經濟部中央標準局員工消費合作社印製 «3224 A7 B7 五、發明説明（1) PU人造皮革之製作一般是以非織物上塗佈PU樹脂液形成面 層。在美觀上，其著色之方式是以顏料和PU樹脂液混合再加以塗 膜，其顏色較爲灰暗，欠缺鮮艷性，且顏料容易因熱而產生遷徙 (Migration)現象。Ρϋ彈性絲的染色方面，一般使用分散性染料 或酸性染料，在高溫（9G〜1G0°C)高壓下，行長時間（50〜60 min·)染色，相當浪費時間及能源，且PU之硬鏈節（Hard segment)區域的結晶會遭受破壞，導致物性變差；另一方面，這 種染色方式雖然容易染著，但也容易褪色，且有色差之問題。 要避免PU在染色方面的缺失，本案之「可結合染料之聚氨 基甲酸酯聚合體合成」可以共價鍵結合的染色方式，將染料接枝 於PU分子鏈上，使PU聚合後即帶有顏色，或可將本法合成之PU無 色聚合體塗層在織物或非織物上，或溶液紡成彈性纖維，再進行 染料之共價結合染色。 本發明爲在合成聚氨基甲酸酯中加入N-( 2-羥基乙基） 乙嫌二胺（HEDA)(N-(2-Hydroxyethyl) Ethylene diamine 使其分子鏈中具有二級醇，此可與已環氧氯丙烷（Epi -chi orohydri II)改質之含氯基分散性染料或反應性染料 反應以形成聚氨基甲酸酯與染料共價鍵結合的材料爲 特徵。本發明之合成方法分下面幾個步驟： 1 .含二級醇聚氨基甲酸酯聚合體之合成（第一步驟） 在合成聚氨基甲酸酯中加入N-( 2-羥基乙基）乙烯二 胺（HEDA)(N-(2-Hydroxyethyl) Ethylene diamine)使分子 鏈中含有二級醇，使其能與已環氧氯丙烷（Epichloro-hydr in)改質之含氯基分散性染料或反應性染料反應（染 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (諸先聞讀背面之注意事項再填寫本頁) 訂 A7 B7 經濟部中央標準局員工消費合作社_製 413224 五、發明説明（2) 色〉。即其爲將二醇與過量之二異氰酸鹽在5Q-90°C下反應 1.-2小時以形成末端基爲二異氰酸鹽之聚氨基甲酸酯預聚 合體，再加入N-(2-羥基乙基）乙烯二胺（HEDA)(N-(2~ H yd roxyethyl) Ethylene diamine 於 0-5 °C 下反應 1 .5-2’. 0小時以完成鏈延長反應；或加入不足量之HEDA再 加入二胺在6 0 -8 0 °C反應卜2小時完成反應，此即含二級 醇聚氨基甲酸酯聚合體。此處之二醇可爲聚醚之聚四甲基 二醇 PTMG(Polytetramethylene glycol )或聚乙基二 醇〔Polyethylene glycol);聚酯之聚丁基己二酸酯 PBACPolybutyl adipate)或聚 1，4己丙酮二酉享 (Polycapro lactone)等；其中之二異氰酸鹽可爲二甲基 二異截酸鹽 MDI(Dimetliylene di isocyanate)或甲苯 二異氰酸鹽 TDI(Tolylene diisocyanate)等；其中之 鏈延長劑可爲二胺如乙二胺（Hydrazine)，乙基二胺 (Ethylene diamine)或二醇如 丁二醇（Butanediol ) 等。 2. 環氧氯丙烷改質之含氯基分散性染料 以環氧氯丙烷改質之含氯基分散性染料，其改質反應 爲將含胺基分散性染料溶與DMF溶液中，加入環氧氯丙烷 在5G°C ’反應0.5小時。此即爲末端含有氯基之分散性染 料。 3. 含二級醇聚氨基甲酸酯聚合體與已環氧氯丙烷改質之 含氯基分散性染料或反應性染料反應以形成聚氨基曱酸酯 與染料共價鍵結合的材料 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公楚） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs «3224 A7 B7 V. Description of the invention (1) PU artificial leather is generally made by coating a PU resin solution on a non-woven fabric to form the surface layer. In terms of aesthetics, the coloring method is to mix the pigment with the PU resin solution and apply the coating. The color is relatively dark, lacks vividness, and the pigment is liable to generate migration due to heat. As for the dyeing of PY elastic yarns, disperse dyes or acid dyes are generally used. Dyeing for a long time (50 ~ 60 min ·) under high temperature (9G ~ 1G0 ° C) high pressure is a waste of time and energy, and the hardness of PU The crystals in the hard segment area will be damaged, resulting in poor physical properties. On the other hand, although this dyeing method is easy to dye, it is also easy to fade, and it has the problem of color difference. To avoid the lack of PU dyeing, the "synthesis of polyurethane polymer that can bind dyes" in this case can be covalently bonded in a dyeing manner. The dye is grafted onto the PU molecular chain, which will bring the PU to the belt after polymerization. It is colored, or the PU colorless polymer