201127642 六、發明說明： 【發明所屬之技術領域】 本發明係關於用於熱噴墨列表機的噴墨墨水。開 目的主要是爲了使加熱器元件重複促動之後的結垢減 少〇 【先前技術】 形成熱氣泡的噴墨列印頭藉著在噴嘴室的列印流 產生一定量的熱起作用。此熱造成氣泡形成，當流體 經過噴嘴時氣泡最終崩潰。氣泡崩潰接著造成更多流 入該噴嘴室以供相同程序再開始。 本申請人已經開發出一系列形成熱氣泡的列印頭 申請人之形成熱氣泡的列印頭包括具有懸吊式加熱器 者（例如，US 6,755,509; US 7,246,886;及 US 7,40 所述’在此以引用方式將其全文倂入本文）及具有嵌 加熱器元件者（例如，US 7,377,623 ; US 7,431，431 2006/250453;及US 7,491，911所述，在此以引用方 其全文倂入本文）。熟於此藝之士知道其他形成熱氣 列印頭的設計 > 如可自Canon及Hewlett-Packard取 〇 形成熱氣泡之列印頭用的噴墨墨水通常爲包含顏 底或染料爲底的著色劑之水性墨水調合物。幾乎所有 墨列印頭都有的問題爲固態沉積物累積在用以加熱墨 加熱器元件上-在此技藝中習稱爲1結垢，。結垢會有問 發的 至最 體中 被迫 體進 。本 元件 ,910 入式 ；US 式將 泡的 得者 料爲 熱噴 水的 題， -5- 201127642 因爲其降低加熱器元件的效率，但是結垢也可能造成噴嘴 失效》包含顏料分散液的噴墨墨水通常更傾向於結垢，但 是在染料爲底的墨水中也還是會有結垢的問題，且特別是 任何包含聚合物添加物的墨水。 此技藝中藉由不同手段解決結垢的問題。在一些噴墨 列表機中’結垢係透過應用非射出驅動脈衝加以解決，該 等脈衝使加熱器元件上的結垢沉積物充分瓦解使得沉積物 可以被清除。US 5,440,330及US200 7/0 52761描述能用於 移除結垢之指定脈衝電壓、脈衝寬度、脈衝頻率等等的應 用。然而，此等方法具有有限的成效且不可用於移除所有 類型的結垢。 EP-A- 1 3 02 3 2 1描述經具體設計以解決結垢問題的列 印頭。各墨水射出裝置包含由撓性膜分隔的二室，藉以使 第一室用以產生氣泡及第二室射出墨水。從第一室穿過該 撓性膜傳送至第二室的壓力波造成墨滴射出。此配置的優 點爲第一室中可使用單純不結垢的流體（例如水）使加熱器 元件沒有結垢。然而’此裝置有複雜性且必然佔據比習用 形成熱氣泡的室大的列印頭區域。 其他降低先前技藝的結垢之方法在噴墨墨水中運用添 加物。例如，US 2002/1 1 3842描述在顏料爲底的墨水中應 用醛糖酸添加物（例如葡萄糖醛酸）。自我分散性顏料及以 聚合物分散劑分散的顏料都有描述到。然而，據記載在所 有醛糖酸添加物不存在的案例中結垢很多。 EP-A-1279707描述應用有機膦酸添加物降低結垢。 201127642 US 2 00 8/066644描述應用胺添加物與二表面活性劑的 組合降低結垢。 US 6,616，273描述將銅鹽加至墨水，墨水將銅離子遞 送至加熱器元件以助於移除結垢。 US 4,790,880描述將冠醚加至墨水以降低結垢並改善 列印品質。 W097/3 1984描述含有乙烯基矽酮聚合物之顏料爲底 的墨水，據記載其能降低結垢。 吾人所欲爲藉由噴墨墨水，特別是顔料爲底的墨水， 提供使加熱器元件的結垢減至最少之新方法。 【發明內容】 在第一個方面中，提供一種使熱噴墨列印頭中之加熱 器元件的結垢減至最少之方法，該方法包含下列步驟： (i)供應噴墨墨水至該列印頭的至少一個噴嘴室；及 (i〇促動該噴嘴室中的加熱器元件以便將一部分墨 水加熱至足以在該噴嘴室內形成氣泡的溫度，藉以造成墨 滴從該噴嘴室相關的噴嘴開口被射出， 其中該墨水包含具有低於約i 〇(TC的玻璃轉移溫度 (Tg)之丙稀酸系聚合物’該丙烯酸系聚合物使該加熱器元 件的結垢減至最少。 本發明藉著以在此所述的指定類型丙烯酸系聚合物調 配噴墨墨水達到最少的結垢。 該加熱器兀件係任意促動至少1千萬次，或任意至少 201127642 2千萬次，並顯示出比沒有該丙烯酸系聚合物的墨水少的 結垢。根據本發明的墨水顯示比沒有聚合物的相容性墨水 及含有具有約100 °C或更高的玻璃轉移溫度（Tg)之丙烯酸 系聚合物的墨水少的結垢。 該墨水包含著色劑，其可爲顏料或染料。該墨水任意 包含顏料，其可爲自我分散性及/或表面改質顏料。換句 話說’該墨水可包含顏料，其不需要任何聚合物分散劑以 分散於水性墨水媒液。 該丙烯酸系聚合物任意爲烯烴-丙烯酸系共聚物，如 苯乙烯-丙烯酸系共聚物。 該苯乙烯·丙烯酸系共聚物任意具有低於約…它的Tg 。該苯乙烯-丙烯酸系共聚物任意具有在〇至6(TC範圍中 的Tg，或任意在10至50°c範圍中。 該苯乙烯-丙烯酸系共聚物具有在 1〇〇至 300 mgKOH/g範圍中的酸値，或任意在1〇〇至180 mgKOH/g 範圍中。 該墨水媒液任意爲水性墨水媒液，其經常含有至少 5〇重量％水。 該墨水媒液任意包含以介於5重量％至4 0重量％的量 存在之至少一溶劑。 該墨水媒液任意包含以介於〇.1重量％至5重量％的 量存在之至少一表面活性劑。 該至少一溶劑係任意選自由下列所構成的群組：乙二 醇、丙三醇及2 -吡咯烷酮。例如，該溶劑可包含乙二醇 -8 - 201127642 、丙三醇及2-吡咯烷酮的混合物。 該顏料係任意以介於0 · 0 1重量％至2 5重量％的量存 在’任意0 · 1至1 0重量。/。。 該丙烯酸系聚合物係任意以介於〇.】重量％至15重量 %的量存在’或任意〇·2至1〇重量％，或任意〇5至5重 量％。 在第二個方面中’提供一種丙烯酸系聚合物添加物在 噴墨墨水中之用途’其係用於使熱噴墨列印頭中之加熱器 元件的結垢減至最少，其中該丙烯酸系聚合物具有低於約 100 °C的玻璃轉移溫度（Tg)。第二個方面的不同任意具體 實施例可依據上述與第一個方面有關的那些任意具體實施 例。 在第三個方面中，提供一種用於使熱噴墨列印頭中之 加熱器元件的結垢減至最少之噴墨墨水，該墨水包含： 墨水媒液； 自我分散性著色劑；及 具有低於約1 0 0 °c的玻璃轉移溫度（T g)之苯乙烯-丙烯 酸系共聚物。 根據第三個方面的噴墨墨水至今尙屬未知，因爲自我 分散性著色劑，由於其真正的本質，不需要任何聚合物分 散劑以便能被調配於噴墨墨水中。然而，利用特定丙烯酸 系聚合物以助於降低結垢意指根據第三個方面之墨水提供 明顯優於沒有丙烯酸系聚合物的墨水之優點。 該自我分散性著色劑任意爲表面改質顏料。該表面改 -9- 201127642 質顏料任意包含表面磺酸基或表面羧酸基。該顏料可爲黑 色 '魅藍、洋紅、黃色、紅色'綠色、藍色、紅外線吸收 等等。 該第三個方面的不同其他任意具體實施例可依據上述 與第一個方面有關的那些任意具體實施例。 在第四個方面中，提供—種用於熱噴墨列印頭之墨水 匣，該墨水匣含有根據第三個方面之噴墨墨水。該熱噴墨 列印頭可與根據第四個方面的墨水匣整合在一起。 在第五個方面中，提供一種噴墨列表機’其包含與含 有根據第三個方面之噴墨墨水的墨水槽流體流通之熱噴墨 列印頭。 該熱噴墨列印頭任意包含多個含有該墨水的噴嘴室， 各噴嘴室包含懸在或嵌入該噴嘴室中的加熱器元件，該加 熱器元件係被建構以供將該墨水的一部分加熱至足以形成 氣泡的溫度，藉以自該噴嘴室射出該墨水的液滴。在此處 描述具有懸吊式加熱器元件的熱噴墨列印頭之實例。熟於 此藝之士熟知其他類型的熱噴墨列印頭。 【實施方式】 用於此處時，該措辭“丙烯酸系聚合物”係用以意指 任何類型的丙烯酸系聚合物樹脂，其包括丙烯酸系均聚物 、丙烯酸系共聚物、丙烯酸系三聚物等等。丙烯酸系聚合 物可由任何適合的丙烯酸系單體形成，如丙烯酸、甲基丙 烯酸、丙烯酸酯、甲基丙烯酸酯等等。 -10- 201127642 本發明運用包含丙烯酸系聚合物的噴墨墨水，該丙烯 酸系聚合物具有低於約100 °C的玻璃轉移溫度（Tg)。本申 請人顯示此等丙烯酸系聚合物能使熱噴墨列印頭中之加熱 器元件的結垢減至最少。至今，咸瞭解加熱器元件的結垢 主要係由許多噴墨墨水中所包括的非揮發性聚合物分散劑 引起。聚合物分散劑經常被加至噴墨墨水以助於顏料分散 。的確令人驚訝的是當與不含此等丙烯酸系聚合物的墨水 及/或不含任何聚合物添加物的墨水相比時包括指定類型 的丙烯酸系聚合物將降低加熱器元件的結垢。經過至少1 千萬滴射出或至少2千萬滴射出之後目視比較加熱器元件 顯示本發明所運用的墨水與不含聚合物的墨水有顯著的差 異。特別是，與不含聚合物的墨水相比當該墨水含有具有 低於約1 oo°c的Tg之丙烯酸系聚合物時將觀察到明顯較 少的結垢。假使至今咸相信聚合物爲熱噴墨列印頭中結垢 的主要成因之一，那這真是一個非常令人驚訝的結果。 本發明可與任何類型的墨水聯合使用，如染料爲底的 墨水或顏料爲底的墨水。然而，結垢的降低以顏料爲底的 墨水最爲有利。 在習用顏料爲底的墨水之案例中，具有低於約1 0(TC @玻璃轉移溫度（Tg)之丙烯酸系聚合物可兼用於分散該等 顏料及降低結垢。換句話說，利用此等丙烯酸系聚合物避 免任何添加其他降低結垢的添加物之需求，因爲該丙烯酸 系聚合物作爲習用顏料的分散劑並同時使結垢減至最少。 在自我分散性著色劑（其通常不需要任何聚合物分散 -11 - 201127642 劑）的案例中，添加具有低於約100t&玻璃轉移溫度（Tg: 之丙烯酸系聚合物可單獨用於降低結垢。自我分散性著色 劑包括染料及經表面改質的顏料，該二者均爲熟於此藝之 士眾所周知。現在將更詳細描述用於本發明的噴墨墨水之 各成分。 丙烯酸系聚合物 該丙稀酸系聚合物經常爲丙烯酸系共聚物，如烯烴_ 丙嫌酸系共聚物。最佳爲苯乙烯-丙烯酸系共聚物。 該丙嫌酸系聚合物的玻璃轉移溫度（Tg)爲低於約1〇〇 °c ’任意低於約9(rc，且任意低於約6〇〇c。當該丙烯酸 系聚合物爲具有在〇至5〇。(：範圍中，或任意5至30〇c的 Tg之苯乙烯-丙烯酸系聚合物時將觀察到最佳結垢結果。 該丙稀酸系聚合物經常具有在100至300 mgKOH/g 範圍中，或任意在1〇〇至180mgKOH/g範圍中的酸値。 該丙烯酸系聚合物可具有在3000至1 5,000 g/m〇l範 圍中的分子量。201127642 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to an inkjet ink for use in a thermal inkjet lister. The purpose of the opening is mainly to reduce the scale after the heater element is repeatedly actuated. [Prior Art] The ink jet print head which forms the hot bubble acts by generating a certain amount of heat by the printing flow in the nozzle chamber. This heat causes bubbles to form, and the bubbles eventually collapse as the fluid passes through the nozzle. The collapse of the bubble then causes more flow into the nozzle chamber for the same procedure to begin. The Applicant has developed a series of printheads that form thermal bubbles. Applicators for forming thermal bubbles include those having a suspended heater (e.g., US 6,755,509; US 7,246,886; and US 7,40 It is hereby incorporated by reference in its entirety herein in its entirety herein in its entirety in its entirety in the the the the the the the the the the the the the the the the the the This article). Those skilled in the art are aware of other designs for forming hot gas print heads. For example, ink jet inks for print heads that can be used to form thermal bubbles from Canon and Hewlett-Packard are usually colored with a base or dye base. Aqueous ink blend of the agent. A problem with almost all ink jet heads is that solid deposits accumulate on the heated ink heater elements - known in the art as 1 fouling. The scaling will be asked to the body and forced into the body. This component, 910-in; US-style foam is the subject of hot water spray, -5- 201127642 because it reduces the efficiency of the heater element, but fouling may also cause nozzle failure. Inkjet containing pigment dispersion Inks are generally more prone to fouling, but there is still the problem of fouling in dye-based inks, and in particular any ink containing polymer additives. This technique solves the problem of scaling by different means. In some ink jet listers, fouling is