TW201700522A - A flame retardant material of waterborne polyurethanes - Google Patents
A flame retardant material of waterborne polyurethanes Download PDFInfo
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本發明為一種水性聚氨酯阻燃性材料，為含有雙酚芴結構之水性聚氨酯(waterborne polyurethane,WPU)新型環保材料，該材料為可生物分解、無VOC之汙染、製程簡易並具優異耐熱性質。本發明是以預聚物混合法製備不同雙酚芴結構含量的水性聚氨酯分散液，製備時由具有雙酚芴構造及親水基之多元醇化合物與多異氰酸酯反應生成預聚合物，加入水，形成預聚物水性分散液，其後再以鏈延長劑和預聚合物之NCO基反應增加分子量而形成水性聚氨酯阻燃性材料，以此製成各種成型品，或塗佈於各種基材上，而獲得具有優異阻燃性之製品。 The invention relates to an aqueous polyurethane flame retardant material, which is a novel environmentally friendly material of waterborne polyurethane (WPU) containing a bisphenol fluorene structure, which is biodegradable, VOC-free, simple in process and excellent in heat resistance. The invention prepares an aqueous polyurethane dispersion with different bisphenolphthalein structure content by a prepolymer mixing method, and a polyol compound having a bisphenol fluorene structure and a hydrophilic group is reacted with a polyisocyanate to form a prepolymer, and water is added to form a prepolymer. The prepolymer aqueous dispersion is then reacted with a chain extender and a NCO group of a prepolymer to increase the molecular weight to form an aqueous polyurethane flame retardant material, thereby preparing various molded articles or coating them on various substrates. A product having excellent flame retardancy is obtained.
水性PU的發展已有30多年，商品化也有近20年的歷史，在製程技術已經相當純熟，然而在產品的應用上仍不十分廣泛，主要的原因如下： The development of water-based PU has been more than 30 years, and the commercialization has a history of nearly 20 years. The process technology is quite mature. However, the application of the product is still not very extensive. The main reasons are as follows:
(1)乾燥較慢：由於水的熵(Enthalpy)較有機溶劑高，在相同固含量下，水性PU乾燥所需的能量為溶劑型PU的3倍多，導致應用廠商在不修改現有乾燥設備的情形下，唯有降低生產速率，才能確保產品的乾燥。 (1) Slow drying: Since the entropy of water is higher than that of organic solvents, the energy required for drying of aqueous PU is more than three times that of solvent-based PU at the same solid content, resulting in the application manufacturer not modifying existing drying equipment. In this case, only by reducing the production rate can the product be dried.
(2)溼潤性不佳：由於水性PU的表面張力很大，對於極性較低的基材如離型紙、PP膜等的溼潤性不佳，須借助流變改質劑以及其他界面改質劑， 以達到理想的溼潤以及塗佈效果。 (2) Poor wettability: Due to the large surface tension of aqueous PU, the wettability of substrates with lower polarity such as release paper and PP film is not good, and rheological modifiers and other interface modifiers are required. To achieve the desired wetting and coating effect.
(3)耐水性較差：由於在水性PU主鏈上導入親水性官能基，相對上具有較高的親水性，因此耐水性較差。 (3) Poor water resistance: Since a hydrophilic functional group is introduced into the aqueous PU main chain, it has relatively high hydrophilicity, and thus has poor water resistance.
水性與溶劑型PU性能之比較如表1 The comparison of waterborne and solvent-based PU properties is shown in Table 1.
(4)耐燃性較差：傳統之水性PU作為塗料時，由於耐燃性不足很難作為防火阻燃性材料。 (4) Poor flame resistance: When the conventional water-based PU is used as a coating, it is difficult to be used as a fire-retardant material due to insufficient flame resistance.
(5)價格較高：芳香族二異氰酸酯對水的高反應性，因此商業上的產品還是使用單價較高的脂肪族或環脂肪族二異氰酸酯為原料，使得水性PU的原料成本較溶劑型PU高，水性PU與溶劑型PU的原料成本比較如表2。 (5) Higher price: the high reactivity of aromatic diisocyanate to water, so the commercial product is still based on the higher unit price of aliphatic or cycloaliphatic diisocyanate, making the raw material cost of aqueous PU more solvent-based PU. The raw material costs of high, water-based PU and solvent-based PU are shown in Table 2.
水性PU分散液是將親水性之官能基引入PU分子鏈上，使之具有類似乳化劑的功能，在不添加乳化劑的狀況下，亦可乳化(分散)於水中。由於所引入之離子基性質不同，可將PU離子化物分為： The aqueous PU dispersion is a function of introducing a hydrophilic functional group into a PU molecular chain to have an emulsifier-like function, and can be emulsified (dispersed) in water without adding an emulsifier. Due to the different nature of the ionic groups introduced, the PU ionization can be divided into:
1、陽離子性(Cationomer)：於PU主鏈上導入具氮的官能基，並予以四級銨化，使得PU具有親水性。 1. Cationomer: a functional group having nitrogen is introduced into the PU main chain, and is subjected to quaternization to make the PU hydrophilic.
2、陰離子子性(Anionomer)：於PU主鏈上導入具羧酸基(Carboxylic Acid)或磺酸基(Sulfonic Acid)的官能基，並以三級胺予以中和產生Carboxylate及Sulfonante，使得PU具有親水性。 2. Anionomer: a functional group having a Carboxylic Acid or a Sulfonic Acid is introduced into the PU main chain, and neutralized with a tertiary amine to produce Carboxylate and Sulfonante, so that PU It is hydrophilic.
3、兩性離化物(Zwitterionomer)：即於PU主鏈上同時具有上述兩種離子性。製造方法為先合成具NCO末端基之預聚合物，再分別與N-methyl-diethanolamine及1,3-propane sultone反應。 3. Zwitterionomer: It has the above two ionicities on the PU main chain. The method comprises the steps of: synthesizing a prepolymer having an NCO terminal group and reacting with N-methyl-diethanolamine and 1,3-propane sultone, respectively.
4、非離子性：將具親水性之Ethylene oxide或Propylene oxide repeating unit之長鏈polyols導入PU主鏈或側鏈中，使PU具水分散性。 4. Nonionic: The long chain polyols of hydrophilic Ethylene oxide or Propylene oxide repeating unit are introduced into the PU main chain or side chain to make the PU water-dispersible.
水性PU所使用的陰離子親水性單體，商業上最常用的是二羥甲基丙酸(Dimethylol Propionic Acid,DMPA)，此外尚有親水性較高的磺酸鈉鹽型親水基，二者的比較如表3。一般而言，非離子型PU毒性小、 不易水解、且其電解質穩定性佳、耐低溫剪切等性質均優於離子性聚合物，惟具高溫不安定性。離子型PU因分子間相互作用力大且易產生庫倫力，其薄膜具有較佳的機械性質，同時對溫度的安定性較高，惟由於在水中會解離成離子，其電解質穩定性差。 The anionic hydrophilic monomer used in water-based PU, the most commonly used commercially is Dimethylol Propionic Acid (DMPA), in addition to the hydrophilic hydrophilic sodium sulfonate-type hydrophilic group, both Compare as shown in Table 3. In general, non-ionic PU is less toxic, It is not easy to be hydrolyzed, and its electrolyte stability is good, and its resistance to low temperature shearing is superior to that of ionic polymer, but it has high temperature instability. The ionic PU has large intermolecular interaction force and is easy to generate Coulomb force. The film has better mechanical properties and high stability to temperature, but its electrolyte stability is poor due to dissociation into ions in water.
