TW201506074A

TW201506074A - Polymer material and method for preparing the same and touch panel utilizing the same

Info

Publication number: TW201506074A
Application number: TW103124492A
Authority: TW
Inventors: Gokalp Bayramoglu; Gui-Bao Yang
Original assignee: Tpk Touch Solutions Xiamen Inc
Priority date: 2013-08-06
Filing date: 2014-07-17
Publication date: 2015-02-16
Also published as: CN104341703A; CN104341703B

Abstract

Disclosed is a polymer material including a first polymer copolymerized of N-(R)acrylamide and 4-styrenesulfonate, and a second polymer polymerized of 3,4-ethylenedioxythiophene, wherein R is C1-12 alkyl group or C1-12 alkoxy group. The first polymer is doped in the second polymer. The polymer material may serve as a thermal sensitive electrode pattern on a substrate of a touch panel.

Description

高分子材料與其製備方法及觸控面板 Polymer material, preparation method thereof and touch panel

本發明係關於高分子材料，更特別關其製備方法及在觸控面板的應用。 The invention relates to a polymer material, more particularly to a preparation method thereof and application to a touch panel.

高分子如聚噻吩及其衍生物如聚(3,4-乙烯二氧噻吩)(PEDOT)具有優異的物理及化學性質、低成本、與泛用前景，因此吸引廣泛注意。PEDOT與聚(4-苯乙烯磺酸鹽)(PSS)之混掺物(PEDOT：PSS)所形成的薄膜具有可見光的高透光率(90%)、高導電性(1000S‧cm)、氣敏性、與溫敏性(PEDOT：PSS薄膜在243K至343K之間的平均電阻溫度係數可達-0.2%/℃)。然而PEDOT：PSS薄膜的電阻溫度係數較差。舉例來說，PEDOT：PSS薄膜在人類體溫(~310K)的電阻溫度係數只介於-0.2%/℃至-0.3%/℃之間，如第1圖所示。 Polymers such as polythiophene and its derivatives such as poly(3,4-ethylenedioxythiophene) (PEDOT) have attracted excellent attention due to their excellent physical and chemical properties, low cost, and general use prospects. The film formed by the blend of PEDOT and poly(4-styrenesulfonate) (PSS) (PEDOT:PSS) has high transmittance (90%) of visible light, high conductivity (1000S‧cm), gas Sensitivity, and temperature sensitivity (PEDOT: PSS film average temperature coefficient of resistance between 243K and 343K can reach -0.2% / °C). However, the PEDOT:PSS film has a poor temperature coefficient of resistance. For example, the temperature coefficient of resistance of the PEDOT:PSS film at human body temperature (~310K) is only between -0.2%/°C and -0.3%/°C, as shown in Figure 1.

現有PEDOT：PSS薄膜在人類體溫(~310K)的電阻溫度係數只介於-0.2%/℃至-0.3%/℃之間。 The temperature coefficient of resistance of the existing PEDOT:PSS film at human body temperature (~310K) is only between -0.2%/°C and -0.3%/°C.

本發明一實施例提供一種高分子材料，包括：第一聚合物，係由N-(R)丙烯醯胺與4-苯乙烯磺酸鹽共聚而成，其中R係C_1-12烷基或C_1-12烷氧基；以及第二聚合物，係由3,4-乙烯二氧噻吩聚合而成，其中第一聚合物係掺雜於第二聚合物中。 An embodiment of the present invention provides a polymer material comprising: a first polymer obtained by copolymerization of N-(R) acrylamide and 4-styrene sulfonate, wherein R is a C _1-12 alkyl group or a C _1-12 alkoxy group; and a second polymer obtained by polymerizing 3,4-ethylenedioxythiophene, wherein the first polymer is doped in the second polymer.

本發明一實施例提供一種觸控面板，包括：基板；以及熱敏性電極圖案，位於基板上，其中熱敏性電極圖案包括上述之高分子材料。 An embodiment of the present invention provides a touch panel including: a substrate; and a heat sensitive electrode pattern on the substrate, wherein the heat sensitive electrode pattern The case includes the above polymer materials.

