201002760 六、發明說明： 【發明所屬之技術領域】 本發明係關於在染色紙製造中用於改善染料堅牢性之組 合物、反應產物及其相應的鹽，其可經在水溶液中令哌嗪 衍生物與脂肪族胺之混合物與齒代醇類反應而獲得。 【先前技術】 在染色紙製造中，使用的染料與染色條件未必能達到令 人滿意的固色與給色量，如果添加輔助劑，則可能干擾於 濕式部分使用的其它輔助劑之作用。因此，需要提供^種 可與可能使用的其它輔助劑相容之產品。在纖維素纖維加 工中，尤其在造紙中’主要在濕式部分，聚院基胺適宜作 爲整體陽離子輔助劑，及尤其適宜作爲改善染色紙染料固 色之有效染色助劑。 已知許多此等縮聚物、其製備方法及其增加直接染料之 染色堅牢性的錢。常_多胺1«型產品雖可有效 清理染色回水，但對成品板片 叹乃的色調（色相）與亮度（色度） 卻有負面影響。 與使用多胺-表氣醇樹脂相關沾 關的缺點之一為有害的氣化 化合物會排放於紙漿與紙薇的永 叩水糸統中。此等氯化化合物 (包含1，3-二氯-2-丙醇、表氯醇歲 > -、1-氣-2,3-丙二醇）因爲僅 部分直接染色於纖維素紙漿纖 % 故通常破排放於廢水系 統中。此等化合物之可允許量诼 、却減小且因此已努力降低 此等物質量。 【發明内容】 138387.doc 201002760 本發明係關於在染色紙製造中用力改善染料堅牢性之組 合物、反應產物及其鹽。此等組合物、及其改善直接染料 之木色堅牢ί·生的用途已為人所知。已知的水溶性組合物不 月匕滿足工業中如上述的所有目前需求。需要用於滿足工業 上目前需求地將染料固定於紙上之水溶性組合物及反應產 物’尤其係關於當施用於紙時，色調改變及/或亮度損 失。 令人吃驚的是，當以板片染色製程施用時，本發明中所 述的水心丨生組合物、反應產物或其水溶性鹽僅引起非常小 或未引起色調之改變且亮度只有微小或無損失。當在鮮徵 色調存在下施用時，組合物與反應產物顯示極佳之性質。 此等組合物與反應產物可藉由多官能團、經取代或未經取 代之胺或其等之混合物與表_醇之反應製得。 本發明係關於作爲特定的紙染料之固定劑（尤其是保存 色凋之鮮豔）的特定性组合物、反應產物與水性組合物之 製備’及製造經後處理之染色紙的方法。 以下，如未另陳述，烷基意指直鏈或支鏈烷基，伸烷基 意指直鏈伸烷基，鹵素意指氟、氯、溴或碘。 【實施方式】 本發明提供可由組分A、組分Β與組分C之陽離子縮聚反 應而獲得的組合物、反應產物及其鹽， 其中 組分A為結構式（I)之多官能團胺 138387.doc 201002760 \201002760 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to compositions, reaction products and corresponding salts thereof for improving dye fastness in the manufacture of dyed paper, which can be derived from piperazine in aqueous solution. The mixture of the substance and the aliphatic amine is obtained by reacting with a dentate alcohol. [Prior Art] In the production of dyed paper, the dyes and dyeing conditions used may not be satisfactory for fixing and coloring, and if an adjuvant is added, it may interfere with the action of other adjuvants used in the wet portion. Therefore, there is a need to provide products that are compatible with other adjuvants that may be used. In the processing of cellulose fibers, especially in papermaking, the poly-based amines are suitable as integral cationic adjuvants, and are particularly suitable as effective dyeing aids for improving the fixing of dyes for dyed paper. A number of such polycondensates, methods for their preparation, and their use to increase the dye fastness of direct dyes are known. The often-polyamine 1« type product can effectively clean the dyed back water, but it has a negative effect on the hue (hue) and brightness (chroma) of the finished sheet. One of the disadvantages associated with the use of polyamine-epi-alcohol resins is that harmful gasification compounds are emitted into the hydration system of pulp and paper. These chlorinated compounds (including 1,3-dichloro-2-propanol, epichlorohydrin aged > -, 1-gas-2,3-propanediol) are usually only partially dyed directly to cellulose pulp fibers. Breaking emissions into the wastewater system. The allowable amount of these compounds is reduced, but is reduced and therefore efforts have been made to reduce the quality of such materials. SUMMARY OF THE INVENTION The present invention relates to compositions, reaction products and salts thereof which are used to improve dye fastness in the manufacture of dyed paper. The use of such compositions, and their improved wood color for direct dyes, is well known. Known water soluble compositions do not meet all of the current needs of the industry as described above. There is a need for water soluble compositions and reaction products that are used to meet the current industry needs to immobilize dyes on paper', particularly with regard to hue changes and/or loss of brightness when applied to paper. Surprisingly, when applied in a sheet dyeing process, the centrifugation composition, reaction product or water-soluble salt thereof described in the present invention causes only a very small or no change in hue and the brightness is only slight or No loss. The composition and the reaction product show excellent properties when applied in the presence of fresh color tones. These compositions and reaction products can be prepared by reacting a polyfunctional group, a substituted or unsubstituted amine or a mixture thereof with a watch alcohol. The present invention relates to a specific composition as a fixing agent for a specific paper dye (especially for the preservation of vivid color), a preparation of a reaction product and an aqueous composition, and a method for producing a post-treated dyed paper. Hereinafter, unless otherwise stated, an alkyl group means a straight or branched alkyl group, an alkyl group means a linear alkyl group, and a halogen means fluorine, chlorine, bromine or iodine. [Embodiment] The present invention provides a composition, a reaction product, and a salt thereof obtainable by cationic polycondensation reaction of component A, component hydrazine and component C, wherein component A is a polyfunctional amine of formula (I) 138387 .doc 201002760 \
