200530461 (1) 九、發明說明 【發明所屬之技術領域】 · 本發明爲關於纖維用濃色化劑及使用其之纖維製品的 -濃色化法。更詳言之，本發明爲關於含有酸性條件下經具 有胺基之矽烷偶合劑處理之矽石微粒子和聚醚改質聚矽氧 烷的濃色化劑，及使用其染色之纖維製品的濃色化法。本 發明之纖維用濃色化劑爲提供染料固黏性優良，且改善染 色物的帶深色、吸水性優良。且不會損害此染色物本來的 g 洗滌堅年度、水堅牢度等的染色纖維加工物。 【先前技術】 關於經染色纖維製品的濃色化方法，已於20年以前 被提案，且至目前已提案各種濃色化劑、濃色化方法，並 且亦具有已實用化的技術。經染色之纖維製品的濃色化技 術爲對經染色的纖維表面賦予微細的凹凸，且以光的反射 、折射等改善顏色的帶深色，賦予凹凸之藥劑已提案矽石 φ 微粒子 '胺基甲酸酯系樹脂乳化劑、丙烯酸系樹脂乳化劑 等。 矽石微粒子系之濃色化劑爲記載於例如專利文獻1、 專利文獻2、專利文獻3、專利文獻4、專利文獻5等，但 如其中之專利文獻1所記載般，矽石微粒子系之濃色化劑 基本上爲由含有矽石微粒子的水性懸浮液所構成。專利文 獻6中，提案將矽石微粒子的懸浮液以具有胺基的矽烷偶 合劑處理，於纖維上附著後再予以低溫電漿處理使用的濃 -5- 200530461 (2) 色化劑，但此濃色化劑爲以使用於聚酯纖維爲目的，於應 用在纖維素纖維的情形中則引起吸水性的降低。更且，專 利文獻7及專利文獻8所記載之濃色化劑，爲對於預先經 環氧化合物處理之聚酯纖維所用的濃色化劑，爲以具有胺 基之矽烷偶合劑處理之矽石微粒子所構成的濃色化劑。但 是，將此濃色化劑應用於纖維素纖維之情形中，則無法期 待確保充分的吸水性。更且，專利文獻9中，提案由矽石 微粒子和聚矽氧烷化合物所構成的濃色化劑，但此濃色化 劑爲被應用於聚酯纖維及羊毛，但關於對於重視吸水性之 纖維素纖維的應用則無任何記載。 更且，於專利文獻1 0中，提案不僅於聚酯纖維，且 於聚醯胺、丙烯酸、人造絲等之合成纖維或再生纖維亦可 應用的濃色化劑：樹脂乳化劑。但是，此樹脂乳化劑由樹 脂的構造上而言並無法期待賦予充分的吸水性，又，以濃 色化劑處理時之處理浴安定性有問題，難應用浸漬處理法 等之簡單的處理法 如上述’先前所提案的濃色化劑爲以聚酯纖維等斥水 性纖維用爲主體，因此於羊毛、纖維素纖維等之較具親水 性的纖維染色物中若進行濃色化處理，則對纖維造成濃色 效果且同時賦予撥水性，多損害親水性或吸水性。 如此’迄今並未發現應用斥水性纖維及親水性纖維兩 者且賦予充分效果的濃色化劑。 [專利文獻1 ]特開昭5 6 - 1 1 2 5 8 3號公報 [專利文獻2 ]特開平2 - 2 5 9 1 6 0號公報 -6- 200530461 (3) [專利文獻3]特開平3 -2 69 1 7 1號公報 [專利文獻4]特開平4-2 1 4482號公報 [專利文獻5]特開平9-2 5 6280號公報 [專利文獻6]特開昭5 6- 1 1 2 5 8 3號公報 [專利文獻7 ]特開平2 - 2 5 9 1 6 0號公報 [專利文獻8]特開平3 -269 1 7 1號公報 [專利文獻9]特開平3 -42 1 44 82號公報 [專利文獻10]特開平9-2 5 62 8 0號公報 [專利文獻11]特開平9-3 774號公報 【發明內容】 [發明之揭示] (發明所欲解決之課題） 本發明之課題爲在於開發出濃色化處理中之安定性優 良，且對於經染色加工之纖維製品、濃色效果優良，且同 時於濃色化處理所得之纖維製品中的吸水性優良，且重複 洗滌耐性優良的濃色化劑，以及使用此類纖維用濃色化劑 經染色加工的纖維製品予以濃色化的方法。 (解決課題之手段） 本發明者等人爲了解決上述課題致力硏究，結果發現 於酸性條件下’將具有胺基之矽烷偶合劑所處理的矽石微 粒子懸浮液與聚醚改質聚矽氧烷混合所得之混合物，可提 供濃色效果優良且同時吸水性’重複洗滌耐性優良的纖維 200530461 (4) 製品’以及此混合物爲於濃色化處理中的安定性優良，並 且達到完成本發明。 即，本發明爲關於 (1 ) 一種纖維用濃色化劑，其特徵爲含有於酸性條 件下以具有胺基之矽烷偶合劑處理的矽石微粒子與聚醚改 質矽氧烷； (2 )如（1 )記載之纖維用濃色化劑，其中聚醚改質 聚矽氧烷的含量爲相對於矽石微粒子以5〜2 0重量％ ; (3 )如（1 )或（2 )記載之纖維用濃色化劑，其爲 令矽石微粒子之懸浮液於酸性條件下，以具有胺基之矽烷 偶合劑處理，其次混合聚醚改質聚矽氧烷則可取得； (4 ) 一種經染色加工之纖維的濃色化方法，其特徵 爲令經染色加工之纖維，以上述（1 )至（3 )中任一項記 載之纖維用濃色化劑予以處理； (5 )如（4 )記載之纖維的濃色化方法，其中經染色 加工的纖維爲纖維素纖維； (6 )如（4 )記載之纖維的濃色化方法，其中經染色 加工的纖維爲聚酯纖維； (7 ) —種纖維染色加工物，其特徵爲根據如上述（4 )至（6 )中任一項記載之濃色化方法則可取得。 (發明之效果） 經由以本發明之濃色化劑，處理經染色的纖維製品， 則可取得濃色性、吸水性、耐洗滌堅牢度等優良的纖維染 -8- 200530461 (5) 色加工物。不僅對於已被廣泛實施濃色化處理的聚酯纖維 ，且對於先前困難之經染色的木棉、人造絲等之纖維素纖 維，亦可繼續保持吸水性且取得濃色化之效果。特別，應 用於禮服等之染色成濃黑色之染色物時的效果極大。本發 明之濃色化劑爲對於聚酯纖維爲首之斥水性纖維和木棉、 人造絲、羊毛等之親水性纖維的混紡纖維製品，提供親水 性、斥水性之兩纖維高的濃色化並且同時提高此些纖維所 具有之吸水性的效果。 如此，本發明之濃色化劑爲以提供附加價値極高之纖 維製品之染色物的理由而言，於染色加工產業中爲極高價 値的發明。 (實施發明之最佳形態） 本發明之濃色化劑爲含有於酸性條件下以具有胺基之 矽烷偶合劑處理的矽石微粒子和聚醚改質聚矽氧烷，較佳 ，令矽石微粒子之懸浮液於酸性條件下，以具有胺基之矽 烷偶合劑處理，其次混合聚醚改質矽氧烷則可取得。 於本發明中，於酸性條件下以具有胺基之矽烷偶合劑 處理所用之矽石微粒子，其粒徑通常爲使用30〜85 nm者， 且可使用已以懸浮液形態販售者。懸浮液之介質以水爲佳 〇 具有胺基之矽烷偶合劑可使用α -胺丙基三乙氧基矽 烷、Ν -(胺醚基）-胺丙基三甲氧基矽烷等一般販售的矽 烷偶合劑（例如，ΚΒΕ903 (信越化學（股）製）。 200530461 (6) 於酸性條件下以具有胺基之矽烷偶合劑處理時’相對 於矽石微粒子之具有胺基之矽烷偶合劑的使用比例通常爲 5〜2 0重量％，具有胺基之矽烷偶合劑的使用比例若少於此 範圍，則所得濃色化劑的耐洗滌堅牢度降低’相反地’使 用比例若大於此範圍則恐令濃色化劑的安定性降低。 將矽石微粒子，以具有胺基之矽烷偶合劑於酸性條件 下處理時，所使用之酸性物質可列舉無機酸、有機酸、較 佳爲甲酸、醋酸、乙醇酸、琥珀酸、順丁烯二酸等之一價 或二價之有機酸。於酸性條件下處理時之pH若爲6以下 即可，特別若爲pH3〜5則濃色化劑之經時安定性提高，故 爲佳。於酸性條件下處理時矽石微粒子懸浮液中之矽石微 粒子濃度通常爲5〜20重量％。濃度若低於此範圍則處理時 間變長，濃度若高於此範圍則恐溶液的安定性降低。矽石 微粒子於酸性條件下以具有胺基之矽烷偶合劑處理時的各 藥劑混合順序並無特別限制，但以在如前述酸性條件所調 製之矽石微粒子懸浮液中，加入矽烷偶合劑之水性懸浮液 或醇溶液爲佳。如此混合後，通常以5〜3 0 °C ，較佳爲 15〜2 5 °C混合，且較佳爲熟化至安定化爲止爲佳。 其次’本發明所用之聚醚改質聚矽氧烷爲於含有矽烷 基之聚矽氧烷中，附加烯丙醇的環氧乙烷、環氧丙烷、或 彼等之無規或分段共聚物所構成的聚醚。可使用一般已販 售者（例如，SII 190，東雷Dowcorning (股）製）。 經由混合具有親水性之聚醚改質聚矽氧烷，則可大幅 提高所得濃色化劑的吸水性，且重複洗滌耐性優良。聚醚 -10- 200530461 (7) 改質聚矽氧烷的使用比例爲相對於該處理後之矽石微粒子 通常以3〜30重量％，5〜20重量。/〇爲佳。 對於酸性條件下以具有胺基之矽烷偶合劑處理之矽石 微粒子的懸浮液，將聚醚改質聚矽氧烷混合的方法並無特 別限定，但爲了取得更均勻的分散狀態，將聚醚改質聚矽 氧烷溶解於醇等中予以混合爲佳。 於本發明中，視需要將界面活性劑、柔軟劑等本身公 知的添加劑於調製本發明之濃色化劑時，或者於處理經本 發明之濃色化劑所染色之纖維製品的浴中添加亦可。 其次，說明關於使用本發明之濃色化劑所染色之纖維 製品的濃色化處理法。 適於應用本發明之濃色化劑染色之纖維製品中的纖維 可列舉木棉、麻、銅氨纖維（人造絲）、黏膠人造絲、波 里諾西克（polynosic)纖維等之天然或再生的纖維素纖維 、羊毛、絹等之蛋白質纖維、醋酸纖維等之半合成纖維、 聚酯纖維（包含CDP纖維（陽離子可染性聚酯纖維）） 聚丙烯腈纖維、尼龍等之聚醯胺纖維等之合成纖維等及此 些纖維之二種以上纖維所構成的混紡纖維。其中較佳之纖 維爲纖維素纖維、聚酯纖維、蛋白質纖維、聚醯胺醯胺、 及此些纖維與其他纖維的混紡纖維。 經染色之纖維製品的形狀可爲織物、編物、纖維狀等 任何形態均可。 本發明之濃色化法可根據軋染處理法、浸瀆法等之通 常方法進行。 -11 - 200530461 (8) 以軋染處理法的濃色化法爲於濃色化劑30〜70重量份 中加水製作全量1 〇〇〇重量份左右的軋染浴，並於此軋染 浴中將前述經染色之纖維製品予以浸染後，以軋液機以擰 濟率約80重量％予以擰擠，且擰擠布通常以90〜；not乾 燥約3分鐘後，通常以130〜17(rc進行乾熱處理卜3分鐘 爲佳。 以浸漬法的濃色化方法爲相對於該經染色之纖維製品 100重量份，本發明之濃色化劑通常爲使用2〜20重量份、 較佳爲5〜10重量份，且以水做爲介質，通常以3〇〜7〇°c 通常處理10〜60分鐘即可。浴比通常爲調整至1: 20〜50 〇 於本發明之濃色化法中，相對於本發明之濃色化劑施 以染色之纖維製品1 0 〇重量份，濃色化劑以賦予0.5〜9 0 重量份、較佳爲5〜30重量份、更佳爲3〜6重量份處理爲 佳。賦予量爲經由測定實施濃色化法前和後之各乾燥重量 而決定。 經染色之前述纖維製品爲根據本身公知的染色方法將 前述纖維製品予以染色則可調製，以下例示性敘述關於取 得經染色之纖維素纖維及聚酯纖維。 纖維素纖維的染色方法，可根據以反應染料之染色方 法’直接以染料之染色方法等之公知方法進行。以反應染 料之染色方法中，於染色步驟終了後，水洗、熱水洗後， 以含有市售的皂洗劑通常0. 1〜5克/升的皂洗浴進行洗淨即 可。以反應染料之染色方法例如於木棉等之纖維素纖維的 -12· 200530461 (9) 染色中，於染浴中加入反應染料，且將公知的無機中性鹽 ，例如，無水芒硝、食鹽等與酸結合劑，例如，碳酸鈉、 重碳酸鈉、苛性鹼、第三磷酸鈉等單獨或倂用進行染色。 經染色的聚酯纖維製品爲例如經由將聚酯纖維布帛， 於調整至PH4.5之含有分散染料的水性介質中浸漬，且於 加壓下進行13〇°C，60分鐘染色則可取得。染色終了後， 水洗、熱水洗後，於含有亞硫酸氫鹽2克/升和苛性蘇打2 克/升之鹼還原浴中以約8 0 °C進行洗淨，令染色步驟終了 。經染色之陽離子可染型聚酯纖維製品爲將陽離子可染型 聚酯纖維等，在調整至pH4.5之含有指定量陽離子染料的 水性介質中浸漬，且於加壓下進行1 20°C，3 0分鐘染色。 本發明之濃色化劑爲對於經染色加工的纖維，顯示高 的濃色化效果，且對於斥水性纖維賦予高吸水性且同時對 於纖維素纖維等之較親水性的纖維具有不損害吸水性的特 微’更且不會損害所得染色加工物中所使用之各染料固有 的耐光性、洗滌性、水堅牢度、摩擦堅牢度並爲良好。 【實施方式】 以下，根據實施例、參考例及試驗例更加詳細說明本 發明’但本發明不被限定於此。實施例中之％及份爲重量 基準。 參考例1 試驗布之製作 -13- 200530461 (10) 於1克反應染料（C.I.Reactive Black 5 )、無水芒硝 1 6份、水1 8 0份所調製之染浴中投入纖維素纖維（木棉） 纖維1 〇份，並升溫至60，以此溫度下維持1 0分鐘後，加 入20 %蘇打灰溶液20份，進行60分鐘染色，其後，將所 得之染布水洗並進行2 0分鐘煮沸皂浴、水洗、乾燥取得 木棉染色物之試驗布。 實施例1 濃色化劑之調製及經染色之纖維素纖維製品的濃色化 處理 於粒徑4 0〜5 0 n m之矽石微粒子的2 0 %水懸浮液中，加 入甲酸及r -胺丙基三乙氧基矽烷之水溶液並於PH4之酸 性條件下以 25 °C處理後，混合聚醚改質聚矽氧烷（SII 190東雷- Dowcorning Silicone (股）製），取得本發明之 濃色化劑。此濃色化劑爲具有20%矽石微粒子水懸浮液 41%、甲酸 1.9%、7 -胺丙基三乙氧基矽烷 0.6%、聚醚改 質聚矽氧烷1.5%及水55.0%的組成。 於此濃色化劑5 0份中加水製作全量1 0 0 0份的軋染浴 。於此軋染浴中將前述所得之經染色的參考例1試驗布予 以乳染後，並以軋液機以擰擠率80%予以擰擠。將擰擠之 布以100 °C乾燥3分鐘後，以150t進行乾熱處理3分鐘 ，取得經濃色化處理的染色纖維素纖維製品。 實施例2 -14- (11) 200530461 經染色之纖維素纖維製品以浸染處理法的濃 於實施例1所得之濃色化劑1 〇份中加水9 0 理浴，於其中投入參考例1之試驗布；! 〇 〇份，並 行3 0分鐘處理’取得經濃色化處理的染色纖維 品。 比較例1 使用 Sunotec OL (臼產化學公司製）40份伯 微粒子、KBE903 (信越化學工業公司製）0.8份伯 胺基的矽烷偶合劑，並以甲酸調整至p Η 4處理矽Ϊ ’取得不含有聚醚改質聚砂氧院之比較用的濃色化 使用此濃色化劑’同實施例1處理並以軋染g 行濃色化處理’取得經濃色化處理之比較用的纖翻 製品。 比較例2 除了使用比較例1所製作之比較用的濃色化 同實施例2處理並以浸染處理法進行濃色化處理 較用之纖維素纖維製品。 比較例3 使用 Sunotec OL (日產化學公司製）40份 微粒子、KBE 903 (信越化學工業公司製）〇.8份 胺基之砂院偶合劑，並以甲酸調整至P Η 4處理石夕 化處理 -作成處 6(TC 進 纖維製 [爲矽石 〔爲具有 [微粒子 劑A。 ;理法進 :素纖維 以外， 取得比 爲ϊ夕石 爲具有 微粒子 -15- 200530461 (12) 後，加入Polon MF-18(信越化學工業公司製，環氧改質 聚矽氧烷）2份取得比較用的濃色化劑B。 