TWI434888B - Heat sensitive composition and use thereof - Google Patents
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本發明係關於一種熱敏組合物，尤指一種可用於熱敏平版印刷中之熱敏性塗料組合物，及使用該熱敏組合物製造圖像的方法。The present invention relates to a heat sensitive composition, and more particularly to a heat sensitive coating composition useful in thermal lithography, and a method of making an image using the heat sensitive composition.
習知的印刷技術，主要分成四大類方法：凹版印刷、凸版印刷、網版印刷，以及平版印刷。The conventional printing techniques are mainly divided into four major types of methods: gravure printing, letterpress printing, screen printing, and lithography.
上述平版印刷，其係一種間接印刷。透過滾輪塗佈上油墨後再經由一個中介的膠皮版(blanket)轉印到基材上，即如紙張、布料等表面。而其上墨的原理是利用油水不互溶的原理，使得親油區與親水區對油墨具有不同的親合力，當施加油墨(ink)時，非圖像區吸著水而排斥油墨，同時圖像區(image area)接受油墨而排斥水。The above lithographic printing is an indirect printing. The ink is applied through a roller and then transferred to a substrate via an intermediate rubber blanket, such as a surface such as paper or cloth. The principle of inking is to use the principle that oil and water are not mutually soluble, so that the oleophilic zone and the hydrophilic zone have different affinity for the ink. When the ink is applied, the non-image area absorbs water and repels the ink, and at the same time The image area accepts ink and repels water.
平版印刷常見的兩種主要方法為：PS(presensitized plate)版印刷及CTP(computer to plate)版印刷。PS版主要是利用一個底片或是光阻的選擇性曝光來達到製作圖像的目的，其缺點為底片或光阻的製作與黃光室的使用(PS常以紫外光為光源)，以及需要人工校正的技術問題。The two main methods common to lithography are: PS (presensitized plate) printing and CTP (computer to plate) printing. The PS version mainly uses a negative exposure of a negative film or photoresist to achieve the purpose of image production. The disadvantages are the fabrication of the negative film or photoresist and the use of the yellow light chamber (PS often uses ultraviolet light as a light source), and Manually corrected technical issues.
近來使用CTP版來取傳統PS版，CTP版由於透過電腦控制熱源，因此不需要人工校正印版的動作以及無需使用黃光室，可在一般室內製版，而且製版效率、輸出速度與印量相較於PS版皆較為優異。Recently, the CTP version is used to take the traditional PS version. Since the CTP version controls the heat source through the computer, there is no need to manually correct the movement of the printing plate and the need to use the yellow light chamber, and it can be used in general indoor printing, and the plate making efficiency, output speed and printing quantity are It is superior to the PS version.
CTP製程需使用熱敏性塗料組合物，其可分為兩大類，即正型熱敏性塗料組合物和負型熱敏性塗料組合物。正型熱敏性塗料組合物：在受熱部分，會溶於顯影液；未受熱區域則不溶解。解析度比負型熱敏性塗料組合物佳，故大部分的平版印刷製程使用正型熱敏性塗料組合物。負型熱敏性塗料組合物：受熱區域會形成鏈結(cross linkage)，使結構強度增加，所以不會溶於顯影液，但未照射區則會溶解。The CTP process requires the use of a heat sensitive coating composition which can be divided into two broad categories, namely a positive heat sensitive coating composition and a negative heat sensitive coating composition. Positive heat sensitive coating composition: in the heated part, it will dissolve in the developer; in the unheated area, it will not dissolve. The resolution is better than that of the negative heat sensitive coating composition, so most of the lithographic processes use a positive heat sensitive coating composition. Negative heat-sensitive coating composition: The heat-receiving area forms a cross linkage, which increases the structural strength, so it does not dissolve in the developer, but the unirradiated area dissolves.
在平版印刷製程中的圖像區及非圖像區係經曝光過程，使該版曝露於光源(此光源由近紅外輻射(NIR)構成)後而形成。近紅外輻射較佳可直接轉成熱，或藉組合物之一種成份經由化學反應轉換成熱。如果使用正型感光版，對應於該版上之圖像區為不受光區域(area)，但對應於非圖像區則允許光線透過至正型熱敏性塗料組合物，使其變為更易溶解而去除。若是使用負型感光版則情形與上述相反。The image area and the non-image area in the lithographic process are formed by exposing the plate to a light source (this source is composed of near-infrared radiation (NIR)). The near-infrared radiation is preferably converted directly to heat or converted to heat via a chemical reaction by a component of the composition. If a positive photosensitive plate is used, the image area corresponding to the plate is an unaffected area, but corresponding to the non-image area allows light to pass through to the positive heat sensitive coating composition, making it more soluble. Remove. If a negative-type photosensitive plate is used, the situation is opposite to the above.
美國專利US 6063544,US5372907,US 5340699,US 5372915,US 5466577,US 5491046及US 5663037揭露有關平版印刷的方法，唯彼等所面臨的共通問題在於單層印刷版顯像後，其顯現之圖像區常有殘像(smudging)，無法供於長時間下有效印刷，以致印刷產生之圖像清晰度及印刷品質均差。U.S. Patent No. 6, 635, 435, U.S. Patent No. 5, 372, 907, U.S. Patent No. 5, 340, 699, U.S. Patent No. 5, 729, s, U.S. Patent No. 5, 466, 577, U.S. Patent No. 5, 491, 046, and U.S. Patent No. 5, 663, 037, each of which are incorporated herein by reference. The area often has smudging, which cannot be used for effective printing for a long time, so that the image clarity and printing quality produced by printing are poor.
美國專利US 6352811、US 6358669、US 6440633、US 6534238、US 6537735、US 6555291、US 6649324及US 7582407係針對US 6280899提出改良技術。An improved technique is proposed for US 6,280,899 for U.S. Patent No. 6,528, 811, U.S. Patent No. 6,358,669, U.S. Patent No. 6,406, 533, U.S. Patent No. 6,534, 238, U.S. Pat.