HN (Ί) N—R2 I \ HN-Rl 其中 R1代表H或CVCU烷基， R2代表C2-C4伸烷基； 組分B為伸烷基多胺或聚伸烷基多胺，其條件為組分6不 具有結構式（I)之結構， 且組分c為表_醇， 其特徵在於：聚合反應（即，陽離子縮聚反應）係於不存在 甲苯、不存在任何二i代烴且*存在任何二幽代烧基越於 溶劑中進行。 陽離子、《反隸佳⑽衫在任何有機溶劑且不存在 任何其他_代化合物（除表函醇）下進行。 本發明另—目的為一種製造以上定義的組合物、反應產 物及其鹽之方法，其特徵在於上述定義的製程步驟。 :且分A與組分B彼此獨立地包含—種以上的物質，較佳 係1、2 ' 3、4或5種，更佳俦〗、0七 物質。 μ 2或3種’甚至更佳係1種 較佳的是HN (Ί) N—R2 I \ HN-Rl wherein R1 represents H or CVCU alkyl, R2 represents C2-C4 alkyl; Component B is alkylene polyamine or polyalkylene polyamine, provided that Component 6 does not have the structure of formula (I), and component c is a table-alcohol, characterized in that the polymerization reaction (i.e., cationic polycondensation reaction) is in the absence of toluene, in the absence of any di-generation hydrocarbons and * The presence of any two genomic alkyl groups is carried out in a solvent. The cation, "Ri Lijia (10) shirt is carried out in any organic solvent and in the absence of any other _ generation compounds (except for the alcohol). Another object of the invention is a process for the manufacture of a composition, a reaction product and a salt thereof as defined above, characterized by the process steps defined above. And the component A and the component B independently comprise one or more substances, preferably 1, 2 '3, 4 or 5, more preferably 、, 0 七 substances. μ 2 or 3 species even better one is preferred
Rl代表Η或Ch3，更佳係Η; R2代表Cr或c3_伸烷基 在更佳的組分A中， 更佳係C2伸烧基。 Rl為氫原子或甲基，更佳係 氫原 138387.doc 201002760 子；R2為亞甲基。組分A較佳為1 -胺乙基d辰嗓。 較佳的組分B為具有通式（II) H2N-P-H (II) 其中 P為[CHZ-(CH2)n-NR]x，或[CH2-(CHZ)m-(CH2)n-NR]x， 當 P為[CHZ-(CH2)n-NR]x時，n=l 至 7 ; x=l 至 6 ; R=H 或 CH2Y ; Z=H 或 CH3 ;及 Y=CH2Z、Η、NH2 或 CH3， 當 P 為[CH2-(CHZ)m-(CH2)n-NR]x 時，m=l 至 6 ; n=l 至 6 ; m+n=2 至 7，R=H 或 CH2 Y，Z=H 或 CH3，及 Y=CH2Z、Η、 f NH2或CH3 ;及其混合物。 組分B進一步較佳具有通式（III) H2N-X_H (III) 其中 X 代表[<^〇((^2)11-风尺3)])£或[(：112-(〇1(乙))„1-((：112)11-\尺\， 在X代表[CH(Z)-(CH2)n-NR3]>^ 情況下，則 η 為1至7之整數， X 為1至6之整數， R3 代表氫Η或CH2Y， z 代表氫或CH3，及 - Y 代表氫、CH2Z、NH2 或 CH3 ; 在 X代表[CHHCHCZDm-CCHA-NCR3)]^^ 情況下，貝 m 代表1至6之整數， η 代表1至6之整數， m+n等於2至7之整數， R3 代表氫或CH2Y， 138387.doc 201002760 z 代表氫或ch3，及 Y代表氫、CH2Z、叫或叫。 組分B較佳係選自由i，心丁二胺 三胺、叫胺基乙基）#丙二胺、Ν，Ν·=、；·伸丙基 基胺、聚伸乙基亞胺、伸乙基多胺 土）甲 合物所組成之群。 基夕胺及其混 、’且刀B更佳係選自由M_丁二胺 三胺、胺^其^。 已一胺、二伸丙基 V胺乙基）_1，3_丙二胺、 胺' 乙二胺、-伸厂A ，又（2·恥丙基）曱基 一伸乙基三胺、三伸乙基四 胺及其混合物所組叙群。 目伸乙基五 胺、三如 刀B甚至更佳係選自由乙二胺、二伸乙基： 土四胺、四伸乙基五胺及其混合物所組 組分B尤其為三伸乙基四胺。 之群。 、”且刀C較佳係由—種 '兩種、三種或 或其混合物所組成。表鹵醇較佳包含表氣醇不 料及表氣醇。表,醇較佳為表氣醇。…_、 醇表W較佳為未經取代，尤其使用結構式Μ)之表R1 represents hydrazine or Ch3, more preferably hydrazine; R2 represents Cr or c3_alkylene. In the more preferred component A, more preferably C2 is extended. R1 is a hydrogen atom or a methyl group, more preferably a hydrogenogen 138387.doc 201002760; R2 is a methylene group. Component A is preferably 1-amine ethyl group. Preferred component B is of the formula (II) H2N-PH (II) wherein P is [CHZ-(CH2)n-NR]x, or [CH2-(CHZ)m-(CH2)n-NR] x, when P is [CHZ-(CH2)n-NR]x, n=l to 7; x=l to 6; R=H or CH2Y; Z=H or CH3; and Y=CH2Z, Η, NH2 Or CH3, when P is [CH2-(CHZ)m-(CH2)n-NR]x, m=l to 6; n=l to 6; m+n=2 to 7, R=H or CH2 Y , Z = H or CH3, and Y = CH2Z, Η, f NH2 or CH3; and mixtures thereof. Component B further preferably has the formula (III) H2N-X_H (III) wherein X represents [<^〇((^2)11-风尺3)])£ or [(:112-(〇1(( B)) „1-((:112)11-\尺\, where X represents [CH(Z)-(CH2)n-NR3]>^, then η is an integer from 1 to 7, X is An integer from 1 to 6, R3 represents hydroquinone or CH2Y, z represents hydrogen or CH3, and -Y represents hydrogen, CH2Z, NH2 or CH3; in the case of X represents [CHHCHCZDm-CCHA-NCR3)]^^, m represents An integer from 1 to 6, η represents an integer from 1 to 6, m+n is equal to an integer from 2 to 7, R3 represents hydrogen or CH2Y, 138387.doc 201002760 z represents hydrogen or ch3, and Y represents hydrogen, CH2Z, nickname or Preferably, component B is selected from the group consisting of i, butyl diamine triamine, which is called aminoethyl) #propylenediamine, hydrazine, hydrazine, hydrazine, propylamine, polyethylenimine, a group of methyl polyamines). The base amine and its mixture, 'and the knife B is more preferably selected from the group consisting of M-butylenediamine triamine, amine ^ ^ ^. Propyl V amine ethyl) _1,3- propylene diamine, amine 'ethylene diamine, - extension plant A, and (2 · propyl propyl) fluorenyl-extended ethyltriamine, tri-ethylidene tetramine and The mixture is grouped as a group. The ethyl pentamine, the three knives B and even more preferably are selected from the group consisting of ethylenediamine, diethylidene: tetramine, tetraethylamamine and mixtures thereof. In particular, it is a group of three-extended ethyltetramine. "And the knife C is preferably composed of two kinds, three kinds or a mixture thereof. The epihalohydrin preferably comprises a surface gas alcohol and a surface gas alcohol. Preferably, the alcohol is epigas alcohol. ..._, the alcohol table W is preferably unsubstituted, especially using the structural formula Μ)