除了使用此濃色化劑B以外，同實施例1處理並以軋 染處理法進行濃色化處理，取得比較用的纖維素纖維製品 比較例4 除了使用比較例3所製作之比較用的濃色化劑B以外 ’同實施例2處理並以浸染處理法進行濃色化處理，取得 比較用的纖維素纖維製品。 比較例5 對於參考例1之染色纖維素纖維製品的試驗布，未施 以濃色化處理，取得比較用的纖維素纖維製品。 試驗例1 使用實施例1及2所得之經濃色化處理的染色纖維素 纖維製品’比較例1至4所得之經濃色化處理的染色纖維 素纖維製品’及比較例5之未經濃色化處理的染色纖維素 纖維製品，根據下述方法，進行濃色化度、吸水性、耐光 堅牢度、汗耐光堅牢度、洗滌堅牢度、氯堅牢度、氮氣（ NOx)堅牢度之各試驗。 (a )濃色化度之測定 -16- 200530461 (13) 試驗布之濃色化度爲使用根據反射率所計算之Qtotal 値以未處理布視爲100%表示濃度。所謂Qt〇tal値爲考慮 視感特性之表面濃度的代用値（K/S値的積分値）。 (b )吸水性之判定 於試驗布上滴下水滴（0.5毫升），測定水滴的吸水 時間，並根據下列基準判定。 〇：立即吸收。 △·· 1〜6 0秒鐘吸收。 X : 1分鐘以上未吸收。 (c )耐光堅牢度之判定 根據耐光試驗法（J I S L 0 8 4 2碳照射2 0、4 0小時）， 以JIS Blue Scale判定變極色。 (d )汗耐光（Alkali JIS 5倍法）堅牢度之判定 根據耐光試驗法（JIS L0 8 8 8碳照射10小時），以 JIS變褪色用Gray Scale判定變褪色。 (e )洗滌堅牢度之判定 根據洗滌試驗法（JIS L0 844 A-2法），以JIS污染用 Gray Scale判定附上絹（白布）的污染。 (f )氯堅牢度之判定 根據氯堅牢度（JIS L0 8 8 4 JIS強），以JIS變褪色用 -17- 200530461 (14) G r a y S c a 1 e判定變極色。 (g )氮氣（NOx )堅牢度之判定 根據氯試驗法（JIS L 0 8 5 5 (單位），以JIS變褪色用 G r a y S c a 1 e判定變極色。 根據上述（a )至（g )之各判定所得之結果示於表1 及表2。 表 1 試驗項目 實施例1 比較例1 比較例3 比較例5 濃色化度 155 115 116 1 00 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 汗耐光堅牢度 4 4 4 4 洗滌堅牢度 4-5 4-5 4-5 4-5 氯堅牢度 3-4 3-4 3-4 3-4 氮氣堅牢度 4 4 4 4 -18- 200530461 (15) 表」 試驗項目 實施例2 比較例2 比較例4 比較例5 濃色化度 13 5 120 116 100 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 汗耐光堅牢度 4 4 4 4 洗滌堅牢度 4-5 4-5 4-5 4-5 氯堅牢度 3-4 3-4 3-4 3-4 氮氣堅牢度 4 4 4 4 由表1可知，實施例1之經濃色化處理的染色纖維素 纖維製品爲較比較例1、3、5之濃色化度高，且吸水性爲 與未進行濃色化處理之比較例5同水準，比使用比較用之 濃色化劑A及同B的比較例1及3更高。關於耐光堅牢度 、汗耐光堅牢度、洗滌堅牢度、氯堅牢度、氮氣耐性、與 未進行濃色化處理之比較例5同水準’可確認經由濃色處 理並未令其耐性降低。關於表2亦進行與表1相同趣旨之 考察。 參考例2 聚酯試驗布之作成 將分散染料（Cayalon Polyester Black ECX 300;日 本化藥公司製）相對於斥水性纖維布帛使用5 %，且以浴 比1 : 20，ρΗ4·5進行】3 0°C，60分鐘之染色，並以常法 -19- 200530461 (16) 進行還原洗淨’取得經染色的聚酯纖維製品。 實施例3 經染色之聚酯纖維製品的濃色化處理 於實施例1所得之濃色化劑5份中加水2 0 0 0份，其 · 次加入爹考例2所染色之聚醋纖維製品1 〇 〇份（浴比1 : ， 2 0 )，並於4 0 °C下處理3 0分鐘，取得經濃色化處理的染 色聚酯纖維製品。 比較例6 使用比較例1之濃色化劑A，同實施例3處理予以濃 色化處理，取得經濃色化處理的染色聚酯纖維製品。 比較例7 使用比較例3之濃色化劑B，同實施例3處理予以濃 色化處理，取得經濃色化處理的染色聚酯纖維製品。 | 比較例8 將分散染料（Cayalon Dolyester Black ECX 300;日 本化藥公司製）相對於聚酯纖維布帛使用5 %且以公知公 用之方法予以染色加工，未進行以濃色化劑的處理，作成 經染色的聚酯纖維製品。 試驗例2 -20- 200530461 (17) 對於實施例3之經濃色化處理的染色纖維素纖維製品 、比較例6及7所得之經濃色化處理的染色纖維素纖維製 品，及比較例8之未經濃色化處理的染色纖維素纖維製品 ，根據下述記載之試驗方法，評價濃色化度、吸水性、耐 光堅牢度、汗耐光堅牢度、洗滌堅牢度、水堅牢度、摩擦 堅牢度等。 (1 )濃色化度之判定 試驗布之反射率（L値）以濃度表示。數値愈小，則 濃度愈高，具有濃色效果。 (2 )吸水性之判定 於試驗布上滴下水滴（0.5毫升），判定水滴的吸水 時間，並根據下列基準判定。 〇：立即吸收。 △ : 1〜6 0秒鐘吸收。 X : 1分鐘以上未吸收。 (3 )耐光堅牢度之判定 根據耐光試驗法（JI S L 0 8 4 2碳照射2 0、4 0小時）， 以JIS Blue Scale判定變褪色。 (4 )洗滌堅牢度之判定 根據洗滌試驗法（JIS L0 844 A-2法），以JIS污染用 G r a y S c a 1 e判定附上棉白布的污染。 -21 - 200530461 (18) (5 )水堅牢度之判定 根據水試驗法（JIS L0 8 4 6 )，以 JIS污染用 Gray Scale判定附上棉白布的污染。 (6 )摩擦堅牢度之判定 根據水試驗法（JIS L0 8 4 9 )，以 JIS污染用 Gray Scale判定附上棉白布的污染。以乾燥狀態和濕潤狀態之 兩者或任一者適當進行。 根據上述（1 )至（6 )之各判定所得之結果示於表3 表 3 試驗項目 實施例3 比較例6 比較例7 比較例8 濃色化度 8.5 10.6 10.9 12.3 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 洗滌堅牢度 4 4 4 4 水堅牢度 4-5 4-5 4-5 4-5 摩擦堅牢度 (乾燥） 4 4 4 4 如表3之結果所判定般，實施例3所得之經濃色化處 理的染色聚酯纖維製品，較比較例6及比較例7之經濃色 -22- 200530461 (19) 化處理的染色聚酯纖維製品無撥水性且爲不損害聚酯系纖 維之特性的品質。又，濃色效果亦優良。更且，實施例3 所得之經濃色化處理的染色聚酯纖維製品爲在耐光堅牢度 、洗滌堅牢度、水堅牢度、摩擦堅牢度對於所使用之染料 的固有特性不會造成任何不良影響。 參考例3 經染色之陽離子可染型聚酯試驗布的作成 將陽離子染料（Kayacryl Black BS-ED;日本化藥公 司製）相對於陽離子可染型聚酯纖維（CDP )布帛使用8% 並以120°C進行60分鐘染色，作成試驗布。 實施例4 經染色之CDP纖維以浸染處理法的濃色化處理 將參考例3之經染色CDP纖維製品的試驗布1 〇〇份 加至水2000份中（浴比1 : 20 )，其次加入實施例1之濃 色化劑5份，並於4 0 °C下處理3 0分鐘，取得經濃色化處 理的CDP纖維製品。 比較例9 使用比較例1之濃色化劑A，同實施例4處理進行濃 色化處理，取得經濃色化處理的CDP纖維製品。 比較例1 〇 -23- 200530461 (20) 使用比較例3之濃色化劑B，同實施例4處理進行濃 色化處理，取得經濃色化處理的CDP纖維製品。 比較例1 1 將陽離子染料（Kayacrgl Black BS-ED;日本化學公 司製）相對於CDP纖維布帛使用8%並以公知公用之方法 予以染色加工，且未以濃色化劑進行處理，作成經染色的 CDP纖維製品。 試驗例3 對於實施例4之經濃色化處理的CDP纖維製品、比 較例9及1 〇之經濃色處理的CDP纖維製品、及比較例i j 之未經濃色化處理的C D P纖維製品’根據試驗例2同樣 之試驗方法、評價濃色化度、吸水性、耐光堅牢度、洗滌 良·牛度、水堅牛度、摩擦堅牢度等。所得之各評價結果示 於表4。 -24- 200530461 (21) 表 4 試驗項目 實施例4 比較例9 比較例1 0 比較例1 1 濃色化度 10.2 11.9 11.5 13.4 吸水性 〇 X X 〇 耐光堅牢度 5以上 5以上 5以上 5以上 洗滌堅牢度 4-5 4-5 4-5 4-5 水堅牢度 4-5 4-5 4-5 4-5 摩擦 (乾燥） 4 4-5 4-5 4-5 摩擦 (濕潤） 4-5 4-5 4-5 4-5 如表4之結果所判定般，實施例4之方法所處理的 CDP纖維製品爲較比較例9〜1 1所得之CDP纖維製品，濃 色效果優良，吸水性亦大，且對於其他CDP纖維製品所 使用之染料的固有特性不會造成損傷。 參考例4 經染色之尼龍纖維製品及羊毛纖維製品（試驗布）的 作成 將酸性染料（Kayacalan Black 2RL ;日本化藥公司製 )相對於尼龍纖維布帛及羊毛纖維布帛分別使用3.5%， 並以p Η 5 . 5，溶比1 : 2 0，染色溫度1 〇 〇 °C，染色時間6 0 分鐘之條件染色，進行水洗，熱水洗，分別取得經染色的 -25- 200530461 (22) 尼龍纖維製品及羊毛纖維製品。 實施例5 經染色加工之尼龍纖維製品以浸染處理法的濃色化處 理 於水20 0 0份中’投入參考例4所得之經染色的尼龍 纖維製品1 0 0份（浴比1 : 2 0 )，其次加入實施例1之濃 色化劑1 〇份，並於4 (TC下處理3 0分鐘，取得經濃色化處 理的尼龍纖維製品。 比較例1 3 使用比較例1之濃色化劑A，同實施例5處理進行濃 色化處理，取得經濃色化處理的尼龍纖維製品。 比較例1 4 使用比較例3之濃色化劑B，同實施例5處理進行濃 色化處理，取得經濃色化處理的尼龍纖維製品。 比較例1 5 將酸性染料（Kayacalan Black 2RL ;日本化學公司製 )相對於參考例4所得之尼龍纖維製品使用3.5%並以公 知公用之方法予以染色加工，且未以濃色化劑進行處理， 作成經染色的尼龍纖維製品。 -26- 200530461 (23) 試驗例4 對於實施例5之經濃色化處理的尼龍纖維製品、比較 例1 3及1 4之經濃色處理的尼龍纖維製品、及比較例1 5 之未經濃色化處理的尼龍纖維製品，根據試驗例2同樣之 試驗方法、評價濃色化度、吸水性、耐光堅牢度、洗滌堅 牢度、水堅牢度、摩擦堅牢度等。所得之各評價結果示於 表5。 表 5 試驗項目 實施例5 比較例1 3 比較例1 4 比較例1 5 濃色化度 9.5 11.0 10.9 12.7 吸水性 〇 X X △〜〇 耐光堅牢度 5以上 5以上 5以上 5以上 洗滌堅牢度 3-4 3-4 3-4 3-4 水堅牢度 4-5 4-5 4-5 4-5 摩擦堅牢度 (乾燥） 5 5 5 5 摩擦堅牢度 (濕潤） 4-5 4-5 4-5 4-5200530461 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a thickening method for fiber and a fiber product using the same. More specifically, the present invention relates to a thickening agent containing silica fine particles treated with a silane coupling agent having an amine group and polyether-modified polysiloxane under acidic conditions, and a thickening agent using the dyed fiber product Colorization method. The thickening agent for fibers of the present invention is to provide dyes with excellent tackiness, improve the coloration of dyed materials, and have excellent water absorption. It does not damage the original dyed fiber processed products such as g washing year and water fastness. [Prior art] A method for thickening a dyed fiber product has been proposed 20 years ago, and various thickening agents and thickening methods have been proposed so far, and the technology has been put into practical use. The thickening technology of the dyed fiber product is to provide fine unevenness on the surface of the dyed fiber, and to improve the color with dark color by the reflection and refraction of light. Formate resin emulsifiers, acrylic resin emulsifiers, and the like. The thickening agent of the silica fine particle system is described in, for example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, etc. However, as described in Patent