TW200406253A - Defoaming dispersion agent for photosensitive protective film developer - Google Patents

Abstract

A defoaming dispersion agent for a anti-corrosive developer is characterized in providing an excellent defoaming property to a developer during the developing process of the anti-corrosive developer to have a good dispersion to the precipitation formed by the developer. The invented defoaming dispersion agent for a photosensitive protective film developer includes, based on 100 part by mass of a high aliphatic acid containing a carbon number of 15 and higher, 5~300 part by mass of C6~C14 intermediate aliphatic acid mixture, and a portion of aliphatic acid ester capable of reacting with aliphatic tri-valenced alcohol.

Description

200406253 五、發明說明（1) 發明内容 【發明所屬之技術領域】 本發明係有關使用顯像液之感光保護膜之顯像工程，針璧士 顯像液之發泡的消泡性優越，且對於顯像液中發生之沉幾 物的分散性亦有優良效果之保護膜顯像液用消泡分散劑。 【先前技術】 從來抗蝕劑廣為一般印表機基板迴路、集積迴路、濾色器 (color filter)等形成配線圖像（pattern)時所使用。200406253 V. Description of the invention (1) Summary of the invention [Technical field to which the invention belongs] The present invention relates to a development process of a photosensitive protective film using a developing solution, and the foaming property of the needle developer developing solution is superior, and An antifoaming dispersant for a protective film developing solution which also has an excellent effect on the dispersibility of the precipitates in the developing solution. [Prior art] It has been widely used in the formation of wiring patterns from substrates, integrated circuits, color filters, etc. of conventional printer substrates.

又配線圖像（pattern)之形成工程通常以膠狀或是液狀的 抗#劑於基板上形成薄膜又或塗佈之，之後於上記之抗麵 劑（resist)經紫外線、X光線、電磁線等活性放射線照射 曝光後，使抗姓劑（r e s i s t)成圖像（p a 11 e r η )硬化後，利 用顯像液除去未硬化之抗餘劑（r e s i s t)部分（非照射部分 )，使抗蝕劑顯現影像，從而形成圖像（pattern)之感光 保護（resist)膜。The formation process of the wiring pattern (pattern) usually uses a gel or liquid anti- # agent to form a thin film on the substrate or coat it, and then the above-mentioned anti-resist is subjected to ultraviolet, X-ray, and electromagnetic radiation. After exposure to active radiation such as radiation, the anti-resist agent is cured into an image (pa 11 er η), and then the uncured anti-resist agent (non-irradiated part) is removed with a developing solution to make the anti-resistance The etchant develops an image, thereby forming a photosensitive resist film of the pattern.

至於顯像液通常為驗性（a 1 ka 1 ine)之水溶液，而顯像液之 驗性劑則多用驗性金屬碳酸鹽（b a s i c i t y m e t a 1 carbonate)，水酸化鹼金屬（alkaline metal)等無機鹼性 化合物或疋沒基四曱基錢（tetra methyl ammonium hydroxyl group)等有機驗性化合物。 像這樣的鹼性顯像液，通常於抗蝕劑之顯像過程中將未硬 化之抗蝕劑，亦即樹脂成分、抗蝕劑中所含之染料、顏 料、重合開始劑、架橋劑等，於顯像液中溶解分散並混合As for the imaging solution, it is usually an aqueous solution of a 1 ka 1 ine, and the test agent of the imaging solution is mostly an inorganic alkali such as basicity metal carbonate (akaline metal), water acidified alkali metal (alkaline metal), etc. Organic compounds such as sex compounds or tetra methyl ammonium hydroxyl group. Such an alkaline developing solution usually uses an uncured resist during the development of the resist, that is, a resin component, a dye contained in the resist, a pigment, a superposition initiator, a bridging agent, etc. , Dissolve and mix in the developing solution

第6頁 五、發明說明（2) 之，而於顯像液中凝集進而浮於 — 顯像液中，即是於顯像液中生点”、、員像液之表面或是沉澱於 物，於顯像時附著於顯像裝成所謂的沉澱物。此沉澱 像，上記之沉澱物，於顯像=，不僅會妨礙抗蝕劑之顯 蝕劑或是塗佈抗蝕劑之基材，會附著於被顯像物諸如抗 是無法形成良好 土 ’造成抗餘劑解像度不佳，或 圖像之感光保護膜等問題。因 顯像過程中可分散所產生沉二對於顯像液多要求其於 另一方面，抗蝕劑顯像時，^ _可防止沉澱物的凝集。 液產生氣泡，由於顯像液通常可中混入空氣使顯像 所產生之氣泡未能完全消除 、：2用，如在顯像液中 特別是由於顯像液可循環使用、，$，包㈢積存於顯像液中。 分散之抗蝕劑成分增加（樹脂而使在顯像液中溶解而 泡更形困難。這種氣泡不但對ϋ像二：消！顯像液之氣 害，更會阻礙顯冑液與抗钱劑之 1循$使用有所妨 未硬化之抗蝕劑部分，或是盔法^ ^ &成無法完全去除 膜等問題。近年成為主流之抗银劑像感光保護 之方式’使顯像液更容易混入空氣：：：顯像液使之顯像 液中如何抑制發泡及消泡是非常n’因此對於顯像 如欲抑制顯像液之發泡，於顯像液中 的方法’但該消泡劑於顯像液中會凝：口二’包劑雖是有效 沉澱物於顯像過程中會附著於抗蝕劑=龙t之沉澱物，該 形成良好之圖像减来俘镬膜 承合一 /、土反，不但無法 α先保蔓膜更會〉7染抗蝕劑顯像用之基 200406253Page 6 V. Description of the invention (2) Among them, the agglutination in the developing solution floats on—in the developing solution, that is, the growth point in the developing solution ”, the surface of the imaging solution or the sediment At the time of development, it is attached to the development device and installed as a so-called deposit. This precipitation image, the above-mentioned deposit, is used in the development image =, it will not only hinder the resist or the resist coating substrate. It will attach to the object to be developed, such as the inability to form good soil, resulting in poor resolution of the residual agent, or the photosensitive protective film of the image. Due to the dispersibility during the development process, Shen Er has a lot of imaging fluid. It is required that on the other hand, when the resist is developed, ^ _ can prevent the agglomeration of the precipitate. The liquid generates bubbles, because the developing solution can usually be mixed with air, so that the bubbles generated during the development cannot be completely eliminated. It can be used in the developing solution, especially because the developing solution can be reused. $, And the baggage is accumulated in the developing solution. The dispersed resist component is increased (the resin will dissolve in the developing solution and foam more. It ’s difficult to shape. This kind of air bubble not only prevents the second image: elimination! The use of diarrhea solution and anti-money agent may cause problems such as unhardened resist parts or the helmet method ^ ^ & the film cannot be completely removed. In recent years, it has become the mainstream anti-silver agent such as photosensitive protection. Method 'Make the developer easier to mix into the air ::: The developer makes the developer to suppress foaming and defoaming in the developer. It is very n'. Therefore, if you want to suppress the developer's foam in the developer, Method in liquid ', but the defoamer will coagulate in the developing solution: Although the second agent is an effective deposit, it will adhere to the resist = dragon's deposit during the development process, which forms well. The image is reduced, the capture film is integrated, and the soil is reversed. Not only can the alpha film be protected, but also the film will be better.

