物型400瓦燈來的輻射下以測試樣品的抗 UV老化。以國際照光有限公司之IL1 400A輻射計量器測量 UV光強度。該燈安裝在樣品上面一段距離以產生1 〇〇微瓦 /平方公分的UV測量強度。將有影像的〇.250”板子或 0 . 040”厚的固體薄板連續地輻照1 20小時，然後檢查以測 定在有影像的板子中的符號之抗損害、或張力強度及薄板 的延伸度。 竇例1V. Description of the invention (5) Disclosure of the invention The present invention provides a photopolymerizable resin composition that can be used to prepare a letterpress printing plate, which comprises: (A) 50% to 98% by weight of a polyurethane prepolymer (B) 1.0% to 50% of a vinyl-based unsaturated monomer or a mixture of these monomers, (C) 0.2% to 5.0% of a photoinitiator, and (D) 0.5% to 5.0 % Viscosity reducing additive. The prepolymer used as the component (A) in the present invention is a polyurethane prepolymer having one or more terminal ethylenically unsaturated groups such as methacrylates or acrylates. The urethane prepolymer may be prepared by reacting a polyether glycol (or a mixture of polyether glycols), a molecule having at least two isocyanate groups (preferably diisocyanates), At least one (meth) acrylate (also known as a hydroxy-functional (meth) acrylate) molecule is formed. Suitable polyether glycols include Acclaim 3 20 1, Acrylic 3 20 5, Acrylic 4220, and Acrylic 2220, which are commercially available from Arco Chemical of Newtowne Square, PA Got. Other polyether glycols are also suitable. The diisocyanate used to prepare the polyurethane prepolymer of the present invention is preferably an aromatic diisocyanate, although an aliphatic diisocyanate can also be used in the same manner. Typical aromatic diisocyanates include methylene diphenyl diisocyanate (also known as diphenylmethane-4,4'-diisocyanate), m- and p-xylylene diisocyanate, toluene-2 , 4-diisocyanate, toluene-588216 5. Description of the invention (6) 2, 6-diisocyanate, or the isomers of the latter two (also known as 2, 4-and 2,6-toluene diisocyanate) Mixtures, naphthalene-1,5-diisocyanate, phenylbenzyl ether 4,4'-diisocyanate and the like. As the diisocyanate component, aliphatic and / or cycloaliphatic diisocyanates can be used. For example, suitable aliphatic diisocyanates include those having 2 to 12 carbon atoms in the aliphatic group, for example, hexamethylene diisocyanate, 2, 2, 4-trimethyl diisocyanate Hexamethylene and its analogs. For example, suitable cycloaliphatic diisocyanates include 1,4-diisocyanate-cyclohexane, dicyclohexylmethane-4,4 1_diisocyanate (also known as diisocyanate bis-cyclohexylmethylene) , Isophorone diisocyanate and its analogs. The excess diisocyanate is preferably reacted with a diol to produce an isocyanate-terminated polyurethane oligomer. The molar ratio of the diol component to the diisocyanate component is preferably between about 1.0: 1.08 and 1.0: 1.5, more preferably about 1.0: 1.12. And 1.0: 1.3. The number average molecular weight of the polyurethane oligomer is preferably between about 6,000 and 40,000, more preferably between about 8,000 and 30,000, and most preferably between about 1 2,000 and 20,000. Preferably, the reaction between the diol and the diisocyanate is caused by an effective concentration (preferably from about 50 to about 100 ppm) of a catalyst (preferably dibutyltin dilaurate or other catalyst of this alkyltin). ) Is carried out by contacting the reactants with each other. The reaction temperature is about 60 ° C, and the reaction time is about 4 hours at this temperature. After the polyether diol is reacted with an excess of diisocyanate to obtain isocyanate 588216 V. Description of the invention (7) Polyurethane oligomer terminated with oligomer and hydroxyacrylate or hydroxymethacrylic acid The ester is reacted to introduce an unsaturated alkenyl group into an oligomer to obtain a urethane prepolymer. Suitable hydroxyacrylates or hydroxymethacrylates include, but are not limited to, 2-hydroxypropyl (meth) acrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, or acrylated caprolactone Ester oligomers. Of these, polypropylene glycol monomethacrylate and acrylated caprolactone oligomers are more suitable for making soft photopolymers that need to be printed on wrinkled sheets or other fibrous substrates with irregular surfaces. good. The monomer used in the component (B) of the photosensitive resin composition of the present