Literature 1 therein, The thickening agent is basically composed of an aqueous suspension containing silica fine particles. Patent Document 6 proposes a thick -5- 200530461 (2) coloring agent for treating a suspension of silica fine particles with a silane-based coupling agent having an amine group and attaching it to a fiber, followed by low-temperature plasma treatment. The thickening agent is used for the purpose of polyester fiber, and when it is used for cellulose fiber, it causes a decrease in water absorption. Furthermore, the thickening agents described in Patent Documents 7 and 8 are thickening agents used for polyester fibers previously treated with epoxy compounds, and are silica treated with a silane coupling agent having an amine group. A thickening agent composed of fine particles. However, in the case where this thickening agent is applied to cellulose fibers, it cannot be expected to ensure sufficient water absorption. Furthermore, Patent Document 9 proposes a thickening agent composed of fine silica particles and a polysiloxane compound. However, this thickening agent is applied to polyester fibers and wool. There is no record of the application of cellulose fibers. Furthermore, in Patent Document 10, a thickening agent that can be applied not only to polyester fibers but also to synthetic fibers or recycled fibers such as polyamide, acrylic, and rayon: a resin emulsifier is proposed. However, this resin emulsifier cannot be expected to impart sufficient water absorption from the viewpoint of the structure of the resin. Furthermore, the stability of the treatment bath when the treatment with the thickening agent is problematic, and it is difficult to apply a simple treatment method such as an immersion treatment method. As mentioned above, the thickening agent proposed previously is mainly used for water-repellent fibers such as polyester fibers. Therefore, if a thickening treatment is performed on more hydrophilic fiber dyes such as wool and cellulose fibers, Causes a strong color effect on the fiber and simultaneously imparts water repellency, which often damages hydrophilicity or water absorption. As described above, no thickening agent has been found which uses both water-repellent fibers and hydrophilic fibers and provides sufficient effects. [Patent Document 1] JP 5-6-1 1 2 5 8 3 [Patent Document 2] JP 2-2 5 9 1 6 0-6 200530461 (3) [Patent Document 3] JP 5 3 -2 69 1 7 JP [Patent Document 4] JP 4-2 1 JP 4482 [Patent Document 5] JP 9-2 5 JP 6 [Patent Document 6] JP 5 6- 1 1 2 5 8 [Patent Document 7] JP 2-2 5 9 1 60 0 [Patent Document 8] JP 3 -269 1 7 [Patent Document 9] JP 3 -42 1 44 [Patent Document 10] JP 9-2 5 62 8 0 [Patent Document 11] JP 9-3 774 [Summary of the Invention] [Disclosure of the Invention] (Problems to be Solved by the Invention) The subject of the invention is to develop a solution with excellent stability in the thickening treatment, and excellent dyeing and processing effect on the fiber product, and at the same time excellent water absorption in the fiber product obtained by the thickening treatment, and repeat A thickening agent with excellent washing resistance and a method for thickening a fiber product dyed and processed using such a thickening agent for fibers. (Means for Solving the Problems) The inventors of the present inventors made intensive research in order to solve the above-mentioned problems. As a result, they found that the silica fine particle suspension treated with the silane-containing silane coupling agent and the polyether modified polysiloxane under acidic conditions The mixture obtained by mixing alkane can provide fiber 200530461 (4) product which is excellent in dense color effect and absorbs water at the same time, and the mixture has excellent stability in the thickening process, and has completed the present invention. That is, the present invention relates to (1) a thickening agent for fibers, which is characterized in that it contains silica fine particles treated with a silane coupling agent having an amine group under acidic conditions and a polyether modified siloxane; (2) The thickening agent for fibers according to (1), wherein the content of the polyether modified polysiloxane is 5 to 20% by weight based on the silica fine particles; (3) as described in (1) or (2) The fiber is used as a thickening agent, which makes the suspension of silica particles under acidic conditions treated with a silane coupling agent having an amine group, and then can be obtained by mixing polyether modified polysiloxane; (4) a A method for thickening a dyed processed fiber, characterized in that the dyed processed fiber is treated with the thickening agent of the fiber described in any one of (1) to (3) above; (5) such as ( 4) The method for thickening fibers according to the description, wherein the fiber subjected to dyeing process is cellulose fiber; (6) The method for the thickening of fibers according to (4), wherein the fiber subjected to dyeing is polyester fiber; ( 7) A fiber dyed processed product according to any one of (4) to (6) above Color depth method of load can be achieved. (Effects of the Invention) By treating the dyed fiber products with the thickening agent of the present invention, excellent fiber dyeing, water absorption, and washing fastness can be obtained. 