五、發明說明（3) 板0 一般而言作為消泡用途的藥劑，多以矽氧烷（s i丨丨） 類消泡劑之消泡效果較良好，矽氧烷（silic〇ne)類消泡 劑則易形成沉澱物’如以顯像液用之消泡劑而[例如乙 炔醇（acetylene alcohol)類界面活性劑（參考如特許 文獻1 )，聚亞烷基二醇（polyalkylene 導體（參考如特許文獻2一7)，單（_。）高級脂)肪戈酸甘誘 油8曰（glycerol)(參考如特許文獻8)等為普遍 藥劑。 像液中所產生之沉澱物的分 用初期對消泡之功能雖有一 解及刀散之抗钕劑成分增加 ’且又有易發生沉澱物之缺 但是這些既有之消泡劑對於顯 散性並不足夠，該消泡劑在使 定之效果，但隨著顯像液中溶 之後，其消泡效果便急遽下降 【特許文獻1】特公平4-5 1 020號公報 【特許文獻2】特開平7 —丨28865號公報 【特許文獻3】特開平8-1〇6〇〇號公報 【特許文獻4】特開平8-87382號公報 【特許文獻5】特開平9_1 72256號公報 【特許文獻6】特開平1〇_3196〇6號公報 【特許文獻7】特開20 0 1 —222 1 1 5號公報 【特許文獻8】特開平9_293964號公報 200406253 五、發明說明（4) 因此，本發明之目的在於提供一 便是顯像液中溶解或是分於抗蝕劑顯像 液之消泡效果依然良好=成分增加， 殿物，亦能防止沉澱物附著於d?像液中 顯像液用消泡分散劑。 μ或疋其基板 ^此本發明者群對於顯像液H 性」略稱之）與顯像液中產 2 j下僅以 以「沉殿物分散性」略稱之性 討，並發現以具有特定脂肪 :::丨： 三價醇的部分脂肪酸醋，對於上述之 性有優良之效果，故提出本發明。即是，本ς 高級脂肪酸ι〇°質量部，•以5二。〇 比率之奴兀素6-14以上之中級脂肪酸混合成的、、曰 與產生反應的脂肪族三價醇之部分脂肪酸:旨 =成之抗蝕劑顯像液用消泡分散劑（以下亦稱之 脂肪酸酯」）卩及含有上列敘述為特徵的鹼性抗 液。 【實施方式】 $發明的效果在於提供一種於抗蝕劑在顯像液中 時，即便增加顯像液中溶解又或分散之抗蝕劑成 顯像液仍有強效之消泡劑，並對於顯像液中產生 有優良之分散性，且能防止該沉澱物附著於抗蝕 基板之抗蝕劑顯像液用消泡分散劑。 基於本發明，高級脂肪酸代表碳元素丨5以上之脂 第9頁 之時，即 對於顯像 產生之沉 之抗餘劑 「消泡 (以下僅 深入的檢 與脂肪酸 ;殿物分散 以含有碳 質量部之 合脂肪 為特徵所 為「部分 蝕劑顯像 顯像之 分，對於 之沉澱物 劑又或其 肪酸，中 200406253 五、發明說明（5) 級脂肪酸代表碳元素6 -1 4以上之脂肪酸。本發明的部分脂 肪酸酯的原料混合脂肪酸’係指以含有碳元素1 5以上之高 級脂肪酸100質量部，與以5-300質量部之比率之碳元素 6 - 1 4以上之中級脂肪酸混合成的混合脂肪酸。中級脂肪酸 的比率少於5質量部時，則本發明之抗钱劑顯像液用消泡 分散劑的沉殿物分散性便不佳；比率多於3 0 0質量部時， 則消除顯像液中產生的氣泡之消泡性便不良。與高級脂肪 酸100質量部比較之，中級脂肪酸之比例以1 0-200質量部 為佳，25-1 50質量部更佳，40- 1 00質量部為最佳。 對碳元素1 5以上之高級脂肪酸而言，例如：十五烷酸 (pentadecane )、十六烧酸（hexadecane )(絲躐烧） (cetane)、十七烧酸、十八烧酸（octadecylic acid) (硬脂酸）（stearic acid) 、12 -經基十八烧酸（12-hydroxyl octadecylic acid )(12-經基硬脂酸） （12 -hydroxy 1 stearic acid )、二十烧（eicosane CH3[CH2]18CH20H )(花生酸）（arachi acid )、二十二烷 酸（docosanoic acid)(山榆酸）（behenic acid)、二 十四烧酸（tetracosanoic acid)(木躐酸）（lignoceric acid )、二十六(hexacosanoi c acid )(堪酸）（cerotic acid)、二十八（octacosanoic acid)(褐煤酸） (montanic acid)等的直鏈飽和脂肪酸；2 -戊基壬酸 (2-pentyl nonanoic acid ) 、2-己基癸酸（2 - hexyl decane acid) 、2-庚基十二烷酸（2-heptylic dodecane acid)、異硬脂酸（isostearic acid)等的分枝脂肪V. Description of the invention (3) Board 0 Generally speaking, it is used as a defoaming agent. Siloxane (si 丨 丨) defoamers have better defoaming effects. Foaming agents tend to form precipitates, such as defoamers used in imaging solutions [such as acetylene alcohol surfactants (see, for example, Patent Document 1), polyalkylene glycol (polyalkylene conductor (see For example, Patent Document 2-7), single (_.) Higher fat) fatty acid and glycerol oil (glycerol) (refer to, for example, Patent Document 8) and the like are universal medicines. Although the precipitation of the precipitate generated in the image liquid has a defoaming function in the early stage of decontamination, the anti-neodymium component of the anti-neodymium agent is increased, and there is a lack of precipitation. The defoaming effect is not sufficient. The defoaming effect of the defoaming agent decreases sharply as it dissolves in the developing solution. [Patent Document 1] JP 4-5 1 020 [Patent Document 2] Japanese Patent Application Laid-Open No. 7-丨 28865 [Patent Document 3] Japanese Patent Publication No. 8-1106 [Japanese Patent Document 4] Japanese Patent Publication No. 8-87382 [Japanese Patent Application] Japanese Patent Publication No. 9_1 72256 [Japanese Patent Application] 6] Japanese Unexamined Patent Publication No. 10_3196〇6 [Patent Document 7] Japanese Unexamined Patent Publication No. 20 0 1 -222 1 1 [Japanese Patent No. 8] Japanese Unexamined Patent Publication No. 9_293964 200406253 5. Explanation of the invention (4) Therefore, the present invention The purpose of the invention is to provide a solution that is dissolved in the developing solution or divided into the resist developing solution. The defoaming effect is still good = the composition is increased, and the artifact can also prevent the sediment from adhering to the imaging solution. Liquid defoaming dispersant. μ or 疋 its substrate ^ This inventor group is referred to as "developing solution H property" and "2" in the developing solution is only referred to as "sinking material dispersion", and found to have Specific fat ::: 丨: Partial fatty acid vinegar of trivalent alcohol has excellent effects on the aforementioned properties, so the present invention is proposed. That is, the quality department of this ς higher fatty acid ι0 °, • Take 5 to two. 〇Ratio of 6-14 or more intermediate fatty acids, a part of the fatty acids that are reacted with the aliphatic trivalent alcohol that reacts: a defoaming dispersant for the resist developing solution (hereinafter also referred to as It is called fatty acid ester ") and contains alkaline anti-liquid which is characterized by the above description. [Embodiment] The effect of the invention is to provide a strong defoamer even when the resist is in the developing solution, even if the resist dissolved or dispersed in the developing solution is increased to form a developing solution, and A defoaming dispersant for a resist developing solution that has excellent dispersibility in a developing solution and prevents the deposit from adhering to a resist substrate. Based on the present invention, when higher fatty acids represent carbons with lipids of 5 or more on page 9, it is the anti-foaming agent for anti-foam produced by imaging "defoaming (the following is only an in-depth examination of fatty acids; The combination of fats is characterized by the "partially corrosive agent imaging and development. For the precipitation agent or its fatty acid, the 200406253. V. Description of the invention (5) Grade fatty acids represent fatty acids with carbon elements 6 -1 4 or more. The mixed fatty acid of the raw material of the partial fatty acid ester of the present invention is a mixture of 100 parts by mass of higher fatty acids containing 15 or more carbon elements and 6-14 or more intermediate fatty acids with carbon elements at a ratio of 5-300 parts by mass. When the ratio of the intermediate fatty acid is less than 5 parts by mass, the dispersibility of the antifoam dispersant for the antifoam imaging solution of the present invention is not good; when the ratio is more than 300 parts by mass , The defoaming property of eliminating the bubbles generated in the developing solution is poor. Compared with the 100 parts by mass of higher fatty acids, the proportion of middle fatty acids is preferably 10-200 parts by mass, 25-1 by 50 parts by mass, 40 -1 00 quality For the higher fatty acids with a carbon element of 15 or more, for example: pentadecane, hexadecane (cetane), heptadecant Octadecylic acid (stearic acid), 12-hydroxyl octadecylic acid (12-hydroxy 1 stearic acid), 20 (Eicosane CH3 [CH2] 18CH20H) (arachiic acid), docosanoic acid (behenic acid), tetracosanoic acid (tetrakidic acid) ) (Lignoceric acid), hexacosanoi c acid (cerotic acid), octacosanoic acid (montanic acid), and other straight-chain saturated fatty acids; 2-pentylnonyl Acid (2-pentyl nonanoic acid), 2-hexyl decane acid, 2-heptylic dodecane acid, isostearic acid, etc. fat