合成製備時必需使用與水反應性較低的脂肪族或環脂族(Cycloaliphatic)二異氰酸酯，例如二異氰酸異佛爾酮酯(Isophorone diisocyanate，IPDI)、二異氰酸六亞甲基酯(Hexamethylene diisocyanate，HDI)或二異氰酸4,4'-二環己基甲烷酯(4,4'-Dicyclohexylmethane diisocyanate，H12MDI)等，這些二異氰酸酯的價格昂貴，使得水性PU的原料成本較其他 材料高出甚多，另傳統的水性PU在浸漬、塗佈後，由於水性PU顆粒間的融合性不好，遂在乾燥成膜時容易龜裂，導致成膜後的皮膜物無法展現PU原本的高功能特性。因此，如何製備原料成本較低，且能適用於浸漬、塗佈製程，在薄膜成形後，仍維持高韌性及高功能特性的水性PU，乃是手套業及薄壁彈性製品業界共同努力的目標。 It is necessary to use an aliphatic or cycloaliphatic diisocyanate which is less reactive with water, such as Isophorone diisocyanate (IPDI), hexamethylene diisocyanate. (Hexamethylene diisocyanate, HDI) or 4,4'-Dicyclohexylmethane diisocyanate (H 12 MDI), etc., these diisocyanates are expensive, making the raw material cost of aqueous PU more Other materials are much higher. In addition, after the traditional water-based PU is impregnated and coated, the fusion between the water-based PU particles is not good, and the crucible is easily cracked when it is formed into a film, so that the film material after film formation cannot exhibit PU. Original high-performance features. Therefore, how to prepare a water-based PU with low cost and suitable for impregnation and coating processes and maintaining high toughness and high functional properties after film formation is a joint goal of the glove industry and the thin-walled elastic products industry. .
另一方面，為了符合消防安檢法規，工業用或室內裝潢使用之紡織布料也需要進行阻燃處理，其中現有紡織布料之阻燃技術使用之阻燃塗料大多以鹵素化合物為主成份，並再搭配一部份銻系阻燃劑。該鹵素成份例如為聚氯乙烯(PVC)，其具有優異的阻燃效果，並廣泛應用於表面貼皮、壁紙等室內裝飾用途。然而，含有PVC等鹵素成份之阻燃塗料在火場中受熱時容易分解產生戴奧辛等有毒氣體；同時，此類阻燃塗料也因添加了鹵素成份及大量塑化劑，而造成無法符合歐盟等地區之環保法規，導致使其相關產品無法輸出至歐洲等地區販售。 On the other hand, in order to comply with the fire safety inspection regulations, textile fabrics used for industrial or interior decoration also need to be flame-retardant. Among them, the flame retardant coatings used in the flame retardant technology of the existing textile fabrics mostly use halogen compounds as the main component, and then match A part of the lanthanide flame retardant. The halogen component is, for example, polyvinyl chloride (PVC), which has excellent flame retardant effect and is widely used for interior decoration applications such as surface skinning and wallpaper. However, a flame retardant coating containing a halogen component such as PVC is easily decomposed to generate toxic gas such as dioxin when heated in a fire field; at the same time, such a flame retardant coating is also incapable of complying with the European Union due to the addition of a halogen component and a large amount of a plasticizer. Environmental regulations in the region have prevented the export of related products to Europe and other regions.
故，有必要提供一種阻燃塗料及阻燃基材，以解決習用技術所存在的問題。 Therefore, it is necessary to provide a flame retardant coating and a flame retardant substrate to solve the problems of the conventional technology.
本發明開發一種水性聚氨酯阻燃性材料，為主鏈含有芴結構(Cardo)之水性聚氨酯(WPU)樹脂，為一新型環保材料、具生物可分解性、無揮發性有機物(VOC)之汙染、製程簡易並具優異耐熱及阻燃性質，係為一種無鹵素成份之塗佈型阻燃性材料，不但可提供優良之阻燃性質，而且亦可符合無毒塗料環保法規，可以達成上述之目的。 The invention develops an aqueous polyurethane flame retardant material, and a waterborne polyurethane (WPU) resin containing a ruthenium structure (Cardo) as a main chain, which is a new environmentally friendly material, biodegradable, volatile organic compounds (VOC)-free, The process is simple and has excellent heat resistance and flame retardant properties. It is a halogen-free coating type flame retardant material, which not only provides excellent flame retardant properties, but also meets environmental regulations of non-toxic paints, and can achieve the above objectives.
本發明為一種水性聚氨酯阻燃性材料，該阻燃性材料是 以預聚物混合法製備，將多異氰酸酯與多元醇混合物先反應成預聚物，隨後加入適當的鹼中和該預聚物，然後分散於水中，之後加入含有羥基或胺基之烷氧基矽氧烷之鏈延長劑與預聚物反應，最後加入其它不含矽氧烷之鏈延長劑與預聚物剩餘之NCO基反應而得到本發明之水性聚氨酯阻燃性材料，其中，多元醇包含：(A)具有雙酚芴構造之多元醇化合物、(B)具有親水基(羧酸基及/或磺酸基及/或磷酸基，及/或膦酸基)之多元醇化合物，以及(C)不同於(A)與(B)且分子量500至8000之多元醇，並藉由調控(A)、(B)、(C)之含量比例，來獲得不同的水性聚氨酯阻燃性材料之性質，以此製成各種成型品，或塗佈於各種基材上，而獲得具有優異阻燃性之製品。 The invention is an aqueous polyurethane flame retardant material, and the flame retardant material is Prepared by a prepolymer mixing method, the polyisocyanate and the polyol mixture are first reacted into a prepolymer, and then the prepolymer is neutralized by adding a suitable base, and then dispersed in water, followed by adding an alkoxy group having a hydroxyl group or an amine group. The chain extender of the siloxane is reacted with the prepolymer, and finally the other chain extender containing no siloxane is reacted with the remaining NCO group of the prepolymer to obtain the waterborne polyurethane flame retardant material of the present invention, wherein the polyol And comprising: (A) a polyol compound having a bisphenol fluorene structure, (B) a polyol compound having a hydrophilic group (a carboxylic acid group and/or a sulfonic acid group and/or a phosphoric acid group, and/or a phosphonic acid group), and (C) a polyol different from (A) and (B) and having a molecular weight of 500 to 8000, and obtaining different water-based polyurethane flame-retardant materials by adjusting the ratio of contents of (A), (B), and (C) The properties are obtained by forming various molded articles or coating them on various substrates to obtain articles having excellent flame retardancy.
本發明所述之水性聚氨酯阻燃性材料，以不同含量之具有雙酚芴構造之多元醇化合物(A)，例如含9,9-雙酚4-(2-羥乙氧基)芴(9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorine,BHEOPF)所製成之水性聚氨基甲酸酯(BHEOPF/WPU)阻燃性材料，結果發現該水性聚氨酯隨雙酚芴之多元醇化合物含量增加，BHEOPF/WPU分散液的黏度及Zeta potential均約維持不變，水性聚氨酯分散液之乳液微胞粒徑隨雙酚芴含量增多而增大。而將此水性聚氨酯分散液經逐步升溫烘乾鑄膜形成BHEOPF/WPU薄膜。則該水性聚氨酯薄膜隨雙酚芴之含量增加，接觸角度變大了，表示薄膜愈疏水，且薄膜熱穩定性上升。而此薄膜的表面型態均極為平整，不隨雙酚芴含量增加而變化。將製備之BHEOPF/WPU分散液塗抹或含浸在布上，經乾燥後測其耐燃特性增加，得知含有雙酚芴之水性聚氨酯阻燃性優於單純之水性聚氨酯。 The water-based polyurethane flame-retardant material according to the present invention has different contents of the polyol compound (A) having a bisphenol fluorene structure, for example, a 9,9-bisphenol 4-(2-hydroxyethoxy) ruthenium (9). , an aqueous polyurethane (BHEOPF/WPU) flame retardant material prepared by 9-Bis [4-(2-hydroxyethoxy)phenyl]fluorine, BHEOPF), and found that the aqueous polyurethane is a polyol with bisphenol oxime When the content of the compound increased, the viscosity and Zeta potential of the BHEOPF/WPU dispersion remained unchanged. The particle size of the emulsion of the aqueous polyurethane dispersion increased with the increase of the content of bisphenol quinone. The aqueous polyurethane dispersion was dried and dried to form a BHEOPF/WPU film. Then, the aqueous polyurethane film increases with the content of bisphenol quinone, and the contact angle becomes larger, indicating that the film is more hydrophobic and the thermal stability of the film increases. The surface morphology of the film is extremely flat and does not change with increasing bisphenol quinone content. The prepared BHEOPF/WPU dispersion was applied or impregnated on the cloth, and the flame resistance of the prepared BHEOPF/WPU dispersion was increased after drying, and it was found that the water-based polyurethane containing bisphenolphthalein was superior to the simple water-based polyurethane.