(IV) 在本發 混合。組 明組合物令，組分A)與組分B)可以任意比例彼此 乃C)與組分A)及B)的混合物之間的總莫耳比包含 138387.doc 201002760 在0.9至1.8之間，較佳在丨.0至丨.6之間。組分A)及B)較佳的 是彼此以任何相對比率使用。組分c與組分八及8之合併量 的莫耳比較佳在0.90至1.00與1.8〇至1〇〇之間，更佳在丨〇〇 至1.00與1.60至1.00之間。 多胺之混合物與表氯醇係在10_7〇重量％水與9〇_3〇重量 %多胺混合物，較佳為30_60%水與7〇_4〇%多胺混合物的溶 液中反應。 溶劑亦可為不同溶劑的混合物，或水與非水性溶劑之混 合物。使用的溶劑較佳為水。 組分Α與Β較佳係溶於溶劑中。 因此，本發明目的為可藉由所述製程得到的聚合物；本 發明另一目的為包含可藉由所述製程得到的聚合物與溶劑 的組合物。 組分A及組分B與組分C反應，該混合物較佳包含： 10至70重量％溶劑，及 90至30重量％組分A與B的合併量； 更佳包含 30至60重量％溶劑，及 70至40重量％組分A與B的合併量； 在所有情況下，重量％係基於組分A、B與溶劑合併量。 發現藉由將水量控制在此等限制之間，可限制藉由表氯 醇與水反應的1-氯-2,3-丙二醇形成。為促進表_醇與胺混 合物之反應，且為阻礙表齒醇與氣形成1，3-二惠。二— —丙酵之 反應，反應混合物中組分A、Β與C濃度應盡可能保持高 138387.doc 201002760 值。 縮合製程較佳僅在水溶液中且不存在任何有機溶劑下進 行。 反應混合物較佳亦不含任何其他齒代化合物（該表齒醇 除外）。較佳的是不使用任何其他鹵代化合物（該表鹵醇除 外）。 通常，反應時間係在約i至24小時之間變化，較佳為在3 至8小時之間。 組分A及B與C的聚合反應時間較佳在1至24 h之間，更 佳在3至8 h之間。 組分A、B與C的聚合反應期間，反應溫度較佳在溶劑沸 點以下，該溶劑沸點較佳係〇至1 〇〇。匸。 將表ΐ醇加入多胺的水性混合物中，使得在添加期間， 溫度小於或等於60。(：。溫度範圍較佳為約25°c至約6(rc。 溫度範圍最佳係約3 〇 °C至約5 0 。 使用30-50°C的反應溫度幫助防止氯離子與表氯醇反應 开> 成1,3-二氯-2-丙醇及表氣醇與水反應形成丨_氣_2,3_丙二 醇。不需要的反應副產物之含量可藉由將溫度降低至3〇。〇 以下而進一步減少’但隨後卻必須冷卻。另外，即使是較 低溫度使得可更充分地控制縮聚反應，但過低溫度可在系 統内累積危險之潛在反應性。 因反應為放熱性，表鹵醇係隨時間之經過緩慢添加於A) 與B)型多胺混合物中以使來自反應媒介的熱傳更有效。反 應媒介的熱傳可根據已知步驟完成，例如將反應器浸入冷 138387.doc 10- 201002760 康環境（例如冰水浴）中，或將冷凍蛇管通入反應器内。藉 此’反應期間的内部溫度保持在所需值。因此，因反應的 放熱性質’表氯醇的添加時間亦取決於批量大小。 較佳的是調節反應條件，以使基於3 0%多胺-表鹵醇縮聚 物的最終含量’產物+ 1,3_二氯_2_丙醇量小於1〇〇〇 ppm， 較佳小於500 ppm，更佳小於3〇〇 ppm，且產物中丨氣_23_ 丙一醇蓋小於5〇〇 ppm，較佳小於3〇〇 ppm，更佳小於1〇〇 ppm 〇 杈佳的是如上建議調節反應條件，以使組合物或聚合物 中1,3-二氯-2-丙醇量小於1〇〇〇 ppm，更佳小於5〇〇 ppm， 甚至更佳小於300 ppm，尤其小於1〇〇 ppm ;及/或如上建 議調整反應條件’以使組合物或聚合物中1-氯-2,3-丙二醇 菫】於5〇〇 Ppm，更佳小於300 ppm，甚至更佳小於1〇〇 ppm ° 在完全添加表_醇後’升高混合物溫度及/或加熱混合 物以達成父聯。交聯率係隨濃度、溫度、授拌、及表㈣ 至多胺混合物中的添加條件而變化。 以黏度立曰加而偵測到形成才封脂，#纟聚合反應形成聚合 物，且該反應繼續直至達到所需的黏度值，但在物質固化 為水不 >谷性樹脂前。撰+ u * — & &擇所需的黏度值以使最終產物基於 3 0重量％的總含固| 1 士 ^ * 里 〇 有 50-700 mPa s 之 Brookfield黏度 (ISO 2555:1989)。一舻二― 版而&，所需黏度為藉由Ubbelohde 黏度劑測量的至少相對勒# & , c 。 2了黏度值 1.5 (ISO 3 105:1994)，在該 黏度下停止加熱。 138387.doc 201002760 聚合反應隨後較佳為藉由無機或有機酸中和，即在聚合 反應後，在第二反應步驟中，拉士、兵上 > 水α 糟由添加無機或有機酸而中 和聚合物。 中和反應較佳的是利用選自由鹽豸、硫酸、墙酸、甲 酸、磷酸及乙酸之群的酸完成’更佳是使用甲酸。 較佳是使用酸的水性溶液進行中和。 添加酸、或以水稀釋、或兩者組合可將樹脂安定化，防 止進一步交聯而凝膠化。在ρΗ 4.0或更小下酸化可達到良 好之安线。it宜的酸包含鹽酸、硫酸、石肖酸、曱酸、填 酸及乙酸。較佳使用曱酸。在大於約3.5的阳下，物質開 始固化為水不溶性樹脂，但在小於約2.5的卩11下，物質開 始分解。 因此，藉由使最終pH在6.0以下，較佳5 〇以下，甚至更 佳4.0以下的酸量來進行中和。 本發明組合物之水溶性鹽可藉由在pH 4.0或 更小下酸化 而獲得。 最終水性組合物具有1 5至65重量％，較佳20至55重量 % ’尤佳25至45重量。/。之固體含量。 在由無機或有機酸中和後，組合物具有i 5至6 5重量％， 更佳20至55重量％，甚至更佳25至45重量％之固體含量， 重量％係基於組合物總重量。 且，多胺-表氣醇縮聚物之分子量係在約500至約 1，000,000之間，較佳在約2,500至約500,000之間，及更佳 在約5,000至約250,000道爾頓之間。 138387.doc 12· 201002760 陕速發生胺的烷基化，視反應條件而形成第二或第三 胺。表鹵醇與多胺之比率係為使40至1〇〇%有效胺氮位置 被=基化者。組分A)中存在的第三胺基之反應性在與第一 與第二胺基之反應性相比時可忽略。在本發明組合物中， 易於添加表鹵醇後存在游離胺基且其可由習用第四銨化劑 .進行第四銨化。可使用的第四銨化劑為硫酸二甲酯、硫酸 二乙酯、曱基-或乙基-齒化物，較佳使用硫酸二曱酯。 在水作爲溶劑的情況下，不需要最終陽離子縮聚物或組 合物之繁璃的純化製程（例如，有機溶劑的蒸餾）。此使得 本發明組合物與聚合反應產物及使其製造方法對生態之衝 擊極為有限。 本發明組合物與聚合物係作爲纖維素基材的染料固定 劑較佳的疋將染料固定於包含羥基的纖維素基材上，亦 使包含羥基之經染色纖維素基材固色。 如果用於固定鮮豔染料，本發明水性組合物之量較佳為 〇 木料固疋劑中活性物質與基材乾重的0.1-5重量％,更佳為 0.5-3重量 ％。 （' 通常，使用組合物的（^至㈣量％，更佳〇」至5重量 % ’甚至更佳0.1至4.0重量％，特別是〇 5至3重量％之聚合 物，重量％係基於纖維素基材的乾重。 用於染色的染料性質不重要。本發明之染料固^劑適於 固定反應性、直接或酸性染料形式的陰離子染料。基材較 佳係由鮮盤且尤其無金屬的染料染色及隨後由本發明製劑 固定。 338387.doc 13 201002760 本發明又一目的盏 ^ 的為―經固色的纖維素基材，其已經染色 奸七明聚合物或組合物處理。本發明進一步提供-種 ^色的基材’其為已經染色並隨後由本發明染料固定劑 =纖維素基材。在-較佳實施例中，經固色的基材已 由陰離子染料染色。較佳之基材為纖維素材料。 纖維素基材較佳為紙、板與不織布類。 本發明組合物可作爲染料的固定劑，較佳為纖維素物質 (車X it在...氏、板與非織物上）的陰離子染料。 由^固㈣處理可更有效地將染料保留於纖維或基材 t ’得到更高的給色量與更透明的回水。另，該染色的抗 ^出性強於未固定染色的彼等。料前技術的固定劑相 本發月固定劑的益處為染料具有更亮的色調（對染料 色調的較小影響)及更佳料光性(對此參 影響）。 九本’X明固疋劑’當在紙上施用日寺’亦有用於改善陰離子 :料之者色的兩面I，及當使用再循環原料時或當存在大 置填料或微粒時’改善陽離子直接染料之給色量。 由本發明固定劑處理基材時，該基材係由組合物或聚合 物水溶液、驗性縮聚物水溶液，或較佳由其與無機或錢 酸：鹽處理。取決於染料的選擇及其含量，縮聚物或其鹽 之置可在寬廣範圍内變化。通常，基於基材重量的〇1至 $% K圭〇‘5%至3 〇重量％之量可適宜得到所需的 果。 處理係經由將纖維浸入包含染料與鹼性縮聚產物或其鹽 I38387.doc -14- 201002760 與無機或有機酸的水性處理浴而進行。在板片形成後，經 染色及壓縮的板片在90°C下乾燥約1〇分鐘。 如果以本發明鹼性縮聚產物處理纖維’可在完成基材染 色刚或後幾分鐘添加固定劑進行處理，在繼續造紙製程 前，在室溫下攪拌該混合物一段短時間通常已足夠。 因此，本發明組合物、聚合物與縮聚產物作爲紙、薄織 物與板基材的染料固定劑。且，本發明亦關於一種纖維素 f·., 材料染色方法或一種紙染色方法，其包含在染色製程中， f 施用作爲添加劑的本發明組合物、聚合物或縮聚產物之步 驟。且，本發明亦關於一種在纖維乡^ ^ ^ ^ ^ (直接染料較佳）染色之預處理製程，其包含於纖維素= 材料上施用本發明組合物、聚合物或縮聚產物作為染料 (較佳係直接染料）染色之預處理的步驟，且本發明亦關於 一種將纖維素纖維材料上之染料（直接染料較佳）染色之固 定製纟包含&用本發明植合物、$合物或縮聚產物作 Ο 為在纖維素纖維材料上之染料（直接染料較佳）染色的固定 劑之步驟。 以下以實例闡述本發明。説明書與實例中所有％數據皆 -視為重量％(=% w/w) ’重量％係基於組合物重量，除另說 ，明，份均爲重量份。 實例 以一步製程製備樹脂，其中多胺與表_醇混合物在水性 媒介中反應直至達到所需的分子量。測量黏度。反應由水 稀釋及由添加的酸安定化在酸性pH。 138387.doc -15- 201002760 殘餘的表氯醇、1,3-二氯-2-丙醇與^氯。,％丙二醇之含 量係藉由氣相色譜法確定。 儀器：Agilent 6850 系列，具有 Agilent Chemstati〇n 及 Agilent 68S0系列自動取樣器；柱：ΗΙΜΝΝ〇λ^χ_Α_ηΐ Technologies-30 mx〇_32 mm;箱溫：起始溫度 9(rc，最終 溫度250°C，溫度上升率lot/min ;注射器溫度：2〇〇<t ; 柱流速：3.0 ml/min ;檢測器：火焰電離檢測器（fid);檢 測器溫度：300°C。 殘留之表氯醇、1，3-二氯-2-丙醇與1_氯_2,3_丙二醇在檢 測樣品中的含量係以外標法（三點校準）比較確定。表氯 醇、1，3-二氯-2-丙醇與丨-氯'%丙二醇之標準溶液係經將 0.1 g物質溶於1〇 ml乙酸乙酯㈠寺純乙酸乙酯，Fluka)中製 得。 樣品製備：將1 g樣品溶於丨g水中。將丨g所得溶液載於 Extrelut® NT1玻璃柱（Merck)上。1〇分鐘後，將樣品以5 ml乙酸乙酯洗提兩次及將燒瓶中收集的洗提液用於分析。 檢測極限約為20 ppm 實例1 在氮氣下，將116份胺乙基哌嗪與66份三乙烯四胺、182 份去離子水在配備有氮氣進口、溫度計與機械攪拌器的反 應燒瓶中混合。在2小時内，添加166份表氯醇，且藉由恆 溫槽保持溫度在5CTC。完全添加後，添加2〇〇份去離子水 及將混合物稀釋成含約48%固體，並在6〇t下加熱小 時，直至以Ubbelohde黏度儀測量的聚烷基胺之相對黏度 138387.doc • 16 - 201002760 為1.5為止。此時，添加水與曱酸以在30%固體含量（由烘 相蒸發）下達到pH 3.0及90 mPa s之Brookfield黏度。 殘留的表氯醇量：<20 ppm 殘留的1,3-二氯·2 -丙醇量：<20 ppm 殘留的1-氯·2,3 -丙二醇量：<20 ppm 實例2 將116份胺乙基哌嗪與27份乙二胺、160份去離子水在配 備有氮氣進口、溫度計與機械攪拌器的反應燒瓶中混合。 在2小時内，添加1 6 6份表氣醇，且藉由怪溫槽保持溫度 在50°C。完全添加後，添加1 80份去離子水及將混合物稀 釋成約含48%固體，在60°C下加熱6.5小時，直至以 Ubbelohde黏度儀測量的聚烷基胺之相對黏度為1.7為止。 此時’添加水與曱酸以在30%固體含量（由烘箱蒸發）下達 到 pH 3_5及 1〇〇 mPa s之Brookfield黏度。 殘留的表氯醇量：<20 ppm 殘留的1,3-二氣-2-丙醇量：<20 ppm 殘留的1-氯-2,3 -丙二醇量：<20 ppm 實例3 將116份胺乙基哌嗪與46份二乙稀三胺、160份去離子水 在配備有氮氣進口、溫度計與機械攪拌器的反應燒瓶中混 合。 在2小時内，添加166份表氯醇，且藉由恆溫槽保持溫度 在50°C。完全添加後，添加200份去離子水及將混合物稀 釋成含約48%固體，在60°C下加熱4.5小時，直至以 138387.doc 201002760(IV) Mixed in this issue. The composition of the composition, component A) and component B) can be in any ratio between each other, C) and the total molar ratio between the mixtures of components A) and B) comprises 138387.doc 201002760 between 0.9 and 1.8 Preferably, it is between 丨.0 and 丨.6. Preferably, components A) and B) are used in any relative ratio to each other. The molar amount of component c and the combined amounts of components 8 and 8 is preferably between 0.90 and 1.00 and 1.8 Torr to 1 Torr, more preferably between 1.00 and 1.00 and 1.00 to 1.00. The polyamine mixture is reacted with an epichlorohydrin solution in a mixture of 10-7 wt% water and 9 wt% wt% polyamine, preferably 30-60% water and 7 wt% tetraamine. The solvent may also be a mixture of different solvents or a mixture of water and a non-aqueous solvent. The solvent used is preferably water. The components Α and Β are preferably dissolved in a solvent. Accordingly, the present invention is directed to a polymer obtainable by the process; another object of the present invention is to include a composition of a polymer and a solvent obtainable by the process. Component A and component B are reacted with component C. The mixture preferably comprises: 10 to 70% by weight of solvent, and 90 to 30% by weight of the combined amount of component A and B; more preferably 30 to 60% by weight of solvent. And 70 to 40% by weight of the combined amounts of components A and B; in all cases, the weight % is based on the combined amount of components A, B and solvent. It was found that by controlling the amount of water between these limits, the formation of 1-chloro-2,3-propanediol which reacts with epichlorohydrin and water can be restricted. In order to promote the reaction between the epi-alcohol and the amine mixture, and to prevent the formation of 1,3-dioxol from the alcohol and gas. In the reaction of di-propanol, the concentrations of components A, Β and C in the reaction mixture should be kept as high as possible 138387.doc 201002760 value. The condensation process is preferably carried out only in an aqueous solution and in the absence of any organic solvent. The reaction mixture preferably also does not contain any other dentate compound (except for the dentate alcohol). It is preferred not to use any other halogenated compound (except for the epihalohydrin). Generally, the reaction time varies between about 1 and 24 hours, preferably between 3 and 8 hours. The polymerization time of the components A and B and C is preferably between 1 and 24 h, more preferably between 3 and 8 h. During the polymerization of components A, B and C, the reaction temperature is preferably below the boiling point of the solvent, and the boiling point of the solvent is preferably from 1 to 〇〇. Hey. Epiphenol is added to the aqueous mixture of polyamines such that during the addition, the temperature is less than or equal to 60. (: The temperature range is preferably from about 25 ° C to about 6 (rc. The temperature range is preferably from about 3 ° C to about 50. Using a reaction temperature of 30-50 ° C helps prevent chloride ions and epichlorohydrin The reaction is carried out into 1,3-dichloro-2-propanol and the surface alcohol reacts with water to form 丨_gas_2,3-propanediol. The content of unwanted reaction by-products can be lowered to 3 by the temperature. 〇 〇 〇 而 further reduces ' but then must be cooled. In addition, even lower temperatures allow more complete control of the polycondensation reaction, but too low temperature can accumulate dangerous potential reactivity in the system. Because the reaction is exothermic The epihalohydrin is slowly added over time to the mixture of A) and B) polyamines to make heat transfer from the reaction medium more efficient. The heat transfer of the reaction medium can be accomplished according to known procedures, such as immersing the reactor in a cold environment (e.g., an ice water bath) or passing a frozen coil into the reactor. The internal temperature during this reaction is maintained at the desired value. Therefore, the addition time of epichlorohydrin due to the exothermic nature of the reaction also depends on the batch size. It is preferred to adjust the reaction conditions such that the final content of the 30% polyamine-epihalohydrin polycondensate is less than 1 〇〇〇ppm, preferably less than the amount of the product + 1,3 -dichloro-2-propanol. 500 ppm, more preferably less than 3 〇〇 ppm, and the helium _23_ propanol cover in the product is less than 5 〇〇 ppm, preferably less than 3 〇〇 ppm, more preferably less than 1 〇〇 ppm. The reaction conditions are adjusted so that the amount of 1,3-dichloro-2-propanol in the composition or polymer is less than 1 〇〇〇 ppm, more preferably less than 5 〇〇 ppm, even more preferably less than 300 ppm, especially less than 1 〇. 〇ppm; and/or as suggested above to adjust the reaction conditions 'to make 1-chloro-2,3-propanediol oxime in the composition or polymer> at 5 〇〇 Ppm, more preferably less than 300 ppm, even more preferably less than 1 〇〇 Ppm ° After the table_alcohol is completely added, 'raise the temperature of the mixture and/or heat the mixture to reach the parent. The crosslinking rate varies depending on the concentration, temperature, mixing, and addition conditions in the mixture of the (iv) to polyamine. The formation of the grease was detected by the viscosity addition, and the polymerization was continued until the desired viscosity value was reached, but before the material solidified to water > Write + u * — &&& Select the desired viscosity value so that the final product is based on 30% by weight of the total solids | . The viscosity required is at least relative to the Ubbelohde viscosity measured by the Ubbelohde viscosity, c. 2 Viscosity value 1.5 (ISO 3 105:1994), at which the heating is stopped. 138387.doc 201002760 The polymerization reaction is then preferably neutralized by an inorganic or organic acid, that is, after the polymerization reaction, in the second reaction step, the water is removed by the addition of an inorganic or organic acid. And polymers. The neutralization reaction is preferably carried out using an acid selected from the group consisting of salt hydrazine, sulfuric acid, wall acid, formic acid, phosphoric acid and acetic acid. More preferably, formic acid is used. It is preferred to carry out neutralization using an aqueous solution of an acid. The addition of an acid, or dilution with water, or a combination of both can stabilize the resin to prevent further crosslinking and gelation. Acidification at ρΗ 4.0 or less can achieve a good safety line. Suitable acids include hydrochloric acid, sulfuric acid, tartaric acid, citric acid, acid and acetic acid. Preferably, citric acid is used. At a temperature greater than about 3.5, the material begins to solidify into a water insoluble resin, but at a crucible 11 of less than about 2.5, the material begins to decompose. Therefore, neutralization is carried out by setting the final pH to 6.0 or less, preferably 5 Å or less, or even more preferably 4.0 or less. The water-soluble salt of the composition of the present invention can be obtained by acidification at pH 4.0 or less. The final aqueous composition has from 15 to 65% by weight, preferably from 20 to 55% by weight, particularly preferably from 25 to 45 parts by weight. /. Solid content. After neutralization by an inorganic or organic acid, the composition has a solids content of from i5 to 65 wt%, more preferably from 20 to 55 wt%, even more preferably from 25 to 45 wt%, based on the total weight of the composition. Further, the polyamine-gas alcohol polycondensate has a molecular weight of from about 500 to about 1,000,000, preferably from about 2,500 to about 500,000, and more preferably from about 5,000 to about 250,000 daltons. 138387.doc 12· 201002760 The alkylation of amines occurs in the form of a second or third amine depending on the reaction conditions. The ratio of epihalohydrin to polyamine is such that 40 to 1% of the effective amine nitrogen position is =. The reactivity of the third amine group present in component A) is negligible when compared to the reactivity of the first and second amine groups. In the composition of the present invention, the free amine group is present after the easy addition of epihalohydrin and it can be subjected to the fourth ammoniumation by a conventional fourth ammonium amide. The fourth ammonating agent which can be used is dimethyl sulfate, diethyl sulfate, mercapto- or ethyl-dentate, and dinonyl sulfate is preferably used. In the case of water as a solvent, a purification process of the final cationic polycondensate or the glass of the composition (e.g., distillation of an organic solvent) is not required. This makes the ecological impact of the composition of the present invention and the polymerization reaction product and its manufacturing method extremely limited. Preferably, the composition of the present invention and the polymer are used as a dye fixing agent for a cellulose substrate. The dye is fixed to a cellulose substrate containing a hydroxyl group, and the dyed cellulose substrate containing a hydroxyl group is also fixed. If used to immobilize a bright dye, the amount of the aqueous composition of the present invention is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, based on the dry weight of the active material to the substrate in the wood solidifying agent. ('Generally, the use of the composition of (^ to (four) amount %, more preferably 5 to 5% by weight ' even more preferably 0.1 to 4.0% by weight, especially 〇 5 to 3% by weight of the polymer, the weight % is based on fiber Dry weight of the substrate. The nature of the dye used for dyeing is not critical. The dye fixing agent of the present invention is suitable for fixing an anionic dye in the form of a reactive, direct or acid dye. The substrate is preferably a fresh disk and especially metal free. The dye is dyed and subsequently fixed by the formulation of the invention. 338387.doc 13 201002760 A further object of the invention is a "fixed-colored cellulose substrate which has been treated with a dyed polymer or composition. Further A substrate is provided which is dyed and subsequently cured by the dye fixing agent of the present invention = cellulose substrate. In the preferred embodiment, the fixed substrate has been dyed with an anionic dye. It is a cellulosic material. The cellulosic substrate is preferably paper, board and non-woven fabric. The composition of the invention can be used as a fixing agent for dyes, preferably cellulosic material (car X it in ..., plate and non-woven fabric) Anionic dye The solid (4) treatment can more effectively retain the dye on the fiber or substrate t' to obtain a higher color yield and a more transparent backwater. In addition, the dyeing resistance is stronger than that of the unfixed dye. The benefits of the pre-formation fixative phase of the present fixative are that the dye has a brighter hue (a smaller effect on the hue of the dye) and a better photonability (for this effect). Nine Ben 'X Minggu Tincture 'When applying Japanese temple on paper' also has two sides I for improving the color of the anion: material, and 'improving the color yield of the cationic direct dye when using recycled raw materials or when large fillers or fine particles are present. When the substrate is treated with a fixative, the substrate is treated with a composition or an aqueous polymer solution, an aqueous solution of an anatizing polycondensate, or preferably with an inorganic or nicotinic acid: salt. Depending on the choice of dye and its content, the polycondensate The setting of the salt or the salt thereof can be varied within a wide range. Generally, the amount of 〇1 to $% K 〇 5% to 3% by weight based on the weight of the substrate can be suitably obtained to obtain the desired fruit. Immersion containing dyes and basic polycondensation products or their salts I38 387.doc -14- 201002760 is carried out with an aqueous treatment bath of an inorganic or organic acid. After the sheet is formed, the dyed and compressed sheet is dried at 90 ° C for about 1 minute. If it is alkaline polycondensation according to the invention The product-treated fiber 'can be treated with a fixative just a few minutes after the completion of the dyeing of the substrate, and it is usually sufficient to stir the mixture at room temperature for a short period of time before continuing the papermaking process. Thus, the composition, polymer of the present invention And a polycondensation product as a dye fixing agent for paper, tissue and board substrates. Moreover, the invention also relates to a cellulose f·., a material dyeing method or a paper dyeing method, which is included in the dyeing process, f is applied as an additive The step of the composition, polymer or polycondensation product of the present invention. Moreover, the present invention also relates to a pretreatment process for dyeing in a fiber village, which is preferably applied to cellulose = material. The composition, polymer or polycondensation product of the invention is used as a pretreatment step for dyeing dyes, preferably direct dyes, and the invention also relates to a cellulose fiber material The fixed material (the direct dye is preferably dyed) is fixed and contains the planting agent, the compound or the polycondensation product of the present invention as a fixing agent for dyeing the dye on the cellulose fiber material (preferably the direct dye). step. The invention is illustrated by the following examples. All % data in the specification and examples are considered to be % by weight (=% w/w). 重量% is based on the weight of the composition, and unless otherwise stated, parts are parts by weight. EXAMPLES A resin was prepared in a one-step process in which a polyamine was reacted with a surface alcohol mixture in an aqueous medium until the desired molecular weight was achieved. Measure the viscosity. The reaction is diluted with water and stabilized at the acidic pH by the added acid. 138387.doc -15- 201002760 Residual epichlorohydrin, 1,3-dichloro-2-propanol and chlorine. The content of % propylene glycol was determined by gas chromatography. Instrument: Agilent 6850 series with Agilent Chemstati〇n and Agilent 68S0 series autosampler; column: ΗΙΜΝΝ〇λ^χ_Α_ηΐ Technologies-30 mx〇_32 mm; chamber temperature: starting temperature 9 (rc, final temperature 250 ° C Temperature rise rate lot/min; injector temperature: 2 〇〇 <t; column flow rate: 3.0 ml/min; detector: flame ionization detector (fid); detector temperature: 300 ° C. Residual epichlorohydrin The content of 1,3-dichloro-2-propanol and 1-chloro-2-propanediol in the test sample is determined by external standard method (three-point calibration). Epichlorohydrin, 1,3-dichloro A standard solution of 2-propanol and hydrazine-chloro'% propylene glycol was prepared by dissolving 0.1 g of the substance in 1 ml of ethyl acetate (I), pure ethyl acetate, Fluka). Sample preparation: 1 g of sample was dissolved in 丨g water. The solution obtained from 丨g was placed on an Extrelut® NT1 glass column (Merck). After 1 minute, the sample was eluted twice with 5 ml of ethyl acetate