以US 6440633為例，該文中提及先前技術多層的系統係用以改善原先組成物(親油性)與基材(親水性)密著不佳的問題，但多層系統中仍存在著許多問題，如：顯影後殘污(smudging)的產生，然單層印刷版亦存在相同的問題。因此，如何有效的改善習知單層印刷版所面臨的問題，是相對而言較為重要的發展方向。Taking US 6440633 as an example, the prior art multi-layer system is mentioned to improve the poor adhesion between the original composition (lipophilic) and the substrate (hydrophilic), but there are still many problems in the multi-layer system. Such as: the occurrence of smudging after development, but the same problem exists in single-layer printing plates. Therefore, how to effectively improve the problems faced by conventional single-layer printing plates is a relatively important development direction.
台灣專利TW 583508、TW 200617591及TW 584787揭示嘗試改進印刷圖像之清晰度及印刷品質之內容，其特點在於添加交聯劑與熱化學酸/光酸產生劑(photoacid generators)，來改善原有顯影與剝除的均質性。該等技術乃針對熱敏組合物添加交聯劑與熱化學酸，而熱化學酸可能使組合物的儲存性變差，特別當存在於組合物中的熱化學酸在未塗佈前，於紫外輻射的條件下易導致質變。因此，習知組合物中需要額外添加酸安定劑作為安定的组份。但是，於熱敏組合物中添加交聯劑與熱化學酸，並不能改善原先組合物耐溶劑性。Taiwan patents TW 583508, TW 200617591 and TW 584787 disclose attempts to improve the clarity and print quality of printed images, which are characterized by the addition of cross-linking agents and photochemical generators to improve the original The homogeneity of development and stripping. These techniques are directed to the addition of a crosslinking agent and a thermochemical acid to the heat sensitive composition, while the thermochemical acid may degrade the storage properties of the composition, particularly when the thermochemical acid present in the composition is uncoated before Under the condition of ultraviolet radiation, it is easy to cause qualitative change. Therefore, an additional acid stabilizer is required in the conventional composition as a stable component. However, the addition of a crosslinking agent to a thermochemical acid in the thermosensitive composition does not improve the solvent resistance of the original composition.
平版印刷技術係根據油及水不相混的特性，其中油性物質或油墨(ink)被吸著於圖像區(image area)，而非圖像區係具親水性，潤版液則被吸著於非圖像區，該潤版液會防止油墨黏著於非影像區。當適當調配之表面施加油墨時，非圖像區排斥油墨，同時圖像區接受油墨，隨後圖像區上之油墨轉移至待複製圖像之材料表面，即如紙張、布料等表面。但是，由於潤版液中含有溶劑，會慢慢侵蝕圖像區，減少印刷版的使用壽命，因此，如何讓熱敏組合物對潤版液具有耐溶劑性，成為平版印刷技術的重要課題，惟先前技術中鮮有討論如何提升組合物對潤版液之耐溶劑性。The lithographic technique is based on the characteristics of oil and water that are not miscible, in which an oily substance or ink is absorbed into the image area, while the non-image area is hydrophilic, and the fountain solution is sucked. In the non-image area, the dampening solution prevents the ink from sticking to the non-image area. When the ink is applied to the surface to be properly formulated, the non-image area repels the ink while the image area receives the ink, and then the ink on the image area is transferred to the surface of the material of the image to be reproduced, that is, a surface such as paper, cloth, or the like. However, since the fountain solution contains a solvent, it will slowly erode the image area and reduce the service life of the printing plate. Therefore, how to make the thermosensitive composition have solvent resistance to the fountain solution is an important issue in lithographic printing technology. However, there has been little discussion in the prior art on how to improve the solvent resistance of the composition to fountain solutions.
鑒此，本發明之目的係提供一種對潤版液具較高耐溶劑性之熱敏組合物，其可應用於熱敏平版印刷製程中。本發明之熱敏組合物包含(a)酚醛樹脂，(b)溶解抑制劑，(c)具紅外輻射吸收性化合物及(d)耐溶劑性添加劑。Accordingly, it is an object of the present invention to provide a heat sensitive composition having a high solvent resistance to fountain solutions which can be used in a thermal lithography process. The heat-sensitive composition of the present invention comprises (a) a phenol resin, (b) a dissolution inhibitor, (c) an infrared radiation absorbing compound, and (d) a solvent resistance additive.
本發明另一目的係提供一種使用上述熱敏組合物以製造圖像的方法。Another object of the present invention is to provide a method of producing an image using the above heat sensitive composition.
除非另外說明，本說明書中所有組合物的含量百分比皆為重量百分比。All percentages of the compositions in this specification are by weight unless otherwise indicated.
本發明組合物中，以整體組合物之100重量%固成份重量計，組分(a)酚醛樹脂之含量為50~99重量%，較佳為60~95重量%；組分(b)溶解抑制劑之用量為0.1~45重量%，較佳為1~35重量%；組分(c)具紅外輻射吸收性化合物之用量為0.5~10重量%，較佳為1~6重量%；及組分(d)耐溶劑性添加劑之用量為0.1~40重量%，較佳為1~20重量%。In the composition of the present invention, the content of the component (a) phenolic resin is 50 to 99% by weight, preferably 60 to 95% by weight, based on 100% by weight of the solid component of the whole composition; the component (b) is dissolved. The inhibitor is used in an amount of 0.1 to 45% by weight, preferably 1 to 35% by weight; and the component (c) has an infrared radiation absorbing compound in an amount of 0.5 to 10% by weight, preferably 1 to 6% by weight; The component (d) solvent-resistant additive is used in an amount of from 0.1 to 40% by weight, preferably from 1 to 20% by weight.