addressed by the application of non-ejecting drive pulses that cause the scale deposits on the heater elements to fully disintegrate such that deposits can be removed. US 5,440,330 and US200 7/0 52761 describe applications that can be used to remove the specified pulse voltage, pulse width, pulse frequency, etc. of fouling. However, these methods have limited effectiveness and are not available to remove all types of fouling. EP-A-1 2 02 3 2 1 describes a print head that is specifically designed to solve the scaling problem. Each of the ink ejecting devices includes two chambers separated by a flexible membrane, whereby the first chamber is used to generate bubbles and the second chamber to eject ink. Pressure waves transmitted from the first chamber through the flexible membrane to the second chamber cause ink droplets to be ejected. The advantage of this configuration is that a non-fouling fluid (such as water) can be used in the first chamber to prevent the heater element from fouling. However, this device is complex and inevitably occupies a print head area that is larger than the chamber in which the hot bubbles are conventionally formed. Other methods of reducing fouling in prior art techniques use additives in inkjet inks. For example, US 2002/1 1 3842 describes the use of aldonic acid additives (e.g., glucuronic acid) in pigment-based inks. Self-dispersible pigments and pigments dispersed with polymeric dispersants are described. However, it has been reported that there is a lot of scaling in the case where all aldonic acid additives are not present. EP-A-1279707 describes the use of organic phosphonic acid additives to reduce fouling. 201127642 US 2 00 8/066644 describes the use of a combination of an amine additive and a two surfactant to reduce fouling. US 6,616,273 describes the addition of a copper salt to an ink which delivers copper ions to a heater element to aid in the removal of fouling. US 4,790,880 describes the addition of crown ether to ink to reduce fouling and improve print quality. W097/3 1984 describes a pigment-based ink containing a vinyl fluorenone polymer which is reported to reduce fouling. What we would like to provide is a new method of minimizing fouling of heater elements by inkjet inks, particularly pigment-based inks. SUMMARY OF THE INVENTION In a first aspect, a method of minimizing fouling of a heater element in a thermal inkjet printhead is provided, the method comprising the steps of: (i) supplying inkjet ink to the column At least one nozzle chamber of the printhead; and (i) actuating a heater element in the nozzle chamber to heat a portion of the ink to a temperature sufficient to form a bubble within the nozzle chamber, thereby causing ink droplets from the nozzle opening associated with the nozzle chamber Being ejected, wherein the ink comprises an acrylic polymer having a glass transition temperature (Tg) of less than about 〇 (the PEG) minimizes fouling of the heater element. The inkjet ink is formulated with the specified type of acrylic polymer as described herein to achieve minimal fouling. The heater element is arbitrarily actuated at least 10 million times, or any at least 201127642 2 million times, and is shown Less fouling than ink without the acrylic polymer. The ink according to the present invention exhibits a compatible ink than the polymer and a propylene having a glass transition temperature (Tg) of about 100 ° C or higher. The ink of the polymer is less fouling. The ink contains a colorant, which may be a pigment or a dye. The ink optionally contains a pigment which may be a self-dispersible and/or surface-modified pigment. In other words, the ink may be A pigment is included which does not require any polymer dispersant to be dispersed in the aqueous ink vehicle. The acrylic polymer is optionally an olefin-acrylic copolymer such as a styrene-acrylic copolymer. The styrene-acrylic copolymer Any having a Tg lower than about .... The styrene-acrylic copolymer optionally has a Tg in the range of 〇 to 6 (TC range, or optionally in the range of 10 to 50 ° C. The styrene-acrylic copolymer Having an acid enthalpy in the range of from 1 Torr to 300 mg KOH/g, or optionally in the range of from 1 Torr to 180 mg KOH/g. The ink vehicle liquid is optionally an aqueous ink vehicle liquid, which often contains at least 5% by weight water. The ink vehicle optionally contains at least one solvent in an amount of from 5% by weight to 40% by weight. The ink vehicle optionally contains at least one of the amount of from 0.1% by weight to 5% by weight. Surfactant. The at least one solvent is optionally selected from the group consisting of ethylene glycol, glycerol and 2-pyrrolidone. For example, the solvent may comprise a mixture of ethylene glycol-8 - 201127642, glycerol and 2-pyrrolidone The pigment is optionally present in an amount of from 0. 01% by weight to 255% by weight of 'any 0. 1 to 10% by weight. The acrylic polymer is optionally present in a weight ratio of 〇. An amount of up to 15% by weight of 'or any 〇·2 to 1% by weight, or any 〇5 to 5% by weight. In a second aspect, 'provides an use of an acrylic polymer additive in an inkjet ink 'It is used to minimize fouling of the heater elements in the thermal inkjet printhead, wherein the acrylic polymer has a glass transition temperature (Tg) of less than about 100 °C. Any particular embodiment of the second aspect may be in accordance with any of the specific embodiments described above in relation to the first aspect. In a third aspect, there is provided an inkjet ink for minimizing fouling of a heater element in a thermal inkjet printhead, the ink comprising: an ink vehicle; a self-dispersing colorant; A styrene-acrylic copolymer having a glass transition temperature (Tg) of less than about 10 °C. The inkjet ink according to the third aspect is not known until now because the self-dispersible colorant, due to its true nature, does not require any polymer dispersant so that it can be formulated in the inkjet ink. However, the use of a specific acrylic polymer to help reduce fouling means that the ink according to the third aspect provides an advantage over the ink without the acrylic polymer. The self-dispersing colorant is optionally a