本發明一實施例提供一種高分子材料的製備方法，包括：自由基共聚N-(R)丙烯醯胺與4-苯乙烯磺酸鹽以形成第一聚合物，其中R係C_1-12烷基或C_1-12烷氧基；將3,4-乙烯二氧噻吩加入第一聚合物中；以及聚合3,4-乙烯二氧噻吩以形成第二聚合物，並形成第一聚合物摻雜第二聚合物之高分子材料。 An embodiment of the present invention provides a method for preparing a polymer material, comprising: radically copolymerizing N-(R) acrylamide and 4-styrene sulfonate to form a first polymer, wherein the R system is a C _1-12 alkane. Or a C _1-12 alkoxy group; adding 3,4-ethylenedioxythiophene to the first polymer; and polymerizing the 3,4-ethylenedioxythiophene to form a second polymer and forming a first polymer blend A polymer material of a second polymer.

本發明一實施例提供一種高分子材料，包括：第一聚合物，係由N-(R)丙烯醯胺與4-苯乙烯磺酸鹽共聚而成，其中R係C_1-12烷基或C_1-12烷氧基。 An embodiment of the present invention provides a polymer material comprising: a first polymer obtained by copolymerization of N-(R) acrylamide and 4-styrene sulfonate, wherein R is a C _1-12 alkyl group or C _1-12 alkoxy.

本發明之高分子材料薄膜在人類體溫(~310K)的電阻溫度係數介於-0.35%/℃至-0.6%/℃之間，可改善現有PEDOT：PSS薄膜在人類體溫的電阻溫度係數不足的問題。 The temperature coefficient of resistance of the polymer material film of the present invention at human body temperature (~310K) is between -0.35%/°C and -0.6%/°C, which can improve the temperature coefficient of resistance of the existing PEDOT:PSS film at human body temperature. problem.

第1圖係PEDOT：PSS分散液製備之薄膜的電阻-溫度曲線；第2圖係本發明一實施例中，SS與NIP之聚合物的IR光譜；第3圖係本發明一實施例中，SS與NIP之聚合物、NIP單體、與PEDOT：PSS分散液的IR光譜比較圖；第4圖係本發明一實施例中，以高分子材料製備之薄膜的電阻-溫度曲線；第5圖係本發明一實施例中，以高分子材料製備之薄膜的電阻-溫度曲線；第6圖係本發明一實施例中，以高分子材料製備之薄膜的電阻-溫度曲線；第7圖係本發明一實施例中，以高分子材料製備之薄膜的電阻-溫度曲線；以及第8圖係本發明一實施例中，以高分子材料製備之薄膜的電阻-溫度曲線。 1 is a resistance-temperature curve of a film prepared from a PEDOT:PSS dispersion; FIG. 2 is an IR spectrum of a polymer of SS and NIP in an embodiment of the present invention; and FIG. 3 is an embodiment of the present invention, Comparison of IR spectra of SS, NIP monomer, NIP monomer, and PEDOT:PSS dispersion; Figure 4 is a resistance-temperature curve of a film prepared from a polymer material in an embodiment of the present invention; In one embodiment of the present invention, a resistance-temperature curve of a film prepared from a polymer material; 6 is a resistance-temperature curve of a film prepared from a polymer material in an embodiment of the present invention; and FIG. 7 is a resistance-temperature curve of a film prepared from a polymer material in an embodiment of the present invention; Figure 8 is a graph showing the resistance-temperature curve of a film prepared from a polymer material in an embodiment of the present invention.

本發明一實施例提供一種高分子的製備方法。首先，以自由基聚合機制使N-(R)丙烯醯胺與4-苯乙烯磺酸鹽(SS)共聚形成聚合物1，如式1所示。 An embodiment of the invention provides a method for preparing a polymer. First, N-(R) acrylamide is copolymerized with 4-styrene sulfonate (SS) to form polymer 1 by a radical polymerization mechanism, as shown in Formula 1.