本發明所使用之酚醛樹脂，為適當酚類與適當醛類行縮合反應而得之聚合物。適當酚類，例如但不限制於酚、甲酚、二甲酚、對第三丁基酚、對苯酚、壬酚或雙酚A(2,2-雙(4-羥苯基)丙烷；2,2-Bis(4-hydroxyphenyl) propane)。適當醛類，例如但不限制於甲醛、三氯乙醛、乙醛或糠醛。本發明較佳之酚醛樹脂為線性酚醛樹脂(novolak resin)。The phenol resin used in the present invention is a polymer obtained by subjecting a suitable phenol to a condensation reaction with an appropriate aldehyde. Suitable phenols such as, but not limited to, phenol, cresol, xylenol, p-tert-butylphenol, p-phenol, indophenol or bisphenol A (2,2-bis(4-hydroxyphenyl)propane; , 2-Bis(4-hydroxyphenyl) propane). Suitable aldehydes such as, but not limited to, formaldehyde, trichloroacetaldehyde, acetaldehyde or furfural. A preferred phenolic resin of the invention is a novolak resin.
可用於本發明之溶解抑制劑係選自由含氮化合物、羰基化合物、茂鐵鎓化合物、馬來酐衍生物及其混合所構成之群組，較佳之溶解抑制劑係選自由含氮化合物、馬來酐衍生物及其混合所構成之群組。The dissolution inhibitor which can be used in the present invention is selected from the group consisting of a nitrogen-containing compound, a carbonyl compound, a ferrocenium compound, a maleic anhydride derivative, and a mixture thereof. Preferably, the dissolution inhibitor is selected from the group consisting of nitrogen-containing compounds and horses. A group consisting of an anhydride derivative and a mixture thereof.
可用於本發明組合物中作為溶解抑制劑之含氮化合物包含第四化氮化合物、含氮雜環化合物或第四化雜環族環氮化合物。上述第四化氮化合物係指三芳基甲銨，例如三(對-二甲基胺基苯基)甲烷、或乙基紫或四烷基銨化合物。其中四烷基銨化合物，例如溴化十六基三甲銨(Cetrimide)。上述含氮雜環化合物係指喹啉或***化物，如1,2,4-***化物。上述第四化雜環族環氮化合物係指咪唑啉鎓化合物、吡鎓化合物、喹啉鎓化合物(如喹啉鎓陽離子性花青染料)或苯并噻唑鎓化合物(如苯并噻唑鎓陽離子性花青染料，其例如但不限於1,1'-二甲基-2,2'-羰花青碘(Quinaldine blue)，3-乙基-2-[3-(3-乙基-2(3H)-亞苯并碱唑醯基)-2-甲基-1-丙烯基]苯并噻唑鎓碘化物)。The nitrogen-containing compound which can be used as a dissolution inhibitor in the composition of the present invention contains a fourth nitrogen compound, a nitrogen-containing heterocyclic compound or a fourth-substituted heterocyclic ring nitrogen compound. The above-mentioned fourth nitrogen compound means triarylmethylammonium such as tris(p-dimethylaminophenyl)methane or ethyl violet or tetraalkylammonium compound. Among them, a tetraalkylammonium compound such as Cetrimide bromide. The above nitrogen-containing heterocyclic compound means a quinoline or a triazole compound such as a 1,2,4-triazole compound. The above fourth heterocyclic ring nitrogen compound means an imidazolinium compound, a pyridinium compound, a quinolinium compound (such as a quinolinium cationic cyanine dye) or a benzothiazolium compound (such as a benzothiazolium cation). Cyanine dyes such as, but not limited to, 1,1'-dimethyl-2,2'-carbocyanine iodine (Quinaldine blue), 3-ethyl-2-[3-(3-ethyl-2() 3H)-Biabenzoxazinyl)-2-methyl-1-propenyl]benzothiazolium oxime iodide).
可用於本發明組合物中作為溶解抑制劑之羰基化合物，例如但不限於α-萘并黃素酮，β-萘并黃素酮，2,3-二苯基-1-茚酮，黃素酮，黃素烷酮，黃酮(xanthone)，二苯甲酮，N-(4-溴丁基)酞二醯亞銨或菲醌或其混合物。A carbonyl compound useful as a dissolution inhibitor in the compositions of the present invention, such as, but not limited to, alpha-naphthoflavinone, beta-naphthoflavinone, 2,3-diphenyl-1-indanone, flavin Ketone, flavogenone, xanthone, benzophenone, N-(4-bromobutyl)phosphonium iodide or phenanthrenequinone or a mixture thereof.
可用於本發明組合物中作為溶解抑制劑之鐵茂鎓(ferrocenium)化合物，例如可為鐵茂鎓六氟磷酸酯。A ferrocenium compound which can be used as a dissolution inhibitor in the composition of the present invention may be, for example, iron lanthanum hexafluorophosphate.
可用於本發明組合物中作為溶解抑制劑之馬來酐衍生物例如可為馬來酸半酯；苯乙烯與馬來酸之共聚合物、苯乙烯與馬來酐之共聚合物或苯乙烯與馬來酸半酯之共聚合物、丙烯酸與馬來酐之共聚合物、甲基乙烯基醚與馬來酐之共聚合物；或其混合物。The maleic anhydride derivative which can be used as a dissolution inhibitor in the composition of the present invention can be, for example, a maleic acid half ester; a copolymer of styrene and maleic acid, a copolymer of styrene and maleic anhydride or styrene. a copolymer with a maleic acid half ester, a copolymer of acrylic acid and maleic anhydride, a copolymer of methyl vinyl ether and maleic anhydride; or a mixture thereof.
為了提高熱敏組合物之敏感度，本發明組合物包含可吸收光並將其轉換成熱之紅外輻射吸收化合物(後文稱做「具紅外輻射吸收性化合物」)。具紅外輻射吸收性化合物可為染料或顏料。In order to increase the sensitivity of the thermosensitive composition, the composition of the present invention contains an infrared radiation absorbing compound (hereinafter referred to as "infrared radiation absorbing compound") which absorbs light and converts it into heat. The infrared radiation absorbing compound can be a dye or a pigment.
根據本發明之一實施例，具紅外輻射吸收性化合物吸收選定供成像之射線並將其轉成熱，上述射線可選自紅外光，例如來自紅外線雷射或二極體雷射波長830 nm射線。According to one embodiment of the invention, the infrared radiation absorbing compound absorbs the selected radiation for imaging and converts it into heat, which may be selected from infrared light, such as from an infrared laser or a diode laser having a wavelength of 830 nm. .