surface modifying pigment. The surface modification -9- 201127642 pigment optionally contains a surface sulfonic acid group or a surface carboxylic acid group. The pigment can be black 'magic blue, magenta, yellow, red 'green, blue, infrared absorption and so on. Different other specific embodiments of the third aspect may be in accordance with any of the specific embodiments described above in relation to the first aspect. In a fourth aspect, there is provided an ink cartridge for a thermal ink jet print head, the ink cartridge comprising the inkjet ink according to the third aspect. The thermal inkjet printhead can be integrated with the ink cartridge according to the fourth aspect. In a fifth aspect, there is provided an ink jet lister comprising a thermal inkjet printhead fluidly circulated with an ink reservoir containing the inkjet ink according to the third aspect. The thermal inkjet printhead optionally includes a plurality of nozzle chambers containing the ink, each nozzle chamber including a heater element suspended or embedded in the nozzle chamber, the heater element being configured to heat a portion of the ink A temperature sufficient to form a bubble, whereby droplets of the ink are ejected from the nozzle chamber. An example of a thermal inkjet printhead having a suspended heater element is described herein. Those skilled in the art are familiar with other types of thermal inkjet print heads. [Embodiment] As used herein, the phrase "acrylic polymer" is used to mean any type of acrylic polymer resin, including acrylic homopolymer, acrylic copolymer, acrylic terpolymer. and many more. The acrylic polymer can be formed from any suitable acrylic monomer such as acrylic acid, methacrylic acid, acrylate, methacrylate, and the like. -10- 201127642 The present invention utilizes an ink jet ink comprising an acrylic polymer having a glass transition temperature (Tg) of less than about 100 °C. The Applicant has shown that such acrylic polymers minimize fouling of the heater elements in thermal inkjet printheads. To date, it has been well known that fouling of heater elements is primarily caused by non-volatile polymer dispersants included in many inkjet inks. Polymeric dispersants are often added to the inkjet ink to aid in pigment dispersion. It is indeed surprising that the inclusion of a specified type of acrylic polymer when compared to inks that do not contain such acrylic polymers and/or inks that do not contain any polymer additives will reduce fouling of the heater elements. Visual comparison of the heater elements after at least 10 million drops or at least 20 million drops has been shown to show significant differences between the inks used in the present invention and the inks containing no polymer. In particular, significantly less fouling is observed when the ink contains an acrylic polymer having a Tg of less than about 1 oo C compared to a polymer free ink. This is a very surprising result, given that it is believed that the polymer is one of the main causes of fouling in thermal inkjet print heads. The invention can be used in conjunction with any type of ink, such as dye-based inks or pigment-based inks. However, the reduction in fouling is most advantageous with pigment-based inks. In the case of conventional pigment-based inks, acrylic polymers having a temperature below about 10 (TC @ glass transition temperature (Tg) can be used to disperse the pigments and reduce fouling. In other words, to utilize such The acrylic polymer avoids any need to add other scale-reducing additives because the acrylic polymer acts as a dispersant for conventional pigments while minimizing fouling. In self-dispersing colorants (which usually do not require any In the case of polymer dispersion -11 - 201127642), an acrylic polymer having a glass transition temperature (Tg: less than about 100t & glass) can be used alone to reduce fouling. Self-dispersible colorants include dyes and surface modification The pigments are well known to those skilled in the art. The components of the inkjet inks used in the present invention will now be described in more detail. Acrylic Polymers The acrylic polymers are often acrylic copolymers. A styrene-acrylic copolymer, preferably a styrene-acrylic copolymer. The glass transition temperature (Tg) of the acrylic acid polymer is less than about 1 Torr. °c 'arbitrarily less than about 9 (rc, and optionally less than about 6 〇〇 c. When the acrylic polymer is having a Tg of 〇 to 5 〇. (: range, or any 5 to 30 〇c) The best scale results will be observed for styrene-acrylic polymers. The acrylic polymers often have an acid in the range of 100 to 300 mg KOH/g, or any range from 1 Torr to 180 mg KOH/g. The acrylic polymer may have a molecular weight in the range of from 3,000 to 15,000 g/m.
Joncryl® HPD 296 及 Joncryl® ECO 684 (可自 BASF 購得）爲兩種苯乙烯丙烯酸系共聚物的實例，其可用於本 發明。 該丙烯酸系聚合物經常以介於0.1重量％至1 5重量％ 的量存在，任意0.2重量％至10重量％，或任意0.5重量 %至5重量％。 -12- 201127642 著色劑 如上文所註釋~ ’該著色劑可任意爲染料爲底的著色劑 或顏料爲底的著色劑，但是結垢的降低利用顔料最有利。 染料及經表面改質的顏料爲自我分散性著色劑，就某個程 度來說其不需要任何聚合物分散劑以分散於典型墨水媒液 中。根據本發明的新穎噴墨墨水包含自我分散性著色劑、 上述的丙烯酸系聚合物及墨水媒液。 噴墨著色劑爲熟於此藝之士眾所周知且根據本發明之 降低結垢的方法不限於任何特定型式的染料或顔料。 適用於本發明之方法的習用顏料可爲無機顏料或有機 顏料。實例爲碳黑、鎘紅、鉬紅、鉻黃、鎘黃、鈦黃、氧 化鉻、鉻綠、鈦鈷錄、群青 '普魯士藍、鈷藍'二酮基吡 咯並吡咯、蒽醌、苯並咪唑酮、蒽素嘧啶、偶氮顏料、酞 化青顏料（包括萘花青顏料）、喹吖啶酮顏料、異吲哚啉酮 顏料、二噁嗪顏料、陰丹士林顏料、茈顏料、芘酮顏料 。一些顔料的指 gment Y 1 5 1 及 硫辭顔料、喹啉黃顏料及金屬錯合物顏料 定例爲 Pigment 15:3、Pigment V19、Pi Pigment PK-7。 適用於本發明的染料包括偶氮染料 '金屬錯合物染料 、萘酚染料 '蒽醌染料、帛藍染料、㈣翁染料、醌-亞胺 染料、咕噸染料、％青染料、喹啉染料、硝.基染料 '亞硝 基染料 '苯醌染料、帛醌染肖、酞花青染料(包括萘花青 染料）及金屬酞花青染料（包括金屬萘花青染料）。—些染 [S1 -13- 201127642 yellow 82 及 Solvent black 27 ° 經表面改質的顏料爲已經利用表面陰離子基團或表面 陽離子基團改質過的顔料。典型之表面改質基團爲羧酸基 及磺酸基。式（i)顯示經羧酸改質的黑色顏料，而式（ii)顯 示經磺酸改質的彩色顏料。然而，其他表面改質基團也可 使用，如陰離子磷酸基或陽離子銨基。