synthesized by this method can be coated on woven or non-woven fabrics, or spun into solution to form elastic fibers, and then covalently combined with dyes for dyeing. In the present invention, N- (2-hydroxyethyl) ethylene-diamine (HEDA) (N- (2-Hydroxyethyl) Ethylene diamine) is added to the synthetic polyurethane to make it have a secondary alcohol in the molecular chain. It is characterized by reacting with chlorine-containing disperse dyes or reactive dyes modified with epichlorohydrin (Epi-chi orohydri II) to form a covalent bond between polyurethane and dye. Synthetic method of the present invention It is divided into the following steps: 1. Synthesis of secondary alcohol-containing polyurethane polymer (first step) Add N- (2-hydroxyethyl) ethylenediamine (HEDA) to the synthetic polyurethane (N- (2-Hydroxyethyl) Ethylene diamine) makes the molecular chain contain a secondary alcohol, which enables it to react with chlorine-containing disperse dyes or reactive dyes modified with epichloro-hydr in ( Standards for dyeing this paper are in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) (please read the notes on the back before filling out this page) Order A7 B7 Staff Consumer Cooperative of Central Standards Bureau of the Ministry of Economic Affairs _ System 413224 V. Invention Explanation (2) Color> That is, it is a diol with an excess of diisocyanate Reaction at 5Q-90 ° C for 1.-2 hours to form a polyurethane prepolymer with a diisocyanate terminal group, and then adding N- (2-hydroxyethyl) ethylenediamine (HEDA) (N- (2 ~ H yd roxyethyl) Ethylene diamine reacted at 0-5 ° C for 1.5-2 '. 0 hours to complete the chain extension reaction; or add insufficient amount of HEDA and then add diamine at 6 0 -8 The reaction is completed at 0 ° C within 2 hours, which is a secondary alcohol-containing polyurethane polymer. The diol here may be polytetramethylene glycol PTMG (Polytetramethylene glycol) or polyethyl diethylene glycol. Alcohol (Polyethylene glycol); polyester polybutyl adipate (PBACPolybutyl adipate) or poly 1,4 hexane acetone dioxan (Polycapro lactone), etc .; the diisocyanate can be dimethyl diisocyanate MDI (Dimetliylene di isocyanate) or toluene diisocyanate TDI (Tolylene diisocyanate), etc .; the chain extender may be a diamine such as ethylene diamine (Hydrazine), ethyl diamine (Ethylene diamine) or a glycol Such as butanediol, etc. 2. Chlorine-based disperse dyes modified with epichlorohydrin Disperse dyes, which the reforming reaction is an amine-containing solvent and disperse dyes DMF was added epichlorohydrin 'reaction 5G ° C 0.5 h. This is a disperse dye containing a chlorine group at the end. 3. Secondary alcohol-containing polyurethane polymer reacts with epichlorohydrin-modified chlorine-containing disperse dyes or reactive dyes to form a covalent bond of polyurethane and dye. Paper Standards are applicable to China National Standard (CNS) A4 specifications (21〇297297) (Please read the precautions on the back before filling this page)
