200538601 玖、發明說明： 【發明所屬之技術領域】 本發明係關於-種用於織物整理加工的ρνρ/^〇2混成 材藥劑及其製備方法，大 W ^尤^ 一種用於製備織物染色後整理 加工所需的藥劑’使其可增進織物吸濕排汗性及耐氯染色 堅牢度之藥劑及其製備方法設計。 【先前技術】 汰目前有關織物之染色加工處理，主要係使用染料以浸 木或印木手奴施作於織物上，使織物的纖維染著染料而形 成預定的色彩或圖案化之色彩。 唯別述、我物經染色加工處理後，因該染色織物之色澤 、吸濕'排汗性以及耐氣染色堅牢度等方面，尚有未盡理想 之處’而為目前纺織相關業界研究的重點項目之一。 ,近年來’因受奈米科技之賜，奈米材料不斷被開發出 來，且各種奈米材料不斷被應用於各項技術領域，唯今染 色織物之整理加工用之藥劑應用技術領域中，尚未研發出 «適的奈米#料作藥劑施作於染色織物上，來提升其吸濕 排汗性及耐氣染色堅牢度。 μ 【發明内容】 本^月之主要目的在於提供一種用於織物整理加工的 pvp九/Si〇2混成材藥劑及其製備方法，使該混成材藥劑應用 於染色織物上’來增進織物吸濕排汗性及财氣染色堅牢度 〇 為達成刖揭目的，本發明所提出之技術方案係令該 PVP/Si〇2此成材藥劑之製備方法主要係選取以預定的 200538601 重量比溶於醇類溶液中，均勻攪拌作為a溶液，另選取 TE0S(睛提供中文譯名）以預定的重量比溶於醇類溶液，再 加入預定濃度且預定量的無機酸攪拌均勻作為b溶液，取 用預定量的a溶液及b溶液於室溫下混合均勻擾拌預定的 時間，製成液悲的PVP/Si〇2混成材藥劑，該混 成材藥劑並可應用於染色織物的整理加工處理，於織物上 形成具有奈米級孔洞的被覆層，用以增進該染色織物的吸 濕排汗性及耐氯染色堅牢度。 【實施方式】 有關本發明用於織物整理加工的pvp/si02混成材藥劑 其化學式如下··200538601 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a ρνρ / ^ 〇2 mixed material agent used for fabric finishing and a preparation method thereof. A large W ^ especially ^ is used for preparing fabric after dyeing Agents required for finishing processing are agents that can improve the fabric's moisture wicking and perspiration resistance and the fastness to chlorine dyeing and the design of preparation methods. [Previous technology] The current dyeing and processing of fabrics are mainly based on the use of dyes to impregnate wood or wooden hand slaves on fabrics, so that fabric fibers are dyed with dyes to form predetermined colors or patterned colors. It is only mentioned that after the dyeing process of our products, there are still unsatisfactory aspects of the dyed fabric's color, moisture absorption, perspiration resistance, and fastness to air dyeing. One of the key projects. In recent years, due to the gift of nanotechnology, nanomaterials have been continuously developed, and various nanomaterials have been continuously used in various technical fields. However, in the field of pharmaceutical application technology for finishing and processing of dyed fabrics, Developed «Suitable Nanometer # material as a medicament to be applied to dyed fabrics to improve its moisture absorption and perspiration resistance and fastness to air dyeing. [Summary of the invention] The main purpose of this month is to provide a pvp IX / Si02 mixed material agent for fabric finishing and a preparation method thereof, so that the mixed material agent is applied to dyed fabrics to improve fabric moisture absorption. Perspiration resistance and fastness of wealth dyeing 0 In order to achieve the purpose of disclosure, the technical solution proposed by the present invention is to make the preparation method of the PVP / Si〇2 material agent is mainly to select a predetermined 200538601 weight ratio to dissolve in alcohol In the solution, uniformly stir as the solution a, and select TE0S (Chinese translation provided by the eye) to dissolve in the alcohol solution at a predetermined weight ratio, and