可用於本發明之具紅外輻射吸收性化合物可為顏料，其為黑色本體或寬譜吸收劑，例如碳黑或石墨，例如市售此類顏料例子包含如BASF供給之酞菁綠(Heliogen green)或NH實驗室公司供給之苯銨黑(Nigrosine base NG1)或Aldrich公司供給之鐵藍(Milori blue,C.I. B27)(C.I.顏料藍27)。The infrared radiation absorbing compound which can be used in the present invention may be a pigment which is a black bulk or a broad spectrum absorbent such as carbon black or graphite, for example, a commercially available pigment example includes Heliogen green as supplied by BASF. Or Nigrosine base NG1 supplied by NH Laboratories or Milori blue (CI B27) supplied by Aldrich (CI Pigment Blue 27).
具紅外輻射吸收性化合物亦可為有機顏料或染料，如酞花青顏料，或為方酸菁(squarylium)、部花青、吲哚、花青、吡喃鎓(pyrylium)，或金屬二硫啉類之染料或顏料。The infrared radiation absorbing compound may also be an organic pigment or dye such as phthalocyanine pigment, or squarylium, merocyanine, anthracene, cyanine, pyrylium, or metal disulfide. A dye or pigment of a porphyrin.
顏料通常不可溶於組合物中，故形成顆粒。其通常為廣譜吸收劑，較佳可有效吸收電磁射線並將其於超過200 nm，較佳超過400 nm範圍之射線轉成熱。顏料通常不被射線分解，對未經加熱組合物於顯影劑中之溶解度不會造成顯著影響。相反地，染料通常可溶於組合物，其通常為窄譜吸收劑，典型可有效吸收電磁波並僅於典型不超過100 nm之波長範圍將其轉成熱，因此，需就用於成像之射線波長加以選擇。Pigments are generally insoluble in the composition, thus forming granules. It is typically a broad spectrum absorber which preferably absorbs electromagnetic radiation and converts it into heat in the range of more than 200 nm, preferably in excess of 400 nm. Pigments are generally not decomposed by radiation and do not have a significant effect on the solubility of the unheated composition in the developer. Conversely, dyes are generally soluble in the composition, which is typically a narrow-spectrum absorber, typically absorbing electromagnetic waves effectively and converting them to heat only in the wavelength range typically not exceeding 100 nm, thus requiring ray for imaging The wavelength is chosen.
根據本發明之一具體實施例，較佳的具紅外輻射吸收性化合物係可吸收高於600 nm之射線之染料，其例如但不限於具下述結構的喹啉鎓花青染料：In accordance with an embodiment of the present invention, a preferred infrared radiation absorbing compound is a dye that absorbs radiation above 600 nm, such as, but not limited to, a quinolinium cyanine dye having the following structure:
上述喹啉鎓花青染料於800 nm有最大吸收值。The above quinoline phthalocyanine dye has a maximum absorption at 800 nm.
可用於本發明組合物中之耐溶劑性添加劑，可為乙酸丁酸纖維素、乙酸丙酸纖維素、硝基纖維素、(甲基)丙烯酸酯樹脂、氯醋樹脂或其混合物，較佳為乙酸丁酸纖維素或(甲基)丙烯酸酯樹脂或其組合。根據本發明之一實施例，使用乙酸丁酸纖維素除可作為耐溶劑性添加劑外，亦可作為溶解抑制劑。The solvent resistant additive which can be used in the composition of the present invention may be cellulose acetate butyrate, cellulose acetate propionate, nitrocellulose, (meth) acrylate resin, chloroacetic resin or a mixture thereof, preferably Cellulose acetate butyrate or (meth) acrylate resin or a combination thereof. According to an embodiment of the present invention, cellulose acetate butyrate may be used as a solvent inhibitor in addition to a solvent resistance additive.
本發明組合物視需要可加入此技術領域具有通常知識者所熟知之添加物，其例如，但不限於，酸安定劑、濕潤劑、界面活性劑、增塑劑、惰性著色劑，及/或惰性聚合物黏結劑或填料或其組合。舉例言之，本發明組合物可含有著色劑(指示劑染料)，其於印刷版顯像後有助肉眼鑑別圖像區。本發明組合物亦可含有任何一種習知之染料或顏料，例如花青色、黃色及洋紅色染料。較可取之著色劑包括維多利亞藍、海洋藍、鹼性藍、亞甲藍、結晶紫、分散紅1、4或13以及甲基紫等。The compositions of the present invention may optionally be added to the art as well known to those of ordinary skill in the art, such as, but not limited to, acid stabilizers, wetting agents, surfactants, plasticizers, inert colorants, and/or Inert polymer binder or filler or a combination thereof. For example, the compositions of the present invention may contain a colorant (indicator dye) which aids in visual identification of the image area after development of the printing plate. The compositions of the present invention may also contain any of the conventional dyes or pigments such as cyan, yellow and magenta dyes. Preferred coloring agents include Victoria Blue, Marine Blue, Basic Blue, Methylene Blue, Crystal Violet, Disperse Red 1, 4 or 13, and Methyl Violet.
本發明之組合物具有熱敏性，適用於熱敏平版印刷中作為正型熱敏性塗料組合物，藉由適當射線加熱組合物，可使曝光區對水性顯影劑的溶解度增高。The composition of the present invention is heat sensitive and is suitable for use as a positive heat sensitive coating composition in thermal lithography. By appropriately heating the composition, the solubility of the exposed area to the aqueous developer can be increased.
本發明另提供一種製造圖像之方法，該方法包含下列步驟：The invention further provides a method of manufacturing an image, the method comprising the steps of:
(i) 將本發明之熱敏組合物塗佈於基版上形成成像層(imaging layer)；(i) applying the heat sensitive composition of the present invention to a substrate to form an imaging layer;
(ii) 使該成像層之成像區曝露於一近紅外輻射之能源下，使其形成一曝露的潛像(latent image)；(ii) exposing the imaged area of the imaging layer to an energy source of near-infrared radiation to form an exposed latent image;
(iii) 使該成像區與顯影劑(devoloper)接觸，以將該成像層之該曝露區選擇地從該基版去除；(iii) contacting the imaging zone with a developer to selectively remove the exposed zone of the imaging layer from the substrate;
(iv) 於基版上塗佈潤版液；及(iv) applying a fountain solution to the base plate;
(v) 塗佈油墨進行平版印刷。(v) Coating the ink for lithography.