在式1中，R為直鏈、支鏈、或環狀(具有低立體障礙)的C_1-12烷基或C_1-12烷氧基。舉例來說，R可為甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、月桂基、或上述之衍生物。此外，R可為甲氧基、乙氧基、丙氧基、異戊氧基、或上述之衍生物。M可為一價金屬離子如鈉離子或鉀離子。單體的重複數目m與n之間的比例(即N-(R)丙烯醯胺與SS的莫耳比例)介於0.01：1至1.2：1之間(0.01：1≦m/n≦1.2：1)，並且聚合物1之重均分子量介於14,000至500,000之間。此外，自由基聚合採用之起始劑可為偶氮化合物如偶氮二異丁腈(AIBN)、偶氮二異丁腈(ABVN)、或類似物；過氧化合物如過二硫酸鉀、過氧化二苯甲醯(BPO)、過硫酸銨(APS)、或類似物；或氧化還原系統如過硫酸氨/亞硫酸氫鈉或類似物。 In Formula 1, R is a linear, branched, or cyclic (having a low steric hindrance) C _1-12 alkyl group or a C _1-12 alkoxy group. For example, R can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, lauryl, or the like a derivative. Further, R may be a methoxy group, an ethoxy group, a propoxy group, an isopentyloxy group, or a derivative thereof. M may be a monovalent metal ion such as a sodium ion or a potassium ion. The ratio of the number of repeats of the monomers m to n (ie, the molar ratio of N-(R) acrylamide to SS) is between 0.01:1 and 1.2:1 (0.01:1≦m/n≦1.2) :1), and the polymer 1 has a weight average molecular weight of between 14,000 and 500,000. Further, the initiator used in the radical polymerization may be an azo compound such as azobisisobutyronitrile (AIBN), azobisisobutyronitrile (ABVN), or the like; a peroxy compound such as potassium peroxydisulfate, Benzoyl sulfonium oxide (BPO), ammonium persulfate (APS), or the like; or a redox system such as ammonium persulfate/sodium hydrogen sulfite or the like.

接著，將3,4-乙烯二氧噻吩(EDOT)加入聚合物1之溶液中，並使EDOT聚合形成聚合物2(PEDOT)，如式2所示，藉以形成聚合物1摻雜聚合物2(PEDOT)的高分子材料。在一實施例中，式2中EDOT單體的重複單元p較佳介於33至1000之間(33≦p≦1000)。換言之，PEDOT之重均分子量較佳介於20,000至600,000之間，且聚合物1與EDOT之莫耳比例介於1：1至1：10之間。 Next, 3,4-ethylenedioxythiophene (EDOT) is added to the solution of polymer 1, and EDOT is polymerized to form polymer 2 (PEDOT), as shown in formula 2, thereby forming polymer 1 doped polymer 2 (PEDOT) polymer material. In one embodiment, the repeating unit p of the EDOT monomer of Formula 2 is preferably between 33 and 1000 (33 ≦p ≦ 1000). In other words, the weight average molecular weight of PEDOT is preferably between 20,000 and 600,000, and the molar ratio of polymer 1 to EDOT is between 1:1 and 1:10.

承上所述，以重均分子量來看式2，若聚合物1之重均分子量過高，將會降低本實施例之高分子材料在形成薄膜後的導電性；若聚合物1之重均分子量過低，則高分子材料無法輕易分散於溶劑中，不但會讓高分子材料在形成薄膜時的均勻性降低，甚至無法成膜。反過來講，若PEDOT之重均分子量過高，高分子材將無法輕易分散於溶劑中，不但難以成膜，且溫度電阻係數將得不到提高；若PEDOT之重均分子量過低，將降低高分子材料在形成薄膜後的導電性。 According to the above, the weight average molecular weight is considered to be 2, and if the weight average molecular weight of the polymer 1 is too high, the polymer material of the present embodiment is lowered. Conductivity after film; if the weight average molecular weight of the polymer 1 is too low, the polymer material cannot be easily dispersed in the solvent, which not only reduces the uniformity of the polymer material when forming a film, but also does not even form a film. Conversely, if the weight average molecular weight of PEDOT is too high, the polymer material will not be easily dispersed in the solvent, and it is difficult to form a film, and the temperature resistivity will not be improved; if the weight average molecular weight of PEDOT is too low, it will decrease. The conductivity of the polymer material after forming the film.

此外，由上述可知，N-(R)丙烯醯胺、SS與EDOT之莫耳比例是例如介於0.01~1.2：1：1~10之間。因此，以莫耳比例來看式1及式2，若N-(R)丙烯醯胺之莫耳比例過高，將會降低聚合物1摻雜於PEDOT的掺雜效應，也就是高分子材料將無法輕易分散於溶劑中，具有低導電性；若N-(R)丙烯醯胺之莫耳比例過低，高分子材料的電阻溫度係數將無法有效增加。若EDOT之莫耳比例過高，則高分子材料將無法輕易分散於溶劑中，不但難以成膜還具有低電阻溫度係數；若EDOT之莫耳比例過低，將使高分子材料具有低導電性而無法作為電極。 Further, as apparent from the above, the molar ratio of N-(R) acrylamide, SS and EDOT is, for example, between 0.01 and 1.2:1:1 to 10. Therefore, considering the molar ratio of formula 1 and formula 2, if the molar ratio of N-(R) acrylamide is too high, the doping effect of polymer 1 doped on PEDOT will be reduced, that is, polymer material. It will not be easily dispersed in the solvent and has low conductivity; if the molar ratio of N-(R) acrylamide is too low, the temperature coefficient of resistance of the polymer material will not be effectively increased. If the molar ratio of EDOT is too high, the polymer material will not be easily dispersed in the solvent, and it is difficult to form a film and has a low temperature coefficient of resistance; if the molar ratio of EDOT is too low, the polymer material will have low conductivity. It cannot be used as an electrode.