8- 200530461 (5) Color processing Thing. Not only for polyester fibers that have been extensively color treated, but also for cellulose fibers such as dyed kapok, rayon, etc., which have previously been difficult to maintain, they can continue to absorb water and achieve the effect of thickening. In particular, it is extremely effective when applied to a dyed substance which is dyed to a thick black, such as a dress. The thickening agent of the present invention is a blended fiber product of water-repellent fibers such as polyester fibers and hydrophilic fibers such as kapok, rayon, wool, etc., which provide high-density thickening of two fibers that are hydrophilic and water-repellent. At the same time, the water absorption effect of these fibers is improved. As described above, the thickening agent of the present invention is an extremely expensive invention in the dyeing and processing industry for the reason of providing a dyed product of an extremely expensive fiber product. (The best form of carrying out the invention) The thickening agent of the present invention contains silica fine particles treated with a silane coupling agent having an amine group under acidic conditions, and polyether-modified polysiloxane, preferably silica. The microparticle suspension is treated with an amine-based silane coupling agent under acidic conditions, followed by polyether modified siloxane. In the present invention, the particle size of silica particles used for treating silica particles with an amine-containing silane coupling agent under acidic conditions is generally 30 to 85 nm, and those which have been sold in the form of a suspension can be used. The medium of the suspension is preferably water. Silane coupling agents having an amine group can use commonly sold silanes such as α-aminopropyltriethoxysilane, N- (aminoether group) -aminopropyltrimethoxysilane, and the like. Coupling agent (for example, KBE903 (manufactured by Shin-Etsu Chemical Co., Ltd.). 200530461 (6) Use ratio of silica-based silane-based silane coupling agent relative to silica particles when treated with silane-based silane coupling agent under acidic conditions It is usually 5 to 20% by weight. If the use ratio of the silane-based coupling agent having an amine group is less than this range, the washing fastness of the obtained thickening agent is reduced. On the contrary, if the use ratio is greater than this range, it may cause an order The stability of the thickening agent is reduced. When the silica fine particles are treated with an amine-based silane coupling agent under acidic conditions, the acidic materials used include inorganic acids, organic acids, preferably formic acid, acetic acid, and ethanol. Acid, succinic acid, maleic acid, and other monovalent or divalent organic acids. If the pH is 6 or less when processed under acidic conditions, especially if the pH is 3 to 5, the time of the thickening agent It is better to improve the stability. The concentration of silica fine particles in the silica fine particle suspension when treated under acidic conditions is usually 5 to 20% by weight. If the concentration is lower than this range, the processing time becomes longer, and if the concentration is higher than this range, the stability of the solution may be reduced. The order in which the silica fine particles are mixed with the silane-based coupling agent having an amine group under acidic conditions is not particularly limited, but the silica fine particle suspension prepared by the aforementioned acidic conditions is added with a silane coupling agent. An aqueous suspension or an alcohol solution is preferred. After mixing in this way, it is usually mixed at 5 to 30 ° C, preferably 15 to 25 ° C, and preferably it is matured to stabilize. Secondly, 'used in the present invention Polyether modified polysiloxane is a polysiloxane composed of silane-containing polysiloxane, allyl alcohol-added ethylene oxide, propylene oxide, or a random or segmented copolymer thereof. Ether. Normally sold ones (for example, SII 190, manufactured by Toray Dowcorning Co., Ltd.) can be used. By mixing a polyether modified with a hydrophilic polysiloxane, the water absorption of the obtained thickening agent can be greatly increased. Performance, and repeated washing resistance Excellent. Polyether-10-200530461 (7) The use ratio of the modified polysiloxane is usually 3 to 30% by weight and 5 to 20% by weight relative to the silica particles after the treatment. It is preferably acidic. The method of mixing polyether-modified polysiloxane with a suspension of silica fine particles treated with a silane-based silane coupling agent under conditions is not particularly limited, but in order to obtain a more uniform dispersion state, the polyether is modified. It is better to dissolve and mix polysiloxane in alcohol, etc. In the present invention, if necessary, a well-known additive such as a surfactant, a softener, etc. is used to prepare the thickening agent of the present invention, or when it is processed by the present invention. It is also possible to add in the bath of the fiber product dyed by the thickening agent. Next, the method of thickening the fiber product dyed by using the thickening agent of the present invention will be described. The fibers suitable for dyeing the fibrous product dyed with the thickening agent of the present invention include natural or regenerated natural materials such as kapok, hemp, copper ammonia fiber (rayon), viscose rayon, polynosic fiber, etc. Cellulose fibers, protein fibers such as wool, silk, semi-synthetic fibers such as acetate fibers, polyester fibers (including CDP fibers (cationically dyeable polyester fibers)) polyacrylonitrile fibers, polyamide fibers such as nylon, etc. Synthetic fibers, etc. and blended fibers composed of two or more of these fibers. Among them, preferred fibers are cellulose fibers, polyester fibers, protein fibers, polyamides, and blended fibers of these fibers with other fibers. The shape of the dyed fibrous product may be any form such as a fabric, a knitted fabric, or a fibrous shape. The thickening method of the present invention can be carried out according to a general method such as a pad dyeing method, a dipping method, or the like. -11-200530461 (8) The thickening method by pad dyeing method is to add water to 30 ~ 70 parts by weight of the thickening agent to make a total padding bath of about 1,000 parts by weight, and use this padding bath After the dyed fiber product is impregnated in the medium, it is squeezed with a rolling mill at a twist rate of about 80% by weight, and the squeeze cloth is usually 90 ~; after not drying for about 3 minutes, it is usually 130 ~ 17 ( The RC is preferably subjected to a dry heat treatment for 3 minutes. The thickening method by the dipping method is 100 parts by weight relative to the dyed fiber product, and the thickening agent of the present invention is usually used in an amount of 2 to 20 