本發明以預聚合物混合法(prepolymer mixing process)製備 具有芴(Cardo)結構之水性聚氨酯(WPU)阻燃性材料，以(A)具有雙酚芴構造之多元醇化合物作為部分之多元醇，例如9,9-雙酚4-(2-羥乙氧基)芴(9,9-bis(4-hydroxyphenyl)fluorene)，它和多異氰酸酯反應獲得主鏈段含有雙酚芴單位之預聚合物，該雙酚芴單位具有良好耐熱及高折射性的芴(Cardo)骨架，賦予此聚合物具有高耐熱、高折射、高耐候及高機械性質，該預聚物進一步使用含有羥基或胺基之烷氧基矽氧烷作為鏈延長劑，例如採用3-胺基-丙基-三乙氧基矽氧烷(3-amino-propyl-triethoxysilane)，其胺基(amino group)會和預聚合物之NCO基反應，而其三乙氧基矽氧烷(triethoxysilane)官能基在塗膜乾燥過程中於常溫即可進行溶膠-凝膠反應產生交聯結構而提升水性聚氨酯之機械與耐熱阻燃性質。 The invention is prepared by a prepolymer mixing process A waterborne polyurethane (WPU) flame retardant material having a Cardo structure, (A) a polyol compound having a bisphenol fluorene structure as a partial polyol such as 9,9-bisphenol 4-(2-hydroxyethyl) (9,9-bis(4-hydroxyphenyl)fluorene), which is reacted with a polyisocyanate to obtain a prepolymer containing a bisphenolphthalein unit in the main segment, which has good heat resistance and high refractive index. The Cardo skeleton imparts high heat resistance, high refraction, high weather resistance and high mechanical properties to the polymer. The prepolymer further uses alkoxy oxirane having a hydroxyl group or an amine group as a chain extender, for example, 3 -amino-propyl-triethoxysilane, the amino group reacts with the NCO group of the prepolymer, and its triethoxy oxirane The triethoxysilane functional group can perform a sol-gel reaction at room temperature to produce a crosslinked structure at room temperature to enhance the mechanical and heat-resistant flame retardant properties of the aqueous polyurethane.
本發明所述之水性聚氨酯阻燃性材料，其中多元醇包含：(A)具有雙酚芴構造之多元醇化合物、(B)具有親水基(選自羧酸基及/或磺酸基及/或磷酸基，及/或膦酸基)之多元醇化合物，以及(C)不同於(A)與(B)且分子量500至8000之多元醇，該(A)具有雙酚芴構造之多元醇化合物，例如9,9-雙酚4-(2-羥乙氧基)芴(9,9-bis(4-hydroxyphenyl)fluorene)，(B)含親水基(選自羧酸基、及/或磺酸及/或磷酸基，及/或膦酸基)之多元醇，例如二羥甲基丙酸(dimethylol propionic acid,DMPA)，該(C)多元醇(polyol)，例如使用分子量500-8000之聚(四亞甲基醚)二醇(polytetramethylene ether glycol,PTMEG)，約在75℃與多異氰酸酯反應，聚合成末端基為NCO之預聚合物，隨後加入適當量鹼，例如三乙胺中和預聚合物上之羧酸基、及/或磺酸基、及/或磷酸基、及/或膦酸基成為預聚合物離子體，然後分散於水中，最後加入鏈延長劑，例如乙二胺(ethylene-diamine)或其它二胺(diamines)、或其它 二醇、或胺醇化合物為，較佳為二胺類化合物，其中，胺基將預聚合物多餘的NCO官能基反應完畢並延伸水性聚氨酯之分子量，得到水性聚氨酯阻燃性材料，在上述與預聚合物的NCO官能基反應時，胺基比水之OH基快近1000倍，所以二胺類化合物可以更有效的進行鏈延長反應。 The water-based polyurethane flame-retardant material according to the present invention, wherein the polyol comprises: (A) a polyol compound having a bisphenol oxime structure, and (B) having a hydrophilic group (selected from a carboxylic acid group and/or a sulfonic acid group and/or Or a phosphate compound, and/or a phosphonic acid group, and (C) a polyol having a molecular weight of 500 to 8000 different from (A) and (B), the (A) polyol having a bisphenol oxime structure a compound such as 9,9-bis(4-hydroxyphenyl)fluorene, (B) a hydrophilic group (selected from a carboxylic acid group, and/or a polyhydric alcohol of a sulfonic acid and/or a phosphoric acid group, and/or a phosphonic acid group, such as dimethylol propionic acid (DMPA), the (C) polyol, for example, having a molecular weight of 500-8000 Polytetramethylene ether glycol (PTMEG), which is reacted with a polyisocyanate at about 75 ° C to polymerize into a prepolymer having a terminal group of NCO, followed by the addition of a suitable amount of a base such as triethylamine. And a carboxylic acid group and/or a sulfonic acid group, and/or a phosphoric acid group, and/or a phosphonic acid group on the prepolymer are prepolymer ion bodies, then dispersed in water, and finally a chain extender is added. Such as ethylenediamine (ethylene-diamine) or another diamine (diamines), or other The diol or the amine alcohol compound is preferably a diamine compound in which the amine group reacts the excess NCO functional group of the prepolymer and extends the molecular weight of the aqueous polyurethane to obtain an aqueous polyurethane flame retardant material. When the NCO functional group of the prepolymer is reacted, the amine group is nearly 1000 times faster than the OH group of water, so that the diamine compound can carry out the chain extension reaction more efficiently.
本發明之水性聚氨酯阻燃性材料，可進一步包含金屬氧化物之無機難燃劑添加至預聚合混合物中，以其中該多異氰酸酯類化合物之該些異氰酸基分別與該水性聚氨酯樹脂及該金屬氫氧化物產生鍵結。係將金屬氧化物加入多異氰酸酯與(A)、(B)、(C)之多元醇之混合物中進行預聚合，該金屬氫氧化物之微粒係經表面改質而具有數個胺基(-NH2)或羥基(-OH)。較佳者，該金屬氫氧化物之平均粒徑介於0.5至15微米(um)之間。該金屬氧化物無機難燃劑，包括(但不限於)：氫氧化鋁、氫氧化鎂、氧化矽、氧化鈦、碳酸鈣、或前述之組合。其中又以氫氧化鋁、氫氧化鎂較佳，待後續該阻燃性材料在火場中受熱時，該金屬氫氧化物之微粒才會受熱釋放出水氣並轉而成為金屬氧化物，以阻隔熱能。 The aqueous polyurethane flame retardant material of the present invention, further comprising an inorganic flame retardant containing a metal oxide added to the prepolymerized mixture, wherein the isocyanate groups of the polyisocyanate compound and the aqueous polyurethane resin and the The metal hydroxide produces a bond. Pre-polymerization is carried out by adding a metal oxide to a mixture of a polyisocyanate and a polyol of (A), (B), and (C), and the particles of the metal hydroxide are surface-modified to have a plurality of amine groups (- NH 2 ) or hydroxyl (-OH). Preferably, the metal hydroxide has an average particle size of between 0.5 and 15 microns (um). The metal oxide inorganic flame retardant includes, but is not limited to, aluminum hydroxide, magnesium hydroxide, cerium oxide, titanium oxide, calcium carbonate, or a combination thereof. Among them, aluminum hydroxide and magnesium hydroxide are preferred. When the flame-retardant material is heated in the fire field, the particles of the metal hydroxide will be released by the heat and turn into metal oxide to block the metal oxide. Thermal energy.
本發明之水性聚氨酯阻燃性材料，可額外添加其它阻燃劑，諸如：磷系阻燃劑，例如聚磷酸銨，氮系難燃劑，例如三聚氰胺，另外，也可額外包含一種膨脹石墨，以使阻燃性材料適合作為飾板，該膨脹石墨之固體重量比例則依產品需求調整，本發明並不加以限制。本發明之水性聚氨酯阻燃性材料，更可包括一種金屬粉或金屬網。 The water-based polyurethane flame-retardant material of the present invention may additionally be added with other flame retardants, such as: a phosphorus-based flame retardant such as ammonium polyphosphate, a nitrogen-based flame retardant such as melamine, or an expanded graphite. In order to make the flame-retardant material suitable as a plaque, the solid weight ratio of the expanded graphite is adjusted according to the product requirements, and the invention is not limited. The waterborne polyurethane flame retardant material of the present invention may further comprise a metal powder or a metal mesh.
本發明之水性聚氨酯阻燃性材料，較佳之實施樣態中，係以塗料方式呈現。 The water-based polyurethane flame-retardant material of the present invention, in a preferred embodiment, is presented in the form of a coating.
另外，本發明提供一種阻燃基材，其包含：一薄材；以及一 如上所述之阻燃性材料，其塗佈在該薄材上。 In addition, the present invention provides a flame-retardant substrate comprising: a thin material; and a A flame retardant material as described above, coated on the thin material.
在本發明之一實施例中，該薄材係選自布料、紙類、金屬、或塑料薄板。 In one embodiment of the invention, the thin material is selected from the group consisting of cloth, paper, metal, or plastic sheet.
另外，本發明之水性聚氨酯阻燃性材料可進一步應用於各種成型品，例如應用於防火材料、防火塗料、接著劑、油墨、纖維織物防火處理劑、皮革表面處理劑，本發明之水性聚氨酯阻燃性材料亦同時具有良好的抗化學性、抗溶劑性、耐磨性、以及優異的彈性和耐熱變形性質，可製成薄膜、發泡成型、模塑成型、鑄模成型、塗佈於基材上、含浸於基材，故能在各種用途上具有所需的物性，例如傢俱、床椅墊、襯裡、建築之絕緣體、電纜線、冰箱絕熱層、封劑及填空劑、耐磨胎、接合劑、防水劑及彈性纖維品等。 In addition, the water-based polyurethane flame-retardant material of the present invention can be further applied to various molded articles, for example, for fireproof materials, fireproof coatings, adhesives, inks, fiber fabric fireproof treatment agents, leather surface treatment agents, and waterborne polyurethane barriers of the present invention. The flammable material also has good chemical resistance, solvent resistance, wear resistance, and excellent elasticity and heat deformation resistance, and can be formed into a film, foam molding, molding, molding, and coating on a substrate. It is impregnated with the substrate, so it can have the required physical properties in various applications, such as furniture, bed cushions, linings, building insulation, cable, refrigerator insulation, sealant and fill-in agent, wear-resistant tire, joint Agents, waterproofing agents and elastic fiber products.
本發明所述之(A)具有雙酚芴構造之多元醇化合物，具有下列化學通式(1)之構造 (A) a polyol compound having a bisphenol fluorene structure according to the present invention, having the structure of the following chemical formula (1)
本發明所述之(B)含親水基之多元醇，親水基例如羧酸基、磺酸基(-SO3H)及/或磷酸基(-OPO3H2)，及/或膦酸基(-PO3H2)，該(B)含親 水基之多元醇，例如具有下述通式(2)或(3)或(4)之多元醇化合物 (B) a hydrophilic group-containing polyol according to the present invention, a hydrophilic group such as a carboxylic acid group, a sulfonic acid group (-SO 3 H) and/or a phosphate group (-OPO 3 H 2 ), and/or a phosphonic acid group (-PO 3 H 2 ), the (B) hydrophilic group-containing polyol, for example, a polyol compound having the following formula (2) or (3) or (4)
本發明所述之多元醇除了(A)具有雙酚芴構造之多元醇化合物、(B)具有親水基(選自羧酸基、及/或磺酸基、及/或磷酸基、及/或膦酸基)之多元醇化合物外，還包含(C)不同於(A)與(B)且分子量500至8000之多元醇，該(C)之多元醇，選自：聚醚多元醇、結晶性聚酯多元醇、非晶性聚酯多元醇、聚碳酸酯多元醇、聚乙二醇、聚丁二醇、聚丙二醇、聚(四亞甲基醚)二醇，或上述之混合物。較佳地，該(C)之多元醇，係為聚(四亞甲基醚)二醇之聚醚多元醇。 The polyol of the present invention has, in addition to (A) a polyol compound having a bisphenol oxime structure, (B) having a hydrophilic group (selected from a carboxylic acid group, and/or a sulfonic acid group, and/or a phosphate group, and/or The polyhydric alcohol compound of the phosphonic acid group further comprises (C) a polyol different from (A) and (B) and having a molecular weight of 500 to 8000, the polyol of (C) selected from the group consisting of polyether polyols, crystals Polyester polyol, amorphous polyester polyol, polycarbonate polyol, polyethylene glycol, polytetramethylene glycol, polypropylene glycol, poly(tetramethylene ether) glycol, or a mixture thereof. Preferably, the polyol of (C) is a polyether polyol of poly(tetramethylene ether) glycol.
本發明所述之(C)之多元醇，其中，聚酯二元醇之來源係由下列所選擇之兩類單體而合成：(1)第一類單體為二酸，例如己二酸(adipic acid)；及(2)第二類單體為二醇，選自乙二醇(ethylene glycol)、1.2-丙二醇 (1,2-propylene glycol)、1,4-丁二醇(1,4-butanediol)、1,5-二乙烯戊二醇(1,5-diethylene glycol)、1,6-己二醇(1,6-hexanediol)及1,4-環己烷二甲醇(1,4-dimethylolcyclohexane)所組成之群中的一者或多者。其中，在本實施態樣中所使用的聚酯二元醇之分子量係為500至8000，且所使用的聚酯二元醇為依據上述所得到的一至五種聚酯二元醇組合而成之混合物。 The polyol of (C) according to the present invention, wherein the source of the polyester diol is synthesized from the following two types of monomers selected: (1) the first monomer is a diacid such as adipic acid. (adipic acid); and (2) the second type of monomer is a diol selected from ethylene glycol and 1.2-propylene glycol (1,2-propylene glycol), 1,4-butanediol, 1,5-diethylene glycol, 1,6-hexanediol (1,6-hexanediol) One or more of the group consisting of 1,6-hexanediol) and 1,4-dimethylol cyclohexane. Wherein, the molecular weight of the polyester diol used in the embodiment is 500 to 8000, and the polyester diol used is a combination of one to five polyester diols obtained as described above. a mixture.
本發明所述之(C)之多元醇，其中，聚醚二元醇為選自聚四亞甲基醚二醇(PTMEG，分子量為500至8000)、聚丙二醇(PPG，分子量為500至8000)及主鏈及側鏈之聚乙二醇(PEG，分子量為500至8000)所組成之群中的一者至五者。較佳者，含乙氧基之二元醇係使用聚乙二醇，此時所使用的聚乙二醇之分子量係介於500~8000之間。 The polyol of (C) according to the present invention, wherein the polyether diol is selected from the group consisting of polytetramethylene ether glycol (PTMEG, molecular weight 500 to 8000) and polypropylene glycol (PPG, molecular weight 500 to 8000). And one or five of the group consisting of polyethylene glycol (PEG, molecular weight 500 to 8000) of the main chain and the side chain. Preferably, the ethoxy group-containing diol is polyethylene glycol, and the molecular weight of the polyethylene glycol used in this case is between 500 and 8,000.
本發明所述之(C)之多元醇，其中，聚碳酸酯多元醇原料之多元醇，可列舉：乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇等或1,3-丁二醇、3-甲基戊烷-1,5-二醇、2-乙基己烷-1,6-二醇、2-甲基-1,3-戊烷二醇、新戊二醇、2-甲基-1,8-辛烷二醇等脂肪族二醇；1,3-環己烷二醇、1,4-環己烷二醇、2,2’-雙(4-羥基環己基)丙烷、1,4-環己烷二甲醇等脂環式二醇；1,4-苯二甲醇等芳香族二醇；三羥甲基丙烷、季戊四醇等多官能多元醇等。前述多元醇可僅使用一種而作成前述聚碳酸酯多元醇，亦可併用複數種而作成聚碳酸酯多元醇。前述聚碳酸酯多元醇，較佳為含有前述脂肪族二醇或脂環式二醇單元之聚碳酸脂多元醇，更較佳為含有前述脂環式二醇單元之聚碳酸酯多元醇，特別較佳為含有1,4-環己烷二甲醇單元之聚碳酸酯多元醇。 The polyol of (C) according to the present invention, wherein the polyol of the polycarbonate polyol raw material may, for example, be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane. Glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecane Glycol or the like or 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, 2-methyl-1,3-pentane An aliphatic diol such as an alkanediol, neopentyl glycol or 2-methyl-1,8-octanediol; 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2, 2'-bis(4-hydroxycyclohexyl)propane, alicyclic diol such as 1,4-cyclohexanedimethanol; aromatic diol such as 1,4-benzenedimethanol; trimethylolpropane, pentaerythritol, etc. Polyfunctional polyols and the like. The above polyol may be used as the polycarbonate polyol alone or in combination of plural kinds to form a polycarbonate polyol. The polycarbonate polyol is preferably a polycarbonate polyol containing the above aliphatic diol or alicyclic diol unit, more preferably a polycarbonate polyol containing the alicyclic diol unit, particularly A polycarbonate polyol containing a 1,4-cyclohexanedimethanol unit is preferred.
本發明所述之多異氰酸酯，可為脂肪族、環狀脂肪族或芳香族多異氰酸酯，較佳為二異氰酸酯(diisocyanate)，例如為異佛爾酮二異氰酸酯(Isophorone diisocyanate，IPDI)。由於芳香族的二異氰酸鹽(如toluene diisocyanate，TDI、4,4-diphenyl methane diisocyanate，MDI)所製作出PU樹脂，會有黃變現象，因此，本發明所述之多異氰酸酯，若作為阻燃性塗料時，則選用脂肪族或環狀脂肪族之二異氰酸酯，所合成的PU樹脂，並無黃變現象，因此在一般淺色塗料或塗層時都使用脂肪族或環狀脂肪族所合成的PU樹脂。 The polyisocyanate of the present invention may be an aliphatic, cyclic aliphatic or aromatic polyisocyanate, preferably a diisocyanate, such as Isophorone diisocyanate (IPDI). Since the PU resin is produced by an aromatic diisocyanate (such as toluene diisocyanate, TDI, 4,4-diphenyl methane diisocyanate, MDI), there is a yellowing phenomenon, and therefore, the polyisocyanate of the present invention is used as In the case of flame retardant coatings, aliphatic or cyclic aliphatic diisocyanates are used, and the synthesized PU resin has no yellowing phenomenon, so aliphatic or cyclic aliphatics are used in general light paints or coatings. The PU resin synthesized.
本發明所述之芳香族二異氰酸酯至少具有一芳香環，例如為苯基、聯苯基或萘，其中芳香環上可更包括鹵素、硝基、氰基、C1~C6烷基、C1~C6烷氧基、鹵烷基、羥基、羧基、醯胺基或胺基等取代基。 The aromatic diisocyanate of the present invention has at least one aromatic ring, such as phenyl, biphenyl or naphthalene, wherein the aromatic ring may further include halogen, nitro, cyano, C 1 -C 6 alkyl, C. a substituent such as a 1 to C 6 alkoxy group, a haloalkyl group, a hydroxyl group, a carboxyl group, a decylamino group or an amine group.
本發明所述之芳香族二異氰酸酯，例如為二異氰酸甲苯酯(Toluene diisocyanate，TDI)、對-二異氰酸苯酯(p-Phenylene diisocyanate，PPDI)、二異氰酸4,4'-二苯基甲烷酯(4,4'-Diphenylmethane diisocyanate，MDI)或二異氰酸p,p'-二苯基酯(p,p'-Bisphenyl diisocyanate，BPDI)、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、2,4-伸甲苯基二異氰酸酯(TDI)、2,6-伸甲苯基二異氰酸酯、2,4-二苯基甲烷二異氰酸酯、4,4’-二異氰酸基聯苯、3,3’-二甲基-4,4’-二異氰酸基聯苯、3,3’-二甲基-4,4’-二異氰酸基二苯基甲烷、1,5-伸萘基二異氰酸酯、間-異氰酸基苯基磺醯基異氰酸酯、對-異氰酸基苯基磺醯基異氰酸酯等芳香族多異氰酸酯化合物。 The aromatic diisocyanate of the present invention is, for example, Toluene diisocyanate (TDI), p-Phenylene diisocyanate (PPDI), diisocyanate 4,4' -4,4'-Diphenylmethane diisocyanate (MDI) or p,-diphenyl cyanide (p,p'-Bisphenyl diisocyanate, BPDI), 1,3-phenylene Diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolyl diisocyanate (TDI), 2,6-tolyl diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4 '-Diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate An aromatic polyisocyanate compound such as bisphenylmethylmethane, 1,5-anaphthyl diisocyanate, m-isocyanatophenylsulfonyl isocyanate or p-isocyanatophenylsulfonyl isocyanate.
本發明所述之脂肪族或環狀脂肪族之二異氰酸酯，例如為六亞甲基二異氰酸酯(Hexamethylene diisocyanate,HDI)、脂肪族二異氰酸酯 (Aliphatic diisocyanate,ADI)、三甲基己二異氰酸酯(Trimethyl-hexamethylene diisocyanate,TMDI)及伸乙基二異氰酸酯、四亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2,6-二異氰酸基甲基己酸酯、雙(2-異氰酸基乙基)富馬酸酯、雙(2-異氰酸基乙基)碳酸酯、2-異氰酸基乙基-2,6-二異氰酸基己酸酯等脂肪族多異氰酸酯化合物；異佛爾酮二異氰酸酯(Isophorone diisocyanate，IPDI)、1,3-雙(異氰酸根合甲基)環己烷(1.3-Bis(isocyanatomethyl)cyclohexane,H6XDI)、4，4’-二環己基甲烷二異氰酸酯(I,4,4'-Methylene dicyclohexyl diisocyanate,H12MDI))、1,4-環己烷二異氰酸酯(1,4-Cyclohexane diisocyanate,CHDI)、伸環己基二異氰酸酯、甲基伸環己基二異氰酸酯(氫化TDI)、雙(2-異氰酸基乙基)-4-環己烯-1,2-二羧酸酯、2,5-降冰片烷二異氰酸酯、2,6-降冰片烷二異氰酸酯等脂環式多異氰酸酯化合物，該等多異氰酸酯化合物可單獨使用一種，亦可併用複數種。較佳地，該異氰酸酯為異佛爾酮二異氰酸酯(IPDI)、六亞甲基二異氰酸酯(HDI)。 The aliphatic or cyclic aliphatic diisocyanate of the present invention is, for example, Hexamethylene diisocyanate (HDI), Aliphatic diisocyanate (ADI), Trimethylhexamethylene diisocyanate (Trimethyl). -hexamethylene diisocyanate, TMDI) and ethyl diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl six Methylene diisocyanate, diazonium diisocyanate, 2,6-diisocyanatomethyl hexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanate) Aliphatic polyisocyanate compounds such as ethyl ethyl carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate; Isophorone diisocyanate (IPDI), 1, 3-bis(isocyanatomethyl)cyclohexane (H 6 XDI), 4,4'-dicyclohexylmethane diisocyanate (I,4,4'-Methylene dicyclohexyl diisocyanate , H 12 MDI)), 1,4-cyclohexane diisocyanate (CHDI), cyclohexyl diisocyanate Ester, methylcyclohexyl diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate An alicyclic polyisocyanate compound such as 2,6-norbornane diisocyanate may be used alone or in combination of plural kinds. Preferably, the isocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI).
本發明之多元醇包含：(A)具有雙酚芴構造之多元醇化合物、(B)具有親水基(羧酸基、及/或磺酸、及/或磷酸基、及/或膦酸基)之多元醇化合物，以及(C)不同於(A)與(B)且分子量500至8000之多元醇，並藉由調控(A)、(B)、(C)之含量比例，來獲得不同的水性聚氨酯之性質，而進一步做不同的各種應用。多元醇之含量調控該聚氨酯的透濕性、疏水性與黏度，(B)愈多時，親水官能基的含量愈高，親水性愈高，且會令聚合後得到的聚氨酯的透濕性愈高，但含量過高將使合成之聚氨酯黏度增高，使得100℃加工黏度過高，造成貼合效果不佳；反之，親水官能基的含量愈低，親水性愈 低，即聚合後得到的聚氨酯的透濕性愈低；(A)愈多時，雙酚芴結構含量愈高，聚合後得到的聚氨酯疏水性、阻燃性、機械性質等均增加；因此，本發明利用將該(C)之多元醇，例如聚醚多元醇或聚酯多元醇或聚碳酸酯多元醇的分子量控制在介於500~8000之間，再配合調控(A)具雙酚芴結構之多元醇與(B)含親水基之多元醇之含量，可使作為接著劑可同時具有良好的透濕性及耐洗滌性，故用於織物有很好的效果，並且同時使織物具有優異之阻燃性。 The polyol of the present invention comprises: (A) a polyol compound having a bisphenol fluorene structure, and (B) having a hydrophilic group (carboxylic acid group, and/or sulfonic acid group, and/or phosphate group, and/or phosphonic acid group). a polyol compound, and (C) a polyol having a molecular weight of 500 to 8000 different from (A) and (B), and obtaining different ratios by adjusting the ratio of contents of (A), (B), and (C) The nature of waterborne polyurethanes, and further different applications. The content of the polyol controls the moisture permeability, hydrophobicity and viscosity of the polyurethane. The more (B), the higher the content of the hydrophilic functional group, the higher the hydrophilicity, and the higher the moisture permeability of the polyurethane obtained after polymerization. High, but the content is too high, so that the viscosity of the synthesized polyurethane is increased, so that the processing viscosity at 100 ° C is too high, resulting in poor bonding effect; on the contrary, the lower the content of hydrophilic functional groups, the more hydrophilic Low, that is, the lower the moisture permeability of the polyurethane obtained after the polymerization; the more (A), the higher the content of the bisphenol quinone structure, and the polyurethane obtained after the polymerization has increased hydrophobicity, flame retardancy, mechanical properties, etc.; The invention utilizes the molecular weight of the polyol (C), such as polyether polyol or polyester polyol or polycarbonate polyol, to be between 500 and 8000, and then cooperates with the regulation (A) with bisphenol quinone The content of the polyol of the structure and (B) the hydrophilic group-containing polyol can be used as an adhesive agent to have both good moisture permeability and washing resistance, so that the fabric has a good effect and at the same time, the fabric has Excellent flame retardancy.
本發明之多元醇較佳地比例，以聚合用的多元醇的總莫耳百分比為100mole%計，該(A)具雙酚芴結構之多元醇的莫耳百分比介於0.1~90mole%，該(B)含親水基之多元醇的莫耳百分比介於10~80mole%；以及該(C)分子量500至8000之多元醇的莫耳百分比介於1~60mole%。 The polyol of the present invention is preferably a ratio of 100% by mole of the total molar percentage of the polyol for polymerization, and the percentage of moles of the polyol having the bisphenol fluorene structure (A) is from 0.1 to 90 mole%. (B) The hydroxyl group-containing polyol has a molar percentage of 10 to 80 mole%; and the (C) polyol having a molecular weight of 500 to 8000 has a molar percentage of 1 to 60 mole%.
本發明所述之含有羥基或胺基之烷氧基矽氧烷作為鏈延長劑，較佳為胺基烷氧基矽烷，該胺基烷氧基矽烷之化學式為H2N-R3-Si(R2)a(OR1)3-a，其中R1、R2為H或C1-C4烷基，a為0或1，R3為C1-C10之烷基或R5-NH-R4，R4、R5為C1-C10之烷基。胺基烷氧基矽烷可包含一級胺基、二級胺基或其組合。舉例來說，胺基烷氧基矽烷可為N-[3-(三甲氧基矽基)丙基]乙二胺(N-[3-(trimethoxysilyl)propyl]ethylenediamine)或3-氨基丙基三乙氧基矽烷(3-aminopropyltriethoxysilane)。 The alkoxy oxirane having a hydroxyl group or an amine group according to the present invention is preferably a metal alkoxy decane having a chemical formula of H 2 NR 3 -Si(R) as a chain extender. 2 ) a (OR 1 ) 3-a , wherein R 1 , R 2 are H or C 1 -C 4 alkyl, a is 0 or 1, and R 3 is a C 1 -C 10 alkyl group or R 5 -NH -R 4 , R 4 and R 5 are C 1 -C 10 alkyl groups. The amino alkoxydecane may comprise a primary amine group, a secondary amine group or a combination thereof. For example, the amino alkoxydecane can be N-[3-(trimethoxysilyl)propyl]ethylenediamine or 3-aminopropyltri 3-aminopropyltriethoxysilane.
此外，該聚氨酯還可包含一用於提升聚合分子量的非矽氧烷之鏈延長劑，及抗氧化劑，該鏈延長劑可為多元醇類化合物、或多元胺類化合物、或多元醇胺類化合物，較佳為二胺類化合物，胺類化合物鏈延長劑並無特別限制，例如可列舉：乙二胺(ethylenediamine)伸乙二胺、1,4-四亞 甲基二胺、2-甲基-1,5-戊二胺、1,6-六亞甲基二胺、1,4-六亞甲基二胺、3-胺基甲基-3,5,5-三甲基環己基胺、1,3-雙(胺基甲基)環己烷、伸二甲苯二胺(xylylenediamine)、六氫吡(iperazine)、2,5-二甲基六氫吡、二伸乙三胺、三伸乙四胺、聯胺(hydrazine)、亞乙基三胺、肼(hydrazine)、琥珀酸二醯肼、對苯二甲酸二醯肼、哌嗪(piperazine)等胺類物等；其中較佳可列舉如一級二胺化合物。該等可單獨使用一種，亦可併用複數種。其中多元醇化合物以脂肪族多元醇為宜，可包括但不限於脂肪族二醇、脂肪族三醇等，選自乙二醇、1,3-丙二醇(1,3-dihydroxypropane)、1,4丁二醇(1,4-dihydroxy-butane)、1,6-己二醇(1,6-dihydroxyhexane)、2-甲基-1,3-丙二醇、1,3丁二醇(1,3-butanediol；1,3BG)、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊基二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、1,10-癸二醇。脂肪族三醇之具體例可包含但不限於丙三醇、三甲醇甲烷、三甲醇乙烷、三甲醇丙烷(trimethylolpropane；TMP)對苯二酚二乙醇醚(Hydroquinone bis(2-hydroxyethoxy)benzene，HQEE)，然以三甲醇丙烷(TMP)、丙三醇為較佳。聚乙二醇所代表之聚烷二醇類。多元醇胺類化合物選自二乙醇胺(Diethanol amine)、3-((羥基乙基)氨基)丙醇(3-[(2-hydroxyethyl)amino]propan-1-ol或4-((2-羥基乙基)氨基)丁醇(4-[(3-hydroxypropyl)amino]butan-1-ol)。 In addition, the polyurethane may further comprise a non-oxyalkylene chain extender for increasing the molecular weight of the polymerization, and an antioxidant, and the chain extender may be a polyol compound, a polyamine compound, or a polyol amine compound. The diamine compound is preferred, and the amine compound chain extender is not particularly limited, and examples thereof include ethylenediamine ethylenediamine, 1,4-tetramethylenediamine, and 2-methyl group. -1,5-pentanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine , 1,3-bis(aminomethyl)cyclohexane, xylylenediamine, hexahydropyridyl (iperazine), 2,5-dimethylhexahydropyridyl , diethylenetriamine, triamethylenetetramine, hydrazine, ethylene triamine, hydrazine, diterpene succinate, diterpene terephthalate, piperazine, etc. Amines and the like; among them, preferred are, for example, a primary diamine compound. These may be used alone or in combination of plural kinds. Wherein the polyol compound is preferably an aliphatic polyol, which may include, but is not limited to, an aliphatic diol, an aliphatic triol, etc., and is selected from the group consisting of ethylene glycol, 1,3-dihydroxypropane, and 1,4. 1,4-dihydroxy-butane, 1,6-dihydroxyhexane, 2-methyl-1,3-propanediol, 1,3 butanediol (1,3- Butanediol; 1,3BG), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol. Specific examples of the aliphatic triol may include, but are not limited to, glycerol, trimethylol methane, trimethylolethane, trimethylolpropane (TMP) hydroquinone bis (2-hydroxyethoxy)benzene, HQEE) is preferably trimethylolpropane (TMP) or glycerol. A polyalkylene glycol represented by polyethylene glycol. The polyol amine compound is selected from the group consisting of Diethanol amine, 3-((hydroxyethyl)amino)propanol (3-[(2-hydroxyethyl)amino)propan-1-ol or 4-((2-hydroxyl) Ethyl)amino)butanol (4-[(3-hydroxypropyl)amino]butan-1-ol).
由於該鏈延長劑及抗氧化劑的使用為聚氨酯合成過程中常用之試劑，且非為本發明之重點，因此對其相關用量及特性不再多加說明。 Since the use of the chain extender and the antioxidant is a commonly used reagent in the polyurethane synthesis process, and is not the focus of the present invention, the related amounts and characteristics thereof will not be further described.
本發明係提供一種水性聚氨酯阻燃性材料，所使用(B)具有親水基(羧酸基、磺酸基及/或磷酸基、及/或膦酸基)之多元醇，該親水基係 陰離子基團，該陰離子基團以中和劑來中和；該中和劑，其係為鹼類。包含有機中和劑及/或無機中和劑。前述適合之有機中和劑可包括但不限於三甲胺、三乙胺、三正丙胺、三丁胺、三乙醇胺、三異丙醇胺、N-甲基嗎啉(N-methylmorphorine)、胺基甲基丙醇、胺基甲基丙烷二醇、胺基乙基丙烷二醇、三羥基甲基胺基甲烷、單乙醇胺等有機胺類。該等可單獨使用一種，亦可併用複數種。前述適合之無機中和劑可包括但不限於氫氧化鉀、氫氧化鈉、氫氧化鋰或上述之任意組合。前述之中和劑可單獨一種或混合兩種或兩種以上使用。 The present invention provides an aqueous polyurethane flame retardant material using (B) a polyol having a hydrophilic group (a carboxylic acid group, a sulfonic acid group and/or a phosphoric acid group, and/or a phosphonic acid group), the hydrophilic group An anionic group neutralized with a neutralizing agent; the neutralizing agent, which is a base. Containing an organic neutralizing agent and/or an inorganic neutralizing agent. Suitable organic neutralizing agents may include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N-methylmorphorine, and amine groups. An organic amine such as methyl propanol, aminomethylpropanediol, aminoethylpropanediol, trishydroxymethylaminomethane or monoethanolamine. These may be used alone or in combination of plural kinds. Suitable inorganic neutralizing agents may include, but are not limited to, potassium hydroxide, sodium hydroxide, lithium hydroxide or any combination of the foregoing. The aforementioned neutralizing agents may be used singly or in combination of two or more kinds.
基於水性聚氨酯分散液之總重量為100重量百分比，有機溶劑之使用量一般為3重量百分比至15重量百分比。 The organic solvent is generally used in an amount of from 3 to 15% by weight based on 100% by weight based on the total weight of the aqueous polyurethane dispersion.
又，在本發明之一態樣中，水性聚氨酯阻燃性材料中包含主鏈具有雙酚芴結構之聚氨酯樹脂，且該聚氨酯樹脂具大量親水性基團，由於該等親水性基團具有極性，故該聚氨酯樹脂之分子間吸引力强，因而使得包含該水性聚氨酯分散液之散熱組成物具有良好的成膜性，能夠在基材上形成機械強度佳且附著力高的潤滑層。 Further, in one aspect of the invention, the aqueous polyurethane flame-retardant material contains a polyurethane resin having a bisphenol fluorene structure in its main chain, and the polyurethane resin has a large amount of hydrophilic groups, since the hydrophilic groups have polarity Therefore, the urethane resin has a strong intermolecular attraction force, so that the heat dissipating composition containing the aqueous polyurethane dispersion has good film forming properties, and a lubricating layer having good mechanical strength and high adhesion can be formed on the substrate.
另一方面，在本發明其他態樣中，水性聚氨酯阻燃性材料中包含主鏈具有雙酚芴結構之聚氨酯樹脂，且該聚氨酯樹脂更具有大量親水性基團及適量之雙酚芴疏水基，因此於紡織塗層加工時，可增進織物之透濕防水功能及阻燃性功能。 On the other hand, in another aspect of the invention, the aqueous polyurethane flame retardant material comprises a polyurethane resin having a bisphenol fluorene structure in its main chain, and the polyurethane resin further has a large amount of hydrophilic groups and an appropriate amount of bisphenol hydrazine hydrophobic groups. Therefore, when the textile coating is processed, the moisture permeability and the flame retardancy function of the fabric can be improved.
上述之水性聚氨酯阻燃性材料，於紡織塗層應用時須添加適量之架橋劑，以增進聚氨酯樹脂對纖維之接著性及耐水洗性。 The above-mentioned water-based polyurethane flame-retardant material must be added with an appropriate amount of bridging agent in the textile coating application to improve the adhesion and water-washing resistance of the polyurethane resin to the fiber.
本發明之該(C)多元醇係可為聚酯多元醇、聚碳酸酯多元醇 或聚醚多元醇，亦可為包含聚酯多元醇、聚碳酸酯多元醇及聚醚多元醇之組合物，其等之非離子基團位於該聚氨酯樹脂之主鏈及側鏈上，例如由含乙氧基之二元醇所形成，例如聚乙二醇。應注意的是，該非離子基團係用於增加聚氨酯樹脂之親水性，因此，本發明之非離子基團係表示非屬離子化合物且具有親水性之多元醇類，而當上述聚多元醇其中一者可提供良好親水性質時亦可作為本發明之非離子基團。 The (C) polyol of the present invention may be a polyester polyol or a polycarbonate polyol. Or a polyether polyol, which may also be a composition comprising a polyester polyol, a polycarbonate polyol, and a polyether polyol, wherein the nonionic group is located on the main chain and the side chain of the polyurethane resin, for example, An ethoxylated diol is formed, such as polyethylene glycol. It should be noted that the nonionic group is used to increase the hydrophilicity of the polyurethane resin, and therefore, the nonionic group of the present invention means a non-ionic compound and a hydrophilic polyol, and when the above polypolyol is One can also provide a nonionic group of the present invention when it provides good hydrophilic properties.