then add a predetermined concentration and a predetermined amount of inorganic acid to stir as the solution b. Take a predetermined amount of Solution a and solution b are mixed uniformly at room temperature and stirred for a predetermined time to prepare a liquid PVP / Si02 mixed material agent. The mixed material agent can be applied to the finishing treatment of dyed fabrics and formed on the fabric. A coating layer with nano-sized holes is used to improve the moisture wicking property and the fastness to chlorine dyeing of the dyed fabric. [Embodiment] The pvp / si02 mixed material medicament for fabric finishing of the present invention has the chemical formula as follows: ·
SiSi
HO 0 OH OH 0HO 0 OH OH 0
0H I H0-Si-OH 0— H0-Si-0-Si-0-Si-0H · I I HO 〇 - (¾ - CH~~0H I H0-Si-OH 0— H0-Si-0-Si-0-Si-0H · I I HO 〇-(¾-CH ~~
ch9ch9
CHCH
Η0-έί-0-έί- 0 —Si- OH / I / \Η0-έί-0-έί- 0 —Si- OH / I / \
〇H Si OH OH /\〇H Si OH OH / \
HO OH 上揭之化學式中，“—，，及“―，，係分別表示氫鍵。 有關该PVP/Si〇2混成材藥劑製備方法的具體實施例， 如第一圖所示，其主要包括有以下步驟·· 將重量百分比 15 〜25% 的 pVp(p〇iyViyPyrrolidone)( 睛提供中文譯名）溶於重量百分比7〇〜85%的異丙醇或其它 200538601 之醇類溶，中，並予以均勾授拌作為a溶液，· 將重量m 20〜繼的 _(TetraethGxysilane)( 請提供中文譯名）溶於重量百分Λ 6(^嶋異丙醇（ιρΑ)或 其它之醇類溶液中，並加人預定量濃H〇3~(MN的鹽酸 或其它之無機酸，並攪拌均勻為b溶液； 取預定量的a溶液及b溶液以溶膠_凝膠手段於室溫 下此口搜拌預^的時間，使其中之醇類溶液蒸發預定量， 製成本發明液態的PVP/Si〇2混成材藥劑。 刖述中，a溶液及b溶液之成份比例，以a溶液重量 百分比為25〜55%、b溶液重量百分比為45〜75%為最佳實施 例。 刖述之液態PVP/Si〇2混成材藥劑亦可放置於真空烘箱 中作乾燥處理，使其成為固態的pvp/Si〇2混成材藥劑，作 為備用，待該混成材藥劑使用時，再將其置入異丙醇或其 它之醇類溶液中還原為液態的混成材藥劑。 本發明製備的PVP/Si〇2混成材藥劑以FT-IR圖譜分析 ’如第二圖所示’在PVp/si〇2混成材藥劑之FT—IR圖中， 不同重量比的PVP/Si〇2混成材藥劑分別在1646cnrl、 1644cm 1、1643cm 1有明顯的>〇〇基團吸收峰，且隨te〇§ 的重量比增加而逐漸向低頻區偏移，而在1〇78cnrl、 1086CHT1、1082CHT1亦有明顯的吸收峰，此為Si—〇-Si基 團吸收峰，由此可證明，所合成之PVP/Si〇2混成材藥劑是 可以被確認的，而且，兩者間由於PVP之〉C：r〇基團吸收峰 有偏移現象，可證明兩者間有氫鍵的存在。 200538601 又，本發明製備的PVP/Si〇2以C_NMR分析時，如第三 圖所示’不同重量比的PVP/Si〇2混成材藥劑在ΐ78· 2、 Π8.0及㈣.4酬有C=〇基’依過去相關技術報告得知 ，一混成材中，兩種物質間如發生氫鍵結 定基團在-c.圖形上的偏移，而且是向高頻^移某= 此結果顯示，混成材藥劑中pvp之>c=〇基團會與無機相中 之Si〇2產生氫鍵結合，且當TE0S含量愈多時，愈往高頻 區偏移，此結果與PVP/Si〇2混成材藥劑之FTIR圖譜分析 互相印證。 如第四圖所示，係本發明pvp/si02混成材藥劑進行 TGA熱性質分析之情形，由圖中可以得知，不同重量比之 PVP/Si〇2混成材藥劑起始分解溫度會隨著TE〇s量增加而 降低’但分解速度卻隨著減緩，此係因TE〇s在混成材藥 劑中水解形成S i (0H)4，進而聚縮合生成s i 02之過程仍有 Si (0H)4未完成聚縮合，此現象隨te〇S量加而越明顯，但 sK〇H)4分解後，混成材藥劑中大多為pvp與Si〇2所形成 之網狀構造，而使其分解速度減緩，亦即會使該混成材藥 劑的熱穩定性相對提高，且無機相TE0S含量越多，其熱 穩定性越佳。 有關本發明製備成的PVP/Si02混成材藥劑於織物整理 加工之應用情形，以尼龍（Ny 1 on )織物為例，其係該尼龍 織布浸入先配置的染液中，於90GC下浸染45分鐘，再經 水洗、烘乾後裝袋，前述之染液中可添加親水劑及耐氣固 色劑，或可不添加；另取本發明液態的PVP/Si02混成材藥 200538601 劑溶液預定量，並加入預定量的水均勻攪拌，耗一浸潰 液備用其人，將染色織物浸置於前述該配置好的浸潰液 中預疋時間’並施以二浸二壓手段，達到壓吸率8 〇 %，然 後施以75〜85GC、1〜3分鐘之預乾處理，以及145〜155Gc、 1〜2分鐘之熱培處王里，使織物上形成被覆層，而完成該染 色織物之整理加工處理作業。 該染色織物經由本發明PVP/Si〇2混成材藥劑整理加工 處理後之表面型態，如第五圖所示之電子顯微照片所示， 其中，照片（A)顯示，純PVP表面是光滑密且平整的，照 片（B)顯示其|面光滑平整，但有小孔洞存在，照#⑹也 有孔洞的存在，但表面不平滑且有重疊狀，照片（D)、（ E) 不但顯不孔洞存在，而且顆粒較大且呈連續狀，此主要是 因TE0S量少時，其經由水解及聚縮合後所形成之顆粒狀 Si〇2較少，故能呈現出明顯的孔洞，孔洞的直徑極小，如 附件一所示，僅有2·3ηιη〜3·7ηπι左右。相反的，te〇s的比 例增加時，因所生成之Si〇2顆粒多且大多形成三度空間之 排列，使顆粒彼此間之距離縮小甚至於呈連續狀，故呈現 的圖形明顯具有顆粒狀，且由表知，其孔洞雖然偏大，可 達5.