五、發明説明（3) 經濟部中央標率局員工消費合作社印製 將上述含二級醇聚氨基甲酸酯聚合體溶液在6Q_9(rcT 加入已環氧氯丙院改質之含氯基分散性染料或反應性染料 反應，反應後可得與染料共價結合染色之聚氦基甲酸酯聚合 體。 4· PU無色聚合體塗層在織物或非織物上，或溶液紡成彈性纖 維，再進行染料之共價結合染色 將上述之含二級醇聚氨基甲酸酯聚合體（即PU無色聚合 體）塗層在織物或非織物上，或溶液紡成彈性纖維，再進行與已 環氧氯丙烷改質之含氯基分散性染料或反應性染料染色，可 得共價鏈結合染色。 爲了更了解本發明起見，特舉下例加以說明； 1 .將0 . 0 4摩爾的二甲基二異氰酸鹽（MDI)溶於30毫升 之溶劑二甲基甲醯胺（DMF)中，升溫至65°C攪拌之， 並充入氮氣。 2.稱取二醇（聚四甲基二醇PTMG) 0.02摩爾，溶於15 毫升之DMF後，自滴管緩慢滴入反應系統中’然後升溫 至70°C並反應1 .5小時。 3.降溫至5 °C，稱取N-(2 -羥基乙基）乙烯二胺 (HEDA ) (N-(2-Hydroxyethy1) Ethylene diamine 0.01摩爾溶於10毫升之DMF中，緩慢滴入反應系統 中，完畢後回溫至70°C反應0.5小時（不加乙二胺 (Hydrazine)時，則爲0.02摩爾反應1_〇小時）。 4.再降溫至5°C，稱取乙二胺G . 01摩爾溶於毫升之DMF 中，緩慢滴入反應系統中，完畢後回溫至^^反應 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (諳先閱讀背面之注$項再填寫本頁)V. Explanation of the invention (3) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, dispersing the above-mentioned secondary alcohol-containing polyurethane polymer solution in 6Q_9 (rcT with chlorine group modified by epichlorohydrin institute) The reactive dye or reactive dye reacts, and polyhelium carbamate polymer dyed covalently with the dye can be obtained after the reaction. 4. PU colorless polymer coating on fabric or non-woven fabric, or solution spinning into elastic fibers, Covalent binding dyeing of the dye is then applied to coat the above-mentioned secondary alcohol-containing polyurethane polymer (that is, PU colorless polymer) on the woven or non-woven fabric, or the solution is spun into elastic fibers, and then the cyclic Cochloro-chain disperse dyes or reactive dyes modified with oxychloropropane can be dyed to obtain covalent chain-linked dyes. In order to better understand the present invention, the following examples are given to illustrate; 1. 0.4 mol of Dimethyl diisocyanate (MDI) is dissolved in 30 ml of solvent dimethylformamide (DMF), heated to 65 ° C, stirred, and filled with nitrogen. 2. Weigh the diol (polytetramethylene) Methyl glycol PTMG) 0.02 mol, dissolved in 15 ml of DMF, Drop into the reaction system and then warm to 70 ° C and react for 1.5 hours. 3. Reduce the temperature to 5 ° C and weigh N- (2-hydroxyethyl) ethylenediamine (HEDA) (N- (2- Hydroxyethy1) 0.01 mole of Ethylene diamine is dissolved in 10 ml of DMF and slowly dropped into the reaction system. After completion, it is warmed to 70 ° C and reacted for 0.5 hours. 〇Hour). 4. Reduce the temperature to 5 ° C again, weigh out 0.01 moles of ethylenediamine G and dissolve in ml of DMF, slowly drop into the reaction system, and then return to the temperature after completion. Standard (CNS) A4 size (210X297 mm) (谙 Please read the note on the back before filling in this page)