附帶一提的是，本實施例的EDOT的聚合機制不同於聚合物1之自由基聚合機制。舉例來說，EDOT係於酸性條件(pH值介於2至3之間)下，搭配觸媒如硫酸鐵(或氯化鐵)，聚合形成PEDOT。如此一來，聚合物1掺雜於PEDOT中就如式2所示，聚合物1之陰離子將與PEDOT之正電荷結合。 Incidentally, the polymerization mechanism of the EDOT of the present embodiment is different from the radical polymerization mechanism of the polymer 1. For example, EDOT is polymerized to form PEDOT under acidic conditions (pH between 2 and 3) with a catalyst such as iron sulphate (or ferric chloride). As such, polymer 1 is doped in PEDOT as shown in Formula 2, and the anion of Polymer 1 will combine with the positive charge of PEDOT.

在另一實施例中，式2中由聚合物1摻雜PEDOT而成的高分子材料將進一步置於極性溶劑如二甲基甲醯胺(DMF)、二甲基亞碸(DMSO)、山梨醇、或類似物中，並進行超音波震盪，使PEDOT之主鏈所包含的苯式結構(benzoid)及醌式結構(quinoid)中至少部分的苯式結構轉變為醌式結構。醌式結構的導電性高於苯式結構的導電性。雖然式3中是以所有的苯式結構均轉變為醌式結構來說明，但實際應用上可只轉變部分的苯式結構至醌式結構，並使其他部分的苯式結構維持原有的苯式結構。關於上述苯式結構/醌式結構的轉變機制，可參考期刊Organic Electronics 9(2008)第727至734頁。不論PEDOT為苯式結構、醌式結構、或上述之組合，聚合物1之陰離子均與PEDOT之負電荷結合，如式中虛線所示。 In another embodiment, the polymer material of Formula 2 in which PEDOT is doped with Polymer 1 is further placed in a polar solvent such as dimethylformamide (DMF), dimethyl hydrazine (DMSO), and Yamanashi. In the alcohol or the like, ultrasonic vibration is performed to convert at least a part of the benzene structure and the quinone structure contained in the main chain of the PEDOT into a quinoid structure. The conductivity of the 醌 structure is higher than that of the benzene structure. Although in Equation 3, all the benzene structures are converted into a 醌 structure, but the practical application can be Only a part of the benzene structure is converted to the 醌 structure, and the benzene structure of other parts is maintained to maintain the original benzene structure. For the above-mentioned transformation mechanism of the benzene structure/醌 structure, reference is made to the journal Organic Electronics 9 (2008) at pages 727 to 734. Whether PEDOT is a benzene structure, a quinoid structure, or a combination thereof, the anion of polymer 1 is combined with the negative charge of PEDOT, as indicated by the dashed line in the formula.

進一步的，可將DMSO加入式3中的高分子材料後進行攪拌，接著加入乙醇以進一步超音波振盪式3中的高分子材料。上述步驟可增加PEDOT之主鏈中的醌式結構莫耳比例，並降低PEDOT之主鏈中的苯式結構莫耳比例。在一實施例中，DMSO與式3中的高分子材料之重量比例介於2wt%至10wt%之間，較佳為5wt%。在一實施例中，乙醇與式3中的高分子材料之重量比例介於1wt%至5wt%之間，較佳為2wt%。本實施例經超音波振盪後所製備成的高分子材料溶液可塗佈、印刷、旋塗、或電鍍至基板上以形成薄膜。此薄膜具有高透光性、高導電性(500S/cm)、氣敏性、與高溫敏性(在-30℃至70℃之間的平均電阻溫度係數介於-0.3%/℃至-0.5%/℃之間)。如此一來，本實施例之薄膜可作為觸控面板的基板上的溫敏性電極圖案。至於如何以高分子材料形成溫敏性電極圖案，請參考美國專利申請號10/152,260。 Further, DMSO may be added to the polymer material in Formula 3, followed by stirring, followed by the addition of ethanol to further ultrasonically oscillate the polymer material in Formula 3. The above steps can increase the molar ratio of the 结构 structure in the main chain of PEDOT and reduce the proportion of benzene structure in the main chain of PEDOT. In one embodiment, the weight ratio of DMSO to the polymeric material in Formula 3 is between 2% and 10% by weight, preferably 5% by weight. In one embodiment, the weight ratio of ethanol to the polymeric material of Formula 3 is between 1% and 5% by weight, preferably 2% by weight. The polymer material solution prepared by ultrasonic vibration in this embodiment can be coated, printed, spin-coated, or plated onto a substrate to form a film. The film has high light transmittance, high conductivity (500S/cm), gas sensitivity, and high temperature sensitivity (average temperature coefficient of resistance between -30 ° C and 70 ° C is between -0.3% / ° C to -0.5 Between %/°C). In this way, the film of the embodiment can be used as a temperature sensitive electrode pattern on the substrate of the touch panel. For how to form a temperature sensitive electrode pattern from a polymeric material, please refer to U.S. Patent Application Serial No. 10/152,260.

為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明。其中，下文實施例中的N-(R)丙烯醯胺是以R為C_1-12烷基類的N-異丙基丙烯醯胺(NIP)來舉例說明。 The above and other objects, features, and advantages of the present invention will be apparent from the accompanying drawings. Among them, the N-(R) acrylamide in the following examples is exemplified by N-isopropyl acrylamide (NIP) wherein R is a C _1-12 alkyl group.

【實施例】 [Examples]

實施例1 Example 1

以減壓蒸餾法分別純化NIP與EDOT。以氧化鋁管柱純化4-苯乙烯磺酸鈉鹽(SS)。將反應瓶抽真空後，將氮氣灌入/抽出反應瓶數次。接著將純化後的NIP(0.0025mole)、純化後的SS(0.025mole)、與100mL的去離子水加入反應瓶中。之後以NIP與SS之總重量為基準，將1wt%的過硫酸鉀加入反應瓶中。上述混合物在充份攪拌後，於氮氣下加熱至85℃並於85℃下反應24小時，再降溫至室溫。降溫後之粗產物先經透析導管進行透析4小時，以移除重均分子量小於14,000之化合物，並得到SS與NIP之聚合物溶液。SS與NIP之聚合物的IR光譜如第2圖所示。SS與NIP之聚合物、NIP單體、與PEDOT：PSS(Clevios PH 500)之IR光譜比較圖如第3圖所示。 NIP and EDOT were separately purified by vacuum distillation. The sodium 4-styrenesulfonate (SS) was purified on an alumina column. After the reaction flask was evacuated, nitrogen was poured/extracted from the reaction flask several times. The purified NIP (0.0025 mole), purified SS (0.025 mole), and 100 mL of deionized water were then added to the reaction flask. Thereafter, 1 wt% of potassium persulfate was added to the reaction flask based on the total weight of NIP and SS. After the mixture was thoroughly stirred, it was heated to 85 ° C under nitrogen and reacted at 85 ° C for 24 hours, and then cooled to room temperature. The cooled crude product was dialyzed through a dialysis catheter for 4 hours to remove a compound having a weight average molecular weight of less than 14,000, and a polymer solution of SS and NIP was obtained. The IR spectra of the SS and NIP polymers are shown in Figure 2. The IR spectrum comparison of SS, NIP polymer, NIP monomer, and PEDOT:PSS (Clevios PH 500) is shown in Figure 3.

接著將EDOT(0.025mole)加入上述聚合物溶液，並將鹽酸加入上述混合物，將其pH值調整至2至3之間。以酸化混合物重量為基準，將1wt%之過硫酸銨與1wt%之硫酸鐵加入酸化混合物中。上述混合物(NIP/SS/EDOT之莫耳比為0.1：1：1)於室溫下攪拌24小時後，以超音波振盪2小時，以陰離子交換樹脂(717，購自廣東西隴化工有限公司，中國)進行離子交換4小時，再以陽離子交換樹脂(734，購自廣東西隴化工有限公司，中國)進行離子交換。接著將離子交換後之粗產物經透析導管進行透析48小時，以移除重均分子量小於20,000之化合物。至此所得之產物為NIP與SS之聚合物掺雜於PEDOT中的高分子材料，其產率為60%。接著以高分子材料重量為基準，將5wt%之DMSO加入高分子材料後攪拌，再將5wt%之乙醇加入高分子材料以進一步超音波振盪高分子材料。將超音波振盪後的高分子材料溶液塗佈於基板上以形成薄膜。此薄膜在-30℃至70℃之間的平均電阻溫度係數為-0.60%/℃，如第4圖所示。 Next, EDOT (0.025 mole) was added to the above polymer solution, and hydrochloric acid was added to the above mixture to adjust the pH to between 2 and 3. 1 wt% of ammonium persulfate and 1 wt% of ferric sulfate were added to the acidified mixture based on the weight of the acidified mixture. The above mixture (NIP/SS/EDOT molar ratio of 0.1:1:1) was stirred at room temperature for 24 hours, and then ultrasonically shaken for 2 hours to anion exchange resin (717, purchased from Guangshen Chemical Co., Ltd. , China) Ion exchange for 4 hours, and then ion exchange with cation exchange resin (734, purchased from Guangzhou East and West Chemical Co., Ltd., China). The crude product after ion exchange was then dialyzed through a dialysis catheter for 48 hours to remove compounds having a weight average molecular weight of less than 20,000. The product thus obtained was a polymer material in which a polymer of NIP and SS was doped in PEDOT, and the yield was 60%. Then, based on the weight of the polymer material, 5% by weight of DMSO is added to the polymer material, and then stirred. 5 wt% of ethanol was added to the polymer material to further ultrasonically oscillate the polymer material. The polymer material solution after the ultrasonic vibration is applied onto the substrate to form a thin film. The film has an average temperature coefficient of resistance between -30 ° C and 70 ° C of -0.60% / ° C, as shown in Figure 4.

實施例2 Example 2

實施例2之製程與實施例1類似，差異在於實施例2的起始物(NIP/SS/EDOT)莫耳比例由0.1：1：1改變為0.01：1：1。與實施例1相較，實施例2之SS/EDOT的莫耳比例固定於1：1，而NIP/SS之莫耳比例由0.1：1改變為0.01：1。實施例2製備之高分子材料所形成的薄膜在-30℃至70℃之間的平均電阻溫度係數為-0.36%/℃，如第5圖所示。 The process of Example 2 was similar to that of Example 1, except that the starting material (NIP/SS/EDOT) molar ratio of Example 2 was changed from 0.1:1:1 to 0.01:1:1. Compared with Example 1, the molar ratio of the SS/EDOT of Example 2 was fixed at 1:1, and the molar ratio of NIP/SS was changed from 0.1:1 to 0.011. The film formed by the polymer material prepared in Example 2 had an average temperature coefficient of resistance between -30 ° C and 70 ° C of -0.36% / ° C, as shown in FIG.

實施例3 Example 3

實施例3之製程與實施例1類似，差異在於實施例3的起始物(NIP/SS/EDOT)莫耳比例由0.1：1：1改變為1.2：1：1。與實施例1相較，實施例3之SS/EDOT的莫耳比例固定於1：1，而NIP/SS之莫耳比例由0.1：1改變為1.2：1。實施例3製備之高分子材料所形成的薄膜在-30℃至70℃之間的平均電阻溫度係數為-0.45%/℃，如第6圖所示。 The procedure of Example 3 was similar to that of Example 1, except that the starting material (NIP/SS/EDOT) molar ratio of Example 3 was changed from 0.1:1:1 to 1.2:1:1. Compared with Example 1, the molar ratio of the SS/EDOT of Example 3 was fixed at 1:1, and the molar ratio of NIP/SS was changed from 0.1:1 to 1.2:1. The film formed by the polymer material prepared in Example 3 had an average temperature coefficient of resistance between -30 ° C and 70 ° C of -0.45% / ° C, as shown in FIG.

實施例4 Example 4

實施例4之製程與實施例1類似，差異在於實施例4的起始物(NIP/SS/EDOT)莫耳比例由0.1：1：1改變為0.1：1：3。與實施例1相較，實施例4之NIP/SS的莫耳比例固定於0.1：1，而SS/EDOT之莫耳比例由1：1改變為1：3。實施例4製備之高分子材料所形成的薄膜在-30℃至70℃之間的平均電阻溫度係數為-4.36%/℃，如第7圖所示。 The process of Example 4 was similar to that of Example 1, except that the starting material (NIP/SS/EDOT) molar ratio of Example 4 was changed from 0.1:1:1 to 0.1:1:3. Compared with Example 1, the molar ratio of NIP/SS of Example 4 was fixed at 0.1:1, and the molar ratio of SS/EDOT was changed from 1:1 to 1:3. The film formed by the polymer material prepared in Example 4 had an average temperature coefficient of resistance between -30 ° C and 70 ° C of -4.36% / ° C, as shown in FIG.

實施例5 Example 5

實施例5之製程與實施例1類似，差異在於實施例5的起始物(NIP/SS/EDOT)莫耳比例由0.1：1：1改變為0.1：1：10。與實施例1相較，實施例5之NIP/SS的莫耳比例固定於0.1：1，而SS/EDOT之莫耳比例由1：1改變為1：10。實施例5製備之高分子材料所形成的薄膜在-30℃至70℃之間的平均電阻溫度係數為-0.45%/℃，如第8圖所示。 The procedure of Example 5 was similar to that of Example 1, except that the starting material (NIP/SS/EDOT) molar ratio of Example 5 was changed from 0.1:1:1 to 0.1:1:10. Compared with the first embodiment, the molar ratio of the NIP/SS of the embodiment 5 is fixed at 0.1:1. The molar ratio of SS/EDOT changed from 1:1 to 1:10. The film formed by the polymer material prepared in Example 5 had an average temperature coefficient of resistance between -30 ° C and 70 ° C of -0.45% / ° C, as shown in FIG.

雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims

一種高分子材料，包括：一第一聚合物，係由N-(R)丙烯醯胺與4-苯乙烯磺酸鹽共聚而成，其中R係C_1-12烷基或C_1-12烷氧基；以及一第二聚合物，係由3,4-乙烯二氧噻吩聚合而成，其中該第一聚合物係掺雜於該第二聚合物中。 A polymer material comprising: a first polymer obtained by copolymerization of N-(R) acrylamide and 4-styrene sulfonate, wherein R is a C _1-12 alkyl group or a C _1-12 alkane And a second polymer obtained by polymerizing 3,4-ethylenedioxythiophene, wherein the first polymer is doped in the second polymer.

如申請專利範圍第1項所述之高分子材料，其中該N-(R)丙烯醯胺與4-苯乙烯磺酸鹽之莫耳比例介於0.01：1至1.2：1之間。 The polymer material according to claim 1, wherein the molar ratio of the N-(R) acrylamide to the 4-styrene sulfonate is between 0.01:1 and 1.2:1.

如申請專利範圍第1項所述之高分子材料，其中該N-(R)丙烯醯胺、4-苯乙烯磺酸鹽、與3,4-乙烯二氧噻吩之莫耳比例為0.01~1.2：1：1~10。 The polymer material according to claim 1, wherein the N-(R) acrylamide, the 4-styrene sulfonate, and the molar ratio of the 3,4-ethylenedioxythiophene are 0.01 to 1.2. :1:1~10.

如申請專利範圍第1項所述之高分子材料，其中該第一聚合物之重均分子量介於14,000至500,000之間。 The polymer material according to claim 1, wherein the first polymer has a weight average molecular weight of between 14,000 and 500,000.

如申請專利範圍第1項所述之高分子材料，其中該第二聚合物之重均分子量介於20,000至600,000之間。 The polymer material according to claim 1, wherein the second polymer has a weight average molecular weight of between 20,000 and 600,000.

如申請專利範圍第1項所述之高分子材料，其中該N-(R)丙烯醯胺包括N-異丙基丙烯醯胺。 The polymer material according to claim 1, wherein the N-(R) acrylamide comprises N-isopropyl acrylamide.

如申請專利範圍第1項所述之高分子材料，其中該第二聚合物之主鏈包括一苯式結構及/或一醌式結構。 The polymer material according to claim 1, wherein the main chain of the second polymer comprises a benzene structure and/or a quinone structure.

一種觸控面板，包括：一基板；以及一熱敏性電極圖案，位於該基板上，其中該熱敏性電極圖案包括申請專利範圍第1項所述之高分子材料。 A touch panel includes: a substrate; and a heat sensitive electrode pattern on the substrate The heat sensitive electrode pattern includes the polymer material described in claim 1 of the patent application.