and the eluate collected in the flask was used for analysis. The detection limit was approximately 20 ppm. Example 1 Under nitrogen, 116 parts of amine ethylpiperazine was mixed with 66 parts of triethylenetetramine, 182 parts of deionized water in a reaction flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer. Within 2 hours, 166 parts of epichlorohydrin were added and the temperature was maintained at 5 CTC by means of a constant temperature bath. After complete addition, add 2 parts of deionized water and dilute the mixture to about 48% solids and heat at 6 Torr until the relative viscosity of the polyalkylamine measured by Ubbelohde viscometer 138387.doc • 16 - 201002760 is 1.5. At this time, water and citric acid were added to achieve a Brookfield viscosity of pH 3.0 and 90 mPa s at a solid content of 30% (evaporated by the drying phase). Residual amount of epichlorohydrin: <20 ppm Residual amount of 1,3-dichloro-2-propanol: <20 ppm Residual amount of 1-chloro-2,3-propanediol: <20 ppm Example 2 116 parts of amine ethylpiperazine were mixed with 27 parts of ethylenediamine and 160 parts of deionized water in a reaction flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer. Within 6 hours, 166 parts of surface gas alcohol were added and the temperature was maintained at 50 ° C by means of a strange temperature bath. After complete addition, 180 parts of deionized water was added and the mixture was diluted to about 48% solids and heated at 60 ° C for 6.5 hours until the relative viscosity of the polyalkylamine measured by a Ubbelohde viscometer was 1.7. At this time, water and citric acid were added to achieve a Brookfield viscosity of pH 3_5 and 1 〇〇 mPa s at a solid content of 30% (evaporated by an oven). Residual amount of epichlorohydrin: <20 ppm Residual amount of 1,3-dialdehyde-2-propanol: <20 ppm Residual amount of 1-chloro-2,3-propanediol: <20 ppm Example 3 116 parts of amine ethylpiperazine were mixed with 46 parts of diethylenetriamine, 160 parts of deionized water in a reaction flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer. Within 2 hours, 166 parts of epichlorohydrin were added and the temperature was maintained at 50 ° C by means of a thermostat. After complete addition, 200 parts of deionized water was added and the mixture was diluted to contain about 48% solids and heated at 60 ° C for 4.5 hours until 138387.doc 201002760
Ubbelohde黏度儀測量的聚烷基胺之相對黏度為1.5為止。 此時，添加水與甲酸以在2 8 %固體含量（由供箱蒸發）下達 到 pH 3.0及 80 mPa*s之Brookfield黏度。 殘留的表氯醇量：<2〇 ppm 殘留的1,3-二氯-2-丙醇量：<20 ppm 殘留的1-氯-2,3-丙二醇量：<20 ppm 實例4 將11 6份胺乙基哌嗪與85份四乙烯五胺、1 60份去離子水 在配備有氮氣進口、溫度計與機械攪拌器的反應燒瓶中混 合。 在2小時内’添加1 66份表氣醇’且藉由恆溫槽保持溫度 在50°C。完全添加後，添加1 80份去離子水及將混合物稀 釋成含約48%固體’在60°C下加熱4.5小時，直至以 Ubbelohde黏度儀測量的聚烷基胺之相對黏度為丨6為止。 此時’添加水與甲酸以在30%固體含量（由烘箱蒸發）下達 到 pH 3.0 及 1〇〇 mPa*s 之 Brookfield黏度。 殘留的表氯醇量：<20 ppm 殘留的1，3 -二氯-2-丙醇量：<20 ppm 歹成留的1-氣-2,3 -丙二醇量：<20 ppm 實例5 將116份胺乙基哌嗪、38份四乙烯五胺與15份乙二胺、 170份去離子水在配備有氮氣進口、溫度計與機械攪拌器 的反應燒瓶中混合。 在2小時内，添加166份表氯醇，且藉由恆溫槽保持溫度 138387.doc -18- 201002760 在50°C。完全添加後，添加1 60份去離子水及將混合物稀 釋成含約48%固體，在60°C下加熱5小時，直至以 Ubbelohde黏度儀測量的聚烷基胺之相對黏度為u-a.o為 止。此時，添加水與曱酸以在30%固體含量（由烘箱蒸發） 下達到 pH 3.0及 280 mPa s之 Brookfield黏度。 殘留的表氣醉量：<20 ppm * 殘留的1，3 -二氣-2-丙醇量·· <20 ppm 殘留的1-氣-2,3 -丙二醇量：<20 ppm x 應用實例 將含50%漂白的軟木、5〇。/0漂白的硬木之配料（紙纖維的 紙料懸浮液）以2.5%稠度與20度Schopper-Riegler游離度製 得（ISO 5267/1)。 在持續攪拌下’將表中給出的常用陰離子染料溶液以根 據所需的最終濃度之含量加入該纖維懸浮液中，例如1/2 標準濃度。5分鐘後，添加實例丨的固定劑。添加量取決於 {J 就抗滲出性、給色量與回水透明度而言所需的最終結果。 另攪拌幾分鐘後，利用一般方法，在利用手動模具之情況 下，由染色的纖維懸浮液製得紙片，但機械的紙片成形器 • 同樣佳（IS〇 5269/1 或 ISO 5269/2)。 ， 然後，將紙片置於濾紙上及在毛氈間以10噸/m2的壓力 壓細幾分鐘。移除紙及在平床乾燥器中於90。〇下乾燥10分 鐘。收集染色的回水且與未固定染色的回水比較。將所有 染色紙與未施用任何固定劑的染色紙比較。將紙色調及深 又…i由相同杂料及二甲胺與表氯醇（Cladant〗nt⑽ati〇nai 138387.doc -19- 201002760 有限公司的Cartafix F liq.)的縮合所被 叮後仔的常用固定劑製 備的另一紙片比較。發現由新縮聚 φ ^ 吻製付的紙片顏色明顯 更焭且耐光性更佳。相較於未固定 的木色’抗滲出性被改 良且回水比未固定的染色更清澈。 測量上述參數的常用方法列舉於下· 回水率 ISO 105-Α04The relative viscosity of the polyalkylamine measured by the Ubbelohde viscometer is 1.5. At this point, water and formic acid were added to achieve a Brookfield viscosity of pH 3.0 and 80 mPa*s at a solids content of 28% solids (evaporated from the tank). Residual amount of epichlorohydrin: < 2 〇 ppm Residual amount of 1,3-dichloro-2-propanol: < 20 ppm Residual amount of 1-chloro-2,3-propanediol: <20 ppm Example 4 Eleven 6 parts of amine ethylpiperazine were mixed with 85 parts of tetraethylenepentamine, 160 parts of deionized water in a reaction flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer. 1 66 parts of surface gas alcohol was added in 2 hours and the temperature was maintained at 50 ° C by a constant temperature bath. After complete addition, 180 parts of deionized water was added and the mixture was diluted to contain about 48% solids' heated at 60 °C for 4.5 hours until the relative viscosity of the polyalkylamine measured by a Ubbelohde viscometer was 丨6. At this time, water and formic acid were added to reach a Brookfield viscosity of pH 3.0 and 1 〇〇 mPa*s at a solid content of 30% (evaporated by an oven). Residual amount of epichlorohydrin: <20 ppm Residual amount of 1,3 -dichloro-2-propanol: <20 ppm amount of 1-gas-2,3-propanediol