invention is a monomer having at least one acrylate group, and is also well known as a reactive monomer, or simply a monomer. The reactive monomer of the present invention may be any molecule that is generally available and has one or more photopolymerizable functional groups. The preferred reactive monomer is a mono- or polyacrylate or methacrylate compound (including its esters). Specific (meth) acrylates will be used herein to refer to either or both of methacrylates and acrylates. The use of compounds with two or more ethylenically unsaturated groups in the molecule will increase the hardness of the printing plate. Therefore, the amount of this compound should be controlled to obtain a printing plate having a desired hardness. For this reason, a preferred reactive monomer is a mixture of mono- (meth) acrylate and poly (meth) acrylate. Typical reactive monomers are acrylic acid and / or methacrylic acid and monohydroxy 588216. 5. Description of the invention (8) or esters of polyhydric alcohols, including (for example and without limitation) (meth) acrylic acid Butyl acetate; 2-ethylhexyl (meth) acrylate; isodecyl (meth) acrylate; lauryl (meth) acrylate; phenethoxylate (meth) acrylate; monoethyl glycol Ether mono (meth) acrylate; diethylene glycol monoethyl ether mono (meth) acrylate; triethylene glycol monoethyl ether mono (meth) acrylate; ethylene glycol di (meth) acrylate Esters; 2-hydroxyethyl (meth) acrylate, 丨, 6 _ hexanediol di (meth) acrylate; 丨, 丨, __ trimethylolpropane tri (meth) acrylate; di, tri , And tetraethylene glycol di (meth) acrylate; tripropylene glycol di (meth) acrylate; pentaerythritol tetra (fluorenyl) acrylate; propoxylated di-methyl propylene mono-, di-, and Tri- (meth) propionic acid ester; ethoxylated trimethylolpropane tri (meth) acrylate and (meth) propane Oligomeric polybutadienes, i.e., oligomeric polybutadienes with activated, photopolymerizable olefinic double bonds. Preferred monomers are lauryl methacrylate, polypropylene glycol monomethacrylate, diethylene glycol monoethyl ether monoacrylate, trimethylolpropane trimethacrylate, and tetraethylene glycol dimethyl. Acrylate. The proportion of reactive monomers in the photosensitive resin formulation of the present invention at least partially dominates the desired viscosity of the resulting liquid photosensitive resin. For a polyurethane prepolymer that has been given a molecular weight, the greater the amount of monomer incorporated in the photosensitive resin, the lower the viscosity of the resulting resin. The viscosity of the photosensitive resin at the used temperature is preferably between 10,000 cps and 100,000 cps, and more preferably between 20,000 cps and 50,000 cps. Optimally, about 25,000 cps to about 40,000 cps. For polyurethane prepolymers with molecular weights already paid -10- 5. Description of the invention (9), the amount of unsaturated reactive monomers needed to achieve the viscosity of the photosensitive resin, It can be easily measured by those skilled in the art without undue experimentation. Typically, the amount of the reactive monomer is from about 10 to about 35 weight percent of the photopolymerizable mixture, and more preferably from about 15 to about 30 weight percent of the mixture. The photoinitiator used as the component (C) of the photosensitive resin composition of the present invention may be any photoinitiator conventionally used for letterpress printing plates. Typical photoinitiators include fluorenyl phosphorus oxide, benzoin methyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzophenone, 2 , 2-dimethoxy-2-phenylacetophenone (ie, Irgacure® 651 (Ciba-Geigy)), benzophenone 1-methyl 1-ethyl ketal, 2- Chlorothanthone, dibenzocycloheptanone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-dimethoxybenzidine Diphenylphosphine oxide, 4,4'-bis (dimethylamino) benzophenone, 2, 4, 6-trimethylbenzylphenylphenyl phosphite, 1-hydroxycyclohexyl Phenyl ketone, 4'-morpholine deoxybenzoin and 2,4,6-trimethylbenzophenazine diphenyl phosphorus oxide. The amount of the photopolymerization initiator can be any effective concentration, and a back layer can be formed on the offset printing plate by exposing the back surface for a reasonable time, and a relief image having a desired image resolution can be formed. This time is related to the type of image to be formed and the thickness of the desired offset printing plate. The effective amount of the photopolymerization initiator depends on the type of the initiator selected. It is recommended to use a photoinitiator concentration range of 0.1 to 10% by weight. When the light initiation -1 1-588216 V. Description of the invention (10) The amount of the agent is less than 0.1%, the density of the ultraviolet light setting will decrease and the physical properties of the photopolymer plate will be extremely reduced. When the amount of the photoinitiator exceeds 5% by weight, no gain effect on any characteristic is observed, so that the cost of the formulation becomes commercially undesirable. Higher photoinitiator concentrations will also make the resulting printed plates more susceptible to aging in the presence of low levels of actinic radiation. For 2,2-dimethoxy-2-phenylacetanilide, the The light starting dose used in the polymerizable mixture is from about 0.1% to about 5%, preferably from about 0.2% to about 1.5%, and more preferably from about 0.25% to about 0.5%. 75%. The viscosity-reducing additive used as the component (D) of the photosensitive resin composition of the present invention may be an aromatic carboxylic acid or an aromatic carboxylic acid ester, a polyunsaturated carboxylic acid or a polyunsaturated carboxylic acid ester, or a mixture thereof. The additive can absorb actinic radiation with a wavelength from 200 nanometers to 300 nanometers, preferably from about 245 nanometers to about 265 nanometers, more preferably about 254 nanometers, and The additive does not substantially absorb actinic radiation at a wavelength of 300 nm or higher, more preferably 3300 nm or higher. Suitable viscosity reducing additives include 4-hydroxybenzoic acid, 4-methoxybenzoic acid, 4-alkoxybenzoic acids, methyl 4-hydroxybenzoate, methyl 4-methoxybenzoate, 2-thiophene Carboxylic acid, cinnamic acid, 2,4-hexadenoic acid and mixtures thereof. Preferred viscosity reducing additives include 4-hydroxybenzoic acid and 4-methoxybenzoic acid. The viscosity-reducing additive amount may be from about 0.5% by weight to about 5% by weight. More preferably, the amount is from about Q.75 to about 3% by weight. Most preferably, the amount is from about 1% to about 2% by weight. In addition to the components A, B, C and D described above, the photopolymerizable 1-2 2-588216 of the present invention V. Description of the invention (11) The resin may also contain other additional additives, such as thermal antioxidants, UV light absorber, hindered amine light stabilizer, dye, pigment or plasticizer. For example, typical antioxidants include sterically hindered monophenols (such as 2,6-di-third-butyl-p-cresol (BHT)), alkylated thiobisphenols, and alkylenebisphenols Class (such as 2,2-methylenebis- (4-methyl-6-tert-butylphenol) or 2,2-bis (1.hydroxy-4-methyl-6-tert-butylphenyl) ) Sulfide). BHT is a better antioxidant. The photosensitive resin of the present invention can be used to prepare a printing plate by any method commonly used for other photosensitive resins. That is, the photosensitive resin can provide a layer of uniform thickness between the substrate backing plate and the shutter facing the photographic film, and the backside and image exposure of the layer subjected to actinic radiation, and then the plate is developed. The substrate backing plate (also known as a support) can be any elastic photosensitive material traditionally used for making offset printing plates. Examples of suitable substrate materials include polymeric films, such as those formed from addition polymers and linear condensation polymers, transparent foams, and fabrics. The preferred substrate is a polyester film; particularly preferred is polyphthalic acid-ethylene glycol. Typical substrate thicknesses range from 2 to 10 mils (0.005 1 to 0.025 cm), with a preferred thickness of 4 to 7 mils (0.010 to 0.018 cm). Examples of suitable actinic radiation sources are daylight and commercial UV fluorescent tubes; medium, high and low pressure mercury lamps; ultra-photochemical fluorescent tubes; pulsed xenon lamps; metal iodide-doped lamps and carbon arc lamps. Preferably, the photopolymer plate used in the present invention is hardened by ultraviolet rays having a wavelength of 1 50-500 nm (especially 3 00-400 nm), and this wavelength can be low-pressure mercury lamp, high-pressure mercury lamp, carbon- 1 3- V. Description of the invention (12) Arc lamp, ultraviolet fluorescent lamp, chemical lamp, xenon lamp or krypton lamp are generated. There are actually several types of devices used to develop photopolymer plates. One of them uses pressure spraying a washing solution on a board to form a relief. The other uses compressed air to blow off the unexposed parts to form a relief. The other uses a brush to rub the plate fixed to a flat surface or a cylinder, so the unexposed part is dissolved in the solution to form a relief. Preferably, the photopolymer plate is hardened by exposure to the light source mentioned above, and then developed with a developer (also known as a washing solution) to remove the non-exposed non-image portion. This process forms a relief image on a photopolymer plate. The unexposed portion that has been removed with the rinsing solution is present in emulsified or suspended form in the rinsing solution in the rinsing bath. An aqueous developer is preferably used. The most desirable developer is water (tap water) having a pH of 5.0 to 9.0, which optionally includes a basic metal compound and a surfactant. It is necessary for the photopolymer to add a surfactant to easily disperse into the water and maintain a dispersed state in the water. Preferred surfactants are sodium alkyl-naphthalenesulfonate and sodium alkylbenzenesulfonate. Examples of other surfactants include anionic surfactants, including carboxylates, sulfate-esters, sulfonates, or phosphate-esters; non-ionic surfactants, such as polyethylene glycol derivatives, polyhydric alcohols Derivatives and sorbitan derivatives; cationic surfactants, including primary, secondary, tertiary amine salts or quaternary ammonium salts; and amphoteric surfactants containing amino acid hydrophilic groups or betaine hydrophilic groups. Preferred alkali metal compounds are hexametaphosphate: sodium, sodium tripolyphosphate, sodium hydroxide and sodium carbonate. The rinse solution should be at 25. -Use at 50 ° C, preferably -14-588216. 5. Description of the invention (13) is 30 ° -40 & c. The concentration of surfactant in water is not limited, but usually the IS range is from about 0.5% to about 4%. Although the skin is most often dissolved with an aqueous developer for night spraying, development and development, the other techniques mentioned above can be used for development. If necessary, a defoamer (such as a silicone antifoaming agent) can be added to the aqueous developer. Solution. After the development step, the photosensitive resin partially polymerized on the substrate and the sides of the board can be cured in an oxygen-absorbing compound (such as sodium bisulfite) solution by exposing it to actinic radiation to prevent oxygen from inhibiting the polymerization reaction. . The two boards are then exposed to actinic radiation with a wavelength from about 200 nm to about 300 nm to obtain permanent non-stickiness. Preferred actinic radiation has a wavelength of 2 54 nm and can be generated by a germicidal lamp, such as a Voltarc GRFX 5058 lamp manufactured by Voltarc Technologies. The debonding reaction is preferably performed at a temperature from about 100 ° F to about 40 ° F. More preferably, the debinding reaction is performed at a temperature of from about 125 ° F to about 140 ° F. The following examples provide better disclosure and teaching for preparing the photosensitive resin composition and printing plate of the present invention. These examples are for illustrative purposes only, and it is understood that changes and modifications can be made without substantially affecting the spirit and scope of the present invention, such as in the scope of the patent application described below. The general procedure is to measure the surface adhesion of the printed board by separating the stress required for the steel feet that have been imposed on the surface of the sample plate. This measurement uses the European and American force gauge of model DFU-2 produced by Omega Engineering Co. . The following description 588216 5. Description of the invention (14) A detailed method for measuring surface adhesion as mentioned above. The printed board is joined to a horizontal support with the relief surface of the board directly facing up. A steel foot with a radius of 0.25 " connected to a digital force gauge was brought into contact with the flat portion of the relief surface of the board. A 500 gram load measured by the European and American plus force meter was applied to the steel feet and held for 10 seconds. Next, lift the foot up at a fixed lifting rate of 0.5 inches / minute until the board is separated from the foot. The stress 测量 is measured only with a European and American force gauge before the board is separated from the feet. The tackiness of the printing plate prepared according to the present invention is 50 g or less, preferably 25 g or less, as measured using the above procedure. The photopolymerizable composition of each of the following examples formed a photocopolymer printing plate according to the following procedure. A 0.250 " thick photosensitive resin composition layer was formed between a polyester backing plate coated with an adhesive and a masking plate of a polypropylene film using a Merigiraph® type 3048 exposure unit. The photoresin is separated from the photographic film as shown in the clarification. The photopolymer received a 2:30 back exposure and then exposed through the negative image at 6:00. After exposure, the mask and uncured resin were removed at 35-4 ° C using a spraying aqueous solution for ten minutes to remove to obtain a relief. The aqueous solution included 2% by weight of Marie Graffen. Scale agent W64 10L and 2% by weight of sodium triphosphate. The board was then immersed in an aqueous sodium bisulfite solution and exposed to actinic radiation having a minimum intensity of 8 mW / cm² to completely harden the relief portion of the board. The board is then dried at 40 ° C for 30 to 45 minutes. Then the board is subjected to a post-drying exposure step under a germicidal lamp for about 10 to 20 minutes, where the germicidal lamp is a voltac GRFX 505 8 germicidal lamp column and placed -1 6-588216 V. Description of the invention (15) At a distance of about 15 cm from the surface of the photopolymer printing plate. Measure the surface adhesion of each plate as described above. By using an uncoated polyester at 0.04 A 0.040 "thick photosensitive resin composition layer was cast between the sheet and the polypropylene film to harden the photosensitive resin composition to measure tensile strength and elongation. The photopolymer was exposed for 30 seconds on the back and 400 seconds on the front. Peel poly And polypropylene film, and die-cutting the sample in accordance with ASTM D-4 12 to test the tension. The hardened sample was exposed to a metal-halide type, model M-59, which was illuminated from Coope r The 400 watt lamp was used to test the UV aging resistance of the sample. The intensity of UV light was measured with the IL1 400A radiation meter of International Lighting Co., Ltd. The lamp was installed at a distance above the sample to produce 1000 microwatts per square centimeter. The intensity is measured by UV. The imaged 0.250 "board or 0. 040" thick solid sheet is continuously irradiated for 120 hours, and then checked to determine the damage resistance or tensile strength of the symbols in the imaged board and Extensibility of sheet. Sinus example 1
將1 349克（ 0.429莫耳）的亞克克蘭320 5、90克（0.515 莫耳）的TDI及〇.1〇克的二丁基錫二月桂酸酯（DBtDl)催 化劑充入配有氮淸洗、空氣攪拌器及熱電偶之2升樹脂壺 。在起始的放熱反應後，將反應混合物保持在6(rc下2小 時直到異氰酸酯的濃度到達〇 . 5 〇重量％，其可利用滴定法 以二-正丁基胺來測定。然後將丨6〇 . 〇克（〇 . 42丨莫耳）的多 丙二醇單甲基丙烯酸酯（„ 3δ〇克/莫耳）、16克的BHT -17- 五、發明說明（16) 及0.06克的DBTDL混合物加入反應混合物，及將該內容 物維持在6(TC下另一個2小時，直到滴定法指出並無殘餘 的異氰酸酯。 將1 4 . 5克的多丙二醇單甲基丙烯酸酯、7 . 2克的甲基丙 烯酸月桂酯、0 · 9克的三羥甲基丙烷三甲基丙烯酸酯、3 . 0 克的四乙二醇二甲基丙烯酸酯、1 . 8克的甲基丙烯酸N，N-二乙基胺基乙酯、0.5克的咢加昆爾651、0.1克的BHT 及2.0克的4 -羥基苯甲酸加入至70.0克產生的胺基甲酸 乙酯預聚物。將所得的混合物攪拌2小時以獲得感光樹脂 組成物。測量以該樹脂製成的光聚合物印刷板或〇 , 040”厚 的薄板之張力特性。硬化的樣品之張力強度及延伸度各別 地爲1 3 3 1磅/平方英寸及3 3 0%。在UV老化1 2 0小時後， 張力強度及延伸度爲1023磅/平方英寸及27 0%。在曝露至 殺菌燈15分鐘之前及之後測量由該感光樹脂製得之光聚 合物印刷板的表面黏著，而顯示在表1。 上述之光可聚合的樹脂可根據下列程序形成光聚合物印 刷板。使用瑪俐葛來芙⑧型式3048的曝光單位，在塗佈著 黏著劑的聚酯背板及聚丙烯薄膜遮板間形成一層〇 . 250 "厚 的感光樹脂組成物層，其將光樹脂與照相底片分離。光聚 合物接受2 : 00的背面曝光，接著透過底片影像曝光5 : 3 0。在曝光後，移除遮板及未硬化的樹脂在3 5 - 4 0 °C下利 用噴灑水性溶液沖洗移除十分鐘以獲得凸版，該水性溶液 包括2重量％的瑪俐葛來芙®沖洗去垢劑W64 1 0L及2重量％ -18- 588216 五、發明說明（彳7) 的三磷酸鈉。然後將該板子浸入重亞硫酸鈉水溶液中，及 將其在具有最小強度9毫瓦/平方公分的光化輻射下接受 後曝光以完全地硬化板子的凸版部分。然後將板子在50°C 下乾燥30分鐘。然後將板子在殺菌燈下接受乾燥後曝光 步驟1 5分鐘。使用因此製備的印刷板來印刷33，000片的 起皺片。墨水轉換、覆蓋及顏色密度皆優良，及在製造數 片額外的薄板後任何沉積在板子上的紙塵或纖維變得容易 釋放。在全部操作期間並不需要停止印刷機來淸潔板子。 實例2 根據實例1之程序製備感光樹脂，除了使用1 . 0克的4 -甲氧基苯甲酸取代4 -羥基苯甲酸。硬化的樣品之張力強度 及延伸度各別地爲1 240磅/平方英寸及315%。在UV老化 120小時後，張力強度及延伸度爲1 075磅/平方英寸及 285% °在曝露至殺菌燈1 5分鐘之前及之後測量從該感光 樹脂製得之光聚合物印刷板的表面黏著，其顯示在表1。 實例3 根據實例1之程序製備感光樹脂，除了使用1 . 7克的2 -_吩_酸取代‘羥基苯甲酸。硬化的樣品之張力強度及延 伸度各別地爲1 1〇〇磅/平方英寸及340%。在UV老化120 小時後’張力強度及延伸度爲800磅/平方英寸及280%。 & _ H至殺菌燈20分鐘之前及之後測量從該感光樹脂製 得之光聚合物印刷板的表面黏著，其顯示在表i。 實例4 -19- 五、發明說明（18) 根據實例1之程序製備感光樹脂，除了使用丨.5克的4 -經基苯甲酸甲酯取代4 _羥基苯甲酸。硬化的樣品之張力強 度及延伸度各別地爲1 225磅/平方英寸及300%。在UV老 化1 20小時後，張力強度及延伸度爲n 60磅/平方英寸及 2 8 0% °在曝露至殺菌燈1 5分鐘之前及之後測量從該感光 樹脂製得之光聚合物印刷板的表面黏著，其顯示在表1。 實例5 根據實例1之程序製備感光樹脂，除了使用〇 . 7克的 2，4 -己二烯酸取代4 -羥基苯甲酸。硬化的樣品之張力強度 及延伸度各別地爲900磅/平方英寸及3 1 5%。在UV老化 120小時後，張力強度及延伸度爲700磅/平方英寸及 27 5%。在曝露至殺菌燈20分鐘之前及之後測量從該感光 樹脂製得之光聚合物印刷板的表面黏著，其顯示在表1 實例6 將7 0 . 0克實例1的聚胺甲酸酯預聚物與1 4 . 5克的多丙 二醇單甲基丙烯酸酯、7 . 2克的甲基丙烯酸月桂酯、〇 . 9 克的三羥甲基丙烷三甲基丙烯酸酯、3 . 0克的四乙二醇二 甲基丙烯酸酯、0 . 5克的咢加昆爾 65 1、0 . 1克的BHT及 2 . 0克的4 -羥基苯甲酸混合2小時以製備感光樹脂。將該 樹脂製成光聚合物印刷板或〇 . 040”厚的薄板以測量張力特 性。硬化的樣品之張力強度及延伸度各別地爲1 3 3 1磅/平 方英寸及3 3 0%。在UV老化120小時後，張力強度及延伸 度爲1 023磅/平方英寸及270%。在曝露至殺菌燈1 5分鐘 -20- 588216 五、發明說明（19 ) 之前及之後測量從該感光樹脂製得之光聚合物印刷板的表 面黏著，其顯示在表1。 使用上述的感光樹脂，使用實例1之程序製備印刷板。 使用此印刷板印刷超過1 5，000片起皺片。在此測試期間 不須停止印刷機來淸潔板子。在全部的測試中在印刷板上 在符號邊並無產生乾燥的墨水或紙纖維。 實例7 根據實例1之程序製備感光樹脂，除了使用1 . 5克的4 -羥基苯甲酸外。硬化的樣品之張力強度及延伸度各別地爲 1 220磅/平方英寸及320%。在UV老化120小時後，張力 強度及延伸度爲1 060磅/平方英寸及2 7 5%。在曝露至殺菌 燈20分鐘之前及之後測量從該感光樹脂製得之光聚合物 印刷板的表面黏著，其顯示在表1。 比較例 1 〇 將7 0.0克實例1的聚胺甲酸酯預聚物、14.5克的多丙 二醇單甲基丙烯酸酯、7 . 2克的甲基丙烯酸月桂酯、0 . 9 克的三羥甲基丙烷三甲基丙烯酸酯、3 . 0克的四乙二醇二 甲基丙烯酸酯、1 . 8克的甲基丙烯酸Ν,Ν-二乙基胺基乙酯 、0.5克的咢加昆爾 651、0.1克的ΒΗΤ及0.7克的二苯 甲酮混合2小時以製備感光樹脂。硬化的樣品之張力強度 及延伸度各別地爲1 080磅/平方英寸及3 00%。在UV老化 1 20小時後，無法測量張力強度及延伸度。在短時間如24 小時的老化後，張力強度及延伸度已降低至400磅/平方 -21 - 588216 五、發明說明（2〇 ) 英寸及1 50%。在曝露至殺菌燈7 . 5分鐘之前及之後測量從 該感光樹脂製得之光聚合物印刷板的表面黏著，其顯示在 表1。 比較例2 將7 0 . 0克實例1的聚胺甲酸酯預聚物、丨4 . 5克的多丙 二醇單甲基丙烯酸酯、7 . 2克的甲基丙烯酸月桂酯、〇 . 9 克的三羥甲基丙烷三甲基丙烯酸酯、3 . 0克的四乙二醇二 甲基丙烯酸酯、1 . 8克的甲基丙烯酸N，N -二乙基胺基乙酯 、〇.5克的咢加昆爾6 5 1、0 . 1克的BHT及2 . 0克的宣蔻 酸混合2小時以製備感光樹脂。硬化的樣品之張力強度及 延伸度各別地爲1 200磅/平方英寸及3 30%。在UV老化 120小時後，張力強度及延伸度爲980磅/平方英寸及 290%。在曝露至殺菌燈1 5分鐘之前及之後測量從該感光 樹脂製得之光聚合物印刷板的表面黏著，其顯示在表1。 根據實例1之方法用此感光樹脂製備印刷板及用來印刷 2 5, 000片起皺片。印刷機在約每3000至40 00片後必需停 止’以移除在印刷板上已產生及不釋放的乾墨水及紙纖維 -22- 588216 五、發明說明（21 ) I丄：光聚合物板之表面黏著· 實例 在254奈米輻照 之前的表面黏著 在254奈米輻照之後 的表面黏著 殺菌燈的後曝光時間 1 304 2 15 2 275 0 15 3 150 10 20 4 257 0 15 5 365 24 20 6 320 2 15 7 233 1 20 比較例1 330 18 7.5 比較例2 240 225 15 注意：在將板子表面曝露至以水爲基底的墨水及以水爲基 底的墨水淸潔劑淸潔之後測量表面黏著。 -23-Charge 1 349 grams (0.429 moles) of Akram 320 5, 90 grams (0.515 moles) of TDI and 0.10 grams of dibutyltin dilaurate (DBtDl) catalyst with nitrogen scrubbing , 2 liter resin kettle of air stirrer and thermocouple. After the initial exothermic reaction, the reaction mixture was maintained at 6 ° C for 2 hours until the isocyanate concentration reached 0.50% by weight, which can be determined by titration with di-n-butylamine. 〇〇〇〇 (〇42 丨 mol) of polypropylene glycol monomethacrylate ("3δ〇g / mol), 16 grams of BHT-17- 5. Description of the invention (16) and 0.06 grams of DBTDL mixture The reaction mixture was added and the contents were maintained at 6 ° C for another 2 hours until no residual isocyanate was indicated by titration. 14.5 grams of polypropylene glycol monomethacrylate, 7.2 grams of Lauryl methacrylate, 0.9 g of trimethylolpropane trimethacrylate, 3.0 g of tetraethylene glycol dimethacrylate, 1.8 g of N, N-dimethacrylate Ethylaminoethyl ester, 0.5 g of sugaquine 651, 0.1 g of BHT and 2.0 g of 4-hydroxybenzoic acid were added to 70.0 g of the resulting urethane prepolymer. The resulting mixture was stirred 2 Hours to obtain a photosensitive resin composition. Measure a photopolymer printed board made of the resin or 0,040 Tensile properties of thick thin plates. Tensile strength and elongation of the hardened samples were 1 3 31 psi and 3 30%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 1023 Pounds per square inch and 27.0%. The surface adhesion of a photopolymer printing plate made of the photosensitive resin was measured before and after 15 minutes of exposure to the germicidal lamp, and is shown in Table 1. The above-mentioned photopolymerizable resin may be A photopolymer printing plate was formed according to the following procedure. Using an exposure unit of the Marie Greve type 3048, a layer of 0.250 " thick is formed between a polyester backing plate coated with an adhesive and a polypropylene film shutter. Photosensitive resin composition layer, which separates the photoresist from the photographic film. The photopolymer is exposed at 2:00 on the back, and then exposed through the film image at 5:30. After exposure, the mask and uncured resin are removed. Rinse with a spraying aqueous solution at 3 5-40 ° C for ten minutes to obtain a relief. The aqueous solution includes 2% by weight of Mary Greve® Rinse and Remover W64 1 0L and 2% by weight -18- 588216. V. Description of the invention () 7) Triphosphate Sodium. The board was then immersed in an aqueous solution of sodium bisulfite and subjected to post-exposure under actinic radiation with a minimum intensity of 9 mW / cm² to completely harden the relief portion of the board. The board was then placed at 50 ° C Dry for 30 minutes. Then the board was subjected to a post-drying exposure step for 15 minutes under a germicidal lamp. The printed board thus prepared was used to print 33,000 creped sheets. Ink conversion, coverage and color density were excellent, and in the manufacturing After a few extra sheets, any paper dust or fibers deposited on the board becomes easy to release. There is no need to stop the printing press to clean the board during all operations. Example 2 A photosensitive resin was prepared according to the procedure of Example 1, except that 1.0 g of 4-methoxybenzoic acid was used instead of 4-hydroxybenzoic acid. The tensile strength and elongation of the hardened samples were 1 240 psi and 315%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 1 075 psi and 285% °. The surface adhesion of the photopolymer printing plate made from the photosensitive resin was measured before and after 15 minutes of exposure to the germicidal lamp. , Which is shown in Table 1. Example 3 A photosensitive resin was prepared according to the procedure of Example 1, except that 1.7 g of 2-phenic acid was used in place of 'hydroxybenzoic acid. The tensile strength and elongation of the hardened samples were 110 psi and 340%, respectively. After 120 hours of UV aging 'the tensile strength and elongation were 800 psi and 280%. The surface adhesion of the photopolymer printing plate made from the photosensitive resin was measured before and after 20 minutes from the germicidal lamp, and is shown in Table i. Example 4 -19- V. Description of the invention (18) A photosensitive resin was prepared according to the procedure of Example 1, except that 1.5 g of 4-hydroxymethylbenzoate was used instead of 4-hydroxybenzoic acid. The tensile strength and elongation of the hardened samples were 1 225 psi and 300%, respectively. After UV aging for 1 to 20 hours, the tensile strength and elongation were n 60 psi and 280% °. Photopolymer printing plates made from the photosensitive resin were measured before and after 15 minutes of exposure to the germicidal lamp. The surface is adhered, which is shown in Table 1. Example 5 A photosensitive resin was prepared according to the procedure of Example 1, except that 0.7 g of 2,4-hexadienoic acid was used instead of 4-hydroxybenzoic acid. The tensile strength and elongation of the hardened samples were 900 psi and 3 15%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 700 psi and 27 5%. The surface adhesion of the photopolymer printing plate made from the photosensitive resin was measured before and after being exposed to the germicidal lamp for 20 minutes, which is shown in Table 1. Example 6 70.0 g of the polyurethane of Example 1 was prepolymerized With 14.5 grams of polypropylene glycol monomethacrylate, 7.2 grams of lauryl methacrylate, 0.9 grams of trimethylolpropane trimethacrylate, 3.0 grams of tetraethyl Diethylene glycol dimethacrylate, 0.5 g of sugaquin 65, 0.1 g of BHT, and 2.0 g of 4-hydroxybenzoic acid were mixed for 2 hours to prepare a photosensitive resin. This resin was made into a photopolymer printed board or a 0.040 "thick sheet to measure the tensile properties. The tensile strength and elongation of the hardened samples were 1 3 31 psi and 3 30%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 1023 pounds per square inch and 270%. After exposure to the germicidal lamp for 15 minutes -20- 588216 V. Description of the invention (19) Before and after measurement from the photosensitive resin The surface of the obtained photopolymer printing plate was adhered, and the results are shown in Table 1. Using the above-mentioned photosensitive resin, a printing plate was prepared using the procedure of Example 1. This printing plate was used to print more than 5,000 corrugated sheets. Here It is not necessary to stop the printer to clean the board during the test. In all the tests, no dry ink or paper fibers were produced on the sides of the symbols on the printed board. Example 7 A photosensitive resin was prepared according to the procedure of Example 1, except that 1.5 was used. Grams of 4-hydroxybenzoic acid. The tensile strength and elongation of the hardened samples were 1 220 psi and 320%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 1 060 psi. Inch and 2 7 5%. In exposure The surface adhesion of the photopolymer printing plate made from the photosensitive resin was measured before and after the sterilization lamp for 20 minutes, and the results are shown in Table 1. Comparative Example 10 〇7 0.0 g of the polyurethane prepolymer of Example 1, 14.5 grams of polypropylene glycol monomethacrylate, 7.2 grams of lauryl methacrylate, 0.9 grams of trimethylolpropane trimethacrylate, 3.0 grams of tetraethylene glycol dimethyl Acrylate, 1.8 g of Ν, Ν-diethylaminoethyl methacrylate, 0.5 g of Ingaquin 651, 0.1 g of BHT and 0.7 g of benzophenone were mixed for 2 hours to prepare a photosensitizer Resin. Tensile strength and elongation of hardened samples are 1080 psi and 300% respectively. Tensile strength and elongation cannot be measured after UV aging for 1 to 20 hours. Aging in a short time, such as 24 hours After that, the tensile strength and elongation have been reduced to 400 lbs / sq. -21-588216. 5. Description of the invention (20) inches and 150%. 7.5 minutes before and after exposure to the germicidal lamp. The surface of the obtained photopolymer printing plate was adhered, and it is shown in Table 1. Comparative Example 2 7 0 0 grams of the polyurethane prepolymer of Example 1, 4.5 grams of polypropylene glycol monomethacrylate, 7.2 grams of lauryl methacrylate, 0.9 grams of trimethylolpropane Trimethacrylate, 3.0 g of tetraethylene glycol dimethacrylate, 1.8 g of N, N-diethylaminoethyl methacrylate, 0.5 g of sagaquinol 6.5 1.1 g of BHT and 2.0 g of myristic acid were mixed for 2 hours to prepare a photosensitive resin. The tensile strength and elongation of the hardened samples were 1 200 psi and 3 30%, respectively. After 120 hours of UV aging, the tensile strength and elongation were 980 psi and 290%. The surface adhesion of the photopolymer printing plate made from the photosensitive resin was measured before and after 15 minutes of exposure to the germicidal lamp, and is shown in Table 1. A printing plate was prepared from this photosensitive resin according to the method of Example 1 and used for printing 25,000 sheets of corrugated sheets. The printing machine must be stopped after every 3,000 to 40,000 pieces' to remove the dry ink and paper fibers that have been generated and not released on the printing plate-22-588216 V. Description of the invention (21) I 丄: Photopolymer plate Surface adhesion · Example Surface adhesion before 254 nm irradiation Surface adhesion after 254 nm irradiation Post-exposure time of germicidal lamp 1 304 2 15 2 275 0 15 3 150 10 20 4 257 0 15 5 365 24 20 6 320 2 15 7 233 1 20 Comparative Example 1 330 18 7.5 Comparative Example 2 240 225 15 Note: After exposing the surface of the board to water-based ink and water-based ink cleaner, measure the surface Sticky. -twenty three-