本發明製造圖像之方法中所使用之基版係用於平版印刷之基版，上述基版例如陽極化鋁版或多元酯薄膜，根據一具體實施例該基版可為表面已經受平版印刷業界眾所周知之尋常陽極晶粒化及後陽極處理之鋁板。The base plate used in the method for producing an image of the present invention is for use in a lithographic base plate, such as an anodized aluminum plate or a polyester film, which according to a specific embodiment may have the surface already lithographically printed Aluminium sheets that are well known in the art for conventional anode graining and post-anodizing.
使用本發明之熱敏組合物可先將其溶解於適當之有機溶劑中調製成溶液，再塗佈於選定之例如陽極化鋁版或多元酯薄膜等基版上，並使該基版表面做為印刷表面。塗佈方法可用習知之輥塗法，凹印法、滾塗法或斗式塗敷法(hopper coating)等任一方法。上述溶劑可選自例如1-甲氧基-2-乙醇、1-甲氧基-2-丙醇、丙酮、丁酮、二異丁基酮、甲基異丁基酮、正-丙醇、異丙醇、四氫呋喃、丁內酯或乳酸甲酯或其混合物，塗佈用溶劑較佳為1-甲氧基-2-丙醇、丙酮或甲基異丁基酮或其混合物。The thermosensitive composition of the present invention can be first dissolved in a suitable organic solvent to prepare a solution, and then coated on a substrate such as an anodized aluminum plate or a polyester film, and the surface of the substrate is made. For printing surfaces. The coating method may be any of a conventional roll coating method, a gravure method, a roll coating method, or a hopper coating method. The above solvent may be selected, for example, from 1-methoxy-2-ethanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, n-propanol, Isopropanol, tetrahydrofuran, butyrolactone or methyl lactate or a mixture thereof, and the solvent for coating is preferably 1-methoxy-2-propanol, acetone or methyl isobutyl ketone or a mixture thereof.
塗佈本發明組合物於基版表面後，在進行傳熱(曝露於近紅外輻射能源)之前，為增加儲存安定性，視需要可進行一熱處理，可使本發明組合物之靈敏度降低，不易隨儲存時間而產生變化。After coating the composition of the present invention on the surface of the substrate, prior to heat transfer (exposure to near-infrared radiation energy), in order to increase storage stability, a heat treatment may be performed as needed to reduce the sensitivity of the composition of the present invention. Changes with storage time.
熱敏組合物塗層於基版上之「積層量」可藉由將每單位面積以單面塗佈塗層之基材之總重量減去未塗佈前之基材重量而得。根據本發明，上述熱敏組合物塗層之積層量係介於約0.8 g/m2 至約3.5 g/m2 之間，較佳介於約1.1 g/m2 至約2.7 g/m2 之間，最佳為約1.3~2.4g/m2 。乾燥塗層係將該經塗佈組合物之基版置於能有效地去除溶劑但又不引起組合物劣化的條件下實施。塗佈層係在能有效去除溶劑且又不引起染料劣化或聚合物間之反應等條件下實行乾燥。一如前述，輻射熱敏性組合物可應用於電腦至印刷版(computer-to-plate)之圖像技藝。由於這些組合物之多功能性，使其可應用於「寫入圖像」或「寫入背景」於印刷版上。應用於「寫入圖像」時，受雷射而曝光之部份變成圖像，一如負型感光版之場合，並於雷射曝光後，將該版加熱進行交聯。然後使用適當之鹼性顯像水溶液顯像以供印刷。應用「寫入背景」時，受雷射而曝光之部份乃在顯像處理時被去除，留下之圖像區變成背景。且應用「寫入背景」時之技術時，在顯像處理前不必預熱。The "layering amount" of the thermosensitive composition coating on the substrate can be obtained by subtracting the weight of the substrate before coating without coating the total weight of the substrate per unit area coated with one side. According to the present invention, the coating layer of the above heat sensitive composition coating is between about 0.8 g/m 2 and about 3.5 g/m 2 , preferably between about 1.1 g/m 2 and about 2.7 g/m 2 . The best is about 1.3~2.4g/m 2 . The dry coating is carried out by placing the base of the coated composition under conditions effective to remove the solvent without causing deterioration of the composition. The coating layer is dried under conditions effective to remove the solvent without causing deterioration of the dye or reaction between the polymers. As mentioned above, the radiation-sensitive composition can be applied to computer-to-plate imagery. Due to the versatility of these compositions, they can be applied to "write images" or "write backgrounds" on a printing plate. When applied to "write image", the portion exposed by the laser becomes an image, as in the case of a negative-type photosensitive plate, and after laser exposure, the plate is heated and cross-linked. It is then imaged using an appropriate alkaline imaging aqueous solution for printing. When "Write Background" is applied, the portion exposed by the laser is removed during the development process, leaving the image area to become the background. When applying the technique of "writing background", it is not necessary to warm up before the development process.