remaining in 歹: <20 ppm Example 5 116 parts of amine ethylpiperazine, 38 parts of tetraethylenepentamine and 15 parts of ethylenediamine, 170 parts of deionized water were mixed in a reaction flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer. Within 2 hours, 166 parts of epichlorohydrin were added and the temperature was maintained by a thermostat 138387.doc -18-201002760 at 50 °C. After complete addition, 1 60 parts of deionized water was added and the mixture was diluted to contain about 48% solids and heated at 60 ° C for 5 hours until the relative viscosity of the polyalkylamine measured by Ubbelohde viscometer was ua. . At this point, water and citric acid were added to achieve Brookfield viscosity at pH 3.0 and 280 mPa s at 30% solids (evaporated by oven). Residual surface gas intoxication: <20 ppm * Residual 1,3 - di-Ga-2-propanol amount ·· <20 ppm Residual 1-gas-2,3-propanediol amount: <20 ppm x The application example will contain 50% bleached cork, 5 〇. The /0 bleached hardwood furnish (paper stock suspension of paper fibers) was prepared with a 2.5% consistency and a 20 degree Schopper-Riegler freeness (ISO 5267/1). The usual anionic dye solution given in the table is added to the fiber suspension at a final concentration according to the desired concentration under continuous agitation, for example, a 1/2 standard concentration. After 5 minutes, the fixative of the example hydrazine was added. The amount added depends on the final result required for {J in terms of anti-bleeding, color yield and backwater transparency. After stirring for a few more minutes, the paper was made from the dyed fiber suspension using a conventional method, but a mechanical paper former was equally good (IS〇 5269/1 or ISO 5269/2). Then, the paper was placed on a filter paper and pressed under a pressure of 10 tons/m 2 for a few minutes between the felts. Remove the paper and at 90 in a flat bed dryer. Dry under the arm for 10 minutes. The stained backwater was collected and compared to the unfixed stained backwater. All dyed papers were compared to dyed paper without any fixative. The color and depth of the paper are...by the same miscellaneous materials and the condensation of dimethylamine with epichlorohydrin (Cladant nt(10)ati〇nai 138387.doc -19-201002760 Ltd. Cartafix F liq.) Another paper prepared by the agent was compared. It was found that the paper made by the new polycondensation φ ^ kiss was significantly more opaque and lightfast. The anti-bleeding property was improved compared to the unfixed wood color and the back water was clearer than the unfixed dyeing. Common methods for measuring the above parameters are listed below. Backwater ratio ISO 105-Α04
回水率： 5.00 =最佳括 (灰度） 100=最差性能 而才光性ISO 1 05-B02 耐光等級： 8.00 =最佳性能 (藍色羊毛標度）1.〇〇 =最差性能 色差’即色調、亮度與染色強度·· BS 6923 : 1988 直接紫035 固定劑 色調 亮度 回水 色強度— 100% 無 0.0 0.0 1.00 實例1 1.0較紅 0.2較暗 4.50 ~~ 108% 實例2 1.6較紅 0.3較暗 4.50 ~ 實例3 ~ ~~ 1.7較紅 0.7較暗 4.50 實例4 1.5較紅 0.5較暗 4.50 ' —-------- 實例5 3.3較紅 0.7較暗 4.50 ----- Cartafix F liq. - , 5.9較紅 4.3較暗 4.50 T〇6%~~ ' 直接黃168 1 ---一 | 固定劑 色調 亮度 回水 耐光~~Ί 無 0.0 0.0 2.00 實例1 1.4較紅 0.5較暗 4.50 Ί Cartafix F liq. 3.5較紅 〇_7較暗 4.50 Tio 138387.doc •20· 201002760 直接黃157 固定劑 色調 亮度 回水 耐光性. 益 0.0 0.0 1.00 4.00 實例1 1.2較紅 0.6較亮 4.50 3.50 Cartafix F liq. 2.4較紅 0.9較亮 4.50 2.50 直接黃137 固定劑 色調 亮度 回水 耐光性 無 0.0 0.0 1.00 3.50 實例1 2.3較紅 1.0較亮 4.50 1.00 Cartafix F liq. 13·3較紅 2.6較暗 4.50 1.00 直接黃147 固定劑 色調 亮度 财光性 無 0.0 0.0 4.50 實例1 2.0較紅 1.2較暗 2.50 Cartafix F liq. 8.2較紅 2.3較暗 1.50 由根據實例2至5之產品得到類似的結果。測試每個實例 2、3、4與 5。 138387.doc -21 -Water return rate: 5.00 = best bracket (grayscale) 100 = worst performance and light ISO 1 05-B02 Lightfastness rating: 8.00 = best performance (blue wool scale) 1. 〇〇 = worst performance Chromatic aberration' ie hue, brightness and dyeing intensity·· BS 6923 : 1988 Direct Violet 035 Fixing agent Tone brightness Back to water intensity — 100% None 0.0 0.0 1.00 Example 1 1.0 Redder 0.2 Darker 4.50 ~~ 108% Example 2 1.6 Red 0.3 is darker 4.50 ~ Example 3 ~ ~~ 1.7 is redder 0.7 is darker 4.50 Example 4 1.5 is redder 0.5 is darker 4.50 ' —-------- Example 5 3.3 is redder 0.7 is darker 4.50 ----- Cartafix F liq. - , 5.9 is redder 4.3 is darker 4.50 T〇6%~~ ' Direct yellow 168 1 --- one | Fixing agent tone brightness back water resistant light ~~Ί No 0.0 0.0 2.00 Example 1 1.4 Redder 0.5 Dark 4.50 Ί Cartafix F liq. 3.5 is more red 〇7 darker 4.50 Tio 138387.doc •20· 201002760 Direct yellow 157 fixer tone brightness back water resistance. Benefit 0.0 0.0 1.00 4.00 Example 1 1.2 Redder 0.6 Brighter 4.50 3.50 Cartafix F liq. 2.4 brighter red 0.9 brighter 4.50 2.50 direct yellow 137 fixative tone brightness back water resistance no zero. 0 0.0 1.00 3.50 Example 1 2.3 Redder 1.0 Brighter 4.50 1.00 Cartafix F liq. 13·3 Redder 2.6 Darker 4.50 1.00 Direct Yellow 147 Fixing agent Hue Brightness No photo 0.0 0.0 4.50 Example 1 2.0 is darker than 1.2 2.50 Cartafix F liq. 8.2 is redder 2. Darker 1.50 Similar results were obtained from the products according to Examples 2 to 5. Test each instance 2, 3, 4, and 5. 138387.doc -21 -