A7 B7 418224 五、發明説明（4) 1.5小時。此即爲含二級醇聚氨基甲酸酯聚合體。 5. 將上述之含二級醇聚氨基甲酸酯聚合體溶液升溫至65 °C，加入已環氧氯丙烷改質之含氯基分散性染料或反 應性染料反應1-2小時，並以甲醇將未反應之染料 去除。 6. 將上述之含二級醇聚氨基甲酸酯聚合體（即PU無色聚合 體）塗層在織物上，可得聚氨基甲酸酯薄膜，在85°C下 以已環氧氯丙烷改質之含氯基分散性染料或反應性染 料染色1-2小時，並以甲醇將未反應之染料去除。 (二）、改質聚氨基甲酸酯聚合體之染色牢度測試： 本實驗做各型已染色聚氨基甲酸酯聚合體薄膜之遷徙牢 度（根據AATCC test method，測定其染料遷徙率（Mp%));如圖 1，玻璃平板上塗以薄膜（厚約G. 02cm)，A區罩以9cm直徑之錶玻 璃，B區不加任何覆蓋物，置於6〇°C密閉烘箱中，經過24小時之 後，分別取得A、B區之試樣溶於NMP中，濃度爲1(Γ3 Μ，置入石 英管中’以分光光電比色計求出其各別吸光度，可依下列公式求 出染料遷徙率（Mp%) : Mp%=((CB-CA)/CA)xlGQ%，此處(^爲八區之 吸光度’ 4爲3區之吸光度。其結果如表1所示，而日光牢度則如 表2所示;由實驗結果可知；熱遷徙牢色幾乎都在4%以下，而 曰光牢度多在4級以上。此顯示聚氨基甲酸酯與染料形成共價 鍵結合之材料，其染料不易因熱而遷徙及耐更高之日光牢 度。 本紙張纽適用中國國家;^率（CNS) M規格（21〇χ297公瘦） ---------------ϊτ (請先聞讀背面之注意事項再填寫本頁} - . 經濟部中央標準局—工消費合作社印製A7 B7 418224 V. Description of the invention (4) 1.5 hours. This is a secondary alcohol-containing polyurethane polymer. 5. The secondary alcohol-containing polyurethane polymer solution is heated to 65 ° C, and the epichlorohydrin-modified chlorine-containing disperse dye or reactive dye is added to react for 1-2 hours. Methanol removes unreacted dye. 6. Coating the above-mentioned secondary alcohol-containing polyurethane polymer (that is, PU colorless polymer) on the fabric to obtain a polyurethane film, which was modified with epichlorohydrin at 85 ° C. Dyed with a chlorine-containing disperse dye or reactive dye for 1-2 hours, and remove unreacted dye with methanol. (II) Dyeing Fastness Test of Modified Polyurethane Polymers: In this experiment, the migration fastness of various types of dyed polyurethane polymer films is measured (according to the AATCC test method, the dye migration rate is determined ( Mp%)); As shown in Figure 1, the glass plate is coated with a film (thickness about G. 02cm), and the area A is covered with a 9cm diameter glass. The area B is not covered with any cover and placed in a 60 ° C closed oven. After 24 hours, the samples in areas A and B were respectively dissolved in NMP, and the concentration was 1 (Γ3 Μ, put in a quartz tube 'to obtain their respective absorbances using a spectrophotometric colorimeter, which can be calculated according to the following formula Dye migration rate (Mp%): Mp% = ((CB-CA) / CA) xlGQ%, where (^ is the absorbance of eight regions' 4 is the absorbance of 3 regions. The results are shown in Table 1, and The light fastness is shown in Table 2. According to the experimental results, the thermal migration color is almost below 4%, and the light fastness is mostly above 4. This shows that polyurethane forms a covalent bond with the dye. Combined materials, its dyes are not easy to migrate due to heat and have higher light fastness. This paper is suitable for China; ^ rate (CNS) M specification (21〇χ297 Public thin) --------------- ϊτ (Please read the notes on the back before filling out this page}-. Printed by the Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives