TW460489B - Carbon black graft polymer, the production method and use thereof - Google Patents

Abstract

A carbon black graft polymer that is prepared by mixing a block or graft polymer comprising a segment (A) having groups reactive with the functional groups on the carbon black surface and a segment (B) with a different skeletal structure from the segment (A), and carbon black under heating and is excellent of dispersion stability in various media, pigmentation and light screening properties. As it contains unsaturatred double bond and/or a carboxylic group in the graft chain, it exhibits photosensitivity, alkali developability, insulating characteristics or the like, which particularly useful as a black photo-curable resin composition suitable and Dot matrix forming material for a color filter.

Description

460489 A7 B7 五、發明説明（ 發明之背景 <技術範圍> (請先閲讀背面之注意事項再填寫本頁) 本發明是有關碳黑接枝聚合物，其製造方法及其使用 更詳細的說，即為有關於一種對於各種媒體具有極優異分 散安定性的碳黑接枝聚合物。本發明又是有關在於添加至！] 各種媒體時，具有發揮良好的著色性仍至遮光性、慼光性 、驗顯性及絕緣特性等的碳黑接枝聚合物。本發明又亦是 ，有關於能有效的用在如黑色矩陣（Matr i X)形成材料等的 黑色光硬化性樹脂組成物上的碳黑接枝聚合物。 本發明亦是有關於改菩如上列Μ碳黑所代表的顔料* 磁性粉末、陶瓷粉體等的固體微粒子的水分，有機溶劑或 有機高分子等媒體的分散性之表面性質處理方法者，特別 是有關使用於廣大適用範園的改善聚合物表面性質上，且 Μ使甩其少量即能獲得完全改善表面性質效果的改善表面 性質虛理方法。 <先前之技術> Μ碳黒所代表的各種顔料、磁性粉末、陶瓷粉體等固 體微粒子，多不Μ其原來的單體單獨使用，而以賦與著色 ，補強填充等的功能為目的*添加在各棰組成物中使用於 各種用途上的比較多。 然而，尤其一次粒子直徑為亞微綑粒以下的固體微粒 子，其粒子間的凝集力要比其他物質，例如：水、有機溶 劑或高分子有機物等的親和力為小，所Μ易生二次凝集的 現象。因此，若欲使上列各種組成物具備比較優秀的特性 -3 本紙乐尺度適用中國國家標準ί CNS ) Α4規格（210x 297公釐）460489 A7 B7 V. Description of the invention (Background of the invention < Technical scope > (Please read the notes on the back before filling out this page) The present invention is about carbon black grafted polymer, its manufacturing method and its use are more detailed That is to say, it is a carbon black graft polymer which has excellent dispersion stability for various media. The present invention is also related to being added to!] In various media, it has good coloring properties and still has light-shielding properties. Carbon black graft polymer with optical properties, testability, insulation properties, etc. The present invention also relates to a black photocurable resin composition that can be effectively used in materials such as a black matrix (Matr i X) forming material. The present invention also relates to pigments represented by the above-mentioned M carbon black, as shown in the above description. * Dispersion of water in solid particles such as magnetic powders, ceramic powders, organic solvents or organic polymers. The surface treatment method of nature, especially for the improvement of the surface properties of polymers used in a wide range of applicable fields, and Μ makes it possible to obtain a complete improvement of surface properties Good surface properties virtual method. ≪ Previous technology > Various pigments, magnetic powders, ceramic powders and other solid particles represented by MU carbon, most of the original monomers are used alone to impart color. For the purpose of functions such as reinforcing filling * It is often added to various concrete compositions and used for various purposes. However, especially for solid particles having a primary particle diameter of less than submicron bundles, the cohesion between particles is greater than other substances For example, the affinity of water, organic solvents, or high-molecular organic substances is small, so the phenomenon of secondary agglutination is easy to occur. Therefore, if you want to make the various components listed above have better characteristics -3 This paper scale is applicable to China Standard ί CNS) Α4 size (210x 297 mm)

I 4 60 4 89 at B7 ___ 五、發明説明（） 時，要如何地將這些固體微粒子分散均勻，就成為問題了 〇 (請先閱讀背面之注意事項再填寫本頁) 為了解決這種問題，即檢討了許多方法，如以各種界 面活性劑或樹腊來被覆固體微粒子的表面而提升與固體或 液狀媒體的親和力，使固體微粒子混合或分散均旬。 例如，有關碳黑者，（:1.)在碳黑共存之下，使聚合性 單體重合所得的碳黑接枝聚合物•由於選擇適當的聚合性 單體即能變換其親水性没/或親油性的事實，吸引了很大 的注目（例如，特公昭-22047號，特昭44-3826號，特公昭 45-17248號，美國專利3557040號）。 (2)又，有人提案，使具有環氧基或截丙啶（Azi「idine) 基等反應性基在其分子内的聚合體與碳黑相作用Μ得碳黑 接枝聚合物的方法（特公平2-24868號，特公平6-27269號 )° 然而，在上列（1)的方法所得的碳黑接枝聚合物的收 量只有數％至10%左右，大都以乙烯基均聚物的形態存在 於其中，而極度降低碳黑的表面處理效率。因此，無法期 望與其他物質的親和性有所改善，而視混合或分散等條件 發生許多不同的分散狀態。 又，在上列（2)的方法，雖然能夠少許改菩碳黑接枝 聚合物與各種物質的分散性*卻由於本碳黑接枝聚合物具 有該聚合體與碳黑發生作用的官能基的聚合鎖鏈，而只有 親油性或親水性的一種特性，對於欲增加碳黑的接枝效用 ，及由進行接枝所得的聚合鎖鍵賦與各種媒體的分散性提 —4 - 本纸汝尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 460489 _B7_ 五、發明説明（） 升上*在互相货向的要求中就難於+分滿足雙方的要求了 Ο 因此，就出現了 1.無法增大該碳黑接枝聚合物中的含 碳童，2.無法賦與十分的分散性於高極性的媒體，例如酵 類、溶纖劑系溶劑等*或低極性的媒體，例如碳化氫糸溶 劑或娃系落劑等，3.難於在有機溶劑中進行接枝化等問題 〇 又，在上列特公平6-27267號上，已被公開表示了將 碳黑一分子與壞氧基1〜2個及/或使硫璃氧基（Th ioepoxy Group)分子内的聚合體在50〜250°C的溫度條件下攪伴混 合令其反應來製造碳黒接枝聚合物的方法。侬本法來製造 時•由於能使聚合體分子内的反應基與碳黑的表面官能基 進行極有效率的反應作用而產生具有優良分散性的碳黑接 枝聚合物。用這個方法使固體微粒子與反應性聚合物溶融 練合以改善固體微粒子表面上接枝聚合鎖鰱•即成為獲得 優秀分散性的方法了。 然而，由於使用針線機，球磨機等來溶融練合固體微 粒與反應性聚合物時，若對於固體微粒子降低反應性聚合 物，即難於使聚合物接枝鏈均勻的馆蓋固體微粒子的全體 表面，必然的就無法多得經過微粒子表面改質處理後的固 體微粒子之含有量，而將發生許多減小目的的固體微粒子 本來的特性。 又，假設是靥於低級分子量的反應性聚合物，或相當 於每一分子的反應性基過多時，將使接枝化難於充分進行 -5 — 本紙乐尺度適用中國國家棣準（CN:S ) A4規格（210X297公釐） ---------^----aT------^ (請先W讀背面之注意事項再填莴本頁) A7 1 6 0 4 89 B7 五、發明説明（） (请先閱讀背面之注意事項再填将本頁) ，或如發生滕化，即相關的使用可能的反應性聚合物，如 官能基數、分子量等，多將增加其限制，又若欲得所希望 的分散液體，即必須在溶融練合操作後再進行將其分散於 分散媒液的操作而使步驟更趨複雜等問題。 同時，為欲得發生這種二次凝集作用的固體微粒的分 敗液時，即可加人適當的分散安定劑於分散媒液中，施與 物理的搜拌來進行分散處理，是眾所周知的技術了。在進 行均一的分散作業上，即應同時考量巨視的混合及基於小 規模的亂流運動的微視的混合作業，從來•為製造這種分 散液的装置即有特別加以研究的各種形狀的盛裝欲處理液 體的容器，搅拌子的形狀，數量及設置位置或其轉速，播 板及隔板等的是否配置，甚至使用的分散媒體如放在容器 內的球珠，其形狀材質等濕式分散處理裝置及濕式粉碎處 理裝置。 其中•現在的各領域上通常都在使用攪拌子與分散媒 體的併用型式者，因其能夠獲得比較良好的分散效果。 如在特公昭59-22577號，特公平2-27018號，持開平2 -68151號，特開平3-101820號，特公平7-12441號，特公 平7-4552號，特開平4-326934號，特公平6-73620號，特 開平5-38425號，特開平4-281855號，特開平6-351號，特 開平6-212876號，特開平6-21014明虎，特開平式6-134271 號，均有提出這棰型式的分散處理裝置。 然而，Μ此種型式的濕式分散處理装置及濕式粉碎處 理裝置來調製固體微粒子的分散液是藉由該處理裝置在常 —6 — 本紙铁尺度適用中國國家標準（CNS ) Α4規格（210Χ2!>7公釐） A7 ^ 60 4 B9 B7 五、發明説明（） 溫下將固體微粒子與分散媒液進行攪拌混合而成*即由攬 拌混合發生的物理的外力來形成分散狀態，其所得分散液 的安定性是不屜於十分安定，又需長時間的分散處理作業 等問題。 可是，使用在彩色液晶顯示裝置等的據色器，即具有 最少二種Μ上的色層做為微細領域的番因素，而欲遮掩處 在這種畫因素間的光線Μ提升被顯示出來的盡像的彩色對 比，一直就以黑色矩陣來彩成。 這種黑色矩陣圖，通常均在玻璃基板上以鉻、線、鋁 等的金屬薄膜構成微綑的圖案，藉由蒸著法、腺射法（ Sputter)，真空成膜法等堆積於基板上的金靥薄膜，利用 照相技術形成圖案。 然而，用這種方法製造的黑色矩陣圖，因其煩雜的製 程使其原價高昂而影響及於要使用黒色矩陣的漶色器的原 價鼯之提高的問題。 再者，將使用這種鉻等金屬薄膜的黑色矩陣圖的瀘色 器裝配到透過型顯器時，會發生由於外光照射在漶色器時 金屬表面的反射率過強而反射光的強度太大以致於顯著的 減低顯示品質的問題。 同時，由於欲解決上列使用金鼷薄膜的黑色矩陣圖所 發生的問題，有人就提出了各種Μ含有著色劑的樹脂組成 物來形成黑色矩陣圖的方法。 如在特開平2-239204號中，即有在聚亞胺（polyimide) 糸樹脂分散碳黑等遮光衬料以形成黑色矩陣圖的方法。依 -7 - 本纸块尺度適用_國國家椟準（CNS ) A*規格（2丨.0X297公釐） ¾----^—*tr------.# (請先Η讀背面之注意事項再填寫本頁) J 6 Ο 4 89 A7 B7 五、發明説明（） (請先閲讀背面之注$項再填寫本頁) 這種方法，雖然可Μ得到少受外光反射的影響且由於具育 高度耐熱性基材的聚亞胺糸樹脂之高依頼性黑色矩陣圖， 卻由須用含有遮光材料的聚亞胺糸樹脂組成基材來進行塗 敷·烘乾後，再進行塗敷阻光劑*製作圖案、蝕刻、去除 阻光劑等工程，而無法達到工程的簡省化，減低原價等目 的。 又，有人曾嘗試將碳黑等黑色顔料調合在光硬化性樹 脂組成物中，併將之塗敷在基材上，烘乾後，把規定的圖 案覆蓋在上面使其緊密固定，經露光，顯像過程來形成規 定圆察的黑色矩陣圖。 為欲獲得黑色矩陣圖具備充分的遮光性而博加碳黑的 份量，卻反而會極度減低硬化光硬化性樹脂所餺的光譜如 400 rnn左右的紫外部光謂的透過率，致使進行光硬化極為 困難，及使碳黑獲取接受紫外線的光重合開始劑所產生的 基（Redical)而阻礙光重合作用，無法進行以很經濟的曝 光量來充分完成簠因素的彤成更加困難。再說，若增加碳 黑添加量，形成的皮膜即成為導電性，就不能以黑色矩陣 圖用在液晶顯示等方面，不但如此，一如上列所述，碳黑 粒子間的凝集力要比其他物質，如與高分子機物、水及有 機溶劑等的親和性薄弱*即在上列的光硬化性樹脂組成物 中亦極難於混合或分散均勻，又難於得到既安定且均一的 黑色層膜。 在特開平4-63870號中，曾提栗使用由調配成黑色的 不同色彩的一組有機顔料如碳黑一同做為光硬化性樹脂組 —8 _ 本紙ft尺度適用t國圉家標準·（ CNS ) A4規格（210 X 公釐） 4 60 4 89 a? _B7_ 五、發明説明（） 成物著色劑，來抑制欲得規定的遮光性而添加的碳黑份星 ，併由此來控制光硬化所需紫外部的光譜透過率趨於下降 而且企求維持皮膜的絕緣性不變。 然而，如此併用有機顔料，與僅使用碳黑作比較時· 即會提高可視部的光譜透過性*使其難於形成在低度膜厚 而具有充分遮光性的黑色矩陣圃，且又不會解決如上列所 述碳黑的分散和起因於碳黑獲取基而發生的光硬化阻礙等 問題。 在特開平6-67421號中，建設以上列2.的配合有碳黑 接枝聚合物成份的光硬化樹脂組成物為黑色著色劑，由於 這種物質會使形成黑色矩陣圖具備極其儍良的遮光性，解 像性和恰當感光性，分散安定性的黑色光硬化性樹脂組成 物。卻由於如上列所述不能增加該碳黑接枝聚合物中的含 碳量Μ致於得不到充分的遮光性及能夠十分滿意的分散性 水準*而在光硬化上的感度及硬化皮膜的強度上，尚未達 到十分滿意的程度。 尤其在使用這種硬化性樹脂組成物來形成黑色矩陣圖 的皮膜時，為提高曝光硬化，顯像處理後*使皮膜完全硬 化的同時為提高基本與皮膜間的緊密性等目的，而進行約 100〜300°C的熱處理（後續烘焙）作業，卻仍有疑應會在 這種熱處理當中使存茌於皮膜中的碳黑甚至於碳黑枝聚合 物的分敗狀態會起變化，而檢測了經後纊烘焙後有皮膜的 抵抗效率大大降低的情形。因此，即不適用於須有高度抵 抗的液晶濾色器之黑色矩陣圖上。 -9 ~ 本纸張尺度適用中國國家揉準（CNS ) A4規格（2! 0 X 297公釐_) ---------^-------1T------.# (請先閲讀背面之注意事項再填寫本頁) d 60 ά 89 A7 ___B7_ 五、發明説明（） 又* Μ光硬化性樹脂組成物來形成黑色矩陣圖等的皮 膜時，即希望其成為齡ί可溶型樹脂組成物，卻被指出由於 此時Μ著色劑的一成份而添加的碳黑或從來就有的碳黑接 枝聚合物，會引起驗顯像性降低的情形而須加以改菩。 換個話題，來說明何為墨水噴射（Ink jet)記錄法。 將所謂的墨水記錄媒體液以液體滴流形式飛散使其附著於 記錄材料上來進行記綠的方法，就是墨水噴射記錄法。這 個方法，可由產生記錄媒體液的液滴及控制方法等的差異 而有各種方法的提案且已被實用化了。如其液滴的產生方 法，則有1.將墨水室的#15分壁面由胆電素子（Piezo素子） 所構成，供給記錄信號於此處併使墨水加壓*因應該信號 來生液滴的歷電加應方式，2.將因應於記錄信號熱能加諸 於墨水室內的記錄液，使墨水發生氣泡所產生的壓力來發 生液滴的加熱加壓方式，本法為實用化的代表方式，其外 尚有3.在較高的壓力下，使墨水自噴嘴嗔出併在其飛散中 藉由表面張力及帶電化而使液滴粒子化的方式，4.在較低 腔力下*使墨水噴出，再加Μ超音波振動· 5.用高電壓來 吸引在液體表面形成的墨水球的方式〇 用在這種墨水嗔射記錄法的墨水亦即記錄媒體液，應 具備適合於嗔射（吐出）條件（如壓電素子的驅動電壓， 驅動頻率，嗔射孔的形狀及材質，嗔孔口徑等）的液性（ 粘度，表面張力，導電度等），附於長期保存而不堵塞墨 水噴射裝置，確實又快速的固定往記錄用材料（紙、軟片 )而點的周圍要平滑完蝥*所形成的墨水畫像色調要鮮明 —10 - 本紙張尺度速用中國國家標準（CNS ) Α4規格（2Ϊ0Χ297公釐） ^..ir------^ <诗先閏讀背面之注意事項再填寫本頁) A7 SO 4 89 ____B7_ 五、發明説明（） 濃厚而優於耐水性及耐光性，對墨水的周圍材料（保存器 、連接管、封色材料等）不具侵腐性等各種特性〇 從來，一直係Μ染料及其溶媒所組成的著色劑為主的 混合液做為墨水噴射記錄法之記錄媒體溶液。由於記錄媒 體溶液的物性大都受染料的固有性質所左右，例如使用含 有水溶性染料的記錄媒體溶液來進行墨水噴射記錄時》所 得的墨水盡像會被水溶性染料的物性來左右而發低質的而兮 水性，耐光性等缺點。再說，含有這種水溶性染料的墨水 本身的保存安定性亦十分安定。 因此，就嘗試了以碳黑等的頭料為著色成份而用在墨 水噴射記錄法的顔料系墨水來代替染料糸墨水的是否能適 用。這種顔料糸墨水，在所得的墨水畫像上，其耐光性或 耐水性均比染料糸墨水所得的畫像有極其良好的優點。然 而*卻由於顏料不易解於墨水的液性媒體，即須要高度技 術來促使顔料微分散於墨水的液性媒體中了。然而欲提高 其分散安定性是很困難的。 或者可以考庙:利用上列的碳黑接枝聚合物做為泡沫噴 射記錄法的記錄媒體溶液之著色劑成份，卻由於有如上列 各種問題，將會發生1.無法加大碳黑的含有量而提高墨水 輋像的色調至十分鮮明及其高潘度，2.難於設定適合於唄 出條件的導電度_ 3.難於保捋安定的分散狀態，在長期保 存性上不十分安定等問題。 又，近年以來，在利用電子照相法的印刷及靜電複寫 等領域上，有其高度畫質化的動向。即，由於數宇技術的 本紙張尺度速用中國國家標羋（CNS ) A4現格（210X297公釐） ^----—ir------^ (請先聞讀背面之注f項再填寫本頁) S04 89 A7 ___B7__ 五、發明説明（） 進步，在顯像形成水準上，成功於能夠保證比從來的技術 更高精佃性了。然而，在使靜電荷顯像時使用粉體著色劑 者，卻由於其粒徑在約為10« m程度的大小，而得不到較 高番質。因此，就發生了重新注目於利用著色劑粒徑細小 的液體顯像劑來形成高精细性的盡像的方法。 如眾所知，靜電荷潛像顯像用液體顯像劑是由具備電 疯絕緣性的有機液體，例如將著色劑粒子分散在劳香族碳 化氫糸箱劑中者，而由於著色劑粒子須有著色性、帶電性 、固著性及分散安定性，即由顔料、樹脂及他種添加劑所 構成。在液體顯像法上，著色劑粒子通常都有靜電顯像電 荷及向反對極性帶電，這盛著色刚粒子在電氣絕緣液體* 將被吸引到顯像電荷上，由於電氣泳動的關係移動到顯像 ，再K選擇的附著在顯像上而進行顯像過程。 茌這種液體顯像劑，尚須要求提高碳黑等顔料或樹胞 的分散性，例如在專利公告1995-253688號即建議以使用 於芳香族碳化氫糸溶劑中加入接枝化的可溶性高分子物質 於不溶性髙分子物質的同一溶劑為宜，又在專利公告1995 -104524號建議可使用如上列的碳黑接枝聚合物為著色劑 ，然而兩者均未達到成為液艘顯像劑具備十分安定的分散 性。 <發明的總論> 由於上列各種原因，本發明的目的兹於提供做為新產 品碳黑接枝聚合物的製造方法及其用途上。 本發明的其他目的，即在於提供具備高度含有碳黑及 -12 - 本紙伕尺度適用中國國家樣準（CNS ) A4规格（2丨OX 297公釐) ---------I---^-I:--iT------0 {請先閱請背面之注意事項再填寫本瓦) 60489 at __B7_ 五、發明説明（） (請先閲讀背面之注意事項再填艿本頁) 同時尚有對各種媒體圼優秀的分散性，添加於各種光譜以 及熱硬化性媒體時，亦不阻礙該媒體的硬化程度，設使在 高添加量亦能易於形成高強度的皮膜，且為具備優越的電 氣絕緣性等各種物理性質的新產品碳黑接枝聚合物及其製 造方法上。 本發明堪有其他的目的，即在提供將此物添加到各種 媒體時，將會發揮其優秀的著色性以反遮光性、感光性、 鹼顯像性、絕緣性等的新產品碳黑接枝聚合物及其製造方 法。 本發明亦提供對於濾色器上為黑色矩陣圖形成材料等 很有功效的使用在黑色光硬化性樹脂組成物的碳黑接枝聚 合物及其製造方法為目的。 本發明更進而可提供為進行墨水噴射記錄法時，有效 的使用於記錄媒體液、靜電荷顯像顯像用液體顯像劑等之 新產品碳黑接枝聚合物及其製造方法。 本發明亦將提供可使用於各種樹脂組成物，被覆組成 物、墨水、感熱轉寫用墨水、感熱轉寫用墨水帶被覆劑、 磁性記錄媒體用背面被覆劑、靜電荷顯像用著色劑、塗料 、高阻抗併需遮光性的材料，液晶用滤色器的黑色矩陣之 人工大理石、塑膠及橡膠成形材料，遮光性纖維等的著色 劑、聚烯煙或聚脂等塑膠與橡膝改質劑及充填劑、面狀發 熱體、潤滑劑、曳引驅動流體、電氣粘性流賴!及非線形光 學材料、電氣電阻調整，例如帶電防止材料、複寫機内的 阻抗材料及利用PTC特性的面狀發熱體等的新產品碳黑接 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） β〇4 89 αβ] 五、發明説明（） 枝聚合物及其製造方法為目的。 本發明亦κ提供如κ碳黑為其代表的顔料、磁性粉末 、陶瓷粉體等固體微粒子對水、有機溶劑或高分子有機物 等可改善其分散性的新型表面改質處理方法為其目的。 本發明又為提供適用範圍廣泛又使用量較少即有效進 行表面改質的聚合物成份的表面改質處理方法為目的。 本發明的另一目的為提供滤色器為形成黑色矩陣有實 效的新型光硬化性樹脂組成物。 能夠達成上列各種目的的本發明之特點在，其第一點 為可以獲得將能與碳黑表面的官能基起反懕的反應性基與 具有乙烯性不飽和二重結合的聚合體加於碳黑中施於加熱 混合所成而在接枝鏈中具有不飽和二重聚合為其特色的碳 黑接枝聚合物。 有關於第一項的發明的碳黑接枝聚合物，由於在其接 枝鏈中具有不飽和二重結合》若將之添加於各種呢及熱硬 化性樹脂組成物時，該不飽和二重結合能夠參與硬化反應 。因之，加Μ高添加量，亦能易於形成高度皮膜，而可得 到優秀的遮光性，黑化度的皮膜。又會在硬化樹脂層中的 造成矩陣的樹脂分子内仍能保持碳黑接枝聚合物進行化學 結合的形態，而使分散狀態趨於安定化，併不會由於凝集 作用而圼現電氣的阻抗率下降之不良現象，使所得皮膜具 有優越的電氣絕緣性等各種物理性。所Μ，可以在將如上 列所述的光及熱硬化性樹脂組成物為首的各種媒體上，Μ 著色劑、充填劑及遮光劑等的用途來使用是最好不過的。 本纸張尺度逍用中國國家標準（CNS )六4坑格（210X297公釐）· (請先閲讀背面之注意事項再填寫本頁) .,1_ -ΪΤ 结 A7 4 60 4 89 ___B7_ 五、發明説明（） 其第二點為： (诗先閔讀背面之注意事項再填寫本頁} 將具有能與碳黑表面的官能基進行反應的反應性基及 氬氣基的聚合體加在碳黑中加熱混合後，Μ酸軒（酸無水 物）來處理反應後的混合物所得的以在接枝趟中具有搂基 (Carboxyl Group)為其特色的碳黑接枝聚合物。 有關於本第二項的發明之碳黑接枝聚合物，由於在其 接鏈中具有俊基，若將其添加在鹼可溶型硬化性樹脂組成 物時，使用驗溶液來顯像其未硬化部份，即能得到良好的 顯像性。 其第三點為： 將具有與碳黑表面的官能基起反應的反應性基的継段 (A)與上列鏈段（A)互異骨格構造的鏈段（B)的塊狀及接枝 型聚合體加在碳黑中一起加熱混合所得的碳黑接枝聚合物 Ο 相顒於本第三項的發明的碳黑接枝聚合物，因為屬於 其形成聚合體部分為塊狀或接枝型的聚合體*即能發揮更 為有效的接枝化及對各種目的媒體顯示優越的分散性。 可K這麼說，將聚合物依其功能分化成為二種鍵段的 塊狀或接枝型聚合體》即能提升其接枝效率及提升對目的 媒體的親和性，有時或可能使相反的要件趨向兩立的狀態 C» 其第四點為： 將具有碳黑表面的反應官能基能起反應的反應性基的 鏈段（A)，及含有乙烯性不飽和二重結合而與上列鏈段（A) 本纸張尺度適用中国國家梂準（CNS ) A4規格（210X297公釐） 4 604 89 A7 B7 五、發明説明（） 互異费格結構的鏈段（B)之塊狀或接枝型聚合體加在碳黑 一起加熱混合所得的碳黑接枝聚合物。 (請先聞讀背面之注項再填寫本頁) 有關於本第四項的發明的碳黑接枝聚合物是共享有上 列有關於第一項的發明的特性及有關於第三項的發明的特 性二者。 為達成上列各種目的的本發明之特點，尚有其第五項 ，是*將具有與碳黑表面的反應官能基起反懕的反應性 基的鏈段（A) *及與上列鰱段（A)互異骨格構造的鍵段（B) 中，至少也要在趟段（B)上有氪氣基的塊狀或接枝型聚合 體加入碳黑中一起加熱混合所得反應混合物，再Μ酸酐加 Μ處理所得的碳黑接枝聚合物。 有關本第五項的發明的碳黑接枝聚合物，將享有相關 於上列第二項的發明與有關第三項的發明的雙層特性。 像這樣地有關於本發明的碳黑接枝聚合物*不但具有 高度的碳黒含有率，同時埋具有對各棰媒體的優越分散性 Ο 本發明的碳黑接枝聚合物，可以很有的用在樹脂組成 物，被覆組成物、墨水、感熱轉寫墨水、感熱轉寫用墨水 帶被湲劑、磁性記錄媒體用贸面被覆劑、靜電荷現像用著 色劑、塗料，需高阻抗及遮光性材料、液晶用濾色器的黑 色矩陣圖、人工大理石、塑膠及祿驟成形材料、遮光性纖 ，維等的著色劑、聚嫌烴没聚脂等塑膠及橡腰的改質劑與充 填劑、面狀發熱體、潤滑油、曳引驅動流體、電氣粘性流 體及非線型光學材料、電氣阻抗控制，又如帶電防止材料 -16 - 本紙掁尺度適用中國S家榡準（CNS ) Α4規格（210X297公釐） - 4 60 4 89 A7 B7_ 五、發明説明（） 、複寫機内的阻抗材料及利用PTC特性的面狀發熱體等用 途上0 又如上列所述*在碳黑接枝聚合物的製造時*最好能 從環氧基、氮丙陡基、硫環氧基及卩亞哩嚇基所成的群中挑 選一種或二種Μ上的基來使用為宜。 如上列製造碳黑接枝聚合物有關的本發明時，宜將上 列反應聚合體與碳黑加入分散媒體溶液中•使其在加熱下 分散處理，Μ加熱混合。 即，為欲達成上列各種目的的本發明又是，將具有能 與固體微粒子表面的官能基起反應的反應性基聚合雅和固 體微粒子一靼加入於分散媒體溶液中，使其在加熱之下進 行分散處理為其特點的固體微粒子表面改質處理方法。 再就疸種固體微粒子的表面改質處理方法來說，上列 的分散處理由於須將欲被處理的流體裝入容器内，即使用 在容器内部具備能夠迴轉的攪拌子，為加熱容器內的被處 理流體的加熱裝置，及加在容器內的複數粒狀媒體（珠子 )的濕式分散處理装置來進行為宜。 又，欲製造相關於所述第3〜5項的發明之碳黒接枝聚 合物時，在加熱混合塊狀或接枝型聚合體和碳黑，意欲在 分敗媒體溶液中進行其加熱混合者，宜予先進行分子設計 使用自具有能與該凿塊狀或接枝型聚合體的碳黑表面官能 棊起反應的反應性基之鏈段（Α.)和上列鏈段（Α)互異骨格構 造的鏈段（Β)中，Μ鏈段（Β)為主體而選擇與該當分散媒體 潜液有較高親和性者。 -17 - 伕尺度適用中國固家標率（CNS ) Α4規格（210Χ297公釐) · "" -------^----：---1T------^ (请先《讀背面之注意事項再填寫本頁) ^ 60489 at B7 五、發明説明（） (請先Μ讀背面之注意事項再填寫本頁) 亦就是，鍵段（B)與分散媒體液的親和性高，當在該 當分散媒體液中加入碳黑及該當塊狀或接枝型聚合體時· 即能使該當塊狀或接枝型聚合體的鏈段（B)趨向分散媒體 液*同時使趟段（A)趨向碳黑配合*而視為能使鍵段（A)所 有的反應基與碳黑的表面官能基間的反應進行得有很效率 Ο 假如將該當分散媒體液視做最後所得碳黑接枝聚合物 配合於樹脂組成物，有機媒體等的目的媒體相同或近似性 狀時，即能得到對於目的媒體具有高度分散性及使碳黑極 有效的與聚合體進行接技化而得到具有安定特性的碳黑接 枝聚合物。 因此，本發明亦視為，在目的媒體或具有與此類似性 狀的媒體所組成的分散媒體液之存在下，使具有能與碳黑 表面官能基起反應的反應基鏈段（A)，和具備比上列趟段（ A)對上列分散媒體液圼更高親和性的鏈段（B)之塊狀或接 枝型聚合體加在碳黑中一起加熱混合為特色的碳黑接枝聚 合物的製造方法。 本發明又可視為，將具有能與碳黑表面的官能基起反 應的反應性基継段（A)及比上列鐽段（A)具有對碳黑圼低度 親和性鏈段（B)的塊狀或接枝型聚合體接枝於碳黑為其特 色的碳黑接枝聚合物製造方法。 此時亦將如上列同樣，使碳黑與聚合體進行極為有效 的接枝化。 本發明亦可視為，含有如同上列以碳黑接枝聚合物為 本纸乐尺度速用中國國家榡準（CNS ) Α4規格（2丨0 X 2?7公釐） BO 4 89 · A7 _____B7_ 五、發明説明（） 著色劑成分的光硬化性樹脂組成物，特別是指驗可溶型光 硬化性樹脂組成物。 本發明可作為指上列由光硬化性樹脂組成物所形成的 滤色器用的黑色矩陣圖。 本發明尚可視為，含有如同前列Μ碳黑接枝聚合物為 著色成分的墨水嗅射記錄用記錄媒體液，靜電荷影像顯像 用液體顯像劑。 本發明更含有如同下列细說的其他各種實施形態。又 ，若為同行時*基於下述詳细說明，即能理解在不超出本 發明所提出的請泶範園的記載事項所限定的本發明的思想 或範_内，加以變更甚至改造類似其他為數甚多的貿施形 態之限制了。 <就圖面加以簡單的解說> 第1圖為，有關本發明的碳黑接枝聚合物製造方法在 實施形態時的碳黑表面周邊狀態的横式圖。 第2圖的（a)〜（e)為，有關本發明在製造碳黑接枝聚 合物的一種實施形態下所使用的塊狀或接枝型聚合體的各 種構造例之模式，又，（f)為這些各棰塊狀或接枝型聚合 體结合在碳黑粒子（CB)表面的狀態摸式圖。 第3圖的（a)〜（e)為，有翮本發明在製造碳黑接枝聚 合物方法上的其他實施形態下所使用的塊狀或接枝型聚合 體的各種構造例之模式圖，又，（f)為，這些各棰塊狀或 接枝型聚合體結合在碳黑粒子（CB)表面的狀態模式圖。 第4圖的（a)〜（e)為，有關本發明在製堦碳黑接枝聚 本紙張尺度逋用中國國家插準（CNS } A4規格（210X297公釐） ^------1T------絲 (請先閲讀背面之注意事項再填寫本頁) A7 160489 __B7___ 五、發明説明（） 合物方法上，更為另一曆的實施形態下所使用的塊狀或接 枝型聚合體的各種構造例之模式圖，又·（f)為，埴座各 種塊狀或接枝型聚合體結合在碳黑粒子（CB)表面的狀態横 式圖。 第5圖為，有關本發明在固體微粒子的表面改質處理 方法上所使用的濕式分散處理裝置的構成其一種實施形態 模式的斷面圖。 第6圖為*有關本發明在固體微粒子的表面改質處理 方法上所使用的濕式分散處理装置的另一種構成實施形態 的模式的斷面圖。 <較佳具體實例的詳細說明> 茲Μ實施例的形態來詳細解說本發明如下： 1.碳黑接枝聚合物 本解說所說的「碳黑接枝聚合物」即為在碳黑上加Μ 聚合體接枝化的微粒子。碳黑接枝聚合物為在碳黑的一次 粒子或在複數個凝集體上結合了聚合體接枝化所成者。再 說，在此所謂的「接枝化」，即指杜尼Uean-Baptiste Donet)等在其著作「碳黑」（1978年5月1日股份公司講談 社發行）所作定義，往對於如同碳黑的基質上附加不可逆 反應的聚合體之謂。 由於進行不可逆的附加反應，即能使聚合體起化學結 合於碳黑粒子表面，而完成上列兩者的確實結合。能起「 接枝化j的附加反應者，即有吸電子附加反應，加基附加 反應*吸核附加反應及附加環化反應等。 -20 - 本紙伕尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^^iT-------線 (锖先閲讀背面之注意事項再填寫本頁) ‘10 4 89 A7 ____B7_ 五、發明説明（） 碳黑通常有數rm〜數百nm大小的粒子徑。然而，卻由 於碳黑粒子間的凝集力很大，通常均以數個微张（w )以 上的粒子徑凝集體來處理。又，因碳黑粒子間的凝集力要 比其本身與其他媒體間的親和性為大，要將碳黑的亞微细 粒分散在媒體中*是一件非常困難的事情。另外的碳黒接 枝聚合物，即有在碳黑粒子間極其效的吸入聚合賭而減低 碳黑粒子間的凝集力等儍點。加上，若聚合物與媒體有親 和性時，碳黑接枝聚合物即能以亞微细粒的狀態分散在媒 體中〇 設若·聚合物與媒體有高度親和性，而無法使聚合體 極有效的與碳黑形成接枝化者，即不能成就安定的特性而 易生差異以致於欲得在親和性有一定水準的碳黑接枝聚合 物的碳黑含量降低，受到用途上的限制。再說，哲只Μ在 碳黑被接枝化的聚合物的親和性在媒體中企求其分散安定 性，即有其界限的問題，更將使在應用碳黑接枝聚合物的 各種用途上，難於滿足所要求的功能附加要件。 本發明群晋經考慮到對於從來就有的碳黑接枝聚合物 在1.各種用途上所要求的功能性給與面，和2.各種用途上 所要求的提升分散性等，加Μ銳意檢討的結果，認為以聚 合體做為形成聚合體結構體時*使用具有能與碳黑表面功 能基起反應的反應基與乙烯性不飽和二重結合體及俊基等 的特定功能基，即能得到更為優越的分散性及其他功能特 性的碳黑接枝聚合物的事實。 即，.若碳黑接枝聚合物的接枝鏈屬於不飽和二重結合 本紙張尺度適用中國国家榡準（CNS ) Α4規格（2〗0x：297公嫠） ,裝----；--^------^ (_先閱讀背面之注ί項再填寫本頁) 460489 A7 _ B7五、發明説明（） 者，例如當被其加入於光硬化性樹脂組咸物，熱硬化性樹 脂組成物時，由於光硬化反應、熱硬化反應被固定在樹脂 矩陣上而成為能維捋甚赛定的分散狀態，又有利於該當組 成物的硬化反應自身上。 又*若碳黑接枝聚合物的接枝鏈含有梭基時，例如將 之加入於鹼可溶型硬化性樹脂組成物者•即能提升該樹脂 組成物的酿顯像性。 又，欲得在聚合體鏈中含有俊基的碳黑接枝聚合物時 ，將具有能與碳黑表面功能基起反應的反應基及含有搜基 的聚合體一起加在碳黑中加熱混合，由於該當聚合體的反 應性基會與梭基起反應而成為膠化，即無法進行企求的接 枝化.所Μ，本發明即採取予先將含有氮氧基的聚合體接 枝於碳黑後，Μ酸酐來處理，藉由該氫氧基與酸軒的半脂 化反應以引進梭基的方法。以這個方法•即極其容晃的得 到具有所企求構造的碳黑接枝聚合物了。 本發明又係，自形成聚合體結構的聚合體的構造面上 加以銳意的檢討所得結果為，即發現了以使用塊型或接枝 型聚合體為該當聚合體，即能獲得更為有效的接枝化及比 從來的碳黑接枝聚合物之對於各種媒體具有更為優越分散 性的碳黑接枝聚合物。 可以說，用於製造舊有的碳黑接枝聚合物的碳黑及具 有反應性的聚合體是屬於随機共聚合體或在片末端只含有 一個反應性基的聚合體，能與碳黑起反應的反應基很不規 則地分散在一個分子趟中，或以只含有一個的形態。若將 -22 - ^^ ------^ (#先閱讀背面之注意事項再填寫本頁) 本纸伕尺度適用中國國家標準（CNS )八4说格（2丨ΟΧ297公釐） 4 6 Ο 4 09 Α7 _Β7__ 五、發明説明（） 之與有關本發明的塊狀或接枝型聚合體作一比較時，即在 本發明的聚合體，就有其特定的位置，即成為在鏈段（A) 上聚集了碳黑及能起反應的反應性基*而可視為能高度提 升與碳黑間的反應確實率。 又，例如K般成聚合體結構的聚合體來說時，即同時 具有對目的媒體高親和性的鏈段（B)及比這個鍵段（B)對目 的媒體較低親和性的趟段（A),而且又加意地設計了只容許 鏈段（A)與碳黑的表面功能基起反應而含有利於接枝化的 反應性基，將之入於目的媒體或與此類似性狀（極性）的 媒體所成的分散媒體液中進行接枝化時，可能會使提升接 枝化效率更為顯著。 第1圖為，如同上列所述，在目的媒體或在與其類似 性狀的媒體所成的分散媒體液，使碳黑與上列具有反應性 基的塊狀或接枝型聚合體進行反應時，圼顯於碳黑表面周 邊的狀態模式圖。如同上列所述，因為聚合艘是由具有反 應性基的_段（幻及具有與媒體親和性的鏈段（B)所成，在 反糸中成為如圖所示希望鏈段（B)朝向分敗媒體液中成為 極力伸張的形態，將使ϋ段（A)不得不包圍碳黑粒子的表 面，而可提供絕好的反應空間給碳黑與此聚合體進行接枝 化，使其接枝化更為有效。 由此所得的碳黑接枝聚合物上結合在其表面的接枝鏈 ，即因為對於目的媒體有高度親和性的鰱段（Β)被按排朝 向外側露出，即能對目的媒體圼顯高度親和性而使碳黑接 枝聚合物可以亞微细粒的單位形態分散於媒體中。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210x297公釐） ^.^-ΪΤ------# (诗先聞讀背面之注意事項再填寫本頁) A7 4 60 4 89 B7 五、發明説明（） (請先聞讀背面之注意事項再填寫本頁) 或者又可Μ同樣的想法，可Μ使碳黑表面的功能與具 有能起反應的反應基的鏈段（Α),和實質上不具有前述反應 性基而比前述鍵段（Α)對碳黑有較低親和性的鍵段（Β)(換 言之，而具有對碳黑高度親和性的鍵段（Α)和對目的媒體 有高度親和性的鏈段（Β)兩者）的塊狀或接枝型聚合體與碳 黑進行接枝化。 就反懕糸來說，由於本聚合體的鍵段（Α)會向碳黑配 對，可使存在於該當鍵段（Α)的反應基更能有效的在碳黑 表面進行接枝化。 由此所得的碳黑接枝聚合物在其表面所结合的接枝鍵 ，由於被配對成尉目的媒體具有高度親和性的鍵段（Β)朗 向外側而露出，即能對目的媒體顯示高度親和性而使碳黑 接枝聚合物能以亞微綑粒的單位分敗於媒體中。又，在此 時，即不同於所述或具有與此類Μ性狀的媒體所成的分散 媒體液中使其進行接枝化，僅Μ該當聚合體與碳黑溶融練 合，或者可能使其在對鍵段（Α)及鏈段（Β)任何一方均會顯 示略為同等程度的親和性分散媒體液中進行反應，然而若 欲使接枝化進行得更為確實完全而高效率者，即應使其在 對鏈段（Β)有親和性的分散媒體液中施行為宜。 照這樣地Μ塊型或接枝型聚合體倣為形成聚合體構成 部來造就的碳黑接枝聚合物，其聚合體構成部即有更為有 效於被接枝化及更為優越的分散性，較從來的碳黑接枝聚 合物易分散於各種媒體中，又能大量的增加碳黑接枝聚合 樹中的含碳量，又能鍰和碳黑本身具有的禁止重合效果， 本紙張尺度適用中國國家橾窣（CNS ) Α4規格（210X297公釐） 460489 A7 __B7__ 五、發明説明（） 提升電氣絕緣性及甚至在有機溶劑中亦易進行接枝化等特 點。 (請先Μ讀背面之注意事項再填寫本页} 若以塊型或接枝型聚合體來造成聚合髏構造部使其形 成碳黑接枝聚合物時，雖能提升其分散性，緩和禁止重合 效果，提高其電氣絕緣性等的改菩*如在光硬化性樹脂組 成物中將這種碳黑接枝聚合物配合進去使其成為黑色光硬 化性樹脂組成物者，以這種構造的碳黑接枝聚合物，尚不 能以光聚合式光架橋參與實質的任何硬化反應，如欲得十 分完善的光硬化特性，即須加入比碳黑接枝聚合物的調配 量更為多量的光硬化性化合物，就必然的發生碳黑接枝聚 合物的調配量趨向其上限，終於難得Μ薄度皮膜獲取充分 的遮光性了。如同樣的情形，在調配有碳黑接枝聚合物的 媒體，經光重合、熱重合、加熱橋反應等而成為硬化物的 情形時，若能使碳黑接枝聚合物對於形成矩陣的媒體有反 應，在欲得優良的硬化特性及碳黑的分散安定性等觀點上 ，可3胃是有利的。 於此，本發明群更加銳意的檢討，而發現了在形成上 列聚合體結構部的塊型或接枝型聚合體中，若引進不飽和 二重給合於不與碳黑表面的功能基反應而配向在外側的鍵 段，亦即鏈段（Β),而將由此所得的碳黑接枝聚合物調配到 光硬化性樹脂組成物等時，即能該當組成物的硬化反應順 利迆行，Μ十分薄度的皮膜就能獲得充分的遮光性，而且 在皮膜強度，碳黑的分散安定性等面上具有特優的現象。 又如间上列所述，自調配於驗可溶型光硬化性樹脂組 -25 _ 本紙佚尺度適用中§國家榡準（〇^)人4規格（210/297公楚) 4 604 89 ' A7 B7 五、發明説明（） (请先Μ讀背面之注意事項再填寫本頁) 成物而能提升驗顯像性的面來說者•本發明群即發現了將 上列形成聚合體結構部的塊型或接枝型聚合體視為具有厘 氧基的混合物，特別是，配對在朝向外側的鍵段，就是鏈 段（B)視為含有氫氣基，而在對碳黒胞行接枝化後，以酸酐 處理徑由該當氧基與酸酐的半脂化反應而引進俊基所得 的碳黑接枝聚合物和鹼可溶型硬化性樹脂組成物等相調配 即能獲得碳黑的分散安定性的同時具有儍越的鹼顯像性的 事實。 甚至* Μ碳黑以外的顔料供作顔料成分•而依上列有 關本發明的使聚體成分複合化而成的顔料複合聚合物，將 同樣的均具有如有關本發明的上列碳黑接枝聚合物一樣的 優越特性。 又，在本說明書所說的「顔料複合聚合物」是指顔料 與在其表面功能基具有能起反懕性的反應性基聚合體經一 起加熱處理後所得者，亦即在顔料的一次粒子在數個的凝 集體表面付著安定的聚合體*雖然在理論上可將視作在顔 料粒子表面與聚合體間發生化學結合，如上列所述的已發 生了接枝化，卻要在分析面上指出是否發生了這種接枝化 ，就伴有某種程度的困難，又實際上，許多情形之下，亦 可視作不但有這種化學結合力的存在遝有不少物理的附著 力在作用的可能，因之，為涵蓋像這種狀態的情形下，而 將其定義為「複合聚合物」成為「複合化」。 遯要在下列Μ碳黑為頭料，荏這種碳黑加入聚合體使 其複合化來製造顔料複合聚合物的形式為其中心說明本發 本纸張尺度適用中國囤家樣準（CNS ) Α4現格（21〇Χ2〇7公釐） 460489 A7 _____B7 五、發明説明（） (請先Μ讀背面之注意事項再填寫本頁) 明。又，為晃於理解本發明起見*雖然在下列將κ該當形 式所得的顔料複合聚合物稱為「碳黑接枝聚合物」，卻在 赏際上，不僅涵蓋如上列所定義的聚合體經過「接枝化」 的產物，亦有更為廣義的聚合體經由「聚合化」的產物， 即應留心於為製造碳黑複合聚合物的這件事上。 1.1碳黑 使用在本發明的製造碳黑接枝聚合物的碳黑，不特定 在其表面含有俊基及氫氧基等功能基者，亦可使用如爐黑 、構法度黑、乙缺黑、燈黑等的任何一種，雖然可以直接 使用通常的市售品•卻最好使用含有羧基的碳黑。又•使 用其pH值未滿7，尤其pH值在1〜5的碳黑為宜。含有稷基 的碳黑》雖然易Mgg性碳黑的形態購入，甚至其經酸化處 理的中性或鹽基性碳黑亦可作為本發明的原枓加以大大的 使用。若碳黑未含有俊基等功能基，或pH值茌7以上者， 或將無法很有效的加以接枝化。又，碳黑的pH值測定法是 侬據Jis K 6211來質行。 又，碳黑的平均粒子徑在0.0005〜0.5 的範圍内* 特別在0.001〜0.2 範園的為最好。由於無法獲得平均 粒子徑未滿0.0005 的碳黑，即不具產業上的意義。又 ，若平均粒子徑越過0.5 ，或即無法賦與碳黑接枝聚合 物充分的分散性。 使用在有關本發明的碳黑接枝聚合物Μ外的顔料複合 聚合物製造時的顔料，併不特別加以限制應使用何種顔料 ，只要是有機顔料、無機顔料或其混合物均可Μ使用。 _ 27 - 本紙張尺度適用中国國家標準（CNS ) 規格（2丨0X297公釐) ' 4 6〇4 89 A7 __ B7_ 五、發明説明（） 無機顔料，即有如上列的碳黑之外，遷有如，氧化銘 、二氧化欽、欽酸鋇、紘酸_、软§楚縛、紋酸總、氧化鉾 、矽砂、粘土雲母、砂質石、砂满土，各種無機氣化物顔 料、氧化格、氧化鈽、氧化亞鐵、三氧化練、氧化鎂、氣 化蹈、硫酸鋇、炭酸鋇、實酸耗、硅石微粉體、坎化石圭、 氮化鞋、皮化硼、碳化鎢、從化§太、氣化鈽等的粉末或粒 。而且，瑄座無機顔料來自紘偶合劑，鞋焼偶合劑或高級 脂肪酸金屬鹽等經眾所周知的找水化處理劑處理而得的物 質亦可Μ使用。 又有機顔料即有*如尼普魯土黃（Naples yellow)茶 酚黃-S、漢撒黃-G、漢撒黃-10G、聯苯胺黃-G、聯苯胺黃 -GR、奎〇林黃色澱、永久黃-NCG、酒石黃色殺等黃色顔料 、雜撥（molybdenuni orange)、永久撥RK、聯苯胺撥G、陰 丹士林亮橙GK等的撥色顏料、永久紅4R、立索組、etb啤·# 酮4R、渥岑紅（v/atchung red)弼鹽、色源紅D、亮咽脂紅6B 、愛我神沈澱色料（eros in lake)、若丹明色澱B、茜素沈 殺色料（alizarin lake)、亮咽脂紅B等的紅色顔料、堅牢 紫B、甲基紫色源等的紫色顔料、鹼性Μ色殿、維多利亞 藍色澱、花青藍、無金屬ftt花青藍、紗花青Μ部分（局 咅13)親化物、堅牢天藍、陰丹士林M — BC等的Μ色顔料， 顔料綠Β ·孔雀綠色源、法納魯黃綠G(Fanal yellow green G)等的綠色顔料等。 1,2反應性基 在接枝於碳黑的聚合體時，可做為能與碳黑的表面反 -28 - _本纸伕尺度適用中國國家榇準（CNS ) A4規格（2IOX297公釐] ~ ^----_--1T------0 (請先閱讀背面之注意事項再填寫本育) a 604 89 A7 A7 _ B7 五、發明説明（） 應的反應性基，如是靨於能限碳黑表面所有的功能基反應 而賦與Μ該當聚合體的形態與δ炭黑進行接枝化者，即不加 以任何的限制而可Μ利用為各種反應性基。 在此，如欲使接枝化成為徹底而安定時，即要求聚合 體結構部介由共有結合來與碳黑相結合，尤其自脂化结合 、δ荒脂化結合、醯胺結合、氨基結合、酿結合、硫醚結合 、羰基結合、疏鑛结合、及硝酿結合等所成為群中最少選 取一種結合，又自脂化結、硫脂化結合及酿胺結合等所成 的群中最少選取一種結合來進化接枝化為宜》若考慮到這 些問題時，g卩應自環氧基、硫撰氧基、氮丙陡基及嗯唯 基等所成群中最少選取一種或二種以上做為其反應性基為 宜。 雖然對碳黑結合的反應性基僅限定於上列所舉者，若 使用具有這些反應性基以外的基之聚合體時，或會產生能 於使用的碳黑的種類之限制。聚合體的含有所述反應性基 比較適宜的理由在無關其種類或形狀而能供為使用的碳黑 均能在溫和的條件之下，使碳黑與聚合體以極高接枝化效 率來進行其附加反應上。特別在碳黑含有如上列羧基為其 表面功能基時，能使梭基與環氧基、硫環氣基、氣丙u定基 或噁唑啦基進行熱反應而K高收率成功不可逆的附反應， 即由這種附加反應來使碳黑與聚合體形成上列的共有结合 是最好的。 將埴些反應性基引進聚合體的方法，雖然通常均依如 在W088/03 545 (PCT/JP87/00867)所公告的方法，例如， -29 - 本紙張尺度適财顏家制t ( CNS )八4麟· (+21GX297公楚) " --------狀衣-- (請先閲讀背面之注意事項再填寫本頁)I 4 60 4 89 at B7 ___ 5. In the description of the invention, how to disperse these solid particles uniformly becomes a problem. (Please read the precautions on the back before filling this page) In order to solve this problem, That is, many methods were reviewed, such as coating the surface of solid particles with various surfactants or waxes to improve the affinity with solid or liquid media, and to make solid particles mix or disperse uniformly. For example, for carbon black, (: 1.) A carbon black graft polymer obtained by superposing polymerizable monomers under the coexistence of carbon black. • The hydrophilicity can be changed by selecting the appropriate polymerizable monomer. Or lipophilic facts have attracted much attention (for example, Japanese Patent No. 22047, Japanese Patent No. 44-3826, Japanese Patent No. 45-17248, and US Patent No. 3557040). (2) In addition, some people have proposed a method in which a polymer having a reactive group such as an epoxy group or an aziridine group in its molecule interacts with the carbon black phase to obtain a carbon black graft polymer ( Special Fair No. 2-24868, Special Fair No. 6-27269) ° However, the yield of the carbon black graft polymer obtained by the method (1) above is only about several to 10%, and most of them are homopolymerized with vinyl. The form of the substance exists in it, and the surface treatment efficiency of carbon black is extremely reduced. Therefore, it is impossible to expect an improvement in the affinity with other substances, and many different dispersion states occur depending on conditions such as mixing or dispersion. Also, as listed above (2) Although the dispersibility of the carbon black graft polymer with various substances can be slightly changed *, the carbon black graft polymer has a polymer chain that has functional groups that interact with the carbon black. There is only one characteristic of lipophilicity or hydrophilicity. For the purpose of increasing the grafting effect of carbon black, and the dispersibility of various media given by the polymerized key bonds obtained from the grafting, this paper applies the Chinese national standard ( CNS) Α4 specification (210 × 297 male ) A7 460489 _B7_ V. Description of the invention () It is difficult to meet the requirements of both parties by + points in the requirements of mutual goods. ○ Therefore, 1. It is impossible to increase the content of the carbon black graft polymer. Carbon child, 2. Can't impart very dispersibility to high-polarity media, such as leaven, cellosolve solvents, etc. *, or low-polarity media, such as hydrocarbon solvents or silicon-based solvents, etc. 3. Difficult Issues such as grafting in organic solvents. Also, in the above listed fair No. 6-27267, it has been publicly stated that one molecule of carbon black and bad oxygen groups are 1 to 2 and / or the thioloxy group is (Thioepoxy Group) A method for producing carbon-grafted polymers by stirring and mixing the polymers in the molecule at a temperature of 50 ~ 250 ° C. When manufactured by Nongben method • Because the polymer molecules can be made The reactive group inside reacts with the surface functional group of carbon black to produce a highly effective carbon black graft polymer with extremely efficient dispersing properties. In this way, the solid fine particles are fused with the reactive polymer to improve the solid particles Grafted polymer chains on the surface A method of excellent dispersibility. However, when using a needle threader, a ball mill, etc. to melt and knead solid particles and reactive polymers, if the reactive polymer is reduced for solid particles, it is difficult to make the polymer graft chain uniform. Covering the entire surface of the solid particles, it is inevitable that the content of the solid particles after the surface modification treatment of the particles cannot be increased, and many original characteristics of the reduced solid particles will occur. Also, it is assumed that the particles have a low molecular weight. Reactive polymers, or when there are too many reactive groups per molecule, will make grafting difficult to fully proceed -5 — This paper scale is applicable to China National Standard (CN: S) A4 (210X297 mm)- -------- ^ ---- aT ------ ^ (Please read the precautions on the back before filling this page) A7 1 6 0 4 89 B7 V. Description of the invention () ( Please read the notes on the back before filling in this page), or if there is a Tenghua, that is, the use of related reactive polymers, such as the number of functional groups, molecular weight, etc., will increase its limit, and if you want to get the desired Disperse liquid Be dispersed in the liquid dispersion medium operation more complex problems in the step of melt kneading and after operation. At the same time, in order to obtain the liquid separation solution of the solid particles that have undergone such secondary agglomeration, it is well known to add a suitable dispersion stabilizer to the dispersion medium liquid and apply physical search and mixing to perform the dispersion treatment. Technology out. In the uniform dispersion operation, that is, the mixing operation of giant vision and the mixing operation based on small-scale turbulent motion should be considered at the same time. It has been specially researched in various shapes for the device for manufacturing this dispersion. The container to be processed, the shape, quantity and setting position of the stirrer or its rotation speed, whether the seeding plates and partitions are arranged, and even the dispersion medium used, such as balls placed in the container, its shape and materials are wet-dispersed. Processing device and wet crushing processing device. Among them, those who use a combination of a stirrer and a dispersing medium in various fields are usually able to obtain a relatively good dispersing effect. For example, in No. 59-22577 of Special Gong, No. 2-27018 of Special Fair, No. 2-68151 of Kaiping, No. 3-101820 of Special Kaiping, No. 7-12441 of Special Fair, No. 7-4552 of Special Fair, and No. 4-326934 of Special Kaiping , Special Fair No. 6-73620, JP-A No. 5-38425, JP-A No. 4-281855, JP-A No. 6-351, JP-A No. 6-212876, JP-A No. 6-21014 Minghu, JP-A No. 6-134271 No., both have proposed this type of dispersion processing device. However, this type of wet dispersion treatment device and wet pulverization treatment device used to prepare the dispersion of solid particles is processed by the treatment device in the normal—6— This paper iron standard applies to China National Standard (CNS) A4 specification (210 × 2 ! > 7 mm) A7 ^ 60 4 B9 B7 V. Description of the invention () The solid particles and the dispersion medium are stirred and mixed at a temperature * that is, the dispersed state is formed by the physical external force generated by the mixing. The stability of the obtained dispersion liquid is not stable enough, and it requires a long time dispersion processing operation. However, color sensors used in color liquid crystal display devices, that is, having at least two kinds of color layers as the sub-factors of the fine field, and the increase in light M to be hidden between such drawing factors are displayed. The full color contrast has been colored with a black matrix. This black matrix diagram is usually formed on a glass substrate with a pattern of micro-bundles made of metal thin films such as chromium, wire, and aluminum, and is deposited on the substrate by a vapor deposition method, a sputter method, a vacuum film formation method, or the like. Gold thin film, using photographic technology to form a pattern. However, the black matrix diagram manufactured by this method has a problem that the original cost of the black matrix diagram is high due to its complicated process, and the problem of an increase in the original cost of a color filter to be used with a black matrix. In addition, when a color filter using a black matrix diagram of a metal thin film such as chromium is mounted on a transmissive display, the intensity of reflected light may occur due to excessive reflectance of the metal surface when external light is irradiated on the color filter. Too big to significantly reduce the problem of display quality. At the same time, in order to solve the above-mentioned problems that occur with the black matrix diagram using the gold thin film, various people have proposed various methods of forming a black matrix diagram by using a resin composition containing a colorant. For example, in Japanese Patent Application Laid-Open No. 2-239204, there is a method of dispersing a light-shielding lining material such as carbon black in polyimide (R) resin to form a black matrix diagram. According to -7-This paper block size is applicable _ National Standard (CNS) A * size (2 丨 .0X297 mm) ¾ ---- ^ — * tr ------. # (Please read first Note on the back then fill out this page) J 6 〇 4 89 A7 B7 V. Description of the invention () (Please read the note on the back before filling out this page) This method, although it can get a low reflection of external light The black matrix diagram of polyimide resin with high heat-resistant substrate is affected. However, the substrate is coated and dried with a polyimide resin containing a light-shielding material. The application of light-blocking agents *, patterning, etching, and removal of light-blocking agents has been carried out, but the project can not be simplified and the original cost can be reduced. In addition, some people have tried blending black pigments such as carbon black in a photocurable resin composition, coating it on a substrate, and drying it, then covering it with a predetermined pattern to tightly fix it, and exposing it to light. The development process is to form a black matrix diagram of prescribed circles. In order to obtain a black matrix diagram with sufficient light-shielding properties, the amount of carbon black is added, but it will extremely reduce the spectrum of the hardened photocurable resin, such as the ultraviolet transmittance of about 400 rnn, resulting in photohardening. It is extremely difficult, and it is more difficult for carbon black to obtain the radicals generated by the photo-registration starter that receives ultraviolet rays and to hinder photo-recombination. In addition, if the amount of carbon black added is increased, the formed film becomes conductive, and it cannot be used in liquid crystal displays in a black matrix diagram. Not only that, as mentioned above, the cohesion between carbon black particles is greater than other substances. For example, it has weak affinity with polymers, water, organic solvents, etc. * Even in the photocurable resin composition listed above, it is extremely difficult to mix or disperse uniformly, and it is difficult to obtain a stable and uniform black layer film. In Japanese Patent Application Laid-Open No. 4-63870, Zeng Tili used a group of organic pigments such as carbon black with different colors formulated as black together as the light-hardening resin group—8 _ This paper applies the national standard of ft. CNS) A4 specification (210 X mm) 4 60 4 89 a? _B7_ V. Description of the invention () Product colorant to suppress the carbon black star added for the desired light-shielding property, and thus control the light The spectral transmittance of the ultraviolet portion required for curing tends to decrease and the insulation properties of the film are maintained intact. However, when organic pigments are used in this way, compared with carbon black alone, the spectral transmittance of the visible area will be improved *, making it difficult to form a black matrix with low film thickness and sufficient light-shielding properties, and it will not solve the problem. The problems of dispersion of carbon black and hindering of light hardening due to the carbon black acquiring group as described above. In Japanese Patent Application Laid-Open No. 6-67421, the light-curing resin composition with a carbon black graft polymer component as listed in 2. above is constructed as a black colorant. Because of this substance, the formation of the black matrix diagram is extremely stupid. Black light-curing resin composition with light-shielding property, resolving property, and appropriate photosensitivity, and stable dispersion. However, because the carbon content M in the carbon black graft polymer cannot be increased as described above, it is not possible to obtain sufficient light-shielding properties and a satisfactory level of dispersibility *. In terms of strength, it has not yet reached a very satisfactory level. In particular, when using this curable resin composition to form the film of the black matrix diagram, in order to improve the exposure and hardening, after the development process *, the film is completely hardened, and for the purpose of improving the tightness between the film and the film. 100 ~ 300 ° C heat treatment (subsequent baking) operation, but it is still suspected that during this heat treatment, the carbon black stored in the film and even the breakdown state of the carbon black branch polymer will change, and the detection The situation that the resistance efficiency of the film is greatly reduced after baking by the posterior palate. Therefore, it is not applicable to the black matrix diagram of liquid crystal color filters that must be highly resistant. -9 ~ This paper size is applicable to China National Standard (CNS) A4 (2! 0 X 297 mm_) --------- ^ ------- 1T ----- -. # (Please read the precautions on the back before filling in this page) d 60 ά 89 A7 ___B7_ V. Description of the invention () and * Μ photocurable resin composition to form a film such as a black matrix diagram, I hope it It becomes an age-soluble resin composition, but it has been pointed out that the carbon black added or a conventional carbon black graft polymer due to a component of the M colorant at this time may cause a decrease in the testability. Change it. Let's change the topic to explain the ink jet recording method. The ink jet recording method is a method in which a so-called ink recording medium liquid is scattered in the form of a liquid droplet and adhered to a recording material to perform green recording. Various methods have been proposed for this method depending on differences in the droplets of the recording medium liquid, the control method, and the like, and they have been put to practical use. For example, the droplet generation method is as follows: 1. The # 15 part wall surface of the ink chamber is composed of piezo elements, and a recording signal is supplied here and the ink is pressurized. The method of adding electricity by electricity, 2. The method of heating and pressurizing the liquid droplets according to the recording signal heat energy is added to the recording liquid in the ink chamber, and the pressure generated by the bubbles in the ink is generated. This method is a practical representative method. There are also 3. ways to make the ink burst out of the nozzle under high pressure and to make the droplets particle by surface tension and electrification in the scattering, 4. under low cavity force * Ink ejection, plus M ultrasonic vibration. 5. A method of using high voltage to attract the ink balls formed on the surface of the liquid. ○ The ink used in this ink jet recording method, that is, the recording medium liquid, should be suitable for jetting. (Spit out) liquidity (viscosity, surface tension, conductivity, etc.) of liquid conditions (viscosity driving voltage, driving frequency, radon perforation shape and material, radon perforation, etc.) for long-term storage without clogging Ink ejection device Fast fix to the recording material (paper, film), and the surroundings of the dots should be smooth. * The ink image formed must have a clear tone—10-This paper is a standard for the national standard (CNS) A4 (2Ϊ0 × 297 mm). ^ .. ir ------ ^ < Read the notes on the back of the poem before filling in this page) A7 SO 4 89 ____B7_ V. Description of the invention () Thick and better than water resistance and light resistance, the surrounding materials of ink (preserver, connection tube, color seal) (Material, etc.) Does not have various characteristics such as erosiveness. 从来 Never, it has always been a colorant composed of M dye and its solvent as the recording medium solution for the ink jet recording method. Since the physical properties of the recording medium solution are mostly affected by the inherent properties of the dye, for example, when using inkjet recording with a recording medium solution containing a water-soluble dye, the resulting ink will be affected by the physical properties of the water-soluble dye and become inferior. And the shortcomings of water, light resistance and so on. Furthermore, the stability of the ink containing the water-soluble dye itself is also very stable. Therefore, it has been tried whether a pigment-based ink used in the ink jet recording method using a head material such as carbon black as a coloring component instead of the dye-based ink is applicable. The pigmented ink has an excellent light resistance or water resistance in the resulting image of the ink over the image obtained by the dyed ink. However, * because the pigment is not easy to dissolve in the liquid medium of the ink, a high level of technology is required to promote the pigment to be slightly dispersed in the liquid medium of the ink. However, it is difficult to improve its dispersion stability. Or you can test it: use the above-mentioned carbon black graft polymer as the colorant component of the recording medium solution of the foam jet recording method, but due to various problems as listed above, it will occur 1. Cannot increase the content of carbon black Increase the color tone of the ink image to a very bright and high degree of transparency, 2. it is difficult to set the conductivity suitable for the ejection conditions_ 3. it is difficult to maintain a stable dispersion state, and it is not very stable in long-term storage . Furthermore, in recent years, there has been a trend toward high image quality in fields such as printing using electrophotography and electrostatic copying. That is, due to the rapid use of the Chinese paper standard (CNS) A4 (210X297 mm) by Digital Technology, ^ ----— ir ------ ^ (Please read the note f on the back first Please fill in this page again) S04 89 A7 ___B7__ 5. Description of the invention () Progress, in the level of development of the image, succeeded in ensuring higher precision than the previous technology. However, when a powder colorant is used to develop an electrostatic charge, the particle size of the powder colorant is about 10 m m, and a higher quality is not obtained. Therefore, there has been a renewed focus on a method for forming a high-resolution image using a liquid developer having a small particle diameter. As is well known, the liquid developer for electrostatic charge latent image development is an organic liquid having electrical insulation properties, such as those in which colorant particles are dispersed in a lauric hydrocarbon carbohydrate box. Must have colorability, electrification, fixation and dispersion stability, that is, composed of pigments, resins and other additives. In the liquid imaging method, the colorant particles usually have electrostatic imaging charges and are charged to the opposite polarity. This colored rigid particles will be attracted to the imaging charges in the electrically insulating liquid *, and will move to the display due to the electrophoretic relationship. The image is selected and attached to the image for development.茌 This liquid developer needs to improve the dispersibility of pigments such as carbon black or dendritic cells. For example, in Patent Publication No. 1995-253688, it is recommended to add grafted solvents to aromatic hydrocarbons. The solubility is high. The molecular substance is preferably the same solvent as the insoluble fluorene molecular substance, and it is suggested in patent publication 1995-104524 that the carbon black graft polymer as listed above can be used as a colorant, but neither of them has reached the level of a liquid ship imaging agent. Very stable dispersion. < General of the invention > For various reasons listed above, an object of the present invention is to provide a method for producing a carbon black graft polymer as a new product and its use. The other object of the present invention is to provide a carbon black with a high content of -12-the standard of this paper is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 OX 297 mm) --------- I- -^-I:-iT ------ 0 {Please read the notes on the back before filling in this tile) 60489 at __B7_ V. Description of the invention () (Please read the notes on the back before filling in 艿(This page) The same fashion has excellent dispersibility for various media. When added to various spectrums and thermosetting media, it does not hinder the degree of hardening of the media. It is designed to easily form a high-strength film at high addition levels. It is a new product of carbon black graft polymer with various physical properties such as superior electrical insulation and its manufacturing method. The present invention has another object, that is, when it is added to various media, it will exert its excellent coloring properties, and it will be a new product, such as anti-shading, photosensitivity, alkali developability, insulation, etc. Branch polymers and methods of making same. The present invention also provides a carbon black graft polymer used in a black photocurable resin composition, which is very effective for forming a black matrix pattern on a color filter, and a method for producing the same. The present invention further provides a carbon black graft polymer, which is a new product that is effective for use in a recording medium liquid, a liquid developer for electrostatic charge development and the like, and a method for producing the same when performing the ink jet recording method. The present invention will also provide various resin compositions, coating compositions, inks, thermal transfer inks, thermal transfer ink ribbon coating agents, back surface coating agents for magnetic recording media, colorants for electrostatic charge development, Coatings, high-resistance materials that require light-shielding, black matrix artificial marble for plastic color filters, plastic and rubber molding materials, colorants such as light-shielding fibers, plastics such as polyolefin smoke or polyester, and rubber knee modification Agents and fillers, planar heating elements, lubricants, traction drive fluids, electrical viscous fluids, and non-linear optical materials, electrical resistance adjustments, such as anti-charge materials, impedance materials in duplicators, and planar heating using PTC characteristics New products such as carbon black are compatible with the Chinese paper standard (CNS) A4 (210X297 mm) β〇4 89 αβ] 5. Description of the invention () Branch polymer and its manufacturing method. The present invention also provides a new surface modification treatment method for improving the dispersibility of solid particles such as pigments, magnetic powders, and ceramic powders such as kappa carbon black, to water, organic solvents, or high-molecular organic compounds, which can improve its dispersibility. The present invention also aims to provide a surface modification treatment method for a polymer component having a wide application range and a small amount of use, that is, an effective surface modification. Another object of the present invention is to provide a novel photocurable resin composition which is effective for forming a black matrix in a color filter. A feature of the present invention that can achieve the above-mentioned various objectives is that the first point is to obtain a polymer having a double bond of a reactive group capable of reacting with a functional group on the surface of carbon black and an ethylenically unsaturated double bond. The carbon black is a carbon black graft polymer which is formed by heating and mixing and has unsaturated double polymerization in the graft chain. The carbon black graft polymer related to the first invention has an unsaturated double bond in its graft chain. If it is added to various kinds and thermosetting resin compositions, the unsaturated double polymer Binding can participate in the hardening reaction. Therefore, even if a high amount of M is added, a high-grade film can be easily formed, and a film having excellent light-shielding properties and blackness can be obtained. In the hardened resin layer, the matrix resin can still maintain the form of the carbon black graft polymer for chemical bonding, so that the dispersion state tends to be stable, and the electrical impedance will not be revealed due to agglomeration. The adverse phenomenon of lowering the rate makes the obtained film have various physical properties such as superior electrical insulation. Therefore, M can be used in various media including the above-mentioned light and thermosetting resin composition, and the use of M colorants, fillers, and light-shielding agents is best. The dimensions of this paper are in accordance with Chinese National Standards (CNS) 6 4 pits (210X297 mm) · (Please read the precautions on the back before filling this page)., 1_ -ΪΤ knot A7 4 60 4 89 ___B7_ V. Invention Explanation () The second point is: (Notes on the back of Shi Xianmin, please fill in this page again) Add a polymer with reactive groups and argon groups that can react with functional groups on the surface of carbon black to carbon black After heating and mixing in the middle, the acid black (acid anhydride) is used to process the reaction mixture to obtain a carbon black graft polymer characterized by having a carboxyl group in the grafting process. Since the carbon black graft polymer of the invention of the item has a base in its graft chain, if it is added to an alkali-soluble hardening resin composition, the uncured portion can be visualized by using a test solution. The third aspect is: a segment (A) having a reactive group that reacts with a functional group on the surface of carbon black and a segment (A) having a bone structure different from each other ( B) The block and graft polymers are added to the carbon black and heated and mixed together. Polymer 0 is a carbon black graft polymer that is inferior to the invention of the third aspect, because it belongs to the polymer whose block forming part is block or graft type *, which can exert more effective grafting and Various destination media show superior dispersibility. But as K said, dividing polymers into block or graft polymers with two bond segments according to their functions can improve their grafting efficiency and affinity for the destination media. It may or may make the opposite requirements tend to be opposite to each other. The fourth point is: the segment (A) of the reactive group that will react with the reactive functional group on the carbon black surface, and the ethylenic group Unsaturated double combination with the above-mentioned chain segments (A) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 4 604 89 A7 B7 V. Description of invention () The carbon black graft polymer obtained by adding the block or graft polymer of the segment (B) to carbon black and heating it together. (Please read the note on the back before filling this page) About this fourth item The invention of the carbon black graft polymer is shared with the first item listed above Both the characteristics of the invention of the invention and the characteristics of the invention of the third invention. In order to achieve the characteristics of the invention of the above-mentioned various objectives, there is still a fifth invention, which is to * reverse the functional group having a reaction with the surface of carbon black. The segment (A) of the reactive group of fluorene and the bond segment (B) with a bone structure different from the fluorene segment (A) listed above must also have at least a fluorene-based block on the segment (B). Or the grafted polymer is added to carbon black and heated to mix the obtained reaction mixture, and then the carbon black grafted polymer obtained by the treatment of the anhydride with M. The carbon black grafted polymer related to the fifth invention will enjoy the related The two-layered invention and the third-layered invention are listed above. The carbon black graft polymer according to the present invention has not only a high content of carbon fluorene, but also has a high carbon fluorene content. Excellent dispersibility of the media 〇 The carbon black graft polymer of the present invention can be very useful in resin compositions, coating compositions, inks, thermal transfer inks, thermal transfer ink ribbons, tinctures, and magnetic recording media Use a surface coating agent, a colorant for electrostatic charge imaging, a coating Materials, high-resistance and light-shielding materials, black matrix diagrams of color filters for liquid crystals, artificial marble, plastics and plastics, light-shielding fibers, pigments such as vitamins, plastics such as polyethylene and polyester Modifiers and fillers for waists, planar heating elements, lubricating oils, traction drive fluids, electrically viscous fluids and non-linear optical materials, electrical impedance control, as well as anti-charge materials -16 Standard (CNS) A4 specification (210X297 mm)-4 60 4 89 A7 B7_ V. Description of the invention (), impedance materials in the copy machine and surface heating elements using PTC characteristics, etc. 0 and as described above * In the production of carbon black graft polymers, it is best to use one or two kinds of M groups from the group consisting of epoxy groups, aziridine groups, thioepoxy groups, and fluorenyl groups. Better. In the present invention related to the production of a carbon black graft polymer as described above, it is preferable to add the above reaction polymer and carbon black to a dispersion medium solution. • Disperse it under heating, and heat and mix it. That is, in order to achieve the above-mentioned various objects of the present invention, a reactive group having a reactive group capable of reacting with a functional group on the surface of the solid microparticles is polymerized and the solid microparticles are added to the dispersion medium solution at a time, and the solution is heated. The surface modification treatment method of solid particles with dispersion treatment as its characteristic is performed next. As for the surface modification treatment method of solid particles of jaundice type, the above-mentioned dispersion treatment requires the fluid to be treated be filled into the container, that is, a stirrer provided with a revolvable inside the container is used for heating the container. The heating fluid to be processed and the wet dispersion processing apparatus for a plurality of granular media (beads) added to the container are preferably performed. In addition, when it is desired to produce a carbon-fluorinated graft polymer related to the inventions of 3 to 5 above, the block or graft polymer and the carbon black are mixed by heating, and the heating and mixing are performed in a dividing medium solution. For molecular design, it is advisable to perform molecular design first using the segments (A.) and the above-listed segments (A) having a reactive group capable of reacting with the carbon black surface function of the chiseled or grafted polymer. Among the segments (B) of the dissimilar bone structure, the M segment (B) is selected as the main body, and the one having the higher affinity with the potential liquid of the dispersed medium should be selected. -17-伕 scale is applicable to China's solid standard rate (CNS) Α4 specification (210 × 297 mm) · " " ------- ^ ----: --- 1T ------ ^ (Please read the “Notes on the back side before filling out this page”) ^ 60489 at B7 V. Description of the invention () (Please read the “Notes on the back side before filling out this page”) That is, the key segment (B) and the dispersion media solution High affinity, when carbon black is added to the Dangdang dispersing medium solution and the Dangdang or grafted polymer is used to make the segment (B) of the Dangdang or grafted polymer toward the Dangdang solution * At the same time, the segment (A) is tended to be carbon black, and it is considered that the reaction between all the reactive groups of the bond segment (A) and the surface functional group of the carbon black can be performed efficiently. If this is regarded as a dispersion medium solution, When the obtained carbon black graft polymer is mixed with the target composition of the resin composition, organic media, etc., the same or similar properties can be obtained, which can have a high degree of dispersion for the target media and make carbon black extremely effective for grafting with polymers. A carbon black graft polymer having stable properties was obtained. Therefore, the present invention is also regarded as having a reactive group segment (A) capable of reacting with a functional group on the surface of carbon black in the presence of a target medium or a dispersion medium composed of a medium having similar properties, and Carbon black grafted with a block or graft polymer having a higher affinity than the above-mentioned segment (A) for the above-mentioned dispersing media liquid (B) is heated and mixed together in carbon black. Method for manufacturing polymers. The present invention can also be regarded as having a reactive group (A) having a reactive group capable of reacting with a functional group on the surface of carbon black and having a lower affinity segment (B) for carbon black than the above (A). A method for manufacturing a carbon black graft polymer having a characteristic of block or graft type polymer grafted on carbon black. In this case, as described above, the carbon black and the polymer are extremely effectively grafted. The present invention can also be regarded as containing the carbon black graft polymer as listed above. This paper is a fast-moving Chinese national standard (CNS) A4 specification (2 丨 0 X 2? 7 mm) BO 4 89 · A7 _____B7_ 5. Description of the invention () The photocurable resin composition of the colorant component, especially the soluble photocurable resin composition. The present invention can be referred to as a black matrix diagram for a color filter composed of a photocurable resin composition listed above. The present invention can be regarded as a recording medium liquid for ink olfactory recording and a liquid developer for electrostatic charge image development, which contains a coloring component similar to the fore-mentioned carbon black graft polymer. The present invention further includes various other embodiments as detailed below. In addition, if you are a colleague *, based on the following detailed description, you can understand the idea or scope of the present invention within the scope of the present invention, which is limited by the description of the request of the model garden, and can be changed or even modified similar to other There are many restrictions on trade patterns. < A brief explanation of the drawing > Fig. 1 is a horizontal view showing the state of the surface of the carbon black surface in the embodiment of the method for producing a carbon black graft polymer according to the present invention. (A) to (e) of FIG. 2 are modes of various structural examples of the block or graft polymer used in the embodiment of the present invention for producing a carbon black graft polymer, and ( f) A schematic diagram showing a state in which each of these agglomerates or graft polymers are bonded to the surface of carbon black particles (CB). (A) to (e) of FIG. 3 are schematic diagrams of various structural examples of a block or graft polymer used in other embodiments of the method for producing a carbon black graft polymer of the present invention. In addition, (f) is a schematic view showing a state in which each of these fluorene-like or graft-type polymers is bonded to the surface of carbon black particles (CB). (A) ~ (e) of FIG. 4 are the Chinese National Standards (CNS) A4 (210X297 mm) for the present invention in the carbon black grafted polymer paper size standard ^ ------ 1T ------ Silk (Please read the precautions on the back before filling this page) A7 160489 __B7___ V. Description of the invention () In the method of compound, it is a block or Schematic diagrams of various structural examples of the grafted polymer, and (f) is a horizontal view showing the state where various block or grafted polymers of the fluorescein are bonded to the surface of the carbon black particles (CB). A sectional view of one embodiment of the structure of a wet dispersion treatment device used in the method for modifying the surface of a solid fine particle according to the present invention. FIG. 6 is a diagram showing the modification of the surface of a solid fine particle according to the present invention. A cross-sectional view of a mode of another embodiment of the wet dispersion processing apparatus used in the method. < Detailed description of preferred specific examples > The present invention is explained in detail by the morphology of the embodiments as follows: 1. Carbon black graft polymer The "carbon black graft polymer" described in this explanation is the carbon black graft polymer. Add M polymer-grafted microparticles. The carbon black graft polymer is obtained by grafting a polymer with a combination of primary particles of carbon black or a plurality of aggregates. In addition, the so-called "grafting" here refers to the definition of "Carbon Black" (published on May 1, 1978 by Kodansha Co., Ltd.) by Danny Uean-Baptiste Donet, etc. It is said that an irreversible polymer is attached to a substrate. Due to the irreversible additional reaction, the polymer can be chemically bonded to the surface of the carbon black particles, and the actual combination of the two listed above is completed. Those who can act as "additional reacters of grafting j" include electron-withdrawing additional reactions, radical-addition additional reactions * nuclear-absorbing additional reactions and additional cyclization reactions, etc. -20-This paper's standard applies to China National Standard (CNS) A4 specifications (210X297 mm) ^^ iT ------- line (锖 Read the precautions on the back before filling this page) '10 4 89 A7 ____B7_ V. Description of the invention () Carbon black usually has several rm to several hundred nm The size of the particle diameter. However, because the cohesion between the carbon black particles is very large, it is usually treated with a particle diameter of more than a few micro-sheets (w). Also, the cohesion between the carbon black particles is more than The affinity between itself and other media is great, it is very difficult to disperse the submicron particles of carbon black in the media *. Another carbon graft polymer, which is extremely Effective inhalation polymerization reduces the cohesion between carbon black particles and other silly points. In addition, if the polymer has affinity with the media, the carbon black graft polymer can be dispersed in the media in a sub-fine particle state. Suppose that the polymer has a high affinity with the media and cannot make the polymer Those who are extremely effective in forming grafts with carbon black, that is, unable to achieve stable properties and are prone to differences, so that the carbon black content of the carbon black graft polymer that has a certain level of affinity is reduced, which is affected by the use. Furthermore, the affinity of Zhezhi M for carbon black grafted polymers seeks for dispersion stability in the media, that is, the problem of its limits, and it will make various uses of carbon black graft polymers. It is difficult to satisfy the required additional functional requirements. The present invention takes into account the functionality required for the conventional carbon black graft polymers in 1. various applications, and 2. various applications The required improvement of dispersibility, etc., plus the results of an intensive review, it is believed that when a polymer is used to form a polymer structure *, a reactive group that reacts with a carbon black surface functional group and a double bond of ethylenic unsaturated are used. Polymer and specific functional groups such as Junki, that is, the fact that carbon black graft polymers with better dispersibility and other functional characteristics can be obtained. That is, if the graft chain of the carbon black graft polymer is unsaturated weight The standard of this paper is applicable to China National Standards (CNS) Α4 specifications (2〗 0x: 297 cm), installed ----;-^ ------ ^ (_read the note on the back first and then (Fill in this page) 460489 A7 _ B7 V. Invention description () For example, when it is added to the photocurable resin group salt, thermosetting resin composition, it is fixed to the resin due to the photohardening reaction and the thermosetting reaction. The matrix becomes a dispersed state that can maintain hydrazine, which is also beneficial to the hardening reaction of the composition itself. * If the graft chain of the carbon black grafted polymer contains a fumarium group, for example, it is added to a base Those who can dissolve the hardenable resin composition can improve the developability of the resin composition. In addition, if a carbon black graft polymer containing Junki in the polymer chain is desired, it will have a surface capable of contacting the carbon black. The functional group reacts with the reactive group and the polymer containing the radical are added to the carbon black and heated and mixed. Since the reactive group of the polymer will react with the shuttle group to become gelatinized, that is, the desired grafting cannot be performed. . Therefore, in the present invention, the polymer containing nitroxy group is firstly connected. After the carbon black, [mu] acid anhydride process, a method by reaction of the semi-aliphatic hydroxyl group with an acid to introduce a Hin shuttle group. In this way, a carbon black graft polymer with the desired structure is obtained with great tolerance. The present invention is also that the result of an intensive review from the structural surface of the polymer forming the polymer structure is that it is found that using a block or graft polymer as the proper polymer can obtain a more effective Grafted and carbon black graft polymers have superior dispersibility to various media than the carbon black graft polymers. It can be said that the carbon black and reactive polymers used to make the old carbon black grafted polymers are random copolymers or polymers containing only one reactive group at the end of the sheet, which can interact with carbon black. The reactive groups of the reaction are scattered irregularly in one molecular stream or in a form containing only one. If you set -22-^^ ------ ^ (#Please read the notes on the back before filling in this page) The dimensions of this paper are in accordance with Chinese National Standards (CNS) 8 and 4 (2 丨 〇297mm) 4 6 Ο 4 09 Α7 _Β7__ V. Description of the invention () When compared with the block or graft polymer of the present invention, that is, the polymer of the present invention has its specific position, that is, it is in the chain The carbon black and reactive groups that can react are gathered on the segment (A), which can be regarded as a high degree of improvement in the reaction rate with carbon black. Also, for example, for a polymer with a K-like polymer structure, that is, a segment (B) having a high affinity for the target media and a segment having a lower affinity than the key segment (B) for the target media ( A), and deliberately designed to allow only the segment (A) to react with the surface functional groups of carbon black and contain reactive groups that are favorable for grafting, and put them into the target medium or similar properties (polarity) When grafting is carried out in a dispersion medium solution made of a medium, the improvement of the grafting efficiency may be more significant. Fig. 1 shows the case where carbon black reacts with a block or graft polymer having a reactive group as described above in a dispersing medium liquid formed in a target medium or a medium having similar properties as described above. , 圼 is a state pattern diagram around the surface of carbon black. As described in the above column, because the aggregating vessel is made of a _ segment with a reactive group (magic and a segment (B) with affinity to the media), it becomes the desired segment (B) in the reaction It will form a strong stretch in the media solution, which will make the segment (A) have to surround the surface of the carbon black particles, and can provide an excellent reaction space for the carbon black to polymerize with this polymer. Grafting is more effective. The carbon black grafted polymer has a graft chain bonded to its surface, that is, because the fluorene segments (B) that have high affinity for the target media are exposed outward in rows, that is, It can show high affinity to the target media, so that the carbon black graft polymer can be dispersed in the media in the form of sub-fine particles. This paper size applies the Chinese National Standard (CNS) A4 size (210x297 mm) ^. ^- ΪΤ ------ # (Read the notes on the back of the poem before filling this page) A7 4 60 4 89 B7 V. Description of the invention () (Please read the notes on the back before filling this page) or The same idea can make the carbon black surface function and have the ability to react The segment (A) of the reactive group, and the bond segment (B) which does not substantially have the aforementioned reactive group and has a lower affinity for carbon black than the aforementioned segment (A) (in other words, has a high affinity for carbon black) Blocks or grafted polymers of both the bond (A) and the segment (B) that have a high affinity for the target media are grafted with carbon black. The polymer's bond segment (A) will be paired with carbon black, so that the reactive groups existing in the current bond segment (A) can be more effectively grafted on the surface of carbon black. The carbon black graft polymer thus obtained The graft bond bonded on its surface is exposed to the outside because the key segment (B) of the medium with which it is paired has a high affinity, that is, it can show high affinity to the target medium and make the carbon black graft polymer. It can be defeated in the media by sub-micro-bundled units. Also, at this time, it is grafted in a dispersion medium liquid that is different from the media having the traits such as this or M, and only M The polymer should be melt-melted with carbon black, or it may be in any one of the opposite bond (A) and chain (B). Both will show a slightly equal degree of affinity to disperse the reaction in the media solution. However, if the grafting is to be performed more completely and efficiently, it should be dispersed in the affinity of the segment (B). The application behavior in the media solution is suitable. In this way, the M block or graft polymer is like a carbon black graft polymer formed by forming a polymer constituent part, and the polymer constituent part is more effective for grafting. And better dispersibility, it is easier to disperse in various media than the conventional carbon black graft polymer, and it can greatly increase the carbon content in the carbon black graft polymerization tree. The effect of prohibition of coincidence is applicable to the size of the Chinese national standard (CNS) A4 (210X297 mm) 460489 A7 __B7__ 5. Description of the invention () Improve electrical insulation and easy grafting even in organic solvents. . (Please read the precautions on the back before filling out this page.) If a block or graft polymer is used to cause the cross-section structure to form a carbon black graft polymer, it can improve its dispersibility and ease the ban. Superimposed effects, improved electrical insulation, etc. * For example, if this carbon black graft polymer is incorporated in a photocurable resin composition to make it a black photocurable resin composition, Carbon black graft polymers cannot yet participate in any hardening reaction with photopolymerization optical bridging. For very perfect light hardening characteristics, it is necessary to add more light than the blending amount of carbon black graft polymers. The hardening compound will inevitably occur. The amount of the carbon black grafted polymer tends to its upper limit, and it is finally rare for the M thin film to obtain sufficient light-shielding properties. As in the same situation, in the media prepared with the carbon black grafted polymer, In the case of photocuring, thermal superposition, and heating bridge reaction to become a hardened material, if the carbon black graft polymer can be made to react to the medium forming the matrix, it is necessary to obtain excellent hardening characteristics and carbon black. From the viewpoints of dispersion stability, etc., the stomach is advantageous. In this regard, the group of the present invention conducted a more intensive review, and found that in the block-type or graft-type polymer forming the above-mentioned polymer structure, The saturated double bond is given to the external bond segment, that is, the segment (B), which does not react with the functional group on the carbon black surface, and the thus obtained carbon black graft polymer is blended into the photocurable resin composition. After waiting, the hardening reaction of the composition should proceed smoothly, and the very thin film can obtain sufficient light-shielding properties, and it also has excellent phenomena in terms of film strength, carbon black dispersion stability, etc. As mentioned in the above list, it is self-dispersed in the soluble photocurable resin group -25 _ This paper is applicable in the standard § National Standards (0 ^) People 4 Specifications (210/297 Gong Chu) 4 604 89 'A7 B7 V. Description of the invention () (please read the precautions on the back before filling in this page) For those who can improve the inspection and visualization, the group of the present invention has discovered that the above list forms the polymer structure part Block or graft polymers are considered as mixtures with centioxy groups. Yes, the bond segment facing outward, that is, the segment (B) is regarded as containing a hydrogen group, and after the carbohydrate cells are grafted, an acid anhydride treatment path is formed by the semi-lipidation reaction of the oxygen group and the acid anhydride. The fact that the carbon black graft polymer and the alkali-soluble hardening resin composition obtained by the introduction of Junji are blended, can obtain the dispersion stability of the carbon black, and have the silly alkali developability. Even * M carbon black Pigments other than pigments are used as pigment components. The pigment composite polymers obtained by compounding the polymer components according to the present invention will have the same properties as the carbon black graft polymers of the present invention. Excellent characteristics. The term “pigment composite polymer” as used in this specification refers to a pigment obtained by heat-treating a reactive polymer having a reactive functional group on the surface of the pigment, that is, a pigment The primary particles on the surface of several aggregates are stable polymers * Although theoretically it can be regarded as a chemical bond between the surface of the pigment particles and the polymer, as described above, grafting has occurred, but To be It is pointed out on the analysis surface whether this kind of grafting has occurred with some degree of difficulty. In fact, in many cases, it can be regarded as not only the existence of this chemical bonding force, but also a lot of physical adhesion. The possibility of force acting, therefore, in order to cover the situation like this, it is defined as "composite polymer" and becomes "composite".遁 It is necessary to use the following M carbon black as the head material. 荏 This carbon black is added to the polymer to make it composite to form a pigment composite polymer. The description of this paper is based on the Chinese standard of the paper (CNS). Α4 is present (21〇 × 207 mm) 460489 A7 _____B7 V. Description of the invention () (Please read the notes on the back before filling in this page). Also, for the sake of understanding the present invention * Although the pigment composite polymer obtained in the form of κ should be referred to as "carbon black graft polymer" in the following, it does not only cover the polymers as defined in the above list. Products that have undergone "grafting" also have products in a broader sense that undergo "polymerization", that is, attention should be paid to the matter of producing carbon black composite polymers. 1.1 Carbon black The carbon black used in the production of the carbon black graft polymer of the present invention does not specifically contain functional groups such as a benzyl group and a hydroxyl group on its surface. For example, furnace black, structural black, ethyl black, Although any of commercially available products such as lamp black can be used directly, it is best to use carbon black containing a carboxyl group. Also, it is better to use carbon black whose pH is less than 7, especially pH 1 ~ 5. Although carbon black containing fluorenyl group is commercially available in the form of easy-to-Mgg carbon black, even its neutralized or salt-based carbon black that has been acidified can be used as the original fluorene of the present invention. If carbon black does not contain functional groups such as Junki, or a pH value of 7 or higher, grafting will not be effective. The pH value of carbon black is determined by Jis K 6211. The average particle diameter of carbon black is in the range of 0.0005 to 0.5 *, and it is particularly preferable to be in the range of 0.001 to 0.2. Since carbon black with an average particle diameter of less than 0.0005 cannot be obtained, it has no industrial significance. If the average particle diameter exceeds 0.5, the carbon black graft polymer cannot be sufficiently dispersed. The pigment used in the production of the pigment composite polymer other than the carbon black graft polymer M of the present invention is not particularly limited as to which pigment should be used, as long as it is an organic pigment, an inorganic pigment, or a mixture thereof. _ 27-This paper size applies Chinese National Standards (CNS) specifications (2 丨 0X297 mm) '4 6〇 89 89 A7 __ B7_ 5. Description of the invention () Inorganic pigments, that is, carbon black, as listed above, For example, oxidized oxide, dioxin, barium octylate, osmic acid, soft § Chu bound, total grain acid, hafnium oxide, silica sand, clay mica, sandy stone, sandy soil, various inorganic gaseous pigments, oxidation Grid, thorium oxide, ferrous oxide, magnesium oxide, magnesium oxide, gasification, barium sulfate, barium carbonate, real acid consumption, silica fine powder, kanfossil, nitrided shoes, boronized leather, tungsten carbide, from Powders or granules of §tai, vaporized plutonium, etc. In addition, the purine inorganic pigment is derived from a hydrazone coupling agent, a shoe last coupling agent, a higher fatty acid metal salt and the like obtained by a well-known hydration treatment agent. And organic pigments are * such as Naples yellow, catechol yellow-S, Hansa yellow-G, Hansa yellow-10G, benzidine yellow-G, benzidine yellow-GR, quinol yellow lake , Permanent yellow-NCG, yellow pigments such as tartrazine, molybdenuni orange, permanent RK, benzidine dial G, indanthrene bright orange GK, permanent red 4R, Litho group , Etb beer · # ketone 4R, v / atchung red salt, color source red D, pharyngeal fat red 6B, eros in lake, rhodamine lake B, Alizarin lake, red pigments such as pharyngeal red B, purple pigments such as fast violet B, methyl violet source, basic M color house, Victoria blue lake, cyan blue, no Metal ftt cyan blue, safflower cyan M (local 咅 13) affinities, fast sky blue, indanthrene M — BC and other M color pigments, pigment green β · malachite green source, fanaru yellow green G ( Fanal yellow green G). 1,2 Reactive groups can be used to reverse the surface of carbon black when grafted to the polymer of carbon black -28-_ This paper is compliant with China National Standard (CNS) A4 specification (2IOX297 mm) ~ ^ ----_- 1T ------ 0 (Please read the notes on the back before filling in this education) a 604 89 A7 A7 _ B7 V. Description of the invention () The reactive group should be Those who react with all the functional groups on the surface of the energy limit carbon black and give M should be grafted with the morphology of the polymer and δ carbon black, that is, it can be used as various reactive groups without any restrictions. Here, If the grafting is to be thorough and stable, it is required that the polymer structure part is combined with carbon black through a common bond, especially self-lipidation bond, δ-lipidation bond, amidine bond, amino bond, and alcohol bond. , Thioether binding, carbonyl binding, ore-removal binding, and nitrification-binding combination, at least one combination was selected from the group, and at least one combination was selected from the group consisting of lipid-binding, thiolipid-binding, and amine-binding combination. If evolution is needed, grafting should be appropriate. ”When considering these issues, g 卩 should be selected from epoxy, thiol, nitrogen It is advisable to select at least one or two or more reactive groups as the reactive groups among the groups such as propidyl and humic groups. Although the reactive groups for carbon black binding are only limited to those listed above, if used with these When a polymer other than a reactive group is polymerized, the type of carbon black that can be used may be limited. The reason why the polymer contains the reactive group is more suitable because it can be used regardless of its type or shape. Carbon black can make carbon black and polymer carry out its additional reaction under extremely high grafting efficiency under mild conditions. Especially when carbon black contains carboxyl group as its surface functional group as listed above, it can make shuttle group Thermal reaction with epoxy, thionyl, carbamoyl, or oxazolyl, and K high yield successful irreversible side reaction, that is, the carbon black and polymer are formed by this additional reaction The common binding is the best. The method of introducing some reactive groups into the polymer, although generally following the method disclosed in W088 / 03 545 (PCT / JP87 / 00867), for example, -29-this paper is suitable for Caiyan Family System (CNS) 8 4 Lin (+ 21GX297 Gong Chu) " -------- Zhuang Yi-(Please read the notes on the back before filling this page)

、1T 線 4 604 89 A 7 __B7 五、發明説明（） (1)將在其分子内含有反應性基的聚合性單量體以其必要 的程度使與其他聚合性單量體起重合作用的方法及（2)將 在其分子中含有反應性基的化合物與能和該化合物起反應 的聚合體互相反應而把該反應性基引進於該聚合體等二種 方法，而在本發明中，由於採用不但含有這種反應性基的 同時還含有不飽和二重結合鏈或氫氣基等，又將形成接枝 於聚合體及塊型結構物，即或須有如下所示的特別合成條 件的情形發生。 又，在本說明書中亦將採用摘自所述W088/03545(PCT /JP87/00867)公告的有關部分。 1.3含有不飽和二重結合鏈的聚合體 在本發明上所使用的碳黑的表面功能棊與能起反應的 如上列的反應性基和含有乙烯性不飽和二重結合鏈的聚合 體的费格構造體，併未加Μ特定的限制，雖然可Μ使用如 具有各種乙蹄系聚合構造、聚脂系構造、聚醚系構造等各 種化合物，卻宜於使用在下列1.5節所述的含有塊型及接 枝型構造的化合物。 又，相關於含有不飽和二重結合的塊型及接枝型構造 的聚合體的詳細情形，即將在1.6節中說明。 若欲提起塊型Μ及接枝型結構體Μ外的異體例者，如 此最單純的形態來說*即有能與碳黑起反應的含有反應性 基之聚合體以随機性地進共其重合，將含有氫氧基的單體 在聚合體中加Μ引進氫氧基後，使其與不飽和異氰酸鹽化 合物互相反應，就可得能與碳黑起反應的含有反應性功能 -30 — 本纸乐尺度適用中國國家標準reNS ) A4規格（210X297公釐） ---------私衣----^--1Τ------^ (請先閏讀背面之注f項再填寫本頁) 4^0439 A 7 ___ B7 _ 五、發明説明（） 基及含有不飽和二重結合_的聚合體了。 若欲再要求具有耐熱性者，即有在其一個分子中各含 有一個以上的環氧基及乙'烯性不飽和二重結合體的不飽和 環氧脂樹脂。 這種不飽和環氧脂樹脂是由一個分子中含有二個Μ上 環氣基的壞氧樹脂與不飽和一鹽基酸使其在一分子中能夠 留存一個Κ上的壞氧基的比例將不飽和一鹽基酸中的羧基 與該環氧樹脂中的塘氧基互相反應而得。 在此所使用的環氧樹脂即指未加於特定的瓖氣樹脂， 即由所有在其一分子中含有二個以上塌親基的塌氧樹脂* 如酚醛清漆型環氣樹脂、雙酿型環氧樹脂、脂環式環氣樹 脂、四縮水甘油氨基二苯甲烷等的多功能性縮水甘油継樹 脂、酚、0-甲酿、nr*甲酚等的酚類或祭酿類與含有酚性氣 氣基的芳香族酸進行縮合反應而得的多價酿化合物而表截 醇的反應生成物，由酿類與二乙蹄基聚或二聚壞成二烯等 二烯靥烴化合物起附加反應而得的多價酿化合物與表氣酵 的反懕生成物，及4-2烯基環己焼-1-氣化鹽的開環聚合物 以過氣化物使其撰氧化所生成的化合物等*尚涵蓋由這些 各種類的環氧樹脂與多鹽基酸、多價齡、多功能氨基化合 物或多價硫赶所反應而加長其継鏈者。 另外，所用的不飽和一鹽棊酸，即有丙烯酸、異丁烯 酸及含有一個羧基及含有二個以上（甲基）丙燏酸鹽類等。 將該環氯樹脂與不飽和—鹽基酸，以該環氧樹脂中的 塌氧基的一化學當量與不飽和一鹽基酸中酸後基酸〇. 〇5〜 本紙張尺度適用中國國家標準（CNS ) A4说格（210X297公釐）. ^------ix------辟 (請先閱讀背面之注意事項再填寫本頁) 4 60 4 89 A7 _B7 _五、發明説明（） 0.95化學當量之比例使其進行反懕即可得在樹脂一分子中 含有留存一個以上撰氧基的不飽和環氣脂樹脂° 在一分子中含有二個以上壞氣基的環氧樹脂與不飽和 一餓基酸反應所使用的脂化觸媒為，如三乙胺等的第三鈒 胺類、三乙T基氯化鎮等的第四鈒鎮搠、2-乙基-4-甲基 邮啤等的邮哩化合物、三苯麟等憐化合物、金屜有機鹽、 金靥無機鹽、金屬蝥形化合物等。Μ這些觸媒在後述的稀 釋劑存在下或未存在下，在溫度80〜130它使其反應，即 可得不飽和環氧脂樹脂了，此時所使用脂化觸媒的最通常 是對於參與反懕的環氧樹脂及不飽和一鹽基酸總霣的0.001 〜10w/w%，而以0.005〜5w/w%為宜。若使用量未及O.OOlw /w%時，即不能使該環氧樹脂與不飽和一鹽基酸逍行十分 的反應，而超過10w/w%時，如使用此生成物來造成碳黑接 枝聚合物，洌如調配到光硬化性樹脂組成物中，即將降低 該樹脂組成物的安定性了。 在合成上列不皰和環氧樹脂時，必要時可Μ使用由一 種或二種溶媒來做為稀釋劑。如·甲笨、二甲苯等碳化氫 類、溶纖劑、丁基溶纖朝I等溶纖劑類、卞必醇、丁基卞必 醇等卞必醇類、醋酸溶纖劑、醋酸卞必酵等脂類、丁酮等 g同類、二甘酵二甲基脂等脂類、二甲替甲醯胺、Η-甲替-2-叶匕喀P妹、7 -丁基丙脂等為溶媒稀釋液。 然而，含有不飽和二重结合鏈的聚合體併不限定為， 如上列的不飽和環氧脂樹脂，或如下面1.6節將述及的塊 型Μ及接枝型聚合體，邋涵蓋如上列所述的各種反應性基-32 - 本纸铢尺度適用申困S家標準{ CNS ) Α4規格（210X297公釐）- ^----.--W------^ (請先閏讀背面之注意事項再填寫本頁) -i 6 Ο 4- 8 9 五、發明説明（） 及含有乙鋪性不飽和雙聚合體，即具有如上述一樣的各種 贵格構造體者，均可从使用° 又，對含有不_和雙重結合鏈的聚合體分子最’雖未 特為限制卻為考慮到對碳黑的接枝效果及對於碳黑反應時 的作業性，即上列分子最應為平均分子量500〜1000000範 圍的較好，而最好是在1000〜1〇⑻⑻範圍内。 1.4含有Μ頌:基聚合體 在本發明上，用於製造含有能與搜基的碳黑接枝聚合 物的碳黑表面的功能基起反應的反應性基及Μ氣基的聚合 體骨格構造，併不是未加Μ特別限制，雖可使用各種構造 的聚合體，卻Μ含有如下列所述1-5節的具有塊型Μ及接 枝型構造的聚合體為宜。又*有關具有氯氣基的塊型Μ 及接枝型構造的聚合體，即詳細說明於1.6節。 若欲提示塊型以及接枝型構造Μ外的具體例時，即有 *如聚（甲基）两輝酸經基焼脂糸構造，（甲基）丙ί；希酸烷脂 -(甲基）丙烯酸經基院脂共聚合體糸構造等上含有經基聚 合鏈的片末端附加壞氧基等反應性基的構造體等。這種聚 合體的製造，即可依所述W088/03545(PCT/JP87/00867)公 告的方法來進行。又，在所述1.3節所提出的不飽和環氣 脂樹脂是含有經基的聚合體。 然而’以含有羥基的聚合體來說時，茌上列出的聚合 f耋不是不受任何限制，若含有如上列所說的各種反應性基 及控基者，即具有上列一般的各種费格構造的均可以使用 C) _ 33 — 本紙張尺度適财轉（CNS)域格（2mx297公瘦）；" I n I 11— ,^1ϋ n ^ Φ· (請先閱讀背面之注意Ϋ項再填寫本頁) 4 60 4 89 A7 B7 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 又，對於含有經基的聚合體分子量，即不加K特別限 制，若以考量對碳黑的接枝化效果或與碳黑起反應時的作 業面來說，即上列分子最即K其平均分子量在500〜7000000 範圍内的為宜，卻K在1000〜100000範圍的為最適當。 1.5塊型以及接枝型聚合體 在本發明中最適宜用為使碳黑被接枝化以形成聚合體 的聚合體構造的是，含有能與碳黑表面的功能基起反應的 反應性基鍵段（A)及實質上具有未含有所述反應性基而與 所述鏈段（A)有不同赞格構造的鍵段（B)二物的塊型以及接 枝型聚合體。 能做為塊型以及接枝型聚合體者，併不僅限定為含有 如圖2 (a)所示的A-B型塊型共聚合體及如圖2所示的A-B型 接枝共聚合體等單純構造者，而及於含有如圖2(C)所示的 B-A-B型塊共聚合體或更為高度的交互塊共聚合體•如圖2 (d)所示的於A鏈段上加以複數的B鍵段形成的梳子形接枝 共聚合體，甚至如圖2(e)所示的星型狀的共聚合體等各棰 共聚合體。又，圖中的X即表示反應性基。圖2(f)雖為表 示此種種的塊Μ及接枝型聚合體結合在碳黑粒子（CB)表面 的结合狀態，只要是結合在碳黑粒子表瓸的狀態之下，能 朝向碳黑粒子表面外側配對具有某種程度的自由度的一個 Μ上鏈段（Β)，不分其為塊以及接枝型聚合賭靥於何種彤 態，又如雖被分類為鏈段（Α)而含有複數種鏈段（鍵段（Β) 莎相同），或具有與鏈段（Α)及鏈段（Β)不同性質的，如具 有此二者的中間性質者，或能加長接枝鍵，能附加提高接 -34 - 本紙铁尺度適用中國國家橾準（CNS ) Α4規格（210X297公釐） 460 489 A7 _B7_ 五、發明説明（） 枝鏈在媒體中的「擺動」（運動性）Μ及降低其擺動等功 能的他種鰱段（在下面說明中，將稱為〔C)鏈段）等於鏈段 (Α)及鏈段（Β)的中間者均靥之。這種（C)趟段雖可有無含有 反性基•通常卻以未含有的視為適宜於提升接枝效率。又 ，有時亦能在造種（C.)鍵段上引進可Κ互相架橋的反應基 等聚合體。又，為說明的方便，將其稱為（C)鏈段，若Κ 擴大分類時*亦可將本（C)鍵段分類於鍵段（4)或_段汨） 之中。 在本塊型Μ及接枝型聚合體上，含在鍵段（Α)中的反 應性基不加以特別限制，屜於能與碳黑表面的功能基起反 應而能賦與該當聚合體對碳黑的接枝化有肋者，如上列所 述各反應性基即均可Μ利用。 含有這種反應性基的鍵段（Α),應Μ在其鍵段的趟鍵構 造上含有對目的媒體低度親和性的為宜。又，此時的親和 性究竟由於他方與鍵段（Β) 對比為相對性，而以目的媒艘 的種類或鏈段（Β)的構成情形是如何，鏈段（Α)即能成為各 種的構成狀態*不能加以特定。然而，再從其他的觀點來 說，所述鏈段（Α)能對碳黑顯出高度親和性以對碳黑顯示優 越的配對性，即可說為一良好的鏈段。從這個觀點來說的 話，所述鏈段（Α),應以其主鏈由碳一碳化合物為主幹所形 成的為宜，然而，最好是在其主鏈上含有如苯ϊ溝、祭谓及 茆環等芳香環，而且又在其分子内含有如所述反應性基者 ，一方，所述鏈段（Β)應比鏈段（Α)少含碳一碳结合，尤其 少含芳’香環的骨格構造者，如聚硅氧烷構造、或醱結合、 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） ^----〆--,訂------^ (许先W讀背兩之注意事項再填寫本頁) 4 60 4 89 at _ B7 五、發明説明（） 脂結合等多含碳一碳結合以外的結合鍵段的為宜。 但是，由於鏈段（A)在其實質上僅以具有高度的縮合多 環構造的鰱段來構成時，將會使鏈段（A)的剛性極端升高， 致使在接枝於碳黑時命鏈段（A)難於接近碳黑表面之虜，因 此，Μ具適度的線狀構造物為宜。 如上列所述，趟段（Α)的鍵鍵構造，Μ因應於欲為碳黑 賦與分散性上來選取的趟段（Β)之鏈鏈構造而可以適宜選 擇，如苯乙烯糸單霣髖、（甲基）两嫌糸單量體、亞經基系 單量體等的單獨一個或由共其聚合所成的各種乙烯糸聚合 物，聚脂、聚醚等（含有上列反應性基的）來形成聚合鍵鐽 ，其中，卻Μ乙嫌系聚合物，特別是Κ含有50克分子％从 上芳香壞的乙締糸單最體，最好Μ含有(50克分子％以上又 含有反應性基的乙烯糸聚合物而能與因應目的媒體所選取 的各種鏈段（Β)相結合者為宜。 再由經濟性等面考量時*即Μ含有苯乙烯糸單量體及 (甲基）乙烯糸單量體為主的單獨聚合物以及其共聚合聚合 物•尤其是含有50克分子％以上或更高的<30克分子％以上 的苯乙嫌糸單量體成分（含有上列反應性基的）的聚合鏈 的為最好。 然而，在含有反應性基的鏈段（Α),將其視為在鏈段的 鏈構造上對於目的媒體具有較鰱段（Β)十分低度的親和性 時，就不必使鏈段（Α)有對碳黑圼高度親和性，實質上趟段 (Α)及鍵段（Β)對碳黑的親和性雖然沒有差異•或者觴於比 鏈段（Β)圼低度親和性者亦能掌來使用，有時，亦可能使用 本紙伕尺度適用中國國家標準（CNS)A4#Jl格（2丨0><297公釐）· ^----^_|1Τ------紙 ί锖先Μ讀背面之注意事項再填寫本頁) A7 460489 _B7_ 五、發明説明（） 在鏈段（B)有如苯乙嫌糸構造的鍵段。 {請先聞讀背面之注意事項再填寫本頁) 一方面*謎段（B),由於將對目的媒體的分散性等賦與 碳黑的特性，如自含有聚鞋氧焼糸構造、聚（甲基）乙烯糸 構造、聚亞烴基乙二醇等的聚醚糸構造、聚脂糸構造、聚 亞烴基系構造、聚醯胺構造、聚亞胺構造、聚氣基甲酸脂 等的聚合趟構造物中選出適當的來使用。 如，聚硅氣焼糸構造鏈可使用於改菩對低極性媒體中 的分散性，更有極其優越的拒水性、離型性、耐熱性、耐 候性、柔軟性、低粘性等，或為給與不具低溫脆性的目的 ，又，（甲基）乙烯糸链是為引進乙蹄脂單量體成分而給與 廣泛的親水性一疏水性或、结晶性及拒水性等目的（如· 引進（間）乙烯酸羥烷基脂等來提升共親水性*以（甲基）乙 締酸十二烷脂提升其疏水性，Μ (甲基）乙婦酸硬脂醯脂提 高共結晶性，Μ氟（甲基）乙烯酸脂提高其拒水性），又， 聚亞經基二乙酸鏈即有給與親水性、潤濟性、柔軟性，防 止帶電等特性為目的者*均可加以使用。 又，可將含有能與碳黑表面的功能基起反應的反應性 基的縫段（Α),加Μ設計使其成為比對目的媒體圼現高度親 和性的鏈段（Β)更具有對碳黑呈現高度親和性。 此時，就有必要將含有反應性基的（Α)趟段上的鍵段 _鍵構造使其能與碳黑圼現較高親和性。又，在此所指的 高度親和性是由於與他方的（Β)継段作比較的相對者，可_ (Β)趟段的構造形態來使（Α)鍵段成為各種構造，即無法加 以特定的限制了。然而，由於所述（Α)趟段，是Κ碳一碳结 -37 - 本纸伕尺度逋用中國國家標準（CNS ) Α4規格（210 X Μ7公'' 4 60 4 89 A7 A7 B7 五、發明説明（） 合為主的主鏈所成*而最好者，以含有如笼環、薪環及節 環等的芳香環為其主鏈，又含有如所述反應性基在其鏈段 分子內的，而他方的所述（B)鰱段，即Μ屬於比（A)鏈段少 含碳一碳結合，特別少含劳香撮的骨格構造者，如多含有 聚鞋氧燒構造，或醚結合、脂結合等的碳一碳結合Μ外的 結合者為宜。 但是，在實質上若使（Α)鏈段僅由高度的縮合多摄構 造來構成者即將使（Α)鍵段的剛性極端升高，致使在對碳黑 接枝時，將有難使（Α)縫段接近於碳黑表面之虡，因此，應 有適度的線狀構造為宜。 如上列所述，（Α)鍵段的鐽構造是由欲使分散性給與碳 黑的觀點所選取的（Β)鏈段鏈構造，如所述的聚鞋氧烷糸構 造，聚（甲基）乙嫌糸構造、聚亞烴基乙二醇糸構造等的聚 醚系構進、聚脂糸構造、聚亞烴基糸構造、聚酿胺構造、 聚亞胺構造、聚氣基甲酸脂等含有的聚合鍵所決定，將其 能對碳黑圼現高度親和性的就可以，而不加以特別的限制 •通常卻以含有乙婦糸聚合物，特別是，含有芳香環的乙 締糸單量體成分50.克分子％以上，最好以含有60克分子％ 以上而且含有反應性基的乙蹄糸聚合物為適宜，若再Μ經 濟性等考量者，特Μ苯乙烯系單虽體及（甲基）丙烯糸單量 體為主的單獨Μ及共重合聚合物，尤其含有苯乙稀糸翬量 體成分為50克分子％以上，或更高濃度的60克分子％以上 (具有上列反應基的）聚合鏈者。又，鏈段（Β)為聚鞋氣烷 糸聚合鐽時，可以所述鏈段（Α)來使用的聚合鍵種類為數雖 —38 — 本紙張尺度適用中國國家標準{ CNS ) Α4規格（2丨0 X 297公釐） · I ^1Τ------線· (诗先閱讀背面之注意事項再填寫本頁) 4- 60 4 89 A7 __B7__五、發明説明（） 然較多，若在鏈段（B)如為聚（甲基）丙烯糸構造等的乙烯糸 構造者，能構成所述_段（A)的聚合趟，卽將有許多限制， 就只有聚苯乙烯糸構造及（甲基）丙烯一苯乙烯共聚合糸構 造等而已了。 欲得含有這種反應性基的鏈段（A)及與鍵段（A)不同骨 格構造的最好具有比鰱段（A)對目的媒體有高度親和性的 趟段（B)的塊型Μ及接枝型聚合體的製造方法，併不加Μ 特別限制，可由眾所周知的各種塊型Μ及接枝型聚合體的 聚合技術，及反應性聚合物的製造技術加Μ配合來製造。 若Μ製造接枝型聚合體的方法來說，即有如能成為接 枝鏈的高分子量體存在下，Μ聚合開冑台劑及聚合性單量體 為溶液聚合，乳化聚合、塊狀聚合或懸濁聚合而Μ聚合體 為其主鍵的聚合方法。然而*若所述高分子量體不含有聚 合性功能基者，會在所得接枝共聚合體中殘留大量未被接 枝化的聚合體而發生極低接枝效果的缺點。 因此，即應使用基聚合性高分子量體為該當高分子量 體來進行為宜。然而，茌所得碳黑接枝聚合物上的聚合髏 鏈之鏈段（Β),為由以該當碳黑接枝聚合物添加分散於成為 矩陣的阻成物的粘合樹脂，溶媒等有屬於同種的或具有較 高相溶性時，如由上列方法所得，屬於有某種程度低接枝 效果者，亦可Κ企望成為高度安定性的產物。這種基聚合 性高分子蠆體，通常稱做「大型聚合物（macro monomer') 」*在片末端含有基聚合性基，如*含有（甲基）丙烯酸基 、苯乙烯基等高分子量體，如在有機溶劑中使含有片末端 务 ；-ΪΤ------錄· (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度通用中國國家榡準（CN’S > A4規格（210X 297公釐） .〇0 4 89 7丨.八 Α7 Β7 Λ 曰 五、發明説明（ m 俊基的聚合體與含有縮水甘油基的基聚合性單量體相反應 而得的（如，在專利公告1968-11224號上，Μ在有機溶劑 中含有Si基醋酸之下，使基聚合性輩量體進行基聚合所得 的預聚物（P「e-p〇 1 ymer )與縮水甘油異丁烯酸鹽在二甲基 磁胺為觸媒相反應的製造方法）。 因此，如欲得有關本發明的接枝其聚合體者，即可Μ 在含有形成鏈段（Β)成分的基聚合性高分子量體（b)下*使 如所述碳黑分子内含有反應性基的聚合性單最體（a)及因 應其他必要調配的含有形成_段（A)费格的聚合性單量體（ C)相反應。 對碳黑於分子内含有反應性基的聚合性簞量體（a)有： f.j CH2 = CH™CH-CH2 Λ〇/ ch2=ch >-ch-ch2 1丨裝---------訂^-------線 {請先聞讀背面之注意事項再填寫本頁) 40 本饫伕尺度適用中国國家榡卒（CNS ) A4現格（210X29"?公釐） 4 6〇489、 1T line 4 604 89 A 7 __B7 V. Description of the invention () (1) The polymerizable single body containing a reactive group in its molecule is used to lift and cooperate with other polymerizable single body to the extent necessary. Method and (2) two methods of introducing a reactive group into the polymer by reacting a compound containing a reactive group in its molecule with a polymer capable of reacting with the compound, and in the present invention, Because it contains not only such reactive groups, but also unsaturated double bond chains or hydrogen groups, etc., it will form grafts on polymers and block structures, that is, special synthesis conditions as shown below may be required. The situation happened. In addition, in this specification, the relevant part extracted from the publication of W088 / 03545 (PCT / JP87 / 00867) will also be used. 1.3 Polymers containing unsaturated double-stranded chains The surface function of carbon black used in the present invention 棊 costs with reactive groups such as those listed above that can react and polymers containing ethylenically unsaturated double-stranded chains The lattice structure is not subject to specific restrictions. Although various compounds such as ethyl acetate-based polymer structures, polyester-based structures, and polyether-based structures can be used, it is suitable to use the compounds described in section 1.5 below. Bulk and grafted compounds. The details of the polymer containing the unsaturated double bond bulk and graft structure will be described in Section 1.6. If you want to mention the variants other than the block M and the grafted structure M, in the simplest form *, there is a polymer that contains reactive groups that can react with carbon black to randomly coexist. It is superposed. After adding a hydroxyl group-containing monomer to the polymer to introduce a hydroxyl group, it is allowed to react with an unsaturated isocyanate compound to obtain a reactive function that can react with carbon black. -30 — This paper music scale is applicable to the Chinese national standard reNS) A4 specification (210X297 mm) --------- Private clothing ---- ^-1Τ ------ ^ (Please first Read the note f on the back and then fill out this page) 4 ^ 0439 A 7 ___ B7 _ 5. Description of the invention () and polymers containing unsaturated double bonds _. If heat resistance is required, there is an unsaturated epoxy resin containing one or more epoxy groups and an ethylenically unsaturated double bond in each molecule. This unsaturated epoxy resin is composed of a bad oxygen resin containing two M upper ring gas groups in one molecule and an unsaturated monobasic acid which makes it possible to retain a bad oxygen group on a K in one molecule. The carboxyl group in the saturated monobasic acid is obtained by reacting the epoxide group in the epoxy resin with each other. The epoxy resin used here refers to the resin that is not added to the specific radon gas, that is, all of the epoxy resins containing two or more nitrogen groups in one molecule * such as novolac-type resins, double-brew type Multifunctional glycidyl resin such as epoxy resin, cycloaliphatic resin, tetraglycidylaminodiphenylmethane, phenols, 0-cresol, nr * cresol, etc. The reaction product of epivalent alcohol and polyvalent alcohol obtained by the condensation reaction of aromatic gas-based aromatic acids, starting from the polymerization of diacetyl with diethylhexyl or dimerization to diene fluorene compounds such as diene. The reaction product of the multivalent brewing compound and the super-aerobic reaction obtained from the additional reaction, and the ring-opening polymer of the 4-2 alkenylcyclohexyl-1-gasification salt are generated by over-gasification and oxidation. Compounds and the like * also include those whose epoxy chains are lengthened by the reaction of these various types of epoxy resins with polybasic acids, polyvalent ages, multifunctional amino compounds, or polyvalent sulfur compounds. In addition, the unsaturated monosalmic acid used includes acrylic acid, methacrylic acid, one carboxyl group, and two or more (meth) propionic acid salts. 〇5 ～ This paper scale is applicable to the country of China Standard (CNS) A4 grid (210X297 mm). ^ ------ ix ------ Pipe (Please read the notes on the back before filling in this page) 4 60 4 89 A7 _B7 _Fifth, Description of the invention () The ratio of 0.95 chemical equivalents makes it possible to obtain an unsaturated cycloaliphatic resin containing one or more oxygen groups in one molecule of the resin. ° A ring containing two or more bad gas groups in one molecule The lipid catalyst used in the reaction between oxyresin and unsaturated monobasic acid is, for example, tertiary amines such as triethylamine, triethyl amines, etc. -4-methyl post beer and other postal compounds, triphenyllin and other lingering compounds, gold drawer organic salts, gold tincture inorganic salts, metal halide compounds and the like. Μ These catalysts are reacted in the presence or absence of a diluent described below at a temperature of 80 to 130 to obtain unsaturated epoxy resins. At this time, the most commonly used lipid catalysts are The total rhenium of the epoxy resin and unsaturated monobasic acid involved in the reaction is 0.001 to 10 w / w%, and preferably 0.005 to 5 w / w%. If the amount is less than 0.00lw / w%, the epoxy resin cannot react with unsaturated monobasic acid very much, and when it exceeds 10w / w%, if the product is used to cause carbon black If the graft polymer is blended into the photocurable resin composition, the stability of the resin composition will soon be reduced. When synthesizing the above listed blister and epoxy resin, one or two solvents can be used as a diluent if necessary. For example, hydrocarbons such as methylbenzyl, xylene, cellosolve, cellosolve such as butyl cellosolve I, apicol, carbitol, butyl apicol, acetic acid cellosolve, acetic acid Isolipids, similar substances such as methyl ethyl ketone, lipids such as diglyme dimethyl lipid, dimethylformamide, pyrene-metidine-2-leaf dagger, and 7-butyl propyl ester as solvents Diluent. However, polymers containing unsaturated double bond chains are not limited to, such as the unsaturated epoxy resins listed above, or block M and graft polymers as described in section 1.6 below. The various reactive groups mentioned are -32-this paper baht scale is applicable to the standard S family standard {CNS) A4 specification (210X297 mm)-^ ----.-- W ------ ^ (please first (Please read the notes on the back and fill in this page) -i 6 〇 4- 8 9 V. Description of the invention () and containing the dimer unsaturated unsaturated polymer, that is, those who have various kinds of quack structure as above, all It can be used from the above. The polymer molecules containing non- and double binding chains are the most 'although not specifically limited', but are considered for the grafting effect on carbon black and the workability when reacting to carbon black, that is, the molecules listed above. The average molecular weight should preferably be in the range of 500 to 1,000,000, and most preferably in the range of 1,000 to 10,0. 1.4 M-containing: base polymer In the present invention, a polymer bone structure containing reactive groups capable of reacting with functional groups on the surface of the carbon black grafted polymer of the carbon black graft polymer and M gas group is used. It is not particularly limited without adding M. Although polymers of various structures can be used, M preferably contains a polymer having a block M and a graft structure as described in sections 1-5 below. Also, the polymer of a block type M and a graft structure having a chlorine gas group is described in detail in Section 1.6. If you want to show specific examples other than the block type and the graft type structure M, there is a structure such as poly (methyl) difluoric acid via a phospholipid structure, (meth) propyl; alkyl hexanoate-(formaldehyde) Base) Acrylic polymer structure, such as a polyester copolymer, and structures containing reactive groups such as bad oxygen groups attached to the end of the polymer chain. The production of such an aggregate can be carried out according to the method disclosed in the aforementioned W088 / 03545 (PCT / JP87 / 00867). The unsaturated cycloaliphatic resin proposed in Section 1.3 is a polymer containing a warp group. However, in the case of a polymer containing a hydroxyl group, the polymerization f 茌 listed above is not unlimited. If it contains various reactive groups and control groups as described above, it has the general fees listed above. All grid structures can be used. C) _ 33 — This paper scale is suitable for financial transfer (CNS) domain grid (2mx297 male thin); " I n I 11—, ^ 1ϋ n ^ Φ · (Please read the note on the back firstΫ Please fill in this page again) 4 60 4 89 A7 B7 5. Description of the invention () (Please read the notes on the back before filling this page) Also, for the molecular weight of the polymer containing the radical, there is no special restriction on K, if Considering the grafting effect of carbon black or the working surface when reacting with carbon black, that is, the molecular weight of the above listed K is preferably in the range of 500 ~ 7000000, but K is in the range of 1000 ~ 100,000 Is the most appropriate. 1.5 block type and graft type polymers are most suitable for use in the present invention. The polymer structure in which carbon black is grafted to form a polymer contains reactive groups capable of reacting with functional groups on the surface of carbon black. A block type and a graft type polymer having a bond segment (A) and a bond segment (B) which has substantially no zigzag structure different from the segment (A) and does not contain the reactive group. Those who can be used as a block type and a graft type polymer are not limited to those having a simple structure such as the AB type block copolymer shown in FIG. 2 (a) and the AB type graft copolymer shown in FIG. 2 And when it contains a BAB block copolymer as shown in Fig. 2 (C) or a more highly interactive block copolymer, as shown in Fig. 2 (d), a plurality of B bond segments are formed on the A segment. Comb-shaped graft copolymers, even star-shaped copolymers as shown in Figure 2 (e). X in the figure represents a reactive group. Fig. 2 (f) shows the state where the blocks M and graft polymers are bonded to the surface of the carbon black particles (CB). As long as they are bonded to the surface of the carbon black particles, they can face the carbon black. The outer surface of the particle is paired with an M upper segment (B) that has a certain degree of freedom, regardless of whether it is a block or a graft state that the graft-type aggregate is gambling on, as if it is classified as a segment (Α) And contains a plurality of types of segments (the same as the segment (B)), or has different properties from the segment (A) and the segment (B), such as those having the intermediate nature of the two, may lengthen the graft bond Can increase the connection -34-This paper iron scale is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 460 489 A7 _B7_ V. Description of the invention () The "swing" (movement) of the branch chain in the media M And other types of segments (such as (C) segments in the following description) that reduce its swing and other functions are equal to the middle of segment (A) and segment (B). Although this (C) section may or may not contain an anti-radical group, it is generally considered that it is not suitable to improve the grafting efficiency. In addition, it is sometimes possible to introduce a polymer such as a reactive group that can bridge each other at the seeding (C.) bond. In addition, for convenience of explanation, it is called (C) segment, and if K is expanded to classify, * (C) key segment can also be classified into key segment (4) or _ segment 汨). In the block type M and the graft type polymer, the reactive group contained in the bond (A) is not particularly limited, and it can react with the functional group on the surface of the carbon black to impart the polymer pair. For carbon black grafted ribs, each of the reactive groups described above can be used. The bond segment (A) containing such a reactive group should preferably have a low affinity for the target media in the bond structure of the bond segment. In addition, since the affinity at this time is relative because of the comparison between the other party and the key segment (B), depending on the type of the target vessel or the composition of the chain segment (B), the chain segment (A) can become various The constitution status * cannot be specified. However, from another point of view, the segment (A) can show a high affinity for carbon black to show an excellent pairing property for carbon black, which can be said to be a good segment. From this point of view, the segment (A) should preferably be formed by carbon-carbon compounds as the backbone of the main chain. However, it is preferable that the main chain contains If it is an aromatic ring such as a fluorene ring and a reactive group as described in the molecule, on the one hand, the segment (B) should have less carbon and one carbon bond than the segment (A), and particularly less aromatic. 'The bone structure of the fragrant ring, such as polysiloxane structure, or 酦 combination, the size of this paper applies the Chinese National Standard (CNS) A4 specifications (210 × 297 mm) ^ ---- 〆--, order --- --- ^ (Xu first, please read the notes on the back two and then fill out this page) 4 60 4 89 at _ B7 V. Description of the invention () Fatty bonds such as carbon bonds and carbon bonds are preferred. However, when the segment (A) is substantially composed of only a fluorene segment having a highly condensed polycyclic structure, the rigidity of the segment (A) will be extremely increased, so that when grafted to carbon black The life chain segment (A) is difficult to get close to the surface of the carbon black. Therefore, it is appropriate that M has a moderate linear structure. As mentioned above, the bond structure of the segment (Α) can be appropriately selected due to the chain structure of the segment (B) selected to impart carbon black with dispersibility, such as styrene, single, hip , (Methyl) two fluorene monomers, submerged monomers, etc. alone or by copolymerization of various ethylene fluorene polymers, polyesters, polyethers, etc. (containing the reactive groups listed above) ) To form a polymer bond, where M is a polymer, especially K contains 50 gm% of the aromatic monomer which is badly aromatic from the above, and preferably M contains (50 gm% or more) Reactive vinyl fluorene polymers can be combined with various segments (B) selected according to the target media. When economic considerations are taken into account *, M contains styrene fluorene monomers and (A Group) Individual polymers based on ethylene fluorene monoliths and their copolymerized polymers • Especially styrene ethyl sulfonium monomers containing 50 mol% or more < 30 mol% or more The polymer chains with the reactive groups listed above are the best. However, in the chains containing reactive groups, (A), when it is regarded as having a low degree of affinity for the target media in the chain structure of the segment compared to the target segment (B), it is not necessary to make the segment (Α) have a high affinity for carbon black, In fact, although there is no difference in the affinity of the segment (A) and the bond (B) for carbon black, or those with a lower affinity than the segment (B) can be used, sometimes, it may be used. The size of this paper is applicable to Chinese National Standard (CNS) A4 # Jl (2 丨 0 > < 297 mm) · ^ ---- ^ _ | 1Τ ------ Pay attention to the back of the paper Please fill in this page again for matters) A7 460489 _B7_ V. Description of the invention () In the chain segment (B) there is a bond segment constructed like acetophenamine. {Please read the notes on the back before filling in this page) On the one hand * The mystery paragraph (B), because of the dispersion of the target media and other characteristics of carbon black, such as Polymerization of (meth) ethylene fluorene structure, polyether fluorene structure such as polyalkylene glycol, polyester fluorene structure, polyalkylene system structure, polyamine structure, polyimide structure, polycarbamate etc. Select the appropriate structure to use. For example, the polysilicon gas radon structure chain can be used to modify the dispersion of low-polarity media, and has extremely excellent water repellency, release, heat resistance, weather resistance, softness, low viscosity, etc., or For the purpose of not having low-temperature brittleness, the (meth) ethylene fluorene chain is used to introduce a wide range of ethoxylated fat components and give a wide range of hydrophilicity-hydrophobicity, crystallinity, and water-repellent purposes (such as · introduction (Meta) vinyl hydroxyalkyl esters, etc. to improve co-hydrophilicity. * (Meth) acrylic acid dodecyl ester to improve its hydrophobicity, M (methyl) acetoate stearic acid ester to improve co-crystallinity, M fluoro (meth) vinyl ester can improve its water repellency). Polyethylene diacetic acid chain can be used for the purpose of giving hydrophilicity, moisturizing property, softness, and preventing charging, etc. *. In addition, the seam segment (A) containing a reactive group capable of reacting with the functional group on the surface of carbon black can be designed with M to make it more effective than the segment (B) that is highly compatible with the target media. Carbon black exhibits a high degree of affinity. At this time, it is necessary to construct the bond segment _ bond on the (A) segment containing a reactive group so that it can exhibit a higher affinity with carbon black. In addition, the high degree of affinity referred to here is due to the counterpart which is compared with the other (B) 継 segment, and the structural form of the (B) segment can be used to make the (Α) key segment into various structures, that is, it cannot be added. Specific restrictions. However, because of the (Α) section, it is K-carbon-carbon junction-37-this paper uses the Chinese National Standard (CNS) A4 specification (210 X M7 male) 4 60 4 89 A7 A7 B7 V. Description of the invention () The combination of the main chain formed by the main chain is the best, and the main chain is an aromatic ring containing a cage ring, a ring ring, a nodal ring and the like, and a reactive group is included in the segment In the molecule, the (B) 鲢 segment of the other, that is, M is a bone structure that contains less carbon and a carbon bond than the (A) segment, and particularly contains a bone structure with a low content of labor. Binding agents other than carbon-carbon bonding M such as ether bonding and lipid bonding are preferred. However, if the (A) segment is made of only a highly condensed and multi-photon structure, it is about to make the (A) bond. The rigidity of the segment is extremely high, so that when grafting carbon black, it will be difficult to make the (A) seam segment close to the surface of the carbon black surface. Therefore, it should be a moderate linear structure. As described in the above column, ( (A) The fluorene structure of the bond segment is selected from the viewpoint of dispersibility to give carbon black. (B) The chain structure of the chain segment, as described in the polysuccinic fluorene structure. (Methyl) ethyl ether structure, polyalkylene glycol structure, etc., polyether system structure, polyester structure, polyalkylene structure, polyamine structure, polyimide structure, polycarbamate It is determined by the contained polymer bonds that it has a high affinity for carbon black, without any special restrictions. It is usually based on polymers containing ethyl acetamidine, in particular ethyl acetate containing aromatic rings. The unit weight of the monomer is 50. mole% or more, and it is preferable to use an ethoxylate polymer that contains 60 mole% or more and contains a reactive group. For considerations such as economic efficiency, special styrene-based monomers Polymer and (meth) acrylic fluorene monomers as the basis of single M and co-overlap polymers, especially containing 50% by weight or more of styrene, or 60% by weight or higher ( Those with a reactive group listed above). When the segment (B) is a polysaccharane polymer, the number of types of polymerization bonds that can be used in the segment (A) is -38 — paper size Applicable to Chinese National Standard {CNS) Α4 specification (2 丨 0 X 297 mm) · I ^ 1Τ ------ line · (Read the notes on the back of the poem before filling in this page) 4- 60 4 89 A7 __B7__ V. Description of the invention () Of course, if it is in the chain (B) Poly (meth) acrylic fluorene structures, such as vinyl fluorene structures, can form the polymerization process of the (A) section. There will be many restrictions. Only polystyrene fluorene structures and (meth) propylene-styrene Copolymerization and other structures. A segment type (A) containing a reactive group and a bone structure different from the bond segment (A) is preferred to have a block type (B) which has a higher affinity for the target medium than the segment (A). The manufacturing method of the M and the graft polymer is not particularly limited, and it can be produced by combining various well-known polymerization techniques of the block M and the graft polymer and the manufacturing technique of the reactive polymer plus M. If the method of manufacturing a graft polymer by M is, in the presence of a high molecular weight body capable of becoming a graft chain, the M polymerization starter and the polymerizable monomer are solution polymerization, emulsion polymerization, block polymerization, or A polymerization method in which the suspension polymerizes and the M polymer is its primary bond. However, if the high-molecular weight body does not contain a polymerizable functional group, a large amount of the non-grafted polymer remains in the obtained graft copolymer, resulting in the disadvantage of extremely low grafting effect. Therefore, it is preferable to use a polymerizable high molecular weight body as the high molecular weight body. However, the segment (B) of the polymerized crossbond on the carbon black grafted polymer obtained is obtained by adding the carbon black grafted polymer to a binder resin dispersed in a matrix inhibitor, and a solvent. When it is the same kind or has high compatibility, as obtained by the method listed above, it belongs to those who have a certain degree of low grafting effect. It can also be expected to become a highly stable product. This kind of polymerizable polymer carcass is usually called "macro monomer '" * contains polymerizable groups at the end of the sheet, such as * containing (meth) acrylic groups, styrene groups and other high molecular weight bodies If the end of the tablet is contained in an organic solvent; -ΪΤ ------ Record · (Please read the precautions on the back before filling out this page) The standard of this paper is China National Standard (CN'S > A4 specification) (210X 297 mm). 0 0 4 89 7 丨. 8 A7 B7 Λ fifth, description of the invention (m Junji polymer and glycidyl group-containing polymerizable monomers react (eg, in In Patent Publication No. 1968-11224, the prepolymer (P "ep〇1 ymer") obtained by subjecting the base polymerizable polymer to base polymerization under the condition that Si base acetic acid is contained in an organic solvent, and glycidyl methacrylate Dimethylmagnetic amine is a method for producing a catalyst phase reaction). Therefore, if one wants to obtain the grafted polymer of the present invention, he can polymerize the polymerizable high-molecular-weight body containing the group forming component (B). (B) Bottom * make the polymerizable monomer containing reactive groups in the carbon black molecule as described above The polymer (a) and the polymerizable monomer (C) phase containing the formation of a segment (A) Ferg should be reacted in accordance with other necessary preparations. For carbon black, the polymerizable polymer (a) contains a reactive group in the molecule. There are: fj CH2 = CH ™ CH-CH2 Λ〇 / ch2 = ch > -ch-ch2 1 丨 install --------- order ^ ------- line {please read the back first (Please note this page before filling out this page) 40 This standard is applicable to the Chinese national standard (CNS) A4 (210X29 "? Mm) 4 6〇489

A A7 B7 五、發明説明（ ch2=chA A7 B7 V. Description of the invention (ch2 = ch

卜 CH2-CH-CH2 \〇/ ch2=chCH2-CH-CH2 \ 〇 / ch2 = ch

>一 CH2—CH2 —CH—CH2> one CH2—CH2 —CH—CH2

ch2=C(ch3) ^ y-ch-ch2 GH2 = C(CH3)ch2 = C (ch3) ^ y-ch-ch2 GH2 = C (CH3)

>-ch2-ch-ch2 \〇/ ^^^1 f — ^^^^1 ^un mV ^^^^1 - m^i ^——κ 1I----S 1 .J x^. i l t c請先閱讀背面之注意事項再填寫未頁) 經濟部中央標準局貝工消f合作社印裝 CH2 = C(CH3)> -ch2-ch-ch2 \ 〇 / ^^^ 1 f — ^^^^ 1 ^ un mV ^^^^ 1-m ^ i ^ —— κ 1I ---- S 1 .J x ^. iltc Please read the notes on the back before filling in the unpaged page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Fong Cooperative Cooperative, CH2 = C (CH3)

CH2-CH2-CH-CH2、〇/ 40 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2!0x W7公釐） 4 604 89 A7 B7 五、發明説明（ ch2=ch-nhcoCH2-CH2-CH-CH2, 〇 / 40 This paper size applies Chinese National Standard (CNS) Λ4 specification (2! 0x W7 mm) 4 604 89 A7 B7 V. Description of the invention (ch2 = ch-nhco

>-ch-ch2> -ch-ch2

CH2 = C(CH3)-NECOCH2 = C (CH3) -NECO

CH- Ό -CHa (請先閱讀背面之注意事項再填寫本頁)CH- Ό -CHa (Please read the notes on the back before filling this page)

Ri \)一 0 ~f~CH2〇HO ·)^"0Η2—CH —CH2 11 、〇/Ri \) 一 0 ~ f ~ CH2〇HO ·) ^ " 0Η2—CH —CH2 11 〇 /

Ri CH2 = C(CH3)Ri CH2 = C (CH3)

0-eCH2CH0 CH2-CH-CH2 疒I. 經濟邦中央樣嗥局員工消費合作社印製0-eCH2CH0 CH2-CH-CH2 疒 I. Printed by the Consumer Cooperatives of the Central State Bureau of Economic Affairs

RI CH2 = CH - COO CH2CHO CH2 - CH - GH2RI CH2 = CH-COO CH2CHO CH2-CH-GH2

4 I 本纸張尺度適用中國國家搮準（CNS ) A4规格（210X 297公釐） 4 604 89 A7 B7 五、發明説明（ R1 CH2 = C(CH3) - coo -f CH2CHO ch2 - CH - ch2 \〇/ 以上列（但，在上列式中的R丨為氫或甲燒基《 n為0或 1〜20的整數）等式所表示的含有壞氧基聚合性單量體類。 CH2 = CH-CH-CH24 I This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 4 604 89 A7 B7 V. Description of the invention (R1 CH2 = C (CH3)-coo -f CH2CHO ch2-CH-ch2 \ 〇 / However, bad oxygen-containing polymerizable cetons represented by the above formula (where R 丨 in the above formula is hydrogen or methyl group, n is an integer of 0 or 1 to 20). CH2 = CH-CH-CH2

CH2 = CHCH2 = CH

ch2=chch2 = ch

(請先閱讀背面之注意事項再填寫本頁) *ch-ch2 xs/ >—CH2 — CH—CH2 、s〆 -42 - 本纸伕尺度適用中國國家標準{ CNS ) A4規格（21 OX 297公釐） 4 604 89 A7 B7 五、發明説明（ ch2=ch(Please read the precautions on the back before filling in this page) * ch-ch2 xs / > —CH2 — CH—CH2 、 s〆-42-The standard of this paper is applicable to Chinese National Standard {CNS) A4 specification (21 OX 297 Mm) 4 604 89 A7 B7 V. Description of the invention (ch2 = ch

CH2-CH2-CH-CH2CH2-CH2-CH-CH2

CH2=C(CH3) -γ y-CH-CH2CH2 = C (CH3) -γ y-CH-CH2

CH2 = C(CH3) -({ \>-CE2-CH-CH2 (請先閏讀背面之注意事項再填寫本頁) 丁CH2 = C (CH3)-({\ > -CE2-CH-CH2 (Please read the precautions on the back before filling this page) D

CH2 = C(CH3) —^ — CH2—CH2—CH -~ΟΉ-2 ch2=ch-nhcoCH2 = C (CH3) — ^ — CH2—CH2—CH-~ ΟΉ-2 ch2 = ch-nhco

>-ch-ch2 xs7 ‘43. 本纸張尺度適用中國國家樣準（CNS ) A4規格（210X 297公釐） Λ60489 A7 B7 五、發明説明（> -ch-ch2 xs7 ‘43. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) Λ60489 A7 B7 V. Description of the invention (

CH2 = C(CH3)-NHCOCH2 = C (CH3) -NHCO

'S ~ce2 ch2=ch'S ~ ce2 ch2 = ch

R1 I 〇 -f CH2CHO ^-CH2 - CH - ch2 D xs7 R1 CH2 = CCCH3)R1 I 〇 -f CH2CHO ^ -CH2-CH-ch2 D xs7 R1 CH2 = CCCH3)

>-0 -eCH2CHO ^-ch2-ch-ch2- α xs7> -0 -eCH2CHO ^ -ch2-ch-ch2- α xs7

Rl ch2=CH - COO -f- CH2CHO ch2 - CH - ch2G xs7 本纸張尺度適用中國國家標準（CNS)六4说格（2I0X 297公釐） ---------^-------ix------.^ (請先閲讀背面之注意事項再嗔寫本頁) 4 604 A7 B7 五、發明説明（ R1 CH2 = C(CH3)-COO -f CH2CH〇t^ CH2-CH-CH2 Μ上列（但，在上列式中的Ri及η與含有環氧基聚合 性單量體的表示相同）等式所表示含有硫環親:基聚合性單 量體類。Rl ch2 = CH-COO -f- CH2CHO ch2-CH-ch2G xs7 This paper size is applicable to the Chinese National Standard (CNS) six 4 cells (2I0X 297 mm) --------- ^ --- ---- ix ------. ^ (Please read the notes on the back before writing this page) 4 604 A7 B7 V. Description of the invention (R1 CH2 = C (CH3) -COO -f CH2CH〇t ^ CH2-CH-CH2 Μ listed above (however, Ri and η in the above formula are the same as those containing epoxy-based polymerizable singular body) The sulfur-containing ring-containing polymerizable singular body expressed by the equation class.

CH2 = CH-N ch2=ch-ch2-n (請先閱讀背面之注意事項再填寫本頁) ch2=chCH2 = CH-N ch2 = ch-ch2-n (Please read the notes on the back before filling this page) ch2 = ch

CH2 = C(CH3)CH2 = C (CH3)

N —45 - 本紙張尺度適用中國國家橾準（CNS )A4規格（210X297公釐） * ^ 460489 A7 B7 五、發明説明（）N —45-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) * 460 489 A7 B7 V. Description of the invention ()

本纸乐尺度適用中國國家榡準（CNS ) A4規格（21〇Χ 297公釐） -1 I H . Ί,1τΐ ii? (請先閱讀背面之注意事項再填寫本頁) 4 60 4 89 A7 B7 五、發明説明（The paper scale is applicable to China National Standards (CNS) A4 (21〇 × 297mm) -1 IH. Ί, 1τΐ ii? (Please read the notes on the back before filling this page) 4 60 4 89 A7 B7 5. Description of the invention (

CH2 = C(CH3)-NHCOCH2 = C (CH3) -NHCO

ch2=CH - COO - CH2CH2 -Nch2 = CH-COO-CH2CH2 -N

CH2 = C(CH3) - COO - CH2CH2 -N ch3 , II . 11~ 111 It^取 I ± ^ 訂-^ (請先閏讀背面之注意事項再填寫本頁)CH2 = C (CH3)-COO-CH2CH2 -N ch3, II. 11 ~ 111 It ^ take I ± ^ order-^ (Please read the notes on the back before filling this page)

CH2 = CH - COO - CH2CH2 -NCH2 = CH-COO-CH2CH2 -N

CH2 = C(CH3) - COO - CH2CH2 -N —4-7™ 本紙張尺度適用中國.國家標準（CNS ) A4規格（210X297公釐） CH3 4 60 4 89 五、發明説明（ A7 B7 CH2 — CH—COO—CH2CH2— CH2=G(CH3) - coo -CH2CH2 - N、 CH2 = CH - COO - CH2CH2 - N、 όη3 'CH3 ch3 ch3 C2H5 C2H5 -----------^-----'—IT------# (请先聞讀背面之注意Ϋ^再填寫本頁) CH2 = C(CH3) - COO - CH2CH2 CH2=CH - COO - CH(CH3) - CH2 •本氓悵尺度適用中國國家標準（CKS ) Α4規格（210X297公釐） 'A7 B7 4 604 89 五、發明说明（ {請先閱讀背面之注意事項再填寫本頁) CH2=C(CH3) - COO - CH(CH3) - ch2 - nCH2 = C (CH3)-COO-CH2CH2 -N —4-7 ™ This paper size is applicable to China. National Standard (CNS) A4 specification (210X297 mm) CH3 4 60 4 89 5. Description of the invention (A7 B7 CH2 — CH —COO—CH2CH2— CH2 = G (CH3)-coo -CH2CH2-N, CH2 = CH-COO-CH2CH2-N, όη3 'CH3 ch3 ch3 C2H5 C2H5 ----------- ^ --- --'— IT ------ # (Please read the note on the back Ϋ ^ before filling out this page) CH2 = C (CH3)-COO-CH2CH2 CH2 = CH-COO-CH (CH3)-CH2 • This standard is applicable to China National Standard (CKS) Α4 specification (210X297 mm) 'A7 B7 4 604 89 V. Description of the invention ({Please read the notes on the back before filling this page) CH2 = C (CH3)-COO -CH (CH3)-ch2-n

CH2 = CH-COO -f CH2CH2〇-)5-CH2CH2-NCH2 = CH-COO -f CH2CH2〇-) 5-CH2CH2-N

CH2 = C(CH3)-COO -fCH2CH2〇^-CH2CH2-NCH2 = C (CH3) -COO -fCH2CH2〇 ^ -CH2CH2-N

CH2 = CH-COO -^CH2CH2O^CO-CH2CH2-NCH2 = CH-COO-^ CH2CH2O ^ CO-CH2CH2-N

CH2=C(CH3) - COO -(- CH2CH2O ^ CO - CH2CH2 -N 本纸伕尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 4 6 0 4 89 A7 B7 五、發明説明（CH2 = C (CH3)-COO-(-CH2CH2O ^ CO-CH2CH2 -N The paper scale is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 4 6 0 4 89 A7 B7 V. Description of the invention (

CH3CH2- C-CH20-COCH2-CH2-N CH2-CH20-C0-CH = CH2 CH - ch2o - coch2 - ch2 - n ch2 - ch2o - CO - ch=ch2 CH2 - CHzO - CO - C(CH3) = ch2CH3CH2- C-CH20-COCH2-CH2-N CH2-CH20-C0-CH = CH2 CH-ch2o-coch2-ch2-n ch2-ch2o-CO-ch = ch2 CH2-CHzO-CO-C (CH3) = ch2

CH - CH20 - COCH2 - CH2 - N CH2 - CH20 - CO - C(CH3) = ch2 CH2〇-CO-CH = CH2 CH20-C0-CH=CH2 CH20 - CO - C(CH3) = ch2CH-CH20-COCH2-CH2-N CH2-CH20-CO-C (CH3) = ch2 CH2〇-CO-CH = CH2 CH20-C0-CH = CH2 CH20-CO-C (CH3) = ch2

CH3CH2- C-CH20-COCH2-CH2-N CH20-C0-C(CH3) = CH2 一5〇 一 本紙張尺度·適用中國國家標準（CNS ) A4規格（210 X 297公釐） ^----^--tT------0 {請先聞讀背面之注意事項再填寫木頁) 4 604 89 A7 B7 五、發明説明（）CH3CH2- C-CH20-COCH2-CH2-N CH20-C0-C (CH3) = CH2 501 paper size · Applicable Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ ---- ^-tT ------ 0 {Please read the notes on the back before filling in the wooden pages) 4 604 89 A7 B7 V. Description of the invention ()

CH2 = CH-CO-NCH2 = CH-CO-N

CH2=C(CH3)-CO-NCH2 = C (CH3) -CO-N

CH2=CH-OCO-N CH2 = C(CH3)-0C0-N_CH2 = CH-OCO-N CH2 = C (CH3) -0C0-N_

CH2=CH-S〇2-N 本纸掁尺度適用中国國家橾準（CNS) A4規樁ΐ 2l〇X297公釐） 4604 89 五、發明説明（） A7 B7CH2 = CH-S〇2-N The standard of this paper is applicable to China National Standard (CNS) A4 gauge (210 × 297 mm) 4604 89 V. Description of invention () A7 B7

CH2=C(CH3)-S〇2-N ch2=ch-nhc〇-n、CH2 = C (CH3) -S〇2-N ch2 = ch-nhc〇-n,

CH2 = C(CH3) — NHCO-NCH2 = C (CH3) — NHCO-N

CH2=CH~NHCS-N I . I 裝 . -ir# (請先閱讀背面之注意事項再填寫本頁)CH2 = CH ~ NHCS-N I. I install. -Ir # (Please read the precautions on the back before filling this page)

CH2 = C(CH3)-NHCS-N 本纸抶尺度速用中國國家橾準（CNS)A4规格（2丨0X297公釐> 460489 A7 B7 五、發明説明（） CH2=CH-CH2-〇CO-N^ ch3 ch2=ch-co-nCH2 = C (CH3) -NHCS-N Paper Standard Quick Use China National Standard (CNS) A4 Specification (2 丨 0X297 mm > 460489 A7 B7 V. Description of Invention () -N ^ ch3 ch2 = ch-co-n

CH2 = C(CH3)-CO-NCH2 = C (CH3) -CO-N

CH2 = CH-CO-NCH2 = CH-CO-N

CH2 = CH-GO-N 本紙張尺度逋用中國國家標準（CNS ) A4洗格（210X 297公釐〉 ch3 /CHs 、ch3 C2H5 1 ; 和木 I ~. 釘 1 ί* ^ (請先閱讀背面之注意事項再填寫本頁) 460489 B7CH2 = CH-GO-N This paper size uses Chinese National Standard (CNS) A4 wash case (210X 297 mm) ch3 / CHs, ch3 C2H5 1; and wood I ~. Nail 1 ί * ^ (Please read the back first (Notes on this page, please fill out this page) 460489 B7

4 604 89 五、發明説明（） A7 B7 CH2=G(CH3)4 604 89 V. Description of the invention () A7 B7 CH2 = G (CH3)

>-NECO-N> -NECO-N

CH2 = CH-CO>iHCH2 = CH-CO > iH

)-S〇2-N) -S〇2-N

CH2=C(CH3)—CONHCH2 = C (CH3)-CONH

)一 S〇2—N I n #衣 - 訂 - 绍 (锖先閱讀背面之注意事項再填寫本頁)) 一 S〇2—N I n # 衣-Order-Shao (锖 Please read the precautions on the back before filling this page)

CH2 = CH - COO - CH2CH2 - NHCOCH2 = CH-COO-CH2CH2-NHCO

CH2=C(CH3) - COO - CH2CH2 - NHCO - N 本饫块尺度逋用中國國家橾率（CNS>A4規格（210X297公釐} 460489 • Λ7 ________B7 五、發明説明（）CH2 = C (CH3)-COO-CH2CH2-NHCO-N The Chinese standard rate (CNS > A4 size (210X297mm) 460489 • 460489 • Λ7 ________B7 for this block size) 5. Description of the invention ()

(诗先閲讀背面之注意事項再填寫本百)(Read the notes on the back of the poem before filling this one hundred)

(CH2=CH-CH2NH·^- PO-N 等所示的含有氮两陡聚合性單量體類。 2-乙綿-2-嗯啤妹，2-乙婦-4-甲基-2-嚼哩咐，2-乙 嫌-5-甲基-2-嗯D坐p抹，2-乙嫌-4-乙基-2-嗯喃*林，2-乙嫌 -5-乙基-2-嗯哩1>林，2-異两鋪基-2-嗯唯I»秣，2-異两輝基-4-甲基-2〜嗯喃_，2-異丙稀基-5-甲基-2-嗯睡〇林，2-異 丙鋪基-4-乙基-2-嗯哩说，2-異两婦基-5-乙基-2-嗯哩咐 ，2_異丙嫌基-4,5-二甲基-2-嗯B坐p袜等的含有嗯挫命基聚 合性單最體類； N-經甲基丙烯醯胺，N—經乙基丙烯醚胺，N-理丁基丙 輝醯胺* N-經異丁基丙烯醯胺，N-羥基-2-乙基.己基两烯 醯胺，經環巳基丙締醯胺，N-經甲偏两婦醯胺，經乙 基偏丙鋪醯肢，N-羥丁基偏丙烯醯胺，N-翔異丁基僑丙烯 酿胺* N-控基-2-乙基.已基偏丙烯醢胺，M-羥瑪巳基偏丙 烯醯胺等的含有N-羥烷醯胺基的聚合性單量體類，併可Μ 從這等群中選取其一種或二種以上來使用。 又，欲使鏈段（Α)含有如上列的構造時，為因應其W要 而能加以使用的聚合性單量體（C),即有，使所述單最體（a )及將在下列所述可Μ形成鏈段（B)的成分如上列的基聚合 -56 - 本纸ft尺度適用中國國家揉準（CNS ) Α4規格（2IOX：297公釐） 4 60 4 89 a? _B7___ 五、發明説明（） 性高分子量體0>)得K進行共聚合的就不加K特別限制使 用，而隨欲得鏈段（A)的分子構造，如自，莱乙烯，Θ-甲基 策乙烯，m-甲基聚乙熥，P-甲基聚乙烯，甲基笨乙烯 ，P-甲氧基苯乙嫌，P-特（tert)—巳基苯乙嫌，P-苯基苯 乙嫌，Θ —氣苯乙鋪，m-氯苯乙嫌，P-氣苯乙烯等的苯乙 嫌糸單聚（體合物）；丙輝酸、丙烯酸甲酯、丙烯酸乙酯 、丙嫌酸丙醋、丙烯酸正丁酯、丙烯酸異丁酿、丙嫌酸十 二院酯、两烯酸硬脂醯Sg、两婦酸2-乙基*己基醋、偏丙 蹄酸、偏丙嫌酸甲酯、偏丙婦酸乙醋、偏丙烯酸丙醋、偏 丙烯酸正丁酯、偏丙烯酸異丁酿、偏两嫌酸正辛酯、偏丙 ΐ希酸十二院酷、偏丙嫌酸2-乙基♦巳酿、偏丙烯酸硬脂醯 酯等的丙烯酸或偏丙烯酸糸單體；乙烯、丙烯、丁烯、氯 乙煉、醋酸乙烯、丙烯_、丙烯醯胺、偏丙烯醯胺、Ν-乙 烯rttj咯烧酮等單體中，選取其一種或二種以上加以適宜使 用。 一方，能構成鏈段（B)成分的基聚合性高分子贵體（b) 時所欲的聚合鐽，即如有聚環乙燒糸構，聚（偏）丙婦糸 構造，聚亞烴乙二醇等的聚醚糸構造、聚脂糸構造、聚亞 烴糸構造、聚醜胺構進、聚亞胺構造、聚氨基甲酸脂構造 等聚合體又在其片末端含有反應基的都可Μ使用。 若，欲鏈段（Β)含有聚硅氧烷糸構造時*即可用聚二甲 r 硅氧基，含有局部置換性烷基的聚二甲硅氧棊，含有局部 置換性芳香基的聚二甲鞋氣基、三（三院硅氣）甲硅院丙 基等含有聚有機硅氧烷構造者。 本纸乐尺度適用中國國家標準（CNS ) Μ規格（21〇x297公釐） I ^ I . .訂------0 (诗先閱讀背面之注意事項再填寫本頁) Α7 Β7 五、發明说明（） 因此，可為含有聚硅氣燒糸構造的基聚合性高分子量 體（bl)的*即有如，含有（甲基）丙烯基的聚二甲娃氧燒· 含有硬脂脑基的聚二甲硅氣烷*含有局部置換性辛基之（ 甲基）丙嫌基的聚二甲δ圭氣烧，硬脂醯基含有局部翌換性辛 基的聚二甲鞋氧烧，硬脂醯基含有眉部置換性萊基的聚二 甲5圭氧烧，三（三甲硅氣）桂丙基（甲基）丙烯酯等的聚合 性聚链氧院類，併自其中選取一種或二種以上來使用，卻 Μ下列基聚合性高分子量體最好。(CH2 = CH-CH2NH · ^-PO-N, etc. Two nitrogen-steep polymerizable singular bodies are shown. 2-ethim-2-um beer sister, 2-ethim-4-methyl-2- Chewing command, 2-ethylan-5-methyl-2-um D sits on the wipe, 2-ethylan-4-ethyl-2-uman * Lin, 2-ethylan-5-ethyl-2 -Um 1 > Lin, 2-Isopyridyl-2-UmI I »秣, 2-Isobifluorenyl-4-methyl-2 ~ Um_, 2-isopropyl-5-methyl Syl-2-um sylamine, 2-isopropylpyridyl-4-ethyl-2-um mile, 2-isodiaphthyl-5-ethyl-2-um mile, 2_isopropyl -4,5-dimethyl-2-um B-sock-containing polymerizable monomers containing humoryl groups; N- via methacrylamide, N- via ethyl allyl ether amine, N -Butyl propyl fluorenamine * N- via isobutyl acrylamide, N-hydroxy-2-ethyl. Hexyl diene fluorenamine, cyclo fluorenyl propyl ammonium amine, N- via methylamine Pyridoxine, via ethyl vinylpropionate, N-hydroxybutyl metapropenylpyridine, N-xiangisobutylpyridylamine * N-controller-2-ethyl.hexyl metapropenylamine, N-hydroxyalkylamido group-containing polymerizable monomers such as M-hydroxymacrolimide, acrylamide, and the like can be used by selecting one or two or more of these groups In addition, when the segment (A) is to contain a structure as listed above, the polymerizable monosome (C) can be used in accordance with its requirements, that is, the monomer (a) and The following components that can form the segment (B) are polymerized as described above. -56-The paper ft scale is applicable to China National Standards (CNS) A4 specifications (2IOX: 297 mm) 4 60 4 89 a? _B7___ 5 2. Description of the invention () High molecular weight body 0 >) K is copolymerized without special restrictions on the use of K, and the molecular structure of the segment (A) can be obtained as desired, such as self, vinyl, Θ-methyl Ethylene, m-methyl polyethylene, P-methyl polyethylene, methyl benzyl, P-methoxyphenethyl, P-tert-fluorenylphenyl, P-phenylstyrene Suspicion, Θ — acetophenone, m-chloroacetophenone, P-aerostyrene, and other styrene ethyl monomers (complex); hyaluronic acid, methyl acrylate, ethyl acrylate, and propionic acid Propane vinegar, n-butyl acrylate, isobutyl acrylate, dodecyl propionate, stearyl dienoate Sg, 2-ethyl * hexyl vinegar, metapropanoate, methylpropionate Esters Acrylic acid vinegar, n-butyl metaacrylate, isobutyl methacrylate, n-octyl bisammonate, twelve methyl acetic acid, 2-ethyl methacrylic acid Acrylic acid or meta-acrylic acid monomers such as tallow ester; in monomers such as ethylene, propylene, butene, vinyl chloride, vinyl acetate, propylene, acrylamide, meta-acrylamide, N-ethylene rttj, ketone, etc. , Select one or more of them for appropriate use. On the one hand, the polymerizable polymer noble (b) that can constitute the component (B) of the segment (b) is the desired polymerization polymer, that is, if there is a polycycloethylene fired structure, a poly (unsymmetrical) feminine structure, or a polyalkylene Polymers such as polyether 糸 structures, polyester 糸 structures, polyalkylene 糸 structures, polyamine structures, polyimide structures, and polyurethane structures, such as ethylene glycol, contain reactive groups at the end of the sheet. Can be used. If the segment (B) contains a polysiloxane fluorene structure *, polydimethylsiloxy, polydimethylsiloxane containing a partially-substituted alkyl group, and polydimethacrylate containing a partially-substituted aromatic group can be used. A shoe gas base, three (three courtyards of silicon gas) and other silicone containing propyl structure containing polyorganosiloxane structure. This paper music scale is applicable to Chinese National Standard (CNS) M specifications (21 × 297 mm) I ^ I.. Order ------ 0 (Read the notes on the back of the poem before filling this page) Α7 Β7 V. Description of the invention () Therefore, the polymerizable high-molecular-weight body (bl) containing a polysilicon gas-fired structure can be used, for example, a polydimethylsiloxane containing a (meth) acrylic group, and a stearyl brain group. Polydimethylsilane * with partially substituted octyl (meth) propanyl polydimethyl δ ketone, and stearyl sulfonyl group containing partially transposed octyl dimethyl ketone, Stereoyl group contains polymerized polyoxymethylene compounds such as polydimethylsiloxane containing eyebrow-replaceable Leky, tris (trimethylsilyl) lauryl (meth) acrylate, etc., and select one of them Two or more kinds may be used, but the polymerizable high molecular weight of the following groups is the best.

(OSlR3R9)aR10 R3 RS(OSlR3R9) aR10 R3 RS

I I I CH2 C B — R2 —Si-(OSi)n-OSi-t?6I I I CH2 C B — R2 —Si- (OSi) n-OSi-t? 6

I I I (OSiRuR12)bR13 R7 (但*式中的B表示-COO-基或苯基’ R;為氳原子或甲焼基 ，R4為有碳數1〜(5的亞烴基，Rs〜各為表示同—種或相 異的芳香基，碳數1〜6的燒基或碳數1〜1〇的烴氧基，a及 b各表示同一或相異的〇〜1〇的整數* η為0〜200的整數）。 同樣的，欲鍵段（Β)含有聚偏（丙婦）糸構造時，即 可使用如下列所示的單體為基聚合性高分子量體（b ) ° 本紙伕尺度適用中國國家橾準（〇^)六4規格（2丨(^297公釐） ----------¾------1T------絲 (請先閲讀背面之注意^項再填寫本頁) 在 6 Ο 4 89 at Β7 五、發明説明（）III (OSiRuR12) bR13 R7 (but B in the formula represents -COO- group or phenyl'R; is a fluorene atom or a methyl group, R4 is an alkylene group having 1 to (5 carbon atoms, Rs ~ each represents Identical or different aromatic groups, alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 10 carbon atoms, a and b each represent the same or different integers of 0 to 10 * η is 0 An integer of ~ 200). Similarly, when the bond segment (B) contains a poly (isopropylammonium) hydrazone structure, the monomer shown below can be used as the polymerizable high molecular weight body (b) ° Paper size Applicable to China National Standard (〇 ^) 6 4 specifications (2 丨 (^ 297mm) ---------- ¾ ------ 1T ------ Silk (Please read first Note on the back ^ item, please fill out this page) at 6 Ο 4 89 at Β7 V. Description of the invention ()

Ri (诗先閲讀背面之注意事項再填寫本頁) CH2 = C p2 I 1 c——0——X -ecH2—c ·)—γ I n 0 丫=0 οRi (Read the notes on the back of the poem before filling this page) CH2 = C p2 I 1 c——0——X -ecH2—c ·) —γ I n 0 YA = 0 ο

I R3 (但，式中的R/、Ri各表示同一或相異的氮原子或甲院基 R3為碳原子數1〜25的焼基，X為任意的结合鍵，可為開始 劑的尾端或Η原子，η表示0〜500的整數）。 丨 R1 0¾ = C R2 R4I R3 (However, each of R / and Ri in the formula represents the same or different nitrogen atom or a mesogen group. R3 is a fluorenyl group having 1 to 25 carbon atoms. X is an arbitrary bond and may be the tail of the initiator Terminal or fluorene atom, n represents an integer from 0 to 500).丨 R1 0¾ = C R2 R4

I II I

C —0 —X -tCH2—C 什CH2—C Ή Y II I m I n " c-=o c=oC —0 —X -tCH2—C and even CH2—C Ή Y II I m I n " c- = o c = o

0 I I 〇 〇0 I I 〇 〇

I I R3 R5 本紙乐尺度適用中國國家榡準（CNS ) A4規格（210X297公釐) 460489 A7 B7_五、發明説明（） (但，式中的Ri、Lh各表示同一或相異的Η原子或甲 基，h * Ri·為同—或相異的C原子數1〜25的烧基，；X為任 意的结合継* γ為開始劑的尾端或Η原子· hi及η B卩各為同 —或相異的〇〜500的整數）。II R3 R5 This paper scale is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 460489 A7 B7_V. Description of the invention () (However, Ri and Lh in the formula each represent the same or different plutonium atom Methyl, h * Ri · is an alkyl group having the same or different C number of 1 to 25; X is an arbitrary bond 継 * γ is the end of the initiator or Η atom · hi and η B 卩 are each Same—or different integers from 0 to 500).

1 R 2 Ηc C-1 R 2 Ηc C-

2 R2 R

4 R4 R

CC

CHCH

C όC ό

-C-ο- RL—ο-C-ο- RL—ο

2 CH ο2 CH ο

Υ4511 s C-C-ο——R ο (但，式中的Rt及Ri表示同一或相異的Η原子或甲基，Rj 為C原子數1〜25的稀基（亞烴基），為C原子數1〜25的 院基，X為任意的結合_，Y為開始劑的尾端或Η原子· η 及m各為同一或相異的0〜500的整數）。 又，欲鍵段（B)含有聚亞烴基乙二醇糸構造時，即可使 用如下列所示的單體為基聚合性高分子量體（b )。 -60 - 本纸ft尺度適用中國國家橾準（CNS ) A4坑格（210X297公釐} ^衣1τ-------^ (婧先閲讀背面之注意事項再填寫本頁) 4604 89 A7 B7 五、發明説明（ R3 R1 ch2 = c C 一 0 十 CH2CHO j—R2 n 0 (但’式中的R/、各表示同一或相異的H原子或甲 基，η為〇〜500的整數）〇 R1 (請先閱讀背面之注意事項再填寫本頁) CH2 c R3 R4 C — 0 十 CH2CH0 i~~t CH2CH0 ?—R2 II m n ο (但，式中的、RA、1^及{?4各表示同一或相異的Η原子 或甲基，η及m為同一或相異的〇〜500的整數）。 又·欲鏈段（B)含有聚苯乙烯糸構造時，即可使用如下 列所示的單體為基聚合性高分子最體0>)。 本紙法尺度適用中國國家標孪（CNS } A4現格（210X297公釐） 4 604 89 A7 _B7_五、發明説明（） R1CH2 = cC—ο —X -eCH2—CH4—Υ (但，式中的R/表示Η原子或甲基，X為任葳的結合鐽， Υ為開始劑的尾端或Η原子，Ζ為Η原子，豳置換基或c原 子數1〜8的焼基，η為0〜500的整數）。 又，在上列式群所示的有關結合鰱X，即可自如「大 型單體（Macro monomer)的化學與工業」〔山下雄也監修 ，（股份公司）愛比西（書局）發行，1988年9月20曰]— 書中詳细言及的單體中選取來使用。 可用眾所周知的聚合方法做為製造上列聚合體的方法 。如，塊狀聚合法、懸濁聚合法、乳化聚合法、溶液聚合 法等。其中，以使用基觸媒的溶液聚合法為最好的一法。Υ4511 s CC-ο——R ο (However, Rt and Ri in the formula represent the same or different fluorene atom or methyl group, Rj is a dilute group (hydrocarbylene group) having 1 to 25 C atoms, and the number of C atoms For the foundation of 1 to 25, X is an arbitrary bond, and Y is the tail end of the starter or fluorene atom. Η and m are each the same or different integers from 0 to 500). When the bond segment (B) contains a polyalkylene glycol fluorene structure, a monomer-based polymerizable high molecular weight body (b) can be used as shown below. -60-The ft dimension of this paper is applicable to China National Standards (CNS) A4 pit (210X297 mm) ^ 衣 1τ ------- ^ (Jing first read the precautions on the back before filling this page) 4604 89 A7 B7 V. Description of the invention (R3 R1 ch2 = c C-0 ten CH2CHO j-R2 n 0 (but R / in the formula each represents the same or different H atom or methyl group, η is an integer of 0 to 500 ） 〇R1 (Please read the notes on the back before filling this page) CH2 c R3 R4 C — 0 十 CH2CH0 i ~~ t CH2CH0? —R2 II mn ο (However, in the formula, RA, 1 ^ and {? 4 each represents the same or different fluorene atom or methyl group, and η and m are the same or different integers from 0 to 500). Also, when the segment (B) contains a polystyrene fluorene structure, it can be used as The monomers shown below are based on the polymerizable polymer 0 >). The size of this paper method is applicable to the Chinese national standard (CNS) A4 (210X297 mm) 4 604 89 A7 _B7_ V. Description of the invention () R1CH2 = cC—ο —X -eCH2—CH4—Υ (However, R / in the formula represents a Η atom or a methyl group, X is a combination of 葳, Υ is a tail end of the initiator or a Η atom, and Z is a Η atom , 豳 substitution group or c atom A fluorene group of 1 to 8 and η is an integer of 0 to 500. In addition, the combination of 鲢 X shown in the above formula group can freely "the chemistry and industry of macro monomers" [Yamashita Xiong also supervised, issued by (Stock Co., Ltd.) Ebisi (Book Office), September 20, 1988]-selected from the monomers used in the book in detail. The well-known polymerization method can be used as a method for manufacturing the above-mentioned polymers For example, a block polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, etc. Among them, a solution polymerization method using a base catalyst is the best method.

通常，常用在聚合乙嫌單量體的基觸媒均可做為本發 明的基觸媒之用。具有代表性者，即有，2,2’一偶氮雙異 丁轉，2,2·—偶氣雙（2,4-二甲基戊續）等偶氮系化合物 ;苯醜過氣化物（Benzoy 1 peroxide)，二一特丁基過氣化物 (di-te「t-Butylper，oxide)，特-丁基過辛酸鹽（^61^-Buty 1 peroetoate),特(.第三級）—丁基過氣（化）_2-乙基己 酸鹽（te「t_Buty 1 peroxy —2_ethy 1 Hexanoate)善過親iYb物J -62 - 表紙張尺度適用中國固家榡準（CNS > A4#見格（2iOX297公釐） {诗先閲讀背面之注意事項再填寫本頁) 4 604 89 A7 B7_ 五、發明説明（） 糸化合物，通常均對100重量份的單體使用0.2〜10重量份 的上列基觸媒，卻在0.5〜5重畺份的範圍內來使用為宜。 (請先W讀背面之注意事項再填寫本頁) 又*應由所使用的單體及基聚合性高分子量體的種類來選 擇適當的溶劑，Μ供使用。 完成聚合反應後，可Μ將含有反懕性基聚合體的原有 溶液直接使用與碳黑相反應，或以除去溶媒後的聚合體與 碳黑進行反應。 在本發明上製造可使用的接枝型聚合體還有其他方法 ，即如，先使對碳黑能起反應的含有反應性基化合物與含 有能起反懕基的鍵段（Α)與能起反應成為趟段（Β)接枝化的 前驅聚合體相反應Μ引進該反應性基於該前驅聚合艘的方 法。 上列化合物有如對於碳黑在其分子内含有二個Μ上的 所述一種反應性基的化合物，對於碳黑在其分子内含有所 述二種Μ上反應基的化合物，及對於碳黑在其分子內含有 所述一種以反應基和含有所述反應基Κ外的功能基化合物 〇 但*上列功能基即應為環氧基、硫環氧基、氮丙D定基 、噁唑基及不牖於噁唑基的化合物•它能與所述前驅 聚合體的反應性基起反應的化合物。前驅聚合賭的能起反 應的基有如異鎮鹽基、氨基、羧基、羥基及乙烯基等。 又，製造塊型複合體的方法，有如陰雛子活化聚合法 、陽離子活化聚合法、鍵轉移劑法（inigertor methodchain transfer' agent method)等已知的方法*再Μ其他方法來 -63 - 本紙張尺度適用中國國家樣準（CN'S )八4規格（210X297公釐） 4 60 4 89 A7 ____B7_ 五、發明説明（） 說，即有以基聚合鏈段（A)或鰱段（B)單體時（在本發明上 因為鏈段（A)會引進反應性基而以鏈段（B)為宜）*使硫赶 碳酸，或2-乙酿硫代乙统酸酯（2-Acetylthoiethylthiol) 、10-乙醜癸洗酸酿（10-Acety lthiodeeanethiol)等的分 子内含有硫赶基及酸酯的化合物共存而行聚合反應•用 氬氧化她或截等酴類來處理所得聚合體，使其成為在片尾 端含有硫赶基的聚合體，再在有這種聚合體之下，使他方 的鍵段的單虽體成分加以基聚合的已知方法。 因此•欲得有關本發明的塊共聚合體者，即可適宜的 加K變更如上列眾所周知T的方法•如同製造所述接枝共聚 合體，使用至少含有部份如所述反應性基的聚合性單董體 (a)做為鏈段（A)的聚合性單霣體，在聚合塊共聚合體時引 進反應性基於趟段（A),或在聚合塊共聚合體後，再將這種 反應性基引進謎段（Λ)即可。 為使能夠理解，將細說其一例如下，以陰離子活化法 為合成方法時，使4-乙嫌聚甲基鍵在四氬呼喃氮氣氣流中 與苯乙烯聚合後*再在低溫下與甲基異丁稀酸酯聚合來製 造A-B塊（苯-申基異丁酸酯）共聚合體，最後將鏈段（A)的 開始尾端上的乙烯基M3—氯過安息香酌變換為瑪氧化基而 在鍵段（A)引進能與碳黑起反應的反應性基。或，在四氳 哺氮氣氣流中，使4-乙輝苯甲基鋰與乙稀聚合Μ得継段 (Α)部後，將縮水甘油異丁婦酷加到反應糸中使鏈段（Α) 上結合含有反應性基的鍵段，再使其在低溫下與異丁烯ft矣 甲基聚合法亦可採用。 -64 - 本紙張尺度適用中國固家標率（CXS ) A4規格（2丨0X297公嫠） ^_I. — 4?------^ C請先閱讀背面之注意事項再填寫本頁) __B7 五、發明説明（） (請先閏讀背面之注意事項再填寫本頁) 以這種方法所得的接枝梨Μ及塊型聚合體的分子量雖 加Μ特別的限制•卻在考量對碳黑的接枝化效果或與碳黑 反應時的作業上，即Μ上列分子最在平均分子虽為1000〜 1000000範圍者為宜，卻Μ5000〜100000範園内的為最好。 又，在接枝型Μ及塊型聚合體的鏈段（Α)及鍵段（Β)等 分子虽亦不加以特別限制，或將由其構成鏈段的聚合鏈種 類有所左右，若由對碳黑接枝效果來說，鏈段（Α)的平均 分子量應在300〜100000範園*卻以5000〜50000的範圃者 為最好，又由將赋與碳黑分散性改質效果上來說，鍵段（ Β)的平均分子蠆應在500〜100000範圍内*最好Μ1000〜 50000範圍的為宜。又，做為接枝型Μ及塊型聚合體的键 段（Α)所有反應基的數董，亦未加以特別的限制，只要聚合 體每分子平均含有50〜1 *最好Μ含有20〜1個的程度為宜 〇 1.6含有不飽和二重结合的塊型Μ及接枝型聚合體 如上列所述為接枝於碳黑所使用的含有能與碳黑表面 的功能基起反應的反應基及含有不飽和二重結合的聚合體 ，是以含有能與碳黑表面功能基起反應的反應基的鍵段（Α )及，含有不飽和二重合結合的鏈段（Β)兩者的塊型Μ及接 枝型聚合體為宜。 在有關本發明的碳黑接枝聚合物的最後形態來說•具 有如上列的企求構造的塊型Μ及接枝型聚合體（因鍵段（Α )的反應性基與碳黑表面的功能基反應成為結合團）即可· 然而，在對碳黒進行接枝聚合體的製程上，不一定要其成 —65 - •本紙張尺度適用中國國家榡準（CNS ) Α4規格（210X29?公釐） . 4 6 0 4 89 a7 B7 五、發明説明（） 為如上列言及的企泶構造聚合體都可Μ。即，如將在下列 所述，κα)預先製成含有能與碳黑表面的功能基起反應 的反懕基鍵段（a)與含有不飽和二重結合的鏈段（Β)的塊型 Κ及接枝型聚合體後，再使其與碳黑進行接枝化的方法， 以及以（2)將含有能與碳黑表面的功能基起反應的反應性 基鍵段（Α)與有未含不飽和二重結合的趟段（Β)之塊型从及 接枝型前驅體聚合體接枝於碳黑後，在趟段（Β)引進不飽 和體二Μ結合的方法，均可用來製造有關本發明的碳黑上 。因為鏈段（Α)含有的反應基種類，會有在較高溫而時間較 長的條件下，才能促使與碳黑表面的功能基完成反應者， 在這種情瑕時，若先使鍵段（Β)會有不飽和二重結合，即可 能在進行這種接枝化當中失去鏈段（Β)所含有的不飽和二 重結合的情形甚高。在這種情形時，即應採用後者（2)的 方法為宜。 又，在下列說明中，為使易於理解本發明，Μ前列（1 )的方法為主要製造法時，即，將在鏈段（Β)引進不飽和二 軎結合等企求構造的塊型Μ及接枝型聚合體接枝於碳黑形 式為其中心來加以說明*卻由於接枝化與引進不飽和二重 結合的工程或會有出入前後的情形，而除此Μ外，將可理 解在（1)的方法時與在（2)的方法上均有其共同的點了。 如在所述1.5節所述，塊型Μ及接枝型聚合體·均能含 有各種化合物，又，圖3 (a)〜（f )是表示有關本形態的各 種塊型Μ及接枝型聚合體的構造例，圖中的X表示反應性 基，而Υ即表示不飽和二結合。 _ 66 - 本ϋ尺度適用中國圉家橾準（CNS ) Αβΐ格（210Χ 297公H ' " 和衣 . 訂------姥 (請先閲讀背面之注意事項再填寫本頁) 4 6 Ο 4 89 Β7 五、發明説明（） 至於有關塊型Μ及接枝型聚合體者*相關於含在鏈段 (Α)的反應性基及鍵段（Α)和鍵段（Β)等各種骨格構造的選 取Μ及配對方法*是如同所述1.5節所述，即在此從略。 然而，在這種瑕態的塊型Μ及接枝型聚合體上，趟段 (Β)就必須在其局部含有不飽和二重結合。瑄種不飽和二 重結合亦可使存在於主鏈中的形態，若由有關本發明的合 成塊型以及接枝型聚合體面上視者，使存在於與鏈段（Β) 主_相結合的側鐽的形態較為適宜。 欲製造這種含有反應性基的鏈段（Α)及有含不飽和二 重結合鍵的鍵段（Β)二者都有的塊型以及接枝型聚合體時 •基本上如同於所述1.5節所述，在此將略去其共同點的 說明。 欲製造有關這種形態的接枝共聚合體者，即如同在所 述1.5節所述，Μ在如前述基聚合性高分子量體（b)存在下 ，將如前述在其分子内含有對碳黑能起反應的反應性基聚 合性單最性（a)與應其需要而加入含有能形成鏈段ίΑ)赞格 構造的聚合性單量體（C)進行聚合，而得由含有對碳黑有反 應性基的鍵段（Α)及鏈段（Β)的主骨格構造所形成為前驅體 的接枝型聚合體。 然後*再在鐽段（Β)的主構造部所設定活化性點上的 反應性基及在其分子內含有不飽和二重結合的化合物（d) 與該當前驅反應，而使鐽段（B)引進含有不飽和二重结合 的側鍵以及延長鍵即可。 又，形成縫段（B)主鏈成分的基聚合性高分子量體（b) -67 - 本纸張尺度適用中國國家樣準（CKS ) A4^格（210X297公釐） ， i I ! n n I» ϋ 1* n I Ml I ^ 貧 (锖先閱讀背面之注意事項再填寫本頁) A7 B7 4 604 8 五、發明説明（） 應設計成為含有將茌後缅製程上引逍不飽和二重結合M及 延長鏈的活化性點（功能基）的形態。 設在所述前驅體聚合體的鏈段（Β)主骨格構造上的活 化性點（功能基）有，只要是觴於對鏈段（Α)的反應性基 的活性比對碳黑的表面功能基低的*即不加Μ特別限制， 任何種類的均可使用。更具體的說，如上列鏈段（Α)含有 的反應性基有*將環氣基、硫環氣基、氣丙隨基及頓哩0抹 基等與碳黑表面的幾基相反應而使其進行接枝化的形式時 ，即趟段（Β)的功能基可以是駿基以外的任何基，如酵性 以及酿性經基、氣基、亞氣基、硫赶基、鞋院酵基及異氰 酸基等，其中Μ醇性以及齢性經基為最宜。又，在所述基 聚合性高分子量體的說明時，列為宜於使用的構造式中· 雖尚未被具體的例示鼷於這種功能性基者，如使用在聚合 此等基聚合性高分子量體的部份單里體上含有這種功能基 ，若加以利用時，即易成為所企求的構造單體，是明白的 事實了。 一方，Μ這種對鏈段（Β)含有的功能基反應性基和在其 分子内含有不飽和二重结合的化合物（d),雖未加以特別的 限制，卻以在其片尾端有不飽和二重結合而在另一尾端有 能與鏈段（B)的活化性點（功能基）起反應性的反應性基 又兩尾端的反應性互異的化合物（雜功能-heterof unct iona 1 -化合物）為宜：又，所述聚合性單量艘（a)雖為同樣的雜 功能化合物，化合物（d)卻應含有多少和所述聚合性單虽體 (a)不同的他棰反應性基。 -68 本纸伕尺度適用中國國家橾準（CNS )A4规格（210X297公釐） ^----_--iT------^ (請先閏讀背面之注意事項再填寫本頁) h :P t 4 SO 4 89 a? __B7_ 五、發明説明（） (請先W讀背面之注意事項再填寫本頁) Μ化合物（d)含有的反應性基來說，如靥於鍵段（B)的 活化性點（功能基）和反應性者，均未加以特別的限制， 卻以異頻:酸基為宜。以使用含有異氰酸基的化备物為其反 應性基時，能做為所述鏈段（B)的功能基的，即有酵性K及 酿性的經基、観基、亞鎮基、硫赶基、鞋燒酵基等，而旦 ，由於選取其適當的條件，即能使這種鍵段（B)的功能基 與引進於鍵段（A)的環氧基、硫環氧基、氮两陡基及嗯哩 基等反應性基起反應*及不使該當異氰酸基與引進於鍵 段（A)的反應性基起反應，而易使鏈段（B)的功能基與異氰 基相反應而結合，即可在趟段（B)引進化合物（d)中的不飽 和二重結合了。尤其在鏈段（B)的功能基為醇性Μ及酿性 的羥基時，即將在與異氰酸基之間起優越的求核反應，而 形成尿燒結合是最好不過的。 或為在其一片尾端有異氰酸基而有不飽和二重結合在 其另一尾端的反應基化合物（d)的最適當含有異氰酸基不 飽和化合物（dl)有，與（甲基）丙烯酸'異氰的醋、異氰酸院 基（甲基）两烯酸酯及翔院基（甲基）丙嫌酸酷等含有經基（ 甲基）两蹄酸酯及聚異氰酸酯化合物所形成的局部反應物， 使含有（甲基）河烯基留存的多元酵與聚異氰酸化合物反應 所得的異氰酸薬尾端有尿院聚合物等，但，以其中含有下 示構造式的（甲基）两鋪基異氰酸_、異氰酸烧基(甲基）两 締酸酯為宜。 -69 - 本紙乐尺度適用中國國家橾準（CNS ) A4規格（2丨0X297公袭） A7 B7 604 89 五、發明説明（） R1 CH2 C —C —N C === 〇 0 (但，式中的Ri為Η原子或甲基） Ε1 CH2 = C —C —〇 — R2 —N-=C = 〇 Ο (但，式中的R丨為Η原子或甲基，Ri為C原子數1〜10亞烴-Alky lene —基 ΰ ) ---------^-------IT------辞 (請先閔讀背面之注意事項再填寫本頁) R1 ch2 ch3In general, the base catalysts commonly used in polymerizing the monomers can be used as the base catalyst of the present invention. The representative ones include azo compounds such as 2,2'-azobisisobutadiene, 2,2 · —azobis (2,4-dimethylpentan), and benzene overgassing. (Benzoy 1 peroxide), di-te "t-Butylper, oxide", tert-butyl peroctoate (^ 61 ^ -Buty 1 peroetoate), special (. Third level) —Butyl over-gas (chemical) _2-ethylhexanoate (te 「Buty 1 peroxy —2_ethy 1 Hexanoate) Good for iYb J-62-The paper size is applicable to China Gujia Standard (CNS > A4 # See the grid (2iOX297 mm) {Read the notes on the back of the poem before filling out this page) 4 604 89 A7 B7_ V. Description of the invention () For hydrazone compounds, 0.2 to 10 parts by weight of 100 parts by weight of monomers are usually used. The base catalysts listed above should be used within the range of 0.5 to 5 parts by weight. (Please read the precautions on the back before filling this page.) Also, the monomers and bases used should be highly polymerizable. Select the appropriate solvent for the type of molecular weight body and use it for the M. After the polymerization reaction is completed, the original solution containing the polymer with a reactive group can be directly used to react with the carbon black phase, or divided by The solvent-soluble polymer reacts with carbon black. There are other methods for producing a graftable polymer that can be used in the present invention. For example, first, a reactive group-containing compound capable of reacting with carbon black and The anti-fluorenyl bond segment (A) reacts with a precursor polymer that can be grafted into a reaction segment (B). The introduction of this reactivity is based on the precursor polymerization method. The compounds listed above are the same as those for carbon black. A compound containing the one reactive group on two M in the molecule, a compound containing the two reactive groups on M in the molecule for carbon black, and a compound containing the one reactive group in the molecule for carbon black. And functional compounds containing functional groups other than the reactive group K. However, the functional groups listed above should be epoxy, thioepoxy, aziridinyl, oxazolyl, and compounds not less than oxazolyl. A compound capable of reacting with a reactive group of the precursor polymer. The reactive groups of the precursor polymer include, for example, an isobasic salt group, an amino group, a carboxyl group, a hydroxyl group, a vinyl group, and the like. In addition, a block compound is produced. Method, like a young chick Polymerization method, cationic activation polymerization method, inigertor method chain transfer 'agent method, and other known methods * and other methods to -63-This paper size applies to China National Standard (CN'S) 8 4 specifications ( 210X297 mm) 4 60 4 89 A7 ____B7_ V. Description of the invention () It is said that when there is a monomer (A) or fluorene (B) monomer based on the polymerization (in the present invention because the segment (A) will be introduced The reactive group is preferably the segment (B)) * to drive sulfur to carbonic acid, or 2-Acetylthoiethylthiol, 10-Acety lthiodeeanethiol And other compounds containing thiol and acid esters in the molecule coexist for polymerization reaction. • The resulting polymer is treated with argon to oxidize her or ammonium to make it a polymer containing thiol at the end of the film. There is a known method for radically polymerizing a monomer component of another bond segment under such a polymer. Therefore, if you want to obtain the block copolymer of the present invention, you can add K as appropriate to change the well-known method of T as listed above. As in the production of the graft copolymer, use the polymerizability that contains at least part of the reactive group as described. Monomer (a) is used as the polymerizable monomer in segment (A). When the block copolymer is polymerized, the reactivity is introduced based on the segment (A), or after the block copolymer is polymerized, the reactivity is then changed. Just introduce the mystery section (Λ). In order to make it easier to understand, one example will be described below. When the anion activation method is used as the synthesis method, the 4-ethylanimine polymethyl bond is polymerized with styrene in a flow of nitrogen gas of argon, and then reacted with formazan at low temperature. Isobutyrate was polymerized to make AB block (benzene-shenyl isobutyrate) copolymer, and finally the vinyl M3-chloroperbenzoate at the beginning and end of the segment (A) was converted into a moxido group as appropriate. In the bond (A), a reactive group capable of reacting with carbon black is introduced. Or, in a nitrogen-feeding nitrogen gas stream, 4-ethylidenelithium and ethylene were polymerized to obtain a segment (A), and then glycidol isobutyramine was added to the reaction to make the segment (Α ) Can also be used to bond reactive segments containing reactive groups, and then polymerized with isobutylene ft 矣 methyl at low temperature. -64-This paper size is applicable to China's solid standard (CXS) A4 specification (2 丨 0X297) 嫠 ^ _I. — 4? ------ ^ C Please read the precautions on the back before filling this page) __B7 V. Description of the invention () (Please read the precautions on the reverse side before filling out this page) The molecular weights of grafted pear M and block polymer obtained by this method are subject to special restrictions on M. However, carbon is being considered. The effect of black grafting or the reaction with carbon black, that is, the molecules listed in M are most preferably in the range of 1,000 to 1,000,000, but the ones in M5000 to 100,000 are the best. In addition, although the molecules such as the segment (A) and the bond (B) of the graft type M and the block polymer are not particularly limited, or the type of the polymer chain constituting the segment is controlled, In terms of the carbon black grafting effect, the average molecular weight of the segment (Α) should be in the range of 300 ~ 100,000 Fan Yuan *, but the Fan Yuan in the range of 5000 ~ 50,000 is the best. In other words, the average molecular weight of the bond segment (B) should be in the range of 500 to 100,000 * preferably in the range of M1000 to 50,000. In addition, as the number of all reactive groups in the bond (A) of the graft type M and the block polymer, there is no particular limitation, as long as the polymer contains an average of 50 to 1 per molecule * It is preferable that M contains 20 to It is preferable to have a degree of 1.6. The block type M and the graft polymer containing unsaturated double bonds are grafted to carbon black as described above. They contain a reaction capable of reacting with functional groups on the surface of carbon black. Group and polymer containing unsaturated double bond are both a bond segment (A) containing a reactive group capable of reacting with a carbon black surface functional group and a segment (B) containing unsaturated double bond Mass M and graft polymers are suitable. Regarding the final form of the carbon black graft polymer of the present invention, it has the functions of a block type M and a graft type polymer (such as the reactive group of the bond segment (A) and the surface of the carbon black surface) having a structure as described above. Radical reaction becomes a binding group). However, in the process of grafting polymer to carbon fluorene, it is not necessary to make it -65-• This paper size is applicable to China National Standard (CNS) A4 specification (210X29? (%). 4 6 0 4 89 a7 B7 V. Description of the invention () It is acceptable to construct the polymer for the enterprise structure as mentioned above. That is, as will be described below, κα) is preliminarily formed into a block type containing an anti-fluorenyl bond segment (a) capable of reacting with a functional group on the surface of carbon black and an unsaturated double bond segment (B). A method of grafting K and a graft type polymer with carbon black, and (2) a reactive group bond (A) containing a reactive group capable of reacting with a functional group on the surface of carbon black, and After the block-type slave and graft type precursor polymer without unsaturated double bond (B) is grafted to carbon black, the method of introducing unsaturated two-M bond into the step (B) can be used. To make the carbon black related to the present invention. Because the type of the reactive group contained in the segment (Α) will be able to promote the completion of the reaction with the functional group on the carbon black surface under the condition of higher temperature and longer time, in this case, if the bond segment is first made (B) There is an unsaturated double bond, that is, it is highly possible that the unsaturated double bond contained in the segment (B) may be lost during such grafting. In this case, the latter method (2) should be adopted. In addition, in the following description, in order to make the present invention easier to understand, when the method of the forefront of M is the main manufacturing method, that is, a block type M and a structure that seeks to construct structures such as unsaturated difluoride bonds are introduced into the segment (B). The graft type polymer is grafted on the carbon black form as its center to explain. * However, due to the engineering of grafting and the introduction of unsaturated double bonds, there may be inconsistencies and inconsistencies. In addition to this, it will be understood that The method of (1) has something in common with the method of (2). As described in Section 1.5, both the block-type M and the graft-type polymer can contain various compounds, and FIGS. 3 (a) to (f) show various block-type M and graft-type related to this embodiment. In the structure example of the polymer, X in the figure represents a reactive group, and Υ represents an unsaturated di-bond. _ 66-This standard is applicable to China National Standards (CNS) Αβ standard (210 × 297 male H '" Japanese clothes). Order ------ 姥 (Please read the precautions on the back before filling this page) 4 6 Ο 4 89 Β7 V. Description of the invention () As for the block type M and the graft type polymer *, it is related to the reactive group contained in the segment (A), the bond segment (A) and the bond segment (B), etc. The selection of various bone structures and the matching method * are as described in section 1.5, which is omitted here. However, in this defective block type M and graft type polymer, the segment (B) is It must contain unsaturated double bonds in its part. This kind of unsaturated double bonds can also make it exist in the main chain. If the synthetic block type and graft type polymer of the present invention are viewed from the surface, The form of the side 鐽 which is combined with the main segment of the segment (B) is more suitable. Both the segment (A) containing a reactive group and the segment (B) containing an unsaturated double bond are desired. When both the block type and the graft type polymer are used, basically the same as described in section 1.5, and the description of the common points will be omitted here. In this form of the graft copolymer, as described in Section 1.5, in the presence of the polymerizable high-molecular-weight body (b) as described above, M will react with carbon black in the molecule as described above. (A) and polymerizable monomers (C) containing a zigzag structure capable of forming a segment ίΑ) are polymerized according to their needs, and the reactive group containing carbon black is reactive The main bone structure of the bond segment (A) and the chain segment (B) of the base is formed as a graft-type polymer of a precursor. Then, the reactive group at the activation point set in the main structural part of the hydrazone segment (B) and the compound (d) containing an unsaturated double bond in its molecule react with the current drive to make the hydrazone segment (B ) Introduce side bonds and extension bonds containing unsaturated double bonds. In addition, the base polymerizable high molecular weight body (b) forming the main chain component of the seam section (B) -67-This paper size is applicable to China National Standard (CKS) A4 ^ (210X297 mm), i I! Nn I »Ϋ 1 * n I Ml I ^ Poverty (锖 Please read the notes on the back before filling in this page) A7 B7 4 604 8 V. Description of the invention () Should be designed to contain the unsaturated double in the process A morphology that binds to the activation site (functional group) of M and the extension chain. The activation point (functional group) on the main bone structure of the segment (B) of the precursor polymer is provided as long as it is active on the reactive group of the segment (A) than on the surface of carbon black * With a low functional group is not particularly limited, and any kind can be used. More specifically, the reactive groups contained in the above-mentioned segment (A) are: * Reacting a ring gas group, a sulfur ring gas group, a gas propionate group, and a molybdenum group with several groups on the surface of carbon black. When it is grafted, the functional group of the segment (B) can be any base other than Junji, such as fermenting and fermenting meridian, air-based, sub-air-based, sulfur-based, and shoe yard. Among the enzyme group and isocyanate group, M alcoholic group and alkaline group are most suitable. In the description of the polymerizable high-molecular weight group, it is listed as a structural formula suitable for use. · Although it has not been specifically exemplified by such functional groups, it is highly polymerizable if used in polymerization of such groups. It is clear that some molecular weight monoliths contain such functional groups, and if used, they will easily become the desired structural monomer. On the one hand, the compound (d), which has a functional group reactive group contained in the segment (B) and an unsaturated double bond in its molecule, is not specifically limited, but it has Heterofunct iona compound which has a saturated double bond and has a reactive group reactive with the activation point (functional group) of the segment (B) at the other end and mutually different reactive groups at the two ends 1-compound) is suitable: In addition, although the polymerizable monolithic vessel (a) is the same heterofunctional compound, the compound (d) should contain how much other polymers than the polymerizable monomer (a) Reactive group. -68 The size of this paper is applicable to China National Standard (CNS) A4 (210X297 mm) ^ ----_-- iT ------ ^ (Please read the precautions on the back before filling this page ) h: P t 4 SO 4 89 a? __B7_ V. Description of the invention () (Please read the precautions on the back before filling out this page) Μ Compound (d) For reactive groups, such as 靥 on the bond (B) The activation point (functional group) and the reactivity are not particularly limited, but a different frequency: acid group is preferred. When an isocyanate-containing chemical compound is used as a reactive group, it can be used as the functional group of the segment (B), that is, fermented K and fermentable warp, fluorene, and Base, thiophene base, shoe base, etc., and once the proper conditions are selected, the functional group of this bond segment (B) can be made into the epoxy group and sulfur ring introduced in the bond segment (A). Reactive groups such as oxo, nitrogen, and aryl groups react * and do not cause the isocyanate group to react with the reactive group introduced in the bond segment (A), but easily make the segment (B) The functional group reacts with the isocyano phase to combine, and the unsaturated double bond in the compound (d) can be introduced in section (B). Especially when the functional group of the segment (B) is an alcoholic M and a fermentable hydroxyl group, an excellent nuclear reaction with an isocyanate group is about to occur, and it is best to form a urinary-fired bond. Or the most suitable isocyanate-containing unsaturated compound (dl) is a reactive group compound (d) which has an isocyanate group at one end and an unsaturated double bond at the other end. Base) Acrylic acid 'isocyanate, isocyanate base (meth) dienoate, Xiangyuan base (meth) propanoic acid, etc. Contains methacrylic acid and polyisocyanate compounds The local reactant formed is a urinary polymer and the like at the tail end of the isocyanuric acid isocyanate obtained by reacting the polyenzyme containing the (meth) hexylenyl group with a polyisocyanate. However, the structure includes the structure shown below. (Methyl) bis (isomethyl) isocyanate and isocyanato (methyl) associate are preferred. -69-This paper scale is applicable to China National Standards (CNS) A4 specifications (2 丨 0X297 public attack) A7 B7 604 89 V. Description of the invention () R1 CH2 C —C —NC === 〇0 (However, in the formula Ri is a fluorene atom or a methyl group) Ε1 CH2 = C —C —〇— R2 —N- = C = 〇〇 (However, in the formula, R 丨 is a fluorene atom or a methyl group, and Ri is the number of C atoms 1 to 10 Alkylene-Alky lene---------- ^ ------- IT ------ (Please read the notes on the back before filling this page) R1 ch2 ch3

H C —C — 0 ~ R2 0 0 -70 - 本紙張尺度適用中國國家橾準（CNS ) A4规格（210X297公釐） ά60 Δ S9 Α7 Β7 五、發明説明（） (但，式中的R丨為Η原子或甲基，R2為C原子數1〜10的亞烴 基.:) Μ含有如上列異氰酸0旨的不飽和化合物（dl)為化合物 (cl)與往鏈段（B)含有當做功能基用的酵性Μ及酿性經基的 前驅體聚合體栢反愿，為成做前驅體聚合體的鏈段（Β)上 引進不飽和二重結合時，化合物（d)的加入量應Μ前驅聚合 體（Β)所有的羥基一當量對異氣酸基之比在0,1〜1當量的 範圍内，最ίί?將其能成為0.3〜1.0當量之比為宜。即*對 經基一當量在異氟酸基未滿0.01當量的比例時，就無法引 進其有效量的不飽和二重合於鏈段（Β)中，一方，若對羥基 —當量加入超過一當量的異氰酸基的比例時，將使所得的 精製尿烷再與異螟酸基反應而產生尿基甲酸酯Μ致於得不 到企班的構造物，又會使未反應的含有異戴酸基不飽和化 合物殘留在其中，均為不適宜。又就其反應條件來說，因 在較高溫度時，將使含有異氤酸基不飽和化合物的不飽和 二重结合起重合反應而膠化，或使異氰酸基與前驅體聚合 體的雛段（Α)中的璃氧基等起反應而發生障礙，應以在20 〜100°C使其反應1〜5小時的條件下進行為宜。又，在及應 時*為控制如上列所述的重合反應起見，可以使用重合防 止劑。又，茌不影響後續化合物的物性時，亦可使用觸媒 來參與此等反愁，若接枝化反應有傾向高溫長時間而發生 問題者*即可使用通常使用的尿烷化觸媒來解決此等問題 Ο 欲製成有關此種形態的接枝型聚合體尚有他法有，雖 本紙伕尺度適用中.國國家標準{ CNS > A4規格（210X297公釐） ---------夢-- (請先閱讀背面之注意事項再填寫本頁) 訂 Α7 Β7 五、發明説明（） 略如同所述1.5節述反的方法，如含有能對碳黑起反應的反 應性基的化合物（e)與含有能與該化合物起反應的基的鏈 段（A)且能在此趟段（A)接枝鏈段（B)的第一前驅體聚合體 相反應而將該反應性基引進於該第一前驅體聚合體中，使 其成為如上列的最終前驅體（含有對碳黑能起反應的反懕 性基鏈段（A)及由鏈段（B)的主構造部所成的接枝型前驅體 聚合體），然後以如同上列所述在鍵段（B)引進有不飽和 二重結合的側鍵Μ及延長鏈的方法。 做為上列化合物（e)者，有如，含有在其分子内能對碳 黑起反應的一種反應性基二個以上的化合物，如所述含有 在其分子内能對碳黑起反應的二種Μ上反應基的化合物， 如所述含有對碳黑的一種以上反應性基及在其分子内含有 如所述反應基Μ外的功能基的化合物等。 但，上列功能基是指摄氧基、硫環氣基、氮丙陡及嗯 哩外的反應性基，且能與所述第一前驅體聚合體的鰱 段（A)具有能起反應的該當基相反應者。做為第一前驅聚 合體的鏈段（A)而能起反應的基，即懕有與如上列趟段（B) 的功能基不同種類的異縝酸基、氨基、羧基、羥基及乙烯 基等。 又，亦能在所述第第一前驅體聚合體上，預先對鏈段 (B)引進不飽和二重結合後，再在鏈段（A)引進能對碳黑起 反應的反應性基的方法〇 又，製造有關於本形態的塊型聚合體的方法，就有如 在所述1.5節述及眾所周知的方法，加以適宜的變更而使用 本紙伕尺度逋巧中國國家揉準（CNS ) A4規格（210 X 297公釐） ---------^-------'1T------M (請先閱讀背面之注意事項再填寫本頁) 4 60 4 89 A7 _B7_五、發明説明（） ，又在製造塊型共聚合體上對链段（B)引進不飽和二重結合 時，亦可用如同前記接枝共聚合體的製造方法。 Μ這種方法所得的接枝型K及塊型聚合體的分子最， 鏈段（Α)及鏈段（Β)的分子量，鍵段（Α)含有的反應性基數等 ，即如同在所述1.5節所述，雖未加以特別的限制，卻以如 同所述的範圍内為宜。 又，鏈段（Β)中的不飽和二重結合鏈數，亦未特別加Μ 限制，而以聚合體每一分子平均含有20〜1，好Μ10〜1為 宜。又，聚合體每一分子的二重結合數，即因應所得的碳 黑接枝聚合物配對的硬化性組成物等媒體間的關係（如， 感度、反射特性等）加Μ適宜決定。如，在後述的黑色光 硬化性組成物時，欲減少光硬化性單體的添加量者，可藉 由增加碳黑接枝聚合物的二重結合數Μ維持其慼度。 1.7含有翔基塊型Κ及接枝型聚合體 使用於製造如上列含有梭基接枝鰱的碳黑接枝聚合物 上，含有能與碳黑表面的功能基反應的反應性基及經基的 聚合體是》以有能與碳黑表面的功能基起反應的反應性基 的鏈段（Α)，及含有有和此鍵段（Α)不同結構的鏈段（Β)的 塊型以及接枝型聚合體為宜。又，在這棰塊型Μ及接枝型 聚合體上*徑基可存在於任何一種鏈段上，最好Μ存在雛 段者為為Γ。 如在所述1.5節所說，塊型Μ及接枝型聚合體，可為各 種化合物。又，圖4 (a)〜（f)為有關本彤態的各種塊型以 及接枝型聚合體的構造例，圖中的X表示反應性基，OH為 裝 „ ^訂 錄 (請先閏讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家榡準.（〇；5}八4規格（2丨0/297公釐） 4 6〇4 89 A7 B7 五、發明説明（） 經基 欲製造共有含有這種反應性基的鏈段（A)及和這種鏈 段（A)有不同結構的鏈段（B)而又有經基的塊型以及接枝型 聚合體的方法，在基本上是與所述1.5節的相同，有關其共 同點，即在此從略之。 又，有關本形態的塊型以及接枝型聚合體上，含於趟 段（A)中的反應性基，或相關選擇以及其組合鍵段（A)鍵段 (B)的各種結構等方法，大略與所述1.5節所述相同，將略 去說明，在這種形態時，趟段（A)及鍵段（B)的主趟構造雖 然可以屬於大略相同的形態，卻只Μ調整含在鍵段（B)(必 要時，可使其含在鏈段（Α)上）的經基數，就能充分的對雙 方的鏈段目的媒體Μ及對碳黑的親和性產生差異。 欲製成這種形態的接枝型共聚合體時，即可依所述1.5 節所述*如，在有形成鏈段（Β)的主鏈成分基重合性高分 子量體（b)下，使對碳黑能起反應而茌其分子内含有反應性 的聚合性單量體（a)與其他因需要而加入為形成鍵段（A)構 造的聚合性單體（c)進行重合即可。 能構成鏈段（B)成分的重合性高分子量體（b)有，含有 , 羥基的企求重合鏈，如聚（甲基）丙烯酸羥烷基脂糸構造， f (甲-基）丙烯酸烷基脂一（甲基）丙烯酸羥烷基脂共聚合體糸 桌 ί Ψ t 本紙伕尺度適用中國國家橾準{ CNS > A4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁) 裝· 訂 構造等的重合鏈Η尾端上有反應性基的均屬之c 例如，欲把鏈段（B)製成有（甲基）丙烯酸烷脂-(甲基） 丙烯酸羥燒.基脂共重合系構造時，所需的基重合性高分子 量體（b)有，如在下列所示的為最適合。 -74 - 60 4 89 A7 B7 五、發明説明（ R1HC —C — 0 ~ R2 0 0 -70-This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ά60 Δ S9 Α7 Β7 5. Description of the invention () (However, R 丨 in the formula is A fluorene atom or a methyl group, R2 is an alkylene group having 1 to 10 C atoms. :) Μ contains an unsaturated compound (dl) as described in the above isocyanate group (dl) as the compound (cl) and the segment (B) as the The precursor polymer of the functional group for fermentative M and the fermentative base of the fermented base is reluctant to introduce an unsaturated double bond into the segment (B) of the precursor polymer, and the amount of the compound (d) is added. The ratio of all the hydroxyl equivalents of the precursor polymer (B) to the isogenic acid group is in the range of 0,1 to 1 equivalent. It is most appropriate to make it into a ratio of 0.3 to 1.0 equivalent. That is, when the ratio of one equivalent of meridian group is less than 0.01 equivalent of isofluoric acid group, it is not possible to introduce an effective amount of unsaturated doubles into the segment (B). On one side, if more than one equivalent is added to hydroxyl group-equivalent When the ratio of the isocyanate group is 5%, the resulting purified urethane is reacted with an isophosphonic acid group again to generate a urethane formate M, which makes it impossible to obtain a structure that is unreliable, and causes unreacted Unsaturated unsaturated compounds remain in them, which are not suitable. As far as its reaction conditions are concerned, at higher temperatures, an unsaturated double bond containing an isocyanic acid group is caused to undergo a gelation reaction to cause gelation, or an isocyanate group and a precursor polymer It is preferable that the reaction of the hydroxyl groups in the young stage (A) and the like cause troubles, and the reaction should be performed at 20 to 100 ° C for 1 to 5 hours. In addition, in order to control the coincidence reaction as described above, a coincidence preventing agent may be used. In addition, when the physical properties of the subsequent compounds are not affected, catalysts can also be used to participate in these anxieties. If the grafting reaction tends to be high temperature and prolonged, and problems occur *, the commonly used urethane catalysts can be used. Solve these problems 〇 There are other ways to make the graft polymer in this form, although the paper size is applicable. National Standards {CNS > A4 Specifications (210X297 mm) ----- ---- Dream-(Please read the notes on the back before filling this page) Order A7 B7 V. Description of the invention () It is similar to the method described in section 1.5, if it contains a reaction that can react to carbon black The compound (e) having a basic group reacts with the first precursor polymer containing a segment (A) containing a group capable of reacting with the compound and capable of grafting the segment (B) at this segment (A) to react The reactive group is introduced into the first precursor polymer, making it the final precursor as listed above (containing the reactive group segment (A) capable of reacting with carbon black and the Grafted precursor polymer formed by the main structural part), and then introduced into the key segment (B) as described above The method and the extension side keys Μ bonded double strand. As the compound (e) listed above, for example, there are two or more compounds containing one reactive group capable of reacting with carbon black in its molecule, and two containing two reactive groups capable of reacting with carbon black in its molecule as described. The compound of the reactive group on the species M is, for example, a compound containing one or more reactive groups for carbon black, and a compound containing a functional group other than the reactive group M as described above. However, the above-mentioned functional groups refer to reactive groups other than photooxy, thionyl, aziridine, and nitrogen, and are capable of reacting with the fluorene segment (A) of the first precursor polymer. The deserved base phase responder. As the group (A) of the first precursor polymer, the group can react, that is, it is different from the functional group of the above-mentioned segment (B). It is different from the isoacid group, amino group, carboxyl group, hydroxyl group and vinyl group. Wait. In addition, it is also possible to introduce an unsaturated double bond to the segment (B) in the first precursor polymer, and then introduce a reactive group capable of reacting with carbon black into the segment (A). Method 〇 Also, the method for manufacturing the block polymer of this form is a well-known method as described in Section 1.5, and the paper is scaled to fit the Chinese National Standard (CNS) A4 standard with appropriate changes. (210 X 297 mm) --------- ^ ------- '1T ------ M (Please read the notes on the back before filling this page) 4 60 4 89 A7 _B7_ V. Description of the invention () When introducing unsaturated double bond to the segment (B) in the production of block copolymers, the method of making graft copolymers as described above can also be used. The molecular weight of the grafted K and bulk polymer obtained by this method is the molecular weight of the segment (A) and the segment (B), and the number of reactive groups contained in the bond (A), as described in the above. As described in Section 1.5, although not particularly limited, it is preferable to be in the range as described. In addition, the number of unsaturated double-bonded chains in the segment (B) is not particularly limited by M, but the average molecular weight of the polymer is 20 to 1, preferably M 10 to 1. In addition, the number of double bonds per molecule of the polymer, that is, the relationship between the media (such as sensitivity, reflection characteristics, etc.) such as the sclerosing composition of the obtained carbon black graft polymer paired with the appropriate combination plus M is appropriately determined. For example, in the case of a black photocurable composition described later, if the amount of the photocurable monomer is to be reduced, the degree of double binding of the carbon black graft polymer can be increased to maintain the degree. 1.7 Contains Xiangji block type K and graft type polymers used in the manufacture of carbon black graft polymers containing fumarium grafted fluorene as listed above, containing reactive groups and warp groups that can react with functional groups on the surface of carbon black The polymer of "is a block (A) with a reactive group capable of reacting with a functional group on the surface of carbon black, and a block type containing a segment (B) having a structure different from that of the bond (A), and Graft polymers are preferred. In addition, in this block-type M and graft-type polymer, the * diameter group may exist on any kind of segment, and it is preferable that M exists in the young segment as Γ. As mentioned in section 1.5, the block type M and the graft type polymer may be various compounds. In addition, Fig. 4 (a) to (f) are examples of the structure of various bulk and graft polymers related to the present state. X in the figure represents a reactive group, and OH represents a device. Read the notes on the reverse side and fill in this page) This paper size is applicable to the Chinese national standard. (〇; 5) 8 4 specifications (2 丨 0/297 mm) 4 6〇 89 89 A7 B7 V. Description of the invention () A method for manufacturing a segment (A) containing the reactive group and a segment (B) having a different structure from the segment (A), and a method of mass-type and graft-type polymers It is basically the same as that described in Section 1.5, and its common points are omitted here. In addition, the block type and graft type polymer of this form are included in the section (A). Reactive groups, or related choices, and the various structures of their combined bond (A) and bond (B) are roughly the same as those described in section 1.5, and the description will be omitted. In this form, the segment ( Although the main trip structure of A) and key segment (B) can belong to almost the same form, only M is adjusted to be included in key segment (B) (if necessary, it can be included in chain segment (A)). By the base number, it is possible to make a difference between the target media M of both chain segments and the affinity for carbon black. If you want to make a graft copolymer of this form, you can follow the description in section 1.5 * In the presence of a high-molecular-weight body (b) having a main chain component group forming a segment (B), it can react with carbon black to contain a reactive polymerizable monomer (a) in the molecule and other The polymerizable monomer (c) which forms the structure for forming the bond segment (A) may be added and superposed if necessary. The superimposable high molecular weight body (b) which can constitute the component of the segment (B) is, and the hydroxyl group is required to be superposed Chain, such as poly (meth) acrylate hydroxyalkyl ester structure, f (methyl- acrylate) alkyl ester mono (meth) acrylate hydroxyalkyl ester copolymers 糸 本 t paper size is applicable to Chinese countries 橾Quasi {CNS > A4 size (210X297 mm) (please read the precautions on the back before filling out this page) binding and binding structures, etc., which have reactive groups on the ends of the chains. For example, if you want Segment (B) is made of (meth) acrylic acid alkyl ester- (meth) acrylic acid. When the system configuration, the required amount of the base body coincides polymer (b) has, as shown in the following as the most suitable in the -74 -. 60 4 89 A7 B7 V. invention will be described (R1