第10頁 200406253 五、發明說明（6)Page 10 200406253 V. Description of the invention (6)

酸；棕摘油酸（pa 1 m i to 1 e i c ac i d CH3 [ CH2 ] 5CH )、油 酸（oleic acid)、異油酸（isooleic acid)、反油酸 (elaidic acid)、亞油酸（linoleic acid)、亞麻酸 (linolenic acid)、蓖麻油酸（ricinoleic acid)、 順式9-二十破稀酸（gadoleic acid)、芥酸（erucic acid)、鯊油酸（selacholeic acid)等不飽和脂肪酸等 等舉例之。在這些高級脂肪酸中亦以碳元素1 6 - 2 2的脂肪 酸為佳，碳元素16-20的脂肪酸更佳，碳元素為16-18的脂 肪酸為最佳。 對碳元素6-14的中級脂肪酸而言，諸如：己酸（hexanoic acid)、庚酸（heptanoic acid CH3[CH2]5C00H)、辛酸 (octane acid)、壬酸(nonane acid )、癸酸(decane acid) 、H--烧酸(undeccano i c acid )、十二烧酸Acid; palm oleic acid (pa 1 mi to 1 eic ac id CH3 [CH2] 5CH), oleic acid, isooleic acid, elaidic acid, linoleic unsaturated fatty acids such as linolenic acid, linolenic acid, ricinoleic acid, cis 9-episodic acid, gadoleic acid, erucic acid, and selacholeic acid Wait for an example. Among these higher fatty acids, fatty acids with a carbon element of 16-2 2 are preferred, fatty acids with a carbon element of 16-20 are more preferred, and fatty acids with a carbon element of 16-18 are most preferred. For intermediate fatty acids of carbon 6-14, such as: hexanoic acid, heptanoic acid CH3 [CH2] 5C00H), octane acid, nonane acid, decane acid), H--undeccano ic acid, dodecanoic acid

(dodecane acid)(月桂酸）、十三烧酸（tridceanoic acid)、十四烧酸（tetra decane acid)(肉豆蔻酸）等 直鏈飽和脂肪酸；異己烧酸（isohexanoic acid)、異肩^ 烧酸（isoheptanoic acid) 、2-乙基己酸（2-ethyl hexoic acid)、異辛烧酸（isooctane acid)、異壬燒 酸（isononane acid) 、2 -丙基庚烧酸（2 - propyl heptanoic acid)、異癸酸（isodecane acid)、異十— 烧酸（isoundeccanoic acid) 、2- 丁基辛炫酸（2-botyi octane acid)、異十二烧酸（isododecane acid)、異 十三烧酸（isotridceanoic acid)等分枝脂肪酸；l〇〜十 一碳烯酸（10-undecenoic acid)等不飽和脂肪酸。這止上(dodecane acid) (lauric acid), tridceanoic acid, tetra decane acid (myristic acid) and other straight-chain saturated fatty acids; isohexanoic acid, iso shoulder Acid (isoheptanoic acid), 2-ethyl hexoic acid, isooctane acid, isononane acid, 2-propyl heptanoic acid acid), isodecane acid, isodeeccanoic acid, 2-botyi octane acid, isododecane acid, isododecane acid Branched fatty acids such as isotridceanoic acid; unsaturated fatty acids such as 10-undecenoic acid. This ends

第11頁 200406253Page 11 200406253

中級脂 脂肪酸 此外， 飽和脂 分枝脂 本發明 該部分 脂肪酸 合脂肪 例更佳 的脂肪酸為佳，碳元素8-13的 更佳奴兀素UM2的脂肪酸為最佳。 分脂肪酸醋的原料混和脂肪酸僅為直鏈 =;二脂肪酸還不如以含有直鏈飽和脂肪酸與 肪酸和直鏈不餉^7 ' 々划八昨#月日肪S夂之混合脂肪酸較佳。藉由 r L s:二总酸酯使顯像液中的沉澱物分散性良好且 :: ::易，顯像液中溶解分散故更為優良。混合 、:知肪酸及直鏈不飽和脂肪酸的比例，以混 酉夂王里之5-80質量％的比例為佳，1〇 — 7〇質量％的比 ，1 5 - 6 0質量％的比例最佳。 再者，本發明的部分脂肪酸酯的原料混和脂肪酸，如以本 發明之抗蝕劑顯像液用消泡分散劑中以不導致消泡性及沉 澱物分散性不良影響之範圍為訴求時，也可以含有前記之 中級S曰肪酸及南級脂肪酸以外之殘酸。 本發明的部分脂肪酸酯的原料脂肪族3價醇，諸如：丙三 )、1，2，4-丁二醇（1，2，4 -butanetriol) 、2-經甲基 -1 (2 hydroxymethyl -1) 、3- 丙二醇（3 - propanediol )、 2 甲基一 1，2，3-丙二醇（2-methyl-1，2，3-propanetriol )、1，2,5-戊三醇（l，2,5-pentanetriol) 、1，3,5-戊三 醇（l，3,5-pentanetriol) 、2-甲基-1，2,4-丙三醇（2- methyl -1，2,4-propanetriol ) 、2 -經曱基 -1，3 -丁二醇 (2—hydroxymethyl-l，3-butanediol )、三甲基乙烧 (tri methyl ethane) 、1，3,5-己烷三醇Intermediate fat fatty acid In addition, the saturated fatty acid branched fat of the present invention is more preferably a fatty acid and a fatty acid, more preferably a fatty acid, more preferably a carbon element of 8-13, and a fatty acid of UM2. Fatty acid vinegar raw material mixed fatty acids are only straight-chain fatty acids; di-fatty acids are not as good as mixed fatty acids containing straight-chain saturated fatty acids and fatty acids and straight-chain fatty acids. The dispersibility of the precipitate in the developing solution by r L s: di total acid ester is good and :: :: is easy to dissolve and disperse in the developing solution, so it is more excellent. Mixing: The proportion of fatty acids and linear unsaturated fatty acids is preferably from 5 to 80% by mass in Wanglili, 10 to 70% by mass, and 15 to 60% by mass. Best proportion. In addition, when the raw material mixed fatty acid of the partial fatty acid ester of the present invention is used in the defoaming dispersant for the resist developing solution of the present invention, the range that does not cause adverse effects of defoaming property and dispersibility of the precipitate is taken as the request. It may also contain residual acids other than the above-mentioned intermediate fatty acids and southern fatty acids. Raw fatty trivalent alcohols of some fatty acid esters of the present invention, such as: glycerol), 1,2,4-butanediol (1,2,4-butanetriol), 2-transmethyl-1 (2 hydroxymethyl) -1), 3-propanediol, 2-methyl-1,2,3-propanetriol, 1,2,5-pentanetriol (l, 2,5-pentanetriol), 1,3,5-pentanetriol, 2-methyl-1,2,4-propanetriol (2-methyl 1,2,4 -propanetriol), 2-hydroxymethyl-1,3-butanediol (2-hydroxymethyl-l, 3-butanediol), trimethyl ethane, 1,3,5-hexanetriol