parts by weight, preferably 5 to 10 parts by weight, and water as a medium, usually at 30 to 70 ° C, usually for 10 to 60 minutes. The bath ratio is usually adjusted to 1: 20 to 50, which is the rich color of the present invention. In the method, 100 parts by weight of the dyed fiber product is applied to the concentrated coloring agent of the present invention, and the concentrated coloring agent is used to impart 0.5 to 90 parts by weight, preferably 5 to 30 parts by weight, and more preferably 3 parts by weight. ~ 6 parts by weight is preferred. The amount to be applied is determined by measuring the dry weight before and after the thickening method is performed. The fiber product can be prepared by dyeing the fiber product according to a well-known dyeing method. The following is a description of how to obtain the dyed cellulose fiber and polyester fiber. The method for dyeing cellulose fiber can be based on the reaction dye. 1〜5 克 The dyeing method is performed directly by a well-known method such as a dyeing method of dyes. In the dyeing method of reactive dyes, after the dyeing step is completed, after washing with water and hot water, it usually contains 0.1 to 5 grams of commercially available soaping agents. Per liter of soap can be washed and washed. The dyeing method of reactive dyes is, for example, -12 · 200530461 (9) for cellulose fibers such as kapok. Add reactive dyes to the dyeing bath, and add known inorganic Basic salt, such as anhydrous thenardite, common salt, etc., and acid binding agents, such as sodium carbonate, sodium bicarbonate, caustic, sodium tertiary phosphate, etc., are dyed alone or in combination. Polyester fiber cloth, dipped in an aqueous medium containing a disperse dye adjusted to pH 4.5, and subjected to dyeing at 13 ° C under pressure for 60 minutes. After the dyeing is finished, after washing with water and hot water, wash in an alkali reduction bath containing 2 g / l of bisulfite and 2 g / l of caustic soda at about 80 ° C to complete the dyeing step. After dyeing Cationic dyeable polyester fiber products are immersed in cationic dyeable polyester fibers in an aqueous medium containing a specified amount of cationic dyes adjusted to pH 4.5, and subjected to pressure at 1 20 ° C, 3 0 Dyeing in minutes. The thickening agent of the present invention exhibits a high thickening effect on the dyed fibers, and imparts high water absorption to water-repellent fibers, and at the same time has relatively high hydrophilic properties such as cellulose fibers. The characteristics that impair the water absorption are good and do not impair the light fastness, washability, water fastness, and rubbing fastness inherent to each dye used in the obtained dyeing and processing. [Embodiment] Hereinafter, the present invention will be described in more detail based on examples, reference examples, and test examples, but the present invention is not limited thereto. The percentages and parts in the examples are based on weight. Reference example 1 Production of test cloth-13- 200530461 (10) Put cellulose fiber (kapok) in a dyeing bath prepared with 1 g of reactive dye (CIReactive Black 5), 16 parts of anhydrous thenardite, and 180 parts of water. 10 parts of fibers were heated to 60, and maintained at this temperature for 10 minutes. 20 parts of a 20% soda ash solution was added and dyed for 60 minutes. Thereafter, the obtained dyed cloth was washed with water and boiled with soap for 20 minutes. The test cloth was obtained by bathing, washing and drying to obtain the dyed material of kapok. Example 1 Preparation of a thickening agent and thickening treatment of a dyed cellulose fiber product In a 20% aqueous suspension of silica fine particles having a particle size of 40 to 50 nm, formic acid and r-amine were added. An aqueous solution of propyltriethoxysilane and treated at 25 ° C under the acidic condition of PH4, mixed with polyether modified polysiloxane (SII 190 Toray-Dowcorning Silicone) to obtain the invention Thickening agent. This thickening agent is 41% with 20% silica microparticles in water suspension, 1.9% formic acid, 7-aminopropyltriethoxysilane 0.6%, polyether modified polysiloxane 1.5% and water 55.0%. composition. Water was added to 50 parts of this thickening agent to make a padding bath of 100 parts in total. In this pad dyeing bath, the dyed test cloth of Reference Example 1 obtained as described above was subjected to milk dyeing, and then squeezed with a rolling mill at a squeeze rate of 80%. The extruded cloth was dried at 100 ° C for 3 minutes, and then subjected to a dry heat treatment at 150t for 3 minutes to obtain a dyed cellulose fiber product subjected to a thickening treatment. Example 2 -14- (11) 200530461 The dyed cellulosic fiber product was concentrated by dyeing in a concentration higher than 10 parts of the thickening agent obtained in Example 1 by adding 90 parts of water to a 10-bath bath. Test cloth; 100 parts, processed in parallel for 30 minutes, to obtain a dyed fiber product subjected to a thickening treatment. Comparative Example 1 Using Sunotec OL (manufactured by Usa Chemical Co., Ltd.) 40 parts of primary particles, KBE903 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.8 parts of primary amine-based silane coupling agent, and adjusting to p 甲酸 with formic acid 4 Concentration for comparison containing polyether modified polysand oxygen laboratory. Use this concentration agent 'same as in Example 1 and treated with pad dyeing g for intensification treatment' to obtain comparative fibers treated with intensification treatment. Flip products. Comparative Example 2 A comparative cellulose fiber product which was treated in the same manner as in Example 2 and was subjected to a thickening treatment by a dip dyeing method was used, except that the comparative thickening prepared in Comparative Example 1 was used. Comparative Example 3 Sunotec OL (manufactured by Nissan Chemical Co., Ltd.) 40 parts of fine particles, KBE 903 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.8 parts of amine-based sand garden coupling agent, and adjusted with formic acid to P Η 4 -Made at 6 (TC made