一種高分子材料的製備方法，包括：自由基共聚N-(R)丙烯醯胺與4-苯乙烯磺酸鹽以形成一第一聚合物，其中R係C_1-12烷基或C_1-12烷氧基；將3,4-乙烯二氧噻吩加入該第一聚合物中；及聚合3,4-乙烯二氧噻吩以形成一第二聚合物，以形成該第一聚合物摻雜該第二聚合物之高分子材料。 A method for preparing a polymer material, comprising: radical copolymerization of N-(R) acrylamide and 4-styrene sulfonate to form a first polymer, wherein R is a C _1-12 alkyl group or a C _{1- 12} alkoxy; adding 3,4-ethylenedioxythiophene to the first polymer; and polymerizing 3,4-ethylenedioxythiophene to form a second polymer to form the first polymer doping A polymer material of the second polymer.

如申請專利範圍第9項所述之高分子材料的製備方法，其中該N-(R)丙烯醯胺與4-苯乙烯磺酸鹽之莫耳比例介於0.01：1至1.2：1之間。 The method for preparing a polymer material according to claim 9, wherein the molar ratio of the N-(R) acrylamide to the 4-styrene sulfonate is between 0.01:1 and 1.2:1. .

如申請專利範圍第9項所述之高分子材料的製備方法，其中該N-(R)丙烯醯胺、4-苯乙烯磺酸鹽、與3,4-乙烯二氧噻吩之莫耳比例為0.01~1.2：1：1~10。 The method for preparing a polymer material according to claim 9, wherein the molar ratio of the N-(R) acrylamide, the 4-styrene sulfonate, and the 3,4-ethylenedioxythiophene is 0.01~1.2:1:1~10.

如申請專利範圍第9項所述之高分子材料的製備方法，其中該第一聚合物之重均分子量介於14,000至500,000之間。 The method for producing a polymer material according to claim 9, wherein the first polymer has a weight average molecular weight of between 14,000 and 500,000.

如申請專利範圍第9項所述之高分子材料的製備方法，其中該第二聚合物之重均分子量介於20,000至600,000之間。 The method for producing a polymer material according to claim 9, wherein the second polymer has a weight average molecular weight of between 20,000 and 600,000.

如申請專利範圍第9項所述之高分子材料的製備方法，其中該N-(R)丙烯醯胺包括N-異丙基丙烯醯胺。 The method for producing a polymer material according to claim 9, wherein the N-(R) acrylamide comprises N-isopropylacrylamide.

如申請專利範圍第9項所述之高分子材料的製備方法，其中聚合3,4-乙烯二氧噻吩以形成該第二聚合物之步驟係於一酸性條件下進行。 The method for producing a polymer material according to claim 9, wherein the step of polymerizing the 3,4-ethylenedioxythiophene to form the second polymer is carried out under an acidic condition.

如申請專利範圍第9項所述之高分子材料的製備方法更包括將該第一聚合物摻雜該第二聚合物之高分子材料置於一極性溶劑中並進行超音波振盪，以增加該第二聚合物之主鏈中的一醌式結構莫耳比例，並降低該第二聚合物之主鏈中的一苯式結構莫耳比例。 The method for preparing a polymer material according to claim 9 further comprises: placing the polymer material of the first polymer doped with the second polymer in a polar solvent and performing ultrasonic oscillation to increase the A monomolecular molar ratio in the backbone of the second polymer and a reduction in the monophenyl structure molar ratio in the backbone of the second polymer.

一種高分子材料，包括：一第一聚合物，係由N-(R)丙烯醯胺與4-苯乙烯磺酸鹽共聚而成，其中R係C_1-12烷基或C_1-12烷氧基。 A polymer material comprising: a first polymer obtained by copolymerization of N-(R) acrylamide and 4-styrene sulfonate, wherein R is a C _1-12 alkyl group or a C _1-12 alkane Oxygen.

如申請專利範圍第17項所述之高分子材料，其中N-(R)丙烯醯胺與4-苯乙烯磺酸鹽之莫耳比例介於0.01：1至1.2：1之間。 The polymer material according to claim 17, wherein the molar ratio of N-(R) acrylamide to 4-styrene sulfonate is between 0.01:1 and 1.2:1.

如申請專利範圍第17項所述之高分子材料，其中該N-(R)丙烯醯胺包括N-異丙基丙烯醯胺。 The polymer material according to claim 17, wherein the N-(R) acrylamide comprises N-isopropyl acrylamide.