〇nm左右，但是本發明的所合成之pvp/Sih混成材藥 劑應用於染色織物整理加工後，其混成材藥劑成形的被覆 層孔洞大小均可達到奈米級尺寸。 如附件二所示，其係織物經染色加工後，再以 Si〇2奈米混成材藥劑進行壓吸處理者，該加工織物之k/s 值，由圖表中可知，加工織物經混成材藥劑壓吸處理，豆 200538601 色澤會稍變深，且隨著TE0S比例之增加，而色澤加深， 此係因染色後之織物經PVP/Si〇2混成材藥劑壓吸後，其一 方面因形成之Si〇2顆粒促使光線產生折射效果，另一方面 PVP對染料中金屬離子具有絡合作用，因此能提升加工織 物之色澤深度，但此增加的幅度是有限度的。另染色織物 、左皂洗後特別疋經過本發明混成材藥劑壓吸處理的織物 更具較高之固色效果。 如附件三所示，其係染色織物之吸濕排汗及耐氣堅牢 度之測定值圖表，由圖表中可以得知，各織物在親水性部 份皆有不錯效果，且多能在5秒内達到完成擴散的效果， 此係因PVP开〉成於織物表面之關係，但該加工織物經5次 水洗後之親水效果則稍有降低，尤其是織物於染色時不加 入親水劑之加工織物，有的甚至不合乎5秒之標準，由此 可見，親水劑的加入對加工織物之吸濕排汗性是有一定的 作用，但是如織物以較高重量比的pvp混成材藥劑壓吸處 理，其耐吸濕排汗性則佳，皆可達到標準，而且還比僅壓 吸PVP聚合物之染色織物好，由此顯示si〇2之適量存在， 使混成材藥劑中之PVP聚合物形成於織物上較不易被洗除 ，具有較佳的耐久性，反之，若無Si02與pvp聚合物結合 ’則形成於織物PVP聚合物則可能較易被洗除。 u、、&由以上說明中可以歸納出：本發明提供的製備方法 所製k出PVP/Si〇2混成材藥劑，可應用於染色織物整理加 工處理上，於織物上形成具有奈米級孔洞的被覆層，且藉 由4混成材藥劑對金屬錯鹽染料染色的織物具有提升吸濕 200538601 排汗性及耐氣染色堅牢度之效用等，因此，本發明所提出 之技術方案確可為織物製造業提供一項深具有產業利用價 值之發明，並符合發明專利要件，爰依法具文提出申請。 【圖式簡單說明】 $ (一）圖式部分 第一圖係本發明PVP/Si〇2混成材藥劑製備方法的流 程圖。 第二圖係本發明數種不同重量比之pVp/Si〇2混成材 藥劑以及純PVP之FT-IR分析圖。 第二圖係本發明數種不同重量比之PVP/Si 混成材 藥劑以及純PVP之C-NMR分析圖。 第四圖係本發明數種不同重量比之pyp/SiQ2混成材 藥劑以及純PVP之TGA分析圖。 第五圖係本發明數種不同重量比之PVP/Si02混成材 藥劑以及純PVP應用於染色織物整理加工後 之表面電子顯微照片。 (一）元件代表符號：無 (三）附件： 1.本發明數種不同重量比之pvp/si〇2混成材藥劑應 用於染色織物整理加工後，其孔洞各種性質表。 2·係本發明數種不同重量比之pyp/si〇2混成材藥劑 應用於尼龍布之染色性影響表。 3 ·係染色織物之吸濕排汗及耐氣堅牢度之測定值圖In the chemical formula disclosed on HO OH, “—,” and “―,” represent hydrogen bonds, respectively. As for the specific example of the preparation method of the PVP / Si〇2 mixed material medicine, as shown in the first figure, it mainly includes the following steps: · pVp (p〇iViyPyrrolidone) (15% to 25% by weight) (provided in Chinese) (Translated name) It is soluble in isopropyl alcohol or other 200538601 alcohols with a weight percentage of 70 ～ 85%, and it is mixed and mixed as a solution. · The weight m 20 ～ Following _ (TetraethGxysilane) (Please provide Chinese translation name) dissolved in Λ 6 (^ 嶋 isopropanol (ιρΑ) or other alcoholic solution by weight, and added a predetermined amount of concentrated H03 ~ (MN hydrochloric acid or other inorganic acid), and stir well Is solution b; take a predetermined amount of solution a and solution b by sol-gel method at room temperature for a predetermined time, evaporate a predetermined amount of the alcohol solution to prepare the liquid PVP / Si of the present invention 〇2Mixed material medicament. In the description, the component ratio of the a solution and the b solution is 25-55% by weight of the a solution, and 45-75% by weight of the b solution is the best embodiment. The liquid PVP described / Si〇2 mixed material agent can also be placed in a vacuum oven for drying treatment, so that The pvp / Si〇2 mixed material agent that becomes a solid state is used as a backup, and when the mixed material agent is used, it is put into isopropanol or other alcohol solution to reduce it to a liquid mixed material agent. Analysis of PVP / Si〇2 mixed material pharmaceuticals by FT-IR spectrum 'as shown in the second figure' In