of fiber [for silica] [with microparticles A .; Ricoh method: in addition to plain fibers, the ratio of obtained is XI Xishi stone with microparticles -15- 200530461 (12), add Polon MF -18 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., epoxy-modified polysiloxane) was obtained in two parts as a thickening agent B for comparison. Except for using this thickening agent B, it was treated in the same manner as in Example 1 and pad dyed. The method was used to perform a thickening treatment to obtain a comparative cellulose fiber product. Comparative Example 4 Except that the comparative thickening agent B prepared in Comparative Example 3 was used, it was treated in the same manner as in Example 2 and was thickened by a dip treatment. Treatment to obtain a comparative cellulose fiber product. Comparative Example 5 The test cloth of reference cellulose dyed cellulose fiber product was not subjected to a thickening treatment to obtain a comparative cellulose fiber product. Test Example 1 Implementation From Examples 1 and 2 Concentrated dyed cellulose fiber products 'Concentrated dyed cellulose fiber products obtained in Comparative Examples 1 to 4' and Comparative Example 5 uncondensed dyed cellulose fiber products, according to the following According to the method described above, various tests were performed for the degree of color density, water absorption, light fastness, light fastness to sweat, fastness to washing, fastness to chlorine, and fastness to nitrogen (NOx). (A) Determination of the degree of dense coloring-16 -200530461 (13) The density of test cloth is Qtotal (calculated based on reflectance) as 100% concentration based on reflectance. The so-called Qt〇tal 値 is a substitute for surface concentration considering visual characteristics ( K / S 値 integration 値). (B) Determination of water absorption Water droplets (0.5 ml) were dropped on the test cloth, and the water absorption time of the water droplets was measured and judged according to the following criteria. 〇: Immediate absorption. △ ·· 1 ~ 6 Absorption in 0 seconds. X: Not absorbed for more than 1 minute. (C) Determination of light fastness According to the light resistance test method (JISL 0 8 4 2 carbon irradiation for 20 and 40 hours), the color change was determined by JIS Blue Scale. (d) sweat resistance (Alkali JIS 5 times method) The fastness is judged according to the lightfastness test method (JIS L0 8 8 8 carbon irradiation for 10 hours), and the JIS discoloration is judged by Gray Scale. The color fastness is judged. (E) The washing fastness is judged by the wash test method (JIS L0 844 A-2). Method), the JIS pollution Gray Scale is used to determine the contamination of the attached silk (white cloth). (F) The chlorine fastness is determined based on the chlorine fastness (JIS L0 8 8 4 JIS is strong), and the color is faded with JIS-17- 200530461 (14) G ray S ca 1 e judged to be polarized. (g) Determination of the fastness of nitrogen (NOx) According to the chlorine test method (JIS L 0 8 5 5 (unit), JIS Gray Sca 1 e is used to determine the extreme color change. According to the above (a) to (g) The results of each judgment are shown in Tables 1 and 2. Table 1 Test item example 1 Comparative example 1 Comparative example 3 Comparative example 5 Concentration degree 155 115 116 1 00 Water absorption 〇XX 〇 Light fastness 4- 5 4-5 4-5 4-5 Lightfastness to sweat 4 4 4 4 Fastness to washing 4-5 4-5 4-5 4-5 Chlorine fastness 3-4 3-4 3-4 3-4 Nitrogen fastness Degree 4 4 4 4 -18- 200530461 (15) Table "Test item example 2 Comparative example 2 Comparative example 4 Comparative example 5 Concentration degree 13 5 120 116 100 Water absorption 〇XX 〇 Lightfastness 4-5 4- 5 4-5 4-5 Lightfastness to sweat 4 4 4 4 Washing fastness 4-5 4-5 4-5 4-5 Chlorine fastness 3-4 3-4 3-4 3-4 Nitrogen fastness 4 4 4 It can be seen from Table 1 that the dyed cellulose fiber product subjected to the thickening treatment in Example 1 has a higher degree of thickening than the comparative examples 1, 3, and 5, and the water absorption is the same as that without the thickening treatment. Comparative Example 5 is the same level, compared with the comparative thickener A and Comparative examples 1 and 3 of B are even higher. Regarding light fastness, sweat fastness, washing fastness, chlorine fastness, nitrogen fastness, and the same level as in Comparative example 5 without the thickening treatment, it was confirmed that the thick color The treatment did not reduce its resistance. Table 2 was also examined for the same purpose as in Table 1. Reference Example 2 Production of a polyester test cloth Disperse dye (Cayalon Polyester Black ECX 300; manufactured by Nippon Kayaku Co., Ltd.) with respect to water repellency The fiber cloth was used at 5% and was dyed at a bath ratio of 1: 20 and ρΗ4.5] at 30 ° C for 60 minutes, and then subjected to reduction and washing using conventional method-19- 200530461 (16) to obtain a dyed polymer. Ester fiber products. Example 3 Dyeing treatment of dyed polyester fiber products Add 5 parts of water to 5 parts of the thickening agent obtained in Example 1, and then add the dyed parts of Dye Test Example 2 100 parts of polyester fiber product (bath ratio 1: 20), and treated at 40 ° C for 30 minutes to obtain a dyed polyester fiber product that has undergone a thickening treatment. Comparative Example 6 Comparative Example 1 The thickening agent A was treated in the same manner as in Example 3 to obtain a thickening agent. Color staining treated polyester fiber article. Comparative Example 7 using concentrated color agent B Comparative Example 3, the processing to be concentrated color process as described in Example 3, made by processing dark color dyed polyester fiber article. Comparative Example 8 A disperse dye (Cayalon Dolyester Black ECX 300; manufactured by Nippon Kayaku Co., Ltd.) was dyed using a known and public method using 5% of polyester fiber cloth, and was not treated with a thickening agent. Dyed polyester fiber products. Test Example 2 -20- 200530461 (17) Concentrated dyed cellulose fiber products obtained in Example 3, Concentrated dyed cellulose fiber products obtained in Comparative Examples 6 and 7, and Comparative Example 8 The dyed cellulose fiber products without thickening treatment were evaluated for the degree of thickening, water absorption, light fastness, sweat fastness, washing fastness, water fastness, and rubbing fastness according to the test methods described below. Degrees and so on. (1) Judgment of the degree of dense color The reflectance (L 値) of the test cloth is expressed by the density. The smaller the number is, the higher the density is. (2) Judgment of water absorption Water droplets (0.5 ml) were dropped on the test cloth, and the water absorption time of the water droplets was determined, and it was judged according to the following criteria. 