第12頁 200406253 五、發明說明（8) (1,3,5-1^又311〇1(：1：1^〇1)、1，2,6-己烷三醇（1，2,6-116父&11〇1(：1；1^〇1)、3-經曱基-1，5-戊三醇（3-hydroxymethyl~l, 5-pentanetriol ) 、3-甲基-1,3,5 -戊 三醇（3- methyl -1,3,5- pentanetriol)、三甲基丙烧 (tri methyl propane )、三甲基丁烧（tri methyl butane ) 、2, 5-二甲基-1，2, 5-己烷三醇 (2，5-dimethyl-1,2,5- hexanoictriol )。這些脂肪族 二醇中，如以沉澱物之分散性觀點而言，碳元素3 — 6 肪族三醇為佳，丙三醇、U’5—戊三醇、乙烧二經甲農曰、 1’2, 6-己烷三醇及丙烷三羥甲基更佳’丙三醇、乙亡 甲，、=烷三羥曱基又更佳，丙三醇為最佳。 疋—㈡ 以脂肪族三價醇為前記之混合脂肪酸 酸酿，通常為單脂肪酸醋（以下以「單酯」斤略的彳處之夕^合脂肪 肪酸酯（以下以「·欠 略摇夕彳β - Bt 稱之）、次脂 「-和 μ 人酉曰」略稱之）及二脂肪酸酯（以下w —S日」略稱之）的混合物。本發明 下乂 三r的：2 — ’則前記之沉澱物分散性便不佳，“ _日、3有里以部分脂肪酸酯全量之2〇質|d/ w 因此 1〇質量％以下更仁「所曰Λ 里心心賢里/从下為佳， 士曰一 史佳，5質量％以下最佳。此外，1 a 有2：過南時，斜卜 如次S旨的含 斜、一抓仏\對顯像液的消泡性便不佳，含右旦、a，各 對、/儿澱物分散性 m ，丄 3有S過少時， 酿與次醋的比例ί I因此本發明的部分脂肪酸，中的單 Κ _質量部V:，醋1〇0質量部為比例，次酿為 最佳。 Ρ為佳，10_5〇〇質量部更佳，2〇-15〇質量部 200406253 五、發明說明（9) 本發明之部分脂肪酸酯可以公知方法製造之。以公知方法 _ 而言，例如：（a )混合脂肪酸與脂肪族三價醇之直接酯 化之方法；（b )混合脂肪酸之低級醇酯與脂肪族三價醇 的酯交換反應之方法；（c )甘油三脂肪酸醋（g 1 y c e r i η t r i )等的三酯與脂肪族三價醇的酯交換反應之方法等列 舉之。此外，反應完成後亦可因應必要將生成之部分脂肪 酸酯再行精製。如分子蒸餾等精製法，藉此可得高含量之 單酯或是次酯的部分脂肪酸酯。 再者因本發明的抗蝕劑顯像液用消泡分散劑含有碳元素 10-20高級脂肪酸之聚醚聚醇酯（polyether polyol e s t e r)，對於沉澱物分散性及消泡性更形優良。如此般之 聚醚聚醇酯（polyether poly〇l ester)可從多價醇又或多 價酚的環氧化物（alkyl ene oxide)附加物上之碳元素 1 0 - 2 0的脂肪酸的反應中得到。 針對前記之多價醇而言，除前記之脂肪族三價醇之外，其 他諸如：乙二醇、丙二醇、1，2 -丙三醇、1，4 -丙三醇、新 戊基二醇（neopentyl glycol H0CH2C (CH3)2CH20H)、 異戊二醇（isoprene glycol)(3-甲基-1，3-丙三醇） (3-methyl-1，3- glycer in ) 、1，6-己烷二醇（1，6- Μ hexanoicdiol)等二價醇；三乙醇胺（tri ethanolamine )、三異丙醇胺（tri isopropanolamine)等其他的三價 醇、季戊四醇（pentaerythritol C (CH20H)4)、雙甘 油（diglycerol)、山梨糖醇酐（sorbitan)、 ^^，^-四（2-羥丙基）乙撐二胺（^1^，，1^，-161^31^3Page 12 200406253 V. Description of the invention (8) (1,3,5-1 ^ and 31101 (: 1: 1 ^ 〇1), 1,2,6-hexanetriol (1,2,6 -116 parent & 1101 (: 1; 1 ^ 〇1), 3-hydroxymethyl-1,5-pentanetriol (3-hydroxymethyl ~ l, 5-pentanetriol), 3-methyl-1, 3,5-pentatriol (3-methyl-1,3,5-pentanetriol), trimethyl propane, trimethyl butane, 2,5-dimethyl 1,2,5-hexanetriol (2,5-dimethyl-1,2,5-hexanoictriol). Among these aliphatic diols, from the viewpoint of the dispersibility of the precipitate, the carbon element is 3 to 6 Aliphatic triols are preferred. Glycerol, U'5-pentatriol, Ethyl Dimethonone, 1'2, 6-hexanetriol and propanetrimethylol are more preferred. Ethyl methyl, alkanetrishydroxyl is more preferred, glycerol is the best. 疋 —㈡ Mixed fatty acid sour with aliphatic trivalent alcohol as the previous description, usually mono-fatty vinegar (hereinafter referred to as "monoester "Jie Lue's place of the ^^ fatty fatty acid esters (hereinafter referred to as" · 略略 摇 夕 彳 β-Bt ", sub-fat"-and μ person ") and difatty acids (Hereinafter abbreviated as "W-S Day"). In the present invention, the following three r: 2-'The dispersion of the precipitate in the previous note is not good. 20 mass | d / w Therefore, it is more kind to be less than 10 mass% "So Λ 里 心心 心 贤 里 / from below is better, Shi Yue is a good history, 5 mass% is the best. In addition, 1 a has 2: South At the same time, the oblique angle is oblique, and it is difficult to defoam the imaging solution. It contains right denier, a, and the dispersibility m of each pair and /, and 丄 3 has too little S. At this time, the ratio of brewing to secondary vinegar I is therefore part of the fatty acids of the present invention, the single K _ mass part V :, vinegar 100 mass part is the ratio, the secondary brew is the best. P is better, 10_500 mass Part is better, 20-150 mass part 200406253 V. Description of the invention (9) Part of the fatty acid ester of the present invention can be produced by a known method. In terms of a known method, for example: (a) mixed fatty acid and aliphatic three Method for direct esterification of valent alcohols; (b) Method for transesterification of lower alcohol esters of mixed fatty acids with aliphatic trivalent alcohols; (c) Triglyceride fatty acids (G 1 yceri η tri) and other methods of transesterification of aliphatic trivalent alcohols and other methods are listed. In addition, after the completion of the reaction, some of the fatty acid esters can be refined if necessary. For example, molecular distillation Refining methods can be used to obtain high levels of mono- or sub-ester fatty acid esters. Furthermore, since the defoaming dispersant for a resist developing solution of the present invention contains a polyether polyol e s t e r of 10-20 higher fatty acids with carbon elements, it is more excellent in dispersibility of precipitates and defoaming properties. Such a polyether polyol ester can be obtained from a reaction of a fatty acid of a carbon element 1 to 20 on a polyvalent alcohol or an alkyl ene oxide addition of a polyvalent phenol. get. Regarding the polyvalent alcohols mentioned above, in addition to the aliphatic trivalent alcohols mentioned above, others such as: ethylene glycol, propylene glycol, 1,2-glycerol, 1,4-glycerol, neopentyl glycol (Neopentyl glycol H0CH2C (CH3) 2CH20H), isoprene glycol (3-methyl-1,3-propanetriol) (3-methyl-1,3-glycerin), 1,6-hexane Divalent alcohols such as 1,6-M hexanoicdiol; other trivalent alcohols such as tri ethanolamine, tri isopropanolamine, pentaerythritol C (CH20H) 4), bis Glycerol (diglycerol), sorbitan, ^^, ^-tetrakis (2-hydroxypropyl) ethylenediamine (^ 1 ^ ,, 1 ^, -161 ^ 31 ^ 3