本發明之製造圖像之方法中係所使用之近紅外輻射較佳係藉雷射傳送，適合波長主要於600至1400 nm之範圍，更佳為700至1200 nm之範圍，最佳為750至1150 nm之範圍。上述近紅外輻射例如為紅外光或可見光。較佳之近紅外輻射為紅外雷射光束。較佳射線係藉雷射傳送。印版最佳置於圖像整定器(imagesetter)上以利成像(imaging)。圖像整定器可輸出不同波長之紫外線、可見光或紅外線，而時下常應用於紅外線成像。可發出830 nm波長之雷射二極體陣列(array)之紅外線光源已有商業化之利用，此等雷射係由一系列之二極體光纖串連組成，總電力可在1-14瓦特之間變化，並施加一定時間以產生高達250 mJ/cm2 之成像所用能量(energy)。較佳之能量範圍為約130-210 mJ/cm2 。成像裝置機台型號：Screen 8600。The near-infrared radiation used in the method for producing an image of the present invention is preferably transmitted by laser, and the suitable wavelength is mainly in the range of 600 to 1400 nm, more preferably in the range of 700 to 1200 nm, and most preferably 750 to 750. Range of 1150 nm. The above near-infrared radiation is, for example, infrared light or visible light. Preferably, the near infrared radiation is an infrared laser beam. The preferred ray is transmitted by laser. The plates are best placed on an imageetter for imaging. The image tuner can output ultraviolet, visible or infrared light of different wavelengths, and is often used for infrared imaging. Infrared light sources that emit a laser array of 830 nm laser arrays are commercially available. These lasers are composed of a series of diode fibers connected in series, and the total power can be 1-14 watts. The time varies and is applied for a period of time to produce energy for imaging up to 250 mJ/cm 2 . A preferred energy range is from about 130 to 210 mJ/cm 2 . Imager machine model: Screen 8600.
顯影劑組合物係由聚合物質之性質決定。上述之所有塗佈組合物係用顯影劑顯像，顯影劑為完全可溶之水溶液且具有高pH值。正型感光版所常用之顯影劑最為適用於本發明之組合物。此顯影劑最能善用曝光形成之區分(differentiation)去除背景塗佈層而保留圖像，使該圖像可用以印刷。顯影劑之常見成份為界面活性劑、螯合劑如伸乙基二銨四乙酸鹽、有機溶劑如苯甲醇、及鹼性成份如無機偏矽酸鹽、有機偏矽酸鹽、氫氧化物或碳酸氫鹽；更佳水性顯影劑為含無機或有機偏矽酸鹽之鹼性顯影劑或為鹼金屬氫氧化物；最佳為有機偏矽酸鹽之鹼性顯影劑。The developer composition is determined by the nature of the polymeric material. All of the above coating compositions were developed with a developer which was a completely soluble aqueous solution and had a high pH. The developer commonly used in positive-type photosensitive plates is most suitable for use in the compositions of the present invention. This developer best utilizes the differentiation of the exposure formation to remove the background coating layer while preserving the image, making the image useful for printing. Common components of the developer are surfactants, chelating agents such as ethyl diammonium tetraacetate, organic solvents such as benzyl alcohol, and basic components such as inorganic metasilicates, organic metasilicates, hydroxides or carbonates. Hydrogen salt; a more preferred aqueous developer is an alkaline developer containing an inorganic or organic bismuth citrate or an alkali metal hydroxide; an alkaline developer which is preferably an organic bismuth citrate.
本發明製造圖像之方法適用於平版印刷，上述平版印刷技術係根據油及水不相混的特性，一般而言，圖像區具有親油性，所以油性物質，例如油墨(ink)被附著於圖像區(image area)，而非圖像區具有親水性。潤版液是一種水性混合物，其包含減感劑、pH值調節劑、緩衝劑、殺菌劑、防黴劑、潤濕劑，及溶劑，所以潤版液會被附著於非圖像區，且該潤版液會防止油墨黏著於非影像區。但由於潤版液中含有溶劑，例如異丙醇或酒精，因此會慢慢侵蝕圖像區，因而減少印刷版的使用壽命，本發明之熱敏組合物含有耐溶劑性添加劑，可以防止潤版液侵蝕圖像區，故對潤版液具有優良的耐溶劑性。The method for producing an image of the present invention is suitable for lithographic printing. The above lithographic printing technique is based on the characteristics of oil and water being immiscible. Generally, the image area is lipophilic, so that an oily substance such as an ink is attached to the ink. The image area, rather than the image area, is hydrophilic. The fountain solution is an aqueous mixture containing a desensitizer, a pH adjuster, a buffer, a bactericide, a mold inhibitor, a wetting agent, and a solvent, so that the fountain solution is attached to the non-image area, and The dampening solution prevents the ink from sticking to the non-image area. However, since the fountain solution contains a solvent such as isopropyl alcohol or alcohol, the image area is slowly eroded, thereby reducing the service life of the printing plate. The heat-sensitive composition of the present invention contains a solvent-resistant additive to prevent dampening. The liquid erodes the image area, so it has excellent solvent resistance to the fountain solution.
本發明將以下述實例作進一步之說明，然非欲以對本發明的範圍作任何限制。The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
於91.0克之1-甲氧基-2-丙醇中溶解9.00克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外線吸收染料HCD23(Hayashibara biochemical laboratories)與6.50克之三(對-二甲基胺基苯基)甲烷(優締化學)製作成塗佈組合物溶液。另準備一經過脫脂、機械粗化、陽極化及用習知之聚乙烯基膦酸處理成親水性之鋁基版，而將上述之被覆組成物溶液塗敷於該鋁基被上。被覆層之乾重為1.7g/m2 。9.00 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared absorbing dye HCD23 (Hayashibara biochemical laboratories) and 6.50 g of tris(p-dimethylaminobenzene) were dissolved in 91.0 g of 1-methoxy-2-propanol. Methane (Excellent Chemical) was prepared into a coating composition solution. Further, a solution prepared by degreasing, mechanically roughening, anodizing, and treating with a conventional polyvinylphosphonic acid to form a hydrophilic aluminum base is applied, and the above-mentioned coating composition solution is applied to the aluminum base. The dry weight of the coating layer was 1.7 g/m 2 .
將塗佈有熱敏組合物之基版置於Screen 8600 Trendsetter(圖像整定器之商品名)中，使用波長830 nm照射能量150 mJ/cm2 ，用盛有傳統正型顯影劑(13%偏矽酸鈉水溶液)之處理機中實施基版之顯像。可看到產生之正像(positive image)。但曝光區有殘影，此版無法適用於商業印刷。The substrate coated with the thermosensitive composition was placed in a Screen 8600 Trendsetter (trade name of the image setter) with an irradiation energy of 150 mJ/cm 2 at a wavelength of 830 nm and a conventional positive developer (13%). The development of the base plate was carried out in a processor of sodium metasilicate aqueous solution. You can see the positive image produced. However, there is a residual image in the exposed area, this version is not suitable for commercial printing.