〇: Immediately absorbed. △: Absorbed in 1 to 60 seconds. X: Not absorbed for more than 1 minute. (3) Determination of light fastness According to the light fastness test method (JI S L 0 8 4 2 carbon irradiation for 20, 40 hours), discoloration was judged by JIS Blue Scale. (4) Judgment of washing fastness According to the washing test method (JIS L0 844 A-2 method), the contamination with cotton cloth was judged according to JIS contamination G r a y S c a 1 e. -21-200530461 (18) (5) Judgment of water fastness According to the water test method (JIS L0 8 4 6), the gray scale attached to cotton and white cloth was judged by JIS gray scale. (6) Judgment of rubbing fastness According to the water test method (JIS L0 8 4 9), the contamination of cotton-white cloth was judged by JIS Gray Scale for contamination. It is suitably performed in either or both of the dry state and the wet state. The results obtained according to the above (1) to (6) are shown in Table 3. Table 3 Test item example 3 Comparative example 6 Comparative example 7 Comparative example 8 Concentration degree 8.5 10.6 10.9 12.3 Water absorption ○ XX 〇 Light fastness Degree 4-5 4-5 4-5 4-5 Washing fastness 4 4 4 4 Water fastness 4-5 4-5 4-5 4-5 Rubbing fastness (dry) 4 4 4 4 Results as shown in Table 3 As judged, the dyed polyester fiber product subjected to the thickening treatment obtained in Example 3 was not as good as the dyed polyester fiber product subjected to the thickening treatment of Comparative Example 6 and Comparative Example 7-22- 200530461 (19). It is water-based and does not impair the characteristics of the polyester fiber. Also, the dark color effect is excellent. In addition, the dyed polyester fiber product obtained in Example 3 after being subjected to the thickening treatment has no adverse effects on the inherent characteristics of the dyes used in light fastness, washing fastness, water fastness, and rubbing fastness. . Reference Example 3 Preparation of Dyeing Cationic Dyeable Polyester Test Cloth Cationic dye (Kayacryl Black BS-ED; manufactured by Nippon Kayaku Co., Ltd.) was used at 8% of the cationic dyeable polyester fiber (CDP) fabric. Dyeing was performed at 120 ° C for 60 minutes to prepare a test cloth. Example 4 Dyeing of the CDP fiber dyed by the dyeing method The 100 parts of the test cloth of the dyed CDP fiber product of Reference Example 3 was added to 2000 parts of water (bath ratio 1: 20), followed by adding Five parts of the thickening agent of Example 1 were treated at 40 ° C for 30 minutes to obtain a CDP fiber product subjected to the thickening treatment. Comparative Example 9 The thickening agent A of Comparative Example 1 was used to carry out the thickening treatment in the same manner as in Example 4 to obtain a CDP fiber product subjected to the thickening treatment. Comparative Example 1 -23-200530461 (20) Using the thickening agent B of Comparative Example 3, the same process as in Example 4 was performed to carry out the thickening treatment to obtain a CDP fiber product subjected to the thickening treatment. Comparative Example 1 1 A cationic dye (Kayacrgl Black BS-ED; manufactured by Nippon Chemical Co., Ltd.) was dyed using a publicly known method using CDP fiber cloth at 8%, and was not treated with a thickening agent, and dyed. CDP fiber products. Test Example 3 For the CDP fiber products subjected to the thickening treatment of Example 4, the CDP fiber products subjected to the thickening treatment of Comparative Examples 9 and 10, and the CDP fiber products not subjected to the thickening treatment of Comparative Example ij ' According to the same test method as in Test Example 2, the degree of denseness, water absorption, light fastness, good washing and bovine strength, water firmness, and rubbing fastness were evaluated. The evaluation results obtained are shown in Table 4. -24- 200530461 (21) Table 4 Test item example 4 Comparative example 9 Comparative example 1 0 Comparative example 1 1 Density 10.2 11.9 11.5 13.4 Water absorption 0 XX 〇 Light fastness 5 or more 5 or more 5 or more or more 5 or more washing Fastness 4-5 4-5 4-5 4-5 Water fastness 4-5 4-5 4-5 4-5 Friction (dry) 4 4-5 4-5 4-5 Friction (wet) 4-5 4-5 4-5 4-5 As judged by the results in Table 4, the CDP fiber products treated by the method of Example 4 are better than the CDP fiber products obtained in Comparative Examples 9 to 11. The CDP fiber products obtained are excellent in color density and water absorption. It is also large and does not cause damage to the inherent properties of the dyes used in other CDP fiber products. Reference Example 4 Preparation of Dyed Nylon Fiber Product and Wool Fiber Product (Test Cloth) Acid dye (Kayacalan Black 2RL; manufactured by Nippon Kayaku Co., Ltd.) was used at 3.5% of nylon fiber cloth and wool fiber cloth, respectively. Η 5.5, dissolving ratio 1: 20, dyeing temperature 1000 ° C, dyeing time 60 minutes, dyeing under water, washing with hot water, and obtaining dyed -25- 200530461 (22) nylon fiber products And wool fiber products. Example 5 A dyed nylon fiber product was subjected to a thickening treatment using a dip dyeing method in 20,000 parts of water, and 100 parts of the dyed nylon fiber product obtained in Reference Example 4 were used (bath ratio 1: 2 0). ), Followed by adding 10 parts of the thickening agent of Example 1 and treating at 4 ° C for 30 minutes to obtain a nylon