第14頁 200406253 五、發明說明（ίο) (2-hydroxy propane ) ethylene diamine )等四價醇； 甲基葡萄昔（methylglucoside)、一縮二季戊四醇 (dipentaerythrite)、蔗糖等的四價以上的醇類等等。 針對前記之多價驗而言，諸如：雙紛A (bisphenol A)、 雙酚F (bisphenol F )、兒茶酚（catechol )、對苯二酚 (hydroquinone )等二價酚；參（4 -羥基苯基）甲基（tris (4-hydroxy phenyl ) methyl )、參（4 -羥基苯基）乙烷 (tris ( 4- hydroxy phenyl ) ethane )等三價酚類。 這些多價醇及多價酚中，以二價醇為佳，乙二醇、丙二醇 及1，2-丙二醇更佳，丙二醇為最佳。 夕"[貝醇又或多價驗附加的壞氧化物（aikylene oxide)， 諸如：環氧乙烷（ethylene oxide)、環氧丙烷 (Propylene oxide )、環氧丁烧（butylene oxide )、 四氫呋2喃（1，4 -環乳丁烧）（tetrahydrofuran)、長鎖α 〜環氧稀烴（olefin oxide)、氧化苯乙烯（styrene oxide )等等。其附加之型態以一種類之環氧化物之單翁 ^合，或是2種類以上的環氧化物等的隨機抽樣共重合， ，塊共重合又或單獨/區塊共重合等方式皆可。特別是環 ，乙烷及％氧丙烷的共重合，如針對此種共重合而言，環 =丙烷100質量部以環氧乙烷5 — 1〇〇質量部為比例為佳， 10-60質量部更佳，15-40質量部為最佳。其因係環氧乙烷 t例未滿5貝$部日守，對顯像液中存在之沉澱物分散性 j不佳；超過100質量部則會導致顯像液之起泡性變高所Page 14 200406253 V. Description of the invention (ίο) (2-hydroxy propane) ethylene diamine) and other tetravalent alcohols; methylgrape (methylglucoside), dipentaerythrite (dipentaerythrite), sucrose and other tetravalent alcohols and many more. For the previous multivalent tests, such as: bisphenol A, bisphenol F, catechol, hydroquinone and other divalent phenols; see (4- Trivalent phenols such as tris (4-hydroxy phenyl) methyl and tris (4-hydroxy phenyl) ethane. Among these polyvalent alcohols and polyvalent phenols, divalent alcohols are preferred, ethylene glycol, propylene glycol, and 1,2-propylene glycol are more preferred, and propylene glycol is most preferred. Evening " [Bei Alcohol or multivalent inspection of additional aikylene oxide, such as: ethylene oxide, propylene oxide (Propylene oxide), butylene oxide (butylene oxide), four Hydrofuran 2 (tetrahydrofuran), long-locking α ~ olefin oxide, styrene oxide, etc. The additional type is a kind of mono-epoxide of epoxide, or random sampling and co- coincidence of more than 2 types of epoxide, etc. . Especially the co-superposition of ring, ethane and% oxypropane. For this kind of co-superposition, the ratio of 100 parts by mass of ring = propane is preferably 5-10 parts by mass of ethylene oxide, 10-60 mass. Parts are better, 15-40 quality parts are the best. The reason is that ethylene oxide is less than 5 parts per day, and the dispersion of the precipitates in the developing solution is not good; more than 100 parts by mass will cause the foaming property of the developing solution to be high.

第15頁 200406253 五、發明說明（11) ----- 前記多價醇又或多價酚的環氧化物（alkylene oxide)附 加物之環氧化物（alkylene oxide)的附加摩耳數以 20-200 為佳 ’ 30-1 50 更佳，40-120 最佳。 此外，前記碳元素10-20以上之脂肪酸中如以沉澱物之分 散性觀點而言，碳元素10-16的脂肪酸為佳，碳元素1〇_14 的脂肪酸更佳，碳元素10-丨4的直鏈飽和脂肪酸為最佳； 以抑泡性觀點而言，碳元素1 4 - 2 〇的脂肪酸為佳，碳元素 16-18的脂肪酸更佳，碳元素16_18的飽和脂肪酸中的直鏈 飽和脂肪酸為最佳。 本發明的抗银劑顯像液用消泡分散劑，在不損害其性能的 _ 範圍内’亦可含有其他成分，例如此類成分：乙醇、乙二 醇、丙一醇、一縮二丙二醇、丙三醇、丁二醇、乙二醇等 水溶性溶劑；一價醇又或一價酚的環氧化物附加物或是脂 肪酸酯、著色劑等。 本發明之顯像液消泡分散劑所使用之顯像液乃為鹼性顯像 液。顯像液之驗性劑’舉例來說，有碳酸链，碳薇納、碳 酸钟等驗性金屬碳酸鹽類。碳酸氫鐘、碳酸氫納、碳酸氫 鉀等鹼金屬碳酸氫鹽類；硼酸鋰、硼酸鈉、硼酸鉀等鹼金 屬硼酸鹽類；矽酸鐘、矽酸鈉、矽酸鉀等驗金屬矽酸鹽；氫丨驗 氧化鐘、氫氧化鈉、氫氧化鉀等氫氧化鹼金屬等之無機鹼 性化合物；1，2-乙二胺（ethylene diamine) 、1，2-二胺 基丙烧（propylene diamine)、四氫化□比咯 (pyrrolidine)、六氫化[I 比卩秦（piperazine)、裝基四 曱基錢（tetra methyl ammonium hydroxy group )、經Page 15 200406253 V. Description of the invention (11) ----- The previous mole number of alkylene oxide of polyvalent alcohol or polyvalent phenol is 20 -200 is better '30-1 50 is better, 40-120 is best. In addition, from the viewpoint of the dispersibility of the precipitate, among the fatty acids with a carbon element of 10-20 or more, the fatty acids with a carbon element of 10-16 are preferred, the fatty acids with a carbon element of 10-14 are more preferred, and the carbon element is 10- 丨 4 The linear saturated fatty acids are the best; from the viewpoint of suds suppression, fatty acids with carbon 14 to 20 are preferred, fatty acids with 16 to 18 carbon are more preferred, and saturated fatty acids in saturated fatty acids with carbon 16 to 18 are preferred. Fatty acids are best. The antifoaming dispersant for the anti-silver agent imaging solution of the present invention may also contain other ingredients within the range of _ which does not impair its performance, such as such ingredients: ethanol, ethylene glycol, glycerol, dipropylene glycol , Glycerol, butanediol, ethylene glycol and other water-soluble solvents; monovalent alcohols or epoxide additives of monovalent phenols or fatty acid esters, colorants, etc. The developing solution used in the developing solution defoaming dispersant of the present invention is an alkaline developing solution. Examples of the test agent for the developing solution include carbonic acid chain, carbamate, and carbonate metal carbonates. Alkali metal bicarbonates such as bicarbonate clock, sodium bicarbonate, potassium bicarbonate, etc .; alkali metal borates such as lithium borate, sodium borate, potassium borate, etc .; metal silicates such as bell silicate, sodium silicate, potassium silicate Salts; hydrogen 丨 test inorganic alkaline compounds such as oxidized bells, sodium hydroxide, potassium hydroxide and other alkali metal hydroxides; 1,2-ethylene diamine, 1,2-diamine propylene (propylene diamine), pyrrolidine, hexahydro [I piperazine, tetra methyl ammonium hydroxy group,