Joncryl® HPD 296 and Joncryl® ECO 684 (available from BASF) are examples of two styrenic acrylic copolymers that can be used in the present invention. The acrylic polymer is often present in an amount of from 0.1% by weight to 15% by weight, optionally from 0.2% by weight to 10% by weight, or alternatively from 0.5% by weight to 5% by weight. -12- 201127642 Colorant As noted above - 'The colorant can be any dye-based colorant or pigment-based colorant, but the reduction of scale is most advantageous with pigments. Dyes and surface-modified pigments are self-dispersible colorants which, to a certain extent, do not require any polymeric dispersant to be dispersed in a typical ink vehicle. The novel inkjet ink according to the present invention comprises a self-dispersible colorant, the above acrylic polymer, and an ink vehicle. Ink jet colorants are well known in the art and the method of reducing fouling according to the present invention is not limited to any particular type of dye or pigment. Conventional pigments suitable for use in the process of the invention may be inorganic or organic pigments. Examples are carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, chrome green, titanium cobalt, ultramarine 'Prussian blue, cobalt blue' diketopyrrolopyrrole, anthracene, benzo Imidazolone, alizarin, azo pigment, antimony pigment (including naphthalocyanine pigment), quinacridone pigment, isoindolinone pigment, dioxazine pigment, indanthrene pigment, anthraquinone pigment, Anthrone pigments. Some pigments refer to gment Y 1 5 1 and sulfur pigments, quinoline yellow pigments and metal complex pigments as Pigment 15:3, Pigment V19, Pi Pigment PK-7. Dyes suitable for use in the present invention include azo dyes 'metal complex dyes, naphthol dyes' anthraquinone dyes, indigo dyes, (iv) dyes, anthraquinone imine dyes, xanthene dyes, % cyan dyes, quinoline dyes. , nitrate-based dyes 'nitroso dyes' benzoquinone dyes, sputum dyes, phthalocyanine dyes (including naphthalocyanine dyes) and metal phthalocyanine dyes (including metal naphthalocyanine dyes). - Some dyes [S1 -13 - 201127642 yellow 82 and Solvent black 27 ° Surface-modified pigments are pigments that have been modified with surface anionic groups or surface cationic groups. Typical surface modifying groups are carboxylic acid groups and sulfonic acid groups. Formula (i) shows a carboxylic acid-modified black pigment, and formula (ii) shows a sulfonic acid-modified color pigment. However, other surface modifying groups may also be used, such as an anionic phosphate group or a cationic ammonium group.
適用於本發明的水性經表面改質的顏料之指定實例爲 Sensijet® Black SDP 2000 (可自 Sensient Colors 股份有限 公司購得）及 CAB-0-JET® 200、300、250C、260M 及 270Y (可自Cabot有限公司購得）。 該等顔料及染料可任意單獨或以其二或更多種的組合 用於噴墨墨水中。 噴墨墨水中的顏料粒子之平均粒徑任意在50至500 nm的範圍中。 墨水媒液 用於噴墨墨水的墨水媒液爲熟於此藝之士眾所周知且 用於本發明的墨水媒液沒有特別限定。申請人最近描述用 於熱噴墨列印頭的非水性噴墨墨水（參見2009年，9月1 1 日申請的US申請案第1 2/5 77,5 1 7號，在此以引用方式將 _ 14 - 201127642 其全文倂入本文）’且此等非水性墨水也在本發明的範圍 以內。用於熱噴墨的非水性墨水媒液經常包含烷 基）_2_吡咯烷酮（例如N-甲基-2-吡咯烷酮）及Cl_6醇（例如 乙醇）。 然而，用於本發明的墨水媒液經常爲習用的水性墨水 媒液，其包含至少40重量％水，至少50重量％水，或至 少60重量％水。存在於該噴墨墨水中的水量係在50重量 %至9 0重量％的範圍中，或任意在6 0重量％至8 0重量％ 的範圍中。 水性噴墨墨水組成物爲文獻中眾所周知且，除了水以 外，可包含其他成分’如共溶劑（包括保溼劑、滲透劑、 潤溼劑等等）、表面活性劑、殺生物劑、螯合劑 (sequestering agent)、pH調節劑、黏度改質劑等等。 共溶劑經常爲水溶性有機溶劑。適合的水溶性有機溶 劑包括C ! .4烷基醇類’如乙醇、甲醇、丁醇、丙醇及2 _ 丙醇；二醇醚類，如乙二醇單甲醚、乙二醇單乙醚、乙二 醇單丁醚、乙二醇單甲醚醋酸酯、二乙二醇單甲醚 '二乙 二醇單乙醚、二乙二醇單正丙醚、乙二醇單異丙醚、二乙 二醇單異丙醚、乙二醇單正丁醚、二乙二醇單正丁醚、三 乙二醇單正丁醚、乙二醇單第三丁醚、二乙二醇單第三丁 醚、1-甲基-1-甲氧基丁醇、丙二醇單甲醚、丙二醇單乙 醚、丙二醇單第三丁醚、丙二醇單正丙醚、丙二醇單異丙 酸、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙 醚 '二丙二醇單異丙醚、丙二醇單正丁醚及二丙二醇單正[ς] -15- 201127642 丁酸；甲醯胺、乙醯胺、二甲基亞颯、山梨醇 、丙三醇單醋酸酯、丙三醇二醋酸酯、丙三 環丁颯；或其組合。 其他有用的水溶性有機溶劑，其可用作共 極性溶劑’如2-吡咯烷酮、N-甲基吡咯烷酮、 、一甲基亞颯、環丁颯、嗎啉、N·乙基嗎咐 基·2-咪唑啶酮及其組合。 該噴墨墨水可含有用作共溶劑的高沸點水 劑’其可用作賦予該墨水組成物保水性及潤淫 劑或保溼劑。此高沸點水溶性有機溶劑包括具 更高沸點者。該具有1 8 0 °C或更高沸點之水溶 的實例爲乙二醇' 丙二醇、二乙二醇、戊二醇 2-丁烯-1，4-二醇、2-乙基-1,3-己二醇、2-甲基 一'丙一·醇單甲酸、一丙—醇單乙二醇、二丙 、二丙二醇單甲醚、二丙二醇、三乙二醇單甲 醇、三乙二醇、二乙二醇單丁醚、二乙二醇單 二醇單甲醚、三丙二醇、具有2000或更低分 二醇類、1，3 -丙二醇、異丙二醇、異丁二醇、 、1，3-丁 二醇、ι，5-戊二醇、ι，6-己二醇、丙 醇、季戊四醇及其組合。 其他適合的潤溼劑或保溼劑包括醣類（包 醣及多醣）及其衍生物（例如麥芽糖醇、山梨醇 玻璃酸鹽類、醛糖酸、羰基糖酸等等）。 該噴墨墨水也可含有滲透劑，作爲共溶劑 、山梨醇酐 三醋酸酯及 溶劑，包括 ε -己內醯胺 、1，3-二甲 溶性有機溶 性質的潤溼 有1 8 0°c或 性有機溶劑 、丙二醇、 -2,4-戊二醇Designated examples of aqueous surface-modified pigments suitable for use in the present invention are Sensijet® Black SDP 2000 (available from Sensient Colors, Inc.) and CAB-0-JET® 200, 300, 250C, 260M and 270Y (available) Purchased from Cabot Co., Ltd.). These pigments and dyes may be used singly or in combination of two or more thereof for use in an inkjet ink. The average particle diameter of the pigment particles in the inkjet ink is arbitrarily in the range of 50 to 500 nm. Ink medium The ink medium used for the inkjet ink is well known and is not particularly limited. The applicant has recently described a non-aqueous inkjet ink for use in a thermal inkjet printhead (see U.S. Patent Application Serial No. 1 2/5 77, No. 5, 197, filed on Sep. It is also incorporated herein by reference in its entirety to the extent that the non-aqueous inks are also within the scope of the invention. The non-aqueous ink vehicle for thermal ink jet often contains an alkyl))-pyrrolidone (e.g., N-methyl-2-pyrrolidone) and a Cl_6 alcohol (e.g., ethanol). However, the ink vehicle used in the present invention is often a conventional aqueous ink vehicle comprising at least 40% by weight of water, at least 50% by weight of water, or at least 60% by weight of water. The amount of water present in the inkjet ink is in the range of from 50% by weight to 90% by weight, or optionally in the range of from 60% by weight to 80% by weight. Aqueous inkjet ink compositions are well known in the literature and may contain other ingredients besides water, such as cosolvents (including humectants, penetrants, wetting agents, etc.), surfactants, biocides, chelating agents. (sequestering agent), pH adjuster, viscosity modifier, and the like. The cosolvent is often a water soluble organic solvent. Suitable water-soluble organic solvents include C. .4 alkyl alcohols such as ethanol, methanol, butanol, propanol and 2-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether 'diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, two Ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol single third Butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl acid, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether 'dipropylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether and dipropylene glycol mono-positive [ς] -15- 201127642 butyric acid; formamide, acetamide, dimethyl Aarene, sorbitol, glycerol monoacetate, glycerol diacetate, propylene triazine, or a combination thereof. Other useful water-soluble organic solvents which can be used as a copolar solvent such as 2-pyrrolidone, N-methylpyrrolidone, monomethylanthracene, cyclobutane, morpholine, N-ethyl fluorenyl 2 - Imidazolidone and combinations thereof. The inkjet ink may contain a high-boiling water agent used as a co-solvent, which can be used as a water-repellent and moisturizing agent or a moisturizing agent for imparting the ink composition. This high boiling water-soluble organic solvent includes those having a higher boiling point. Examples of the water-soluble solution having a boiling point of 180 ° C or higher are ethylene glycol 'propylene glycol, diethylene glycol, pentanediol 2-butene-1,4-diol, 2-ethyl-1,3 - hexanediol, 2-methyl-l-propanol monocarboxylic acid, mono-glycol monoethylene glycol, dipropylene, dipropylene glycol monomethyl ether, dipropylene glycol, triethylene glycol monomethanol, triethylene glycol , diethylene glycol monobutyl ether, diethylene glycol monoglycol monomethyl ether, tripropylene glycol, having 2000 or lower diols, 1,3-propanediol, isopropyl diol, isobutylene glycol, 1, 3-butanediol, iota, 5-pentanediol, iota, 6-hexanediol, propanol, pentaerythritol, and combinations thereof. Other suitable wetting or humectants include sugars (sugars and polysaccharides) and derivatives thereof (e.g., maltitol, sorbitol hyaluronate, aldonic acid, carbonyl sugar, etc.). The inkjet ink may also contain a penetrant as a cosolvent, sorbitan triacetate and a solvent, including ε-caprolactam, 1,3-dimethyl soluble organic solubility, wetting of 180 °c Or organic solvent, propylene glycol, -2,4-pentanediol
乙醚 '二乙 子量的聚乙 1,4- 丁二醇 三醇、丁四 括單醣、_ 、木糖醇、 之一，以使 -16- 201127642 該水性墨水加速滲入該記錄媒介。適合的滲 醇烷基醚類（二醇醚類）及/或1，2-烷基二醇類 醇烷基醚類之實例爲乙二醇單甲醚、乙二醇 醇單丁醚、乙二醇單甲醚醋酸酯、二乙二醇 二醇單乙醚、二乙二醇單正丙醚、乙二醇單 二醇單異丙醚、乙二醇單正丁醚、二乙二醇 乙二醇單正丁醚、乙二醇單第三丁醚、二乙 醚、1-甲基-1-甲氧基丁醇、丙二醇單甲醚 醚、丙二醇單第三丁醚、丙二醇單正丙醚、 醚、二丙二醇單甲醚、二丙二醇單乙醚、二 醚、二丙二醇單異丙醚、丙二醇單正丁醚及 丁醚。適合的1,2-烷基二醇類之實例爲1，2· 己二醇。該滲透劑也可選自直鏈烴二醇類， 、1，4-丁 二醇、1，5-戊二醇、1,6-己二醇' 1，8-辛二醇。丙三醇也可用作滲透劑。 存在該墨水中的共溶劑量係經常在約 重量％的範圍中，或任意1 0重量％至3 0重 系統的指定例，其可用於本發明中，包含乙 烷酮及丙三醇。 該噴墨墨水也可含有表面活性劑，如陰 性劑及/或非離子型表面活性劑。有用的陰 性劑包括磺酸型，如烷磺酸鹽類、α-烯烴磺 苯磺酸鹽類、烷基萘磺酸類、醯基甲基牛擴 磺丁二酸類；烷基硫酸酯鹽類、硫酸化油類 透劑包括多經 。適合的多經 單乙醚、乙二 單甲醚 '二乙 異丙醚、二乙 單正丁醚、三 二醇單第三丁 、丙二醇單乙 丙二醇單異丙 丙二醇單正丙 二丙二醇單正 -丙二醇及1，2-如1，3 -丙二醇 1，7-庚二醇及 5重量％至 4 0 i量％。共溶劑 二醇、2 -吡咯 離子型表面活 離子型表面活 酸鹽類、烷基 酸類及二烷基 、硫酸化烯烴 -17- 201127642 類、聚氧乙烯烷基醚硫酸酯鹽類；羧酸型，例如，脂肪酸 鹽類及烷基肌胺酸鹽類；及磷酸酯型，如烷基磷酸酯鹽類 、聚氧乙烯烷基醚磷酸酯鹽類及甘油磷酸酯鹽類。陰離子 型表面活性劑的指定例爲十二基苯磺酸鈉、月桂酸鈉及聚 氧乙烯烷基醚硫酸銨鹽。 非離子型表面活性劑之實例包括環氧乙烷加成型，如 聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚氧乙烯烷 基酯類及聚氧乙烯烷基醯胺類；多元醇酯型，如甘油烷基 酯類、山梨醇酐烷基酯類及糖烷基酯類；聚醚型，如多羥 醇烷基醚類；及烷醇醯胺型，如烷醇胺脂肪酸醯胺類。非 離子型表面活性劑之指定例爲醚類，如聚氧乙烯壬基苯基 醚、聚氧乙烯辛基苯基醚、聚氧乙烯十二基苯基醚、聚氧 乙烯烷基烯丙基醚、聚氧乙烯油烯基醚、聚氧乙烯月桂醚 及聚氧化烯烷基醚（例如聚氧乙烯烷基醚類）；及酯類，如 聚氧乙烯油酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、 山梨醇酐月桂酸酯、山梨醇酐單硬脂酸酯、山梨醇酐單油 酸酯、山梨醇酐倍半油酸酯、聚氧乙烯單油酸酯及聚氧乙 烯硬脂酸酯。炔二醇表面活性劑，如2,4,7,9-四甲基-5-癸 炔-4,7-二醇、3,6-二甲基-4-辛炔-3,6-二醇或3,5-二甲基· 1-己炔-3-醇，也可使用。 該表面活性劑經常以介於0.1重量％至1 〇重量％，或 任意在〇·2重量％至5重量％範圍中的量存在於該水性噴 墨墨水中。可用於本發明之非離子型表面活性劑的指定例 爲 Surfynol® 465 (可自 Air Products and Chemicals 股份 -18- 201127642 有限公司購得）。 該水性噴墨墨水也可包括pH調節劑，如氫氧化鈉、 氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸 氫鉀、碳酸鋰、磷酸鈉、磷酸鉀、磷酸鋰、二氫磷酸鉀、 氫磷酸二鉀、草酸鈉、草酸鉀、草酸鋰、硼酸鈉、四硼酸 鈉、氫酞酸鉀及氫酒石酸鉀；氨；及胺類，如甲胺、乙胺 、二乙胺、三甲胺、三乙胺、參（羥甲基）胺基甲烷鹽酸鹽 、三乙醇胺、二乙醇胺、二乙基乙醇胺、三異丙醇胺、丁 基二乙醇胺、嗎啉及丙醇胺。 該水性噴墨墨水也可包括殺生物劑，如苯甲酸、二氯 芬（dichlorophene)、六氯芬、己二烯酸、羥基苯甲酸酯類 、脫氫醋酸鈉、1，2-苯噻啉-3-酮、3,4-異噻啉-3-酮或4,4-二甲基噁唑啶。 該水性噴墨墨水也可含有螯合劑，如乙二胺四醋酸 (EDTA)。 熱噴墨列印頭 在此所述的噴墨墨水使熱噴墨列印頭中之結垢減至最 少。下列爲申請人的熱噴墨列印頭之一的簡要說明，如美 國專利案第7,3 03,93 0號所述，在此以引用方式將其全文 倂入本文。 參照第1圖，其顯示包含多個噴墨裝配件之列印頭的 一部分。第2及3圖以側斷面及剖開透視圖顯示這些噴嘴 裝配件之一。 -19- 201127642 各噴嘴組合件包含由MEMS裝配技術在矽晶圓基材2 上所形成的噴嘴室24。該噴嘴室24係由室頂21及自該 室頂21延伸至該砍基材2的側壁22予以界定。如第1圖 所示，各室頂係由一部分噴嘴板56予以定義，該噴嘴板 5 6跨越該列印頭的噴出面。該噴嘴板5 6及側壁2 2係由 相同材料構成，該材料係於MEMS裝配的期間藉由 PECVD沉積在光阻劑的犧牲支架上。經常地，該噴嘴板 56及側壁22係由陶瓷材料構成，如二氧化矽或氮化矽。 這些堅硬的材料具有列印頭堅固性所需的優良性質，且其 固有疏水特性藉由毛細作用供應墨水至該噴嘴室2 4係有 益的。 回到該噴嘴室24的細部，能見到噴嘴開口 26係界定 於各噴嘴室24的室頂中。各噴嘴開口 26 —般爲橢圓形並 具有相關的噴嘴邊緣25。該噴嘴邊緣25在列印的期間有 助於液滴定向性以及降低，至少達某個程度，墨水從該噴 嘴開口 26溢出來。自該噴嘴室24噴出墨水的作動器爲位 於該噴嘴開口 2 6下方並橫跨凹坑8懸著的加熱器元件2 9 。電流經由連至該基材2的CMOS層底下之驅動電路的電 極9供應至該加熱器元件2 9。當電流通過該加熱器元件 29時，其迅速將周圍的墨水過度加熱而形成氣泡，該氣 泡強迫墨水穿過該噴嘴開口 26。藉由使該加熱器元件29 懸著，當該噴嘴室24裝好時該加熱器元件29完全浸在墨 水中。這將改善列印頭效率，因爲較少的熱分散至下方基 材2內並使更多輸入能用以產生氣泡。 -20- 201127642 如第1圖中最清晰見到的’該等噴嘴係成排設置並使 沿著該排縱向延伸的墨水供應通道2 7供應墨水至該排中 的各噴嘴。該墨水供應通道27遞送墨水至各噴嘴的墨水 注入通道1 5，該墨水注入通道1 5 ’自該噴嘴開口 26側經 由該噴嘴室24中的墨水導管23供應墨水。 用於製造此等列印頭的MEMS裝配方法係說明於美 國專利案第7,303,930號，在此以引用方式將其全文倂入 本文。 具有懸吊的加熱器元件之列印頭的操作係詳細說明於 申請人的US 7,278,717，在此以引用方式將其全文倂入本 文。 申請人也說明具有嵌入式加熱器元件的形成氣泡之噴 墨列印頭。此等列印頭係說明於，例如，US 7,246,8 76及 US 2 006/02 5 0453，在此以引用方式將其全文倂入本文。 申請人的熱噴墨列印頭之特徵一般可爲擁有一或多個 下列特性：（i)懸吊的加熱器元件；（ii)具有少於1奈克， 選擇性少於500兆分之一克的加熱器元件；（iii)少於500 nJ，任意少於200 nJ的作動能；及（iv)氮化鈦或氮化鈦鋁 加熱器元件。 如上所述，在此所述的噴墨墨水可與申請人的熱噴墨 列印頭合倂作用以使結垢減至最少。然而，此等墨水的用 途並不限於申請人的熱列印頭且其也可用於習用熱噴墨列 印頭’如Hewlett-Packard及Canon在市場上販售者。 在習用掃描式熱噴墨列印頭（或，真正地，申請人的 [ -21 - 201127642 頁寬列印頭）的案例中，本發明可能關於用於包含在此所 述的噴墨墨水的噴墨列表機之墨水匣。該墨水匣可任意包 含與其整合在一起的熱噴墨列印頭。 爲求完整，倂入申請人的熱噴墨列印頭之列表機係說 明於，例如，us 7,201，468 ; US 7,3 60,86 1 ; US 7,3 80,9 1 0 :及US 7,357，496，在此以引用方式將其全文倂入本文。 第4圖顯示如申請人的美國申請案第1 2/062,5 1 4號 所述之熱噴墨印表機的列印引擎1 03，在此以引用方式將 其全文倂入本文。該列印引擎1 03包括移動式列印匣1 02 ，該移動式列印匣1 02包含頁寬列印頭，及一組使用者可 替換的墨水匣128。各色通道經常具有其本身的墨水槽 128及相應的壓力調節室106以供調節供應至該列印頭的 墨水之液壓。因而，該列印引擎1〇3具有5個墨水槽128 及5個相應的壓力調節室1 06。此5通道列印引擎1 〇3的 典型顏色通道構形爲 CMYKK或CMYK(IR)。各墨水匣 128可包含在此所述的噴墨墨水。 儘管第4圖中並未顯示不同零件之間的流體連結，但 是能分辨的是這些連結係依據，例如，美國申請案第 12/062,5丨4號所述的流體力學系統利用適合的吸水管構成 實驗 根據一般調配方法調配表1及2所述的墨水如下： (1 )在添加表面活性劑及水以提供無色墨水媒液之前 -22- 201127642 稱取共溶劑至適當容器中。 (2) 令該無色墨水媒液攪拌10分鐘。 (3) 將聚合物加至經攪拌的墨水媒液（除了比較例} 以外）。 (4 )在添加經表面改質的顏料之目U令所得的溶液再;^ 拌5分鐘。 (5)在過濾至0.3微米之前令此調合物攪拌15分鐘 。利用 Pall Profile II 1''片段過濾器（segment filter)過濾 墨水並使墨水在通入清洗過的容器之前再循環15分鐘。 表1.包含具有Tg < 100°C的丙烯酸系聚合物之墨水 種類 實施例1 實施例2 實施例3 實施例4 乙二醇 共溶劑 10份 22份 10份 10份 2-吡咯烷酮 共溶劑 9份 9份 9份 丙三醇 共溶劑 3份 3份 3份 SDP20003 顏料 5份 5份 5份 5份 Surfynol®465 表面活性劑 0.5份 0.5份 0.5份 0.5份 Joncryl® HPD296b 聚合物 3份 3份 1份 Joncryl® EC0684b 聚合物 1份 水 水 69.5 份 69.5 份 71.5 份 71.5 份 -23- 201127642 表2.不含具有Tg < 100°C的丙烯酸系聚合物之墨水 麵 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 乙二醇 共溶劑 10份 10份 10份 10份 10份 10份 2-吡咯烷酮 共溶劑 9份 9份 9份 9份 9份 9份 丙三醇 共溶劑 3份 3份 3份 3份 3份 3份 SDP20003 顏料 5份 5份 5份 5份 5份 5份 Surfynol®465 表面活性劑 0.5份 0.5份 0.5份 0.5份 0.5份 0.5份 Joncryl® HPD671b 聚合物 1份 Joncryl® HPD690b 聚合物 1份 Joncryl® HPD675b 聚合物 1份 Joncryl® HPD694b 聚合物 1份 Reactol®5145e 聚合物 1份 水 水 72.5 份 71.5 份 71.5 份 71·5 份 71.5 份 71.5 份 a可自Sensient Colors股份有限公司購得之經表面改質的 黑色顏料 b可自BASF購得之苯乙烯丙烯酸系分散劑樹脂 c可自Hexion Speciality Chemicals購得之聚醋樹脂 墨水解析度之評估 以Memjet®噴墨裝置（如上所述）於X400放大倍率觀 察及拍攝成像記錄（A)。