fiber product having a thickening treatment. Comparative Example 1 3 Using the thickening agent of Comparative Example 1 Agent A was treated in the same manner as in Example 5 to perform a thickening treatment to obtain a nylon fiber product subjected to the thickening treatment. Comparative Examples 1 4 The thickening agent B of Comparative Example 3 was used to perform the thickening treatment in the same manner as in Example 5. Comparative Example 1 5 An acid dye (Kayacalan Black 2RL; manufactured by Nippon Chemical Co., Ltd.) was used at 3.5% of the nylon fiber product obtained in Reference Example 4 and dyed by a publicly known method. Processed and not treated with a thickening agent to make a dyed nylon fiber product. -26- 200530461 (23) Test Example 4 For the thickened nylon fiber product of Example 5, Comparative Example 13 and 1 4 thick nylon Vitamin products, and non-density-treated nylon fiber products of Comparative Example 15 were evaluated in accordance with the same test method of Test Example 2 to evaluate the degree of coloration, water absorption, light fastness, washing fastness, water fastness, Rubbing fastness, etc. The evaluation results obtained are shown in Table 5. Table 5 Test item example 5 Comparative example 1 Comparative example 1 4 Comparative example 15 Concentration degree 9.5 11.0 10.9 12.7 Water absorption ○ △ △ 〇 light resistance Fastness 5 or more 5 or more 5 or more 5 or more washing fastness 3-4 3-4 3-4 3-4 water fastness 4-5 4-5 4-5 4-5 rubbing fastness (dry) 5 5 5 5 Friction fastness (wet) 4-5 4-5 4-5 4-5
如表5之結果所判定般，實施例5所得之經濃色化處 理的染色尼龍纖維製品，較比較例1 3至1 5的染色尼龍纖 維製品，濃色效果、吸水性優良，且亦不損害尼龍纖維染 色物固有的特性。 -27- 200530461 (24) 實施例1 6 經染色加工之羊毛纖維製品以浸染處理法的濃色化處 理 使用參考例4所得之經染色的羊毛纖維製品，同實施 例5處理，取得經濃色化處理的羊毛纖維製品。 比較例1 6 使用比較例1之濃色化劑A，同實施例6處理進行濃 色化處理，取得經濃色化處理的羊毛纖維製品。 比較例1 7 使用比較例3之濃色化劑B，同實施例6處理進行濃 色化處理，取得經濃色化處理的羊毛纖維製品。 比較例1 8 將酸性染料（Kayacalan Black 2RL;日本化學公司製 )相對於參考例4所得之羊毛纖維製品使用3 . 5 %並以公 知公用之方法予以染色加工，且未以濃色化劑進行處理， 作成經染色的羊毛纖維製品。 試驗例5 對於實施例5之經濃色化處理的羊毛纖維製品、比較 例1 6及1 7之經濃色處理的羊毛纖維製品、及比較例1 8 之未經濃色化處理的羊毛纖維製品，根據試驗例2同樣之 -28- 200530461 (25) 試驗方法、評價濃色化度、吸水性、耐光堅牢度、洗滌堅 牢度、水堅牢度、摩擦堅牢度等。所得之各評價結果示於 表6。 表 6 試驗項目 實施例6 比較例1 6 比較例1 7 比較例18 濃色化度 9.6 12.0 11.6 12.8 吸水性 Δ XX XX X 耐光堅牢度 5以上 5以上 5以上 5以上_ 洗滌堅牢度 3-4 3-4 3-4 3-4 水試驗堅牢度 4-5 4-5 4-5 4-5 一 摩擦堅牢度 3-4 3-4 3-4 3-4 (乾燥） 摩擦堅牢度 3-4 4 4 4 (濕潤） ------------- 如表6之結果所判定般，實施例6所得之經濃色化處 理的染色羊毛纖維製品，較比較例1 6至1 8之染色羊毛纖 維製品，濃色效果、吸水性優良，且亦不損害羊毛纖維製 品染色物固有的特性。 [產業上之可利用性] 對於經染色加工之纖維素纖維、聚酯纖維、蛋白質纖 維、聚醯胺纖維等，經由以本發明之濃色化劑處理，則可 -29- 200530461 (26) 取得濃色化、吸水性優良的染色物。更且，所得染色纖維 製品之耐光性、汗耐光性、洗 '滌堅牢性、氯耐性亦均不會 損害所使用染料的特性且爲良好。 本發明之濃色化劑，對於經染色加工的纖維，顯示高 的濃色化效果，且對斥水性纖維賦予高的吸水性且同時對 於纖維素纖維等之較親水性的纖維具有不損害吸水性的特 徵’更且不會損害所得染色加工物中所使用之各染料固有 的耐光性、洗滌性、水堅牢度、摩擦堅牢度且爲良好。 -30-As judged by the results in Table 5, the dyed nylon fiber product obtained in Example 5 after being subjected to the thickening treatment was superior to the dyed nylon fiber products of Comparative Examples 1 to 15 in that the dyeing effect and water absorption were superior, and Impairs the inherent properties of nylon fiber dyes. -27- 200530461 (24) Example 16 Dyeing treatment of dyed wool fiber products by dip-dyeing method The dyed wool fiber products obtained in Reference Example 4 were treated in the same manner as in Example 5 to obtain a dark color. Chemical treatment of wool fiber products. Comparative Example 1 6 The thickening agent A of Comparative Example 1 was used to carry out the thickening treatment in the same manner as in Example 6 to obtain a thickened wool fiber product. Comparative Example 17 The thickening agent B of Comparative Example 3 was used to perform the thickening treatment in the same manner as in Example 6 to obtain a thickened wool fiber product. Comparative Example 18 An acid dye (Kayacalan Black 2RL; manufactured by Nippon Chemical Co., Ltd.) was dyed using a known and publicly-used method using 3.5% of the wool fiber product obtained in Reference Example 4 without using a thickening agent. Processing to make dyed wool fiber products. Test Example 5 For the thickened wool fiber product of Example 5, the thickened wool fiber product of Comparative Examples 16 and 17 and the untreated darkened wool fiber of Comparative Example 18 The product was evaluated in the same manner as in Test Example 2-28-200530461 (25). The test method was used to evaluate the color density, water absorption, light fastness, washing fastness, water fastness, and rubbing fastness. The evaluation results obtained are shown in Table 6. Table 6 Test item example 6 Comparative example 1 6 Comparative example 1 7 Comparative example 18 Concentration degree 9.6 12.0 11.6 12.8 Water absorption Δ XX XX X Lightfastness 5 or more 5 or more 5 or more 5 or more _ Washing fastness 3-4 3-4 3-4 3-4 Water test fastness 4-5 4-5 4-5 4-5 One rub fastness 3-4 3-4 3-4 3-4 (dry) Rub fastness 3-4 4 4 4 (wet) ------------- As judged by the results in Table 6, the dyed wool fiber product obtained in Example 6 after the thickening treatment was compared with Comparative Example 16 to 6 The dyed wool fiber products of 18 are excellent in color density and water absorption, and do not damage the inherent characteristics of dyed wool fiber products. [Industrial Applicability] For cellulose fibers, polyester fibers, protein fibers, polyamide fibers, etc. that have been dyed and processed, they can be treated with the thickening agent of the present invention, -29- 200530461 (26) Obtain a dyed product that is densely colored and excellent in water absorption. Moreover, the lightfastness, sweat fastness, washing fastness, and chlorine fastness of the obtained dyed fiber products are not detrimental to the characteristics of the dye used and are good. The thickening agent of the present invention exhibits a high thickening effect on dyed fibers, imparts high water absorption to water-repellent fibers, and at the same time does not impair water absorption to relatively hydrophilic fibers such as cellulose fibers. The characteristics of the property are good without impairing the light fastness, washing property, water fastness, and rubbing fastness inherent to each dye used in the obtained dyeing and processing. -30-