第16頁 200406253 五、發明說明（12) 基四乙基錄（tetra ethyl ammonium hydroxyl group )、三（2-經基甲基）銨（tri (2-hydroxy group methyl )ammon i um )等有機驗性化合物。在這些驗性劑中，以驗 性金屬碳酸鹽以及有機鹼性化合物為最佳，尤以碳酸鈉及 經基四甲基錢（tetra methyl ammonium hydroxy group )最好。 照片顯像液的驗性劑濃度依其使用之驗性劑之種類及顯像 液所適用之抗蝕劑之種類而異。其中在鹼金屬碳酸鹽類 中’於水質量部100中以〇·；[〜5質量部為最佳。又，於有機 鹼性化合物中，顯像液之鹼性劑濃度，如果水質量部1〇〇 的話，以0· 5〜25為宜，其中以卜15質量部為佳，更有甚 者，以1 · 5〜1 0質量部最佳。 在上1使用顯像液，使抗蝕劑顯像時，顯像液之溫度為 5〜50 °C為宜，20〜40 °C更佳，而以25〜35 t為最佳。如果 j之/皿度在1 5 c之下，會有部分未硬化之抗蝕劑溶解 南兄產生’超過50 °c則會產生部份已硬化之抗蝕 d自基板表面剝離之情況產生。 圍肉ί發明中抗蝕用顯像液，在不損及本發明之目的的範 以周知之久錄U 成分，舉例來說， 為宜。種"面活性劑、潤滑劑、安定劑、溶解助劑等 ΐ發ΐίίίΓί液用消泡分散劑的使用*，並無特殊限 蝕劑的種類等種種停件， 頌像方法抗 你忏而選擇抗蝕顯像液用消泡分散劑 200406253 五、發明說明（13) 之使用量。舉例來說，以質量比1 %之碳酸鈉水溶液作為 顯像液之乾膠卷（底片）【底片狀之抗蝕劑】之顯像情%兄 中，將本發明之影像抗蝕劑用消泡分散劑換算為丙三^部 分脂肪酸酯的情況下以使用〇· 〇〇5〜〇· 〇2質量％為最佳。° 又，添加方法可為直接添加部分脂肪酸g旨，也可添加入以Page 16 200406253 V. Description of the invention (12) Organic tests such as tetra ethyl ammonium hydroxyl group, tri (2-hydroxy group methyl) ammon i um, etc. Sexual compounds. Among these test agents, test metal carbonates and organic basic compounds are the best, and sodium carbonate and tetra methyl ammonium hydroxy group are the best. The concentration of the photosensitizer in the photo developer varies depending on the type of photosensitizer used and the type of resist used in the developer. Among the alkali metal carbonates, 'is the best in the water mass part 100; [~ 5 mass part is the best. In the organic basic compound, the concentration of the alkaline agent in the developing solution is preferably 0.5 to 25 if the water quality part is 100, and the 15 mass part is more preferable, and even more, The best quality is from 1 · 5 to 10 parts. When the developer is used in the above 1, to develop the resist, the temperature of the developer is preferably 5 ~ 50 ° C, more preferably 20 ~ 40 ° C, and most preferably 25 ~ 35 t. If the degree of j / plate is below 1 5 c, some unhardened resist will dissolve. If the temperature exceeds 50 ° c, some hardened resist will be generated. D will be peeled off from the substrate surface. The developing solution for corrosion resistance in the invention of the perimeter meat is preferably recorded in the U component for a long time without detracting from the object of the present invention. For example, it is suitable. Various types of surfactants, lubricants, stabilizers, dissolution aids, etc. are used for defoaming and dispersing agents for liquids *. There are no special stoppers and other types of stoppers. Select the antifoaming dispersant for the resist developing solution 200406253 5. The amount of the invention (13). For example, in the case of developing film (negative film) [film-like resist] using a 1% sodium carbonate aqueous solution as a developing solution, the image resist of the present invention is used for defoaming. In the case where the dispersant is converted to a glycerin part fatty acid ester, it is most preferable to use 0.005% to 0.002% by mass. ° In addition, the method of addition may be to directly add a portion of the fatty acid g, or it may be added to

水稀釋後之部分脂肪酸酯。又，顯像液調配時，也可添I 進部分脂肪酸酯或加水稀釋後之脂肪酸酯，甚者，也ϋ 加入於已經呈現發泡狀態之顯像液中。於本發明中，呷二 脂肪酸酯可單獨使用或者混合兩種類以上之部分脂肪酸二 使用皆可。 曰 又，在本發明中，為顯像液之顯像對象的防蝕 、積極性，尸、要能以驗性水溶液而顯像的話不；二 2何種類的防蝕劑皆可利用。具體來說，（1 ) 时 =有奈醌（naphthoquinone)次迭氮基（azid〇 形μ清漆—resin)(㈣ 二 =防餘劑；（2 )含有因曝光而產生酸之化二)之 刀解之鹼性水溶液之溶解性增加 -夂 樹脂之積極型防钱劑；（3)含二性可溶性 水溶液其溶解性增大之基之驗 夂= ΠΓ劑；⑷含有因曝光產生酸之化合物U : 可性樹脂之消極型防蝕劑·（ 5 含有同 生游離基之化合物、架橋劑、鹼：可(二;=光而產 綮人14 4日/ 有口曝先產生游離基之化合物、游離其 I性根…之驗性可溶性樹脂之消極防餘劑等游離基 第18頁 1^^ 200406253 五、發明說明（14) 實施例 以下，經由實驗組及對照組對於本發明有更進_梦具體的 說明。又，以下的實驗組和對照組中並沒有特別以「部」 和「％」為其質量基準。 實驗中，使用下述實驗組卜9和對照組1〜10所示之消泡 劑。實驗組卜7及對照組卜2為由脂肪族3價醇組成之滿合 脂肪酸酯化之部分脂肪酸酯，其脂肪酸組成（％ )和酯組 成（％ )如表1中所示。又，其脂肪酸組成以基準油脂分析 法為基礎，將實驗材料鹼化後形成甲基酯化，經色譜分析 法（檢驗分析器：F I D )而測定。 又，酯組成以几(：410法（使用儀器為“13111^51^1(3231^ latron， Inc.公司所出產之型式iatronscanMK5 )測定。 表Partial fatty acid ester after dilution with water. In the preparation of the developing solution, I can also add part of the fatty acid ester or the fatty acid ester diluted by adding water, or even add it to the developing solution that has been in a foaming state. In the present invention, the dibasic fatty acid ester may be used alone or as a mixture of two or more kinds of partial fatty acids. That is, in the present invention, for the purpose of anticorrosion and enthusiasm of the developing object of the developing solution, it is not necessary to develop the corpse with a test aqueous solution; any kind of anticorrosive agent can be used. Specifically, when (1) = Naphthoquinone (azid0-shaped μ varnish-resin) (㈣2 = anti-remainder; (2) containing acidification 2 due to exposure) Increased solubility of the alkaline solution of knife solution- 夂 Positive anti-money agent of resin; (3) Test based on the increase of solubility of amphoteric soluble aqueous solution 夂 = ΠΓ agent; ⑷ Contains compounds that generate acid due to exposure U: Negative corrosion inhibitor for resins. (5 Compounds containing syngeneic free radicals, bridging agents, alkalis: can (two; = light and productive people 14 4th / oral exposure to compounds that generate free radicals first, Free radicals such as negative soluble residues of experimental soluble resins that dissociate their I-type roots, etc. Page 18 1 ^^ 200406253 V. Description of the invention (14) The following examples will further improve the present invention through the experimental group and the control group_dream Specific explanation. In addition, the following experimental groups and control groups do not specifically use "parts" and "%" as their quality standards. In the experiments, the following experimental groups 9 and control groups 1 to 10 Foaming agent. The experimental group B7 and the control group B2 are composed of aliphatic trivalent alcohol. The fatty acid esterified part of the fatty acid ester has the fatty acid composition (%) and the ester composition (%) as shown in Table 1. In addition, the fatty acid composition is based on the standard oil and fat analysis method. Esterification was determined by chromatographic analysis (test analyzer: FID). The ester composition was determined by the method (410 method (using the instrument "13111 ^ 51 ^ 1 (3231 ^ latron, Inc.). iatronscanMK5). Table

第19頁 200406253 五、發明說明（15) m例 mm 1 2 3 4 5 6 7 1 2 瞭防族3價醉 G G G 0 0 TP TP G G 辛焼酸(octane細d) 2 螫 2 5 - 2 _ V 異壬)isononane add ) - 30 譬 5 鲁 齡 30 - _ 癸说酸(<teca»e遍） 2 - 2 10 6 2 _ - 1 +Π峨（月桂联） (dodecaoe ackt> 10 10 黌 10 10 - n 十四赚（肉豆棚> ( tetra decane acid ) 38 5 24 - * 38 - 1 柄赚 (hcxa decane add) 4 19 2 通 3 4 24 m 霞 你纖(硬騮1) (pct&dccylicacid) 4 13 2S tl 4 36 61 警 1 mmm < palmitoldc) acid m 會 2 2 - - » 醤 油醏(oldnadd) 34 2 30 77 M m m m 亞油酸、罂酸 (itndeiciicid) $ 3 2 I I 6 m 鲁 • mm (ricinold«acid) - 30 中纖 52 33 n 20 6 52 40 0 100 wmm 48 67 62 SO 94 48 ¢0 100 a mm · 40 65 32 76 80 40 36 0 0 賺 單釀 42 16 69 43 79 65 95 45 摊 mst m 50 S3 22 55 17 31 5 $1 2 m 三酯 8 1 9 2 4 4 0 4 0 G代表甘油（glycerin) TP代表三授甲基丙掠（lri roetliylalpropei^)>Page 19, 200,406,253 V. Description of the invention (15) m cases mm 1 2 3 4 5 6 7 1 2 Anti-family trivalent drunk GGG 0 0 TP TP GG octane fine d 2 螫 2 5-2 _ V Isonon) isononane add)-30 For example 5 Lu Ling 30-_ Decanoic acid (& teca »e times) 2-2 10 6 2 _-1 + Π E (lauric union) (dodecaoe ackt) 10 10 黉10 10-n Fourteen earning (meat bean shed > (tetra decane acid) 38 5 24-* 38-1 handle earning (hcxa decane add) 4 19 2 Tong 3 4 24 m Xia you fiber (hard 骝 1) ( pct & dccylicacid) 4 13 2S tl 4 36 61 Police 1 mmm < palmitoldc) acid m will 2 2--»n 油 醏 (oldnadd) 34 2 30 77 M mmm linoleic acid, itndeiciicid $ 3 2 II 6 m Lu • mm (ricinold «acid)-30 Medium fiber 52 33 n 20 6 52 40 0 100 wmm 48 67 62 SO 94 48 ¢ 0 100 a mm40 65 32 76 80 40 36 0 0 69 43 79 65 95 45 stall mst m 50 S3 22 55 17 31 5 $ 1 2 m triester 8 1 9 2 4 4 0 4 0 G stands for glycerin TP stands for lri roetliylalpropei ^ >

實施例8 於實施例1中，部分脂肪酸酯1 0 0部和聚醚聚醇酯 (polyether polyol ester)(丙稀乙二醇的丙烯氧化物Example 8 In Example 1, a part of 100 fatty acid esters and a polyether polyol ester (propylene oxide of propylene glycol)

第20頁 200406253 五、發明說明（16) --- 8〇摩耳和乙烯氧化物3〇摩耳 山 乎今的甘欠段（b 1 〇 c k )附加物的硬 脂酸(octadecylic acid)两匕 r α α 」θ曰（es ter ) ) 50部之混合 實施例9 : ，施例2之部分脂⑽酸woo部和聚趟聚醇冑（三經甲基丙 f methyl01 propane)中的丙二基氧化物5〇摩耳和 乙烯乳化物30摩耳的亂數添加物的三以烷酸酯 dodecane acid ester)的質量比5〇部之混合物。 比較例3 2’4，7’ 9-四甲基十—5-異-4 (tetra社讣” d⑽ -5-1S〇-4) ，7-二醇之乙烯氧化物1〇摩耳之添加物。 比較例4 聚丙二基醇（數平均分子量7〇〇) 比較例5 聚丙二基丙三基 propyl glycerol (甘油基）含氧之酸醚（poly oxi ester)(數平均分子量1，000 )。Page 20, 200,406,253 5. Description of the invention (16) --- 80 mol and ethylene oxide 30 mol of the current owing section (b 1 〇ck) of stearic acid (octadecylic acid) two D r α α ”θ said (es ter)) 50 parts of the mixture Example 9: part of the lipoic acid woo part of Example 2 and the polypropanol (polymethylpropion) A mixture of 50 parts by weight of a dioxo oxide and 30 moles of an ethylene emulsion by a mass ratio of 50 parts by weight. Comparative Example 3 Addition of 2'4,7 '9-tetramethyldeca-5-iso-4 (tetra Corporation d d -5-1S0-4), 7-diol ethylene oxide 10 mol Comparative Example 4 Polypropylene alcohol (number average molecular weight 700) Comparative example 5 Polypropylene glycerol (glyceryl) poly oxi ester (number average molecular weight 1,000) .

比較例6 18烧醇（甘油酸醇）&丙烯氧化物4 摩耳的嵌段添加物的18烷酸（硬脂酸）2 料化物8Comparative Example 6 18 alcohol (glyceryl alcohol) & propylene oxide 4 mol block additive 18 alkanoic acid (stearic acid) 2 compound 8

第21頁 200406253 五、發明說明（17) 比較例7 二基氧化物2.0摩耳及 添加物。 乙烯氧 2， 2-乙基-；!， 3_丙二醇的丙 化物20摩耳的嵌段（block) 比較例8 比較例7的嵌段添加物之硬脂酸酯（丨8烷酸酯 比較例9 乙烯氧化物30摩耳的嵌段添 丙稀醇的丙烯氧化物80摩耳及 加物之雙硬脂酸酯。 比較例1 0 ^羥甲基丙烧之丙烯氧化物50摩耳及乙婦氧化物3〇摩Page 21 200406253 V. Description of the invention (17) Comparative example 7 Dioxel 2.0 mol and additives. Ethylene oxide 2,2-ethyl-;!, 3-propanediol propionate 20 mol block Comparative Example 8 Comparative Example 7 Stearate (8-alkanoate) Example 9 30 mol of ethylene oxide block propylene oxide 80 mol of propylene oxide and adipate distearate. Comparative Example 1 0 ^ methylol propylene oxide 50 mol of propylene oxide and Otome oxide 30 mol

Ik機添加物之1 2烷酸（月桂酸）酯。 〈試驗溶劑的調置〉 在顯像液1%的碳酸鈉100部中，各添加實施例卜9和比較例 1 — 10之消泡劑0· 05部。在該顯像液中自未曝光的丙烯酸系 之感光性樹脂（該樹脂的濃度為〇· 2g/L溶解而成之實驗溶 液）中所製成之乾膠捲，用於下述實驗。又可代替1%碳酸 鈉水溶液，以2· 5%之羥基四甲基銨（TMAH )水溶液進行 相同的實驗。 200406253 五、發明說明（18) 消泡性實驗 在容量100mL的共栓試管内，倒入實驗液體5〇mi，一分鐘 内搖晃5 0次之後靜置’並觀察泡沫之狀態，以下述之標準 評價其消泡性。 〇：不滿2 〇秒内泡沫即消失，消泡性為良好。 △:需經1 5〜6 0秒泡沫才會消失，消泡性略為不佳。 X ：即使超過秒後，泡沫仍在，消泡性劣。 沉澱物分散性實驗1 在容量400mL付蓋之玻璃容器中，倒入上述實驗液體 3 0OmL ’在3 0 °C的暗處放置_星期後，以目視判定其沉澱 物量，以下述之標準評價其沉澱物分散性。 ◎:看不見沉澱物，沉澱物分散性良好。 〇：僅看見微量沉澱物，沉澱物分散性略佳。 △:看見少量沉澱物，沉澱物分散性略為不佳。 x :可看見多量沉澱物，沉澱物分散性劣。 沉澱物分散性實驗2 在印刷基板上將自丙烯酸系感光性樹脂中製成之乾膠捲製 成薄片，在水銀燈下讓它部分曝光後，以上述實驗液體作 喷灑處理（液體溫度3 〇 °c，喷灑時間1 〇秒，喷灑壓力於 1 5 0 k P a )對於在乾膠捲或是基板上沉殿物之附著經由目視 判定，以下述標準評價其沉澱物分散性。 ◎:看不見沉澱物，沉澱物分散性良好。Ik machine additive 1 2 alkanoic acid (lauric acid) ester. <Preparation of Test Solvent> To 100 parts of 1% sodium carbonate in the developing solution, 0.05 parts of the antifoaming agent of Example 9 and Comparative Examples 1 to 10 were added. A dry film prepared from an unexposed acrylic photosensitive resin (an experimental solution obtained by dissolving the resin at a concentration of 0.2 g / L) in the developing solution was used in the following experiments. Instead of 1% sodium carbonate aqueous solution, the same experiment can be performed with a 2.5% aqueous solution of hydroxytetramethylammonium (TMAH). 200406253 V. Description of the invention (18) Antifoaming experiment In a 100 mL capacity plug tube, pour the test liquid 50mi, shake it 50 times in one minute, and let it stand still, and observe the state of the foam, according to the following standards The defoaming property was evaluated. 〇: The foam disappeared within 20 seconds, and the defoaming property was good. △: It takes 15 to 60 seconds for the foam to disappear, and the defoaming property is slightly poor. X: Even after more than a second, the foam is still present and the defoaming property is poor. Precipitation dispersibility test 1 In a glass container with a capacity of 400 mL, pour the above-mentioned experimental liquid 300 mL into a dark place at 30 ° C for _ weeks, and then visually determine the amount of the precipitate, and evaluate it according to the following criteria. Precipitate dispersibility. :: No precipitate was seen, and the dispersibility of the precipitate was good. ○: Only a slight amount of precipitate was seen, and the dispersion of the precipitate was slightly better. △: A small amount of precipitate was seen, and the dispersibility of the precipitate was slightly poor. x: A large amount of precipitate can be seen, and the dispersion of the precipitate is poor. Precipitate Dispersion Experiment 2 A dry film made from an acrylic photosensitive resin was made into thin sheets on a printed substrate, and after partially exposed under a mercury lamp, the above experimental liquid was sprayed (liquid temperature 30 °). c. The spraying time is 10 seconds and the spraying pressure is 150 kPa. A) The adhesion of the deposit on the dry film or the substrate is determined visually, and the dispersibility of the precipitate is evaluated according to the following criteria. :: No precipitate was seen, and the dispersibility of the precipitate was good.

第23頁 200406253 五、發明說明（19) 〇：僅看見微量沉澱物，沉澱物分散性略佳。 △:看見少量沉殿物，沉澱物分散性略為不佳。 X : 可看見多量沉澱物，沉澱物分散性劣。 表二 mm mtsmam tmah 系實》 !^Sf£ mmi 撇性2 mm 分敗性ι 分_2 實職 1 〇 © 魯 o ◎ 粗 2 0 Q Q o Ο 0 r b © ◎ 0 ◎ @ 4 o © ◎ o 5 Q ◎ 0 o ο ◎ $ o 0 0 ο 7 o o ύ 0 ©&gt; ο 8 o @ @ 0 ύ 9 δ o o ο &amp; m 1 o X K 厶 X X 祖 2 K o Δ X 厶 ο 3 X △ 厶 厶 Δ X 4 A X X X X 厶 5 厶 X X 厶 X X 6 Δ X X Δ Δ X 7 X Δ X X X X 8 Δ X Δ Δ X Δ r 厶 X X Δ X S: ιρ X Δ X X X μ 產業上利用之可能性 依據本發明，當抗蝕劑顯像時，即使當顯像液溶解或分散Page 23 200406253 V. Description of the invention (19) 〇: Only a small amount of precipitate is seen, and the dispersion of the precipitate is slightly better. △: A small amount of sunken objects were seen, and the dispersibility of the precipitate was slightly poor. X: A large amount of precipitate can be seen, and the dispersion of the precipitate is poor. Table 2 mm mtsmam tmah is true! ^ Sf £ mmi Skim 2 mm Difficulty ι 2_2 Practical 1 〇 © 鲁 o ◎ Coarse 2 0 QQ o 〇 0 rb © ◎ 0 ◎ @ 4 o © ◎ o 5 Q ◎ 0 o ο ◎ $ o 0 0 ο 7 oo ύ 0 © &gt; ο 8 o @ @ 0 ύ 9 δ oo ο &amp; m 1 o XK 厶 XX Zu 2 K o Δ X 厶 ο 3 X △ 厶 厶Δ X 4 AXXXX 厶 5 厶 XX 厶 XX 6 Δ XX Δ Δ Δ X 7 X Δ XXXX 8 Δ X Δ Δ X Δ r 厶 XX Δ XS: ιρ X Δ XXX μ According to the present invention, the possibility of industrial use Etchant development, even when the developer is dissolved or dispersed

第24頁 200406253 五、發明說明（20) 中的抗蝕劑成分增加，不僅隨著對抗蝕劑有高度消泡性且 在顯像液中所產生的沉澱物具有優良之分散性，可提供具 有防止沉澱物附著在抗蝕劑以及其基板上特性之抗蝕劑顯 像液用消泡分散劑。 ΦPage 24, 200,406,253 5. The composition of the resist in the description of the invention (20) increases, not only with the highly defoaming property of the resist, but also the excellent dispersibility of the precipitate generated in the developing solution, which can provide Antifoam dispersant for resist developing solution that prevents deposits from adhering to the resist and its substrate characteristics. Φ

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Claims (1)

200406253 、申請專利範圍 1胃針對與碳元素15以上之高級脂肪酸（fatty acid) 100質 量部呈比率為5-30 0之質量部碳元素6-14的中級脂肪酸的 混合脂肪酸，與含有能反應脂肪族3價醇之部分脂肪酸酯 為特徵之感光保護膜顯像液用消泡劑。 2 ·如請求項1所記載之感光保護膜顯像液用消泡劑，與前 述之部分脂肪酸酯中的單酯丨〇 〇質量部呈比率5〜1，5 0 〇質量 部之次酯，為本請求項。 3·如1求項1或請求項2所記載之感光保護膜顯像液用消泡 劑’前述之部分脂肪酸酯中的分支脂肪酸及直鏈不飽和脂 肪酸的含有量為混合脂肪酸全量之5〜8〇%。 4·如請求項1 — 3項中之任一項所記載之感光保護膜顯像液 用消泡劑，前述之脂肪族3價醇為碳元素3〜6之脂肪族3 醇（a 1 coho 1 )。 所記載之感光保護膜 之脂肪酸含有聚喊聚 顯像液 醇酯 5 ·如請求項1 - 4項中之任一項 用消泡劑，其中碳元素1 〇〜2 〇 (polyether polyol ester) 〇 6 ·如請求項1 - 5項中之任一箱&amp; 用消泡劑，其特徵係為驗性^記載之感光保護膜顯像液 巧嫩1王之感光保護膜顯像液。200406253 、 Applicable patent scope 1 Stomach is a mixed fatty acid with intermediate fatty acids with a mass ratio of 5-30 0 and a mass fraction of carbon elements 6-14 with a mass fraction of 15-30 carbon fatty acids (fatty acid) and a mass content of carbon fatty acids, and fatty acids containing reactive fats. A defoamer for a photosensitive protective film developing solution characterized by a part of the fatty acid ester of a trivalent alcohol. 2 · The defoamer for a photosensitive protective film developing solution as described in claim 1, which is in a ratio of 5 to 1,500 mass parts of the secondary ester to the monoester in the aforementioned fatty acid esters. , For this request. 3. The defoamer for a photosensitive protective film developer as described in claim 1 or claim 2, the content of the branched fatty acids and linear unsaturated fatty acids in the aforementioned partial fatty acid esters is 5 times the total amount of mixed fatty acids. ~ 80%. 4. The defoamer for a photosensitive protective film developing solution according to any one of claims 1 to 3, wherein the aliphatic trivalent alcohol is an aliphatic 3 alcohol (a 1 coho 1 ). The fatty acid of the photoprotective film described contains polyalcohol imaging developer alcohol ester 5 · The defoamer for any one of the claims 1 to 4, wherein the carbon element is 1 to 2 (polyether polyol ester). 6 · If any one of the items 1 to 5 of the claim & defoamer is used, it is characterized by the photosensitive protective film developing solution described in ^^ Qiao Nen 1 of the photosensitive protective film developing solution. 200406253200406253 第4頁Page 4