CH2 = C C R2 1 R4 C — 0 — X 1 1 -eCH2-C^CH2-C γ 0 C — 〇 丨 0 ~"···- Q 1 1 0 I 1 0 1 1 K3 I 1 R5 t OH (請先閲讀背面之注意事項再填寫本頁) (但，在式中的R/、Ri表示同一或各異的Η原子或甲基，h 為C原子1〜25的烯基，為C原子數1〜25的焼基，X為任 意的結合鏈，Υ為開始劑尾端或Η原子，η及m為同一或不同 的0〜500的整數）。 —方，做為往其分子内含有對碳黑能起反應的反應基 的重合性單量體（a)者，有如所述1*5節所述相同的聚合性 單量體，又欲使鏈段（A)具有如上列企求的结構時，做為因 應必要所能使用的重合性單虽體（c),亦可使用如同所述1.5 節所述大略相同的重合性單量體，若欲在鏈段（A)引進羥基 時，即可使如，丙烯酸經基甲酯、丙烯酸羥基乙酷、两烯 酸羥基丙酯、丙烯酸羥基2-乙基己酯、偏丙烯酸羥基甲酯 、偏丙烯酸羥基乙酯、偏丙烯酸羥基丙酯、偏丙烯酸羥基 2-乙基己酷等的丙烯酸或偏丙烯酸羥烷基酯糸單體；羥丙 烯醚、羥鵂丙烯醯等的單體；Μ其必要與如所述1.5節所 示的各種重合性單體適宜調配而使用。 -75 — 本紙張尺度適用中國國家樣準（CNS.) Α4規格（2丨OX29?公釐） 4 60 4 89 a7 B7 五、發明説明（） 在製造接枝型聚合體的其他方法，或製造塊型聚合體 的方法，在製造有關本形態的聚合體上，均可利用如所述 1.5所述的方?去。 由上法製成的塊型以及接枝型聚合體的分子虽，継段 (A)及鏈段（B)的分子量以及鏈段（A)所有的反應基數等相 關事項，卽如在所述1.5節所述，雖不加以特別的限制，卻 Μ在如同上列的範園為宜。 至於羥基的數量，即依酸酐處理後所得碳黑接枝聚合 物中的聚合體酸價來決定就可Μ。酸價雖随調配於碳黑接 枝聚合物的齡可溶粘著劑等的酸價而不同，卻Μ10Μ上為 宜。而以50Μ上較好.在100Μ上為最好。因為酸價在10以 下時，即不具其驗顯像性。 1.8製造含有不飽和二重結合的碳黒接枝聚合物 有關第1的發明的碳黑接枝聚合物是，侬所列1.3節 所述，使能與碳黑表面的功能基起反應的反應性基與含有 乙烯性不飽和二重結合的聚合體，加到碳黑中一起加熱混 合而製成，即在其接枝化的聚合體鏈中含育乙烯性不飽和 —重结合者。 其加熱混合條件為，50〜250°C，卻在100〜200°C的 溫度下，使其反應0.5〜10小時，最好以搜洋混合2〜5小時 。若溫度在未滿50°C，即接枝化無法完全而不適宜，一方 ，若超過250°C，即會使重合成分變質，亦不適宜。 又*亦可在適當的溶媒中，使其進行加熱混合作業。 由於這種在接枝化的碳黑與所述聚合體的綢配比例， -76 - 本紙伕尺度適用t國國家標率（CNS) A4現格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 ,tx 460489 A7 ________B7 五、發明説明（） 會被所使用的所述聚合體的種類，欲得製品的用途等來左 右，雖無法作一概的規定，卻Μ碳黑100重量份，加K所述 聚合體1〜1000重量份，最好以2〜500重量份的程度為宜。 即，若聚合體在未滿1重量份者，就會發生難於十分改善 碳黑的表面性狀之虞，一方，若超過1000重量份者，即會 增加结合在碳黑的聚合體童，不但不經濟，又損害到本來 所要求的碳黒特性之虡。 1.9製造含有羧基的碳黑接枝聚合物 有關於第2的發明的碳黑接枝聚合物是得自如所述1.4 節所述》使含有能與碳黑表面的功能基起反應的反應基Μ 及羥基的聚合體與碳黑一起加熱混合後·Μ酸酐處理所得 的反應混合物而製成在接枝趟中含有羧基為其特點。 1耷年尹矢漆辛句員工肖費合作社印" I -- n - I H - ! . _i^---------- 丁 • < (請先閱讀背面之注意事項再填寫本頁) 加熱混合的條件雖為40〜300 °C，最好在70〜250^0的 溫度下，加熱混合0.5〜10小時，而M2〜5小時為宜。若在 未滿40 °C的溫度，或不能使接枝化充分進行，又若在超過 300°C的溫度反應，或會使其聚合體變質，均屬不宜。又， 若使用含有翔基及如上列所述乙稀性不飽和二重結合二物 的反應性聚合體，如在所述1.3節及1，4節所述不飽和環氣 脂樹脂者，其加熱混合條件為50〜250TC,最好在100〜200 °C所限制的溫度範園内使其進行反應為宜。 又，這種加熱混合件業，亦可以在適當的溶媒使其進 行。 將能與碳黑表面的功能基起反應的反應基及羥基的聚 合體接枝於碳黑後所得碳黑接枝聚合物加以酸軒處理•由 本紙伕尺度適用t國國家標芈（CN'S ) A4現格（2丨0：?：297公釐） 4 6〇4 89 A7 ________B7 五、發明説明（） 被接枝化的聚合體中所含所述經基與酸酌1間的半酷化反應 來引進搜基於聚合體鏈中。 酸酐有苯二酸酌1、無水號拍酸、馬來肝、四葡:化gl太酸 酉干、3,6-橋甲擦四厘化私酸酐、六氣化私酸酐、甲四氫化 醎酸醉、甲基橋甲擦四鲺化酸軒、四溴酸軒、偏苯三 酸等的二鹽楚酸酐、脂肪族或芳香族四碳酸二無水物等的 四鹽基二無水物等。 酸酐的用量，即以對碳黑接枝化的聚合體所含羥基一 化學當虽為0.1〜1.1化學當量為宜，而在有稀釋劑或未有 稀釋劑併有或未有對苯二酚或氧等重合禁止劑的條件之下 使其在50〜130°C反應。在這種經基與酸酐的半酿化反應 時，可从使用在一般的文獻，如新實驗化學講座14，「有 機化合物的合成與反應」，由丸春股份公司在1977年12月 20曰發行，第1014頁上所記載的觸媒◊可用的觸媒有酸觸 媒、鹽基性觸媒及金靥無機鹽等。酸觸媒有硫酸P-甲苯磺 酸等或其併用糸的觸媒。鹽基觸媒有第三級胺，如三甲基 胺、三乙烯胺、N-五甲基乙烯三胺、Ν,Ν-二甲基卞胺、N· 卜二甲屎基胺、^『，1^1’-四甲基丙鄱二胺、卜甲基嗎 、Ν-乙基嗎_、Ν,Ν’-甲基啾咬、此啶、4-二甲氨基毗啶· 4-焦木吡σ定，1,8— 二環[5,4,0]-7--f«^(1.8-Diazabicyc 1〇 [5.4.0] -7-Undecene) (DBU.)等成其併用糸混 合物。金屬無機鹽有經、銷、紳、納、錫、鲜、紛等金屬 的氛化物或醋酸納等及其併用糸溫合物。 又，能使含有梭基的聚合體極安定的接枝在碳黑的他 本紙張尺度適用中囷國家標準（CN5 ) Α4規格（210 X 25>7公釐） ^------1T------^ (請先Μ讀背面之注意事項再填寫本頁) 4 6 0 4 89 A7 _B7 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 種方法*即有，將能與碳黑表面的反應性功能基起反應的 反應性基*亦就是以含有名為保護基加Μ保護後基的聚合 體，與碳黑反應使其接枝化後，將所得碳黑接枝聚合物加 Μ脫保護基處理來圼現搜基的方法。做為羧基的保護基有 許多種類，如可使用用在後述實施例的四氫化吡喃基。 1.10塊型Μ及接枝型聚合物接枝碳黑的製法 接下來，將就有關於第三的發明的碳黑接枝聚合物的 製法加Μ說明，雖可Μ所述1.8節的方法來使如所述1.5節 的進行對碳黑接枝塊型Μ及接枝型聚合體，而若欲得更為 優越的接枝效率者，即以如1 + 5節所述，將含有反應性基 的鏈段（Α)加以設計比另一鏈段（Β)對目的媒髁圼現低度親 和性，而使欲做為分散所得碳黑接枝聚合物的目的媒體或 和此媒體類似性狀的媒體所組成的分散媒體的存在之下進 行加熱混合為宜。即是，此分散媒體，只對該當聚合體的 鏈段（Β)圼高度的親和性及相溶性而對鍵段（Α)即圼低度的 親和性及相溶性。 因此*所用的媒體是由因應該當聚合體的鏈段（Α)及 鍵段（Β)的如何配對來做適當的選擇。 如聚合體的鏈段（Α)有聚苯乙烯糸構造而鏈段（Β)有聚 石圭氣烷構造時，即應用聚二甲基鞋氣烧，局部置換辛基的 聚二甲基硅氧烧，局部置換苯基的聚二甲基δ圭氧烷，氣硅 油等硅油為分散媒液。 又若聚合體的鏈段（Α)有聚班乙烯系構造而鏈段（Β)如 有聚甲基異丁締酸酷等的疏水性（甲基）丙烯糸構造者，即 本纸張尺度適用中.國囷家標準（CNS )· Α4規格（210Χ297公嫠） A7 4 0〇4 89' ____B7_ 五、發明説明（） 宜用甲基溶纖劑、乙基溶纖劑等的溶纖劑；醋酸甲脂、乙 酸乙脂、乙酸丁酯等脂類；丙嗣、丁國、甲基異丁酮等_ 類；Π各烧酮、Ν,Ν-二甲替甲醜胺、二甲亞等的非陽雛 子性極性溶劑為其分散媒液。 又若聚合體的鍵段（Α)有聚丙輝糸構造而鍵段（Β)有如 甲基異丁烯酸一羥甲基異丁嫌共聚合物等的親水性（甲基） 丙烯系構造者，即宜以水、水一酵混液、甲酵、乙S?等酵 類；甲基溶纖劑、乙基溶纖劑、丁基溶纖劑等脂類；丙酮 等酿I類；《^略燒酮，Ν,Ν-二甲替甲酿胺、二甲亞鄉筹為其 分散媒液。 又若聚合體的鏈段（Α)有聚丙烯糸構造而鏈段（Β)如有 聚烯化乙二醇糸構造時，g卩宜Κ水、水一酵混液、甲酵、 乙醇等的醇類；乙烯基乙二醇、二乙烯乙二醇等乙二醇類 、甘油等的多價醇類為其分散媒液。 在這等分散溶媒的存在之下〃使碳黑與所述聚合體進 行接枝化時，邐可加人不屬於該聚合體類的聚合物及重合 性單體等其他物質。 本接枝化是如在40〜3001C，最好在70〜2501C的溫度 下攬拌0.5〜10小時最好在2〜5小時操作為宜。反應溫度 未達40 T：者，或將無法進行其接枝化，g卩為不宜。又若超 過300ΐ〕，或將使其聚合體變質，亦不宜。 坟應的步驟為，將碳黑及聚合體，以及所述分散媒體 同入於反應裝置中，在加熱下混合即可。 在本接枝化的碳黑與所述聚合體的調配比，因應所使 _ 80 - 本紙張尺度通用中國國家揉準（CNS Μ4規格（2丨ΟΧ297公釐） 私衣----^---^1Τ------線 (請先閱讀背面之注意事項再填寫本頁) A7 4 S〇4 89 __B7 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 用的所述聚合體的種類，欲製成品的用途等差異而有所變 化，雖不能做大體的規定，卻以對碳黑100重最份調配所述 聚合體1〜1000重最份，最好Μ聚合體2〜500重量份的比為 宜。即*聚合體未達1重量份，或有難於十分的改質碳黑 表面性狀之虞，而他方，若超過1000重量份者，將成為過 多加入與碳黑結合的聚合體量，不但不經濟，又將失去本 來所要求的碳黑的特性之虡。 以這種方法所得的碳黑接枝聚合物具有各種物質，如 對於有機高分子、水、有機溶劑等圼現優起的分散性*大 體上又能提高其電氣絕緣性，由引進所述聚合體的趟段（Β) 而里現更多特性。如，聚合體的鏈段（Β)屬於聚硅焼酸糸 構造•即有儍秀的拒水性、雛型性、耐熱性、耐候性、柔 軟性及低丨占性等*或無低溫脆性等特性，又若是（甲基）丙 烯糸鏈構造者*由於引進各種（甲基）丙嫌酷單體成分而圼 現大幅度的親水性一疏水性，又若為聚稀化乙二醇鍵者， 即將賦與親水性、潤滑性、柔軟性及防止帶電等特性。 1.Π塊型以及接枝型聚接枝化碳黑的製法（其二） 在基本上，本法與所述1.10節的方法略為相似，卻如 所述1.5節所述，在製造接枝型Κ塊型聚合體時，將之設計 成為含有能與碳黒表面的的功能基起反應的反應性基的鏈 段（Α)比對目的媒體呈琨高度親和性的鏈段（Β)有對碳黑能 呈高度親和性的形態，亦能收到有高效率的碳黑接枝化埂 應。 此時，茌接枝化反應系中，含有比較的任意（在鍵段 -81 - 本纸張尺度適用中國國家標準（CN’S ) Α4規格（2ΙΟΧ297公釐） 4 6〇4 89 A7 __B7_ 五、發明説明（） (A)上具有極端的高親和性的分散媒液Μ外的）的分散媒體 下，或在不含這種分散媒體下，因為這種聚合體的鏈段（Α )將傾向碳黑，會使該當鏈段（Α)所含的反應性基有效的被 接枝往碳黑表面，即可製成如上列1.10節所述的方法所製 成的具有同優異特性的碳黑接枝聚合物了。 在本製法上，使碳黑與上列聚合體的接枝化時，若不 使此等成份傾向上列聚合體的鍵段（Α)圼現極端的高度親 和性者，即可Μ在任意的分散媒體下，或在未具這種分散 媒體下進行攪拌混合，或進行溶融混合，即可〇 可以使用的分散媒液，雖然随著該當聚合體的鏈段（Α) 的結構而異，卻有如，水、甲醇、乙酵、異两酵、丁醇等 酵類；流體石蠘、癸焼、癸蹄、甲基祭、禁燒、煤油、二 苯甲院、甲苯、二甲苯、乙苯、二乙聚、两苯、環巳燒、 局部加水的三苯基等的碳化氫；聚二甲基鞋氧院、局部辛 替聚二甲基鞋氧焼、局苯替聚二甲硅氧焼、海[δ圭油等桂油 ;氯苯、二氯苯、漠聚、氯二苯基、氛二苯基甲焼等阑化 碳氫；二糠醯（大金工業（股）公司製），提姆喃（大金 工業（股）公司製）等的氣化物；安息香酸乙酷、安息番 酸辛酯、献酸二辛酷、三苯六梭酸三辛醋、癸二酸二丁酯 、（甲基）丙烯酸乙酷、（甲基）丙蹄酸丁酯、（甲基）丙締酸 十二院酯等的酷化合物。 至於接枝化處理時的其他條件，及所得碳黑接枝聚合 物的特性，即均如同上1.10節所述的方法。 1 · 12 含有不飽和二重結合的塊型以及接枝型聚合物接枝 本紙張尺度適用中國國家標準（CNS) A4规格（210x297公釐> 办衣-- (請先閱讀背面之注項再填窝本頁j 訂 4 60489 A7 B7 五、發明説明（） 碳黑的製造法（其一） 將解說有關於第四的發明的碳黑接枝聚合物的製法於 下。 於1.6節所述將含有能與碳黑表面的功能基起反應的 鏈段（A)及鏈段（B)所有乙烯不飽和性二Μ結合的塊型以及 接枝型聚合體與碳黑行接枝化，亦如同所述1.10節所述， 應使其在所述目的媒體或其類似性狀的媒體形成的分散液 下，分散所得的碳黒接枝聚合物的方式為宜。其所使用的 分散媒液等許多條件，雖然如同所述:L. 10節，其加熱溫度及 混合時間卻要比所述1.10節所述的條件較低，如在50〜150 °C，最好Μ在70〜140°C的溫度下，進行0.5〜10小時，最 攬伴混合1〜5小時為宜。若反應溫未逹50°C者，或會使接 枝化難於進行，是不適宜的。若反而超過150 t者，或將 失去鏈段（B)的不飽和二重結合，亦不宜。又，在本第一種 瑕態的方法上*含在鍵段（A)的反應基即有在比較低溫條 件亦能與碳黑的表面功能基相反應的嚼睡基及氮丙唾基 ，能發揮減低在接枝化時的失去不飽和二重結合的效用， 是為最好的。 又，將含有能與碳黑表面的功能基起反懕的反應性的 鏈段（A)設計成為比對目的媒體圼現高度親和性的鏈段（B) 更能對碳黑圼琨高度親和性的分子構造時，即如同所述1. 11節所述，將使碳黑與上列聚合體間的接枝化，在不極端 傾向上列聚合體的鏈段（A)呈琨極端的高度親和性範圍内， 即使是在任意的分散媒液或不具有這種分散媒液下，使其 本纸張尺度適用中國國家榡皁（CNS ) Α4说格（210Χ297公釐） 扣衣-- (诗先Η讀背面之注意事項再填寫本頁) 訂 A7 4 6〇4 89 B7 五、發明説明（） 搅伴混合，或進行溶融混合，亦能得良好效果。此第二的 形態的加熱溫度及其混合時間，亦如同所述的條件，如為 溫度在50〜150TO *最好是在70〜140°C，搜拌混合0.5〜10 時，最好以1〜5小時為宜。 1.13 含有不飽和二重结合的塊型Μ及接枝型聚合物接枝 碳黑的製法（其二） 再將就含有能與碳黑的表面功能基起反應的反應性基 的鏈段（Α)及在鏈段（Β)含有乙嫌不飽和性二重結合的接枝 型以及塊型的聚合體與碳黑進行接枝化的有關第三形態的 製法加Μ說明如下。 有闞該當第三形態的製法是，除了將如上列1.12節所 述有關第一型態的製法及•對碳黑進行聚合體部的接枝化 及，引進不飽和二重結合體於聚合體的_段出）等工程有 基逆行順序以外，在基本上均約略同樣。即•在有關第三 形態的製法上，如同上列一般，在製成由含有對碳黑有反 應性基的鏈段（Α)及形成鏈段（Β)的主要結構部的塊型以及 接枝型的前驅體聚合體後，將此前驅聚合體與碳黑進行接 枝化，其後，在被接枝化於碳黑的前驅體聚合體上的鋪段 (Β)，以前列所述的化合物（d)引進不飽和二重結合而成。 K這種方法來製造時，由於在進行接枝化時，鏈段（B)未 含有不飽和二簠結合，即如同在使用環氧基等做為鏈段（A) 所含的反應性基時，使接枝化雖需較化費高溫長時間的反 應條件來完成，卻不如所述第一形態的方法會在接枝化時 發生不飽和二重结合淌失的問題，又在引進不飽和二軎結 本纸伕尺度適用中國國家標準（CNS ) A4現格（210X：297公釐） 私衣----r--------線 (請先W讀背面之注意事項再填寫本頁) A7 4 6〇4 89 ____B7_ 五、發明説明（） 合時*使鍵段所含的反應性基已經消費在與碳黑之間的結 合上，就有不發生化合物（d)所含的異氰酸基等的反應性 基與鏈段（A)所含的反應性基間起反應的問題而有利。又 ，摄氧基與碳黑反應，使環氣基裂環後所生的羥基上亦同 樣的或會使異氰酸基結合於該基上，由於自裂環所發生的 控基是存在於碳黑的表面周邊*卻將展開於媒質中的鏈段 (B)與經基產生儍先的反應。 於是，所使用的分散媒液，即因應該當聚合體的鏈段 (A)及鍵段（B)的配對，選其適當的來使用。 在第三形態的前驅體聚合體與碳黑的接枝化，就要比 如同所述第一形態的少受限制，如溫度在100〜250^；，最 好是140〜200T：，搅拌混合0.2〜5小時，最好M0. 5〜3小 時來進行。又用接枝化後的前驅聚合體的趟段（B)來引進 不飽和二重結合於化合物（d)的引進條件亦少受限制，如 可Μ在溫度10〜1〇0°C，携拌混合0.5〜5小時即成。至於 這些Μ外的條件，就如同所述第一形態大約相似，即將之 略'去。 再來，就要說明有關於第四形態的製造方法於下。本 第四形態亦與上列第三形態同樣，在製得含有對碳黑能起 反應的反應性基的鍵段（Α)及由_段（Β)形成主結構的塊型 Μ及接枝型的前驅體聚合體後，將此前驅體聚合體與碳黑 進行接枝化，再於被接枝化在碳黑的前驅體聚合體的鏈段 (Β)上以所述化合物（d)來引進不飽和二重结合，且如同所 述第二形態一般，將於塊型K及接枝型聚合體（前驅聚合 本紙張尺度適用中國國家標芈（CNS > iM規格（2)0X297公釐） 扯衣 . :1T-------0 (請先W讀背面之注意事項再填寫本頁) ‘4 604 89 A7 _______B7五、發明説明（） 體）同樣的較:計用含有能與碳黑表茴的功能基起反應的反 應性基的鏈段（A)成為比要引進不飽和二重結合的鏈段（B) 有對碳黑圼現較高親和性的分子，來與碳黑進行接枝化。 又，有關本第四形態的製法所需各種條件，雖如同所述有 關第二形態的製法之條件大致相同，卻與所述有關第三形 態的製法時相同，在接枝化及引進不飽和二重結合時的反 應溫度等條件，要比在第二形態的製法的條件有較大的範 圍。 1.14 含有羧基的塊型以及接枝型聚合物接枝化碳黑的製 法 有關第五的發明的碳黑接枝化聚合物即由1.7節所述， 將含有羥氣的接枝型以及塊型聚合體與碳黑一起加熱混合 後，再Μ酸酐處理而製成。 如所述1.10節同樣*在能分散所得的碳黑接枝聚合物 的所述目的媒艄或由其類似性狀的媒體形成的分散媒液中 ，使含有羥基的接枝型以及塊型聚合體與碳黑一起加熱混 合來製造是最好的。所使用的分散媒液、溫度、焜合時間 、聚合體與碳黑的調配比等條件，即如冏所述1.10節的條 件一般。 或，可用所述1.11節所述的同樣方法來製造。 亦可用所述1.9節所述的方法來進行其後鑛的酸酐處 理。 1.15 加熱混合法 如在上列1.8節〜1.14節所述有關本發明的製造碳黑 -86 - 本紙伕尺度適用中國园家榡準（CNS ) Α4規格（2丨0'乂297公釐) — 一 --------^----^--1Τ (請先Μ讀背面之注意事項再填寫本頁) A7 6〇4 89 B7 五、發明説明（） {請先閱讀背面之注意事項再填寫本頁) 接枝聚合物時，應使用如上列的反應性聚合體與碳黑一起 加熱混合的處理作業。又懕在分散媒液中迪行這種加熱混 合作業為宜。 這種加熱混合處理，雖可以使用—般的!搜拌作業所用 的攪拌槽或用於混合的球磨機、混合機、捏合機等練合機 ，卻以能裝入被處理流體於内部的容器，在容器内含有可 轉動的攬拌子，可加熱被處理流體的加熱裝置*及能分散 容納在容器內部的複數粒狀媒艘的濕式分散處理裝置為宜 〇 能同時將攬拌子及小珠等粒狀媒體搜拌Μ及粉碎的濕 式分散處理裝置Κ及濕式粉碎處理装置，雖有多種為眾所 周知的形式，在本發明卻須在這種處理裝置上再有掂加熱 被處理流體的加熱裝置的構造裝置。使用具有如此構造的 裝置時，即可Μ極高效率製成含有極小粒徑（即，可使自 二次凝集狀態被十分粉碎的碳黑與聚合體完成接枝化）的 碳黑接枝化聚合物。 又，這種加熱混合法*不但可用於製造有關本發明的 碳黑接枝化聚合物上，又可用做各種固體微粒子的表面改 質處理法。至於該當表面改質處理法，將在後列四節上加 Μ詳說。 1.16碳黑接枝化聚合物的特性 如上列所述有關本發明的碳黑接枝化聚合物所有的平 均粒子徑為0.001〜0.5 ，尤其在0.005〜0.2 "ra範_ 内的為宜。 本紙伕尺度適用令國國家標隼（〇?^)六4洗格（2】0><297公釐> 89 . A7 _B7_ 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 平均粒子徑未滿0.001 “m的碳黑接枝化聚合物，即由 於做為原料的碳黑不易得到，其產業上的意義甚小。又若 其平构子徑超過0.5 win者，或有將難得十分的分散性之麻 Ο 本發明的碳黑接枝聚合物的成分，碳黑與聚合體的配 對比K前者為100重鱼份時，後者為1〜1000重虽份，而Μ 後者5〜500重量份為宜。若後者未達1重虽份時，由於所 得的碳黑接枝化聚合物將互相凝集* Μ致難得茌目的媒體 中充分分散及無法改舂其電氣絕緣性、光重合阻礙性等問 題。又若後者大於1000重虽份時，即將使聚合體造行需要 以上的接枝化，而生無法發揮著色性、遮光性等碳黑本來 就具有的特性之成。 如依上列方法製成的本發明的碳黑接枝聚合物，由於 均有優越的分散安定性，尤其在被接枝化的聚合體含有乙 烯性不飽和二重結合者，不但具有硬化反應性，如在硬化 皮膜上，因其能Μ均勻分散的狀態固定化於矩陣圖，而發 揮極優越的電氣絕緣性。又若被接枝化的聚合體含有羧基 者，即會有良好的鹼顯像性。又，若被接枝的聚合體屬於 塊型以及接枝型的聚合體者，即將對各種物質，如有機高 分子、水、有機溶劑等圼琨特別優越的分散性，又大致會 提升其電氣絕緣性，再加上由於引進所述聚合體的鰱段（Β )而里現更多特性。如*聚合體的鏈段（Β)屬於聚硅氧烧糸 構造鐽者，就會有優秀的拒水性、離型性、耐熱性、耐候 性、柔軟性及低粘性等及無低溫脆性的特性，若是靥於（ 本紙張尺度適用中国國家標準（CNS ) Α4現格（210X297公釐） 4 60 4 89 A7 _B7_ 五、發明説明（） 甲基）丙嫌系_者，由於引進各種（甲基）丙輝酯單體，卽 會特別圼現寬大的親水性一疏水性，又若觴於聚鋪乙二酵 趟者，即將賦與親水性、潤滑性、柔軟性及防止帶電等特 性。 2.用途 本發明的碳黑接枝聚合物由於具有儍秀的著色性以及 遮光性，提升充填強度性及分散安定性等其基本性能以外 ，又有如上列所述的各種功能的優秀特性，所Μ能加人於 各種溶媒、熱及光重合性單體Μ及齊聚物，及/以各種樹 脂等為棊底的各種組成物中。 又，將有關本發明的碳黑接枝化聚合物做為著色劑、 充填劑等用途而加到各種組成物時•不一定要將對於疽等 組成物加入該當碳黑接枝聚合物配對量的同一種被接枝化 的聚合體的碳黑接枝化聚合物的全量，即不必為由有完全 同一特性所構成的，亦可用有不同接枝化的聚合體二棰Κ 及Κ二種Μ上配對的碳黑接枝化聚合物。如，自有關第1 的發明的含有乙烯不飽和性二重結合的碳黑接枝化聚合物 ，有關第2的發明的含有羧基碳黑接枝聚合物，有關第3 的發明的含有塊型以及接枝型聚合體，有關第4的發明的 含有乙烯不飽和二重結合的塊型Κ及接枝型聚合體的聚合 體，及有關Μ5的發明的含有羧基的塊型Μ及接枝型聚合 體等碳黑接枝聚合物中各選取靥於不同分類的二以及三種 Μ上的組合物，又，由碳黑接枝聚合物所含聚合體的不同 分子量的碳黑接枝聚合物組成的組合物，由碳黑接枝聚合 -89 本紙ft尺度適用中圉國家樣準（CNS ) Α4規格（210X297公釐） 460489 A7 B7 五、發明説明（） 物所含聚合體的不同鍵構造所成的組合物來用，鞋因此配 對，未能使該當組合物無法僅w其單一一種來滿足要求的 條件者，或僅以其單一種類雖能完全或十分的滿足各棰條 件，卻自經濟上的觀點來看，會有問題時，若採取同時并 用其複數種，即能發揮其儍越的效果。 2.1光硬化性樹脂組成物 本發明的碳黑接枝聚合物特別適宜的用途為Μ著色劑 加入於光硬化性樹脂組成物上。如，將碳黑接枝化聚合物 加到光硬化性樹脂組成物即可得光硬化性樹脂組成物。此 光硬化性樹脂很適用於形成濾色器矩陣圃上。 本發明的光硬化性樹脂組成物是以該碳黑接枝聚合物 與，如，（i )光簠合性不飽和化物，（ii)光崖合開始劑， (m)粘合劑為其必要成分，另外尚需溶劑，又因應必要， 亦可同時并用可塑劑、變色劑、單功能乙締不飽和化合物 Μ及其他的助劑類，由此等化合物即能產生調節光硬化性 樹脂Μ及光電效應的寫真性、沖相性、膜物性等性質。 (i )光重合性不飽和化合物為在其分子中只少含有二 個乙烯不飽和二重结合又能起軎合作用者。而又能使一種 或二種K上的化合物存在於其中。適宜的具體例有，有如， 記載於特公昭35-5093號，特公昭35-14719號，特公昭44 -28727號等的多元醇丙烯酸酷或異丁烯酸酯類，如，二乙 烯乙二酵二（甲基）两阔酸_、三乙烯乙二酵二（甲棊）丙烯 酸酷、四乙烯乙二醇（甲基）丙烯酸酯、壬烯乙二醇二（ 甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、三羥甲基 一 90 - 本纸張尺度適用中國國家樣孪（CNS ) A4規格（2!0Χ297公釐） (諳先閲讀背面之注意事項再填寫本頁) -丨裝· 、π A7 B7 4 6〇4 8g 五、發明説明（ (請先閲讀背面之注f項再填寫本頁) 两焼三（甲基）丙?:希酸醋、三徑甲基丙焼二（甲基）丙鋪酸酿 、季成四醇四（甲基）丙嫌酸@旨，二季成四酵戊（甲基）丙蹄 酸酷、二季戊四酵已（甲基）丙嫌酸酯、1.6 —己二酵二（甲 基）丙烯酸酯等，或雙（甲基）丙烯醯胺類》如甲撐雙（甲基 )丙烯脑胺、間一苯二甲基雙（甲基）丙烯酿胺等，或含有尿 焼的化合物，如*二（2-甲丙婦氣乙基）2,4-甲次苯基二 尿烧、二一（2-丙賺氣乙基）六乙締二尿院、或先使多元 酵與異氰酸鹽反應而得尾（末）端異氰酸體化合物再與/3 —羥烷（甲基）丙烯酸酯相反應所得的（甲基）丙烯尿烷劑聚 物，如，2,4-甲代苯撐異氮酸酯四克分子與乙二酸三克分 子的反應生成物再與/3 —羥乙基丙稀酷反應所得的劑聚物 ，又，2.2, _雙翔笼基两嫁，2,2 —雙經乙氧苯基丙烷等 的二丙烯酸酯。 (ii)光重合開始劑有，其具體者，芳香族酮類，如笨 酮、4,4·—雙二甲胺基苯嗣、4,4’一雙二乙胺基苯_、4-甲氣基-4-二甲胺基苯_、4,4’一二甲氧基苯笼嗣、4一二 甲胺基莱酮、4-甲氨基笼乙酮、聯苯脑、Μ酿i、2-(tert) 第三級一丁基2-甲基蔥概!、菲_、咕觸酮（Xanthone) 、硫雜激_、1-M—硫雜葸酮、2,4-二乙基硫雜Μ酮、結 酮肪、〇Υ唯酮等，又如苯偁晒、苯偶姻醋類的苯偶姻甲基 醚、苯偶姻乙基_、苯偶姻两基醚、苯偶姻異丙基_、聚 偶姻苯_等，如2· 4,5-三芳基蹄唑二量體類的2-(0 -氣聚 基）-4,5-二聚基邮啤二量體、2-(0 -氯苯基）-4,5-二（m — 甲氧絮基）畔啤二蛋體、2-(0 -氟苯基）-4,5-二苯基邮啤 -91 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 4 6〇4 89 A7 B7 五、發明説明（ 二量體、2-(0 -甲氧策基）-4,5-二苯基ΦΚ唾二量體、2-(0 -甲氧笨基）-4,5-二苯基蹄挫二量體、1-(P-甲氧苯基）-4, 5-二苯基蹄喃二量體等，如聚鹵化合物類的四溴化碳、苯 三漠甲基顿p風、苯三氛甲基哪《^等，及特開昭52-133428 號，特公昭57-1819號，特公昭57-6096號•美國專利第 3615455號等上登載的二種化合物的組合，如2,4,5—三芳 基蹄哩二量體及2-疏苯並嗯啤或無色結晶紫等組合•又如 登在美國專利第3427161號的4,4·-雙（二甲截基）二聚甲 酮與二苯甲酮或苯偶姻甲醚的組合，及美國專利第423985 號上的苯酿-N-甲基蔡》襄唯與2,4-雙（三氯甲基）-6,4-甲氧 笼基三啤的組合，或特開昭57-23602號上的二甲基硫雜Μ 酮與二烴氣基安息香酸酷的組合等。 (iii)粘著劑有，其未暘光部被驗水溶液除去的鹼顯像 型及被有機溶劑除去的溶劑顯像型Μ及被水除去的水顯像 型等三種，均能適用。 又·在本發明的光硬化性樹脂組成物中，如用於滅色 器用黑色矩陣圖者，即宜使用含有齡可溶型粘著劑的驗可 溶型者。能用於驗顯像的光硬化性組成物，基本上是由光 重合開始劑與在其分子中含有多功能單體及驗可溶基的聚 粘著劑所成，當其被光照射即硬化而不溶於齡水溶液中了 可調配於如上列所述含有碳黑接枝聚合物而適用於能 當做驗顯像的感光曆膜之齡Ϊ可溶型硬化性組成物的粘著劑 ，有下列各物質。 -92 - 本紙張尺度適用十國國家標準（CNS )人4规格（210 X 297公釐） t^.1τ------'r (請先閲讀背面之注$項再填寫本頁)CH2 = CC R2 1 R4 C — 0 — X 1 1 -eCH2-C ^ CH2-C γ 0 C — 〇 丨 0 ~ " ···-Q 1 1 0 I 1 0 1 1 K3 I 1 R5 t OH (Please read the precautions on the back before filling out this page) (However, R /, Ri in the formula represent the same or different fluorene atom or methyl group, h is an alkenyl group of C atom 1 to 25, and is C atom A fluorenyl group having a number of 1 to 25, X is an arbitrary bonding chain, Υ is a tail end of the initiator or a fluorene atom, and η and m are the same or different integers of 0 to 500). -Square, as the superpositionable singular body (a) containing a reactive group capable of reacting with carbon black in the molecule, there is the same polymerizable singular body as described in section 1 * 5, and When the chain segment (A) has the structure as set out above, as the coincident unitary body (c) that can be used as necessary, it is also possible to use the same unitary unitary body as described in Section 1.5. When the hydroxyl group is to be introduced into the segment (A), for example, methyl acrylate, hydroxyethyl acrylate, hydroxypropyl dienoate, hydroxy 2-ethylhexyl acrylate, hydroxymethyl methacrylate, methacrylate Acrylic or hydroxyalkyl meta-acrylic acid monomers such as hydroxyethyl acrylate, hydroxypropyl metaacrylate, and hydroxy 2-ethylhexyl methacrylate; monomers such as hydroxypropyl ether, hydroxypropyl acrylate, etc .; necessary It can be used by blending with various overlapping monomers as described in Section 1.5 as appropriate. -75 — This paper size applies to China National Standard (CNS.) A4 specification (2 丨 OX29? Mm) 4 60 4 89 a7 B7 V. Description of the invention () Other methods of manufacturing graft polymers, or manufacturing For the method of producing a block polymer, the polymer according to this aspect can be produced by the method described in 1.5 above. Although the molecules of the block-type and graft-type polymers made by the above method, the molecular weight of the segment (A) and the segment (B), and the number of all reactive groups of the segment (A), etc. As described in Section 1.5, although it is not particularly limited, it is advisable for M to be the same as the above-mentioned Fanyuan. As for the number of hydroxyl groups, it is determined by the acid value of the polymer in the carbon black graft polymer obtained after the acid anhydride treatment. Although the acid value varies depending on the acid value of the age-soluble adhesive and the like to be blended in the carbon black graft polymer, it is preferably M10M. 50M is better. 100M is best. Because when the acid value is less than 10, it does not have its diagnostic imaging properties. 1.8 Manufacture of Unsaturated Double Bonded Carbon Graft Polymers The carbon black graft polymer of the first invention is a reaction capable of reacting with functional groups on the surface of carbon black, as described in Section 1.3 of Lennon. The polymer with the double bond of ethylenic unsaturated group is added to carbon black and heated and mixed together to make it, that is, it contains the ethylenic unsaturated-heavy bonder in its grafted polymer chain. The heating and mixing conditions are: 50 ~ 250 ° C, but at a temperature of 100 ~ 200 ° C, it is allowed to react for 0.5 ~ 10 hours, and it is best to mix with Soyang for 2 ~ 5 hours. If the temperature is less than 50 ° C, that is, the grafting cannot be completely unsuitable. If it exceeds 250 ° C, the recombination component will deteriorate, and it is not suitable. Also, it can be heated and mixed in an appropriate solvent. Due to the ratio of the grafted carbon black to the polymer, the paper size is applicable to the national standard (CNS) A4 standard (210X297 mm) (please read the note on the back first) Please fill in this page again.) Equipment, tx 460489 A7 ________B7 V. Description of the invention () It will be affected by the type of the polymer used, the purpose of the product to be obtained, etc. Although it cannot be specified in general, it is M carbon black. 100 parts by weight, plus 1 to 1000 parts by weight of the polymer, preferably about 2 to 500 parts by weight. That is, if the polymer is less than 1 part by weight, it may be difficult to improve the surface properties of carbon black. On the other hand, if it exceeds 1,000 parts by weight, the number of polymer children bound to carbon black will increase. The economy also undermines the characteristics of carbon dioxide that was originally required. 1.9 Manufacture of a carbon black graft polymer containing a carboxyl group The carbon black graft polymer according to the second invention is obtained from a reactive group M which is capable of reacting with a functional group on the surface of carbon black as described in Section 1.4. After the polymer of the hydroxyl group and carbon black are heated and mixed together, the reaction mixture obtained by the acid anhydride treatment is prepared to contain a carboxyl group in the grafting process. 1 year Yin Yaqin Xinju employee Shao Fei Cooperative Society " I-n-I H-!. _I ^ ---------- Ding • < (Please read the notes on the back before filling this page) Although the conditions for heating and mixing are 40 ~ 300 ° C, it is best to heat and mix at a temperature of 70 ~ 250 ^ 0 for 0.5 ~ 10 hours, and M2 ~ 5 Hours are appropriate. It is not suitable if the temperature is below 40 ° C, or the grafting cannot be performed sufficiently, and if it is reacted at a temperature above 300 ° C, the polymer may be deteriorated. In addition, if a reactive polymer containing Xiangji and an ethylenically unsaturated double-binding dimer as described above is used, such as those described in Sections 1.3 and 1, 4 of the unsaturated cycloaliphatic resin, The heating and mixing conditions are 50 ~ 250TC, and it is best to perform the reaction in a temperature range limited by 100 ~ 200 ° C. It is also possible to carry out such a heating and mixing industry in a suitable solvent. The carbon black graft polymer obtained by grafting a polymer of a reactive group and a hydroxyl group capable of reacting with a functional group on the surface of the carbon black to the carbon black is subjected to acid treatment. • The national standard (CN'S) of this paper applies. A4 is present (2 丨 0:?: 297 mm) 4 6〇4 89 A7 ________B7 V. Description of the invention () The semi-cooling between the base and the acid contained in the grafted polymer Reactions were introduced into search-based polymer chains. The anhydrides include phthalic acid, anhydrous acid, maleic liver, and tetraglucose: glutamate is too acidic, dried, 3,6-bridged tetracarboxylic acid anhydride, hexagasic acid anhydride, methyl tetrahydrofluoride Acid salt, methyl bridge methyl tetrahydroxanthate, tetrabromide salt, trimellitic acid and other di-salt anhydrides, aliphatic or aromatic tetra-carbonate di-anhydride and other tetra-salt-dihydrates and so on. The amount of acid anhydride, that is, the hydroxyl-chemical equivalent contained in the polymer grafted with carbon black is preferably 0.1 to 1.1 chemical equivalents, and when there is a diluent or no diluent with or without hydroquinone It can be reacted at 50 ~ 130 ° C under the conditions of superposition inhibitor such as oxygen or oxygen. In this semi-brewing reaction of the radical and acid anhydride, it can be used from general literature, such as New Experimental Chemistry Lecture 14, "Synthesis and Reaction of Organic Compounds", by Maruharu Co., Ltd. on December 20, 1977 The catalysts listed on page 1014 are acid catalysts, salt-based catalysts, and gold salt inorganic salts. Examples of the acid catalyst include sulfuric acid P-toluenesulfonic acid and the like or a catalyst in which rhenium is used in combination. The salt-based catalysts include tertiary amines, such as trimethylamine, triethyleneamine, N-pentamethylethylenetriamine, Ν, Ν-dimethylamidamine, N · dimethyldimethylamine, ^ 『 , 1 ^ 1'-tetramethylpropanediamine, p-methyl ?, N-ethyl ?, N, N'-methyl 啾, this pyridine, 4-dimethylaminopyrimidine For σ determination, 1,8—bicyclo [5,4,0] -7--f «^ (1.8-Diazabicyc 1〇 [5.4.0] -7-Undecene) (DBU.) and the like are used together and a rhenium mixture is used. Inorganic metal salts include metal oxides, sodium acetate, sodium acetate, and the like, and their combined compounds. In addition, it is possible to make the polymer containing a fumaryl group extremely stable for grafting on carbon black and other paper standards to comply with the National Standard (CN5) A4 specification (210 X 25> 7 mm) ^ ------ 1T ------ ^ (Please read the notes on the back before filling this page) 4 6 0 4 89 A7 _B7 V. Description of the invention () (Please read the notes on the back before filling this page) Methods * That is, a reactive group * capable of reacting with a reactive functional group on the surface of carbon black, that is, a polymer containing a protecting group plus a protected M group, is reacted with carbon black to be grafted, and then The obtained carbon black graft polymer was treated with M deprotection group to find a method for searching the base. There are many types of protective groups for the carboxyl group. For example, a tetrahydropyranyl group used in Examples described later can be used. 1.10 Production method of block type M and graft polymer grafted carbon black Next, there will be a description of the method of manufacturing the carbon black graft polymer of the third invention plus M, although the method described in Section 1.8 can be used. As described in section 1.5, carbon black is grafted to block type M and graft type polymer, and if a better grafting efficiency is desired, it will contain reactivity as described in section 1 + 5. The base segment (Α) is designed to have a lower affinity for the target media than the other segment (B), so that it is intended to be used as a target medium for dispersing the obtained carbon black graft polymer or has similar properties to this media. It is advisable to perform heating and mixing in the presence of a dispersed medium composed of a medium. That is, this dispersion medium has only a high degree of affinity and compatibility with the segment (B) of the polymer, and a low degree of affinity and compatibility with the segment (A), that is, 圼. Therefore, the media used is based on how the segments (A) and bonds (B) of the polymer are paired to make the appropriate choice. For example, when the polymer segment (A) has a polystyrene fluorene structure and the polymer segment (B) has a polysilazane structure, the polydimethyl shoe gas is used to partially replace the octyl polydimethyl silicon. Oxygen firing, silicone oils such as polydimethyl δ-methoxane, which partially replaces phenyl groups, and silicone oil are used as dispersion media. In addition, if the polymer segment (A) has a polyvinyl structure and the segment (B) has a hydrophobic (meth) acrylic fluorene structure such as polymethylisobutyrate, this paper size Applicable. National Standard (CNS) · A4 Specification (210 × 297 cm) A7 4 0〇89 89 '____B7_ 5. Description of the Invention () Methyl cellosolve, ethyl cellosolve, etc. ; Lipids such as methyl acetate, ethyl acetate, butyl acetate; propane, butyl, methyl isobutyl ketone, etc .; 各 various ketones, Ν, Ν-dimethylformamide, dimethylamine And other non-positive polar solvents are their dispersion media. In addition, if the polymer segment (A) has a polypropylene fluorene structure and the bond segment (B) has a hydrophilic (meth) acrylic-based structure such as methyl methacrylic acid methylol isobutyl copolymer, such as It should be fermented with water, water-fermented mixed solution, formic leaven, and B ?; lipids such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; acetone and other class I; Ν, Ν-dimethylformamide and dimethyl methacrylate were used as dispersion media. In addition, if the polymer segment (A) has a polypropylene structure and the segment (B) has a polyalkylene glycol structure, it is preferred to use water, a water-enzyme mixture, formazan, ethanol, etc. Alcohols: Polyethylene glycols such as vinyl ethylene glycol and diethylene glycol, and polyvalent alcohols such as glycerin are used as dispersion media. When the carbon black is grafted with the polymer in the presence of such a dispersing solvent, other substances such as polymers and superpositionable monomers which do not belong to the polymer may be added. The grafting is performed at a temperature of 40 to 3001C, preferably at a temperature of 70 to 2501C, for 0.5 to 10 hours, and preferably for 2 to 5 hours. If the reaction temperature is less than 40 T: it may not be grafted, and g ， is not suitable. If it exceeds 300 ΐ], or its polymer will deteriorate, it is not suitable. The step of the grave reaction is that carbon black and the polymer, and the dispersing medium are introduced into the reaction device and mixed under heating. The blending ratio of the grafted carbon black and the polymer should be _ 80-This paper size is in accordance with the Chinese national standard (CNS M4 specification (2 丨 〇 × 297 mm). -^ 1Τ ------ line (please read the notes on the back before filling this page) A7 4 S〇4 89 __B7 V. Description of the invention () (Please read the notes on the back before filling this page) The type of the polymer used, the purpose of the product to be manufactured and the like vary, although the general requirements cannot be made, but 100 parts by weight of the carbon black are blended with 1 ~ 1000 parts by weight of the polymer. The ratio of 2 to 500 parts by weight of a good M polymer is suitable. That is, the polymer may not reach 1 part by weight, or it may be difficult to modify the surface properties of carbon black. However, if the amount exceeds 1,000 parts by weight, it will become Adding too much polymer combined with carbon black is not only uneconomical, but also loses the characteristics of carbon black originally required. The carbon black graft polymer obtained by this method has various substances, such as for organic polymers , Water, organic solvents, etc., which have excellent dispersibility * in general can improve its electrical insulation, The introduction of the polymer segment (B) has more features. For example, the polymer segment (B) belongs to the polysilicic acid structure. That is, it has silly water repellency, prototype, and heat resistance. , Weather resistance, softness and low occupancy * or no low temperature brittleness and other characteristics, and if it is a (meth) acrylic acid chain structure * due to the introduction of various (meth) acrylic monomer components If it is hydrophilic and hydrophobic, and if it is a polyethylene glycol bond, it will be endowed with hydrophilicity, lubricity, softness, and anti-charge characteristics. 1. Π bulk and grafted polygraft carbon Black method (second) Basically, this method is slightly similar to the method described in Section 1.10, but as described in Section 1.5, when manufacturing the grafted K-block polymer, it is designed to contain energy. The segment (A) of the reactive group that reacts with the functional group on the surface of the carbon fluorene has a high affinity for the target media. The segment (B) has a form that has a high affinity for carbon black and can also be received. In this case, the carbon black is grafted with high efficiency. At this time, the grafting reaction system contains relatively arbitrary (The key segment -81-This paper size applies the Chinese National Standard (CN'S) A4 specification (2 10 × 297 mm) 4 6〇4 89 A7 __B7_ V. Description of the invention ()) (A) has extremely high affinity dispersion In the dispersion medium (except the medium M), or in the absence of such a dispersion medium, the segment (A) of this polymer will tend to carbon black, which will cause the reactivity contained in the corresponding segment (A). The base is effectively grafted to the surface of carbon black, and a carbon black graft polymer having the same excellent properties as the method described in section 1.10 above can be prepared. During the grafting of the matrix polymer, if these components do not tend to have extreme affinity with the bond segment (Α) of the matrix polymer, they can be used in any dispersion medium, or in the absence of this. This kind of dispersion medium can be stirred and mixed, or melt-mixed, that is, the dispersion medium that can be used. Although it varies with the structure of the segment (A) of the polymer, it is, for example, water, methanol, ethyl acetate, Different yeasts, such as yeast, butanol; fluid stone 流体, 焼 焼, 癸 hoof, methyl sacrifice, forbidden Burning, kerosene, xylylene, toluene, xylene, ethylbenzene, diethylene, diphenyl, cyclopropane, locally added triphenyl, and other hydrocarbons; polydimethyl shoe oxygen hospital, local oxal Polydimethyl shoe oxoxane, local benzoate polydimethylsiloxane, sea oil such as Gui Gui oil; chlorobenzene, dichlorobenzene, Mopoly, chlorodiphenyl, diphenylformamidine, etc. Hydrocarbons; Difuran (made by Daikin Industries, Ltd.), Timon (made by Daikin Industries, Ltd.), etc .; Ethyl benzoate, octyl benzoate, dioctyl oxanthate Cool, trioctanoic acid trioctyl vinegar, dibutyl sebacate, ethylene glycol (meth) acrylate, butyl (meth) propanoate, dodecyl (meth) acrylic acid, etc. Compound. As for the other conditions during the grafting treatment, and the characteristics of the obtained carbon black graft polymer, all were the same as those described in the above section 1.10. 1 · 12 Blocks containing unsaturated double bonds and grafted polymers are grafted. This paper is sized for China National Standard (CNS) A4 (210x297 mm > clothing)-(Please read the note on the back first Refill this page j Order 4 60489 A7 B7 V. Description of the invention () Carbon black manufacturing method (Part 1) The method for manufacturing the carbon black graft polymer related to the fourth invention will be explained below. Describe the block type and graft type polymer containing all segments (A) and (B) that can react with functional groups on the surface of carbon black, which are combined with ethylene unsaturated dimers, and graft polymers, and carbon black. Also as described in Section 1.10, the method of dispersing the obtained carbon fluorene graft polymer under a dispersion liquid formed by the target medium or a medium with similar properties should be performed. The dispersion medium used therefor Many conditions, although as mentioned: L. 10, the heating temperature and mixing time are lower than the conditions described in the 1.10, such as at 50 ~ 150 ° C, preferably Μ at 70 ~ 140 ° At a temperature of C, it is performed for 0.5 to 10 hours, and the best mixing is for 1 to 5 hours. If the reaction temperature is not more than 50, C, it may make grafting difficult, which is not suitable. If it exceeds 150 t, it will lose the unsaturated double bond of the segment (B). It is also inappropriate. In the state method, the reactive group contained in the bond (A) has chelating groups and aziridyl groups that can react with the surface functional groups of carbon black even at relatively low temperature conditions, which can play a role in reducing the grafting The effect of losing the unsaturated double bond is the best. In addition, the segment (A) containing reactive groups that can react with functional groups on the surface of carbon black is designed to show a high affinity with the target media. When the molecular segment (B) has a molecular structure with a higher affinity for carbon black, that is, as described in Section 1.11, the grafting between carbon black and the above-mentioned polymers will be made. The extreme tendency is that the segment (A) of the polymer listed above is in the extreme high affinity range, even in any dispersion medium or without such dispersion medium, so that this paper scale is applicable to the country of China 榡Soap (CNS) Α4 said grid (210 × 297 mm) button clothing-(read the notes on the back of the poem before filling in this page) Order A7 4 6〇4 89 B7 V. Description of the invention () Stirring or mixing or melt mixing can also achieve good results. The heating temperature and mixing time of this second form are also the same as the conditions described, such as The temperature is 50 ~ 150TO * It is best at 70 ~ 140 ° C, when searching and mixing for 0.5 ~ 10, it is best to use for 1 ~ 5 hours. 1.13 Block type M and unsaturated type containing unsaturated double bond Method for preparing polymer-grafted carbon black (second) The segment (A) containing a reactive group capable of reacting with the surface functional group of carbon black is further included, and the segment (B) contains ethyl unsaturation. The third manufacturing method plus M of grafting and block-type polymer grafting with carbon black and grafting will be described below. It may be that the third method is to prepare the first type as described in the above section 1.12, and graft the carbon black to the polymer part and introduce unsaturated double bonds into the polymer. The _ paragraph out) and other projects have basically the same except for the retrograde sequence. That is, in the manufacturing method of the third aspect, as in the above, the block type and connection of the main structural part forming the segment (A) containing the carbon black reactive group and the segment (B) are made. After the branched precursor polymer, the precursor polymer is grafted with carbon black, and then, the segment (B) grafted on the precursor polymer of carbon black is described in the foregoing. Compound (d) is introduced by unsaturated double bond. When K is produced by this method, the segment (B) does not contain an unsaturated difluorene bond during the grafting, that is, the epoxy group is used as the reactive group contained in the segment (A). At this time, although the grafting needs to be completed under reaction conditions that require high temperature and long time, it is not as good as the method of the first form, which will cause the problem of unsaturated double bond leakage during grafting. The size of the saturated paper is applicable to the Chinese National Standard (CNS) A4 (210X: 297mm). Clothing ---- r -------- line (please read the precautions on the back first) (Fill in this page again) A7 4 6〇4 89 ____B7_ V. Description of the invention () At the same time * When the reactive group contained in the bond has been consumed in the bond with carbon black, there will be no compound (d) The problem is that the reactive groups such as the isocyanate group contained and the reactive groups contained in the segment (A) react with each other, which is advantageous. In addition, the photooxy group reacts with carbon black, so that the hydroxyl group generated after the ring gas group is split is the same or the isocyanate group is bound to the group. The surface periphery of the carbon black * will unfold the segment (B) in the medium and cause a silly first reaction with the base. Therefore, the dispersion medium to be used should be selected and used appropriately in accordance with the pairing of the segment (A) and the bond (B) of the polymer. In the third form, the grafting of the precursor polymer with carbon black is, for example, less restricted than the first form, for example, the temperature is 100 ~ 250 ^; preferably 140 ~ 200T :, stirring and mixing 0.2 ~ 5 hours, preferably M0. 5 ~ 3 hours. The segment (B) of the grafted precursor polymer is also used to introduce unsaturated double bonds to the compound (d). The introduction conditions are also less limited. For example, the temperature can be 10 to 100 ° C. Stir for 0.5 to 5 hours. As for these conditions other than M, they are approximately similar to the first form, and will be omitted. Next, the manufacturing method of the fourth aspect will be described below. This fourth aspect is also the same as the third aspect above. In the preparation of the bond type (A) containing a reactive group capable of reacting with carbon black and the block type M and graft formed by the _ segment (B), the main structure is prepared. Type precursor polymer, the precursor polymer is grafted with carbon black, and then the compound (d) is grafted onto the segment (B) of the carbon black precursor polymer. Come to introduce unsaturated double bond, and like the second form, it will be block type K and graft type polymer (precursor polymerization, the paper size applies to Chinese national standard (CNS > iM specification (2) 0X297) Li) Pull clothes.: 1T ------- 0 (please read the precautions on the back before filling out this page) '4 604 89 A7 _______B7 V. Description of the invention () Body) The same comparison: plan contains The segment (A) of the reactive group capable of reacting with the functional group of carbon black epithelium becomes a molecule having a higher affinity for carbon black than the segment (B) which is to introduce an unsaturated double bond. Grafting with carbon black. In addition, various conditions required for the manufacturing method of the fourth aspect are substantially the same as those of the manufacturing method of the second aspect, but they are the same as those of the manufacturing method of the third aspect, and are grafted and unsaturated. Conditions such as the reaction temperature at the time of double binding have a larger range than the conditions of the second embodiment. 1.14 Preparation method of carboxyl-containing block type and graft type polymer grafted carbon black The carbon black grafted polymer according to the fifth invention is the graft type and block type containing hydroxyl gas as described in Section 1.7. The polymer is heated and mixed together with carbon black, and then processed by M anhydride. As described in Section 1.10 *, in the target medium or the dispersion medium formed of a medium having similar properties, the obtained carbon black graft polymer can be dispersed, and the hydroxyl-containing graft type and block type polymers are made. It is best produced by heating and mixing with carbon black. The conditions such as the dispersion medium, temperature, mixing time, and blending ratio of polymer and carbon black used are the same as those described in Section 1.10 of 冏. Alternatively, it can be manufactured by the same method as described in Section 1.11. The method described in Section 1.9 can also be used for subsequent acid anhydride treatment. 1.15 The heating and mixing method is as described in the above section 1.8 ~ 1.14 about the production of carbon black-86 of the present invention-the paper size is applicable to China Garden Standard (CNS) A4 specification (2 丨 0 '乂 297 mm) — I -------- ^ ---- ^-1T (Please read the notes on the back before filling in this page) A7 6〇4 89 B7 V. Description of the invention () {Please read the first on the back (Please fill in this page again for precautions) When grafting polymers, use reactive polymers such as those listed above to heat and mix with carbon black. It is also advisable to carry out such heating and mixing in the dispersing medium. Although this kind of heating and mixing treatment can be used-like! The mixing tank used in the search and mixing operation or the kneading machine such as a ball mill, a mixer, a kneader, etc., but a container capable of containing the fluid to be treated inside, The container contains a rotatable basket, a heating device capable of heating the fluid to be processed *, and a wet dispersion processing device capable of dispersing a plurality of granular media vessels contained in the container. Wet dispersing processing device K and wet crushing processing device for searching and mixing M and crushing granular media, although there are many well-known forms, in the present invention, it is necessary to further heat the processed fluid in this processing device. Of the heating device. When a device having such a structure is used, the carbon black can be grafted with extremely small particle size (that is, the carbon black that has been finely pulverized from the secondary aggregation state and the polymer can be grafted). polymer. In addition, this heat mixing method * can be used not only for the production of the carbon black grafted polymer of the present invention, but also as a surface modification treatment method for various solid fine particles. As for the surface modification method, detailed description will be added to the following four sections. 1.16 Characteristics of the carbon black grafted polymer As mentioned above, all the average particle diameters of the carbon black grafted polymer of the present invention are 0.001 to 0.5, and preferably within the range of 0.005 to 0.2. The size of this paper is applicable to the national standard (0? ^) Six 4 wash grid (2) 0 > < 297 mm > 89. A7 _B7_ V. Description of the invention () (Please read the notes on the back before filling in this page) Carbon black grafted polymers with an average particle diameter of less than 0.001 "m. Carbon black, which is a raw material, is not easy to obtain, and its industrial significance is very small. If the diameter of the flat structure is more than 0.5 win, there may be rare dispersibility. The component of the carbon black graft polymer of the present invention When the pairing ratio of carbon black and polymer is 100 parts by weight, the latter is 1 to 1,000 parts by weight, and the latter is 5 to 500 parts by weight. If the latter is less than 1 part by weight, The carbon black grafted polymers will agglomerate with each other. * M will cause sufficient dispersion in the rare media and cannot improve its electrical insulation and photo-registration hindrance. If the latter is more than 1,000 parts by weight, polymerization will soon occur. The above-mentioned grafting is required for the body production, and the characteristics of carbon black, such as coloring property and light-shielding property, cannot be exerted. For example, the carbon black graft polymer of the present invention prepared according to the method described above is Excellent dispersion stability, especially in grafted polymerization The body containing an ethylenically unsaturated double bond not only has hardening reactivity, such as on the hardened film, because it can be uniformly dispersed in the matrix and fixed to the matrix diagram, and exhibits excellent electrical insulation. If it is connected If the branched polymer contains a carboxyl group, it will have good alkali developability. In addition, if the grafted polymer is a block type and a graft type polymer, it will soon be used for various substances such as organic polymers, Water, organic solvents, etc. are particularly superior in dispersibility, which will generally improve their electrical insulation properties. In addition, due to the introduction of the polymer segment (B), there are more characteristics. For example, the polymer chain Segment (B) belongs to the polysilicon fired structure, and it will have excellent water repellency, release, heat resistance, weather resistance, softness and low viscosity, and no low temperature brittleness. Paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 4 60 4 89 A7 _B7_ V. Description of the invention () Methyl) propionate, because of the introduction of various (meth) propionate monomers , It will especially show broad hydrophilic It is hydrophobic in nature, and if it is entrapped in polyethylene glycol, it will be endowed with hydrophilicity, lubricity, softness, and anti-charging properties. 2. Use The carbon black graft polymer of the present invention is silly because In addition to its basic properties such as coloring and light-shielding properties, improved filling strength and dispersion stability, it also has excellent characteristics of various functions as described above. Therefore, it can be added to various solvents, heat and photo-recoverable monomers. M and oligomers, and / or various compositions based on various resins, etc. In addition, the carbon black graft polymer of the present invention is added to various compositions as a colorant, a filler, and the like. When it is not necessary to add components such as gangrene to the same amount of carbon black grafted polymer as the carbon black grafted polymer, the total amount of carbon black grafted polymer, that is, it is not necessary to have exactly the same characteristics It is also possible to use two kinds of carbon black grafted polymers with two grafted polymers, two 棰 K and K. For example, from the first invention related to the ethylene unsaturated double bond-containing carbon black graft polymer, the second invention related to the carboxyl carbon black graft polymer, and the third invention related to the block type And a graft type polymer, a polymer containing the ethylene unsaturated double bond block K and a graft type polymer according to the fourth invention, and a block type M and a graft type containing a carboxyl group according to the invention of M5 Among the carbon black graft polymers such as polymers, two or three kinds of compositions on different classifications are selected, and they are composed of carbon black graft polymers of different molecular weights of the polymers contained in the carbon black graft polymers. The composition is made of carbon black graft polymerized -89 This paper is ft scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 460489 A7 B7 V. Description of the invention () Different bond structures of the polymer contained in the material The resulting composition is used, and shoes are therefore paired. Those who fail to make the composition unable to meet the required conditions with only a single type, or only the single type can fully or fully meet the various conditions, but it is economical. From a point of view, When there is a problem, if taken at the same time and with the plural kinds, that is able to exert its effect more stupid. 2.1 Photocurable resin composition The carbon black graft polymer of the present invention is particularly suitably used as the M colorant added to the photocurable resin composition. For example, a carbon black grafted polymer can be added to a photocurable resin composition to obtain a photocurable resin composition. This photocurable resin is very suitable for forming a color filter matrix. The photocurable resin composition of the present invention comprises the carbon black graft polymer and, for example, (i) a photo-unsaturated unsaturated compound, (ii) a photo-synthesis starter, and (m) a binder. The necessary ingredients, in addition to the need for a solvent, can also be used in combination with plasticizers, discolorants, monofunctional ethylenically unsaturated compounds M, and other auxiliaries, as necessary. These compounds can produce light-curing resin M And the photo effect, photorealism, film properties and other properties. (i) The photo-unsaturated unsaturated compound is a compound that contains only two ethylene unsaturated double bonds in its molecule and is capable of cooperating. Instead, one or two compounds on K can be present. Suitable specific examples are, for example, polyhydric alcohols or methacrylates described in JP 35-5093, JP 35-14719, JP 44-28727, and the like, such as diethylene glycol (Methacrylic acid), triethylene glycol di (methane) acrylic acid, tetraethylene glycol (meth) acrylate, nonene glycol di (meth) acrylate, pentaerythritol tri ( Methacrylic acid ester, trimethylol-90-This paper size is applicable to China National Twin (CNS) A4 size (2! 0 × 297 mm) (谙 Read the precautions on the back before filling this page)-丨 Package ·, Π A7 B7 4 6〇4 8g V. Description of the invention ((Please read the note f on the back before filling this page) Two tris (methyl) propane ?: Glycolic acid vinegar, three diameter methylpropione (Methyl) propionic acid, quaternary tetraol tetra (methyl) propanoic acid @Purpose, the second quaternary tetratetramethylammonium (methyl) propanoate, dipentaerythritol (meth) propanoic acid Esters, 1.6-adipase di (meth) acrylate, etc., or bis (meth) acrylamidoamines "such as methylbis (meth) acrylamide, m-benzene Dimethyl bis (meth) acrylamine, etc., or compounds containing urinary dysfunction, such as * bis (2-methylpropane ethyl) 2,4-methylphenylene diuret, dione (2- Acetyl ethyl) Hexaethylene diurea, or react polyisocyanate with isocyanate to obtain tail (end) terminal isocyanate compound, and then phase with / 3-hydroxyalkane (meth) acrylate The (meth) acrylic urethane polymer obtained by the reaction, for example, the reaction product of four grams of 2,4-methylphenylisocyanate and three grams of oxalic acid is further reacted with / 3-hydroxyethyl The agent polymer obtained from the acrylic reaction, and 2.2, _ shuangxiang cage-based two-married, 2,2-bis-acrylic acid diacrylate and other diacrylates. (Ii) The photorecombination starter is, specifically, Aromatic ketones, such as stupid ketones, 4,4- · bisdimethylaminophenylbenzene, 4,4'-bisdiethylaminobenzene, 4-methylamino-4-dimethylaminobenzene _, 4,4'-dimethoxybenzophenone, 4-dimethylamino erythrone, 4-methylamino cage ethyl ketone, biphenyl brain, methyl alcohol, 2- (tert) tertiary monobutylene 2-methyl onion !, Phenanthrene, Xanthone, Thiazol, 1-M-thiazolidinone, 2,4-diethyl HeteroM ketones, ketogenic fats, acetone, etc., such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin ethyl ether, benzoin Isopropyl _, polybenzoic benzene _, etc., such as 2-, 4-5-triaryl tuberazole dimers such as 2- (0 -air poly) -4,5-dimer post beer dimers , 2- (0-chlorophenyl) -4,5-di (m — methoxyfloc) dimer, 2- (0-fluorophenyl) -4,5-diphenyl post beer- 91-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 4 604 89 A7 B7 V. Description of the invention (dual body, 2- (0-methoxycetyl) -4, 5-Diphenyl ΦK sialdimer, 2- (0 -methoxybenzyl) -4,5-diphenyl hoddimer, 1- (P-methoxyphenyl) -4, 5- Diphenyl hones, such as polytetrabromide carbon tetrabromide, benzenetrimethylol, benzenetrifluoromethyl, etc., and JP 52-133428, No. 57-1819, No. 57-6096, US Patent No. 3615455, etc., a combination of two compounds, such as 2,4,5-triaryl hones and 2-porobenzo Or combination of colorless crystal violet • For example, the combination of 4,4 · -bis (dimethyl truncyl) dimethanone and benzophenone or benzoin methyl ether listed in U.S. Pat. "N-methyl Cai" combination of Xiang Wei and 2,4-bis (trichloromethyl) -6,4-methoxycagel, or dimethylthiazine on JP 57-23602 A combination of a ketone with a dihydrocarbyl benzoic acid and the like. (iii) There are three types of adhesives, which are alkali developing type removed from the aqueous solution of the test portion of the unglazed portion, solvent developing type M removed from organic solvents, and water developing type removed from water. Also, in the photocurable resin composition of the present invention, if it is used for a black matrix diagram for a color extinguisher, it is preferable to use a soluble tester containing an age-soluble adhesive. The photohardenable composition that can be used for inspection and imaging is basically composed of a photorecombination starter and a polyadhesive containing a multifunctional monomer and a soluble group in its molecule. When it is irradiated with light, Hardened and insoluble in aqueous solution. Adhesives that can be formulated into carbon black-grafted polymers as described above and suitable for use as photo-sensitive, age-insoluble, hardening compositions for photographic calendars. The following substances. -92-The size of this paper is applicable to the National Standards of Ten Countries (CNS) and 4 specifications (210 X 297 mm) t ^ .1τ ------ 'r (Please read the note on the back before filling this page)

JL A7 B7五、發明説明（） 苯乙烯/两烯酸共聚合體、苯乙烯/異丁烯酸共聚合 體、笨乙鋪/« —甲基榮乙烯/两鋪酸共聚合體等的含有 苯乙烯齡可溶型樹脂；自丙烯酸τ醋/两婦酸共聚合體、 丙烯酸节酯/異丁烯酸共聚合體、f基異丁烯酸酯/異丁 嫌酸共聚合體等丙嫌酸及異丁締酸所成的化合物群中選取 的一種Μ上化合物衍生出來的重複單位，Μ及自（B)卞基 丙烯酸酿、Τ基異丁嫌酸醋、乙氧苯基丙稀酸酯、乙氣笼 基異丁鋪酸醋、3-苯丙基两烯酸酿及3-苯丙基異丁婦酸醋 所成的化合物群中選取一種以上而衍生重複單位的齡可溶 型樹脂； 含有異丁烯酸甲酷的異丁嫌酸甲酷/異丁肴酸2-乙基 -己基/(甲基）丙輝酸三元共聚合體、異丁嫌酸甲酷/苯 乙大希/丙烯酸乙醋/(甲基）丙蹄酸四元共聚合體、異丁蹄 酸甲醋/丙嫌酸乙酷/(甲基）丙締酸的三元共聚合體等的 齡可溶型樹脂；含有两嫌#的两嫌靖/異丁烯酸2-乙基/ 己基/異丁輝酸的三元共聚合體等驗可溶型樹脂； 含有苯乙嫌/馬來酸一正丁基酿共聚合體、苯乙烯/ 馬來酐共聚合體的有局部半脂化聚合體等的半脂化馬來軒 驗可溶型樹脂； 及由此等組合而成的他種組合物均可用為該當光硬化 組成物的添加劑。 又，因應必要亦可將與上列光聚合性化合物有相溶性 的有機高分子聚合體調入光聚合性樹脂組成物中做為皮膜 形成性成分，而此有機高分子聚合體有，聚两嫌酸酷或其 -93 - (婧先閲讀背面之注意事項再填寫本頁) ，*τ 本紙法尺度適用中國國家椟準（CMS ) Α4规格（210X297公釐) Α7 _Β7五、發明説明（） 部分（局部）加水分解物、聚異丁稀酸酷或其局部加水物 、聚醋酸乙婦S旨或其加水分解物、聚聚乙稀、聚乙輝縮丁 賤、聚氣丁輝、聚氯乙嫌、氯化聚乙輝、氣化聚两稀、聚 乙稀ettjΠ各燒嗣（Pl0yvinylpy「「olidone.)，苯乙：f：希與馬來留干 的共聚合體或其半脂化物等。 又，在不阻礙光硬化性的範圍内•亦可添加如甲酵、 乙醇、两醇等的低級酵類，如二甲替甲醜胺等的醜胺類* 如醋酸甲酯、醋酸乙酯、醋酸丁酯等酿類•如2-甲基*己 基醚、二嗯焼、乙嫌二乙醇一甲基避等継類，如2-甲替四 氮化岐喃（2-Methyltetrahydrofuran),糖酸等 南類 * 如 氯仿、甲基氛仿、三氣乙婦等鹵化合物類，如正己焼、正 庚烷等脂肪族碳氫化合物，如两_、丁銅、甲基異丁基甲 嗣等酮類，如乙鳴、十二烧晴等畴類，如二硫化碳、硫茂 等硫黃衍生體類等適當有機溶劑。又•為防止光硬化過度 反應，有時亦可使用氫喊T對一苯跑等聚合抑制劑。尚可 任意添加眾所周知的其他添加劑，如增帖劑、觸變性賦與 劑、均化劑、消泡劑及密著性附加劑等。 本發明的光硬化性樹脂組成物雖由如前所述碳黑接枝 化聚合物和光硬化性樹脂組成物調配而成，而碳黑接枝聚 合物對光硬化性樹脂組成物的調配量卻將受使用的光硬化 性樹脂組成物的種類來左右，即Ml〜80軎量％，最好Μ含 有碳黑接枝化聚合物5〜60重量％為宜。即，碳黑接枝化聚 合物的調對量未滿1重量％者，或有降低其黑化度之廣· 一方若超過80重量％者*即有降低皮膜強度之廣。 -94 - 本纸技尺度適用中國國家榡準（CN’S )八4说格（2丨0X29?公釐） (請先閱讀背面之注意事項再填寫本頁) A7 4 ^〇4 89 __________ 五、發明説明（） (诗先閱讀背面之注意事項再填寫本頁} 又，如同前述，將被加入到本發明的光硬化性樹脂組 成物的有關本發明的碳黑接枝化聚合物的全畺，不必都用 具有同一接枝化的聚合體的碳黑接枝化聚合物，即由完全 同一特性的化合物所構成的來充數，而可用具有不同接枝 化的聚合體二種甚至二種Μ上組合者。 又•有其必要時，亦可在不損害有關發明的光硬化性 樹脂組成物特性範圍內，調入其他的著色成分，如有機顔 料•由其他方製成的碳黒等物質。 由他法製成的碳黑有•將含有能和碳黑表面的功能基 起反應的反應性基及含有乙蹄性不飽和二重結合的聚合性 單體，即如前所述1.5節所述含有環氣基的聚合性翬體，含 有硫環氧，含有氣丙嗤基*含有嗎啤基及含有經烧酿胺 基等的聚合性單體，在非重合條件下，使其與碳黑反懕而 製成者。又，此等化合物的特性，應圼現如在有關所述第 一的發明的含有乙烯不飽和性二重結合的碳黑接枝化聚合 物時，使其聚合體為低重合度類似的特性者。 有關本發明的碳黑接枝化聚合物，均屬於Μ高度效率 將聚合體成分接枝化於碳黑表面的化合物。因此，當其被 添加於此等光硬化性樹脂組成物時，將使存在於碳黑表面 的自|^及酚性羥基等的重合阻礙性功能基被掩敝起來，而 有抑制光硬化性樹脂組成物的光硬化遲延作用。尤其在碳 黑接枝化聚合物;聚合體鏈串有乙嫌性不gg和二重結合者， 即有利於其硬化反應，不但會促進硬化的進行若再增加其 添加量，亦難於使其降低皮膜的硬化強度。又若碳黑接枝 本紙張尺度通用中國國家橒準（CNS ) A4規格（ZlOxW7公釐） 4^〇489 A7 _B7 _ 五、發明説明（） 化聚合物的聚合體鏈中有後基者，即將對於媒體圼現極優 的分敗性，又能提升在献ί溶劑中的溶解性。若碳黑接枝化 聚合物有如上列塊型以及接枝型聚合體者，碳黑的表面功 能基及所述塊型以及為接枝型聚合體成分的趟段（Α)所有 的反懕性基即會呈現高度反應性，由於以極高效率使該聚 合體成分被接枝化於碳黑表面，即使碳黑表面的阻礙重合 性功能基被完全掩蓋而抑制住光硬化性樹脂組成物的光硬 化遲延傾向，又所得接枝化碳黑是靥於所述聚合體的鍵段 (Β)配對在其外側，而被改良成為能與各種物質圼現親和性 •將使各種光硬性樹脂組成物具有優秀的分敗性測濟性， 使其分散於光硬化性樹脂組成物時，就能發揮適度的粘度 本發明的光硬化性樹脂組成物可Μ捍形、迴轉形、療 苘形、噴射等塗裝、顯影、照相印刷、網印刷等塗敷法將 其塗敷在玻璃板、塑膠板Μ及軟片、紙、合成紙、聚砂氧 乾膠尼（silicon wafer)等各種基材上後，照射紫外線10 〜5000mJ，使其硬化來形成黑色皮膜。 2.2黑色矩陣圖 欲用本發明的如上列光硬化性樹脂組成樹來形成滤色 器的黒色矩陣圖者，即可如下列的方法來操作。 用迴轉塗裝器將該黑色光硬化性樹脂組成物塗抹在玻 璃等基板上，再於溫度下，最好在80〜120¾用熱 風洪乾器或加熱板（Hot Plate)洪乾（予烤-Prebake) 1〜60 分鐘。用此法所得的黑色光硬化性樹脂組成物皮膜的厚度 本纸法尺度適用中国國家榡準（CN’S ) Α4規格（2丨0 X 2S»7公釐} ---------^----;--;1T------^ (請先閱讀背面之注意事項再填寫本頁) 4 60489 A7 B7 五、發明説明（） <請先閱讀背面之注意事項再填寫本頁) ，通常以約為1.0〜3.0 win程度為宜。然後，將點形、條 形等所定形狀的護面（Mask)密著於本黑色光硬化性樹脂組 成物皮膜上，用如高壓水銀燈等的紫外光源經該護面照射 平行光線50〜1000mJ使形狀曝光後，沖洗以得黑色矩陣圖 等的形狀。 用適當的顯像液在約Ο〜1001C的溫度下浸潰該皮膜Μ 溶去該皮膜的未硬化as的方法來维行被曝光皮膜的沖洗。 沖洗顯像後•用適當的洗淨所形成的著色畫面（素）後， 再用熱風琪乾器、加熱板等在溫度約為100〜300X：加Μ熱 處理1〜120分鐘（後腾），使著色重面完全硬化為宜。 欲用有關發明的黒色光硬化性樹脂組成物，在滤色器 形成黑色矩陣圖時，即有下列二法，即先在基板上使其形 成黒色矩陣圖後，再瑕成紅、綠及藍等各種顔色的著色圃 的方法，或先在基板上使其形成紅、綠及Μ等各顔色的著 色圖後，再使其形成黑色矩陣圖的方法*均可利用。 又，添加於光硬化性樹脂組成物的有關本發明的碳黑 接枝化聚合物為*如同前列所述含有不飽和二重結合者· 在曝光時，由於該當不飽和二里結合起作用而產生的架橋 Μ及重合鏈為媒介將使形成皮膜的樹脂矩陣圖相結合。因 此*邇後，雖經如上列的後烤處理，存在於皮膜中的碳黑 的分散狀態還是能保持其安定性，又不會由於後烤處理而 降低其電氣阻抗率。 2.3記錄媒體液 有關本發明的碳黑接枝化聚合物具有代表性的用途為 本紙伕尺度適用中國國家橾率（CNS ) Α4規格（21〇Χ?97公釐） 4 60489 . A7 _________ 五、發明説明（） 黑水噴射記錄法的記錄媒體液。 有關本發明的記錄體液，只含有如上列碳黑接枝化聚 合物為其著色成分即可，併不加以特別限定為由液體或由 其他成分而成，在用該當記錄媒體液為黑水嗔射記錄裝置 的方式時因應其方式（如電壓加壓方式*加熱加壓方式等） *及其嗔出條件（如在電傳加壓方式時，壓電元件的驅動 電®、驅動頻率、唄出口的形狀及材質、噴口口徑等，或 在加熱加壓方式時，在爾位時間内所作用的熱能的多少* 熱交換能的種類、噴出口的形狀、噴口口徑等），及被記 錄劑（紙、軟片）的棰類等而選取適合的液物性（粘度、 表面張力、導電度、沸點、熱傳導率、水溶性Μ及非水溶 性）的組成即可。 可使用的液媒有，水·如甲醇、乙酵、正丙醇、異丙 酵、正丁酵、第二鈒丁酵、第三鈒丁酵、異丁醇、戊醇、 己酵、庚酵、辛醇、壬醇、癸醇、糠醇、四氳糠gf等的一 價酵糸溶劑；如乙烯乙二酵、二乙烯乙二醇、三乙烯乙二 醇、丙烯乙二醇、四乙烯乙二醇、聚乙綿乙二醇、甘油、 1,2,6-己三醇、硫二甘酵等的多價醇糸溶劑：如丙酮、丁 S同、甲基、丙基甲胴、甲基戊基甲酮、二氯己画、雙丙酮 醇等的晒或酮酵糸溶劑；如***、丁醚、四厘咬喃、二噁 院、或乙烯乙二酵一甲基醚、乙鋪乙二酵一乙基醚、二乙 烯乙二醇一甲基醚、二乙嫌乙二醇一乙基醚、丙婦甘酵一 甲基醚、河蹄甘醇一乙基醚、三乙嫌甘酵一甲基醚、三乙 鋪甘酵一乙基醚、二乙稀甘醇二甲基醚、二乙婦甘酵二乙 -98 - 本纸伕尺度適用中國囷家標準（CNS )_人4坑格（2] 0 X 29?公釐） 裂 ^---Γ訂------级 {請先Μ讀背面之注意事項再填寫本頁) 4 60489 A7 B7五、發明説明（） 基醚等醚系溶劑；如甲酸乙酷、乙酸由醋、乙酸乙酷、乙 酸苯酯、乳酸乙酿、碳酸乙稀醋、碳酸丙蹄醋、乙締甘酵 —***甲酯等的醋糸溶劑；如一乙酵胺、二乙酵胺、三乙 醇胺等的胺系溶劑；如二甲基甲醯胺、二甲基乙酿胺等醯 胺系溶劑；如地略烧酮、H-甲基-焼酿|、1,3-二甲 基-2-蹄哩烧二酮等含氮現狀化合物物系溶劑；如已焼、 辛燒、環戊焼、苯、甲苯、二甲苯等碳氳糸溶劑；如四氛 化碳、三氣乙烯、四氣乙院、二氛苯等鹵化碳氫糸溶劑等 〇 自上述化合物中選取能合於所述記錄媒體用的各種特 性的一種或由其複數組成的混合物來供用。 若考虽其採購性、經濟性、環保性及調製記錄媒體的 難易度時，在這等溶媒液體中，即Μ水、一價醇糸Μ及多 價醇系、溶纖劑、溶纖劑乙醋等的液媒體為宜，卻以水及 乙醇最好。若Μ防止黑水的堵塞，即以二乙烯甘醇、硫雙 甘酵為宜，在番像濃度及噴出安定性上，即以含氮環狀化 合物或聚烯氧化物的艇化合物為宜，又從頻革應答（回應 )性來說，即Κ低鈒醇或將夜下列說及的界面活性劑為宜 〇 有關本發明的記錄媒體液相對於液媒體所加的上列碳 黑接枝化聚合物的調配量，併無其特定的限制，如將加入 的碳黑接枝化聚合物量控制在顔料濃度成為1〜20童量％， 最好在2〜12屋量％的範圍内，即宜以液媒體100簠量份加 碳黑接枝化聚合物1〜1〇〇重虽份，最好是2〜50重最份。 - 99 - 本紙伕尺度適用中國國家標準（CNS )八4規格.（2Ϊ0Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) ^ G Ο 4 89 Α7 Β7 五、發明説明（ % l· t 又，有關本發明的記錄媒體液雖是Μ液媒體及碳黑接 枝化聚合物為著色成分的基本構成成分，卻可因應需要加 入如粘度調節劑、表面張力調節劑、pH調節劑、比阻抗調 節劑、濕潤劑、吸收紅外線發熱劑等添加爾及樹脂成分， 又在不阻礙本發明的效果範圍內的著色劑成分如各種染料 及顔料等。 添加粘度調節劑或表面張力調節劑的主要目的在因應 記錄速度使其能圼現以充分的流經噴口，防止在嗔嘴孔內 發生記錄媒體的逆流現象*防止在被記錄材上形成擴散等 在不發生壞影響於記錄媒體及著色成分的限度内，即 可使用眾所周知的任何粘度調節劑及表面張力調節劑。粘 度調節劑有，如聚乙烯酵、經化丙基纖維素、俊二甲基纖 維素、羥乙基纖維素、甲基繼維素、水溶性（甲基）丙稀系 樹脂、聚丙鋪略烧酮、亞拉伯膠、殿粉等，表面張力調 節劑，即有如硫酸聚乙嫌甘酵S旨、脂翻等的陰離子糸界面 活性劑、聚2-乙烯哋啶衍生體、聚4-乙烯《»咖定衍生艘等的 陽離子糸界面活性劑、聚氧化乙烯基院酸、聚氧化乙烯基 院苯醚、聚氧化乙烯基焼酯、聚氧化乙嫌基山梨糖酵一烧 醋、聚氧化乙烯院胺等的非離子糸界面活性蜊等的各棰界 面活性劑；如二乙醇胺、丙醇胺、嗎》林酸等胺酸；如氫氣 化截氫氧化鈉等鹽性物質；如N-甲基-2- GthBS焼酮等的置 換吡略烧酮等。 必要時，可將此等粘度諝節劑及表面張力調節劑，各 -100 - (請先閲讀背面之注項再填寫本頁) 裝· 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -0 4 89 A7 B7五、發明説明（） 調成複數種的組合來使用。粘度調節劑及表面張力調節劑 的添加量雖然會受所用的液媒體種類，著色劑成分的添加 量而變化，卻以如對記錄媒體液100重量份添加粘度調節 劑0.1〜30重虽份，表面張力調節劑為0.01〜10重量份的 程度為宜。pH調節劑，即因應記錄體液的化學安定性，如 由於長期貯存而引起其物性變化或防止著色成分及其他成 分沈降或凝集Μ維持所定的pH值而添加。pH調節劑有，低 級降截基鹼；如氫氧化氨的齡金屬氬氧化物等一價氫氧化 物。 若要使有關本發明的記錄媒體液液滴帶電而進行記錄 時，記綠媒體液的比阻抗*即成為其帶電特性的重要因素 了。在這種記錄方式時，為了要調節記錄媒體液的比阻抗 值在規定的範圍内，就可Μ添加比阻抗調節劑。比阻抗調 節劑有，如氛化按、氯化納及氣化押等無機鹽類；如三乙 醇胺等的水溶性胺類和第四級鑛鹽等。 又，可μ在本發明的記錄媒體液使用mr濕潤Mr，己 ，如聚乙g聽、聚丙二醇等的聚二醇（ -- ~· . polyaIkylene glycol);如乙二酵、两二酵、丁二醇及已 二(Hexylene glycol)等的燒樓乙二醇（Alkylene glcol );如乙二酵甲醚、二甘醇甲醚（diethylene glycol methyl ether)，二甘醇***等的院樓乙二酵及二嫌甘醇的院醚； 如甘油；如甲氣基三甘醇Cmethoyytri-slycol),乙氣基三 甘酵等的烴氧基三甘酵（Alcoxytri-slycol);及如N-乙烯 基-2- Π各烧醜聚合物（N-Vi ny 卜 2-Pyrrol idone oligomer * 1.01 - ^^1 ^ir— 1: ^^1 n - - I HI 1^1 I HI —^n (請先閱讀背面之注iW-項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X 297公釐） '60 4 89 A7 B7 五、發明説明（） )等。可用一種或複數種組合的上列化合物做為藤潤劑。 其中有許多化合物，亦可作為液媒體之用。 若欲Μ電磁波，尤其是以紅外線來加熱而逍行記錄時 ，亦可Μ在記錄媒體液中添加吸收紅外線的發熱劑。如前 列所述，本發明雖然含有能夠吸收紅外線，為發熱劑的碳 黑著色成分之外，尚有如水溶性苯胺黒（Nisrosine),變性 (成）水溶性苯胺黑、酵溶性苯胺黑等的染料、群青、錫 黃、氣化第二锁、絡黃等無機顔料、偶Μ糸、三聚甲焼糸 、奎糸、葱晚糸、祕花青系等的有機頭料亦做為吸收紅 外線的發熱削。其中尚有多種亦具有著色成分的作用。 又為了提高有關本發明的記錄媒體液固定在被記錄材 時被膜的形成性及被膜強度，亦可以添加如酵酸樹脂、丙 締樹脂、两締酿胺樹脂、聚乙稀醇、聚乙嫌咕略院嗣等樹 m - 2.4靜電荷潛像顯像用液體顯像劑 有關本發明的碳黑接枝聚合物具有代表性的另一用途 有靜電荷潛像顯像用液體顯像劑。 ¾耷郎中央樣莩局員工消費合作枉印裝 n in - In n I -- 1 tp I- s I Hr I —丁 0¾"a (請先閲讀背面之注意事項再填寫本頁) 有關本發明的液體顯像劑，只含有上列所述的碳黑接 枝聚合物為著色爾則可，至於帶動液（carrier liquid) · 固定（定著）劑Μ及其他成分，即未加以任何限制*可以 使用已知的各種化合物來代替。又在不阻礙本發明的有關 效果的範圍内，亦可使用各種染料及顔料為其著色劑成分 Ο Μ無極性溶媒 > 如具有誘電率3.5以下的電氣絕緣性（ -102 - 本纸伕尺度適用中國困家標準（CN’S}A4規格（2丨OX297公釐） B O 4 89 A7 ____B7__ 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 體積固有電阻* cmM上）的碳厘糸溶劑為帶動液的代 表性化合物。最好的例有*沸點在150〜22〇π範園的脂肪 族碳氫化合物、芳香族碳氫化合物及此等混合物。更具體 0勺說，如13〇63厂-〇，日丄（益克松公司製），31^1〗3〇1/\48 (Shell公司製），Naphthesol L, m.H (日本石油公製）等， 都可以使用，但併未加以限制。 不使帶動液現出不溶性或膨潤性的樹脂，都可Μ做為 固定劑，如聚乙嫌樹脂，（甲基）丙鋪樹脂、聚乙稀樹胞、 醋酸乙烯樹脂、酯樹脂、醯胺樹脂、酚變性（成）酵酸樹 脂、環氧樹脂、亞麻仁油變性（成）酵酸樹月旨、香豆_ · 茆樹脂、酚一甲醛樹脂、松香樹脂、苯乙烯一丁二烯膠、 環化橡膠等均可使用。 因應必要，亦可以添加電荷調節劑。電荷調節劑有環 院酸、辛稀酸、油酸、硬脂酸、月桂酸等的脂肪酸金靥鹽 、硝基玻泊酸酷的金屬鹽，特公昭45-556號登載的油溶性 磺酸金屬鹽，特公昭48-25666號登載的松香酸（Abietic Ac id)或加氫松番酸的金屬鹽，特公昭55-2620號上的院基 聚硝酸柯鹽，特開昭52-10837號上的芳香族碳酸或碌酸金 屬鹽及聚氧乙基化鋁胺等非離子界面活性劑、卵磷脂、亞 麻仁油等的油脂類、聚nfct略院嗣（Polyvinyl Pyrrolidone) ，多價酵的有機酸酯等眾所周知的電荷附與劑及電荷調酣 劑，均可使用。 2.5其他用途 有關本發明的碳黑接枝聚合物的其他用途，雖未加从 -103 - 本纸ίί：尺度適用中國圉家榡準（CNS } A4規格（2I0X 297公釐）- f?〇4 89 A7 B7五、發明説明（） 特定的限制，卻可供做下列各種用途上。如用在各種樹脂 組成物，被覆組成物、墨汁、感熱復寫用墨水帶被覆劑、 磁性記錄媒體用贸覆（basck coat)劑、靜電荷顯像用碳粉 、塗料，需高電阻及遮光性的材料、人工大理石、塑膠及 橡膠成形材料、遮光性纖維等的著色劑、聚烯烴及聚酯等 的塑膠Μ及橡膠的改質劑和充填劑、潤滑劑、牽引驅動流 體、電氣粘性流體或非線形光學材料、電阻調節，例如防 止帶電材料、利用抗阻材料或PTC特性的複印機内部之面 狀發熱體，半導體設備用封止劑等。 若添加於熱可塑性樹脂時，就能供為具有上列特點的 影印機碳粉、軟片及纖維之用。又，將該當碳黑接枝聚合 物添加到熱硬化性樹脂•亦能發揮相同的特點而可解決從 來就一直使用的碳黑所引起的各種問題。 又，把本發明的碳黑接枝聚合物添加於被覆組成物所 用的粘著劑時，將使被塗抹的各種基體得到更為強固的被 膜。這種粘著劑的成分是眾所周知的熱可塑性樹脂、熱硬 化性樹脂或反應性樹脂所成，由其用途的不同，可使用其 中一種或二種以上的混合物。 又·本發明的碳黑接枝聚合物是使碳黑成為微綑的分 散狀態分散在液相中，就是一種具有分散安定性和優超著 色力功能的油性筆記用、資訊記錄用或印刷用的墨水，可 Μ該碳黑分散液的原狀或追加適當的必要成分混合後來使 用。 3.含有碳黑的樹脂組成物的製造方法 -----D ! (請先Μ讀背面之注f項再填寫本筲) 本纸乐尺度適用中圉國家橾準（CNS )六料見格（210Χ：297公釐） 89 - . Α7 _Β7__ 五、發明説明（） ^衣-- (請先閲讀背面之注意事項再填寫本頁) 又有一種，即如所述1.5節所述的將塊型以及接枝聚合體 接枝在碳黑上的方法。亦就是將成為分散媒體的樹脂成分 和碳黑及含有能與碳黑表面的功能基起反應的反應基越段 (A)及實質上未含有所述反應基的所述鏈段（A)具有對所述 樹脂成分更高親和性的鏈段（B)的塊型以及接枝型聚合體 一同溶融混合為其特點的含有碳黑的樹脂組成物的製造方 法。欲分散碳黑的目的媒體若為樹脂成分時，如同在所述 第一發明一樣，不必在分散媒液中搜拌混合碳黑與接枝型 以及塊型聚合體，只要直接將其在成為目的媒體的樹脂成 分中溶融混合所得的製品，亦將圼現優良的碳黑分散性》 亦即能Μ簡便操作而獲得希望的製品。此時所得的優秀分 散性是，正如同在第一發明所述一樣，來自溶融練合時的 溶融狀態之樹脂成分（在分散媒髖），現出該當塊型Μ及 接枝型聚合體的配向性而很有效率的向碳黑接枝化所致。 4.表面改質處理法 有關本發明的固體微粒子的表面改質處理方法是在分 散媒液中，將固體微粒子與含有能和存在於所述固體微粒 子表面的功能基起反應的反應性基的反應性聚合物在加熱 下來分散處理以表面改質處理固體微粒子。因為存在於分 散媒液中的微粒子，由於分散處理時的搜伴等操作受到物 理的扭力作用，自二次凝集狀態被解辟而成為一次粒子存 在於分散媒液中，又由於分散糸處在加熱狀態之下，將使 固體微粒子表面的功能基與反應性聚合物的反應性基容易 反應而宪成接枝化。然而，由於固體粒子與反應性聚合物 本紙伕尺度適用中國國家標準（CNS ) Α4規格（2丨0X29?公釐） 4 60 4 89 A7 B7 五、發明説明（） 的反應是在分散媒液中進行*就應該比固體微粒子與反應 性聚合物海融練合的方法在系全體上能得比較均一 ’更為 緩和的進行反應•縱使對固體粒子只有低度配合比的反應 性聚合物，或是每一分子中含有較多反應基數的反應性聚 合物，均能完成良好的表面改筲處理。或因為在這種分散 媒液中進行分散處理時，亦能使低分子量的反應性聚合物 獲得十分的扭力作用，而與溶融練合反應所得的相異*卻 有良好的表面處理效果。由於如此，在本發明的方法上， 就不需要如同κ已知的溶融練合反應一樣的多量反應性聚 合物*又不必限定何種反應性聚合物，均可將固體微粒子 的表面性狀因應期望加以適宜的變更。 又，由於依照本發明的方法製成的固體微粒子分敗液 *經過固體敝粒子的表面改質而改菩了對分散媒液的親和 性圼琨均一又安定的分散性，就可Μ其原狀用於各種用途 上*亦可將其自分散媒體中分離出來供做各種用途。 又，所謂對固體微粒子表面進行反應性聚合物的「接 枝化」，即與上列一節所述同一意義了。 坌耷牢令夬溧隼苟员工育费合作钍印裝 (請先W讀背面之注意事項再填寫本頁} 有關本發明的固體微粒子的表面改質方法上，可Κ做 處理對象的固體微粒子者，即不加Μ特別限定為何物，只 含有對反應性聚合物的反應性基能起反應的功能基的化合 物均可使用，涵蓋顔料、磁性粉末、陶瓷粉體、有機微粒 尤其對顔料中的無機顔料，如碳黑、粘土、碳酸縛、 二氧化软、妖白、籮氧化銘、滑石粉、消石灰、氫氧化鎮 -106 - 本纸張尺度適用中國國家標準（CNS ) A4^格（210X297公釐） 4^〇489 A7 _______B7 五、發明説明（） 、氫氧化第二鐵、水泥、氧化銘、锆土、桂石、碳化硅、 氮化鞋等，及磁性粉末是最有效的處理方法，然而對碳黑 ---------^------1Τ <請先閱讀背面之注意事項再填寫本頁) 更具有效。碳黑，即以在所述1.1節所述的同樣物體最適合 〇 同時•使用在本發明的反應性聚合物，即雖从含有能 與這種固體微粒子的表面功能基起反應的反應性基物體均 可供用，例如以反應性基來說，如選自瓖氧基、硫環氣基 、氮丙陡基及嗯哩咐基成的群中至少含有一種功能基的物 體為宜。亦即為在分子内含有此等反應性基的乙嫌糸聚合 物，聚酷及聚醚等的聚合體。在所述1節所述的各種聚合 體亦包含在本反應性聚合物中是當然的了。 欲得埴種反應性聚合物的方法*即如同在所述1.2節 所述之：雖有 ⑴將在其分子内含有反應基的聚合性單體（M下稱為 單Ke)依其必要與其他的聚合性單體（M下稱為單體Λ ) 進行重合的方法， ⑵將在其分子内含有所述反應性基的化合物（Μ下稱 為化合物心）與含有能與該化合物起反應的基的聚合體（Κ 下稱為聚合體ηρ)相反懕，而把所述反應性基引進聚合體d 的方法，又有， (3)用在其分子内含有所述反應性基Μ外的反應性基的 聚合體（Μ下稱為聚合體0«)依照眾所周的方法變換成 含有該反應性基的聚合體之各種方法，卻以⑴之方法最為 適合。 -107 - 本紙伕尺度適用中國囷家揉芈（CNS > Α4現格（210 X 297公釐） 4 60489 A7 ___B7_五、發明説明（） 在上列(1)的方法上，可以供用的單體k *即有，在所 述1.5節所說的簞體a，如含有環氧基的聚合性單體類，含 有硫環氣基的聚合性單體類，含有Μ两喷基的聚合性單體 類、含有嗯啤冰的聚合性單體類及含Ν-經燒醯胺基的聚 合性單體類等*可從這座群中選取其一棰或二種以上來使 用。 在⑴的方法上，因應其需要而能供使用的單體/BP有 ，能與單體k進行重合者就不特別限定其種類均可使用》 如在所述1.5節所述的聚合性單體c或與其同樣的物體。可 Μ使用其一種或二種Μ上來製造。 欲依照⑴的方法來製造含有反應性基的反應性聚合物 時*即可以使用單k與必需的單體/，依從來就已知的重 合法，如塊狀重合法、懸濁重合法、乳化重合法、沈澱里 合法及溶液重合法等來進行重合反應就行了。 能供用於(2)之方法的化合物m有， (2-1)在分子內含有所述任何一種反應性基二個以上 的化合物。 (2-2)在分子内含有所述任何二種Μ反愿性基的化合 物。 (2-3)在分子内含有一種Μ上的所述反愁性基及所述 反應性基Μ外的反應性基之化合物。 但是，記載於（2-3)項的的所述反應性基Κ外之反應 性基是除去氮两陡基、嗯哩基、Ν-羥燒醯胺基、環氣基 及硫環氧基Μ外的反應性基，而能與後述的聚合體（η)的 (請先W讀背面之注f項再填寫本頁) •裝- ,ιτ .本纸乐尺度適用中國國家榡準（CN_S ) Α4規格（210X297公釐） 4 60 4 89 A7 _B7_ 五、發明説明（） 反應性基起反應的化合物，如異镢鹽基、截基、羧基、經 基、乙烯基及鹵族基等。 (請先閲讀背面之注意事項再填寫本頁) ⑵的方法所用的聚合體（η)是指能與所述（2-1)〜（2-3) 所述的化合物c起反應的乙烯系聚合體、聚酯及聚醚等。 能與化合物（m)起反應的功能基有，如羥基（涵蓋酚性羥基 )、梭基、基、氨基及環氧基等，而含有這些反應基的 聚合體（η).即可藉眾所周知的重合、重縮合等的方法，容 易製成的。 欲依⑵之方法來製造含有反懕性基的反懕性聚合物時 ，即將化合物（in)與聚合體（η) Μ能夠殘留一個以上的前列 所述的反懕性基為未反應的狀態之條件下進行反應就可Κ 得到。 在⑶的方法所使用的聚合體（c)有，在分子内含有氮丙 嗤基、嗯峨·#基、Ν-羥院醯胺基、環氣基或能轉變為硫環 氧基的反應性基、如在其分子内含有乙烯基、羧基、氯乙 醇基、甘醇基的聚合體。這呰聚合體均能容易的以已知的 方法引進氮丙陡基、嗯啤I#基、Ν-羥烧醯胺基、環氧基及 /或硫填氧基於反應性聚合物中。 至於使用在本發明的反應性聚合物，即Μ如在所述1.5 節所述一般的，對欲使其結合該當反應性聚合物的固體微 粒子有高親和性的部位（Α),和對欲分散本固體微粒子的目 的媒體呈現高親和性的部位（Β)都具有的方式而具有良好 的結合性及表面改質性雙面的聚合體，亦就是說，要具有 如上列相異特性的部位（_段）的塊型及接枝型聚合物為 本紙張尺度適用中國國家標準丨CNS ) Α4現格（210Χ297公釐）. 4 BO 4 89 A7 B7 五、發明説明（） 宜。卻僅只使對於固體微粒子圼現高親和性的鐽段A上留 存反應性基。又，塊型及接枝型聚合物，即涵蓋單純的A-B型等以及如B-A-B梨有高度交互塊型，由複數的B鍵段接 枝於鏈段A上所成的梳子形的聚合物。 供用於本發明的反應性聚合物的分子量*即可用如同 前列所述一般的廣大範圍的聚合物，如其平均分子量為100 〜1000000，而Μ有5000〜1000QO者較宜〇 又，反應性聚合物每一分子所含的反應基數，亦可使 用如前列所述的較大範圍的聚合物*如平均每一分子含有 1〜5個反應基，卻Ml〜20個的為宜。 在本發明的表面處理方法上，並未特別限定使用一種 分散媒液來調合固體微粒子及反應性聚合物，而可使用各 種水溶性或非水溶性的分散媒液，如水；如甲酵、乙酵、 異丙醇、丁醇*及芳香族醇等的醇類；如乙二酵、丙二酵 、二甘醇、聚乙二醇、聚两二醇、二甘酵一***、聚丙二 醇一乙酿、聚二醇一芳香醚、聚两二醇一芳香_等的二醇 以及其衍生體類；如甘油、甘油一***、甘油一芳香醚等 的甘油Μ及其衍生物；如四Μ咬喃、二嚼烧等的_類；丁 酮、甲基•異丁酮等的酮類；如石油、癸院、癸稀、甲 基多、袭烧、煤油、二苯甲烧、甲苯、二甲苯、乙苯、二 乙苯、两苯、環己烧、局部加水的三苯基等的碳氫化合物 類，如聚二甲基陆氣焼、局部被辛基置換的聚二甲基鞋氧 烧、局部被苯基置換的聚二甲基娃氧慌、氣化鞋油等的石圭 油類，氯聚、二氣苯、漠苯、氯聯笼、氣描g苯甲烧等的鹵 -110 - 本紙張尺度適用中S國家樣準（CNS ) Α4規格（_210x297公变） 私衣--------ί·、1τ------0 (請先閱讀背面之注意事項再填寫本頁) 4 6 04 89 A7 B7 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 化碳Μ類，如Dailrol (大金工業（株）製）、Deronum ( 大金工業（株）製）等的氟化物類，如安息香酸乙醋、安 息香酸辛酯、赋酸二辛酯、偏苯三酸三辛酯、癸二酸二丁 酷、（甲基）丙稀酸乙酯、（甲基）两蹄酸丁醋、（甲基）丙烯 酸十二院醋等的酷化合物類等，應以固體微粒子的種類及 希望的分散液用途而適宜選用。 又，在不阻礙固體微粒子的接枝化反應範圍内，可Μ 添加眾所周知的單體，聚合物及各種安定劑。 本發明的表面處理法，雖為在分散媒液中調配固艘微 粒子及反應性聚合物共同於加熱之下來進行分散處理，卻 由於對固體微粒子所加的反應性聚合物的比是會受到所使 用的反應性聚合物的種類及希望的製品用途之左右，不能 加Μ—概規定*而以固體微粒子100重量份，添加反應性聚 合物5〜500重量份，最好以20〜200重量份的程度為宜。亦 就是，若反應性聚合物未滿日重量份時，或有無法十分改 質固體微粒子的表面性狀之虜，另一方面，若超過500重 量份者*會使结合在固體微粒子表面的反應性聚合物量趨 於過多而損失其本來所要泶的固體微粒子的特性之處。 又，攪拌混合時的加熱溫度，亦將受到所使用的反應 性聚合物的種類等之限制，不能加以一概規定* Μ50〜250 °C，理想溫度為80〜250°C，卻以100〜220°C的程度為最 適當。若溫度未達50C時，即無法使反應性聚合物的反應 性基與固體微粒子表面的功能基充分反應•反之，若超過 250°C時，反應會變為急激而難於控制了。 本紙張尺度適用中國國家標準（CNS ) A4说格（.2丨0 X 297公釐} 460489 A7 _B7 五、發明説明（） 至於分散處理上所加以固體微粒子的剪斷應力，亦會 受到使用的固體微粒子等種類的影響*雖不加Μ特別限制 ，卻以10*· PaM上為宜，理想、的剪斷應力是10$ PaM，而 M104 PaM上為最好。 因為在這種適當的剪斷應力下加熱而進行分散處理的 本發明之分散處理過程中，最好應具備能容納被處理流體 在其中的容器，在容器内部能旋轉的攬拌子，能加熱容器 内的被處理流體的加熱裝置及容器内的複數粒狀分散媒體 所成的濕式分散處理裝置來進行。 併用撹拌子和球狀等粒狀分散媒體的攪拌以及解轉的 濕式分散處理装置及濕式粉辞處理裝置等，眾所周知者雖 然甚多，在本發明上所使用的裝置，卻多了為加熱被處理 體用的加熱装置。其裝置的構成例如下。 圖5及圖β，各為有關本發明所使用的固體微粒子的 表面改質處理方法的一種實施橫式的濕式分散處理裝置斷 面圖。 圖5所示是實施模式的濕式分散處理裝置有由軸線略 圼水平方面的圃筒型閉塞容器體所成的容器1之横型處理 裝置。在容器1外壁面左右之圓盤狀端面部中的一邊（圖 中左側> Μ下稱之為左側端面部）的中心部份設有回轉軸 ***孔，經此孔能自外部沿著容器的軸線向容器内部的空 間以液密的方式***回轉軸2。在位於回轉軸2的容器空 間部，設有略與回轉軸垂直的具有規定間距之複數圓盤狀 授拌子3，回轉軸2則在外部與不在圖示上的驅動装置相 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公茇） 裝 ί I 訂— 11 I I |妹 (請先閲讀背面之注意事項再填寫本頁) 4 604 89 A7 B7 五、發明説明（） (請先W讀背面之注意"項再填寫本頁} 連接。又在容器1的外壁面的圓筒狀周面部的前列左側端 商部附近處在上方位置的部分上，設有流體導出口 14，而 在他方货面上的端面部（M下，稱做右側端面部）附近而 位於下方處按裝具有防止逆流閥12的流體導入口 13，由此 *本裝置即成為連績處理的方式裝置。在容器1的內部空 間內裝有做為分散媒體的球粒4，又在前列流體導出口 14 附近配置前列球粒4無法通過而分散液以及固體微粒子可 以流通的具有間隙15c之媒體分離器15。前列媒體分離器 15的間隙15c是設在略與容器1的軸線成垂直方向的圓壞狀 固定板部15a，及回轉圓盤部15b之間，固定板部15a的全 部外周即連接在容器的內周面（圓苘狀周面部），他方的 回轉圓盤部15b即如同前列撹拌子3的情形，被按装在回轉 軸2上。 然後，在容器1的壁面外周，即繾繞帶狀加熱器11做 為加熱裝置，成為能加熱容器1內部的被分散液的構造。 在容器1的右側端面部，又按裝了檢測容器内部流體溫度 的熱電偶5。 在本裝置上*由流體導入口 13被引進容器1內部空間 的被處理流體*即，例如處在二次凝集狀態的固體微粒子 ，分散媒液及含有能與固體微粒子的表面功能基起反應的 皮應性基反應性聚合物形成的配合物到尚未由流體導出口 14排出的期間中，會受到撹拌子3的旋轉及由回轉而引起 球粒4的各個回轉、旋轉，相互的接觸、衝擊等伴隨而起 的流動蓮動所生的剪斷力及帶狀加熱器Π的加熱被解球成 本紙張尺度適用肀图國家標车（ CNS ) A4说格（210X297公釐） 4 60489 A7 B7 五、發明説明（） 為分離的個個一次粒子之固體微粒子將均勻的分散在分散 媒液中，以致於使該當固體微粒子表面的功能基與反應性 聚合物的反應性基進行極有效率的反應，結果自流體導出 口 14排出的分散液，即不但往取出當時圼現良好的分散狀 態*亦會保持長久時間的良好分敗狀態。 又*如圖6所示實施模式的濕式分散處理裝置是由其 軸線略為垂直方向位置併在其上端有開口的画筒型容器體 本體la及有覆蓋前列開口的蓋體lb形成的容器1所構成的 縱型批次式處理裝置。在容器1的蓋體lb的中心部有回轉 軸***孔，可經此***孔沿著容器軸線自審器外部向容器 内部***回轉軸2。在處於這個回轉軸2的容器內部空間 部，裝有與容器軸線略圼垂直的面上，以回轉軸為其中心 而作放射狀散開，又在容器的軸線方向上各具規定間隔的 多段階的針狀複數攪拌子3a。另在容器1的内周側面上裝 有順著容器的軸線方向不與前列搅子3a互相千涉處有多段 落（即，如同二枝梳子的梳齒各能吻合一般的配置），而 且在略與容器的垂直面上自内周側面向回轉軸形成收束的 放射狀的複數針狀固定子3b，即形成一種擾亂板的作用。 回轉軸2在容器外部與未在圖上出現的驅動裝置相連接。 在容器1的内部空間，即裝入如前列圇5所示的實施模式 一般的球粒4做為分散媒體。 在容器1的圓茼型容器體本體la檗面外周上裝設加熱 器9的熱媒貯藏器8及在其中途配有熱媒循環幫浦7的循 環管路相連接的加熱套管6，利用熱媒的循環來加熱装在 -114 — 本紙張尺度適用中國國家標準（CNS) Α4^格（210X297公釐） (诗先閱讀背面之注意事項再填寫本頁) •丨裝. 訂 4 6〇4 89 Α7 Β7 五、發明説明（） 容器1內部的被分散液所成的構造。 在本裝置中，能使裝在容器1内部空間的被處理流體 ，即使二次凝集狀態的固體微粒子•分散媒液含有能與及 固體微粒子的表面功能基起反應的反應性基反應性聚合物 所成的配合物，在規定時間的攪拌處理而受到搅拌子3a的 旋轉及由此回轉攪拌子3a和固定子3b的存在而引起裝填在 其中的球粒4進行各個的回轉、旋轉、相互接觸。衝擊等 伴起的流動所生的剪斷力，同時又受到加熱套管6的加熱 影響，被解碎成各為分離的一次粒子之固體微粒子，能在 分散媒液中分散均句*同時又使該當固體微粒子表面的功 能基與反應性聚合物的反應性基起有效率的反應，經過規 定時間後•即能製成不但在取出後具有良好分散狀態的分 散液，又能保持其良好分散狀態長久安定的成品。 ί£齊郎中央樣準馬貝工省旁合作汪印敦 (請先閱讀背面之注意事項再填寫本頁} Μ上是基於圖示的貿施模式來說明濕式分散處理裝置 的構造而已。在本裝置上，用來加熱容器内的被處理流體 的加熱裝置，即不限定任何樣式，能夠有效地加熱容器内 的被處理液體者都可使用*有上列的熱媒循環方式•帶狀 加熱器，或如陶瓷加熱器及紅外線加熱方式，高周波誘専 加熱方式，線圈型加熱器等都可以使用。其配置位置亦不 不僅限止於如上列實施模式的按裝在容器外周而已，在未 妨礙攪拌子的旋轉範圍内•設置於容器内部空間，亦可裝 設在容器内面，搜拌子及回轉蚰上，或固定子及擋板上。 然而，就裝置的構造或控制溫度的方便上考慮時，即在容 器外周部裝設加熱裝置為宜。 -115 - 本紙張尺度適用中國国家梯準（CXS )八4说格（210Χ297公釐) ： ~ 4 6〇4 89 A7 _B7_ 五、發明説明（） H - I - - —1 - - ,¾^—1 I ------ (請先閱讀背面之注意事項再填寫本頁) 又，在本裝置上，除去加熱装置Μ外，尚有濕式分散 處理裝置的基本構造，即不特加以限定使用某一種方式， 可自如連鑕式及分批式，容器的材質、形狀、授拌子的材 質、形狀及其配置SI3位、分散媒體的材質、彤狀及其粒徑 等的不同，Μ希望的分散液及被處理的固體微粒子的反應 性等化學性質及其比重、粒度等的物理性質等的差異，選 取適合的方式來使用。 容器的材料，即有如氣化鋁、氧化結、塊滑石、傲化 石圭、碳化鞋、碳化鏡等的各種陶瓷土，各種玻璃，如鋼、 絡鋼、哈斯田線合金（Haste iloy)等的（Ni)糸合金等各種金 屬的一種或二種Μ上的含金來構成。其型式，即有横型及 縱（Μ)式，如圓筒型、圓維型、半圓筒型，如登載在特 公平2-27018號上的容器或續石微磨機（018111〇^^16 1!1111) (三菱重工製）等的斷面W字型及：：（横置U)字型，又如特 公平6-73620號的在内部收容分散媒體而成（裝設有搅拌 子以及由授拌子來形成容壁面的一部分）而容許内外的流 體（分散液）互流的容器裝設在較大外包容器内的型式等 ，各棰型式。 又，撹拌子的材料，即與容器同樣，可 Μ自氣化錯、氧化維、塊滑石、氣化硅、碳化硅、碳化鎢 等的各種陶瓷上*各種玻璃鋼、鉻鋼、哈斯田線合金 (Hastelloy，商品名，Haynes Stellite Co. U.S.A.公司 產品）等的鎳系合金等各種金屬選取適當的來使用。但， 所用材質與容器用材質有所相異亦可Μ使用。又·其形狀 即可使用單一型式或多段式，如上列所述的圓盤狀（圓盤 -116 - 本纸張尺度適用中國國家標準（CNS ) Α4規格（2丨0X297公釐) ： ' ~ 4 6 0.4 89 A7 B7 五、發明説明（） 形-disc型），針型之外，尚有盤形渦輪式、扇形渦輪式、 虫累旋型、螺旋軸翼型、據旋帶翼型、閘門型、錨型、圓筒 型、槳葉型等各狀的形狀，或再在這些攬拌子上設通液性 孔洞的改良型的攪拌子。形成攬ί半子的回轉軸可配置在容 器的轉蚰上，或偏異於中心軸處或二軸及多軸上。 又，分散媒體，即可因應欲處理的固體微粒子種類及 攪拌子的種類，可適宜變更，其能使用者，有氧化鋁、氧 化$告、塊濟石、Μ化鞋、碳化鞋、碳化錦等的各種陶瓷土 ，各種玻璃、鋼、鉻鋼、η台斯田練合金（Hastelloy)等的 鎳糸合金等各種金靥所構成的球狀、圓苘狀、回轉椭圓體 狀等各種形狀*但，其中Μ由氣化紹、氧化i告、鋼、絡鋼 等材質所造成的球狀珠粒而通常直徑在0.05〜20mm程度， 而使用直徑在0,1〜5nm的珠粒的最好。至於對容器的裝入 分散媒體量，即受於容器或攪拌子的型態等而未能加以限 定，在容器的有效容童之20〜90%為宜，最好是30〜80% 。若其充填比極端少量時，將使二次凝集狀態的固體微粒 子無法被十分的解碎及固體微粒子與反應性聚合物的反應 未能充完成，另一方面，莕其充填比極端大董時，或會引 起分散媒體間的磨損而加大污染之虡。 實施例 下面為欲更加具體的說明本發明的實施例，其意只在 易於理解本發明之用，並不表示對本發明的操作有所限制 n. I-Γ *-1 II - ^^1 —^1» I . n^i - ____ (請先閱讀背面之注意事項再填寫本頁) :土 下面若無特別加註時，以「部」代替「重量部份. -117 - 本紙乐尺度逋用中國國家橾率（9NS )八4規_格（2丨0X297公釐） 4 6〇4 89 A7 B7五、發明説明（） Μ「％」表示「重量％」。 合成碳黑處理用聚合體的方法 合成例1 將酿（性）酚酸清漆環氧樹脂YDPN-638Ρ (東都化成製 ，壞氣當量為180) 100部入於附有搅拌冀及IS流冷卻器的 分液瓶中，加丙輝的32部、氯化第三路6水和物0.13部及 甲基氣峨X). 11部，在ll〇°C使其加熱反應二小時，確認反應 物的酸價為0。將此物當做壞氧丙烯酯樹脂⑴。 合成例2 取齡（性）酚酸清漆壞氣樹脂YDPN-638f>(東都化成製 *環氧當量為180) 100部入於附有搜拌酱及埋流冷卻器的 分液瓶中，加丙烯酸41部，氮化第二路6水和物0.14部及 甲基氬酿ι0.12部，在溫度1101C加熱反應二小時，確認了反 應物的酸價為5.5。將此物當倣環氧两烯酷樹脂⑵。 合成例3 取甲_ (性）酿酸清漆環氣樹脂YDPN-638P (東都化成 製，環氧當量為200) 30部入於附有授拌翼及遨流冷卻器的 分液瓶中，加两烯酸δ.64部，乙蹄基卞必酵乙酸醋（Ethylene carbitol acetate) 309.12部，氛化第二絡六水和物0.04 部及甲基氣酿i〇.03部，在溫度ll〇°C，加熱反應三小時，確 認了反應物的酸價為〇。將此物笛敝壞氣两締酷樹脂(3)。 並將反應物視為乙婦基卞必醇乙酸酿和溫和物的原狀。 合成例4 取在合成例2所得的環氧丙烯酸酯樹脂⑵30部和四置 —118 ~ I n I n .^1 ϋ n -1 Ϊ n I m n T 09 - ,T (诗先閱讀背面之注f項再填寫本頁) 本紙尺度適用中國國家標準（CMS ) A4现格（210X297公釐} 4 604 89 A7 ' B7五、發明説明（） 化酞酐42.2部，無水氯化鋰0.14部在溫度1001加熱反應 三小時，製成酸價97的含有搜基環氧丙締酸酷樹脂(4)。 合成例5 取聚乙蹄醇0.3部加入於已溶解苯乙嫌223.2部，2-經 乙基異丁締酸酯5.7部及縮水甘油異丁婦酸酯71.1部的脫 去離子的水700部之聚合性輩體混合物中，再加入溶有過氧 化苯醯24部的混合物，使其成為均匀的懸濁液。一面通入 氮氣加熱至80°C，在此溫度下使其重合反應五小時後冷卻 而得聚合體懋濁液。過濾此聚合體懸濁液，清洗機殘留物 後將之乾燥而得含有環氣基為反應性基的聚合體(5)。 合成例Θ 取溶有聚乙烯酵0.2部的脫去雛子水400部入於附有攪 拌機，不活性氣體等入管、還流冷卻管及溫度計的燒瓶中 。再加入預先調製的含有笼乙烯196部及縮水甘油異丁烯 酸酯4部的聚合性單體混合物中有溶解的過氧化苯醜24部 的混合物，使其成為均一懸濁液。一面通入氣氣，加熱至 8CTC，併在此溫度下使其重合反懕五小時後經冷卻而得聚 合體懋濁液。過漉聚合體懋濁液、沖洗殘留物後供乾之* 即得含有環氧基為反應性基的聚合體（6)。 合成例7 先溶解聚甲基異丁辅酸酷巨大單體（Macro monomer) (AA-6，東亞合成化學製，數平均分子量為6200) 78.17 部於乙基溶纖劑乙酸酷200部後，加入苯乙烯10.92部，縮 水甘油異丁烯酸醏10.19部後，再加偶氮異丁 # 10部做為 1 19 ~ I I I I -----I I n I n I (請先H讀背面之注意事項再填窩本頁) 本纸伕尺度適用中國國家棣準（CNS ) A4規格（210X297公釐） 4 β Ο 4 Q9 Α7 _ Β7_ 五、發明説明（） 開始劑，使其溶解。 ^^1 n In n^i ^^1 I I— I «^1 ^^1 ^^1 ^^1 In (請先閱讀背面之注意事項再填寫本頁) 將25%的上列溶解物入於附有搜拌冀，不活性氣導入 管、遝流冷卻管、溫度計及滴下滤斗的分液瓶中，一®通 入氮氣，在溫度85 °C重合反應三十分種。又在溫度下*將 剩餘的75%上列溶解物在三小時內一滴一滴的慢慢加入， 使其重合。完成滴加後再保持8510三十分鍾，又加入溶有 偶氧異丁0¾ 1部的乙基溶纖劑乙酸酯50部。加入後在85°C 保持一小時，再將溫度提高至95併置一小時後冷卻之。 所得聚合體溶液（7)的不揮發成分有2S. 57%。分離此物， 即得聚合體（7)。聚合體（7)的數平均分子量是Μη = 7500。 合成例8 取2-丁氧基乙醇300部為溶刪人於附有搜拌翼，不活性 氣導入管，還流冷卻管、溫度計及滴下滅斗的分液瓶中， 在溫度S5°C，一面通氮氣，一面將甲基異丁稀酸酷（ΜΜΑ) 200部，徑基乙基異丁鋪酸酯（HEMA) 200部，硫甘醇酸酯8.5 部（9.227 Χ1〇4 Molar)及偶氣異丁靖（AIBN) 0.1部的混合 液在四小時内連續滴加完成重合反應。然後再加AIBN 0.1 部在同溫之下繼缋加熱二小時。 再在溫度95°C加熱一小時，使其完成重合反應。加入 對本反應液的比為17,0部的縮水甘油異丁稀酸酷（1.3部當 星/C00H) 2.5部的四丁基鞍化溴為觸媒及0.08部的氫眺一 甲基醚為重合停（禁）止劑，在溫度95°C使其反應八小時 後，冷卻，而得數Μη = 7000的尾端異丁鋪酸鹽（酯）型的 ΜΜΑ/ΗΕΜΑ共重合型巨大單體之含有不揮發成分57.14%的聚 -120 - 本紙伕尺度適用中國國家標準（CNS ) Α4規洛（2丨0X297公釐） 4 β〇4 89 Α7 _Β7 五、發明说明（） 合體溶液α (請先Μ讀背面之注意事項再填寫本頁) 混合苯乙婦10.92重量部，縮水甘油異丁烯酸醋10· 97 重量部，上列聚合體溶液136.8重量部（巨大單體78.17重 董部）及2-丁氣基乙酵141.4簠虽部，又加二甲基-2,-2'-雙偶氮異丁酸酉旨（d imethy 1 -2，2 ’ -a2〇-bis Isobuty late) 10重量部為重合開始劑。 將上列混合物入於與合成例7所使用的附有滴下滴斗 之分液瓶中，使其Μ合而得聚合體溶液（S)。本溶液含有 28.61%的不揮發分，而所得聚合體（8)的數平均分量Μη為 7800 〇 合成例9 Μ在合成例7中的縮水甘油異丁烯酸醋10.19重量部由 絮乙烯單體10. 19重量部來代替之外，均如同合成例7—樣 操作而得聚合體溶液（9)。所得的聚合體溶液（9)之數平均 分子虽Μη為7500，不揮發分為28.57重量％。 合成例10 取甲苯250部及丁酮50部為溶劑入於附攪拌翼，不活性 氣導入管、還流冷卻管、溫度計及滴下滴斗的分液瓶中， 在溫度85C之下，一面通入Ni氣體，一面連續滴加甲基異 丁締酸酯（MMA) 350部，翔乙基異丁耀酸酯（HEMA) 50部，Μ .基0旨酸（1^〇21:/(；〇111〇3(^(1)8,5部<9.2271><1〇"^1^〇1€) 及偶氮異丙# (ΛΙΒΝ) 0.1部的混合液，使其重合4小時。 然後再加ΑΙΒΝ 部，在同溫下加熱2小時。 其後，在溫度95°C再加熱1小時’使其完成重合反應 本纸張尺度適用中國國家樣準（CNS ) A43it格（2丨0X29?公釐） 4 60 4 89 A7 _B7五、發明説明（） 。對本反應液加縮水甘油異丁蹄酸酿17.0部（1.3倍當量/ C00H)，四丁基跋漠酿2.5部為觸媒及Μ醜一甲基醚〇.〇8 部為重合停止劑，在溫度95TC使其重合反應8小時後*冷 卻，而得到聚合體溶液。 用正己燒使聚合體再沈殺後，減壓乾燥二天而得數平 均分子量7000的片尾端異丁婦酸酷型的聚巨單體（甲基異 丁烯酸酷/經乙基異丁烯酸酯）。將由此所得含有片尾端 異丁輝酸基的聚巨單體（Poly macro monomer)(甲基異丁 鋪酸酯X控乙基異丁締酸醋）5部，苯乙鋪單體15.2部，異 丙烯基嗯唑林單體9.8部，重合開始劑偶氮異丁靖3部溶解 於乙基溶纖劑乙酸酯100部中而得單體組成物。 另外在上列所使用的燒瓶中，加入乙基溶孅劑乙酸醋 50部後加熱至溫度80°C，在此條件之下，在2小時內媛慢 滴加上列製成的患體組成物之全童，並於80°C繼續加熱2 小時使其重合後，將溫度提昇到95°C，令其熱成2小時， 即得含有不揮發分40.0%的聚合體溶液（10)。 合成例11 取由合成例10所得含有不揮發分40%的聚合體溶液（10) 250部在室溫（25C 土ST:)於30分錚的時間内滴加異丁嫌 臨異氰酸酷（分子量為111.1) 8.9部後，攬拌3小時而得 含有二重结合的聚合體溶液（11)。 合成例12 取溶劑乙二醇一甲醚乙酸酷（ECA) 700部於附有攬伴翼 ，不活性氣導入管、遷流冷卻管、溫度計及滴下濾斗的分 -122 - 本紙張尺度適用中國國家標芈（CNS ) A4规格（210X 297公釐） (請先Μ讀背面之注意事項再填寫本頁) 4 604 89 A? B7 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 液瓶中，枉溫度85°C —面通入葡:氣，在4小時內連續滴力口 甲基異丁嫌0突S旨（MMAU80部，翔乙基異丁烯酸酯〔HEMA)20 咅[3，额基酉旨酸8.5部（9.2271 X 1〇4 Mole)及偶氮異丁負（ AIBN)0.1部使其重合。然後再加AIBN 0.1部，在同溫度之 下加熱2小時。 再使其在溫度95T：加熱1小時Μ完成重合反應。在本 反應液中，加縮水甘油異丁嫌&变酿17.0部（1.3倍當S/ C00H)，觸媒四丁基氣漠醋2.5部及重合停止劑氬8¾-甲醚 0.08部，在溫度95eC之下*使其反懕8小時後冷卻之。用 正己院沈殺後，在溫度50°C減聪乾燥2天，即得平均分子 最為7000的尾端異丁嫌酸酯型的MMA-HEMA共聚合體型巨大 簞體聚合體（12)。溶解所得的巨大單體Π2)60部，經乙基 異丁鋪酸酷（HEMAU5部，苯乙鋪（St U5.2部，異两輝基嗯 〇坐t#(IP〇)9.8部，ECA100部，及開始劑AIBN 3部，gp得聚 合性單體組成物。 取ECA 50入作於附有攪拌翼，冷卻管、滴下漶斗、氮 氣流入口的分液瓶中，加熱至80°C，並保持此溫度。 取上列重合性單體組成物於滴下减斗中，在溫度 之下，以3小時的時間，將之連縝滴加於分液瓶中。再於 同溫度使其重合反應2小時，再於溫度95T:熟成3小時， 即得含有不揮發分40%的接枝化共聚合體（12 )。 合成例13 取溶劑丙烯基乙二醇一甲基醚乙酸酯（PGM-Ac) 200部 入於附有攪拌翼，不活性氣通入管=，運流冷卻管，溫度計 本紙伕尺度適用中囡國家橾準（CN_S ) A4規格（210X297公釐） 4 6 0-4 89 A7 B7 五、發明説明（） (請先Μ讀背面之注意"項再填寫本頁) 及滴下滤斗的分液瓶中，在溫度80°C—面通入氣氣，在4 小時的時間内，緩慢滴加異丁鋪酸卞1酯（BZMA) 120部，經两 基異丁烯酸酯（HPMA) 80部，疏基醋酸3部及開始劑A IBM 0.03部的混合液，使其重合反應。然後每隔30分鍾再滴加 AIBN0 + 02部，重合反應4小時後，在溫度95°C加熱2小時 而完成重合反應。 在本反應液中加異丙婦基嗯哩林4. 70部，重合停止劑 氬西|厂·甲基酿0.08部，在溫度100 ^^使其反懕2小時後， 冷卻，即得平均分子量為5000的尾端異婦基型的BZMA-HEMA 共聚合體巨合體（Macromer.) (13)。 溶解所得的巨單體（13) 75部，笨乙烯15部，異丙烯基 嚼啤d棟10部及PGM-Ac 100部Μ及開始劑AIBN 3部，而得 重合性單體。 取PGM-Ac 50部入於附有攪拌機、冷卻管滴下濾斗、 氮氣流入口的分液瓶中，待溫度上升到80°C後，並繼績保 持此溫度。將上列聚合性單體組成物入於滴入濾斗中，在 3小時的時間内，將之媛慢滴入瓶内使其80°C進行重合後 ，在同溫度繼續重合2小時，再使其在溫度ΙΙΟΤ：熟成2小 時，即得含有不揮發分40%的接枝化共聚合體(13)。 合成例14 取分子量約為6000的片尾端異丁烯基化聚甲基異丁烯 酸醋（AS-6，東亞合成化學工業製）40部做巨合體（ macromer)與聚乙ί希25部、異两鋪基嗯啤》林10部、四氬吨 喃基異丁稀酸酿25部、溶劑PGM-Ac 100部及開始劑ΑΙΒΝ 5 •本紙張尺度適用中國國家楳準（CNS ) Α4规格（2丨0 X 29?公釐） 60489 A7 __B7_ 五、發明説明（） 部共同溶解而得聚合性單體組成物。 (請先閱讀背面之注意事項再填寫本頁) 取PGM-Ac50部入於附有搜拌機，冷卻管、滴下濾斗及 氮氣流入口的分液瓶中，升高溫度至80°C。將上列聚合性 翬體入於滴下滤斗中*在3小時的時間内將之滴入分液瓶 中，在溫度80X:進行重合反應。再使其在4小時完成重合 ，巨卩得含有不揮分40%的接枝化共聚合體（14)。 合成例15 共同溶解在合成例12所得的巨大單體（12) 60部，丙烯 酸15部、苯乙嫌15.2部、異两鋪基嗯啤<#9.8部、ECA 100 部、開始酬AIBN 3部，即得聚合性單體組成物。 取ECA 50部入於如同合成例2所用的分液瓶中，待溫 度升至SCTC後，保持此溫度，在3小時的時間内將上列聚 合性翬體組成物滴加完成後，再使其繼續重合2小時•即 有聚合體溶液成為膠狀附著在搜伴棒上（膠化）：， 合成例16 取含有片尾端異丁烯酸酷基聚（甲基異丁铺酸酷一羥 乙基異丁烯酸酷）巨型單體（東亞合成製，AA-714) 75部 ，苯乙稀15部，異丙烯基嗯D坐”林1〇部及AIBN 3部溶解於 PGM-Ac 100部，即聚合性單體組成物。 取PGM-Ac50部入於附育搜拌機，遝流冷卻管、溫度計 、滴下濾斗及氮氣流入口的分液瓶中，加熱至80°C。將上 列聚合性單體組成物入於滴下滅斗中，在3小時内緩慢滴 入分液瓶中，在80°C使其重合反懕。在此溫度使其繼續重 合2小時後，將溫度升高至120°C，熟成2小時後，即得含 -125 - ^紙伕尺度適用中國國家樣準（CNS )八4規格（210X297公釐) ' 460489 A7 B7 五、發明説明（） 有不揮發分40%的聚合體溶液（16)。 合成例17 (請先閱讀背面之注意事項再填寫本頁) 在合成例16上，僅以二甲截基甲基異丁烯酸酯替代異 丙烯基嚼α坐之外，其他成分均相同並與合成例16—樣操 作，g卩得含有不揮發分40%的聚合體溶液（17)。 合成例18 以合成例16的方法及其中的原料異丙鋪基嗯哩β轉由異 丁烯酸替代之外，均相同的操作，即得含有不揮發分40% 的聚合體溶液（18)。 合成例]ί) 取在片尾端含有二重結合的甲氣基聚乙二醇異丁嫌酸 酷（新中村化學工業製，ΝΚ酯M-230G) 75部、苯乙嫌15部 、異丙烯基D惡u坐啩1〇部、開始劑2,2·-偶氮雙（2,4-二甲基 戊味）3部入於附有攪伴翼，不活性氣導入管、還流冷卻 管及溫度計的分液瓶中，在氮氣流及溫度75之下，進行 重合反懕5小時，即得在其分子内含有不揮發分50%反應 基的嗯哩"林基的乙二酵鏈段之聚合體溶液（19)。 合成例20 取環氧基當量為1040的月桂酵（乙嫌化氣）15縮水甘 油醚（長瀬化成工業製，底那哥爾EX-171) 1040部、乙酵 500部人於在合成例19所使用的相同分液瓶中，加丙嫌酸72 部，觸媒量的PtM定（py「ictine)，Μ賊150ρριη，使其在溫度 7〇它反應2小時。然後在減歷下離去乙酵，即得在其片尾 端有雙鍵結合的月桂酵（乙烯化氣）15。 - 126 _ 本紙^尺度適用中g囷家標準（CNS ) Α4^格（210X 297公釐） 1JL A7 B7 V. Description of the invention () Styrene / dienoic acid copolymers, styrene / methacrylic acid copolymers, benzylbenzene / «-methyl vinyl ethylene / two acid copolymers, etc. containing styrene age soluble Type resin; from acrylic acid and methacrylic acid copolymer, acrylic acid acrylate / methacrylic acid copolymer, f-based methacrylic acid / methacrylic acid copolymer and other propionic acid and methacrylic acid compounds A repeating unit derived from a compound selected from M, M and from (B) methyl acrylic acid, T-based isobutyric acid vinegar, ethoxyphenyl acrylate, ethoxylated isobutyric acid vinegar, One or more age-soluble resins derived from 3-phenylpropyl dienoic acid and 3-phenylpropyl isobutyric acid vinegar are selected from one or more compound groups derived from repeating units; methacrylic acid containing methyl methacrylate Methyl / isobutyric acid 2-ethyl-hexyl / (meth) propionic acid terpolymer, methyl isobutyrate, methylphenidate / ethyl acetate / (meth) propanoate tetra Age-soluble copolymers, ternary copolymers of methyl isobutyrate / ethanoic acid / (meth) acrylic acid, etc. Resin; ternary copolymers containing two alkaloids / two methacrylic acid / ethyl 2-hexyl / isobutyric acid, etc .; soluble resins; styrene-maleic acid / n-butyl maleic acid copolymer Semi-lipidated Malayxuan soluble resins such as composites, styrene / maleic anhydride copolymers, such as partially semi-lipidized polymers; and other combinations of these can be used as the light-hardening composition Additives. In addition, if necessary, an organic polymer polymer compatible with the photopolymerizable compounds listed above may be incorporated into the photopolymerizable resin composition as a film-forming component. The organic polymer polymer includes I feel sour or its -93-(Jing first read the notes on the back and then fill out this page), * τ The size of the paper method is applicable to China National Standards (CMS) Α4 specifications (210X297 mm) Α7 _Β7 V. Description of the invention () Partial (local) hydrolysates, polyisobutyric acid or its partial waters, polyacetic acid or its hydrolysates, polyethylene, polybutadiene, polybutadiene, polybutadiene Chlorinated ethyl chloride, chlorinated polyethylene difluoride, gasified polydiene, polyethylene ettjΠ each burned (Pl0yvinylpy "" olidone.), Phenylethyl: f: copolymer of Greek and Malay dry or its semi-lipid In addition, as long as it does not hinder the photo-hardening property, it can also add lower enzymes such as formazan, ethanol, and diol, and other amines such as dimethylformamide * such as methyl acetate and acetic acid. Ethyl esters, butyl acetate and other brewing products such as 2-methyl * hexyl ether, dioxin, diethyl ether Monomethyl avoiding other amidines, such as 2-Methyltetrahydrofuran, sugar acids and other southern classes And n-heptane, such as aliphatic hydrocarbons, such as ketones such as copper, butyl copper, methyl isobutylformamidine, and other domains, such as acetone, dodecaine, etc., such as sulfur derivatives such as carbon disulfide, thiocene, etc. Appropriate organic solvents. Also, in order to prevent over-reaction of light hardening, sometimes polymerization inhibitors such as hydrogen and T-phenylbenzene can be used. Other well-known additives such as tackifiers and thixotropic agents can be added arbitrarily. , Leveling agent, defoaming agent, adhesion additive, etc. Although the photocurable resin composition of the present invention is prepared by the carbon black graft polymer and the photocurable resin composition as described above, the carbon The blending amount of the black graft polymer to the photocurable resin composition depends on the type of the photocurable resin composition used, that is, M1 to 80% by weight, and it is preferable that M contains a carbon black graft polymer. 5 to 60% by weight, that is, the amount of carbon black grafted polymer to be adjusted If it is over 1% by weight, it may reduce the degree of blackening. If it exceeds 80% by weight, * it may reduce the strength of the film. -94-The technical standards of this paper are applicable to China National Standards (CN'S) 8-4. Grid (2 丨 0X29? Mm) (Please read the notes on the back before filling this page) A7 4 ^ 〇4 89 __________ V. Description of the invention () (Read the notes on the back before poetry and fill in this page} Also, As described above, all of the carbon black grafted polymers of the present invention to be added to the photocurable resin composition of the present invention need not all be graft-polymerized with carbon black having the same grafted polymer. The substance, that is, a compound composed of compounds having exactly the same characteristics, is sufficient, and two or even two kinds of polymers having different grafting can be combined. • If necessary, other coloring ingredients, such as organic pigments, and carbon tinctures made by other parties, can be blended within the range that does not impair the characteristics of the photocurable resin composition of the invention. Carbon black made by other methods include: • Reactive groups containing reactive groups that can react with functional groups on the surface of carbon black; and polymerizable monomers containing ethylenically unsaturated double bonds, as described in section 1.5. A polymerizable monomer containing a ring gas group, a sulfur epoxy group, a gas propyl group group, a beer group, and a polymerizable monomer containing a calcined amine group, etc. Black turned into a creator. In addition, the characteristics of these compounds should be similar to those of the polymer having a low degree of coincidence when the carbon black grafted polymer containing an ethylene unsaturated double bond is incorporated in the first invention. By. The carbon black-grafted polymers of the present invention are all compounds having a high efficiency of grafting polymer components onto the surface of carbon black. Therefore, when it is added to these photocurable resin compositions, the superposition barrier functional groups such as ^ and phenolic hydroxyl groups existing on the surface of carbon black are masked, and the photocurability is suppressed. Delayed light hardening of the resin composition. Especially in the case of carbon black grafted polymers; the polymer chain has ethyl susceptibility, non-gg, and double binding, which is conducive to its hardening reaction. It will not only promote the hardening process, but if it is added, it will be difficult to make it. Reduce the hardening strength of the film. If carbon black is grafted on this paper, the standard of China National Standard (CNS) A4 (ZlOxW7 mm) 4 ^ 〇489 A7 _B7 _ V. Description of the invention () Polymerized polymer chain has a back group, It will soon show excellent break-up properties for the media, and can improve the solubility in the solvent. If the carbon black grafted polymer has the above-mentioned block type and graft type polymer, the surface functional groups of the carbon black and the block type and all reactions of the segment (A) which is a component of the graft type polymer The sex group is highly reactive. Since the polymer component is grafted on the surface of carbon black with extremely high efficiency, even if the functional group that prevents the superposition of the carbon black surface is completely masked, the photocurable resin composition is suppressed. The light-curing retardation tendency of the polymer and the resulting grafted carbon black are paired with the bond (B) of the polymer on the outside, and are modified to have affinity with various substances. • Various photo-hardening resins will be made. The composition has excellent measuring properties, and when dispersed in the photocurable resin composition, it can exhibit a moderate viscosity. The photocurable resin composition of the present invention can be shaped, rotated, and cured. And spray coating, development, photographic printing, screen printing and other coating methods apply it on glass substrates, plastic plates M and film, paper, synthetic paper, polysilicon wafer and other substrates After exposure, irradiate ultraviolet rays 10 to 5000m J, it is hardened to form a black film. 2.2 Black matrix diagram To form a black matrix diagram of a color filter using the photocurable resin composition tree of the present invention as described above, the following methods can be used. Apply the black light-curable resin composition to a substrate such as glass with a rotary coater, and then dry it at 80 to 120 ¾ with a hot air drier or hot plate (pre-baked- Prebake) 1 ~ 60 minutes. The thickness of the black light-curable resin composition film obtained by this method is based on the Chinese paper standard (CN'S) A4 (2 丨 0 X 2S »7 mm) --------- ^ ----;-; 1T ------ ^ (Please read the notes on the back before filling this page) 4 60489 A7 B7 V. Description of the invention () < Please read the notes on the back before filling this page), usually about 1.0 ~ 3.0 win. Then, a mask having a predetermined shape such as a dot shape or a strip shape is adhered to the film of the black photocurable resin composition, and an ultraviolet light source such as a high-pressure mercury lamp is irradiated with parallel rays of 50 to 1000 mJ through the surface. After the shape is exposed, it is processed to obtain a shape such as a black matrix diagram. A suitable imaging solution is used to impregnate the film M at a temperature of about 0 to 1001C to dissolve the uncured as of the film to maintain the exposed film. After the development and development • After the colored frame (pure) formed by appropriate washing, then use a hot air dryer, heating plate, etc. at a temperature of about 100 ~ 300X: heat treatment for 1 ~ 120 minutes (after the rise), It is advisable to completely harden the colored heavy surface. If you want to use the black-colored photo-hardenable resin composition of the invention, when forming a black matrix diagram of a color filter, you have the following two methods: first, make the black matrix diagram on the substrate, and then red, green and blue The method of coloring a garden of various colors, or the method of forming a color chart of each color of red, green, and M on a substrate, and then forming a black matrix chart * can be used. The carbon black-grafted polymer of the present invention added to the photocurable resin composition is * as described in the foregoing paragraph, which contains an unsaturated double bond. When exposed, the unsaturated double bond acts as The resulting bridging M and coincident chains will be used as mediators to combine the resin matrix diagrams forming the film. Therefore, even after the post-baking treatment as described above, the carbon black present in the film can maintain the stability of the dispersed state without reducing its electrical resistivity due to the post-baking treatment. 2.3 Recording media solution The carbon black grafted polymer of the present invention has a representative application. The paper's standard is applicable to China's National Standard (CNS) A4 specification (21〇 × 97 mm) 4 60489. A7 _________ V. DESCRIPTION OF THE INVENTION () A recording medium liquid of a black water jet recording method. The recording body fluid of the present invention only needs to contain the carbon black grafted polymer as a coloring component as described above, and is not particularly limited to a liquid or other component. The recording medium liquid used in this case is black water. The method of recording the recording device depends on its method (such as voltage pressurization method * heating pressurization method, etc.) * and its output conditions (such as the telecom pressurization method, the driving voltage of the piezoelectric element, the driving frequency, The shape and material of the outlet, the caliber of the nozzle, etc., or the amount of thermal energy that is applied during the heating time in the heating and pressing method * the type of heat exchange energy, the shape of the nozzle, the diameter of the nozzle, etc.), and the recording agent (Paper, film), etc., and the appropriate liquid physical properties (viscosity, surface tension, electrical conductivity, boiling point, thermal conductivity, water-soluble M and water-insoluble) can be selected. Available liquids include water, such as methanol, acetic acid, n-propanol, isopropion, n-butyrate, second butyrate, third butyrate, isobutanol, amyl alcohol, hexanoate, heptogen Monovalent fermented solvents such as yeast, octanol, nonanol, decanol, furfuryl alcohol, tetrahydrofuran gf, etc .; such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol Polyvalent alcohols and solvents such as ethylene glycol, polyethylene glycol, glycerin, 1,2,6-hexanetriol, and dithioglycerol, such as acetone, butane, methyl, propyl formamidine, Solvents or ketone fermentation solvents such as methylpentyl ketone, dichlorohexanol, diacetone alcohol, etc .; such as diethyl ether, butyl ether, quartane, dioxin, or ethylene glycol dimethyl ether, ethyl acetate Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylglycerol monomethyl ether, river batyl alcohol monoethyl ether, triethyl ether Monoglyceride Monomethyl Ether, Triethyl Glycol Monoethyl Ether, Diethylene Glycol Dimethyl Ether, Diethyl Ethyl Glycol Diethyl Ester-98-Chinese paper standard (CNS) _Person 4 pits (2) 0 X 29? Mm) Rupture ^ --- Γ ------ Grade {Please read the notes on the back before filling this page) 4 60489 A7 B7 V. Description of the invention () Ether solvents such as ethyl ether; acetic acid, acetic acid, and acetic acid Acetic acid solvents such as phenyl acetate, lactic acid ethyl acetate, ethyl vinegar carbonate, propyl vinegar carbonate, ethylene glycol-ether methyl ether; etc .; amine solvents such as monoethylenamine, diethylenamine, triethanolamine, etc. ; Such as dimethyl formamide, dimethyl ethyl amine, and other amine solvents; such as diketone, H-methyl-distillate | Ketones and other nitrogen-containing compounds based solvents; such as carbene, scorch, cyclopentane, benzene, toluene, xylene, and other carbon solvents; such as tetracarbonated carbon, three gas ethylene, four gas ethyl compound, two atmosphere Halogenated hydrocarbon solvents, such as benzene, etc., are selected from the above-mentioned compounds and can be used in combination with one or a combination of various characteristics for the recording medium. If the purchasing, economical, environmental protection, and difficulty of preparing the recording medium are tested, in these solvent liquids, namely, M water, monovalent alcohol Μ and polyvalent alcohols, cellosolve, cellosolve Liquid media such as ethyl acetate are preferred, but water and ethanol are preferred. If M prevents black water clogging, it is better to use diethylene glycol and dithioglycerol. In terms of concentration and ejection stability, it is better to use nitrogen-containing cyclic compounds or polyene oxide boat compounds. In terms of frequency response (response), that is, κ lower alcohol or the surfactant mentioned below is suitable. The above-mentioned carbon black grafted on the liquid phase of the recording medium of the present invention to the liquid medium is grafted. There are no specific restrictions on the blending amount of the chemical polymer. For example, the amount of the carbon black grafted polymer is controlled so that the pigment concentration becomes 1 to 20% by weight, and preferably within the range of 2 to 12% by weight. That is, it is preferable to add 100 to 100 parts by weight of the liquid medium to add 1 to 100 parts by weight of the carbon black graft polymer, and preferably 2 to 50 parts by weight. -99-The size of this paper is in accordance with China National Standard (CNS) 8.4. (2Ϊ0 × 297mm) (Please read the precautions on the back before filling in this page) ^ G 〇 4 89 Α7 Β7 V. Description of the invention (% l · t Although the recording medium liquid of the present invention is the basic constituent of the M liquid medium and the carbon black grafted polymer as the coloring components, it may be added as needed, such as a viscosity modifier, a surface tension modifier, a pH modifier, Specific impedance modifiers, humectants, infrared-absorbing heating agents, and other additives and resin components, as well as colorant components such as various dyes and pigments that do not hinder the effects of the present invention. Addition of viscosity modifiers or surface tension modifiers The main purpose is to respond to the recording speed so that it can fully flow through the nozzle to prevent the backflow phenomenon of the recording medium in the mouth of the mouth. * To prevent the formation of diffusion on the recorded material, etc. without adversely affecting the recording medium and color. Within the limits of the ingredients, any well-known viscosity regulator and surface tension regulator can be used. Viscosity regulators such as polyethylene yeast, propyl cellulose Jun dimethylcellulose, hydroxyethylcellulose, methyladherin, water-soluble (meth) acrylic resin, polypropylene ketone, arabic gum, powder, etc., surface tension modifiers, namely Examples include anionic 糸 surfactants such as polyethylene sulfate sulfate, lipolipid, etc., poly 2-vinyl pyridine derivatives, poly 4-ethylene cations 糸 surfactants such as cadidine derivatives, and polyethylene oxide. Non-fluorine interfacial interface activity such as Kiyanoic acid, polyoxyethylene triphenylene ether, polyoxyethylene fluorenyl ester, polyoxyethylene sorbitan glycoside vinegar, polyoxyethylene triamine, etc. Agents; such as diethanolamine, propanolamine, linoleic acid and other amine acids; such as hydrogenated sodium hydroxide and other salt-like substances; such as N-methyl-2-GthBS fluorenone and other substituted pyrrolidone. If necessary, these viscosity couplers and surface tension regulators, each -100-(Please read the note on the back before filling out this page) The size of the paper is bound to the Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -0 4 89 A7 B7 V. Description of the invention () Adjust to a combination of plural Use. Although the addition amount of the viscosity modifier and surface tension adjuster will vary depending on the type of liquid medium used and the amount of colorant components added, the amount of viscosity modifier added to the recording medium liquid 100 parts by weight is 0.1 to 30 weight. The surface tension adjusting agent is preferably 0.01 to 10 parts by weight. The pH adjusting agent is to record the chemical stability of body fluids, such as changing its physical properties due to long-term storage or preventing sedimentation or agglomeration of coloring ingredients and other ingredients. It is added while maintaining a predetermined pH value. PH adjusters include lower-level nordoxy bases; monovalent hydroxides such as argon oxide, an age metal of ammonia hydroxide. To charge the liquid droplets of the recording medium of the present invention, When recording, recording the specific impedance * of the green media solution becomes an important factor for its charging characteristics. In this recording method, in order to adjust the specific impedance value of the recording medium liquid within a predetermined range, a specific impedance modifier may be added. Specific impedance modifiers include inorganic salts such as flavonoid, sodium chloride, and gasification; water-soluble amines such as triethanolamine, and fourth-grade mineral salts. In addition, μ can be used in the recording medium liquid of the present invention to moisten Mr. Mr., such as polyethylene glycol (polyethylene glycol, polypropylene glycol, etc.) (-~. PolyaIkylene glycol); Alkylene glcol such as butanediol and Hexylene glycol; such as ethanoic acid methyl ether, diethylene glycol methyl ether, diethylene glycol ether, etc. Diether and diethylene glycol ethers; such as glycerol; Alcoxytri-slycol (e.g., Cmethoyytri-slycol), acetyl-triglyceride; and N- Vinyl-2-II each polymer Please read the Note iW-item on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0X 297 mm) '60 4 89 A7 B7 V. Description of the invention ()) and so on. One or more combinations of the compounds listed above can be used as rattan emollients. Many of these compounds can also be used as liquid media. If you want to make electromagnetic waves, especially when you are recording by heating with infrared rays, you can also add a heating agent that absorbs infrared rays to the recording medium liquid. As mentioned above, although the present invention contains a carbon black coloring component that can absorb infrared rays and is a heating agent, there are dyes such as water-soluble aniline (Nisrosine), denatured (formed) water-soluble aniline black, and enzyme-soluble aniline black. , Ultramarine, tin yellow, gasification second lock, Luohuang, and other inorganic pigments, even M 糸, trimer formamidine, quince, onion latex, secret green and other organic head materials are also used as infrared absorption Hot cut. Many of them also function as coloring ingredients. In order to improve the film formation and film strength when the recording medium liquid of the present invention is fixed to a recording material, for example, a yeast resin, an acrylic resin, an ammonium resin, a polyvinyl alcohol, and a polyethylene resin may be added. Guluyuanyuan et al. M-2.4 Liquid developer for electrostatic charge latent image development Another representative application of the carbon black graft polymer of the present invention is a liquid developer for electrostatic charge latent image development. ¾ The consumer cooperation of the Central Bureau of Samples, printed in in-In n I-1 tp I- s I Hr I — 丁 0¾ " a (Please read the precautions on the back before filling this page) Related to the invention The liquid developer contains only the carbon black graft polymer described above as the coloring material. As for the carrier liquid, the fixing agent M and other ingredients, that is, no restrictions are imposed * Various known compounds may be used instead. Within the range not hindering the effects of the present invention, various dyes and pigments may be used as a coloring agent component of the pigment. Μ Non-polar solvent > For example, it has electrical insulation of 3.5 or less (-102-paper size) Applicable to Chinese standards (CN'S) A4 (2 丨 OX297 mm) BO 4 89 A7 ____B7__ V. Description of the invention () (Please read the precautions on the back before filling this page) Carbon of volume intrinsic resistance * cmM) The centipede solvent is a representative compound of the driving fluid. The best examples are * aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof with boiling points in the range of 150 to 2200π. More specifically, 0 spoons, such as 13〇63 Factory-〇, Nissei (manufactured by Yickson Corporation), 31 ^ 1〗 3〇1 / \ 48 (manufactured by Shell Company), Naphthesol L, mH (Japan Petroleum Metric), etc., can be used, but Resins that do not make the driving fluid appear insoluble or swellable can be used as fixatives, such as polyethylene resin, (meth) acrylic resin, polyvinyl chloride, vinyl acetate resin, Ester resin, ammonium resin, phenol denatured (formed) enzyme resin , Epoxy resin, linseed oil denatured (formed) fermented acid tree moon purpose, fragrant beans _ · 茆 resin, phenol-formaldehyde resin, rosin resin, styrene-butadiene rubber, cyclized rubber, etc. can be used. If necessary, charge regulators can also be added. Charge regulators include cyclic acid, octanoic acid, oleic acid, stearic acid, lauric acid, and other fatty acid gold salts, nitroporoic acid, and metal salts. Oil-soluble sulfonic acid metal salt listed in No.-556, Abietic Ac id or metal salt of hydroabietic acid published in Japanese Patent No. 48-25666, and hospital-based poly nitric acid listed in Japanese Patent No. 55-2620 Salt, aromatic carbonic acid or metal acid salt of JP 52-10837 and non-ionic surfactants such as polyoxyethylaluminum amine, oils and fats such as lecithin, linseed oil, etc. (Polyvinyl Pyrrolidone), polyvalent fermented organic acid esters, and other well-known charge adhering agents and charge regulators can be used. 2.5 Other uses The other uses of the carbon black graft polymer of the present invention are not added. -103-Paper: Standards Applicable to Chinese Family Standards (CNS) A4 Specifications (2I0X 297mm)-f? 〇4 89 A7 B7 V. Description of the invention () Specific limitations, but can be used for the following various purposes. For example, it is used in various resin compositions, coating compositions, ink, thermal overwriting Ink tape coating agent, basck coat agent for magnetic recording media, toner and coating for electrostatic charge development, materials with high resistance and light-shielding properties, artificial marble, plastic and rubber molding materials, light-shielding fibers, etc. Colorants, modifiers and fillers for plastics such as polyolefins and polyesters, rubbers, lubricants, traction drive fluids, electrically viscous fluids or non-linear optical materials, resistance adjustments, such as anti-charge materials, use of resistive materials Or flat heating elements inside photocopiers with PTC characteristics, sealants for semiconductor devices, etc. When added to a thermoplastic resin, it can be used as a photocopier toner, film and fiber with the characteristics listed above. In addition, when the carbon black graft polymer is added to a thermosetting resin, the same characteristics can be exerted to solve various problems caused by the carbon black that has been used conventionally. In addition, when the carbon black graft polymer of the present invention is added to an adhesive used in a coating composition, various substrates to be coated will have a stronger film. The composition of this adhesive is made of a well-known thermoplastic resin, thermosetting resin or reactive resin, and depending on the application, one or a mixture of two or more of them can be used. In addition, the carbon black graft polymer of the present invention is used for dispersing carbon black into a micro-bundle dispersed state in a liquid phase, and is an oily note-taking, information recording, or printing function having dispersion stability and excellent super-coloring power. The ink can be used in the original state of the carbon black dispersion or by adding appropriate necessary ingredients after mixing. 3. Manufacturing method of carbon black-containing resin composition ---- D! (Please read the note f on the back before filling in this paper.) The paper scale is applicable to the National Standards of China (CNS). Grid (210 ×: 297 mm) 89-. Α7 _Β7__ 5. Description of the invention () ^ Yi-(Please read the precautions on the back before filling this page) There is another kind, which will be described in section 1.5. Block type and method of grafting polymer to carbon black. That is, the resin component that becomes the dispersion medium, carbon black, and a reactive group segment (A) containing a reactive group capable of reacting with a carbon black surface functional group, and the segment (A) that does not substantially contain the reactive group have A method for producing a carbon black-containing resin composition characterized by melting and mixing the block type and the graft type polymer of the segment (B) having a higher affinity for the resin component. When the target medium for dispersing carbon black is a resin component, as in the first invention, it is not necessary to search and mix carbon black, graft type, and block polymer in the dispersion medium liquid, as long as it is directly used as the target medium. The product obtained by melting and mixing in the resin component will also show excellent carbon black dispersibility. That is, the desired product can be obtained by simple operation. The excellent dispersibility obtained at this time is that, just as described in the first invention, the resin component (in the dispersing medium) from the molten state during the melt-kneading process appears to be the same as that of the block type M and the graft polymer. Aligned and highly effective carbon black grafting. 4. Surface modification treatment method The surface modification treatment method of the solid fine particles according to the present invention is to disperse the solid fine particles with a reactive group capable of reacting with a functional group existing on the surface of the solid fine particles in a dispersion medium. The reactive polymer is subjected to a dispersion treatment under heating to surface-modify the solid fine particles. Because the particles in the dispersion medium are subjected to physical torque due to operations such as searching for partners during the dispersion process, the secondary agglutination state is resolved and they become primary particles in the dispersion medium. Under heating, functional groups on the surface of the solid fine particles and reactive groups of the reactive polymer are easily reacted to form a graft. However, since the solid particles and the reactive polymer paper are sized to the Chinese National Standard (CNS) A4 (2 丨 0X29? Mm) 4 60 4 89 A7 B7 V. Description of the invention () The reaction is in the dispersion medium If you perform *, it should be more uniform than the method of combining solid particles with reactive polymers in the sea, and it can react more gently. Even if there is only a low proportion of reactive polymers for solid particles, or It is a reactive polymer with a large number of reactive groups in each molecule, which can complete a good surface modification treatment. Or because the dispersion treatment in this dispersion medium can also make the low-molecular-weight reactive polymer obtain a very strong torque effect, and the dissimilarity obtained from the melt-kneading reaction * has a good surface treatment effect. Because of this, in the method of the present invention, there is no need for a large amount of reactive polymers like the known melt-kneading reaction of κ *, and it is not necessary to limit which kind of reactive polymer, and the surface properties of the solid particles can be adjusted according to expectations. Make appropriate changes. In addition, the solid microparticles produced by the method of the present invention have been modified according to the surface modification of the solid particles to change the affinity to the dispersion medium. The uniform and stable dispersibility can be maintained as it is. For various purposes * It can also be separated from dispersed media for various purposes. The "grafting" of the reactive polymer on the surface of the solid fine particles has the same meaning as described in the above section.坌 耷 I strongly encourage you to cooperate with employee education expenses in printing (please read the precautions on the reverse side before filling out this page). Regarding the surface modification method of the solid particles according to the present invention, the solid particles can be treated. That is, without adding any special limitation to M, compounds containing only functional groups capable of reacting to the reactive group of the reactive polymer can be used, covering pigments, magnetic powders, ceramic powders, and organic particles, especially for pigments. Inorganic pigments, such as carbon black, clay, carbonic acid, soft dioxide, demon white, oxidized oxide, talc, slaked lime, hydroxide hydroxide -106-This paper size applies to Chinese National Standard (CNS) A4 ^ grid ( 210X297 mm) 4 ^ 〇489 A7 _______B7 V. Description of the invention (), second iron hydroxide, cement, oxide oxide, zircon, clay, silicon carbide, nitrided shoes, etc., and magnetic powder is the most effective treatment Method, however for carbon black --------- ^ ------ 1Τ < Please read the notes on the back before filling this page). Carbon black is the most suitable for the same object as described in section 1.1. At the same time, the reactive polymer used in the present invention is a reactive group that contains reactive groups that can react with the surface functional groups of such solid particles. Objects can be used, for example, in terms of reactive groups, it is suitable to include at least one functional group in a group selected from the group consisting of fluorenyloxy, thione, aziridine, and aryl. In other words, it is a polymer of acetamidine, a polymer of polyether, polyether, and the like containing such reactive groups in the molecule. It is a matter of course that the various polymers described in the above section 1 are also included in the reactive polymer. The method of obtaining a reactive polymer is as described in Section 1.2: Although there is a polymerizable monomer (M hereinafter referred to as mono Ke) containing a reactive group in its molecule, A method in which other polymerizable monomers (hereinafter referred to as monomers Λ) are superimposed, i.e., a compound containing the reactive group in its molecule (hereinafter referred to as a compound core) and a compound that can react with the compound A polymer of a radical (K is hereinafter referred to as a polymer ηρ) is opposite, and the method of introducing the reactive group into the polymer d is (3) used in a molecule that contains the reactive group M The polymer of the reactive group (hereinafter referred to as polymer 0 «) is converted into a polymer containing the reactive group by various methods, but the method of ⑴ is most suitable. -107-The size of this paper is suitable for Chinese households (CNS > Α4) (210 X 297 mm) 4 60489 A7 ___B7_V. Description of the invention () In the method listed in (1) above, it can be used The monomer k * is, for example, the carcass a described in the above 1.5, such as the polymerizable monomers containing epoxy groups, the polymerizable monomers containing sulfur ring gas groups, and the polymer containing M two spray groups. Selectable monomers, polymerizable monomers containing beer ice, and polymerizable monomers containing N-fired amine groups can be used from this group by selecting one or two or more of them. In the method of ⑴, there are monomers / BPs that can be used according to their needs. Those that can be overlapped with monomer k are not particularly limited in their types. They can be used. Polymerizable monomers as described in section 1.5 c or the same object. It can be manufactured by using one or two kinds of M. To manufacture a reactive polymer containing a reactive group according to the method of ⑴ *, you can use a single k and the necessary monomer /, according to The weighting method has been known, such as block weighting method, suspension weighting method, emulsification weighting method, sedimentation method and solution weighting method. The superposition reaction may be performed after waiting. The compound m which can be used in the method of (2) is, (2-1) a compound containing two or more of said reactive groups in the molecule. (2-2) in the molecule A compound containing any of the two M antireactive groups in it. (2-3) A compound containing one of the antisocial group on M and a reactive group other than the reactive group M in the molecule. But The reactive groups other than the reactive group K described in the item (2-3) are the removal of the nitrogen radical, the aryl group, the N-hydroxyalkylamino group, the ring gas group, and the thioepoxy group M. The external reactive group can be compared with the polymer (η) described below (please read the note f on the back before filling this page) • installed-, ιτ. This paper music standard is applicable to China National Standards (CN_S) A4 specification (210X297 mm) 4 60 4 89 A7 _B7_ 5. Description of the invention () Reactive compounds, such as isofluorene salt group, truncation group, carboxyl group, warp group, vinyl group and halogen group, etc. ( Please read the precautions on the back before filling in this page) The polymer (η) used in the method ⑵ refers to the compounds c and (2-1) to (2-3) Suitable vinyl polymers, polyesters, polyethers, etc. Functional groups that can react with compound (m) include, for example, hydroxy (including phenolic hydroxy), shuttle, base, amino, and epoxy groups. Polymers (η) of these reactive groups can be easily produced by well-known methods such as superposition, supercondensation, and the like. To produce an antireactive polymer containing an antireactive group according to the method, the compound (In) can be obtained by reacting with the polymer (η) M under the condition that one or more of the above-mentioned reactive groups are left unreacted. Polymer (c) used in the method of (3). Yes, it contains aziridinyl group, manganese # group, N-hydroxylamine group, ring gas group or reactive group that can be converted into sulfur epoxy group, such as vinyl group in its molecule, Polymer of carboxyl, chloroethanol and glycol groups. All of these polymers can be easily introduced into the reactive polymer by known methods such as aziridine, I #, N-hydroxyalkylamino, epoxy and / or sulfur-filling oxygen. As for the reactive polymer used in the present invention, that is, as described in section 1.5, the site has a high affinity for the solid microparticles to which the reactive polymer is intended to bind (A), and The target medium in which the solid particles are dispersed presents a high-affinity site (B) in a manner that has both good binding and surface modification properties. A double-sided polymer, that is, a site with different characteristics as listed above. (_ Paragraph) The block type and graft type polymer are based on the Chinese paper standard applicable to the standard of paper 丨 CNS) A4 (210 × 297 mm). 4 BO 4 89 A7 B7 V. Description of the invention () However, only the reactive group remains on the segment A, which has a high affinity for the solid particles. In addition, block-type and graft-type polymers include simple A-B type and comb-type polymers which are highly interactive block types such as B-A-B pears and are grafted on the segment A by a plurality of B bond segments. The molecular weight of the reactive polymer for use in the present invention * can be used in a wide range of polymers as described in the previous column. For example, if the average molecular weight is 100 ~ 1000000, and M has 5000 ~ 1000QO, it is more suitable. The number of reactive groups contained in each molecule can also be a larger range of polymers as described in the foregoing column. * If the average molecule contains 1 to 5 reactive groups, it is preferably M1 to 20. In the surface treatment method of the present invention, it is not particularly limited to use a dispersion medium to mix the solid fine particles and the reactive polymer, but various water-soluble or non-water-soluble dispersion vehicles such as water; Alcohols such as yeast, isopropanol, butanol *, and aromatic alcohols; such as ethylene glycol, malonase, diethylene glycol, polyethylene glycol, polyglycol, diethylene glycol monoethyl ether, polypropylene glycol one Ethanol, polyglycol monoaromatic ether, polydiethylene glycol monoaromatic diol and derivatives thereof; such as glycerol M and its derivatives such as glycerol, glycerol monoethyl ether, glycerol monoaromatic ether, etc. _ Categories such as bitumin and eriodon; ketones such as methyl ethyl ketone and methyl isobutyl ketone; such as petroleum, ketone, ketone, methyl poly, radon, kerosene, dibenzyl, toluene, Hydrocarbons such as xylene, ethylbenzene, diethylbenzene, diphenyl, cyclohexane, and locally added triphenyl, such as polydimethyl terpineol, polydimethyl shoes partially replaced by octyl Oxygen burning, polydimethylsilane oxygen substituted by phenyl, oxygenated gas, shoe oil, etc. , Molybdenum, chlorinated cages, gas chromatograph g, benzyl, etc. -110-This paper size is applicable to the S country standard (CNS) Α4 size (_210x297 public change) · 、 1τ ------ 0 (Please read the notes on the back before filling this page) 4 6 04 89 A7 B7 V. Description of the invention () (Please read the notes on the back before filling this page) Chemical Carbon M type, such as Dailrol (made by Daikin Industry Co., Ltd.), Deronum (made by Daikin Industry Co., Ltd.) and other fluorides, such as ethyl benzoate, octyl benzoate, dioctyl acid, trimellitate Sodium trioctyl ester, dibutyryl sebacate, ethyl (meth) acrylic acid, butyl vinegar (methyl) butanoate, and twelve vinegar (meth) acrylate, etc. The type of the solid fine particles and the intended use of the dispersion are suitably selected. In addition, well-known monomers, polymers, and various stabilizers can be added within a range that does not hinder the grafting reaction of the solid fine particles. Although the surface treatment method of the present invention is to disperse solid particles and reactive polymers in a dispersion medium under heating to perform the dispersion treatment, the ratio of the reactive polymer added to the solid particles is affected. Depending on the type of reactive polymer used and the intended use of the product, you cannot add M—General Regulations * and add 100 parts by weight of solid particles, 5 to 500 parts by weight of the reactive polymer, and preferably 20 to 200 parts by weight The degree is appropriate. That is, if the reactive polymer is less than the weight part per day, there may be a case where the surface properties of the solid fine particles cannot be sufficiently modified. On the other hand, if it exceeds 500 parts by weight *, the reactivity bound to the surface of the solid fine particles will be caused. Where the amount of polymer tends to be too large, the characteristics of the solid fine particles that are originally intended to be lost are lost. In addition, the heating temperature during stirring and mixing will also be limited by the type of reactive polymer used, etc. It cannot be specified in general * M50 ~ 250 ° C, ideal temperature is 80 ~ 250 ° C, but it is 100 ~ 220 The degree of ° C is most appropriate. If the temperature does not reach 50C, the reactive groups of the reactive polymer and the functional groups on the surface of the solid microparticles cannot be fully reacted. On the other hand, if the temperature exceeds 250 ° C, the reaction becomes violent and difficult to control. This paper size applies the Chinese National Standard (CNS) A4 grid (.2 丨 0 X 297 mm) 460489 A7 _B7 V. Description of the invention () As for the shear stress of the solid particles applied to the dispersion process, it will also be used. The influence of types such as solid particles * is not particularly limited, but it is preferably 10 * · PaM. The ideal shear stress is 10 $ PaM, and the best is M104 PaM. Because of this appropriate shear In the dispersing process of the present invention, which is carried out by heating under breaking stress to perform the dispersing process, it is desirable to have a container capable of containing the fluid to be processed therein, a basket that can be rotated inside the container, and a container capable of heating the fluid to be processed in the container. A heating device and a wet dispersion processing device made of a plurality of granular dispersion media in a container are used. The wet dispersion processing device and wet powder processing for stirring and disintegrating the granular dispersion media such as a ravioli and a ball are performed. Although there are many well-known devices, there are many devices used in the present invention for heating the object to be processed. The configuration of the devices is as follows. Fig. 5 and Fig. Β are each A cross-sectional view of a horizontal type wet dispersion processing device that implements a surface modification treatment method for solid particles used in the present invention. Fig. 5 shows a wet dispersion processing device of an implementation mode having a horizontal plane slightly from an axis. A horizontal processing device for container 1 formed from a closed cylindrical container body. The center portion of one of the disk-shaped end surfaces on the left and right sides of the outer wall surface of container 1 (the left side in the figure is referred to as the left side surface) A rotary shaft insertion hole is provided through which the rotary shaft 2 can be inserted into the container space from the outside along the axis of the container in a liquid-tight manner. A container space portion located on the rotary shaft 2 is provided to be slightly perpendicular to the rotary shaft. A plurality of disc-shaped bakers 3 with a predetermined pitch, and the rotating shaft 2 are external to the driving device not shown in the figure. The paper size is applicable to China National Standard (CNS) A4 (210X297). Order I — 11 II | Girl (please read the notes on the back before filling this page) 4 604 89 A7 B7 V. Description of the invention () (Please read the notes on the back & fill in this page first} link. Also in the container 1 outer wall surface The peripheral part of the front side of the cylindrical peripheral surface of the front side is provided with a fluid outlet port 14 near the upper part of the commerce part, and is located near the end surface part on the other cargo surface (under M, referred to as the right end surface part). A fluid introduction port 13 with a backflow prevention valve 12 is installed at the lower part, so that the device becomes a continuous processing method device. In the inner space of the container 1, a pellet 4 as a dispersion medium is installed, and it is in the forefront. A media separator 15 having a gap 15c is arranged near the fluid outlet 14 so that the foreline pellets 4 cannot pass and the dispersion liquid and solid particles can flow. The gap 15c of the foreline media separator 15 is provided at a direction slightly perpendicular to the axis of the container 1 The entire outer periphery of the fixed plate portion 15a is connected to the inner peripheral surface of the container (a round-shaped peripheral surface portion) between the round and round fixed plate portion 15a and the rotating disk portion 15b. The other rotating disk portion 15b is like In the case of the front row ravioli 3, it is attached to the rotary shaft 2 as required. Then, the band-shaped heater 11 is wound around the outer periphery of the wall surface of the container 1 as a heating device, and has a structure capable of heating the liquid to be dispersed inside the container 1. On the right end face of the container 1, a thermocouple 5 for detecting the temperature of the fluid inside the container is installed. In this device, the fluid to be processed * introduced into the internal space of the container 1 through the fluid introduction port 13 is, for example, solid fine particles in a secondary aggregation state, a dispersion medium, and a surface functional group that can react with the solid fine particles. While the complex formed by the dermal reactive polymer is not discharged from the fluid outlet 14, it will be subjected to the rotation and rotation of the stirrer 3 and the rotation and rotation of the pellet 4 caused by the rotation, and they will contact and impact each other. Such as the accompanying shear force generated by the flowing lotus movement and the heating of the ribbon heater Π the cost of smashing the paper size is applicable to the national standard car (CNS) A4 grid (210X297 mm) 4 60489 A7 B7 5 Explanation of the invention () The solid fine particles, which are separated primary particles, are uniformly dispersed in the dispersion medium, so that the functional groups on the surface of the solid fine particles and the reactive groups of the reactive polymer react extremely efficiently. As a result, the dispersion liquid discharged from the fluid outlet port 14 will not only be taken out, but it will not only show a good dispersion state at that time, but also maintain a good breakdown state for a long time. Also, as shown in FIG. 6, the wet dispersion processing device of the embodiment mode is a container 1 formed by a barrel-type container body la whose opening is slightly vertical and an opening at the upper end thereof, and a cover lb covering the front-row opening. The constructed vertical batch processing device. A rotary shaft insertion hole is provided in the center of the lid 1b of the container 1, and the rotary shaft 2 can be inserted into the container from the outside of the inspector along the container axis through the insertion hole. Inside the container's internal space portion on this axis of rotation 2, a surface which is slightly perpendicular to the axis of the container is mounted, and the axis of rotation is used as the center to radially spread out, and a plurality of steps at predetermined intervals are arranged in the axis direction of the container. Needle-shaped plural stir bar 3a. In addition, the inner peripheral side of the container 1 is provided with multiple paragraphs along the axis direction of the container that are not interrelated with the front row stirrers 3a (ie, the comb teeth of the two combs can match the general configuration), and A plurality of radial needle-shaped holders 3b which form a bundle from the inner peripheral side to the axis of rotation are formed slightly from the vertical plane of the container, that is, the function of a disturbance plate is formed. The rotary shaft 2 is connected to a drive device not shown in the figure outside the container. The inner space of the container 1, that is, the general pellets 4 as shown in the foregoing embodiment 囵 5, is used as a dispersion medium. A heating medium reservoir 8 of a heater 9 and a heating sleeve 6 connected to a circulation pipe provided with a heating medium circulation pump 7 in the middle are mounted on the outer periphery of the round body of the container body 1 Use the circulation of heat medium to heat in -114 — This paper size applies Chinese National Standard (CNS) Α4 ^ grid (210X297 mm) (Read the notes on the back of the poem before filling in this page) • .. Order 4 6 〇4 89 Α7 Β7 5. Description of the invention () The structure formed by the dispersion liquid inside the container 1. In this device, even the solid particles and dispersion medium in the secondary agglomerated state of the fluid to be treated contained in the internal space of the container 1 contain a reactive group reactive polymer capable of reacting with the surface functional groups of the solid particles. The resulting complex is subjected to the rotation of the stirrer 3a during the stirring treatment for a predetermined time, and the existence of the rotary stirrer 3a and the holder 3b causes the pellets 4 filled therein to perform respective rotations, rotations, and contact with each other. . The shearing force generated by the flow accompanying the impact, etc., is also affected by the heating of the heating sleeve 6, and is broken into solid particles that are separate primary particles, which can be dispersed in the dispersion medium. At the same time, The functional groups on the surface of the solid microparticles react efficiently with the reactive groups of the reactive polymer, and after a predetermined period of time, it can be made into a dispersion that not only has a good dispersion state after being taken out, but also can maintain its good dispersion. Finished product with long-term stability. ί £ Qilang central sample cooperation with Ma Beigong Wang Yin Dun (please read the precautions on the back before filling out this page) Μ is based on the illustrated trade model to explain the structure of the wet dispersion processing device. In this In the device, the heating device for heating the fluid to be processed in the container is not limited in any style, and anyone who can effectively heat the liquid to be processed in the container can use the heating medium circulation method listed above. • Ribbon heater Or, such as ceramic heaters and infrared heating methods, high-frequency induction heating methods, coil heaters, etc. can be used. The configuration position is not limited to the installation on the outer periphery of the container as in the implementation mode listed above, and does not hinder stirring Within the rotation range of the container • It can be installed in the container's internal space, and it can also be installed on the container's inner surface, on the mixing bowl and the rotary bowl, or on the holder and the baffle. However, when considering the structure of the device or the convenience of controlling the temperature That is, it is advisable to install a heating device on the outer periphery of the container. -115-This paper size is applicable to China National Standards of Standards (CXS) 8.4 (210 × 297 mm): ~ 4 6〇4 89 A7 _B 7_ 5. Description of the invention () H-I--— 1--, ¾ ^ —1 I ------ (Please read the precautions on the back before filling this page) Also, on this device, remove the heating In addition to the device M, there is a basic structure of a wet dispersion processing device, that is, a certain method is not particularly limited, and can be freely flailed and batch-type. The material and shape of the container, the material and shape of the blender, and The difference in the SI3 position, the material of the dispersion medium, the shape and particle size, and the differences in the chemical properties such as the reactivity of the desired dispersion and the treated solid particles, and the physical properties such as specific gravity and particle size are selected. Suitable materials are used. The materials of the container include various ceramic soils such as vaporized aluminum, oxidized agglomerates, talc, alumina fossils, carbonized shoes, carbonized mirrors, etc., and various glasses, such as steel, steel, and Hastings wire. Alloys (Haste iloy) and other (Ni) 糸 alloys and other metals of one or two kinds of M are composed of gold. The types are horizontal and vertical (M), such as cylindrical, circular, Semi-cylindrical type, such as the container listed on Teflon 2-27018 or Stone micromill (018111〇 ^^ 16 1! 1111) (Mitsubishi Heavy Industries) and other cross-sections of W-shape and: (horizontal U) shape, as in the case of Special Fair No. 6-73620, which is dispersed inside Containers made of media (installed with stirrers and part of the wall surface formed by stirrers) and allowing internal and external fluids (dispersions) to flow in each other. These are various types. In addition, the material of the ravioli is the same as that of the container. It can be used on various ceramics such as gasification faults, oxidation dimensions, talc, silicon carbide, silicon carbide, tungsten carbide, etc. * Various glass steel, chrome steel, Hastings Various metals, such as nickel-based alloys such as alloys (Hastelloy, trade name, Haynes Stellite Co. USA), are appropriately selected and used. However, the materials used may be different from those used for containers. Also, its shape can use single type or multi-segment type, such as the disc shape described above (Disc-116-This paper size applies to China National Standard (CNS) Α4 specification (2 丨 0X297mm)): '~ 4 6 0.4 89 A7 B7 V. Description of the invention () -disc type), in addition to the needle type, there are disc-shaped turbine type, fan-shaped turbine type, insect-involved spiral type, spiral shaft airfoil type, according to rotary belt airfoil type, Various shapes such as gate type, anchor type, cylindrical type, and paddle type, or modified stirrers with liquid-pervious holes provided in these stirrers. The rotary axis forming the half-blade can be arranged on the rotor of the container, or it may be offset from the central axis or on the two-axis and multi-axis. In addition, the dispersion medium can be appropriately changed according to the type of solid fine particles and the type of agitator to be processed. The users who can use it include alumina, oxide, lump, shoe, carbonized shoes, and carbonized brocade. Various shapes such as various ceramic clays, glass, steel, chrome steel, nickel-rhenium alloys such as n-Hastelloy, and various gold alloys are spherical, round, and spheroidal. * However, M is a spherical bead made of materials such as gasification, oxidation, steel, and steel. Usually, the diameter is about 0.05 ~ 20mm, and the most bead with a diameter of 0,1 ~ 5nm is used. it is good. As for the amount of the dispersion medium to be filled in the container, which is not limited by the type of the container or the stirrer, etc., it is preferably 20 to 90% of the effective capacity of the container, and more preferably 30 to 80%. If the filling ratio is extremely small, the solid particles in the secondary aggregation state cannot be disintegrated sufficiently and the reaction between the solid particles and the reactive polymer cannot be completed. On the other hand, the filling ratio is extremely large. , Or it will cause abrasion between dispersive media and increase pollution. EXAMPLES The following are examples of the present invention for a more specific description, which is intended only for easy understanding of the present invention, and does not mean that the operation of the present invention is limited. N. I-Γ * -1 II-^^ 1 — ^ 1 »I. N ^ i-____ (Please read the notes on the back before filling out this page): If there is no special note below the soil, replace the" weight part "with" part ". -117-Paper scales 逋Using the Chinese National Standard (9NS), 8 gauge (2 丨 0X297 mm) 4 604 89 A7 B7 V. Description of the invention () M "%" means "% by weight". Method for synthesizing a polymer for carbon black treatment Synthesis Example 1 100 parts of a (phenol) phenolic varnish epoxy resin YDPN-638P (manufactured by Toto Kasei Co., Ltd., with a bad gas equivalent of 180) were placed in a cooler with an agitator and IS flow In a separatory bottle, add 32 parts of Binghui, 0.13 parts of Chlorinated 3rd Channel 6 and 0.13 parts of methyl chloride, 11 parts, and heat the reaction at 110 ° C for two hours to confirm the reactants. Has an acid value of 0. This was regarded as a bad propylene resin rhenium. Synthesis Example 2 Take 100 (age) phenolic varnish bad gas resin YDPN-638f > (manufactured by Toto Kasei * epoxy equivalent 180) and put it into a separating bottle with a soy sauce and submerged flow cooler, add There were 41 parts of acrylic acid, 0.14 parts of nitridation compound 2 and 0.12 parts of methyl argon, and the reaction was heated at a temperature of 1101C for two hours. It was confirmed that the acid value of the reactant was 5.5. Think of this as an epoxy diene cool resin. Synthesis Example 3 Take 30 parts of formic acid lacquer lacquer ring gas resin YDPN-638P (manufactured by Toto Kasei Co., Ltd., epoxy equivalent is 200). Put 30 parts into a separatory bottle with a mixing wing and a flow cooler. Dienoic acid δ.64, Ethylene carbitol acetate 309.12, Aerated second hexahydrate and 0.04, and methyl gas io.03, at a temperature of 110. The reaction was heated at ° C for three hours, and it was confirmed that the acid value of the reactant was zero. This object is used to cool the resin (3). The reactant was regarded as the original state of ethynyl acetol and acetic acid. Synthesis Example 4 Take 30 parts of epoxy acrylate resin obtained in Synthesis Example 2 and four sets—118 ~ I n I n. ^ 1 ϋ n -1 Ϊ n I mn T 09-, T (Note on the back of the poem before reading f) Please fill in this page again.) This paper applies Chinese National Standards (CMS). A4 is now standard (210X297 mm) 4 604 89 A7 'B7. 5. Description of the invention (42.2 parts of phthalic anhydride, 0.14 parts of anhydrous lithium chloride) It was heated and reacted for three hours at 1001 to obtain a Sodium Glycidyl Acrylic Acid Resin (4) with an acid value of 97. Synthesis Example 5 0.3 parts of polyethoxylated alcohol was added to 223.2 parts of dissolved phenethyl ether. To a polymerizable mixture of 700 parts of deionized water and 700 parts of deionized water and 71.1 parts of glycidyl isobutyrate, a mixture of 24 parts of benzene peroxide was added to make a mixture Uniform suspension. Nitrogen was heated to 80 ° C, and the mixture was allowed to react for five hours at this temperature, and then cooled to obtain a polymer turbid solution. This polymer suspension was filtered, and the residue of the machine was washed. It was dried to obtain a polymer (5) containing a ring gas group as a reactive group. Synthesis Example Θ 0.2 parts of the polyvinyl fermenter in which the polyvinyl yeast was dissolved was removed. 400 parts were placed in a flask equipped with a mixer, an inert gas inlet pipe, a recirculation cooling pipe, and a thermometer. A pre-prepared polymerizable monomer mixture containing 196 parts of cage ethylene and 4 parts of glycidyl methacrylate was dissolved. The mixture of 24 parts of benzene peroxide is made into a homogeneous suspension. While aerating, aerating, heating to 8CTC, and making it overlap at this temperature for 5 hours, and cooling it to obtain a polymer turbid solution. The polymer was mixed with turbid solution, and the residue was rinsed and then dried * to obtain a polymer (6) containing an epoxy group as a reactive group. Synthesis Example 7 First dissolve the polymethyl isobutanoic acid monomer (Macro monomer) (AA-6, manufactured by Toa Synthetic Chemistry, number average molecular weight is 6200) 78.17 parts are added to 200 parts of ethyl cellosolve acetate, 10.92 parts are added to styrene, and 10.19 parts of glycidyl methacrylate are added. Add azoisobutyl # 10 as 1 19 ~ IIII ----- II n I n I (Please read the precautions on the back before filling in this page) The standard of this paper is applicable to China National Standards (CNS ) A4 size (210X297 mm) 4 β Ο 4 Q9 Α7 _ Β7_ Instructions () Start agent to make it dissolve. ^^ 1 n In n ^ i ^^ 1 II— I «^ 1 ^^ 1 ^^ 1 ^^ 1 In (Please read the precautions on the back before filling this page) Put 25% of the above-mentioned dissolved matter into a separation bottle with a search and mixing tube, an inert gas introduction tube, a flow cooling tube, a thermometer, and a dropping filter. Nitrogen was passed in and overlapped at a temperature of 85 ° C. Thirty minutes of reaction. At the temperature *, the remaining 75% of the dissolved substances listed above were added slowly drop by drop within three hours to make them coincide. After the completion of the dropwise addition, the solution was kept at 8510 for 30 minutes, and 50 parts of ethyl cellulose solubilizer with 1 part of azoisobutene dissolved in 50 parts were added. After the addition, it was held at 85 ° C for one hour, and then the temperature was increased to 95 and the mixture was cooled for one hour. 57%。 The non-volatile component of the obtained polymer solution (7) was 2S. 57%. This material was separated to obtain polymer (7). The number average molecular weight of the polymer (7) was Mη = 7,500. Synthesis Example 8: Take 300 parts of 2-butoxyethanol as a dissolving agent, and place it in a separatory bottle with a search and mixing wing, an inert gas introduction tube, and a cooling tube, a thermometer, and a dropping bucket. At a temperature of S5 ° C, While supplying nitrogen, 200 parts of methyl isobutyrate (MMA), 200 parts of ethyl isobutyrate (HEMA), 8.5 parts of thioglycolate (9.227 × 104 Molar), and The mixture of 0.1 parts of gas isobutene (AIBN) was continuously added dropwise within four hours to complete the superposition reaction. Then add AIBN 0.1 and continue heating for 2 hours at the same temperature. It was heated at 95 ° C for one hour to complete the superposition reaction. Glycidyl isobutyric acid with a ratio of 17,0 parts to this reaction solution was added (1.3 parts per hour / C00H). 2.5 parts of tetrabutylanthracene bromide was used as a catalyst and 0.08 parts of hydrogen monomethyl ether was added. The superposition stop (prohibition) stopper was reacted at a temperature of 95 ° C for eight hours, and then cooled to obtain a number of ηη = 7000 end isobutyrate salt (ester) type MMA / ΗΕΜΑ co-superposition type giant monomer. Poly-120 with 57.14% of non-volatile content-The standard of this paper is applicable to Chinese National Standard (CNS) Α4 gauge (2 丨 0X297 mm) 4 β〇4 89 Α7 _Β7 5. Description of the invention () Composite solution α (please Read the precautions on the back before filling in this page.) 10.92 parts by weight of acetophenone, 10.97 parts by weight of glycidyl methacrylate, 136.8 parts by weight of the polymer solution listed above (78.17 parts by weight of the giant monomer), and 2 -Althylbutyroacetic acid 141.4%, but added dimethyl-2, -2'-bisazoisobutyric acid (d imethy 1 -2,2 '-a2〇-bis Isobuty late) 10 weight The part is a superposition starter. The above-mentioned mixture was put into a separating bottle with a dropping funnel used in Synthesis Example 7 and combined with each other to obtain a polymer solution (S). This solution contains 28.61% of non-volatile matter, and the number average component Mη of the obtained polymer (8) is 7800. Synthesis Example 9 M. The glycidyl methacrylate in Synthesis Example 10.19 parts by weight are composed of vinyl floc monomer 10. Except for 19 parts by weight, a polymer solution (9) was obtained in the same manner as in Synthesis Example 7. Although the number average molecular of the obtained polymer solution (9) was 7,500, the non-volatile content was 28.57% by weight. Synthesis Example 10: Take 250 parts of toluene and 50 parts of methyl ethyl ketone as solvents and put them into a separatory bottle with a stirring wing, an inert gas introduction pipe, a reflow cooling pipe, a thermometer, and a dropping dropping bucket. The temperature is 85 ° C. Ni gas was continuously added dropwise into 350 parts of methyl isobutyrate (MMA), 50 parts of ethyl isobutyrate (HEMA), and M. based 0 acid (1 ^ 〇21: / (; 〇 111〇3 (^ (1) 8,5 < 9.2271 > < 1〇 " ^ 1 ^ 〇1 €) and 0.1 parts of azoisopropane (ΛΙΒΝ) were mixed for 4 hours. Then add AIBN and heat at the same temperature for 2 hours. After that, it is heated for an additional hour at 95 ° C to complete the recombination reaction. The paper size is applicable to the Chinese National Standard (CNS) A43it grid (2 丨 0X29? Mm) 4 60 4 89 A7 _B7 V. Description of the invention (). Add 17.0 parts of glycidyl isobutyric acid to this reaction solution (1.3 times equivalents / C00H), 2.5 parts of tetrabutyl varamine as catalysts and 0.08 parts of dimethyl monomethyl ether as superposition stoppers. The temperature was 95 ° C. and the mixture was allowed to react for 8 hours. * After cooling, a polymer solution was obtained. After the polymer was re-settled with n-hexane, it was dried under reduced pressure for two days to obtain a polymethacrylic monomer (methyl methacrylate / via ethyl methacrylate) having a number average molecular weight of 7000 at the end of the tablet. 5 polypolymonomers (methyl isobutyrate X controlled ethyl isobutyric acid vinegar) containing an isobutyric acid group at the end of the tablet, and 15.2 phenethyl monomers were obtained. 9.8 parts of isopropenyl oxazole monomers, and 3 parts of azoisobutylene, the superposition initiator, were dissolved in 100 parts of ethyl cellulose solvate to obtain a monomer composition. In addition, in the flask used in the above list, add 50 parts of ethyl solvent acetic acid vinegar and heat to a temperature of 80 ° C. Under this condition, the composition of the patient body slowly added to the column within 2 hours. After the whole child is heated at 80 ° C for 2 hours to make it overlap, the temperature is raised to 95 ° C and allowed to heat for 2 hours to obtain a polymer solution (10) containing 40.0% of nonvolatile matter. Synthesis Example 11 250 parts of the polymer solution (10) containing 40% of nonvolatile matter obtained in Synthesis Example 10 were added dropwise at room temperature (25C soil ST :) over 30 minutes. (Molecular weight: 111.1) After 8.9 parts, it was stirred for 3 hours to obtain a polymer solution (11) containing a double bond. Synthesis Example 12 Take 700 parts of the solvent ethylene glycol monomethyl ether acetate (ECA) in a unit with a companion wing, an inert gas introduction pipe, a migration cooling pipe, a thermometer and a dropping filter bucket -122-This paper is for China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling out this page) 4 604 89 A? B7 V. Description of the invention () (Please read the precautions on the back before filling out (This page) In a liquid bottle, the temperature of 枉 is 85 ° C. The surface is filled with glucose: gas, and the methyl isobutyl sulfide is released continuously for 4 hours. (MMAU80, Xiang ethyl methacrylate (HEMA) 20 [3, 8.5 [9.2271 X 104 Mole) and 0.1 azoisobutylene (AIBN) overlapped. Then add 0.1 parts of AIBN and heat at the same temperature for 2 hours. It was then allowed to heat at 95T: 1 hour to complete the superposition reaction. In this reaction solution, 17.0 parts of glycidyl isobutyrate & brewing were added (1.3 times when S / C00H), 2.5 parts of the catalyst tetrabutyl aerobic vinegar and 0.08 parts of the superposition stopper argon 8¾-methyl ether were added. The temperature was below 95eC * and allowed to cool for 8 hours. After being submerged in Zhengjiyuan, it was dried at 50 ° C for 2 days to obtain a giant isomeric carbamate-type MMA-HEMA copolymer with an average molecular weight of 7000 (12). Dissolved 60 large monomers (2) 60 units, ethyl isobutyrate acid (HEMAU5, styrene ethyl shop (St U5.2, isohedrin) ### (IP〇) 9.8, ECA100 And AIBN starter 3 parts, gp to obtain a polymerizable monomer composition. Take ECA 50 into a separatory bottle with a stirring wing, a cooling tube, a dropping bucket, and a nitrogen inlet, and heat to 80 ° C. And keep this temperature. Take the above-listed overlapping monomer composition in the dropping bucket, and add it to the separatory bottle for 3 hours under the temperature. Then make it at the same temperature. The reaction was superposed for 2 hours, and then matured at a temperature of 95T for 3 hours to obtain a graft copolymer (12) containing 40% non-volatile content. Synthesis Example 13 The solvent propylene glycol monomethyl ether acetate ( PGM-Ac) 200 units are equipped with agitating wings, inactive gas inlet pipe =, transport cooling pipe, thermometer, paper size (applicable to China National Standard (CN_S) A4 size (210X297 mm) 4 6 0-4 89 A7 B7 V. Description of the invention () (please read the “Notes on the back” and fill in this page first) and the dropping bottle with the filter, at a temperature of 80 ° C— Aerate the air and slowly add 120 parts of methacrylate 1 (BZMA), 4 parts of 80% of two methacrylic acid esters (HPMA), 3 parts of succinic acid and starter A IBM over 4 hours. 0.03 parts of the mixed solution were allowed to overlap. Then, AIBN0 + 02 was added dropwise every 30 minutes. After 4 hours of the overlap reaction, the mixture was heated at 95 ° C for 2 hours to complete the overlap reaction. 4.70 parts of Bingfujinglin, 0.08 parts of superposition stopper argon | factory · methyl brewing, allowed to react for 2 hours at a temperature of 100 ^^, and then cooled to obtain a tail end of an average molecular weight of 5000 Women-based BZMA-HEMA macropolymer (Macromer.) (13). Dissolved macromonomer (13) 75 units, 15 stupid ethylene, 10 isopropenyl chewing beer d building 10 and PGM-Ac 100 Part M and the starting agent AIBN 3 parts to obtain a recombinable monomer. Take 50 parts of PGM-Ac and place them in a separatory bottle with a stirrer, a cooling tube dropping filter, and a nitrogen inlet. Wait for the temperature to rise to 80 ° C. After that, the temperature was maintained. The polymerizable monomer composition listed above was put into a dropping funnel, and Zhiyuan was slowly dropped into the bottle over a period of 3 hours. After allowing it to overlap at 80 ° C, it was further overlapped at the same temperature for 2 hours, and then allowed to mature at a temperature of 110 ° C for 2 hours to obtain a graft copolymer (13) containing 40% of nonvolatile matter. Synthesis Example 14 Take Isobutylated polymethylmethacrylic acid vinegar (AS-6, manufactured by Toa Synthetic Chemical Industry) with a molecular weight of about 6000, which is made of 40 macromers and 25 polyethylene, and two different beer. 10 forests, 25 argon butyl isobutyric acid brewers, 100 solvents PGM-Ac 100 and starter ΑΙΒΝ 5 • This paper size applies to China National Standard (CNS) Α4 specifications (2 丨 0 X 29? (Centi) 60489 A7 __B7_ 5. Description of the invention () The parts are dissolved together to obtain a polymerizable monomer composition. (Please read the precautions on the back before filling this page) Take the PGM-Ac50 into a separatory bottle with a search mixer, cooling tube, drip filter, and nitrogen inlet, and raise the temperature to 80 ° C. The polymerizable carcass listed above was put into a dropping filter bucket. * It was dropped into a separatory bottle over a period of 3 hours, and the superposition reaction was performed at a temperature of 80X :. It was then allowed to overlap in 4 hours, and the giant pupae contained a non-volatile 40% graft copolymer (14). Synthesis Example 15 Co-dissolved 60 units of the giant monomer (12) obtained in Synthesis Example 12, 15 units of acrylic acid, 15.2 units of styrene, 15 units of isopropylbenzene, <# 9.8, ECA 100, and AIBN 3, to obtain a polymerizable monomer composition. Take 50 ECA into the separation bottle used in Synthesis Example 2. After the temperature rises to SCTC, keep this temperature, and after the dropwise addition of the polymerizable carcass composition listed above is completed within 3 hours, then It continued to overlap for 2 hours. That is, the polymer solution became gel-like and adhered to the search bar (gelation): Synthesis Example 16 Take a polymethyl (methisobutyrate) monohydroxyethyl containing methyl end methacrylate Methacrylic acid) Megamonomer (manufactured by East Asia Synthetic, AA-714) 75 parts, 15 styrene units, isopropenyl DZ "Lin 10 and 3 AIBN were dissolved in 100 parts of PGM-Ac, that is, polymerization Take the PGM-Ac50 part into the separation bottle of the breeding mixer, flow cooling tube, thermometer, dropping filter, and nitrogen inlet, and heat it to 80 ° C. The above polymerizability The monomer composition was put into a dropping funnel, and slowly dropped into a separatory bottle within 3 hours, and was allowed to overlap at 80 ° C. After this temperature was allowed to continue to overlap for 2 hours, the temperature was increased to 120 ° C, after 2 hours of ripening, you will get -125-^ paper 伕 scales applicable to China National Standard (CNS) 8 4 specifications (210X297 mm) '4 60489 A7 B7 V. Description of the invention () Polymer solution with non-volatile content of 40% (16). Synthesis Example 17 (Please read the precautions on the back before filling out this page) In Synthesis Example 16, only the top two Except for methyl methyl methacrylate instead of isopropenyl chelate α, other components are the same and operated in the same manner as in Synthesis Example 16, and a polymer solution (17) containing 40% nonvolatile matter was obtained. Synthesis Example 18 The method of Synthesis Example 16 and the same procedure except that the raw material isopropylpyridine β was replaced with methacrylic acid, the same operation was performed to obtain a polymer solution (18) containing 40% non-volatile content. Synthesis Example] ί) Take 75 parts containing the double-bonded methylaminopolyethylene glycol isobutyrate at the end of the film (produced by Shin Nakamura Chemical Industry, NK ester M-230G), 75 acetophenones, and isopropenyl Doxa. 10 parts, 3 starters, 2,2 · -azobis (2,4-dimethylpentyl flavor), and 3 parts are put into the liquid separation tube with stirring wings, inactive gas introduction pipe, reflux cooling pipe and thermometer In a bottle, under a nitrogen flow and a temperature of 75, carry out a superposition reaction for 5 hours to obtain a non-volatile 50% reactive group in the molecule. t; Linki ’s polymer solution of ethanedine chain segment (19). Synthesis Example 20 Laurylase (acetic acid) 15 glycidyl ether (Changhua Chemical Industry, Dinago) EX-171) 1040 parts and 500 acetic acid yeasts were added to the same separation bottle used in Synthesis Example 19, and 72 propionic acid was used, and the amount of catalyst was PtM (py "ictine"), and 150 ρριη, It was allowed to react for 2 hours at a temperature of 70. Then the acetic acid was removed under the reduced calendar to obtain the lauric acid (ethylenated gas) 15 having a double bond at the end of the film. -126 _ The paper ^ size applies to the Chinese Standard (CNS) Α4 ^ grid (210X 297 mm) 1

1 I h ί :p t A7 B7 4 604 89 五、發明説明（） 在H尾端有雙鏈結合的月桂酵（乙蹄化氧)γ 75部中 ，加乙酵100部，苯乙鋪15部，縮水甘油異丁烯酸醋10部， 開始劑2,2’一偶氮雙（2,4-二甲基戊0) 3部，在氮氣流 及溫度75=0之下，使其重合反應6小時。結果得到了含有 不揮發分50%的月桂醇（乙嫌化氧)/r 鏈之聚合體溶液（ 20) ^ 合成例21 在甲笼72.5部溶有硬脂醯異丁婦g楚S旨169.2部的混合 液中，加顿基酯酸9.2部及開始劑偶氣異丁轉（AIBN)0.82 部，使其反應而得重合性單性組成物。 取甲班87部入於如同合成例8所使用的分液瓶中，在 溫度80°C，M4小時的時間滴加上列單體組成物後，在同 溫繼縝加熟2小時。然後在每隔30分鍾各注加一次的AIBN 0.2部，將其在溫度951進行里合熟成3小時後冷卻之：其 後，再加縮水甘油異丁烯酸醋18.5部*氫鋪:_一甲醚0.06部 及hi, N ’一甲基月桂釀胺（N, N ’-dimehty 1 Laury lamine) 1.7 苔P，在溫度110°C使其反應8小時。冷卻此物後，用甲醇使 其再沈澱。分出沈澱，減壓乾燥後，即得聚硬脂醯異丁烯 酸醋巨形物。 其同溶解所得的聚硬脂醯異丁烯酸酯巨彤物75部•異 两締基嚼哇咐10部及AIBN 5部於甲苯100部中*即得聚合 性體組成物。 取甲苯50部入於附有报拌機、冷卻管、滴下濾斗及氮 氣流入口的分液瓶中，加熱至溫度80 °C。在80 °C，自滴下 -127 - 本紙張尺度適用中國國家標準（CNS ) A4規格{ 210X2?7公釐） t- _ ___ I-I - ....... II ; - n ^^1 I l^i (請先聞讀背面之注意事項再填本頁) ί 卞 i 4 6〇4 89 A7 B7 五、發明说明（ 滅斗以3小時的時間滴加裝在減斗中的上列單體組成物， 使其重合。待熟成後’完成重合而冷卻。再用甲酵再沈锻 •分出沈殺經真空乾燥，即得接枝化共聚合體（21)。 合成例22 將11 十一'院（酸）截基酸（11 Undecamino acid) 300g 及丁蹄酸25.67g入於附有氣體導入管，有接器而與冷卻管 相連的蒸願裝置連結管及攬拌翼的一公升容量金屬製反應 容器中。 用氮氣充滿反應容器後，關閉氮氣導入管检，加熱40 分鍾至溫度達210¾而使歷力升到5 bar。然後使反應容器 内減Μ為0.5 robar，一面攬拌，一面通入30/ /H的氮氣， 在21CTC繼緬加熱4小時。再M〇.5mbar的減壓狀態放置1小 時’使其完成反應，即得其一尾端有不飽和雙鏈結合.而 另一尾端有狻基的聚醯胺。 加入與俊基相等克分子童的十二院基嗯啤!>林，在加歷 下來去除其尾端的搜基。在遭受空氣氧化的狀態之下，將 所合成的百形合物自反應容器移入水槽中M5(TC的真黎度 分離本巨形合物14小時後再真空乾燥，即得在其尾端有雙 _結合的聚醯胺巨形合物。 將在此所的聚醯胺巨形合物75部、丁基丁烯酸酯15部 、異丙婦基嗯哩<^1〇部及AIBN 3部一起溶解於乙醇1〇〇部， 即得聚合性單體組成物。 將乙酵50部入於附有攪拌機、冷卻管、滴下濾斗及氮 氣流入口的分液瓶中，加熱至75°C。再自滴下減斗在3小 -128 - (請先閲讀背面之注意Ϋ項再填寫本萸) 裝1 I h ί: pt A7 B7 4 604 89 V. Description of the invention () In the H tail, there are double-stranded laurel enzymes (ethoxylated oxygen) γ 75, plus 100 yeasts and 15 phenylethyl stores 10 parts of glycidyl methacrylic acid, 3 parts of 2,2'-azobis (2,4-dimethylpentano) starter, and under a nitrogen flow and temperature 75 = 0, the reaction was allowed to overlap for 6 hours . As a result, a polymer solution containing 50% of non-volatile lauryl alcohol (ethoxylated oxygen) / r chain was obtained (Synthesis Example 21) Stearyl isobutyrate was dissolved in the 72.5 part of the cage, Schu 169.2 In the mixed solution of the part, 9.2 parts of the glutamic acid ester and 0.82 part of the starting agent azoisobutyrene (AIBN) were reacted to obtain a coincident unisex composition. Take 87 parts of Class A and put them into the separation bottle used in Synthesis Example 8. After the monomer composition was added dropwise at a temperature of 80 ° C for 4 hours, the mixture was further cooked at the same temperature for 2 hours. Then inject AIBN 0.2 parts every 30 minutes, mix and mature at a temperature of 951 for 3 hours, and then cool it: after that, add 18.5 parts of glycidyl methacrylate * hydrogen shop: _ monomethyl ether 0.06 parts and hi, N'-dimehty 1 Laury lamine 1.7 Moss P. The reaction was performed at a temperature of 110 ° C for 8 hours. After cooling this, it was reprecipitated with methanol. The precipitate was separated and dried under reduced pressure to obtain a polystearic acid methacrylic acid vinegar giant. Polyisostearic acid methacrylate macromolecules obtained by dissolving 75 parts of polyisostearate methacrylate and 10 parts of isoallyl chelate and 5 parts of AIBN were prepared in 100 parts of toluene * to obtain a polymer composition. Take 50 parts of toluene and put it in a separatory bottle with a blender, cooling tube, drip filter, and nitrogen gas inlet, and heat to 80 ° C. At 80 ° C, self-dropping -127-This paper size applies Chinese National Standard (CNS) A4 specification {210X2? 7 mm) t- _ ___ II-....... II;-n ^^ 1 I l ^ i (please read the precautions on the back before filling this page) ί 卞 i 4 6〇4 89 A7 B7 V. Description of the invention (Destruction of the bucket is added to the above list in the bucket for 3 hours. The body composition is allowed to overlap. After the maturation, the reaction is completed and cooled. Then the formic acid is used for re-sinking, separation, and sterilization, followed by vacuum drying, to obtain a graft copolymer (21). Synthesis Example 22 Yi'yuan (acid) 300 g of 11 Undecamino acid and 25.67 g of butyric acid are placed in a liter of steaming device connecting pipe and a mixing wing with a gas introduction pipe, a connector and a cooling pipe Capacity metal reaction vessel. After filling the reaction vessel with nitrogen, close the nitrogen introduction tube inspection, heat for 40 minutes to a temperature of 210¾, and increase the power to 5 bar. Then reduce the inside of the reaction vessel to 0.5 robar while stirring On the one hand, nitrogen gas of 30 / H was introduced, and heating was continued at 21 CTC for 4 hours. Then, it was placed under reduced pressure of 0.5 mbar for 1 hour to complete the reaction. That is, one end has unsaturated double-stranded binding. The other end has a fluorenyl polyamine. Add the twelve courtyard beer that is equal to the junior boy of Junji! ≫ Lin, in the calendar Remove the base at its tail end. Under the condition of being subjected to air oxidation, move the synthesized morphogen from the reaction vessel into a water tank. The macromolecular compound of M5 (TC) is separated for 14 hours and then dried in vacuum. That is to say, there is a bis-conjugated polyamidamine macro complex at its tail end. The polyamidamine macromolecules, 75 parts, 15 butyl butyl acrylates, and isopropyl methacrylate, etc. ^ 100 and AIBN 3 were dissolved together in ethanol 100 to obtain a polymerizable monomer composition. 50 acetic acid enzymes were placed in a separator equipped with a stirrer, a cooling tube, a dropping filter, and a nitrogen inlet. In the liquid bottle, heat to 75 ° C. Then drop the bucket at 3 hours -128-(Please read the note on the back before filling in this section)

.1T 本紙伕尺度通用中國國家標準（CNS ) A4規格（2!ΟΧ2?7公釐） 4 60 4 89 A7 B7 五、發明説明（） I I - - n n n I i - - n -- I T · «、T (請先閱讀背面之注意事項再填寫本頁) 時的時間内滴力D裝在該滅耳中的上列單量體組成物，使其 在同溫度之下重合反應2小時。再提高溫度在運流之下， 使其重合完成後，加Μ冷卻。然後’用乙醇再沈殺、分出 沈殺、真空乾燥，即得接枝共聚合體（22)。 合成例23 共同溶解乙鋪基被各圓1〇〇咨Ρ、ΑΙΒΝ 4咨(3及额基 两酸2.55部，即得簠合製單體組成物◊取乙酵1〇〇部入於 如同合成例8所用的分液瓶中*在反懕溫度75¾，M4小 時的時間將上列單體組成物滴加於分液瓶中，在同溫度再 加熱2小時。然後，每隔30分鍾再各加AIBN 0.2部四次， 使其完成重合後，加以冷卻。用***再沈殿所得聚合物， MTHF沖洗沈殺後冥空乾燥之。 將此沈澱溶解於DMF中，加相當於上列聚合物的羧基之 1,3倍當最氣甲基聚乙蹄酯及50%M氧化納水溶液。將混合 物在30¾授拌24小時，使其反應。用***再沈殺此物，用 THF沖洗沈澱後，再用乙醇再沈澱，分出沈澱，減歴乾燥而 得到有苯乙鋪基為尾端的聚乙鋪基吡略酮巨形合物。 其後，以合成例22除了由聚乙烯吡咯酮替代聚醯胺巨 形合物Μ外均使用相同的原料，依合成例22的操作，即可 得接枝化共聚合體（23)。 合成例24 先以每一分子鏈含有一個不飽和基的樣式_用不飽和 的二鹽基酸（如馬來酸、香豆酸、香康酸、甲基延胡索酸 等）來合成聚酷。再用一價醇類來取代聚醋尾端的羧基等 本紙張尺度適用中囷国家標準（CNS ) A4規格（210X29?公釐） A 6 0 4.89 A7 B7 ------- '~^ >、發明説明（） ^^1 ί n ^^1 ml ^^1 ^^1 i 士l^i m „ ,¾ (請先閱讀背面之注項再填寫本X ) 酉旨化反應將其鎖鏈，或用一價的嗯哩化合物、環两稀化 合物等來鎖鏈，在有此物質的條件之下，使聚乙婶及:縮水 甘油異丁烯酸酿與之重合，而得含有聚酯構造的鏈段（B) 及以環氧基做為其反應性基的聚苯乙烯構造之鍵段（A)二 者的接枝化共聚合體（24)。 合成例25 在100部二甲基苯中，加入尾端含有氫氧基的畏鏈飽和 碳氫化合物的高價（級）醇類益尼*#700 (東洋石油萊特公 司製，融點為99°C，0H基價為65ms K0H/g)75部，在120°C 使其溶解。 在此溶液中滴加異丁烯酸異氰酷9.6部在其尾端引進 雙鏈结合。 在溫度120¾以2小時的時間，將予先調整的苯乙烯15 部，異婦基嗯哩β林1〇部、二甲苯250部及AIBN 0.2部混合 液滴加於上列液體中，使其進行重合後，冷卻，即得有聚 烯基構造的鏈段（B)及有噁唑》林基為反懕性基的聚苯乙烯 構造之鐽段（Α)等二者都具備的接枝化共聚合體（25)。 合成例26 取環己酮112.5部入於附有搅拌機，不活性氣導入管， 遝流冷卻管、滴下濾斗及溫度計的燒瓶中，加熱至80¾ c. 將偁Μ異丁_(AIBN) 7.5部溶解於笼乙鋪35部，徑基 異丁蹄酸酸酯35部、異丙締基嚼啤p林5部的溶液入於滴下 濟上中，在80它以3小時的時間滴加栓上列燒瓶後，再在 同溫度繼镰重合反應2小時 -130 - 本紙法尺度適用中國國家標準 { CNS ) A4*l格（？10Χ297公釐） 4 604 89 A7 _B7___五、發明説明（） 然後，再加入A IBM 0.3部，在120°C使其熟成2小時後 ，冷卻，而得不揮發分40%的含有能與碳黑起反應的反應 性基及氫氧基都有的聚合體（26)。 合成例27 取在合成例26所得的聚合體（26)溶液（含不揮發分40 17.5部在室溫* M30分鍾的時間滴加異丁歸酸異氮酷 (Mw= 111.1) 6.73g，使其引進雙鍵結合，再加入環已酮 10.02部使其反應，即得含有不揮發分40%而具有與碳黑反 應性的基及併有雙鏈結合氫氣基的聚合體（27)的聚合體溶 液(27) 〇 合成例28 取在其尾端有雙鍵結合的甲氧基聚乙二醇異丁烯酸酯 (新中村化學工業製，NK酯M-230G) 75部、苯乙婦15部、 2- (1-氮丙唯基）乙異丁婦酸酯10部及開始劑2,2 ^—偶氮雙 (2,4—二甲基成喊）3部入於附有攪拌翼，不活性氣等入管 ，運流冷卻管及溫度計的分液瓶中，在751氮氣流通之下 使其簠合反應5小時，即得含有不揮發分50%而在其分子 中含有氮丙陡基為反應性基兼有乙二酵鏈的聚合體溶液（ 28) ^ 已處理碳黒的製作 實施例1 取在合成例1所得的環氧丙烯酸醋樹脂（1) 30部及碳 黑MA-100R (三菱化成工業製）30部入於拉謀普拉斯特粉 碎機（東洋精機製）以下由（（同前出）代之），在140 (請先W讀背面之注意事項再填寫本頁) 本紙伕尺度適用中國國家橾準（CN’S ) A4規格（210 X297公釐） 4 604 89 A7 _B7_ 五、發明説明（） (請先閱讀背面之注意Ϋ項再填寫本頁) ; lOOrpm條件之下，練合後，冷卻，粉碎成為已處理碳 黑（EXA-1) 〇 實施例2 取在實施例1所得的已處理碳黑（ExA-1) 30部和四氫 化酉干4.3部，無水氛化經0.01部，在100"C使其反應3小 時後，冷卻*經粉碎，即得已處理碳黑（ExB-1)。 實施例3 將在合成例3所得的環氣丙嫌酸酷樹脂及乙婦基卞必 醇乙酸酯混合物中*加碳黑MA-100R (三菱化成工業製） (以下代為（同前出））38.64部及直徑3腿的不_鋼製小 珠粒800部•在140°C搅拌半小時，即得含有20%已處理碳 黑（ExA-2)和乙基卞必醇乙酸_的混合物（ExA-2)。 比較例1 取在合成例2所得的在實筲上未含有撰氧基的環氣两 輝酸酯樹脂（1)30部及碳黑MA-100R (三菱化成工樂製）30 部入於Laboplast mill (東洋精機製）中，在140°C，100 rpm條件之下，練合，冷卻經粉碑，即得比較用已處理碳 黑（do-Ι)。 比較例2 混合在比較例1所得的碳黑接枝聚合物（C0-1) 30部， 四氬化MSf4.8部及無水氯化鋰0.07部，在1〇〇°C使其反應 3小時後，冷卻，經粉碎，即得比較用已處理碳黑(C0-2) 〇 比較例3 本紙乐尺度通用中國國家標準< CNS ) 210Χ297公釐） 4 P04 89 A7 B7 五、發明説明（） ί請先閱讀背面之注意事項再填寫本頁) 取在合成例1所用的相同酣性醜酸清漆壞氧樹脂YD PN-638P (東都化成製，環氣當量為180) 30部和碳黑MA-100R (同前）30部入於Laboplat mill (同前出）中， 以140C 100 rpm練合後，經冷卻，粉碎，即得比較用已 處理碳黑(C0-3) 〇 比較例4 取在合成例6所得的聚合體(6)30部和碳黑MA^IOOR ( 同前）30部入於Laboplast mill (同前出）中，以140QC， 100rpm練合後，經冷卻、粉碎，即得比較用已處理碳黑 (C0-4) 〇 實施例4 取在合成例5所得的聚合體(5)50部溶解於乙基卞必醇 乙酸酯50部的混合物100部，加丙烯酸5.4部*氯化鞍三乙 基卞酷0.0(3部及苯酿0.04部，在110°C使其反應2小時。 取在上列所得的聚合體57.1部，碳黑MA-100R(同前出 )30部，乙烯基卞必酵乙酸酷212.9部入於附有攬拌翼，遝 流冷卻器的分液瓶中•加直徑3腿的鋼製小珠800部，在160 t攪拌3小時即得含有20%已處理碳黑（Ex-3)的乙基卞必 醇乙酸醋混合物（E-3)。 比較例5 取在合成例5所得的聚合體(5)15部溶觸在乙基卞必醇 乙酸酯中調製為混合物後，將其30入於附有撹拌翼、邐流 冷卻器的分液瓶中，加碳黑MA-100R (同前製）45部，乙 烯基卞必醇乙酸醋225部及直徑3mm的鋼製小珠800部，在160 -133 - 本紙法尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 460489 A7 B7 五、發明説明（） X、授拌30分鍾，即得含有比較用已處理碳黑（C0-5)20%的 乙基卞必酵乙酸酷混合物（C0-5)。 比較例6 將在合成例5所得的聚合體⑸50部溶解於乙基卞必酵 乙酸醋50部中，調成混合物。取此混合物1〇〇部，加丙稀酸 6.2咅!3，氯化多安三乙基卞@旨0.〇6咅|3及^^|10.04部，在110°〇 使其反應2小時。 取在上列所得聚合體56,7部入於附有攪伴翼、堪流冷 卻器的分液瓶中，加碳黑MA-100R (同前出）30部，乙蹄基 卞必醇乙酸醋213.3部及直徑3mm的鋼製小珠800部，在160 °C搅拌30分鍾，即得含有已處理碳黑（C0-6) 20%的乙基卞 醇乙酸醋混合物(C0-6)。 比較例7 取碳黑MA-100R (同前出）60部，乙稀基卞必醇乙酸 酷240部及直徑3 mm的鋼製小珠800部人於附有搜拌翼及遥 流冷卻器的分液瓶中•在1(30°攬拌30分鐘，即得含有碳黑 20%的乙基卞必醇乙酸醋混合物（C0-7)。 實施例5 取在合成例7所得聚合體溶液（7) 23.35部，碳黑MA-100R (同前出）20部，乙基溶雛劑乙酸醋56·65部各入於 附有溫度計，攪拌冀及冷卻管的分液瓶中，分散後再加SUS 製小珠600部。在160QC，以回轉數300rpm的速度搜伴2小 時，使其接枝化，反應後，再加乙基溶纖劑乙酸_100部， 使其分散均匀。分離反應内容物和SUS製小珠，即得含有已 -134 - 本紙伕尺度適用中國國家標準（CNS } A4現格（210X297公釐） '' ^-- (請先閔讀背面之注意事項再填寫本頁) *1Τ 4 6〇4 89 A7 B7 五、發明説明（） 處理碳黑（ExC-l)的分散溶液（ExC-l)。 簧施例6 各取在合成例8所得的聚合體溶液（8) 23.35部及碳黑 ^1/\-1001?(同前出）20部，丁基溶纖劑56.65部入於如同在 實施例5使用的相同裝置中，依實胞例5同一方法操作， 即得含有已處理碳黒（ExC-2)的分散溶液（ExC-2)。 參考例1 取在合成例7所得聚合體溶液（7) 6.67部及碳黒MA-100 R (同前出）20部，丁基溶纖劑73.33部入於附有溫度計， 攪拌翼及冷卻管的分液瓶中，依實施例5的同一操作》即 得含有碳黑20%分散溶液（ReC-1)。將此分散溶液（ReC-l) 與在簧施例5所得的分散溶液（ExC-l)作比較時，即能發現 分散溶液（ReC-Ι)有（液）相分離的形態生沈降（殺），而是靥 於有選擇分散媒液不宜之嫌。 實施例7 各取在合成例16所得的聚合體溶液（16) 23.4部及碳黑 (pH3.1) 31.2部丙（烯）基二酵一甲基醚乙酸酯101.4部入 於附有溫度計、播拌翼及冷卻管的分液瓶中，分散後再加 氣化錯製小珠800部。在lOCTCKTOOrpm的回轉速度使其接 枝化1小時。分出反應肉容物，即得含有已處理碳黑（ExC -3)的分散溶液（ExC-3) ‘: 實施例8 依實施例7的方法，使用聚合體溶液（16) 78.0部，碳 本紙掁尺度適用中國國家標準（CNS ) Α4規格（2]〇Χ：297公釐） 扣衣-- (請先Μ讀背面之注意事項再填寫本頁) *1Τ 4 60489 A7 _B7____ 五、發明説明（） (請先W讀背面之注意事項再填寫本頁；> 黑31.2部，丙（鋪基）二酵一甲基醚乙酸醋46*8部為原料 同樣操作，即可得含有已處理碳黒（ExC-4)的分散溶液（ ExC-4) 比較例8 取在合成例9所得的比較用聚合體溶液（9)為原料，依 實施例5的操作操作，即得比較用碳黑混合溶液（C0-8)。 比較例9 各取在合成例6所得的比較用聚合體（6) 6.67部及碳黑 1^\-100卩（同前出）200部，乙基溶纖劑乙酸醋73.33部入 於與莨施例5相同的裝置中，使其分散，再加入SUS製小珠 600部。依實施例1的同一條件使其反應，待其反應後，再 加乙基溶纖劑乙酸酯100部，使其分散均匀。分出反應内 容物，即得含有比較用已處理碳黑（C0-9)的分散溶液（C0-9) 〇 比較例10 依實施例7的方法，由在合例17所得的比較用聚合體 溶液（17)替代聚合體溶液（16)及以在40°c處理1小時替代 在100°C處理1小時之外，均與實施例7同樣操作，即得含 有比較用已處理碳黑（C0-10)的分散溶液（C0-10)。 比較例11 將實施例8的聚合體溶液（16)由在合成例17所得的比 較用聚合體溶掖（17)來取代及以在4CTC處理1小時替代在 10(TC處理1小時之外均與賀施例7同樣操作，即得含有比 較用已處理碳黑（C0-11)的分散溶液（CO-11) —136 m 本紙張尺度適用中國S家標準（CNS ) A4現格（21 OX 297公釐)： ：~~： 4 S〇4 89 A7 B7 五、發明説明（） 比較例12 用合成例18所得的比較用聚合體溶液（18)替代實施例 7的聚合體溶液（16)及Μ在40°C處理1小時替代在1〇〇處 理1小時之夕卜均與實胞例7 —^素的操作，即得含有比較用 已處理碳黑（CO-12) 6¾分散溶液（C0-12)。 比較例13 用在合成例18所得的比較用聚合體溶液（18)來替代實 施例8的聚合體溶液（16)及以在40°C處理1小時來替代在 100 °C處理1小時之夕卜，均與實皰例17同一操作，即得含有 比較用已處理碳黑（C0-13)的分散溶液（C0-13)。 實施例9 各取碳黒MA-8 (三菱化學製）30部，乙基溶纖劑乙酸 酯97.5部及在合成例10所得含有不揮發分40%的聚合體溶 液（10)22.5部入於附有溫度計、搅拌翼及冷卻管的分液瓶 中，使其分散。 經濟部中夬櫺準馬員工消費合作社印袈 (請先閱讀背面之注意事項再填寫本頁) 再加入氧化結製的小珠800部· M300 rpm的回轉速度 授拌，使其在1〇〇 接枝化反應2小時：·待反應完成後，再 加乙溶纖劑乙酸酷50部，使其分散均句。分出反應内容物 ，即得含有已處理碳黑（ExC-5)的分散溶液（ExC-5)。 實施例10 用在合成例11所得的含有不揮發分43.6%的聚合體溶 液（11)20.6部及乙基溶纖劑乙酸酯108.4部來取代實胞例9 的含有不揮發分40%聚合體溶液（10) 22 · 5部及乙基溶纖劑 乙酸酯97.5部之外，均與質施例完全同一的返復搡作，即 -137 - 本紙乐尺度適用中國國家標準（CNS ) A4規格（210_Χ25»7公釐} 460489 A7 B7 五、發明説明（） 得含有已處理碳黑（ExD-1)的分散溶液（ExD-1)。 實施例11 ί诗先Μ讀背面之注意事項再填寫本頁) 在附有溫度計、攪拌翼及冷卻管的分液瓶中，分散碳 黒ΜΛ-8 (同前出）30部•乙基溶纖劑乙酸酯97.5部及在合 成例所得含有不揮發分40%的聚合體溶液（12)22.5部。 而後，加入氧化_製小珠800部，以300 rpm的回轉速 在100它使其反應3小時後，冷卻，分出反應內容物，即得 含有已處理碳黑（ExC-6)的分散溶液（ExC-6)。 簧施例12 對在實施例11所得的分散溶液（ExC-6) 150部，加無水 玻拍酸（分子量為100.07) 1.49部及觸媒氣化鋰0.009部， 使其在100 C反應12小時，即得在其A鍵段及B鏈段雙方均有 按基的已處理碳黑（ΕχΕ-1)之分敗溶液（ExE-1)。 實施例13 對在實施例11所得分散溶液（ExCH3) 150部，加無水偏 苯三酸（分子量為192.13) 2.86部*觸媒用1.8-二？丫環〔 5,4.0〕-7-十一碳鋪（BBU)O.OOl部，在8CTC使其反應30分 鍾*即得含有在其A鏈段及B鏈段均有羧基的已處理碳黑（ ExE-2)分散溶液(ExE-2)。 實施例14 在如同實施例Π使用的分液瓶中，加入碳黒SB-250 C 特枯撒公司製）30部，PGM-Ac 97.5部，氧化銷小珠800部 及在合成例13所得共聚合體（13) 22.5部。 M70〇rpm回轉速100°C搜伴1小時使其反應後，經冷卻 本紙伕尺度適用中圉国家橾準（CfS ) Α4規格（210X297公釐） 4 6〇4 89 A7 B7_ 五、發明説明（） *分離，即得含有已處理碳黑（ExC-7)的分散溶液（ExC-7) 〇 I 11 I --1 I- - - - - I —'*61 - I - - IE - T* 0¾ -"" {锖先Μ讀背面之注意事項再填寫本頁) 實施例15 對在實施例14所得分散溶液（ExC-7) 150部，加無水馬 來酸（分子量為98.06) 1.8部，觸媒甩DBU 0.09部，在60 °〇使其反應2小時，即得含有在其B鏈段有搜基的已處理碳 黑（ExE-3)分散溶液（ExE-3)。 實施例16 在如同實胞例11使用的分液瓶中*加人碳黑MA-100R( 同前出）30部，PGM-Ac 97.5部，銷土小珠800重虽部及在 合成例14所得的接枝化聚合體（14) 22.5部。 在100°CM600rpin回轉速授拌1小時使其反應後，分出 溶液入於附有蒸餾管的分液瓶内，加熱至140 °CM分解四氳 化喃酯基而除去後 > 即得含有C00H基的已處理碳黑（ExE -5)分散溶液（ExE-4)。 實方ΪΕ例17 取碳黑特種黑250 (Carbon black, special black 250) (特祜撒公司製）10部，結上製小珠1500部及在合成例19 所得含有乙二酵鏈的聚合體溶液（19) 30部一同入於附有感 溫器，搅伴翼及冷卻管的分液瓶中。在75tM600rpin的回 轉速搅拌2小時後，再加熱至120°C，一面餾去乙酵使其反 應1小時。然後冷卻，加脫離子水75部，使其分散，經分 離操作，即得碳黑分散溶液（ExC-8)。 實施例18 本紙伕尺度適用f國國家榡準（CNS ) A4規格（2丨0 X 2们公釐）.1T Standards of this paper: Common Chinese National Standard (CNS) A4 specification (2! 〇 × 2? 7 mm) 4 60 4 89 A7 B7 V. Description of invention () II--nnn I i--n-IT · «, T (please read the precautions on the back before filling out this page) within the time period, the drip force D is installed in the above-mentioned singular body composition in the ear killer, and it is allowed to react at the same temperature for 2 hours. After increasing the temperature under the flow, make it overlap, and then add M to cool. Then, it is further submerged with ethanol, separated and submerged, and dried under vacuum to obtain a graft copolymer (22). Synthesis Example 23 The co-dissolved ethoxylate was prepared with 100% of each circle, AIBN 4 and 3 (2.55 parts of erythroic acid, and the monomer composition was obtained by mixing the 100 parts of ethyl acetate. In the separatory bottle used in Synthesis Example 8 * the monomer composition listed above was added dropwise to the separatory bottle at a reaction temperature of 75¾, M4 hours, and heated at the same temperature for another 2 hours. Then, every 30 minutes Add 0.2 parts of AIBN four times each to complete the superposition, and then cool. The polymer obtained in the temple was re-sinked with ether, rinsed and washed with MTHF, and then dried in the air. This precipitate was dissolved in DMF and added to the polymer listed above. 1,3 times of the carboxyl group when it is the most gaseous methyl polyethylene glycol ester and 50% M sodium oxide aqueous solution. The mixture is stirred at 30¾ for 24 hours to make it react. This material is re-precipitated with ether, and the precipitate is washed with THF. Then, it was reprecipitated with ethanol, the precipitate was separated, and the precipitate was reduced to dryness to obtain a polyvinylpyrrolidone macro complex having a phenethylpyridyl group as the end. Thereafter, the synthetic example 22 was replaced by polyvinylpyrrolidone. The same raw materials were used outside the polyamine macromolecular compound M. According to the operation of Synthesis Example 22, a graft copolymer was obtained. Polymer (23). Synthetic Example 24 Firstly use an unsaturated dibasic acid (such as maleic acid, coumaric acid, xiangconic acid, methyl fumaric acid, etc.) in the form that each molecular chain contains an unsaturated group. To synthesize polycool. Then use monovalent alcohols to replace the carboxyl groups at the end of polyacetate, etc. This paper size is applicable to China National Standard (CNS) A4 specification (210X29? Mm) A 6 0 4.89 A7 B7 ------ -'~ ^ >, description of the invention () ^^ 1 ί n ^^ 1 ml ^^ 1 ^^ 1 i 士 l ^ im „, ¾ (Please read the notes on the back before filling in this X) The reaction will lock the chain, or use monovalent compounds, ring dilute compounds, etc. to lock the chain, in the presence of this substance, polyethylenimide and: glycidyl methacrylic acid will be superimposed with it to obtain a polymer containing Graft copolymer (24) of an ester structure segment (B) and a polystyrene structure bond segment (A) having an epoxy group as its reactive group. Synthesis Example 25 High-grade (grade) alcohols Eini * # 700 (manufactured by Toyo Petroleum Wright Corporation, melting point: 99 ° C, 0H base price) 65ms (K0H / g) 75 parts, dissolved at 120 ° C. To this solution, 9.6 parts of isocyanoisocyanate was added dropwise to introduce double-stranded binding at the end. At a temperature of 120¾ for 2 hours, it will be first The adjusted liquid of 15 parts of styrene, 10 parts of isophylline β, 10 parts of xylene, and 0.2 parts of AIBN was added dropwise to the liquids listed above, and after they were superposed, they were cooled to obtain a polyalkenyl group. The grafted copolymer (25), which has both a structural segment (B) and a polystyrene structure (A) having an oxazole group whose base is an anti-reactive group, is provided. Synthesis Example 26: Take 112.5 parts of cyclohexanone and put it in a flask with a stirrer, an inert gas introduction tube, a flow cooling tube, a dropping filter, and a thermometer, and heat it to 80¾ c. 偁 Μisobutyl_ (AIBN) 7.5 The solution was dissolved in 35 parts of Cangyipu, 35 parts of isobutyric acid ester and 5 parts of isopropenyl chewing beer. The solution was added to the dripping solution, and at 80 it was added with a suppository for 3 hours. After the above-mentioned flasks, the reaction was continued at the same temperature for 2 hours. -130-This paper method applies the Chinese national standard {CNS) A4 * l grid (? 10 × 297 mm) 4 604 89 A7 _B7___ V. Description of the invention () Then, add 0.3 parts of A IBM, ripen it at 120 ° C for 2 hours, and then cool it to obtain a polymer with 40% non-volatile content containing reactive groups and hydroxyl groups that can react with carbon black. (26). Synthesis Example 27 A solution of the polymer (26) obtained in Synthesis Example 26 (containing 40.75 parts of nonvolatile matter was added dropwise at room temperature * M for 30 minutes. 6.73 g of isobutyric acid isonitrogenate (Mw = 111.1) was added to make It introduces double bond binding, and then adds 10.02 of cyclohexanone to make it react, so as to obtain the polymerization of the polymer (27) containing 40% nonvolatile matter and having a group reactive with carbon black and a double chain bonded hydrogen group. Body solution (27) 〇 Synthesis Example 28 Take methoxypolyethylene glycol methacrylate (produced by Shin Nakamura Chemical Industry Co., Ltd., NK ester M-230G) with 75 double bonds and 15 acetophenones 10 parts of 2- (1-Azapropionyl) ethylisobutyrate and 2,2 ^ -azobis (2,4-dimethyl formaldehyde) are placed in the agitator wings, Inactive gas is put into the tube, transport cooling tube and thermometer's separation bottle, and it is allowed to react for 5 hours under the flow of 751 nitrogen gas, so that it contains 50% of nonvolatile matter and contains nitrogen-acrylic radical in its molecule. A polymer solution (28) with a reactive group and an oxalic acid chain. ^ Preparation Example 1 of treated carbon fluorene. Take 30 parts of epoxy acrylic resin (1) obtained in Synthesis Example 1 and carbon black. MA-100R (Mitsubishi Chemical Industries) 30 units are put into the Lamou Plaster Crusher (Toyo Seiki) and replaced by ((same as above)), 140 (please read the precautions on the back first) (Fill in this page) The size of this paper is applicable to China's National Standard (CN'S) A4 specification (210 X297 mm) 4 604 89 A7 _B7_ V. Description of the invention () (Please read the note on the back before filling this page); lOOrpm Under the conditions, after kneading, it is cooled and pulverized into treated carbon black (EXA-1). Example 2 30 parts of the treated carbon black (ExA-1) obtained in Example 1 and 4.3 parts of tetrahydrofluorene dried After 0.01 times of anhydrous atmosphere, after reacting at 100 " C for 3 hours, it was cooled * and pulverized to obtain treated carbon black (ExB-1). Example 3 The cyclopropane obtained in Synthesis Example 3 Acid black resin and ethynyl acetol acetate mixture * added carbon black MA-100R (Mitsubishi Chemical Industries) (hereinafter referred to as the same as the previous) 38.64 parts and 3 legs in diameter _ steel beads 800 granules • Stir at 140 ° C for half an hour to obtain a mixture containing 20% treated carbon black (ExA-2) and ethyl acetol acetate (ExA-2 (Comparative Example 1) 30 parts of the ring gas bisphosphonate resin (1) obtained in Synthesis Example 2 which did not contain an oxy group in the actual product and 30 parts of carbon black MA-100R (manufactured by Mitsubishi Chemical Co., Ltd.) were taken. In Laboplast mill (Toyo Seiki), at 140 ° C, 100 rpm, knead and cool the powder tablet to obtain the treated carbon black (do-1). Comparative Example 2 Mixed in Comparative Example 30 parts of the obtained carbon black graft polymer (C0-1), MSf 4.8 parts tetrahydrogenated and 0.07 parts of anhydrous lithium chloride were reacted at 100 ° C for 3 hours, and then cooled and pulverized. Ready to compare the treated carbon black (C0-2) 〇 Comparative Example 3 The paper is a common Chinese national standard < CNS) 210 × 297 mm) 4 P04 89 A7 B7 V. Description of the invention () Please read the note on the back first Please fill in this page again.) Take the same basic ugly acid varnish bad oxygen resin YD PN-638P used in Synthesis Example 1 (manufactured by Tohto Kasei Co., Ltd., with a ring gas equivalent of 180) 30 and carbon black MA-100R (ibid.) 30 The part was put into a Laboplat mill (same as the previous one). After kneading at 140C 100 rpm, it was cooled and pulverized to obtain a treated carbon black (C0-3). Comparative Example 4 30 parts of polymer (6) obtained in Example 6 and 30 parts of carbon black MA ^ IOOR (same as above) were put into Laboplast mill (same as above), kneaded at 140QC, 100rpm, and then cooled and crushed to obtain Comparative treated carbon black (C0-4) 〇 Example 4 100 parts of a mixture (50) of the polymer (5) obtained in Synthesis Example 5 was dissolved in 50 parts of ethyl methyl alcohol acetate, and 5.4 parts of acrylic acid was added. * Anthracene triethyl hydrazone 0.0 (3 parts and benzene 0.04 parts, react at 110 ° C for 2 hours. Take 57.1 parts of the polymer obtained above, 30 parts of carbon black MA-100R (same as above), 212.9 parts of vinyl carbinol acetate, and put them into a separating bottle with a mixing blade and a flow cooler. • Add 800 steel beads with 3 legs in diameter and stir at 160 t for 3 hours to get an ethyl acetol acetate mixture (E-3) containing 20% treated carbon black (Ex-3). Comparative Example 5 15 parts of the polymer (5) obtained in Synthesis Example 5 were dissolved in ethyl acetol acetate to prepare a mixture. Then, 30 parts of the polymer (5) were placed in a centrifugal mixer equipped with a mixing blade and a flow cooler. In the liquid bottle, add 45 parts of carbon black MA-100R (same as before), 225 parts of vinyl acetol acetate and 800 parts of steel beads with a diameter of 3mm, 160-133-this paper method applies Chinese national standards (CNS) A4 specification (210 × 297 mm) 460489 A7 B7 V. Description of the invention () X. After 30 minutes of mixing, it will contain 20% ethyl acetamidine acetic acid compared with treated carbon black (C0-5). Mixture (C0-5). Comparative Example 6 50 parts of the polymer ⑸ obtained in Synthesis Example 5 were dissolved in 50 parts of ethyl acetamidine acetate and prepared into a mixture. Take 100 parts of this mixture, add acrylic acid 6.2 咅! 3, chlorin triethylammonium @ 旨 0.〇6 咅 | 3 and ^^ | 10.04 parts, and react at 110 ° 〇 for 2 hours. . Take 56,7 parts of the polymer obtained in the above list and put them into a separatory bottle with stirrer wings and Kan-flow cooler, add 30 parts of carbon black MA-100R (same as above), and ethylhexyl acetol acetate 213.3 parts of vinegar and 800 parts of steel beads with a diameter of 3mm were stirred at 160 ° C for 30 minutes to obtain a 20% ethyl acetic alcohol acetate mixture (C0-6) containing treated carbon black (C0-6). Comparative Example 7 Take 60 carbon black MA-100R (same as the previous one), 240 vinyl acetate and acetic acid, and 800 steel beads with a diameter of 3 mm. They are equipped with search and mixing wings and remote flow cooler. In a separatory bottle • Stir at 1 (30 ° for 30 minutes to obtain a 20% carbon black ethyl acetol acetate acetate mixture (C0-7). Example 5 Take the polymer solution obtained in Synthesis Example 7 (7) 23.35 parts, 20 carbon black MA-100R (same as above), and 56.65 parts of ethyl acetic acid vinegar were placed in a separate bottle with a thermometer, stirring tube and cooling tube, and dispersed. Add 600 SUS beads. At 160QC, search for 2 hours at a speed of 300 rpm for 2 hours for grafting. After the reaction, add 100 parts of ethyl cellosolvic acid acetic acid to make the dispersion uniform. The reaction content and beads made of SUS can contain -134-This paper's standard is applicable to Chinese national standards (CNS) A4 (210X297 mm) '' ^-(Please read the notes on the back before filling (This page) * 1T 4 6〇4 89 A7 B7 V. Description of the invention () Disperse solution (ExC-1) for treating carbon black (ExC-1). Spring Example 6 Each polymer solution obtained in Synthesis Example 8 8) 23.35 parts and carbon black ^ 1 / \-1001? (Same as above) 20 parts, butyl cellosolve 56.65 parts are put into the same device as used in Example 5, and operated in the same way as in Example 5 of the cell, that is, A dispersion solution (ExC-2) containing treated carbon fluorene (ExC-2) was obtained. Reference Example 1 Part 6.67 of the polymer solution (7) obtained in Synthesis Example 7 and carbon fluorene MA-100 R (see above) 20 73.33 parts of butyl cellosolve were placed in a liquid separation bottle with a thermometer, agitating wings and cooling tubes, and the same operation as in Example 5 was performed to obtain a 20% dispersion solution (ReC-1) containing carbon black. When the solution (ReC-1) is compared with the dispersion solution (ExC-1) obtained in Spring Example 5, it can be found that the dispersion solution (ReC-1) has a morphological sedimentation (kill) of (liquid) phase separation, and It is considered unsuitable to select a dispersion medium. Example 7 The polymer solution (16) obtained in Synthesis Example 16 (23.4) and carbon black (pH 3.1) 31.2 (propenyl) difermentary monomethyl 101.4 parts of diethyl ether acetate were placed in a separating bottle with a thermometer, sowing wings and cooling tubes, and 800 parts of the beads were gasified after dispersing. Rotation speed at lOCTCKTOOrpm It is grafted for 1 hour. The reaction meat is separated to obtain a dispersion solution (ExC-3) containing treated carbon black (ExC-3). Example 8 According to the method of Example 7, a polymer solution is used (16) Part 78.0, the size of carbon paper is applicable to the Chinese National Standard (CNS) A4 specification (2) 0 ×: 297 mm. Buckle-(Please read the precautions on the back before filling this page) * 1Τ 4 60489 A7 _B7____ 5. Description of the invention () (please read the precautions on the back before filling in this page; > black 31.2, 46 (8) bis (monomethyl) dimethyl ether acetate vinegar as the raw material, the same operation A dispersion solution (ExC-4) containing treated carbon rhenium (ExC-4) can be obtained. Comparative Example 8 Take the comparative polymer solution (9) obtained in Synthesis Example 9 as a raw material, and follow the operation of Example 5. That is, the carbon black mixed solution (C0-8) was obtained. Comparative Example 9 Each of 6.67 parts of the comparative polymer (6) obtained in Synthesis Example 6 and 200 parts of carbon black 1 ^ \-100 卩 (same as above) were used, and 73.33 ethyl acetate was used as a cellosolve. In the same apparatus as in Example 5, they were dispersed, and 600 beads made of SUS were added. The reaction was carried out under the same conditions as in Example 1. After the reaction, 100 parts of ethyl cellosolve acetate was added to make the dispersion uniform. The reaction content was separated to obtain a dispersion solution (C0-9) containing the treated treated carbon black (C0-9). Comparative Example 10 According to the method of Example 7, the comparative polymer obtained in Example 17 was used. The solution (17) was used in place of the polymer solution (16) and treated at 40 ° C for 1 hour instead of being treated at 100 ° C for 1 hour. The same operation was performed as in Example 7 to obtain a comparative treated carbon black (C0 -10) Dispersion solution (C0-10). Comparative Example 11 The polymer solution (16) of Example 8 was replaced with the comparative polymer solution (17) obtained in Synthesis Example 17 and replaced with 10C for 1 hour at 4CTC. The same operation as in He Shi Example 7 is to obtain a dispersion solution (CO-11) containing treated carbon black (C0-11) for comparison — 136 m This paper size is applicable to China Standard S (CNS) A4 (21 OX) 297 mm):: ~~: 4 S〇4 89 A7 B7 V. Explanation of the invention () Comparative Example 12 The polymer solution (18) for comparison obtained in Synthesis Example 18 was used instead of the polymer solution (16) of Example 7 And M were treated at 40 ° C for 1 hour instead of 1 hour at 100 ° C. The same operation as that in Example 7-7 was obtained to obtain a comparative treated carbon black (CO-12) 6¾ dispersion solution ( C0-12). Comparative Example 13 The comparative polymer solution (18) obtained in Synthesis Example 18 was used in place of the polymer solution (16) in Example 8 and treated at 40 ° C for 1 hour instead of 100 ° C. After the treatment for 1 hour, the same operation as in Example 17 was performed to obtain a dispersion solution (C0-13) containing the treated carbon black (C0-13) for comparison. Example 9 Each Take 30 parts of carbohydrate MA-8 (manufactured by Mitsubishi Chemical), 97.5 parts of ethyl cellosolve acetate and 22.5 parts of polymer solution (10) containing 40% nonvolatile matter obtained in Synthesis Example 10, and put them in a thermometer. , Mixing wing and cooling tube in the separatory bottle to disperse it. In the Ministry of Economic Affairs, the Junma employee consumer cooperative seal (please read the precautions on the back before filling this page) and then add the oxidized beads 800 Mixing at a rotation speed of M300 rpm to make the grafting reaction at 1000 for 2 hours: After the reaction is completed, add 50 parts of ethyl cellosolve acetic acid to disperse the homogeneous sentence. Divide the reaction content Then, a dispersion solution (ExC-5) containing treated carbon black (ExC-5) was obtained. Example 10 The polymer solution (11) containing 20.6 parts of non-volatile content 43.6% obtained in Synthesis Example 11 and B 108.4 parts of cellosolve acetate were used to replace the non-volatile 40% polymer solution (10) 22 · 5 of cellulite and 97.5 parts of ethylcellosolve acetate. For example, the exact same repeating work, namely -137-this paper music scale applies the Chinese National Standard (CNS) A4 specification (210_χ25 »7mm} 460 489 A7 B7 V. Description of the invention () A dispersion solution (ExD-1) containing treated carbon black (ExD-1) can be obtained. Example 11 ί Read the notes on the back of the poem before filling this page) A thermometer is attached In the separation bottle of the stirring blade and the cooling tube, 30 parts of carbon 黒 ΜΛ-8 (same as above) are dispersed. 97.5 parts of ethyl cellosolve acetate and a polymer containing 40% of nonvolatile matter obtained in the synthesis example. Solution (12) 22.5 parts. Then, 800 parts of oxidation beads were added, and it was reacted at 100 rpm at 300 rpm for 3 hours. After cooling, the reaction content was separated to obtain a dispersion solution containing treated carbon black (ExC-6). (ExC-6). Spring Example 12 To 150 parts of the dispersion solution (ExC-6) obtained in Example 11, 1.49 parts of anhydrous glassy acid (molecular weight of 100.07) and 0.009 of catalyst lithium gas were added, and allowed to react at 100 C for 12 hours. That is to say, each of the A bond segment and the B chain segment has a radically divided carbon black (EχΕ-1) solution (ExE-1). Example 13 To 150 parts of the dispersion solution (ExCH3) obtained in Example 11 was added anhydrous trimellitic acid (molecular weight of 192.13) 2.86 parts * 1.8-2 for catalyst? A-ring [5,4.0] -7-Eleven Carbon Unit (BBU) O.OOl, reacted at 8CTC for 30 minutes * to obtain a treated carbon black that has a carboxyl group in its A and B segments (ExE-2) dispersion solution (ExE-2). Example 14 Into the separatory bottle used in Example Π, 30 parts of carbon 黒 SB-250 C (produced by Tecumsal Corporation), 30 parts of PGM-Ac 97.5, 800 parts of oxidation pin beads, and copolymerization obtained in Synthesis Example 13 were added. Unit (13) 22.5. After M70〇rpm rotation speed 100 ° C search for 1 hour to make it react, after cooling the paper, the size of the paper is suitable for China National Standards (CfS) A4 specifications (210X297 mm) 4 604 89 A7 B7_ V. Description of the invention ( ) * Separation to obtain a dispersion solution (ExC-7) containing treated carbon black (ExC-7) 〇I 11 I --1 I-----I — '* 61-I--IE-T * 0¾-" " {Read the precautions on the back before filling this page) Example 15 To 150 parts of the dispersion solution (ExC-7) obtained in Example 14, add anhydrous maleic acid (molecular weight is 98.06) 1.8 The catalyst was shaken with 0.09 parts of DBU and reacted at 60 ° C for 2 hours to obtain a treated carbon black (ExE-3) dispersion solution (ExE-3) with a base in its B segment. Example 16 In the separation bottle used as in Cell Example 11 * 30 parts of carbon black MA-100R (same as before), 9 parts of PGM-Ac, 800 parts of dowel beads, and Synthesis Example 14 The obtained grafted polymer (14) had 22.5 parts. After stirring at 100 ° CM600rpin for 1 hour for reaction, the solution was separated and placed in a separation bottle with a distillation tube. The solution was heated to 140 ° CM to decompose and remove the tetramethyl uranyl ester group.> C00H-based treated carbon black (ExE-5) dispersion solution (ExE-4). Example 17 Take 10 carbon black, special black 250 (produced by Teesa Co., Ltd.), bind 1500 beads, and obtain a polymer solution containing adipic acid chain obtained in Synthesis Example 19. (19) Put the 30 parts together in a liquid separation bottle with a temperature sensor, stirring wings and cooling pipes. After stirring at 75 tM600rpin for 2 hours, the mixture was heated to 120 ° C and the acetic acid was distilled off to react for 1 hour. After cooling, 75 parts of deionized water were added to disperse, and a carbon black dispersion solution (ExC-8) was obtained after the separation operation. Embodiment 18 The paper size is applicable to the national standard (CNS) A4 specification (2 丨 0 X 2 mm)

X 4 604 89 A7 ___ B7 五、發明説明（） (請先Μ讀背面之注意ί項再填寫本頁) 取碳黑特種黑250 (特祜撒公司製）（下面Μ (同前製 )代之）10部，維土製小珠1500部及在合成例20所得含有 月桂醇（氧化乙烯基）15鍵段的聚合體溶液（20)30部入於 如同實施例17所用的燒瓶中，在75^：以600^111的回轉速攬 伴2小時後，加熱至160°C，一面飽去乙醇一面使其反應1 小時。冷卻後，加脫離子水75部使其分散，經分離搡作， 即得碳黑分散溶液（ExC-9)。 比較例14 在如同實施例17所用的燒瓶中，加入月桂醇（氧化乙 烯基）15縮水甘油醚（長瀨化成工桊製*特納哥爾EX-171 )15部，碳黑特種黑250 (同前製）10部及銷土製小珠1500 咅P 〇 其後依實施例18的方法操作，即得比較用碳黑分散溶 液（C0-14)。 比較例15 取碳黑MA-100R (同前製）100重量部*月桂醇（氧化 乙铺基）15縮水甘油醚（同前出）25部聚乙二醇（三洋化 成工業製，PEG 200(重合度為4〜5):) 75部入於Laboplast mi 11 (同前製）中，在150°C，M100 rpm的回轉速練合15 分鐘，經冷卻，即得已處理碳黑（C0-15)。取本已處理碳 黑（C0-15) 20重量部與脫離子水80部混合，再Μ攪拌加以分 散，即得比較用碳黑分散溶液（C0-15)。 比較例16 取碳黑特種黑250 (同前製）10部，聚乙二醇15部，界 -140 - 本紙張尺度適玥國家標準（CNS ) Α4規格（210X297公釐） · 4 β〇4 89A7 ·. _Β7_ 五、發明説明（） 面活性劑(花王製，益馬爾芬985)0.05部及脫離子水11.24 部入於砂磨機（sand mi 11)中，_使其分散18小時後，加水使 其顔料濃度為10%，再分散30分鍾，即得比較用碳黑分敗 溶液（C0-16)。 實施例19 取碳黑MA-100R (同前製）10部，碳黑MA-100R (同前 製）10部入於三枝能苘球磨機，在100°C練合使其反應，即 得已處理碳黑（ExC-10)。 實施例20 取碳黑MA-100R (同前製）10及在合成例22所得接枝 化共聚合體（22) 10部入於三枝賴筒球磨機中，在1〇〇。〇練 合使其反應，即得已處理（EjiC-ΙΙ)。又，因為本已處理碳 黑的位在外側的鍵段（B)具有聚醯胺構造，若與各棰聚酿胺 調合而箱融練合後加以，彷絲，即可得纖維中有該當已處理 碳黑均勻分散的聚醯胺糸蔽光性纖維。 實施例21 取碳黑特種黑250 (同前製）31.2部，乙酵106,8部，踏 土製小珠800部及在合成例23所得聚合體溶液（23) 1S. 72部 入於附有溫度計、攪拌翼及冷卻管的分液瓶中。在78〇乂 7001^111的回轉速搜拌5小時後，除去小珠即得碳黑分散溶 液（ExC-12)。 比較例17 依實施例21的方法，由聚乙輝基ptL晦嗣9.3(3部來替代 聚合體溶液(23)及碳黑用量變為31.2部，乙醇量變為115.4 - 141 " 本民張·尺度適用中國§家標準（CNS > A4規格（210X297公釐） . (請先閱讀背面之注意事項再填寫本頁) 經齊郎尹夹慄準馬貝i消珩合泎fi印裝 :460489 A7 B7五、發明説明（） 部外，其餘均如實施例21同樣操作處理，即得比較用碳黑 分散溶液（C0-17)。 實施例22 取在實施例24所得接枝化共聚合體（24) 10部，碳黑AM -100R (同前製）10部在三枝輥筒磨機中於100=0練合使其反 應即得已處理碳黑（ExC-13)。又，因為本已處理碳黑位於 外側的鏈段（B)有聚醯胺構造，若與各種聚醯胺調配而溶融 練合後，經纺絲，即可得該當已處理碳黑均勻分散在纖維 中的聚醯胺糸蔽光性纖維。 實施例23 取在合成例25所得接枝化共聚合體（25) 10部，碳黑MA -100R(同前製）10部在三枝輥简球磨機中，於10CTC練合使 其反應，即得已處理碳黑(ExC-14)。 參考例2 取在合成例26所得聚合體（26)溶液23.4部，碳黑特種 黑250 (同前製）31.2部，環己酮101.4部及锆土製小珠800 部入於附有ί覺伴翼及遨流冷卻器的分液瓶中，在1〇〇°C授拌 處理1小時，即得含有已處理碳黑（ReA-1 )26%的環己酮混 合物。 賀施例24 在參考例2上，用聚合體（27)替代聚合體（26)外，均 以參考例2完全同樣的原料及重複操作，即得含有已處理 碳黑（ExA-4)26%的環己_混合物。 實施例25 -142 - 本紙張尺度通用中國國家標隼（CNS ) A4規格(_210X297公釐) (請先閏讀背面之注意事項再填寫本頁) .丨卜 4 6〇4 89 ' A7 _B7_ 五、發明説明（） 在參考例2所得的已處理碳黑溶液（ReA-1) 100部中， 加無水鵂笼三酸4.16部，加熱至80°0：。在溫度達到80°〇時 ，加入1,8-重氮雙壞[5,4,0]-7-H~碳蹄（DBU) 0.06部後 授拌30分鍾，即得含有俊基的GCB分散溶液（ExB-2)。 實施例26 取在參考例24所得的已處理碳黑溶液（ReA-4) 100部， 加入偏策三軒3.2部，如同實施例25—樣重復操作，即得含 有雙鏈結合及梭基的碳黑接枝化聚合物（GCB)的分散溶液（ (ExB-3) 實施例27 在如同實施例17所用的燒瓶中，加入在合成例（28)所 得含有乙二醇鏈的聚合體溶液（28) 30部，碳黑特種黑250 ( 同前製）1〇部没結土製小珠1500部。在:40°CM700 rpro的回 轉速报拌1小時使其反應後’加熱至觸去乙併重 復水置換作用（反應），然後冷卻，經分離’即得碳黑分 散溶液（ExC-15)。 光硬化性樹脂組成物的綢製 實施例28 取在實施例1所得的已處理碳黑（ExA-1) 90部，加二季 戊四酵四丙締酸醋10部為感光性樹脂’益爾牙丘亞907 (芝 巴豈几其公司製）8重量部為重合開始劑及乙基卞必醇乙酸酯 400為稀釋劑，使其均句分散’即得光硬化性樹脂組成物⑴ 質施洌29 *· 143 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2]0X297公瘦） ---------批衣----.--•訂------0 (讀先閲讀背面之注意事項再填寫本頁) 經齊郎令矢慄隼馬員工消费合作社印製 ! 4 6〇 4 89 A7 _____B7_ 五、發明説明（） 以在實施例28中，將已處理碳黒（ΕχΑ~1)的用量改為80 部，二季戊四醇四丙阔酸酷用量改為10部外，其餘均侬實 施例28的原料及方法操作，即得光硬化性組成物(2)。 實施例30 Μ在實施例28中，除Μ在實施例2所得已處理碳黑 (ΕχΒ-1)取代己處理碳黑（ΕχΑ-1)之外，均依實施例28同樣 的原料及方法操作，即得光硬化性組成物⑶。 實施例31 Μ在實施例28中，除用在實施例3所得的已處理碳黑 (ΕχΑ-2)和含有乙基卞必酵乙酸醋20¾所成的混合物（ΕχΑ-2) 450部取代已處理碳黑（ΕχΑ-1)及將乙基卞必醇乙酸醋用量 改為40部以外，均依實施例28原料及操作，即得光硬化性 樹脂組成物⑷。 實施例32 Μ在實施例28中，除Μ合成例4所得含有羧基環氧丙 ί：希酸醋樹脂取代二季成四醇四丙婦酸酯外，均依實施例28 的原料及操作，即得光硬化性樹脂組成物（5)。 實施例33 Μ賁施例30的方法，用在合成例4所得含有疲基現氧 丙嫌酸酯樹脂⑷取代二季戊四醇四丙蹄酸S旨之外，其餘均 與實施例30—樣操作，即得光硬化性樹脂組成物（6)。 比較例18 在實施例28中，除Μ在比較例1所得比較用已處理碳 黑（C0-1)替代已處理碳黑（ΕχΑ-1)之外，均砍質施例28同樣 -144 - .乐尺度遙用中國圉家標率（CNS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ^. 4 6〇4 89 A7 _B7__ 五、發明説明（） 操作，即得比較用光硬化性組成物（C1)。 比較例19 (請先聞讀.背面之注意事項再填寫本頁) 以蜇施例32的方法，除用在比較例2所得比較用已處 理碳黑（C0-2)來取代已處理碳黑（ExA-1)之外，其餘均如同 實施例32操作，即得比較用光硬化性組成物(C2)。 比較例20 Μ實施例28的方法，除用在比較例3所得比較用已處 理碳黑（C0-3)來取代已處理碳黑（ExA-Ι)之夕卜，其他均如同 實施例28操作，即得比較用光硬化性組成物（C3)。 比較例21 以實施例128的方法，除用在比較例4所得比較用已處 理碳黑（C0-3) 50部來取代已處理碳黑（ExA-1) Q0部，用在合 成例1所得環氧两烯酸醋樹脂（1) 50部來取代已處理碳黑 (ExA-Ι)之外，其他均如同實施例28操作，即得比較用光 硬化性組成物（C4)。 實施例34 Μ實施例31的方法，除用得自實施例4的含有已處理 碳黑（ΕχΑ-3) 20%的乙基卞必醇乙酸幽焜合物（ΕχΑ-3) 450部 (含有（ΕχΑ-3 90部）來取代混合物（ΕχΑ-2)之外，其他均如 同實施例31操作，即得光硬化性樹脂組成物（7)。 實施例35 Μ實施例34的方法，除了將混合物（ΕχΑ-3)的用最改 為400部，季戊四醇四丙蹄酸酷用量改為20部及乙基卞必醇 乙酸酷用虽改為80部之外，其他均如同貢施例34操作，即 -145 - 本紙張尺度適用中國國家標準（CNSΤα4規格（210X297公釐） β〇4 89 A7 _B7___ 五、發明説明（） 得光硬化性樹脂組成物（8)。 比較例22 (請先閏讀背面之注意事項再填寫本頁) Μ實施例34的方法，除了用在比較例5所得含有比較 用已處理碳黑（C0-5)20%的乙基卞必醇乙酸醋混合物（C0- 5) 來取代混合物(ExA-3)之外，其他均如同實施例34操作， 即得比較用光硬化性樹脂組成物（C5)。 比較例23 Μ實施例34的方法，除了用在比較例S所得含有比較 用已處理碳黒（C0-6)20%的乙基卞必酵乙酸酯混合物（C0- 6) 來取代混合物(ExA-3)之外，其他均如同實施例34操作， 即得比較用光硬化性樹脂組成物（C6)。 比較例24 以實施例34的方法，除了用在比較例B所得混合物（C 0-5) 50部及在比較例β所得混合物（C0-6) 400部來取代混 合物（ΕχΑ-3)之夕卜•其他均如同實施例34操作，即得比較用 光硬化性樹脂組成物（C7)。 比較例25 在比較例Τ7所得含有已處理碳黑（C0-7 )的分散溶液（C 0-7)225部中，加在合成例4所得含有搜基環氧丙烯酸醋樹 脂55部，為光重合開始劑用的益爾牙丘907 (芝巴凱宜公 司製）8部及乙基卞必_乙酸酿220重量部，即得比較用光 硬化性樹脂組成物（C8)。 實施例36 在簧施例5所得含有已處理碳黑（ExC-1)的分散溶液 -146 - 本纸張尺度適用中國國家標準（CNS ) A4現格（2丨0X297公釐） 6〇4 89 A7 B7 五、發明説明（） 16部中，加感光性樹脂用的二季成四醇己（六）两締酸酯 4部，光重合開始用的益爾牙丘907 (芝巴軌宜公司製-以 下由（同前製）代之）0.15部及稀釋劑用的乙基溶纖劑乙 酸酯20部，使其分散均句，即得光硬化性樹脂組成物（9 ) 實胞例37 Μ實胞例36的方法，除了用在實施例6所得含有已處 理碳黑（ExC-2)的分散溶液（ExC-2)來取代分散溶液（ExC-1 )之外，其他均如同實施例36操作，即得光硬化性樹脂組成 物（10)。 比較例26 Μ實施例36的方法，除了用在比較例8所得含有比較 用已處理碳黑（C0-8)的分散溶液（C0-8 )來取代分散溶液（ ExC-1)之外，其他均如同實施例36操作，即得比較用光硬 化性樹脂組成物（C11)。 比較例27 Μ實施例36的方法，除了用在比較例9所得含有比較 用已處理碳黑（C0-9)的分散溶液（C0-9)來取代分散溶液（ ExC-1)之外，其他均如同實施例36操作，即得比較用光硬 化性樹脂組成物（C12)。 實施例38 在實施例9所得含有已處理碳黑（ExC-5)的分散溶液（ ExC-5) 500部中，加感光性樹脂闲的強克利爾68 (強生聚合 物公司製一K下由（同前出）代之）21.25部，二季成四醇X 4 604 89 A7 ___ B7 V. Description of the invention () (Please read the note on the back and fill in this page first) Take the carbon black special black 250 (made by Teesa) (the following (the same as before)) (10), 1500 beads made of Uygur soil, and 30 polymer solutions (20) containing lauryl alcohol (oxyethylene) 15 bond segment obtained in Synthesis Example 20 were put into the flask used in Example 17, at 75 ^: After accompany for 2 hours at a speed of 600 ^ 111, heat to 160 ° C, and react with ethanol for 1 hour while saturated with ethanol. After cooling, 75 parts of deionized water were added to disperse the carbon black, and a carbon black dispersion solution (ExC-9) was obtained. Comparative Example 14 In a flask used in Example 17, 15 parts of lauryl alcohol (oxyethylene) 15 glycidyl ether (manufactured by Nagase Chemical Industries, Ltd. * Turner EX-171) and carbon black special black 250 ( Same as before) 10 parts and earth-made beads 1500 P 〇 Then the method of Example 18 was followed to obtain a comparative carbon black dispersion solution (C0-14). Comparative Example 15 100 parts by weight of carbon black MA-100R (same as before) * lauryl alcohol (ethoxylated) 15 glycidyl ether (same as above) 25 polyethylene glycol (manufactured by Sanyo Chemical Industries, PEG 200 ( Coincidence is 4 ~ 5) :) 75 parts were put into Laboplast mi 11 (same as the previous one), kneaded for 15 minutes at 150 ° C, M100 rpm, and after cooling, the treated carbon black (C0- 15). Take 20 parts by weight of the treated carbon black (C0-15) and mix with 80 parts of deionized water, and then stir and disperse them to obtain a comparative carbon black dispersion solution (C0-15). Comparative Example 16 10 carbon black special blacks 250 (same as before), 15 polyethylene glycols, and boundary -140-This paper is compliant with the national standard (CNS) A4 specification (210X297 mm) · 4 β〇4 89A7 .. _Β7_ V. Description of the invention () 0.05 parts of surfactant (made by Kao, Yimalfen 985) and 11.24 parts of deionized water were placed in a sand mill (sand mi 11), and after dispersing for 18 hours, Add water to make the pigment concentration to 10%, and disperse for 30 minutes to obtain a comparative solution of carbon black (C0-16). Example 19: Take 10 carbon black MA-100R (same as before), 10 carbon black MA-100R (same as before), put them into a Sanji energy ball mill, and knead them at 100 ° C to make them react. Carbon black (ExC-10). Example 20 10 carbon black MA-100R (same as previously produced) and 10 graft copolymers (22) obtained in Synthesis Example 22 were put into a three-branch reed ball mill at 100. 〇 Knead and react to get processed (EjiC-II). In addition, because the externally-bonded segment (B) of the treated carbon black has a polyamidamine structure, if it is blended with each polyamidopolyamine and blended in a box, it is silk-like, and the fiber should have the proper content. Polycarbonate homogeneously dispersed treated carbon black masks optical fibers. Example 21 Take 31.2 parts of carbon black special black 250 (previously produced), 106 parts of acetonitrile, 800 parts of beads made of soil, and polymer solution (23) 1S. 72 obtained in Synthesis Example 23 Thermometer, stirring blade and cooling tube in a separatory bottle. After searching for 5 hours at a revolving speed of 7800 to 7001, the beads were removed to obtain a carbon black dispersion solution (ExC-12). Comparative Example 17 According to the method of Example 21, polyethylhexyl ptL is 9.3 (3 parts instead of polymer solution (23), the amount of carbon black is changed to 31.2 parts, and the amount of ethanol is changed to 115.4-141 " Benmin Zhang · The dimensions are in accordance with China's standard (CNS > A4 size (210X297mm). (Please read the precautions on the back before filling in this page)) 460489 A7 B7 5. Except for the description of the invention, the rest are treated in the same way as in Example 21 to obtain a comparative carbon black dispersion solution (C0-17). Example 22 The graft copolymer obtained in Example 24 was taken. (24) 10 carbon black AM-100R (same as before) 10 kneaded in a three-roller mill at 100 = 0 to make the reaction to obtain treated carbon black (ExC-13). Also, because of this The segment (B) of the treated carbon black on the outside has a polyamide structure. If it is blended with various polyamides and melted and kneaded, it can be obtained by spinning. Rhenamine shields the optical fiber. Example 23 Ten graft copolymers (25) obtained in Synthesis Example 25 were used, and carbon black MA-100R (same as before) 1 0 parts were mixed and reacted at 10CTC in a three-roller simple ball mill to obtain treated carbon black (ExC-14). Reference Example 2 Take 23.4 parts of the polymer (26) solution obtained in Synthesis Example 26, carbon black special Black 250 (same as before) 31.2 parts, cyclohexanone 101.4 parts and zirconite beads 800 parts were placed in a separating bottle with wing sensor and flow cooler, and mixed at 100 ° C Within 1 hour, a cyclohexanone mixture containing 26% of the treated carbon black (ReA-1) was obtained. He Shi Example 24 In Reference Example 2, except that the polymer (27) was replaced by the polymer (27), all references were made. Example 2 Exactly the same raw materials and repeated operations, to obtain a cyclohexane mixture containing 26% of the treated carbon black (ExA-4). Examples 25 -142-This paper standard is in accordance with China National Standard (CNS) A4 specifications ( _210X297 mm) (Please read the precautions on the reverse side before filling out this page). 丨 4 4604 ′ A7 _B7_ 5. Description of the invention () The treated carbon black solution (ReA-1) obtained in Reference Example 2 ) Among 100 parts, add 4.16 parts of anhydrous trisolic acid, and heat to 80 ° 0: When the temperature reaches 80 ° 0, add 1,8-diazo double bad [5,4,0] -7-H ~ Carbon Hoof (DBU) 0.06 After 30 minutes of post-mixing, a GCB dispersion solution (ExB-2) containing Junki was obtained. Example 26 100 parts of the treated carbon black solution (ReA-4) obtained in Reference Example 24 were added, and 3.2 parts of Panasonic Sangen As in Example 25, the operation was repeated to obtain a dispersion solution of carbon black grafted polymer (GCB) containing double-chain bonding and shuttle group ((ExB-3). Example 27 In the flask used in Example 17 To this, 30 parts of a polymer solution (28) containing a glycol chain obtained in Synthesis Example (28) and 10 parts of carbon black special black 250 (same as previously manufactured) and 1500 unattached beads were added. At a temperature of 40 ° CM700 rpro, the mixture was stirred for 1 hour to make the reaction ‘heated to contact B and repeated water displacement (reaction), then cooled and separated’ to obtain a carbon black dispersion solution (ExC-15). Photo-curable resin composition silk Example 28 Taken 90 parts of the treated carbon black (ExA-1) obtained in Example 1, and added 10 parts of dipentaerythritol tetra-acrylic acid vinegar as the photosensitive resin 'Yell Yachuya 907 (made by Zhiba Qiqi Company) 8 parts by weight are superposition starter and ethyl acetoacetate 400 is a diluent, so that it is uniformly dispersed, that is, a photocurable resin composition is obtained.施 洌 29 * · 143-This paper size applies to China National Standard (CNS) A4 specifications (2) 0X297 male thin) --------- Approved clothes ----.-- • Order ---- --0 (Read the precautions on the back and then fill out this page) Printed by Qi Langling Yali Yuma Employee Consumer Cooperative! 4 6〇4 89 A7 _____B7_ V. Description of the invention () In Example 28, The amount of treated carbon fluorene (EχΑ ~ 1) was changed to 80 parts, and the amount of dipentaerythritol tetrapropionate was changed to 10 parts. The rest of the raw materials and methods of Example 28 were operated to obtain a photohardenable composition. (2). Example 30 In Example 28, except that the treated carbon black (EχΒ-1) obtained in Example 2 was used instead of the treated carbon black (EχΑ-1), the same raw materials and methods were used as in Example 28. , To obtain a photocurable composition ⑶. Example 31 M In Example 28, 450 parts of the mixture (EχΑ-2) made of the treated carbon black (EχΑ-2) obtained in Example 3 and ethyl acetate and acetic acid acetate 20¾ were used instead of Treating the carbon black (EχA-1) and changing the amount of ethyl acetol acetate to 40 parts were carried out in accordance with the raw materials and operations of Example 28 to obtain a photocurable resin composition ⑷. Example 32 In Example 28, except that the carboxy-epoxy group: hexanoic acid resin obtained in Synthesis Example 4 was used instead of diquaternary tetraol tetrapropionate, the raw materials and operations of Example 28 were followed, that is, A photocurable resin composition (5) was obtained. Example 33. The method of Example 30 was used in the same manner as in Example 30 except that the pentaerythropropionate resin obtained in Synthesis Example 4 was used instead of dipentaerythritol tetrapropionate S. Thus, a photocurable resin composition (6) was obtained. Comparative Example 18 In Example 28, except that the treated carbon black (C0-1) was used instead of the treated carbon black (EχΑ-1) in the comparison obtained in Comparative Example 1, Example 28 was the same -144- .Le scale remotely used Chinese standard rate (CNS) Α4 specification (210X297 mm) (please read the precautions on the back before filling this page) ^. 4 6〇 89 89 A7 _B7__ 5. Description of the invention () Operation, The comparative photocurable composition (C1) was obtained. Comparative Example 19 (Please read first. Note on the back side and then fill out this page) In the same way as in Example 32, except that the treated carbon black (C0-2) obtained in Comparative Example 2 was used instead of treated carbon black Except for (ExA-1), the other operations were the same as in Example 32, so that the photocurable composition (C2) was compared. Comparative Example 20 The method of Example 28 was the same as that of Example 28 except that the treated carbon black (C0-3) was used instead of the treated carbon black (ExA-1) obtained in Comparative Example 3. That is, the photocurable composition (C3) is obtained. Comparative Example 21 Using the method of Example 128, except that the treated carbon black (C0-3) 50 parts were used instead of the treated carbon black (ExA-1) Q0 part obtained in Comparative Example 4, and used in the synthesis example 1 Except that 50 parts of epoxy dienoic acid vinegar resin (1) was used instead of treated carbon black (ExA-1), the operation was the same as in Example 28, and a photocurable composition (C4) was obtained. Example 34 The method of Example 31, except that 450 parts containing 20% of the treated carbon black (EχΑ-3) from ethyl acetate and acetic acid complex (EχΑ-3) from Example 4 were used (containing (EχΑ-3 90) instead of the mixture (EχΑ-2), the rest of the procedure was the same as in Example 31 to obtain a photocurable resin composition (7). Example 35 Μ The method of Example 34, except that The use of the mixture (EχΑ-3) was changed to 400 parts, the amount of pentaerythritol tetrapropanoic acid was changed to 20 parts, and the use of ethyl acetic acid and acetic acid was changed to 80 parts. The others are the same as those in Example 34 ， -145-This paper size is in accordance with Chinese national standard (CNSΤα4 specification (210X297 mm) β〇4 89 A7 _B7___ V. Description of the invention () Photocurable resin composition (8). Comparative example 22 (please first (Read the notes on the back and fill in this page again) The method of Example 34, except that it was used in Comparative Example 5 and contained 20% of ethyl processed acetic acid acetic acid vinegar mixture (C0-) 5) Except to replace the mixture (ExA-3), the other operations were the same as in Example 34, so that the photo-hardenable tree was compared. Fat composition (C5). The method of Comparative Example 23M, Example 34, except that it was used in Comparative Example S and contained 20% ethyl carbinol acetate (C0) -6) Except for the replacement mixture (ExA-3), everything was operated in the same manner as in Example 34 to obtain a comparative photocurable resin composition (C6). Comparative Example 24 The method of Example 34 was used except for comparison. 50 parts of the mixture (C 0-5) obtained in Example B and 400 parts of the mixture (C0-6) obtained in Comparative Example β to replace the mixture (EχΑ-3). • Other operations are the same as those in Example 34, which is for comparison. Photocurable resin composition (C7). Comparative Example 25 In the dispersion solution (C 0-7) containing treated carbon black (C0-7) obtained in Comparative Example T7, 225 was added to the base of Synthesis Example 4 55 parts of epoxy acrylic resin, 8 parts of Yierqiu 907 (manufactured by Shiba Kaiyi Co., Ltd.) and 200 parts by weight of ethyl acetic acid acetic acid for photo-reconstruction starter. Composition (C8). Example 36 The dispersion solution containing treated carbon black (ExC-1) obtained in the spring example 5 -146-the paper size Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 6404 89 A7 B7 V. Description of the invention (16) In the 16th part, the second quaternary tetraol hexahexyl (hexa) dibasic acid ester for photosensitive resin is added 4 parts, Yier Yaqiu 907 (manufactured by Shiba Rail Co., Ltd.-hereinafter) (replaced by the same as before) for photo-registration, 20 parts for ethyl thinner acetate for thinner, The homogeneous dispersion method is the method for obtaining the photocurable resin composition (9), cell example 37, cell example 36, except that the dispersion solution (ExC) containing treated carbon black (ExC-2) obtained in Example 6 was used. -2) Except substituting the dispersion solution (ExC-1), the same operation as in Example 36 was performed to obtain a photocurable resin composition (10). Comparative Example 26 The method of Example 36, except that the dispersion solution (C0-8) containing the comparatively treated carbon black (C0-8) obtained in Comparative Example 8 was used instead of the dispersion solution (ExC-1). In the same manner as in Example 36, a comparative photocurable resin composition (C11) was obtained. Comparative Example 27 The method of Example 36, except that the dispersion solution (C0-9) containing the comparatively treated carbon black (C0-9) obtained in Comparative Example 9 was used instead of the dispersion solution (ExC-1). In the same manner as in Example 36, a comparative photocurable resin composition (C12) was obtained. Example 38 In 500 parts of the dispersion solution (ExC-5) containing treated carbon black (ExC-5) obtained in Example 9, a photosensitive resin was added to a strong clear 68 (manufactured by Johnson & Johnson Polymer Co. (Same as the previous one) Replaced) 21.25, the second quarter into tetraol

? I (诗先W讀背面之注項再填寫本頁) -147 - 本紙張尺度適用中國國家樣準{ CNS ) A4規格（210X297公釐） “ 60 4 89 ' A7 ___B7_ 五、發明説明（） 六丙烯酸酷62.5部*光重合開始劑用益爾牙丘907 (同前出 )9.38部，使其分散均句，即得光硬化性樹脂組成物（11) Ο 實施例3 9 Μ實施例38的方法，除了用在實施例10所得含有已處 理碳黑（ExD-1)的分散溶液（ExD-l)來取代分散溶液（ExC-5) 之外，其他均如同茛施例34操作，而得光硬化性樹脂組成 物(12)。 實施例40 在實施例11所得含有已處理碳黑（ExC-6)的分散溶液（ ExC-6) 175,0部中，加感光性樹脂用的驗可溶性苯乙鋪一丙 嫌樹脂丁一632 (強生聚合物公司製）24.55部，二季成四 醇三丙嫌酸酿30部，及光重合開始劑用的益爾牙丘907 ( 同前製）5部，使其分散均句，即得光硬化性樹脂組成物 (13)。 實施例41 以實施例40的方法，除了用在實施例12所得含有已處 理碳黑（ExE-1)的分散溶液（ΕχΕ-1 Π76.7部來取代分散溶 液（ExC-6) 175.0部及將丁-682用量改為22.8部之外*其他 均如同實施例40操作，即得光硬化性樹脂組成物（14)。 實施例42 Μ實施例40的方法，除了用在實施例13所得含有已處 理碳黑（ΕχΕ-2)的分散溶液（ΕχΕ-2) 178.3部來取代分散溶 液（ExC-6) 176.7部及將丁-682用量改為21.2部之外，其他 -148 — 本紙伕尺度適用中國國家標準（CNS ) A4規格UlOX 297公釐） (請先閲讀背面之注意事項再填寫本f) % ^ 6 Ο 4 89 Α7 __Β7__ 五、發明説明（） 均如同實施例40操作*即得光硬化性樹脂組成物（15)。 實施例43 (請先閱讀背面之注意事項再填寫本頁) 以實施例40的方法，除了用在實施例14所得含有已處 理碳黑（ExC-7)的分散溶液（ExC-7)來取代分散溶液（ExC-6) 之外，其他均如同實施例40操作，即得光硬化性樹脂組成 物（16) ° 實施例44 以實施例40的方法，除了用在實施例15所得含有已處 理碳黑（ExE-3)的分散落液（ExE-3) 177. 7部來取代分敗溶 液（ExC-6) 175.0部及將丁-682用量改為22.4部之外，其他 均如同實施例40操作，即得光硬化性樹脂組成物（17)。 實施例45 K實施例40的方法，除了用在實施例16所得含有已處 理碳黑（ExE-4)的分散溶液（ExE-4) 173.7部來取代分散液 (ExC-6) 175 · 30及將丁-6S2用量改為25，8部之外，其他均如 同實施例40操作，即得光硬化性樹脂組成物(18)。 黑水射出甩（ink Ject)黒水的製法 實施例46〜47及比較例27〜29 Μ實施例17〜18及比較例14〜16所得各種原狀碳黑分 散溶液做為黑水射出用黑水，供為下列評價之用。 液體顯像劑 實施例48 取在實皰例19所得已處理碳黑（ExC-10)，聚乙烯樹脂 (三井Hi-Wax 4202E)36部，Isopar-G (Exon 公司製） -149 -* 本紙張尺度通用中國國家標準< CNS ) A4规格（210 X 29?公釐） 4 6〇489 * A7 __B7_ 五、發明説明（） 160部及銷土製小珠600部入於附有溫度計、攪拌翼及冷卻 管的分液瓶中，使其攪拌.分散20小時，即得液體顯像劑 (請先閲讀背面之注意事項再填寫本頁) ⑴。 實施例30 取在如同實施例48所用的分液瓶中，加人碳黑MA-100R (同前製），聚乙輝樹脂（三井Hi-Wax 4202E)40部，Isopar-G (Exon公司製）160部及踏土製小珠600部，攪拌*分散20 小時，即得比較用液體顯像劑（C1)。 實施例44 表面改善體質的處理 實施例49 取聚乙鋪醇（PVA-205，克拉列公司製）0.1部溶解在脫 離子水200部的水溶液入於附有搅拌機，不活性氣尋入管、 遠流冷卻管及溫度計的分液瓶中。加入預先調成溶解有過 氧化衆_ 8部的由聚乙烯97部及縮水甘油異丁稀酸酯3部 聚合性簞體所成的混合液，Μ高速攪拌使其成為均勻懋濁 液。一面通入氮氣加熱到80°C，在同溫度繼續搅拌5小時 ’使其重合反應後，經冷卻，即得聚合體懋濁液。過濾聚 合體懸濁液、洗淨後乾燥，即得含有瑕氣基為其反應性基 的聚含物（29) ◊ 然後，在如圖6所示構造的装置（容器内容童為l.2i )中裝入直徑lnun的銷土製小珠3kg後，將在上列調製的聚 合體（29)30部，二甲班370部及碳黑1^\-1001?(同前製）1〇0 部加入，再Μ先予加熱的熱媒作循塌加熱容器内部至140 -150 - 本紙張尺度通用中國國家揉隼（CNS)A4坭格（210Χ297公釐> 46〇489 . A7 B7 五、發明説明（） °C，Μ盤的外周速度l〇m/s運轉2小時後經冷卻，分出顔料 分液（ExF-1)。 (請先閑讀背面之注意事項再填寫本頁) 比較例31 取在實施例49所調製的聚合體（29) 10部及碳黑MA-100R (同前製）20部入於Laboplast mill (同前製），在140°C MlOOrpm的回轉速練合，完成反應後冷卻，再用甲.苯70軎 量使其分散*即得比較用顔料分散液（C0-18)。 比較例32 取直徑1 mm的縫土製小珠3kg裝入除了未具有加熱裝置 之外，其他均如同在實施例49所用的鞋置（容器內容量 1.2 /中）*加紹偶合劑普聯亞克特AL-M (味之素公司製） 20部，二甲苯380部及碳黑MA-100R (同前製）100部。以 盤的外周速度10m/s運轉2小時後，分出比較用顔料分散液 (C0-19)-實施例50 取直徑lmm的結製小珠3ks充填如同實施例49所用的裝 置後，加0 —甲酿性酿酸清漆型環氣樹脂（住友化學製， ESCN-195X，環氧當虽為198) 40部，二甘醇一乙基_乙酸 酯380部，碳黑MA-100R (同前製）80部。用預先加熱的熱 媒循携容器内部至2001C，Μ盤的外周速度10m/s運轉3小 時後，經冷卻，分雛，即得顏料分散液（ExF-2)。 比較例33 用與實施例50相同的組成，即取0 —甲酿型酿醒清漆 型璃氧樹腊10部，碳黑MA-100R (同前製）20部如同比較 -151 - 本紙張尺度適用中國國家樣準（CNS ) A4規格Γ210Χ297公釐） 4 60489 A7 · B7 五、發明説明（） (請先Μ讀背面之注意事項再填寫本頁) 例31 入於Laboplast mill (同前製），在200°CM100rpm 的回轉速練合使其反應後冷卻，再加二甘醇一乙酸乙酸酷 70重量部，即得比較用顔料分散液（C0-20)。 性能評價 <性能評價1> 就在實施例28〜35所得光硬化性樹脂組成物（1)〜（8) 與自比較例18〜25所得比較用光硬化性樹脂組成物（C1)〜 (C-8)作比較來評估下列各項目，如顯像性、光硬化性、硬 化膜的蔽光性硬化膜的耐熱性等*對配合在該當樹脂組成 中的各已處理碳黑上聚合體部的結合狀態及在聚合體上是 否含有功能性基（雙鍵结合，羧基）所受影響進行調査。 將其結果，即如表i所示。 •顯像性 用旋轉塗抹器（Spin coater)將各樹脂組成物塗抹於 玻璃基板上，使乾燥膜厚度成為la ro的厚度，併在10CTC 乾燥10秒鍾。用二氯甲烧或：C0彡水溶液沖洗所得乾 燥塗膜60秒鍾後，K目視來評估其殘留的樹脂。 *光硬化性的 用旋轉塗抹器將各種樹脂組成物抹於玻璃基板上，使 其乾燥膜厚度成為lwm後，在100亡乾煉塗抹膜10秒鍾。 用lOjum的線條/空間（Line/Space)光罩(.Photo mask)覆 蓋所得皮膜在超高壓水銀焴下曝光100mJ後，將其浸潰在 二氯甲院或l%N<uC〇i水溶液中，來觀察所形成的橫形。 ‘硬化膜的蔽光性 本紙張又度適用中國國家榡準（CNS ) Α4規格（210乂297公釐） 460489 A7 B7 五、發明説明（） 如同在顯像性測試時製作薄膜玻璃基板的方法製成乾 燥塗抹膜，不用光覃直接在超高壓水銀燈下曝光100 mJM 得硬化皮膜後，進行其吸光度的測定。 -硬化皮膜的耐熱性 將上列測定吸光度後的試料，在250°C加熱1小時後， 用目視的方法來檢査其外觀變化而評價。 本紙法尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） I~^I * n ~~1# (請先閲讀背面之注意事項再填寫本頁) 4 60 4 89 A7 B7 五、發明説明（） 1 ! I s 1 i h •ffl I i i i" 激麴 -a i U^Q Sg 矩 atS i i I I 十1 u> υι § K it 1 g宦 •CO ο Ε· H 1 h- ta s寄 m E CjO ο νετ -Γ>· trJ K ψ H- w 宝 短. CO bt £ K K > to \j!A /vu ίύ £a-一把 与:· V&; b\ w* H > ϋι 滅' 芦 La o >5> -s VSr K X ψ C3 Λ*1. g m m Ml to cn fe is- xi o t ♦—1 〇 U: Ό 、、 to b 5.： z; Ύ> s=r o c o ro Ξ戔 1 «► t-0 1 如 to f +· r〇 ! +► n Cr p rT g?t- \i! to b "Τ' o c 2 V— m I - H. - I.扣衣 n nw 'ITI n t— (诗先閱讀背面之注意事項再填寫本頁) 本纸乐尺度適用申國國家標準（CNS ) A4現格（210X297公4〉 4 6〇4 89 ^ A7 B7 五、發明説明（）I (Read the notes on the back of the poem before filling in this page) -147-This paper size applies to the Chinese National Standard {CNS) A4 specification (210X297 mm) "60 4 89 'A7 ___B7_ V. Description of the invention () 62.5 parts of hexaacrylic acid * 9.38 parts of Yieryaqiu 907 (same as above) for the photo-recombination starter are dispersed uniformly to obtain a photocurable resin composition (11). Example 3 9 Μ Example 38 The method was the same as in Example 34 except that the dispersion solution (ExD-1) containing the treated carbon black (ExD-1) obtained in Example 10 was used instead of the dispersion solution (ExC-5). Photocurable resin composition (12). Example 40 The dispersion solution (ExC-6) containing treated carbon black (ExC-6) obtained in Example 11 was tested for solubility in a part 175,0 containing a photosensitive resin. 24.55 parts of styrene-ethyl resin propylene diene 632 (manufactured by Johnson & Johnson Polymers), 30 parts of quaternary tetraol tripropylene acid acid brewing, and Yier Yaqiu 907 (previously produced) for photoregeneration starter 5 The photo-curable resin composition (13) was obtained by dispersing the homogeneous parts. Example 41 The method of Example 40 was used except that it was used in the example. 12 Dispersion solution containing treated carbon black (ExE-1) (EχΕ-1 Π76.7 part instead of dispersion solution (ExC-6) part 175.0 and the amount of Ding-682 changed to 22.8 parts. * Others are the same Example 40 was performed to obtain a photocurable resin composition (14). Example 42 The method of Example 40 was used except that the dispersion solution (EχΕ-2) containing treated carbon black (EχΕ-2) obtained in Example 13 was used. 2) Part 178.3 replaces the dispersion solution (ExC-6) Part 176.7 and the amount of Ding-682 is changed to 21.2, other -148 — The paper size is applicable to the Chinese National Standard (CNS) A4 specification UlOX 297 mm) ( Please read the precautions on the back before filling in this f)% ^ 6 Ο 4 89 Α7 __Β7__ 5. Description of the invention () All operations are the same as in Example 40 * to obtain the photocurable resin composition (15). Example 43 (Please (Read the precautions on the back before filling this page.) The method of Example 40 was used, except that the dispersion solution (ExC-7) containing the treated carbon black (ExC-7) obtained in Example 14 was used instead of the dispersion solution (ExC- Except for 6), the other operations were the same as those in Example 40 to obtain a photocurable resin composition (16). Example 44 The method of Example 40 was used, except that the dispersion solution (ExE-3) containing the treated carbon black (ExE-3) obtained in Example 15 was used in place of 177.7 to replace the dividing solution (ExC-6). Except for 175.0 parts and the amount of Ding-682 being changed to 22.4 parts, the other operations were the same as in Example 40 to obtain a photocurable resin composition (17). Example 45 The method of Example 40 except that the dispersion solution (ExE-4) containing the treated carbon black (ExE-4) obtained in Example 16 was used instead of the dispersion solution (ExC-6) 175 · 30 and The amount of Ding-6S2 was changed to 25, 8 parts, and the other operations were performed in the same manner as in Example 40 to obtain a photocurable resin composition (18). Method for producing black water jetting and swilling water (Examples 46 to 47 and Comparative Examples 27 to 29 μM) Various original carbon black dispersion solutions obtained in Examples 17 to 18 and Comparative Examples 14 to 16 were used as black water for black water injection. For the following evaluations. Liquid developer Example 48 The treated carbon black (ExC-10) obtained in Example 19 of the blister, 36 parts of polyethylene resin (Mitsui Hi-Wax 4202E), Isopar-G (manufactured by Exon) -149-* this Paper Standard General Chinese National Standards < CNS) A4 Specification (210 X 29? Mm) 4 6〇489 * A7 __B7_ V. Description of the Invention (160) and 600 pins made of earthenware are put into a thermometer, stirring blade And a cooling tube in a liquid separation bottle, and stir it. Disperse for 20 hours to obtain a liquid developer (please read the precautions on the back before filling this page) ⑴. Example 30 In a liquid-separating bottle used in Example 48, 40 parts of carbon black MA-100R (same as previously produced), polyethylene resin (Mitsui Hi-Wax 4202E), and Isopar-G (exon company) were added. ) 160 parts and 600 beads made of soil, stir and disperse for 20 hours to obtain the liquid developer (C1) for comparison. Example 44 Surface treatment for improving physical fitness Example 49 Take 0.1 part of polyethylene glycol (PVA-205, manufactured by Claret) and dissolve 200 parts of deionized water in an aqueous solution into a mixer with an inactive gas search tube. Flow cooling tube and thermometer in a separatory bottle. A polymer solution prepared by dissolving 7 parts of peroxide in 8 parts of polymerized carcass made of polyethylene 97 parts and 3 parts of glycidyl isobutyrate was added, and the mixture was stirred at a high speed to make a homogeneous turbid solution. Nitrogen gas was heated to 80 ° C, and the mixture was stirred at the same temperature for 5 hours. After the reaction was allowed to occur, the mixture was cooled to obtain a polymer turbid solution. The polymer suspension was filtered, washed, and dried to obtain a polymer (29) containing a reactive group as its reactive group. ◊ Then, the device (container content 1.2. ) After inserting 3kg of earthen beads with a diameter of lnun, 30 polymers (29), 370 in Dijiaban and carbon black 1 ^ \-1001? (Same as before) 100 will be prepared as listed above. Partially added, and then the first heating medium is used to collapse the inside of the heating container to 140 -150-this paper size is common Chinese national kneading (CNS) A4 grid (210 × 297 mm > 46〇489. A7 B7 V. Description of the invention () ° C, the peripheral speed of the M disk is 10m / s after 2 hours of operation, after cooling, the pigment liquid separation (ExF-1) is separated. (Please read the precautions on the back before filling this page) Compare Example 31 Ten polymers (29) prepared in Example 49 and 20 carbon black MA-100R (same as before) were put into a Laboplast mill (same as before), and kneaded at a rotation speed of 140 ° C and 100 rpm. After the reaction was completed, the mixture was cooled, and then dispersed with 70.degree. Benzene to obtain a pigment dispersion liquid for comparison (C0-18). Comparative Example 32 A 3 mm bead made of seam soil with a diameter of 1 mm was loaded except Except for the heating device, the rest are the same as the shoe set used in Example 49 (container volume 1.2 / middle) * Gasoline coupling agent Pulianyakete AL-M (manufactured by Ajinomoto Co., Ltd.) 20, xylene 380 100 parts and carbon black MA-100R (same as before). After running at a disk peripheral speed of 10 m / s for 2 hours, the pigment dispersion liquid for comparison (C0-19) was dispensed. Example 50 A knot with a diameter of 1 mm was obtained. The beads 3ks were filled with the same device as used in Example 49, and then 40 parts of 0-methyl alcoholic acid varnish-type ring gas resin (manufactured by Sumitomo Chemical, ESCN-195X, although epoxy was 198) were added. Diethylene glycol monoethyl ether was added. 380 parts of acetate and 80 parts of carbon black MA-100R (same as before). Use a pre-heated heating medium to carry the inside of the container to 2001C, and run at an outer peripheral speed of 10m / s for 3 hours. After cooling, Pigmentation was performed to obtain a pigment dispersion (ExF-2). Comparative Example 33 The same composition as in Example 50 was used, that is, 10 parts of 0-former-type brewing varnish-type glass oxygen wax, carbon black MA-100R ( Same as the previous system) 20 copies as compared -151-This paper size is applicable to the Chinese National Standard (CNS) A4 size Γ210 × 297 mm 4 60489 A7 · B7 V. Description of the invention () (please Read the notes on the back first and then fill in this page.) Example 31 Enter the Laboplast mill (same as before), knead it at 200 ° CM100rpm to make it react, and then cool down, then add diethylene glycol monoacetate 70 weight Part, that is, a pigment dispersion liquid (C0-20) for comparison is obtained. Performance Evaluation < Performance Evaluation 1 > The photocurable resin composition (1) to (8) obtained in Examples 28 to 35 and the photocurable resin composition (C1) to Comparative obtained from Comparative Examples 18 to 25 were ( C-8) The following items were evaluated for comparison, such as developability, photohardenability, heat resistance of the light-shielding hardened film of the hardened film, etc. * Polymers on each treated carbon black blended in the resin composition Investigate whether the binding state of the moiety and the functional group (double bond, carboxyl group) are affected in the polymer. The results are shown in Table i. • Developability: Each resin composition was applied on a glass substrate with a spin coater so that the thickness of the dried film became the thickness of la ro, and dried at 10 CTC for 10 seconds. After washing the obtained dry coating film with dichloromethane or an aqueous solution of CO0 for 60 seconds, K visually evaluated the residual resin. * Light-curing: Various resin compositions were applied to a glass substrate with a spin applicator so that the thickness of the dried film became lwm, and the applied film was dried at 100 d for 10 seconds. Cover the resulting film with lOjum's Line / Space mask (.Photo mask) and expose it to 100mJ under ultra-high pressure mercury, and then immerse it in dichloromethane or 1% N < uCoi aqueous solution. , To observe the resulting horizontal shape. 'The light-shielding property of the hardened film is applicable to the Chinese National Standard (CNS) A4 specification (210 乂 297 mm) 460489 A7 B7 V. Description of the invention () The method of making a thin-film glass substrate as in the imaging test A dry coating film was made, and the hardened film was obtained by exposing 100 mJM directly under an ultra-high pressure mercury lamp without using light tan, and then measuring its absorbance. -Heat resistance of the hardened film The samples after the absorbance measurement described above were heated at 250 ° C. for 1 hour, and the appearance changes were visually inspected and evaluated. The size of the paper method is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I ~ ^ I * n ~~ 1 # (Please read the notes on the back before filling this page) 4 60 4 89 A7 B7 V. Invention Explanation () 1! I s 1 ih • ffl I ii i " 麴 麴 -ai U ^ Q Sg moment atS ii II 十 1 u > υ K 1 1 g 宦 • CO ο Ε · H 1 h- ta s m E CjO ο νετ -Γ > · trJ K ψ H- w Po short. CO bt £ KK > to \ j! A / vu ίύ £ a- a hand and: · V &; b \ w * H > ι extinguish 'Reed La o > 5 > -s VSr KX ψ C3 Λ * 1. gmm Ml to cn fe is- xi ot ♦ —1 〇U: 、, to b 5 .: z; Ύ > s = roco ro Ξ 戋 1 «► t-0 1 such as to f + · r〇! + ► n Cr p rT g? t- \ i! to b " T 'oc 2 V— m I-H.-I. buckle衣 n nw 'ITI nt— (Read the notes on the back of the poem before filling out this page) This paper music standard is applicable to the national standard of China (CNS) A4 (210X297 public 4> 4 6〇4 89 ^ A7 B7 V. Invention description ()

Ifets' 5¾3 升墨Ml〇 硬化膜熱性 硕硬彳b®g的蔽雕tn 麵bft 二氣甲烷 顯像性二規甲烷 1 應里職 光硕化性樹服組成物 良好 CO cn 良好 良好 ExA-3 -0 Vili /νΤ CO ^- ^ g; 'wE-, 良奸 CO •Ο 良好 良好 ExA-3 CO viii CO cn c=^ = I * to i * to 1 : + to 1 私 b〇 Co-5 s 比較例 22 \1ί to bx 欠落 付着物有 Co-6 Ο σϊ 比較例 23 剥妒札 to o 欠落 Co-5,G ο 比較例 24 I 1 CO 硕化u- f 付蔷物苻d Co-7 Ο C0 比較例 25 b? ----------裝----^--,訂------^ (请先閱讀背面之注意事項再填寫本頁) 本纸張尺度速用中國國家樣準（CNS ) A4規格（210X297公釐） A7 4 60489 B7 五、發明説明（） <性能評價2 ：> (請先Μ讀背面之注意事項再填寫本頁) 就在賁施例5、6所得已處理碳黑分散溶液（ExC-1)、 (ExC-2)與在比較例δ、9所得比較用已處理碳黑分散溶液 (CO-8)、（CO-9)M下列的方法檢査其分散安定性，又就各 Μ這些已處理碳黑分散溶液所調製的質例36、37光硬化性 樹脂組成物（9)、（10)與比較例26,27所得比較用光硬化性 樹脂組成物（Cll)、（C12)作顯傑性及光硬化性的評價’ Μ 調査由各已處理碳黑的聚合體不同鍵段構造所引起的影響 情形。其結果，即如表2段表3所示。 •分散安定性 將各樹脂組成物入於直徑18mm的硬質試管中，在室溫 (23亡±1°0放置6個月後，比較其分散定定性。 ♦顯像性檢査法 用旋轉塗採器Μ在乾燥後能聪成1 w m厚度膜的條件之 下，將各種樹脂組成物塗抹於披璃基板上，在l〇〇°C供焙10 分鐘。用丙酮來沖洗乾燥塗膜60秒鍾使其顯像，Μ目視來 評價殘留的樹脂的狀態。 •光硬化性 Μ如同上列顯像性檢査法製成玻璃基板後10 u πι的線 條/空間光罩覆蓋所得皮膜，在超高Μ水銀燈下曝光500 HlJ後，在丙_中浸濱以觀察所形成的圖形。 -156 — 本紙張尺度適用中國國家榡準（CNS ) Α4規格（210X297公釐） 4 4 89 A7 B7 五、發明说明（） 表 2 已處理碳黑分散溶液 EXC-1 ESC-2 C0-8 C0-9 分散安定性 沒有沈降物 沒有沈降物 有少許沈降物 有少許沈降物 表 光硬化性樹脂組成物 9 10 C11 C12 3 顯像性 無未顧像部分 無未顯像部分 有多量未顯像部分 有少壘未顯像部分 光硬化性 無未硬化部份 無未硬化部份 有多量未硬化部份 有少量未硬化部份 <請先Μ讀背面之注意事項再填寫本頁) <性能評價3 > 就在實施7、δ所得已處理碳黑分散溶液（ExC-3) ,(ExC -4)及在比較例所得比較用已處理碳黑分散溶液（CO-10)〜 (C0-13)作下列液體安定性，確緣性及耐熱性評價，Μ調査 由各種已處理碳黑聚合體的不同反應性基所引起的影響。 其结果•即如表4及表5所示。 •液體安定性 取已處理碳黑分散溶液:tOOml入於螺紋管中，在室溫（ 放置1個月後，以其液粘度的變化來比較液體 安定性。用東京計器製B型粘度計，以回轉器(Rotor ) No. 1 -157 -本紙&尺度適用中圉國家榇準（CNS ) Α4規格（210Χ 297公釐） 4 60489 A7 B7 五、發明説明（） (30 rpm測定其粘度。表4上的數值單值為CPS。 *絕緣性及耐熱性 用旋轉塗抹器以在乾燥後能形成1 ^ m厚度膜的條件， 將各種已處理碳黒分散溶液塗抹於玻璃基板上，在loot: 饼培1分鍾後測定其表面電阻值。然後，在200°C再供焙塗 抹膜1小時後，再度測定其表面電β且值。用三菱化學製的 表面電阻（阻抗）測定裝置（Hiresta IP/MCP-HT 260型） 來測定。表4上的電阻數值的單位為Ω/口。 ----.-----^— (請先閱讀背面之注意事項再填寫本頁) 表 已處理碳黑分散溶液 4 第一天 第5天 第15天 第30天 ExC-3 11.1 11.0 11.1 11.5 C0-10 9.1 9.4 9.6 9.2 C0-11 10.1 12.6 16.8 21.4 表 已處理碳黑分散溶液 5 在100°C><1分鐘供焙後在200°CX1小& ExC-4 9.34 X 10'’ 1.35 X 1 C0-12 8.56 X 10^ < 104 CO-13 5.68 X l〇g < l(f 0/ i訂 <性能評價4> 為調査碳黑接枝化聚合物聚合體上有無雙鍵結合而引 起影響，取在實施例38、39所得光硬化性樹脂組成物（11.) t ? i -158 ~ 本纸伕尺度適用中國國家樣準（CNS ) Α4現格（210Χ297公釐） 60 4 89 A7 ' __B7_ 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 、（12)，使其乾燥膜厚能成為lwm的條件之下，用旋轉塗 抹器製玻璃基板後，在10CTC的加熱板拱焙1分鍾。在高壓 水銀燈下使所得皮膜紫外線曝光500mJ/cite硬化。測定其 紫外線曝光後的表面電阻值。然後，將其在200 T:的供箱 上作後期拱焙1小時後，再測定硬化皮膜表面電阻值及測 定吸光度。將其結果以表6示之。 又，將所得硬化皮膜浸在乙基溶纖劑乙酸g旨中來觀察 ，其表面的變化，光硬化性組成物（12)幾乎沒有變化而圼 現優秀的耐溶性。 用三菱化學製的表面電（抗）姐測定儀（Hi「esta IP/ MCP-HT 260型）來測定表面電姐值。表6所示的電阻值的 單位為Ω/口。又，K膜厚度，在可視部550ηπχ測 定其吸光度。Ifets' 5¾3 liters of ink M10 hardened film thermal hard b 彳 g tn face bft digas methane imaging diregular methane 1 Yingli professional photochemical tree suit composition good CO cn good good ExA- 3 -0 Vili / νΤ CO ^-^ g; 'wE-, Good trait CO • 〇 Good Good ExA-3 CO viii CO cn c = ^ = I * to i * to 1: + to 1 Private b〇Co- 5 s Comparative Example 22 \ 1ί to bx Underlying attachments include Co-6 Ο σϊ Comparative Example 23 Deprivation to o Underlying Co-5, G ο Comparative Example 24 I 1 CO 化 化 u- f 付 蔷 物 苻 d Co -7 Ο C0 Comparative Example 25 b? ---------- install ---- ^-, order ------ ^ (Please read the precautions on the back before filling this page) This Quickly use Chinese Standards for Paper Standards (CNS) A4 specifications (210X297 mm) A7 4 60489 B7 V. Description of the invention () < Performance evaluation 2: > (Please read the precautions on the back before filling in this page ) The treated carbon black dispersion solutions (ExC-1) and (ExC-2) obtained in Examples 5 and 6 were compared with the treated carbon black dispersion solutions (CO-8) obtained in Comparative Examples δ and 9, and ( CO-9) M The following methods are used to check the dispersion stability, and the treated carbon black The photo-curable resin compositions (9) and (10) prepared in solution were compared with the photo-curable resin compositions (C11) and (C12) obtained in Comparative Examples 26 and 27 to show the properties and light. Evaluation of sclerosis' M investigated the influence caused by the different bond segment structure of each treated carbon black polymer. The results are shown in Table 2 to Table 3. • Dispersion stability Put each resin composition into a hard test tube with a diameter of 18mm, and compare the dispersion and qualitative properties after standing at room temperature (23 ° C ± 1 ° 0 for 6 months). ♦ Imaging inspection method uses spin coating Under the condition that the device can be made into a film with a thickness of 1 wm after drying, various resin compositions are coated on the glass substrate and baked at 100 ° C for 10 minutes. The dried coating film is washed with acetone for 60 seconds It was visualized, and the state of the remaining resin was evaluated visually. • The photohardenability M was the same as the above-mentioned imaging test method after the glass substrate was made into a 10 u π line / space mask to cover the resulting film. After exposure to 500 HlJ under a mercury lamp, observe the formed figure in C. B. immersion. -156 — This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 4 4 89 A7 B7 V. Description of the invention () Table 2 Processed carbon black dispersion solution EXC-1 ESC-2 C0-8 C0-9 Dispersion stability No sedimentation No sedimentation There is little sedimentation There is little sedimentation Surface hardening resin composition 9 10 C11 C12 3 No image development There is a small amount of undeveloped part. There is a small barrier. The undeveloped part is light-hardened. There is no uncured part. There is no uncured part. There is a large amount of uncured part. There is a small amount of uncured part. ≪ (Page 3) < Performance Evaluation 3 > The treated carbon black dispersion solution (ExC-3), (ExC-4) obtained in Implementation 7, δ and the comparative treated carbon black dispersion solution (CO-10) obtained in the comparative example ) ~ (C0-13) The following liquid stability, reliability, and heat resistance were evaluated. M investigated the effects caused by the different reactive groups of various treated carbon black polymers. The results are shown in Tables 4 and 5. • Liquid stability Take the treated carbon black dispersion solution: tOOml is put into the screw tube, and the liquid stability is compared with the change of its liquid viscosity at room temperature (after leaving it for 1 month. Use a B-type viscometer made by Tokyo Keiki, Rotor No. 1 -157-This paper & standard is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) 4 60489 A7 B7 5. Description of the invention () (30 rpm to measure its viscosity. The single value of the values in Table 4 is CPS. * Insulation and heat resistance were applied using a spin applicator to form a 1 ^ m thick film after drying. Various processed carbon rhenium dispersion solutions were applied on a glass substrate, and the surface was : The surface resistance value is measured after baking for 1 minute. Then, the surface resistance β is measured again at 200 ° C for 1 hour, and the surface resistance β is measured again. Using a surface resistance (impedance) measuring device (Hiresta, manufactured by Mitsubishi Chemical Corporation) IP / MCP-HT 260) to measure. The unit of resistance value on Table 4 is Ω / port. ----.----- ^ — (Please read the precautions on the back before filling this page) Table Treated carbon black dispersion solution 4 Day 1 5 Day 15 Day 30 ExC-3 11.1 11.0 11.1 11.5 C0-10 9.1 9.4 9.6 9.2 C0-11 10.1 12.6 16.8 21.4 Table treated carbon black dispersion solution 5 at 100 ° C > < 1 minute after baking at 200 ° CX1 small & ExC-4 9.34 X 10 '' 1.35 X 1 C0-12 8.56 X 10 ^ < 104 CO-13 5.68 X l0g < l (f 0 / i order < performance evaluation 4 > To investigate the presence or absence of doublets on the carbon black grafted polymer polymer Bonding caused the influence, and the photocurable resin composition (11.) obtained in Examples 38 and 39 (11.) t? I -158 ~ The size of this paper is applicable to China National Standard (CNS) A4 (210 × 297 mm) 60 4 89 A7 '__B7_ V. Description of the invention () (Please read the precautions on the back before filling this page), (12), make the dry film thickness under the condition of lwm, and use a spin applicator to make a glass substrate After that, it was baked on a 10CTC hot plate for 1 minute. The obtained film was cured by UV exposure at 500mJ / cite under a high-pressure mercury lamp. The surface resistance value after UV exposure was measured. Then, it was post-processed on a 200 T: supply box After baking for 1 hour, the surface resistance value and absorbance of the hardened film were measured. The results are shown in Table 6. . Further, the resulting cured film was immersed in ethyl cellosolve acetate in g aims to observe the changes of the surface, the light curable composition (12) is almost no change in current Nie excellent solvent resistance. The surface electrical resistance value was measured with a Mitsubishi chemical surface electrical impedance meter (Hi "esta IP / MCP-HT 260 type"). The unit of the resistance value shown in Table 6 is Ω / port. Furthermore, K film The thickness was measured at 550 ηπχ in the visible portion.

表 S 樹脂組成物（Π) 樹脂組成物（12) 曝光後的表面電阻值 10^ 10'" 後期拱培後的表阻抗率 10^ 10" 後期供培後的蔽光性 3.0 3.0 <性能評價5> 為調查碳黑接枝化聚合物聚合體的狻基是否會引起影 響，曾取在實施例40〜45所得光硬化性樹脂組成物（13)〜 (18)，Κ旋轉塗抹器使其乾燥膜厚度有lwm的條件之下， -159 - -本纸張尺度速用中國國家橾準（CNS ) A4规格（210X297公嫠） 4 6 Ο 4 8 3 Α7 Β7 五、發明説明（） 在玻璃基板上製作樣品後，在loo°c的加熱板上m焙塗膜1 分鍾。用0.5¾ NaOH水溶液來沖洗所得乾燥塗膜30秒及1 分鍾使其顯像，以目視檢査殘留樹脂的狀態，其所得結果 ，即如表7所示。 請 先 閲 表 7 光硬化性樹脂組成物 浸潰時間 30分鍾 60秒 (13) 有較多最的樹脂殘留 幾乎不殘留樹g旨 (14) 幾乎不殘留樹脂 圼清淨的玻塊板3 (15) 幾乎不殘留樹脂 圼清淨的玻璃板面 (16.) 有較多量的樹脂殘留 幾乎不殘留樹脂 (17) 幾乎不殘留樹脂 圼清淨的破璃板面 (18) 幾乎不殘留樹脂 圼淸淨的玻璃板面 面Table S Resin composition (Π) Resin composition (12) Surface resistance value after exposure 10 ^ 10 '" Surface resistivity after post-growth 10 ^ 10 " Light-shielding property 3.0 3.0 after < Performance evaluation 5> In order to investigate whether the fluorenyl group of the carbon black grafted polymer polymer would affect the photocurable resin composition (13) to (18) obtained in Examples 40 to 45, a κ spin applicator Under the condition that the thickness of the dried film is lwm, -159--This paper is a standard for China National Standards (CNS) A4 (210X297). 4 6 〇 4 8 3 Α7 Β7 V. Description of the invention () After preparing a sample on a glass substrate, the coating film was baked on a hot plate at loo ° C for 1 minute. The resulting dried coating film was rinsed with a 0.5¾ NaOH aqueous solution for 30 seconds and 1 minute for development, and the state of the residual resin was visually checked. The results obtained are shown in Table 7. Please refer to Table 7 Immersion time of photocurable resin composition 30 minutes and 60 seconds (13) There are more resin residues and almost no tree residues (14) There is almost no resin residue. Clean glass block 3 (15 ) There is almost no resin residue. Clean glass plate surface (16.) There is a large amount of resin residue. There is almost no resin residue. (17) There is almost no resin residue. Clean glass surface (18). There is almost no resin residue. Glass plate surface

頁 狀 狀 狀 狀 <性能評價6 > Μ下列方法來評價在貿施例46、47及比較例27〜29所 得各記錄媒體液的長期儲存性。亦對實施例27所得分散溶 液（ExC-15)進行相同評價。其結果即如表8所示。 -長期儲存性檢査法 將各碳黑分散體入於的硬質破璃試管中*在室 溫儲存6個月後，比較其分散安定性。 -160 - 本纸張尺度適用t國國家榡準（CNS ) A4规格（210X297公釐） ^ BO489 A7 B7五、發明説明（） -表 碳黑分散溶液 (Εχ08) CExC-9) (ExC-15) (CO-14) (CO-15) (CO-16) <性能評價7 > 為調査在實施例48所得液體顯像劑⑴及在比較例30所 得比較用液體顯像劑（C1)的已處理碳黒分敗安定性，即得 如下的结果。用800目（mesh)金屬鋪各過滤上列二種顯像 劑時，對液體顯像劑⑴的全部成分均通過金龎篩而未留任 何物質，而比較用顯像劑（C1)，即留有殘留物在金牖篩上 *塞注網目。 由上面的结果，即可K知道比較用顯像劑（C1)發生了 已處理碳黑的凝集現象。 <性能評價8 > 為調查聚（醯）亞胺系碳黑分散液的分散安定性，將 在實施例21所得碳黑分散溶液（ExC-12)及在比較例17所得 碳黑分散溶液（C0-17),各用保利弗龍（polyfoln，商品名> 過滅器（Advantic公司製PF020)加壓過滤的結果，即能過 漶99%的碳黑分散溶液（ExC-12)，而他方的比較用碳黑分 -161 - 本紙乐尺度適用中國國家榡準（CN’S ) A4现格（210X297公釐） _ S 長期儲存性 極為安定 極為安定 極為安定 增加粘性 ί曾加粘性 呈布丁（糊）狀 (请先閱讀背面之注意事項再填寫本頁) 4 604 89 a? ___B7_ 五、發明説明（） 散溶液在過减其量的10%時，就塞住無法再進行過濟作業 了。由此即知I道比較用碳黑分散溶液（〇1)已經發生了碳 黑的凝集現象。 <性能評價9 > 為調査對顏料聚合體的不同混合處理法所生的影響， 就在實施例49、50及比較例31〜33所得顔料分散液進行下 列的過濾試驗及分散安定檢查。 *過滤試驗法 用No. 2據紙過滅各種顏料分散液來檢査分散液的濉紙 透過率及有無賤渣留存在滤紙上。 •分散安定性試驗法 取各顔料分散液入於硬質坡璃試管中，在室溫（23°C 士:L °C )靜置10天後比較其分散安定性。 所得結果，實施例45及46的分散（ExF-1)及（ExF-2)的 滤紙透過率為的％，併未在滅紙上殘留未分散的碳黑或膠 化的碳黑，而且在10天的靜置後亦未出現沈降規象。他方 的比較例35的分散液（C0-18)即有75¾的滅紙透過率，併在 濾紙上留有多量的未分散碳黑，又往10天的靜置後，有大 部分的沈降現象，又’比較例36的分散液（C0-19),即有90 %的丨慮紙透過率而在總紙上留存未分散的碳黑，經1〇天的 菁争置亦圼現育部分的沈降現象，至於比較例37的分散液（ C0-20) *即幾乎無法透過總紙，其大部分以未分散的碳黑 成為膠狀殘留在滤紙上，若將其靜置，即立刻又發生沈降 本紙掁尺度適用中國國家標毕（CNS ) A4規格（210X297公釐.) (诗先閱讀背面之注意事項再填寫本頁) ，今 訂 so4 89 A7 __B7 五、發明説明（） <性能評廣1〇> 對在實施例24〜26及參考例2所得的碳黑接枝化聚合 物分敗溶液（ExA-4)、（ExB-2)、（ExB-3)及（ReA-Ι)進行了 如下列所示的光硬化性及在齡Ϊ水溶液中的顯像性評價。 *光硬化性 各取分散溶液100部與二季成四醇四丙鋪酸酿（DPHA) 25部*光合開始劑益爾牙丘907 3.5部的均句混合溶液， 用旋轉塗抹器使其乾燥膜厚度能成為1 w ιηθϋ條件將其塗抹 茌玻璃基板上後，將基板浸漬在丙酮中1分鍾而觀察其表 面狀態的變化情形。將其觀察結果示於表9中。 *鹼顯像性 用旋轉塗抹器以乾燥膜厚度能成為li/m的條件，將:各 分散溶液塗抹在玻璃基板上後，用1 wt % Κ0Η水溶液沖洗 10秒鍾而觀察其鹼顯像性。其结果如表9所示。 表 9 碳黑接枝化聚合物 光硬化性 鹼顯像性 ReA-1 △ X 3 C. f ExA-4 ◎ X » f ExB-2 △ 〇 ϊ ίί fc ExB-3 ◎ 〇 ___ - 163 - 本紙張尺度遘用中國國家榡準（CNS ) A4規格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本頁)Page shape Condition < Performance evaluation 6 > The following methods were used to evaluate the long-term storage properties of each recording medium liquid obtained in Examples 46 and 47 and Comparative Examples 27 to 29. The same evaluation was performed on the dispersion solution (ExC-15) obtained in Example 27. The results are shown in Table 8. -Long-term storage test method Each carbon black dispersion was placed in a hard glass-breaking test tube. * After being stored at room temperature for 6 months, the dispersion stability was compared. -160-This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) ^ BO489 A7 B7 V. Description of the invention ()-Table carbon black dispersion solution (Εχ08) CExC-9) (ExC-15 ) (CO-14) (CO-15) (CO-16) < Performance Evaluation 7 > To investigate the liquid developer obtained in Example 48 and the liquid developer for comparison (C1) obtained in Comparative Example 30 The stability of the treated carbon sulphur was obtained as follows. When using 800 mesh (mesh) metal plates to filter each of the two developers listed above, all the components of the liquid developer 通过 were passed through a gold sieve without leaving any substances, and the developer (C1) was compared, that is, Residues remain on the gold sieves * plugged mesh. From the above results, it can be known that the comparative developer (C1) has aggregated the treated carbon black. < Performance Evaluation 8 > In order to investigate the dispersion stability of the poly (imide) imide carbon black dispersion, the carbon black dispersion solution (ExC-12) obtained in Example 21 and the carbon black dispersion solution obtained in Comparative Example 17 were examined. (C0-17), the results of pressure filtration using a polyfoln (polyfoln, trade name > perforator (Advantic company PF020)), which can pass 99% carbon black dispersion solution (ExC-12), The carbon black for other comparisons -161-this paper scale is applicable to China's National Standard (CN'S) A4 (210X297 mm) _ S long-term storage is extremely stable, extremely stable, extremely stable, and increased viscosity. Paste) (Please read the precautions on the back before filling out this page) 4 604 89 a? ___B7_ V. Description of the invention () When the powder solution is reduced by 10%, it will not be able to be used for economical work. From this, it is known that the carbon black agglomeration phenomenon has occurred in the comparative carbon black dispersion solution (〇1). ≪ Performance Evaluation 9 > In order to investigate the effects of different mixing treatment methods on the pigment polymer, The pigment dispersion liquids obtained in Examples 49 and 50 and Comparative Examples 31 to 33 were charged. The following filtration tests and dispersion stability checks are used. * The filtration test method uses No. 2 according to the paper to eliminate various pigment dispersions to check the paper transmission rate of the dispersion and the presence of scum on the filter paper. • Dispersion stability test method Each pigment dispersion was placed in a rigid sloping glass test tube, and the dispersion stability was compared after standing at room temperature (23 ° C ± L: C) for 10 days. As a result, the dispersion (ExF-1 of Examples 45 and 46) was obtained. ) And (ExF-2)% of filter paper transmittance, no undispersed carbon black or gelled carbon black remained on the extinction paper, and no sedimentation pattern appeared after 10 days of standing. Others The dispersion liquid (C0-18) of Comparative Example 35 had a paper extinction transmittance of 75¾, and a large amount of undispersed carbon black remained on the filter paper. After being left to stand for 10 days, most of the sedimentation phenomenon occurred. 'The dispersion liquid of Comparative Example 36 (C0-19), that is, 90% of the paper transmission rate remained undispersed carbon black on the total paper, and after 10 days of cyanine contention, the sedimentation of the inoculated part was also observed. As for the dispersion liquid (C0-20) of Comparative Example 37, that is, it is almost impossible to permeate the total paper, and most of it is made of undispersed carbon black. The gelatinous residue remains on the filter paper. If it is left to stand, it will immediately settle again. The size of this paper will apply to the Chinese National Standard (CNS) A4 specification (210X297 mm.) (Read the precautions on the back of the poem before filling this page) , This order so4 89 A7 __B7 V. Description of the invention () < Performance evaluation 1 10 > For the carbon black grafted polymer separation solution (ExA-4) obtained in Examples 24 to 26 and Reference Example 2 , (ExB-2), (ExB-3), and (ReA-1) were evaluated for photohardenability and developability in an aqueous solution of erythrium as shown below. * Photo-hardenable 100 disperse solutions and 25 parts of the second quarter tetrakis tetrapropane acid brewing (DPHA) * photosynthetic starter Yier Yaqiu 907 3.5 parts of the homogeneous mixed solution, dry the film with a rotary applicator The thickness can be 1 1θθ. After coating it on a glass substrate, the substrate is immersed in acetone for 1 minute to observe the change of the surface state. The observation results are shown in Table 9. * Alkali developability: Use a rotary applicator to dry film thickness under the condition of li / m. After each dispersion solution is applied on a glass substrate, rinse with a 1 wt% K0Η aqueous solution for 10 seconds to observe its alkali developability. . The results are shown in Table 9. Table 9 Photocurable alkali-imaging properties of the carbon black grafted polymer ReA-1 △ X 3 C. f ExA-4 ◎ X »f ExB-2 △ 〇〇 ίίc ExB-3 ◎ 〇 ___-163- This paper uses China National Standard (CNS) A4 size (2 丨 0X297mm) (Please read the precautions on the back before filling this page)

»1T 4 6〇4 89 <圖式中元件名稱與符號對照> 1…· •容器 2… •回轉軸 3…. ••圓盤狀攪拌子 3a… *回轉攪拌子 3b…· ••針狀固定子 4… •球粒 5..... 6…. ••熱套管 7…·. •熱媒循環幫浦 8…. ••熱媒貯藏器 9，11 + ·····加熱器 12···· ••防止逆流閥 13…·. •流體導入口 14…· "流體導出口 15…·. •媒體分離器 15a.. •…圓盤狀固定板部 15b- …·回轉圓盤部 15c·· •…間隙 熱電偶»1T 4 6〇4 89 < Comparison of component names and symbols in the drawings > 1… · • Container 2… • Rotary shaft 3…. •• Disc-shaped stirrer 3a… * Rotary stirrer 3b… · •• Needle holder 4… • pellets 5 ..... 6…. • • thermowell 7… ·. • heat medium circulation pump 8…. • • heat medium reservoir 9, 11 + ···· · Heater 12 ······ Prevention of backflow prevention valve 13… .. • Fluid inlet 14… " Fluid outlet 15… .. • Media separator 15a ..... Disc-shaped fixing plate portion 15b- … · Turning disk 15c ···· clearance thermocouple

Claims (1)

輕濟部中央榡率局員工消f合作¾印13. α 6〇489 獅細，其製紐及蝴」專利申請案 !_ϋ：不“ Η 90年7月20日修正 $、申請專利範圍丨 . . . L —種碳黑接枝聚合物’具有至少一種下列之特徵： (1) 得自能與碳黑表面的功能基起反應的反應性基和 含有乙烯性不飽和雙鍵結合的聚合體與碳黑共同加熱混 合’而以其接枝化鏈段中含有不飽和雙鍵結合者； (2) 用能與碳黑表面功能基起反應的反應性基及含有 氯氧基的聚合物與碳黑共同加熱混合後所得反應混合物， 再經酸酐處理而得在其接枝化鏈段中具有羧基者； (3) 含有能與碳黑表面功能基起反應的反應性基的鏈 段(A)，及含有與前述鏈段相異骨格構造的鏈段㊉)的塊 塑以及接枝型聚合體與碳黑共同加熱混合所得而含有以塊 型以及接枝型聚合物為其接枝化鍵者； (4) 所述反應性基為含有一種以上或二種以上的環氧 基 '硫環氧基、氮丙啶基及噁唑啉基； (5) 其係以所述塊型以及接枝型聚合體的形態而含有 乙烯性不飽和雙鍵結合的鏈段(B)做為原料，所得再以含有 乙稀性不飽和雙鍵結合的接枝鏈； . (6) 所述鏈段(B)上的不飽和雙够結合以尿烷結合為媒 介而結合在鏈段(B)主鏈的側鏈上； (7) 其係以所述塊型以及接枝型聚合體的形態，用所述 鏈段(A)及最少在鏈段(B)中含有塊型以及接枝型聚合體的 鏈段(B)與碳黑共同加熱混合後所得反應混合物以酸酐來 處理而得含有羧基在其接枝鏈中； (8) 所述反應性基為含有一種以上或二種以上的環氧 基、硫環氧基、氮兩啶基及噁唑啉基； (請先閲讀背面之注意事項再填寫本百) 裝*| 訂 線 本紙張尺度速用 固囤家標羋（CNS ) 格（2】GX29V公犮） ABCD 460489 六、申請專利範圍 V (9)所述鏈段(A)是由最少要含有反應性基的乙烯系單 體所成的乙烯系單體組成物聚合而得，含有碳一碳結合主 鏈； (1〇)所述鏈段(A)是用含有反應性基的乙烯系單體所 成的乙烯單體組成物聚合而得在其重合鏈中有反應性基 及芳香環； (Π)所述鏈段(A)為含有芳香環的乙烯系單體5克分子 〇/〇以上及有乙烯系單體的乙烯系單體組成物重合而得； (12) 所述鏈段出)具有任何一種的聚硅氧系構造，聚 (間）丙烯系構造、聚醚構造、聚（甲基）丙烯腈構造、聚酯 構造、聚烯基構造、聚醯胺構造、聚（醯)亞胺、聚尿烷構 造； (13) 所述碳黑的平均粒子徑在0.0005〜0.4/M範圍； (H)其係所述碳黑h)0重量部與所述聚合物1〜1000 重量部經接枝化所得； (15)其複黑乃含有緩基者。 ’ 2. 如申請專利範園第1項之碳黑接枝聚合物，其中， 碳黑係具有pH值未滿7.0的酸性碳黑者。 3. 如申請專利範圍第1項之碳黑接枝聚合物，其係對 其目的媒體的分散性有所改良者，在所述目的媒體或具有 與其相似性狀的媒體所成的分散媒體中，使含有能與碳黑 表面功能基起反應的反應性基鏈段(A)及實質上未含有所 述反應性基的所述鏈段(A)含有更能對所述分散媒液呈現 高度親和性的鏈段(B)的塊型以及接枝型聚合物一起與碳 165 本紙張尺度適用中國國家榡準（CNS ) A4说格（210X297公釐） ¾ir------^ ΙΜΥΓ (請先閲讀t··面之注意事項孑峨寫本頁) - ， . 經濟部中央榇準扃貝工消費合作社印製 4 60489 A8 B8 - C8 D8 六、申請專利範圍 黑加熱混合者。 4. 如申請專利範圍第1項之碳黑接枝聚合物，其係用 含有能與碳黑表面功能基起反應的反應性基鏈段(A)及實 質上比未含有所述反應基的鏈段(A)對於碳黑呈現低度親 和性的鏈段(B)二者均有的塊型以及接枝型聚合體與碳黑 共同加熱混合者。 5. 如申請專利範圍第1項之碳黑接枝化聚合物，其係 在目的媒體或有相似性狀的媒體所成的分散媒液中，用含 有此與碳黑表面功能基起反應的聚合體鍵段(A)及比含有 不飽和雙鍵結合的鏈段(A)對所述分散溶液更呈現高度親 和性的鏈段(B)的塊型以及接枝型聚合體共同與碳黑加熱 混合者=> 6. 如申請專利範圍第1項之碳黑接枝聚合物，其係， ①在目的媒體或與其類似性狀的媒體所成的分散媒液 中’用含有能與碳黑表©功能基起反應的反應性基鍵段(A) 及含有比所述鏈段(A)對所述分散媒液呈現較高親和性的 鏈段(B)的塊型以及接枝型前驅體聚合體共同與碳黑加熱 混合，之後’以②含有能與所述塊型以及接枝型前驅體聚 合體的鏈段(B)上的功能基起反應的反應性基及含有不飽 和雙鍵結合的化合物(d)共同與在所述①得前驅體聚合體 經接枝化所得碳黑進行反應而引進不飽和雙鍵結合於前 驅體聚合體的鏈段(B)上為其特徵的碳黑接枝化聚合物製 造方法。 7. 如申請專利範圍第6項之碳黑接枝聚合物，所述鏈 166 本纸張尺度適用十國國家榇準（CNS ) A4規格（2丨OX2?7公釐） 裝· 訂 1--線---¥ (锖先閱讀背面之注意事項-，**寫本頁) < , 經濟部中央栳準局員工消費合作社印笨 4 9 8 4 ο ABCD 經濟部中央橾準局員工消费合作社印象 六、申請專利範圍 V 段(B)為具有醇性或酚性氫氧基為其功能基者，而所述化 合物(d)的反應性基為異腈脂基者。 8. 如申請專利範圍第1項之碳黑接枝聚合物，其係用 含有能與碳黑表面功能基起反應的反應性基鏈段(A)及其 有不飽和雙鍵結合又有比所述鏈段(A)呈現較低親和性的 鏈段(B)的塊型以及接枝型聚合物同與碳黑加熱混合者。 9. 如申請專利範圍第1項之碳黑接枝聚合物，其係， ①用含有能與碳黑表面功能基起反應的反應性基鏈段(A) 及，含有比所述鏈段(A)呈現較低親和性鏈段(B)的塊型以 及接枝型前驅體聚合體共同與碳黑加熱混合，之後，以② 含有能與所述塊型以及接枝型前驅體聚合體為鏈段(B)的 功月b基起反應的反應性基及含有不飽和雙鍵結合的化合 物(d)與在所述①所得有前驅聚體合體接枝化的碳黑進行 反應’以在前驅聚合體的鏈段(B)引進不飽和雙鍵結合 者。 1 〇‘如申請專利範圍第1項之碳黑接枝化聚合物，其係， 在目的媒體或由其類似性狀的媒體所成的分散媒液中，用 含有能與碳黑起反應的反應性基的鏈段(A)及，含有比所 述鏈段(A)對所述分散媒液呈現較高親和性的鏈段(B)，又 在所述鏈段(A)及鏈段(B)二者之中至少在(B)有氫氧基的 塊型以及接枝型所成聚合體共同與碳黑加熱混合後，用酸 野處理所得混合物者。 11.如申請專利範圍第3項或第4項或第5項或第6項或 第7項或第8項或第9項或第10項碳黑接枝聚合物，所述加 167 本紙張尺度適用中國國家標準（CNS) A4現格（210X297公釐） ---------裝-------1T------^ (请先Μ讀背S之注意ί項-S4-寫本頁) * , A8 B8 C8 D8 4 4 89 六、申請專利範圍 熱混合處卿.，容納被處理㈣ 進行旋轉的攪拌子，為加埶容 盗，在本容器内 及在容考内古$虹 '、、° 被處理液用的加执裘置 及在μ时複數粒狀分散媒 ?加熟衮置 置進行者。 战的濕式分散處理装 j 12.如申請專利範圍第丨項之碳里 製成硬化性樹敝絲者製成之/、、“ 4 ’係用以 ^如申請專利範圍第12項之碳黑 性樹脂組成物中配合有鹼可溶樹脂者。Λ σ ； 、14‘如申請專利範圍第12項的碳黑接枝聚合物，其所製 成之光硬化性樹脂可用以形成濾色器用黑色矩陣者。 15. π申睛專利範圍第丨項之碳黑接枝聚合物，係可含 於一墨水噴射用記錄媒體液者。 16. 如申請專利範圍第1項之碳黑接枝聚合物，係含於 一種靜電顯像顯像用顯像劑者。 17. 如申請專利旄圍第I項之碳黑接枝聚合物，係含於 一種遮光性纖維者。 . > 18‘一種製造申請專利範圍第1項之碳黑接枝聚合物之 方法，其係以碳黑100重量部以及在5〜500重量部的所述 碳黑表面的功能基起反應的反應性基的反應性聚合物一 同在分散媒液中予以加熱分散處理，藉以改進碳黑表面之 性質者。 19. 如申請專利範圍第18項的碳黑接枝聚合物之製造 方法’其係在攪拌時，加熱溫度為50〜250°C者。 20. 如申請專利範圍第18的碳黑接枝聚合物之製造方 168 本紙依尺度適用中國國家榡φ (CNS)八4規格（21〇><297公釐） 裝‘------5Γ------ (請先閱yf-面之注意事項，1¾寫本頁) .' , 經濟部中央標华局舅工消費合作社印11 460489 A8 B8 - C8 D8 六、申請專利範圍 法，其中碳黑為無機顏料微粒子者。 21. 如申請專利範圍第18項的碳黑接枝聚合物之製造 方法，其中反應性聚合物所含反應性基為環氧基、硫環氧 基、氮丙啶基及噁唑込基等的一種或二種以上者。 a 22. 如申請專利範圍第18項的碳黑接枝聚合物之製造 方法，其中反應性聚合物由在其分子中含有所述反應性基 的鏈段(A)，及含有比所述鏈段(A)對分散液更具有親和性 的鏈段(B) —個以上所成的塊型以及接枝型聚合物者。 裝 訂 _ 線IM - - (請先Μ讀背面之注意^項再填寫本頁) ，ν f 經濟部中央標率局員工消費合作社印裝Staff of the Central Bureau of the Ministry of Light Industry has cooperated with each other to print 13. α 6〇489 Lion fine, its system and butterfly "patent application! _Ϋ: No" 修正 July 20, 1990 amended $, patent application scope 丨... L-Carbon black graft polymer 'has at least one of the following characteristics: (1) Polymerization derived from reactive groups capable of reacting with functional groups on the surface of carbon black and containing ethylenically unsaturated double bonds. And carbon black are heated and mixed together to contain unsaturated double bonds in their grafted segments; (2) Reactive groups capable of reacting with carbon black surface functional groups and polymers containing chlorooxy groups The reaction mixture obtained after heating and mixing with carbon black, and then treated with acid anhydride to obtain a carboxyl group in its grafted segment; (3) a segment containing a reactive group capable of reacting with a carbon black surface functional group ( A), and a block containing a block structure different from the aforementioned chain segment ㊉) The block plastic and graft polymer and carbon black are heated and mixed together to contain block and graft polymers for grafting (4) the reactive group contains one or more Oxy'thioepoxy, aziridinyl, and oxazoline groups; (5) it contains an ethylenically unsaturated double bond-linked segment in the form of the block and graft polymers (B ) As a raw material, and the obtained graft chain containing an ethylenically unsaturated double bond bond is used;. (6) The unsaturated double bond on the segment (B) is bonded to the chain via the urethane bond as a medium. Segment (B) on the side chain of the main chain; (7) It is in the form of the block type and the graft type polymer, and the block (A) and at least the block type is included in the block (B) And the grafted polymer segment (B) is heated and mixed with carbon black, and the reaction mixture is treated with acid anhydride to obtain a carboxyl group in the graft chain; (8) the reactive group contains one or more More than two kinds of epoxy, thioepoxy, aziridinyl and oxazoline groups; (Please read the precautions on the back before filling in this one hundred) Binding * |芈 (CNS) lattice (2) GX29V male 犮 ABCD 460489 6. The scope of patent application (V) (9) The segment (A) is made of vinyl based at least containing reactive groups It is obtained by polymerizing an ethylene-based monomer composition and contains a carbon-carbon bonding main chain; (10) the segment (A) is an ethylene monomer formed by using a vinyl-based monomer containing a reactive group; The composition is polymerized to have a reactive group and an aromatic ring in the overlapping chain thereof; (Π) The segment (A) is an ethylene-based monomer containing an aromatic ring of 5 grams or more and a vinyl-based monomer; (12) The segment is out of any kind of polysiloxane structure, poly (meta) acrylic structure, polyether structure, poly (meth) acrylonitrile structure, etc. , Polyester structure, polyalkenyl structure, polyamidine structure, poly (fluorene) imine, polyurethane structure; (13) the average particle diameter of the carbon black is in the range of 0.0005 ~ 0.4 / M; (H) its It is obtained by grafting the carbon black h) 0 parts by weight and 1 to 1000 parts by weight of the polymer; (15) the compound black contains a retarder. 2. The carbon black graft polymer according to item 1 of the applied patent garden, wherein the carbon black is an acidic carbon black having a pH value of less than 7.0. 3. If the carbon black grafted polymer in item 1 of the patent application scope has improved the dispersion of its target media, in the target media or the dispersion media formed by media with similar characteristics, The reactive group segment (A) containing the functional group capable of reacting with the surface of the carbon black and the segment (A) which does not substantially contain the reactive group are contained to have a higher affinity for the dispersion medium. Block (B) block type and graft polymer together with carbon 165 This paper size is applicable to China National Standards (CNS) A4 grid (210X297 mm) ¾ir ------ ^ ΙΜΥΓ (Please First read the note on t .. Saga writes this page)-,. Printed by the Central Ministry of Economic Affairs, Zhuhai Beigong Consumer Cooperative, 4 60489 A8 B8-C8 D8 6. Application for patents, black heating and mixing. 4. The carbon black graft polymer as described in item 1 of the scope of patent application, which uses a reactive group segment (A) containing a reactive functional group capable of reacting with a carbon black surface functional group, and substantially Segment (A) has a low affinity for carbon black, and segment (B) has both a block type and a graft polymer and carbon black which are heated and mixed together. 5. If the carbon black grafted polymer in item 1 of the patent application scope is a dispersion medium made of the target medium or a medium with similar characteristics, the polymerization is carried out by using the polymer containing the functional group that reacts with the surface of the carbon black. The block type and graft type polymer of the body bond segment (A) and the segment (B) having a higher affinity for the dispersion solution than the segment (A) containing an unsaturated double bond are heated together with carbon black Mixer => 6. For example, the carbon black grafted polymer in the scope of patent application No. 1 is as follows: ① In a dispersion medium formed by a target medium or a medium with similar properties, use a carbon black polymer © The functional group reacts with a reactive group bond segment (A) and a block type and a graft type precursor containing a segment (B) having a higher affinity for the dispersion medium than the segment (A). The polymer is heated and mixed together with carbon black, and then 'containing reactive groups that can react with functional groups on the segment (B) of the block-type and graft-type precursor polymer and containing unsaturated double bonds The combined compound (d) reacts together with the carbon black obtained by grafting the precursor polymer obtained in step (1), and Bound to an unsaturated double bond into a carbon black graft polymer as its manufacturing method wherein the (B) segment drive polymeric precursors thereof. 7. If the carbon black grafted polymer in item 6 of the patent application scope, the chain of 166 paper sizes is applicable to the ten countries' national standard (CNS) A4 specification (2 丨 OX2? 7mm). -Line --- ¥ (锖 Please read the notes on the back-, ** write this page) <, Consumer Cooperatives of the Central Economic and Technical Bureau of the Ministry of Economic Affairs, India Benben 4 9 8 4 ο ABCD Cooperative impression 6. The scope of application for patent (V) Paragraph (B) is one having alcoholic or phenolic hydroxyl groups as its functional group, and the reactive group of the compound (d) is an isocyanate group. 8. For example, the carbon black grafted polymer in the scope of patent application No. 1 uses a reactive group segment (A) containing a reactive group capable of reacting with the functional group on the surface of the carbon black. The block type and graft type polymer of the segment (A) exhibiting a lower affinity are the same as those obtained by heating and mixing with carbon black. 9. If the carbon black graft polymer according to item 1 of the scope of patent application is, ① using a reactive group segment (A) containing a reactive group capable of reacting with a carbon black surface functional group and A) The block type and graft type precursor polymer exhibiting a lower affinity segment (B) are heated and mixed with carbon black together, and then ② contains a polymer that can interact with the block type and graft type precursor polymer as The reactive group that reacts with the functional group b of the segment (B) and the compound (d) containing an unsaturated double bond bond reacts with the carbon black grafted with the precursor polymer complex obtained in step (1) above. The segment (B) of the precursor polymer introduces an unsaturated double bond binder. 10 ′ The carbon black grafted polymer according to item 1 of the scope of the patent application, which uses a reaction containing a reaction capable of reacting with carbon black in a dispersion medium made of a target medium or a medium with similar properties. The segment (A) of the sex group and the segment (B) containing a higher affinity to the dispersion medium than the segment (A), and in the segment (A) and the segment ( B) Among the two, at least (B) a block-type polymer having a hydroxyl group and a graft-type polymer together are heated and mixed with carbon black, and the resulting mixture is treated with an acid field. 11. If the scope of the patent application is No. 3 or No. 4 or No. 5 or No. 6 or No. 7 or No. 8 or No. 9 or No. 10 carbon black grafted polymer, add 167 pieces of paper Applicable Chinese National Standard (CNS) A4 standard (210X297 mm) --------- installation --------- 1T ------ ^ (Please read the note of S first (Lite item-S4-Write this page) *, A8 B8 C8 D8 4 4 89 VI. Patent application scope Thermal Mixing Secretary. It contains the stirrer that is being processed and rotates. In Rongkao Neihonghong, the ° treatment of the treatment liquid and multiple granular dispersion media at the time of μ? Wet dispersing processing equipment 12. If the hardened tree reel is made from the carbon of the scope of the patent application, the "4 '" is used to ^ the carbon of the scope of the patent application Alkali-soluble resins are blended in the black resin composition. Λ σ; 14 ′ If the carbon black graft polymer is the 12th in the scope of the patent application, the photocurable resin can be used to form a color filter. Black matrix. 15. The carbon black graft polymer of item No. 丨 in the patent scope of π, can be contained in a recording medium liquid for ink jet. 16. For example, the carbon black graft polymer of item 1 in the patent scope. Material, which is contained in a developer for electrostatic imaging development. 17. For example, the carbon black grafted polymer of item I in the patent application is contained in a light-shielding fiber. ≫ 18'a A method for producing a carbon black graft polymer according to item 1 of the patent application, which is based on the reactivity of a reactive group that reacts with a functional group on the surface of the carbon black at 100 parts by weight of carbon black and 5 to 500 parts by weight. The polymer is heated and dispersed in the dispersion medium to improve the carbon black. 19. The manufacturing method of the carbon black graft polymer according to item 18 of the scope of patent application 'is a heating temperature of 50 to 250 ° C while stirring. Manufacturer of carbon black graft polymer 168 This paper is applicable to China's national 榡 φ (CNS) 8-4 specification (21〇 > < 297mm) according to the standard. Packing '------ 5Γ ------ (Please read the notes on yf-face first, write this page). ', Printed by the Central Standardization Bureau of the Ministry of Economic Affairs, Printing Industry Cooperatives 11 460489 A8 B8-C8 D8 VI. Patent Application Law, where carbon black is an inorganic pigment Micro-particles. 21. The method for manufacturing a carbon black grafted polymer as described in claim 18, wherein the reactive groups contained in the reactive polymer are epoxy, thioepoxy, aziridinyl, and oxazole. One or two or more of fluorenyl groups, etc. a 22. The method for producing a carbon black graft polymer as described in claim 18, wherein the reactive polymer consists of a chain containing the reactive group in its molecule Segment (A), and a segment (B) containing more than the segment (A) has a more affinity for the dispersion liquid . Block and graft polymer type who stapling _ line IM - - (Please read the back of the note ^ Μ items to fill out this page), ν standard rate of central office employees consumer cooperatives f India with the Ministry of Economy 本紙伕尺度適用中國國家標準（CNS ) A4说格（210X297公釐）The paper scale is applicable to China National Standard (CNS) A4 scale (210X297 mm)