進一步分別檢測，得到非曝光區顯像處理後失重為0.20g/m2 ，低於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留1.0g/m2 ，高於容許範圍(<0.05g/m2 )。並將塗佈感光液的版材裁切完整的大小，經秤其重量，浸泡於50%異丙醇水溶液中1小時後，烘乾再秤重，檢測其浸泡於50%異丙醇水溶液中前後的重量變化，檢測感光層保留為<0.05 g/m2 。此檢測結果顯示，該配方耐溶劑性不足。Further detection was carried out to obtain a weight loss of 0.20 g/m 2 after the non-exposure area development treatment, which was lower than the allowable range (<0.4 g/m 2 ), and 1.0 g/m 2 remained after exposure in the exposed area, which was higher than the allowable range. (<0.05 g/m 2 ). The plate coated with the photosensitive liquid is cut into a complete size, and the weight is weighed, immersed in a 50% isopropyl alcohol aqueous solution for 1 hour, dried and weighed, and tested for immersion in a 50% isopropyl alcohol aqueous solution. Before and after the change in weight, the detection photosensitive layer remained <0.05 g/m 2 . The test results showed that the formulation was insufficient in solvent resistance.
如比較例1製作塗佈組成物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解9.00克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外輻射吸收染料HCD23(Hayashibara biochemical laboratories)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)與6.00克乙酸丁酸纖維素(CAB)(Eastman chemical)製作成塗佈組合物溶液。The coating composition solution and the aluminum base plate were prepared as in Comparative Example 1. 9.00 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared radiation absorbing dye HCD23 (Hayashibara biochemical laboratories), 0.50 g of tris(p-dimethylamino group) were dissolved in 91.0 g of 1-methoxy-2-propanol. Phenyl)methane (Excellian Chemical) and 6.00 g of cellulose acetate butyrate (CAB) (Eastman Chemical) were prepared into a coating composition solution.
進一步分別檢測，得到非曝光區顯像處理後失重為0.1g/m2 ，低於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留1.5 g/m2 ，高於容許範圍(<0.05 g/m2 )。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留約為1.7 g/m2 。比較實施例1，發現在該配方中添加CAB，使得顯像後殘留嚴重，但此配方展現優異的耐溶劑性。Further detection was carried out to obtain a weight loss of 0.1 g/m 2 after the non-exposure area development treatment, which was lower than the allowable range (<0.4 g/m 2 ), and 1.5 g/m 2 remained after exposure in the exposed area, which was higher than the allowable range. (<0.05 g/m 2 ). After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to remain at about 1.7 g/m 2 . Comparing Example 1, it was found that CAB was added to the formulation so that the residue remained severe after development, but this formulation exhibited excellent solvent resistance.
如比較例1製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解11.0克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外輻射吸收染料HCD23(Hayashibara biochemical laboratories)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)、2.00克乙酸丁酸纖維素(Eastman chemical)與2.00克馬來酐共聚物(SMA)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Comparative Example 1. 11.0 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared radiation absorbing dye HCD23 (Hayashibara biochemical laboratories), 0.50 g of tris(p-dimethylamino group) were dissolved in 91.0 g of 1-methoxy-2-propanol. Phenyl)methane (Excellian Chemical), 2.00 g of cellulose acetate butyrate (Eastman Chemical) and 2.00 g of maleic anhydride copolymer (SMA) were prepared into a coating composition solution.
進一步分別檢測，得到非曝光區顯像處理後失重為0.36 g/m2 ，低於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留<0.05 g/m2 ，低於容許範圍。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留約為1.7 g/m2 ，表示此配方具有優異的耐溶劑特性。相較於比較例1，發現加入CAB與馬來酐共聚物後，發現顯像後殘留低於容許範圍內，且耐溶劑性有明顯的改善。可知所添加馬來酐共聚物於該配方中，可解決添加CAB後，感光層顯像嚴重殘留的問題。Further detection was carried out to obtain a weight loss of 0.36 g/m 2 after the non-exposure area development treatment, which was lower than the allowable range (<0.4 g/m 2 ), and remained <0.05 g/m 2 after exposure in the exposed area, which was lower than the allowable range. range. After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to remain at about 1.7 g/m 2 , indicating that the formulation had excellent solvent resistance. Compared with Comparative Example 1, it was found that after the addition of the copolymer of CAB and maleic anhydride, it was found that the residue after development was below the allowable range, and the solvent resistance was remarkably improved. It can be seen that the added maleic anhydride copolymer in the formulation can solve the problem that the photosensitive layer is seriously left after the addition of CAB.
如實施例2製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解11.0克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外輻射吸收染料HCD23(Hayashibara biochemical laboratories)、2.00克乙酸丁酸纖維素(Eastman chemical)與2.00克馬來酐共聚物(SMA)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Example 2. 11.0 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared radiation absorbing dye HCD23 (Hayashibara biochemical laboratories), 2.00 g of cellulose acetate butyrate (Eastman chemical) were dissolved in 91.0 g of 1-methoxy-2-propanol. A coating composition solution was prepared with 2.00 grams of maleic anhydride copolymer (SMA).
此比較例發現，不添加溶解抑制劑則顯像後無法成像。進一步分別檢測，得到非曝光區顯像處理後失重為1.2 g/m2 ，高於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留<0.05 g/m2 ，低於容許範圍。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留約為1.7 g/m2 ，其具有耐溶劑特性。This comparative example found that imaging was not possible after imaging without the addition of a dissolution inhibitor. Further detection was carried out to obtain a weight loss of 1.2 g/m 2 after the non-exposure zone imaging treatment, which was higher than the allowable range (<0.4 g/m 2 ), and remained <0.05 g/m 2 after exposure in the exposed area, below the allowable range. range. After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to have a retention of about 1.7 g/m 2 , which has solvent resistance.