the FT-IR chart of PVp / si〇2 mixed material pharmaceuticals, PVP / Si〇2 mixed material pharmaceuticals of different weight ratios At 1646cnrl, 1644cm1, and 1643cm1, there are obvious > 〇〇 group absorption peaks, and gradually shifted to the low-frequency region as the weight ratio of te〇§ increases, but also obvious at 1078cnrl, 1086CHT1, 1082CHT1. This is the absorption peak of the Si—0-Si group. It can be proved that the synthesized PVP / Si0 2 mixed material agent can be confirmed. Moreover, due to the PVP> C: r There is a shift in the absorption peak of the group 〇, which can prove the existence of hydrogen bonds between the two. 200538601 In addition, when the PVP / Si〇2 prepared by the present invention is analyzed by C_NMR, as shown in the third figure, PVP with different weight ratios / Si〇2 mixed material medicament at ΐ78 · 2, Π8.0 and ㈣.4 have C = 〇 基 'according to past related technical reports It is learned that in a mixed material, if the hydrogen bonding group shift between the two materials occurs on the -c. Pattern, and it is shifted to a high frequency ^ = This result shows that the pvp of the mixed material agent is> ; c = 〇 group will be hydrogen bonded with Si〇2 in the inorganic phase, and the more TE0S content, the more shifted to the high frequency region, this result and the FTIR spectrum of PVP / Si〇2 mixed agent Analysis confirms each other. As shown in the fourth figure, it is the case of the TGA thermal property analysis of the pvp / si02 mixed material agent of the present invention. It can be seen from the figure that the initial decomposition temperature of the PVP / Si02 mixed material agent with different weight ratios will follow The amount of TE〇s increases and decreases', but the decomposition rate slows down. This is because TE 0s is hydrolyzed in the mixed material agent to form S i (0H) 4, and the process of polycondensation to form si 02 still has Si (0H). 4 The polycondensation has not been completed. This phenomenon becomes more obvious as the amount of te0S is increased. However, after the decomposition of SK0H) 4, most of the mixed agent pharmaceuticals have a network structure formed by pvp and Si02, which causes the decomposition speed. Slowing, that is to say, the thermal stability of the mixed material medicament will be relatively improved, and the more TEOS content in the inorganic phase, the better the thermal stability. Regarding the application of the PVP / Si02 mixed material agent prepared by the present invention in fabric finishing, a nylon (Ny 1 on) fabric is taken as an example. The nylon fabric is immersed in a previously-configured dyeing solution, and is dyed at 90GC 45. Minutes, and then washed with water, dried and packed in bags. The aforementioned dyeing liquid may be added with a hydrophilic agent and a gas-resistant fixing agent, or may not be added; another predetermined amount of the liquid PVP / Si02 mixed material medicine 200538601 solution of the present invention, And add a predetermined amount of water to stir uniformly, consume an impregnation solution for its own person, immerse the dyed fabric in the configured impregnation solution for a predetermined period of time ', and apply two-immersion and two-pressure means to achieve pressure absorption rate 80%, and then apply 75 ~ 85GC, 1 ~ 3 minutes of pre-drying treatment, and 145 ~ 155Gc, 1 ~ 2 minutes of heat culture to make the coating layer on the fabric to complete the finishing of the dyed fabric Processing operations. The surface shape of the dyed fabric after finishing treatment of the PVP / SiO2 mixed material agent of the present invention is shown in the electron micrograph shown in the fifth figure, wherein the photo (A) shows that the surface of the pure PVP is smooth Photograph (B) shows that the surface is smooth and flat, but there are small holes. Photo # ⑹ also has holes, but the surface is not smooth and overlapping. The photos (D), (E) are not only insignificant. The pores exist, and the particles are large and continuous. This is mainly because when the amount of TE0S is small, the particulate Si0 2 formed after hydrolysis and polycondensation is less, so it can show obvious pores and the diameter of the pores. Very small, as shown in Annex 1, only about 2.3ηι ~ 3 · 7ηπι. On the contrary, when the proportion of te〇s is increased, the number of Si0 2 particles generated and most of them form a three-dimensional space arrangement, the distance between the particles is reduced or even continuous, so the figure presented is obviously granular. It is known from the table that although the pores are relatively large, up to about 5.0 nm, the synthesized pvp / Sih mixed material agent of the present invention is applied to the coating layer holes of the mixed material agent after the dyeing fabric finishing process is applied. The size can reach nanometer size. As shown in Annex II, after the fabric is dyed and processed with Si0 2 nano-mixed materials, the k / s value of the processed fabric can be seen from the chart. Pressure suction treatment, beans 200538601 will become slightly darker, and with the increase of TE0S ratio, the color will become darker. This is because the dyed fabric is pressure-sucked by the PVP / Si〇2 mixed material agent. Si02 particles promote the refraction of light. On the other hand, PVP has a complexing effect on metal ions in dyes, so it can increase the color depth of processed fabrics, but the increase is limited. In addition, dyed fabrics and fabrics that have been left soap-washed are particularly well treated with the pressure-absorbing treatment of the mixed material agent of the present invention to have a higher color fixing effect. As shown in Annex III, it is a graph of the measured values of moisture absorption and perspiration resistance and air fastness of dyed fabrics. It can be seen from the graph that each fabric has a good effect on the hydrophilic part, and it can be more than 5 seconds. It achieves the effect of complete diffusion, which is due to the relationship between PVP and the surface of the fabric, but the hydrophilic effect of the processed fabric after 5 washings is slightly reduced, especially the processed fabric without adding a hydrophilic agent when the fabric is dyed Some even do not meet the standard of 5 seconds. It can be seen that the addition of a hydrophilic agent has a certain effect on the moisture absorption and sweat wicking properties of processed fabrics. , Its moisture absorption and perspiration resistance are all good, can reach the standard, and it is better than dyed fabrics that only absorb PVP polymer by pressure, which shows that the proper amount of si0 2 is present, so that the PVP polymer in the mixture agent is formed in The fabric is not easy to be washed off and has better durability. On the other hand, if there is no combination of SiO2 and pvp polymer, the PVP polymer formed on the fabric may be easier to be washed off. u ,, & can be summarized from the above description: the PVP / Si〇2 mixed material agent prepared by the preparation method provided by the present invention can be applied to the finishing treatment of dyed fabrics, and has a nanometer grade on the fabrics. The coating layer of holes, and the effect of improving the moisture absorption and the fastness of air-resistant dyeing on fabrics dyed with metal mixed salt dyes by 4 mixed material agents. Therefore, the technical solution proposed by the present invention can be indeed The textile manufacturing industry provides an invention with deep industrial value and meets the requirements for invention patents. [Schematic description] $ (I) Schematic part The first diagram is a flow chart of the preparation method of the PVP / Si02 mixed material agent of the present invention. The second figure is an FT-IR analysis chart of several pVp / SiO2 mixed materials and pure PVP according to the present invention. The second figure is a C-NMR analysis chart of several PVP / Si mixed materials and pure PVP according to the present invention. The fourth graph is the TGA analysis chart of several pyp / SiQ2 mixed materials and pure PVP according to the present invention. The fifth figure is an electron micrograph of the surface of several PVP / Si02 mixed materials and pure PVP used in the dyeing fabric finishing process of the present invention. (1) Symbols of components: None (3) Attachment: 1. Several kinds of pvp / si02 mixed material medicines of the present invention should be used for dyeing fabrics after finishing and processing. 2. It is a kind of pyp / sio2 mixed material medicine with different weight ratios of the present invention. 3 · Dyeing fabrics' moisture wicking and air fastness measurements