該裝接著在於120°C乾燥15分鐘 之前先裝塡流體。噴嘴及加熱器接著於x400放大倍率觀 察及產生成像記錄（B)。 接著在該墨水媒液中靜置30分鐘之前以無色墨水媒 液清洗該裝置。接著給予最後的沖洗並利用氮流乾燥該等 裝置。 接著在拍攝第三個影像記錄（C)之前於x400放大倍率 -24- 201127642 觀察噴嘴及加熱器。 比較記錄（A)、（B)及（C)及利用下列等級爲記錄（C)之 噴嘴及加熱器的清潔度評分。 表3.乾燥墨水膜之溶解度的得分 分數 說明 1 記錄（B)與（C)之間沒有變化 2 記錄（B)與（C)之間稍有變化 3 (C)中的噴嘴及加熱器比記錄（B)乾淨許多 4 (C)中的噴嘴及加熱器看似（A)的噴嘴及加熱器 結垢之評估 以該流體塡入Memjet裝置並開始壽命硏究。此硏究 進行2千萬次作動並利用光學顯微鏡（χ400)評估於1千萬 次及2千萬次的結垢阻塞。頃發現於2千萬次作動的結垢 阻塞與1千萬次作動一致及因此利用於1千萬次作動的結 垢爲該等流體評分。表4描述所用的等級》 表4.結垢阻塞的得分 分數 __- ------------- 說明 1 大部分或整個加熱器上有大量沉積物 2 大部分加熱器上有中等量沉積物 3 該加熱器上有數個中等量沉積物區 4 加熱器稍有沉積物 5 加熱器乾淨且沒有沉積物 應用溶解度及結垢分數評估表1及2所述的墨水調合[S】 -25- 201127642 物。表5中顯示結果。 表5.各墨水之溶解度及結垢的比較 墨水 溶解度分數 結垢分數 聚合物觀 T“。C) Av (mgKOH/g) 實施例1 4 4 苯乙烯丙烯酸系 15 141 實施例2 4 4 苯乙烯丙烯酸系 15 141 實施例3 2 3 苯乙烯丙烯酸系 15 141 實施例4 2 3 苯乙烯丙烯酸系 88 243 比較例1 1 1 無聚合物 比較例2 1 1 苯乙烯丙烯酸系 128 214 比較例3 1 1 苯乙烯丙烯酸系 102 240 比較例4 2 1 苯乙烯丙烯酸系 103 222 比較例5 1 1 苯乙烯丙烯酸系 101 200 比較例6 1 2 聚酯 140 130 從表5，可見到只有那些含有具有<1〇〇°(：之Tg的苯 乙烯·丙烯酸系聚合物之墨水得到最高結垢分數（即較少加 熱器結垢）。在不含聚合物或含有具有>1〇〇。(：之Tg的聚合 物之墨水中，該加熱器元件的結垢一般在1千萬次作動之 後很嚴重。這些結果確定將具有<100°C之Tg的丙烯酸系 聚合物加至噴墨墨水就降低加熱器結垢的觀點來看有相當 有益的效果。假使至今咸瞭解非揮發性聚合物分散劑會造 成顏料爲底的墨水之結垢，則利用指定類型的聚合物分散 劑降低加熱器結垢很令人驚訝。 當然，咸明白本發明僅藉由實施例的方式予以說明且 細節的修飾可在隨附申請專利範圍所界定的本發明範圍以 內完成。 -26- 201127642 【圖式簡單說明】 現在將藉由示範的方式僅參照隨附的圖式描述本發明 的任意具體實施例，其中： 第1圖爲熱噴墨列印頭的一部分之透視圖； 第2圖爲第1圖所示的噴嘴裝配件之一的側視圖； 第3圖爲第2圖所示的噴嘴裝配件之透視圖；及 第4圖爲熱噴墨列印引擎之透視圖。 【主要元件符號說明】 2 :砂晶圓基材 8 :凹坑 9 :電極 1 5 :墨水注入通道 2 1 :室頂 2 2 :側壁 2 3 :墨水導管 2 4 :噴嘴室 25 :噴嘴邊緣 2 6 :噴嘴開口 2 7 :墨水供應通道 2 9 :加熱器元件 56 :噴嘴板 102 :移動式列印匣 103 :列印引擎 -27- 201127642 1 0 6 :壓力調節室 128:使用者可替換的墨水匣 -28-Ethylene 'diethylene amount of polytetramethylene 1,4-butanediol triol, butyl tetrasaccharide, _, xylitol, one of them so that -16-201127642 the aqueous ink accelerates penetration into the recording medium. Examples of suitable percolated alkyl ethers (glycol ethers) and/or 1,2-alkyl glycol alkyl alcohol ethers are ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and B. Glycol monomethyl ether acetate, diethylene glycol glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoglycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol Glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-n-propyl ether , ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diether, dipropylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether and dibutyl ether. An example of a suitable 1,2-alkyl glycol is 1,2. hexanediol. The penetrant may also be selected from the group consisting of linear hydrocarbon glycols, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol '1,8-octanediol. Glycerol can also be used as a penetrant. The amount of cosolvent present in the ink is often in the range of about 5% by weight, or any of the 10% to 30,000 weight systems, which can be used in the present invention, including acetone and glycerol. The inkjet ink may also contain a surfactant such as an anionic agent and/or a nonionic surfactant. Useful negative agents include sulfonic acid types such as alkane sulfonates, α-olefin sulfobenzene sulfonates, alkylnaphthalene sulfonic acids, mercaptomethyl bovine sulfosuccinic acids; alkyl sulfate salts, Sulfated oil-based penetrants include multiple menses. Suitable poly-monoethyl ether, ethylene monomethyl ether 'diethyl isopropyl ether, diethylene mono-n-butyl ether, triethylene glycol single third butane, propylene glycol monoethylene glycol monopropylene glycol mono-n-propylene dipropylene glycol single positive - Propylene glycol and 1,2-such as 1,3 - propanediol 1,7-heptanediol and 5% by weight to 40% by weight. Cosolvent diol, 2-pyrrole ion surface active ion surface active acid salt, alkyl acid and dialkyl, sulfated olefin-17- 201127642, polyoxyethylene alkyl ether sulfate salt; carboxylic acid Types, for example, fatty acid salts and alkyl sarcosinates; and phosphate type, such as alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, and glycerophosphate salts. Designated examples of the anionic surfactant are sodium dodecylbenzenesulfonate, sodium laurate, and polyoxyethylene alkyl ether sulfate. Examples of the nonionic surfactant include ethylene oxide addition molding such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, and polyoxyethylene alkylguanamines. Polyol ester type, such as glyceryl alkyl esters, sorbitan alkyl esters and sugar alkyl esters; polyether type, such as polyhydric alcohol alkyl ethers; and alkanolamine type, such as alkanes Alcohol amine fatty acid guanamines. Designated examples of nonionic surfactants are ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl Ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether and polyoxyalkylene alkyl ethers (such as polyoxyethylene alkyl ethers); and esters such as polyoxyethylene oleate, polyoxyethylene oleic acid Ester, polyoxyethylene stearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate And polyoxyethylene stearate. An acetylene glycol surfactant such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-di Alcohol or 3,5-dimethyl-1-hexyn-3-ol can also be used. The surfactant is often present in the aqueous inkjet ink in an amount ranging from 0.1% by weight to 1% by weight, or optionally in the range of from 2,000% by weight to 5% by weight. A designated example of a nonionic surfactant which can be used in the present invention is Surfynol® 465 (available from Air Products and Chemicals, Inc. -18-201127642, Inc.). The aqueous inkjet ink may also include a pH adjusting agent such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, lithium carbonate, sodium phosphate, potassium phosphate, lithium phosphate. , potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium oxalate, potassium oxalate, lithium oxalate, sodium borate, sodium tetraborate, potassium hydroborate and potassium hydrogen tartrate; ammonia; and amines such as methylamine, ethylamine, two Ethylamine, trimethylamine, triethylamine, cis (hydroxymethyl) aminomethane hydrochloride, triethanolamine, diethanolamine, diethylethanolamine, triisopropanolamine, butyldiethanolamine, morpholine and propanol amine. The aqueous inkjet ink may also include biocides such as benzoic acid, dichlorophene, hexachlorophene, hexadienoic acid, hydroxybenzoic acid esters, sodium dehydroacetate, 1,2-benzene thiazolin-3- Ketone, 3,4-isothialin-3-one or 4,4-dimethyloxazolidine. The aqueous inkjet ink may also contain a chelating agent such as ethylenediaminetetraacetic acid (EDTA). Thermal Inkjet Printheads The inkjet inks described herein minimize fouling in thermal inkjet printheads. The following is a brief description of one of the applicant's thermal inkjet printheads, as described in U.S. Patent No. 7,3,03,93, the entire disclosure of which is incorporated herein by reference. Referring to Figure 1, a portion of a printhead comprising a plurality of inkjet assemblies is shown. Figures 2 and 3 show one of these nozzle assemblies in a side profile and a cutaway perspective view. -19- 201127642 Each nozzle assembly includes a nozzle chamber 24 formed by a MEMS assembly technique on a crucible wafer substrate 2. The nozzle chamber 24 is defined by a chamber top 21 and a side wall 22 extending from the chamber top 21 to the chopping substrate 2. As shown in Fig. 1, each of the chamber tops is defined by a portion of the nozzle plate 56 which spans the discharge surface of the print head. The nozzle plate 56 and the side wall 22 are constructed of the same material which is deposited by PECVD on the sacrificial support of the photoresist during MEMS assembly. Frequently, the nozzle plate 56 and side walls 22 are constructed of a ceramic material such as hafnium oxide or tantalum nitride. These hard materials have the excellent properties required for the robustness of the print head, and their inherent hydrophobic properties are beneficial for supplying ink to the nozzle chamber 24 by capillary action. Returning to the detail of the nozzle chamber 24, it can be seen that the nozzle opening 26 is defined in the roof of each nozzle chamber 24. Each nozzle opening 26 is generally elliptical and has an associated nozzle edge 25. The nozzle edge 25 facilitates droplet orientation and reduction during printing, at least to some extent, and ink overflows from the nozzle opening 26. The actuator that ejects ink from the nozzle chamber 24 is a heater element 2 9 located below the nozzle opening 26 and suspended across the dimple 8. Current is supplied to the heater element 209 via the electrode 9 connected to the drive circuit under the CMOS layer of the substrate 2. As current passes through the heater element 29, it rapidly overheats the surrounding ink to form a bubble that forces the ink through the nozzle opening 26. By suspending the heater element 29, the heater element 29 is completely immersed in the ink when the nozzle chamber 24 is installed. This will improve the efficiency of the printhead because less heat is dissipated into the underlying substrate 2 and more input can be used to create bubbles. -20- 201127642 As seen most clearly in Figure 1, the nozzles are arranged in rows and the ink supply channels 27 extending longitudinally along the row supply ink to the nozzles in the row. The ink supply path 27 delivers ink to the ink injection passages 15 of the respective nozzles, from which the ink is supplied by the ink conduits 23 in the nozzle chambers 24 from the nozzle opening 26 side. The MEMS assembly method for the manufacture of such printheads is described in U.S. Patent No. 7,303,930, the disclosure of which is incorporated herein in its entirety. The operation of a printhead having a suspended heater element is described in detail in the Applicant's U.S. Patent No. 7,278, the entire disclosure of which is incorporated herein by reference. The Applicant also describes a bubble forming ink jet print head having an embedded heater element. Such print heads are described, for example, in US Pat. No. 7,246,8,76, and US Pat. Applicants' thermal inkjet printheads are generally characterized by one or more of the following characteristics: (i) suspended heater elements; (ii) having less than 1 ng, selectivity less than 500 megapixels One gram of heater element; (iii) less than 500 nJ, any less than 200 nJ of kinetic energy; and (iv) titanium nitride or titanium aluminum nitride heater elements. As noted above, the inkjet inks described herein can be combined with Applicants' thermal inkjet printheads to minimize fouling. However, the use of such inks is not limited to Applicant's thermal print heads and it can also be used in conventional thermal ink jet print heads such as Hewlett-Packard and Canon. In the case of conventional scanning thermal inkjet printheads (or, indeed, Applicant's [-21 - 201127642 page wide printheads), the invention may be directed to inkjet inks for use in the inkjet inks described herein. The ink cartridge of the inkjet lister. The ink cartridge can optionally contain a thermal inkjet printhead integrated therewith. For completeness, the list of applicants' thermal inkjet print heads is described, for example, us 7,201,468; US 7,3 60,86 1 ; US 7,3 80,9 1 0 : and US 7,357,496, the entire disclosure of which is incorporated herein by reference. Figure 4 shows a print engine 103 of a thermal ink jet printer as described in U.S. Patent Application Serial No. 1 2/062, No. 5, which is incorporated herein by reference. The print engine 103 includes a mobile print cartridge 102, which includes a pagewidth printhead, and a set of user replaceable ink cartridges 128. Each color channel often has its own ink reservoir 128 and corresponding pressure adjustment chamber 106 for regulating the hydraulic pressure of the ink supplied to the print head. Thus, the print engine 1〇3 has five ink tanks 128 and five corresponding pressure adjustment chambers 106. The typical color channel configuration for this 5-channel print engine 1 〇3 is CMYKK or CMYK (IR). Each ink cartridge 128 can comprise the inkjet ink described herein. Although the fluid connection between the different parts is not shown in Figure 4, it can be distinguished that these connections are based on, for example, the fluid dynamics system described in U.S. Application Serial No. 12/062, No. 4, No. 4, which utilizes suitable water absorption. Tube Composition Experiments The inks described in Tables 1 and 2 were prepared according to the general formulation method as follows: (1) Before adding a surfactant and water to provide a colorless ink medium, -22-201127642 Weigh the co-solvent into a suitable container. (2) The colorless ink medium was stirred for 10 minutes. (3) The polymer was added to the stirred ink medium (except for Comparative Example). (4) Add the solution obtained by adding the surface-modified pigment to the solution for another 5 minutes. (5) The mixture was stirred for 15 minutes before being filtered to 0.3 μm. The ink was filtered using a Pall Profile II 1''s segment filter and the ink was recirculated for 15 minutes before being passed to the cleaned container. Table 1. Ink Types Containing Acrylic Polymers with Tg < 100 ° C Example 1 Example 2 Example 3 Example 4 Ethylene Glycol Cosolvent 10 Parts 22 parts 10 parts 10 parts 2-Pyrrolidone Cosolvent 9 9 parts 9 parts glycerol co-solvent 3 parts 3 parts 3 parts SDP20003 pigment 5 parts 5 parts 5 parts 5 parts Surfynol® 465 surfactant 0.5 parts 0.5 parts 0.5 parts 0.5 parts Joncryl® HPD296b polymer 3 parts 3 parts 1 Joncryl® EC0684b polymer 1 part water 69.5 parts 69.5 parts 71.5 parts 71.5 parts -23- 201127642 Table 2. Ink side without acrylic polymer with Tg < 100 ° C Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Ethylene glycol co-solvent 10 parts 10 parts 10 parts 10 parts 10 parts 10 parts 2-pyrrolidone co-solvent 9 parts 9 parts 9 parts 9 parts 9 parts 9 parts glycerol co-solvent 3 3 parts 3 parts 3 parts 3 parts 3 parts SDP20003 pigment 5 parts 5 parts 5 parts 5 parts 5 parts 5 parts Surfynol® 465 surfactant 0.5 parts 0.5 parts 0.5 parts 0.5 parts 0.5 parts 0.5 parts Joncryl® HPD671b polymer 1 part Joncryl® HPD690b polymer 1 part Joncryl® HPD67 5b polymer 1 part Joncryl® HPD694b polymer 1 part Reactol® 5145e polymer 1 part water 72.5 parts 71.5 parts 71.5 parts 71·5 parts 71.5 parts 71.5 parts a surface modification available from Sensient Colors Co., Ltd. The black pigment b can be obtained from BASF. The styrene acrylic dispersant resin c can be obtained from Hexion Speciality Chemicals. The evaluation of the resolution of the polyester resin ink is observed by the Memjet® inkjet device (described above) at X400 magnification. And shooting imaging records (A). The package was then filled with a helium fluid prior to drying at 120 ° C for 15 minutes. The nozzle and heater then observe and produce an imaging record (B) at x400 magnification. The apparatus was then washed with a colorless ink medium before standing in the ink medium for 30 minutes. The final rinse is then given and the devices are dried using a stream of nitrogen. Then observe the nozzle and heater at x400 magnification -24- 201127642 before taking the third image recording (C). The records (A), (B), and (C) were compared and the cleanliness scores of the nozzles and heaters using the following grades were recorded (C). Table 3. Score scores for solubility of dry ink film Description 1 No change between records (B) and (C) 2 Record slightly change between (B) and (C) 3 Nozzle and heater ratio in (C) Record (B) clean the nozzles in the 4 (C) and the heaters as if (A) the nozzle and heater scale were evaluated to break into the Memjet device and begin life testing. This study was performed 20 million times and was evaluated by 10 to 10 million and 20 million times of fouling obstruction using an optical microscope (χ400). It was found that 20 million actuations of fouling were consistent with 10 million actuations and therefore scaled for 10 million actuations. Table 4 describes the grades used. Table 4. Score scores for fouling blockage __- ------------- Description 1 Large or large deposits on most or all heaters 2 Most heaters There is a moderate amount of sediment on the heater. There are several medium deposits on the heater. 4 The heater has a slight deposit. 5 The heater is clean and there is no deposit. Solubility and fouling fraction are evaluated. The ink blending described in Tables 1 and 2 is evaluated [ S] -25- 201127642. The results are shown in Table 5. Table 5. Comparison of Solubility and Fouling of Each Ink Solubility Fraction Fraction Fraction Polymer View T ".C) Av (mgKOH/g) Example 1 4 4 Styrene Acrylic 15 141 Example 2 4 4 Styrene Acrylic 15 141 Example 3 2 3 Styrene acrylic 15 141 Example 4 2 3 Styrene acrylic 88 243 Comparative Example 1 1 1 No polymer Comparative Example 2 1 1 Styrene acrylic 128 214 Comparative Example 3 1 1 Styrene Acrylic 102 240 Comparative Example 4 2 1 Styrene Acrylic 103 222 Comparative Example 5 1 1 Styrene Acrylic 101 200 Comparative Example 6 1 2 Polyester 140 130 From Table 5, it can be seen that only those containing <1 〇〇° (: Tg of styrene·acrylic polymer ink gives the highest fouling fraction (ie less heater fouling). In the absence of polymer or contains >1〇〇. (: Tg In the polymer ink, the fouling of the heater element is generally severe after 10 million actuations. These results confirm that the addition of an acrylic polymer having a Tg of <100 ° C to the inkjet ink reduces heating. From the point of view of scale formation Beneficial effects. It is surprising to use a specified type of polymer dispersant to reduce heater fouling, provided that the non-volatile polymer dispersant is known to cause fouling of pigment-based inks. The invention will be described by way of example only and the details of the invention may be made within the scope of the invention as defined by the appended claims. -26- 201127642 [Simple description of the drawings] The accompanying drawings describe any embodiment of the invention, wherein: Figure 1 is a perspective view of a portion of a thermal inkjet printhead; Figure 2 is a side elevational view of one of the nozzle assemblies of Figure 1; Figure 3 is a perspective view of the nozzle assembly shown in Figure 2; and Figure 4 is a perspective view of the thermal inkjet printing engine. [Main component symbol description] 2: Sand wafer substrate 8: pit 9 : Electrode 1 5 : ink injection passage 2 1 : chamber top 2 2 : side wall 2 3 : ink conduit 2 4 : nozzle chamber 25 : nozzle edge 2 6 : nozzle opening 2 7 : ink supply passage 2 9 : heater element 56 : Nozzle plate 102: mobile printing 匣 103 :Printing Engine -27- 201127642 1 0 6 : Pressure Regulating Chamber 128: User-Replaceable Ink 匣 -28-