如實施例2製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解11.0克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)、2.00克乙酸丁酸纖維素(Eastman chemical)與2.00克馬來酐共聚物(SMA)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Example 2. 11.0 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of tris(p-dimethylaminophenyl)methane (excellent chemical), 2.00 g of acetic acid were dissolved in 91.0 g of 1-methoxy-2-propanol. A solution of the coating composition was prepared from Eastman Chemical and 2.00 g of a maleic anhydride copolymer (SMA).
此比較例發現，不添加紅外輻射吸收劑，則曝光顯像後無法成像。進一步分別檢測，得到非曝光區顯像後殘留0.4 g/m2 ，高於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留1.0 g/m2 ，高於容許範圍(<0.05 g/m2 )。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留約為1.7 g/m2 ，具有耐溶劑特性。This comparative example found that without the addition of an infrared radiation absorber, imaging could not be performed after exposure imaging. Further detection was carried out to obtain 0.4 g/m 2 after exposure in the non-exposed area, which was higher than the allowable range (<0.4 g/m 2 ), and 1.0 g/m 2 remained after exposure in the exposed area, which was higher than the allowable range (< 0.05 g/m 2 ). After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to have a retention of about 1.7 g/m 2 and was solvent-resistant.
如實施例2製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解11.0克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外輻射吸收染料HCD23(Hayashibara biochemical laboratories)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)與2克馬來酐共聚物(SMA)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Example 2. 11.0 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared radiation absorbing dye HCD23 (Hayashibara biochemical laboratories), 0.50 g of tris(p-dimethylamino group) were dissolved in 91.0 g of 1-methoxy-2-propanol. Phenyl)methane (Excellian Chemical) and 2 grams of maleic anhydride copolymer (SMA) were prepared into a coating composition solution.
此比較例發現，不添加乙酸丁酸纖維素則顯像後無法成像。進一步分別檢測，得到非曝光區顯像處理後感光層殘留1.2 g/m2 ，高於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留<0.05 g/m2 ，低於容許範圍。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留為<0.05 g/m2 。This comparative example found that it was impossible to image after imaging without adding cellulose acetate butyrate. Further detection was carried out separately, and the photosensitive layer remained 1.2 g/m 2 after the non-exposure area development treatment, which was higher than the allowable range (<0.4 g/m 2 ), and remained <0.05 g/m 2 after exposure in the exposed area, lower than Allowable range. After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to remain <0.05 g/m 2 .
如實施例2製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解9.00克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外線吸收染料HCD23(Hayashibara biochemical laboratories)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)與6.00克C12脂肪酸(d1)、C18脂肪酸(d2)、PEG 1000(d3)、PEG 2000(d4)、Tego P50(有機矽添加劑)(d5)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Example 2. 9.00 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared absorbing dye HCD23 (Hayashibara biochemical laboratories), 0.50 g of tris(p-dimethylaminobenzene) were dissolved in 91.0 g of 1-methoxy-2-propanol. Methane (Excellian Chemical) and 6.00 g of C12 fatty acid (d1), C18 fatty acid (d2), PEG 1000 (d3), PEG 2000 (d4), Tego P50 (organic antimony additive) (d5) Solution.
此比較例發現，在該配方中添加d1-d5，則顯像後無法成像。進一步分別檢測，得到非曝光區顯像處理後失重分為1.2 g/m2 ；1.1 g/m2 ；1.7 g/m2 ；1.7 g/m2 ；及1.2 g/m2 ，高於容許範圍內(<0.4 g/m2 )，曝光區顯像後殘留<0.05 g/m2 ，低於容許範圍。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留為<0.05 g/m2 。This comparative example found that by adding d1-d5 to the formulation, imaging was not possible after imaging. Further detection was carried out separately, and the weight loss after non-exposure area development treatment was 1.2 g/m 2 ; 1.1 g/m 2 ; 1.7 g/m 2 ; 1.7 g/m 2 ; and 1.2 g/m 2 , which was higher than the allowable range. Internal (<0.4 g/m 2 ), residual <0.05 g/m 2 after exposure in the exposed area, below the allowable range. After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to remain <0.05 g/m 2 .
如實施例2製作塗佈組合物溶液及鋁基版。於91.0克之1-甲氧基-2-丙醇中溶解9.00克之Novolak EP6050(Asahi organic chemicals industry)、0.50克之紅外線吸收染料HCD23(Hayashibara biochemical laboratories)、0.50克之三(對-二甲基胺基苯基)甲烷(優締化學)與6.00克PMMA(CM207,CM211)製作成塗佈組合物溶液。A coating composition solution and an aluminum base plate were prepared as in Example 2. 9.00 g of Novolak EP6050 (Asahi organic chemicals industry), 0.50 g of infrared absorbing dye HCD23 (Hayashibara biochemical laboratories), 0.50 g of tris(p-dimethylaminobenzene) were dissolved in 91.0 g of 1-methoxy-2-propanol. Methane (excellent chemistry) and 6.00 g of PMMA (CM207, CM211) were made into a coating composition solution.
此比較例發現，在該配方中添加PMMA(CM207,CM211)，則顯像後表面效果不佳，不易均勻塗佈油墨。進一步分別檢測，得到非曝光區顯像處理後失重為0.1 g/m2 ，低於容許範圍內(<0.4 g/m2)，曝光區顯像後殘留1.6 g/m2 ，高於容許範圍(<0.05 g/m2 )。並將上述塗有熱敏組合物之基版浸泡於50%異丙醇水溶液中1小時後，檢測感光層保留約為1.7 g/m2 ，具有耐溶劑特性。In this comparative example, it was found that by adding PMMA (CM207, CM211) to the formulation, the surface effect after development was poor, and it was difficult to uniformly apply the ink. Further detection was carried out to obtain a weight loss of 0.1 g/m 2 after the non-exposure area development treatment, which was lower than the allowable range (<0.4 g/m 2 ), and 1.6 g/m 2 remained after exposure in the exposed area, which was higher than the allowable range ( <0.05 g/m 2 ). After the above-mentioned base plate coated with the heat-sensitive composition was immersed in a 50% aqueous solution of isopropyl alcohol for 1 hour, the photosensitive layer was found to have a retention of about 1.7 g/m 2 and was solvent-resistant.
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