本發明之該(B)具有親水基之多元醇，其中之陰離子基團係作為該聚氨酯樹脂的內乳化劑，意即直接在聚氨酯樹脂之聚合物分子上修飾具高極性且具羧基、磺酸基、磷酸基、膦酸基之化合物，以使該聚氨酯樹脂在水相溶劑中無須額外添加乳化劑即能達成分散。此外，該陰離子基團之結構具有較大的立體障礙(steric barrier)，藉此抑制分散的聚氨酯樹脂間再聚集，進而達到均勻分散之狀態。舉例而言，該陰離子基團之來源可為2,2-二羥甲基丙酸(DMPA,dimethylolpropionic acid)。應了解的是，符合上述性質的任一種具羧基、磺酸基、磷酸基、膦酸基之化合物亦可作為本發明之陰離子基團的來源。 The (B) polyol having a hydrophilic group, wherein the anionic group is used as an internal emulsifier of the polyurethane resin, that is, directly modifying the polymer molecule of the polyurethane resin to have a high polarity and having a carboxyl group and a sulfonic acid. A compound of a benzyl group, a phosphoric acid group or a phosphonic acid group, such that the urethane resin can be dispersed in an aqueous phase solvent without the need for an additional emulsifier. Further, the structure of the anionic group has a large steric barrier, thereby suppressing re-aggregation between the dispersed polyurethane resins, thereby achieving a state of uniform dispersion. For example, the source of the anionic group can be 2,2-dimethylolpropionic acid (DMPA). It is to be understood that any compound having a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group which satisfies the above properties can also be used as a source of the anionic group of the present invention.
該中和劑係為鹼類，該鹼類可為不同碳數的烷基胺類或氫氧化物，例如三乙胺(TEA,triethylamine)、三丙基胺(TPA,tripropylamine)或三丁基胺(TBA,tributylamine)等三級胺。在本發明中之中和劑係用於中和該陰離子基團之羧基、磺酸基、磷酸基、膦酸基以產生離子中心，而當該中和劑與水相溶劑揮發後，該離子中心之中和劑部分被移除而殘留該陰離子基團之羧基、磺酸基、磷酸基、膦酸基，此時，該水性聚氨酯樹脂係形成具交聯的羧基、磺酸基、磷酸基、膦酸基且具良好黏著力之薄膜。 The neutralizing agent is a base, and the base may be an alkylamine or hydroxide of a different carbon number, such as triethylamine (TEA), tripropylamine (TPA, tripropylamine) or tributyl. a tertiary amine such as an amine (TBA, tributylamine). In the present invention, the neutralizing agent is used to neutralize the carboxyl group, the sulfonic acid group, the phosphoric acid group, and the phosphonic acid group of the anionic group to generate an ion center, and when the neutralizing agent and the aqueous phase solvent are volatilized, the ion The central neutralizer portion is removed to leave a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group of the anionic group. At this time, the aqueous polyurethane resin forms a crosslinked carboxyl group, a sulfonic acid group, or a phosphoric acid group. , a phosphonic acid-based film with good adhesion.
本發明所述該有機溶劑例如可為N-甲基吡喀烷酮(N-methyl-2-pyrrolidone，NMP)、異丙醇(isopropyl alcohol)、二丁醇(sec-butyl alcohol)、丙酮(acetone)、丁酮(methyl ethyl ketone)、甲苯(toluene)、N,N-二甲基甲醯胺(DMF,Dimethyl Formamide)或N,N-二甲基乙醯胺(DMAc,Dimethyl Acetamide)。本發明使用之有機溶劑以N-甲基吡喀烷酮、丙酮、丁酮或其任意組合為較佳。 The organic solvent of the present invention may be, for example, N-methyl-2-pyrrolidone (NMP), isopropyl alcohol, sec-butyl alcohol, acetone ( Acetone), methyl ethyl ketone, toluene, N,N-dimethylformamide (DMF, Dimethyl Formamide) or N,N-dimethylacetamide (DMAc, Dimethyl Acetamide). The organic solvent used in the present invention is preferably N-methylpyrrolidone, acetone, methyl ethyl ketone or any combination thereof.
可視實際需要，選擇性添加觸媒及/或抗氧化劑。前述之觸媒可包括但不限於辛酸錫、三乙酸單丁基錫、單辛酸單丁基錫、單乙酸單丁基錫、順丁烯二酸單丁基錫、二乙酸二丁基錫、二辛酸二丁基錫、二硬脂酸二丁基錫、二月桂酸二丁基錫、順丁烯二酸二丁基錫等有機錫化合物；鈦酸四異丙酯、鈦酸四正丁酯等有機鈦化合物；三乙胺、N,N-二乙基環己基胺、N,N,N’,N’-四甲基乙基伸乙基胺、三伸乙基二胺等第三級胺類。前述之抗氧化劑可包括但不限於有機亞磷酸酯化合物，其具體例如：四苯基二丙二醇二亞磷酸酯(tetraphenyl dipropyleneglycol diphosphite；TDD)、二苯基季戊四醇二亞磷酸酯、二苯基異癸基亞磷酸酯三壬基異癸基亞磷酸酯、二苯基酸亞磷酸酯、二(2,4,6-三叔丁基苯基)季戊四醇二亞磷酸酯、二(2,4-二叔丁基苯基)季戊四醇二亞磷酸酯、二(十八烷基)季戊四醇雙亞磷酸酯、三苯基亞磷酸酯、三(壬基酚)亞磷酸酯、四(2,4-二叔丁基酚)-4,4'-聯苯基二亞磷酸酯、苯基二異癸基亞磷酸酯、聚-4,4'-異亞丙基二酚四酚亞磷酸酯、聚(二丙二醇)苯基亞磷酸酯(PDP)、有機金屬化合物之環保酯化觸媒(esterification catalyst)等，然其中以有機金屬化合物之環保酯化觸媒(ES CAT-100E，Seho Tech Inc.,Korea)為較佳。 Optionally add catalyst and/or antioxidants as needed. The foregoing catalyst may include, but is not limited to, tin octylate, monobutyltin triacetate, monobutyltin monooctanate, monobutyltin monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, distearate. Organotin compounds such as butyltin, dibutyltin dilaurate, dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate; triethylamine, N,N-diethylcyclohexane Tertiary amines such as hexylamine, N,N,N',N'-tetramethylethylethylamine, and triethylethylenediamine. The aforementioned antioxidant may include, but is not limited to, an organic phosphite compound, which is specifically, for example, tetraphenyl dipropyleneglycol diphosphite (TDD), diphenyl pentaerythritol diphosphite, diphenylisoindole. Phosphite trimethyl isodecyl phosphite, diphenyl phosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, di(2,4-di Tert-butylphenyl)pentaerythritol diphosphite, di(octadecyl)pentaerythritol diphosphite, triphenylphosphite, tris(nonylphenol) phosphite, tetra (2,4-di-tert Butylphenol)-4,4'-biphenyldiphosphite, phenyldiisodecylphosphite, poly-4,4'-isopropylidenediphenol tetraphenol phosphite, poly(two Propylene glycol) phenyl phosphite (PDP), an esterification catalyst for organometallic compounds, etc., among which is an environmentally friendly esterification catalyst of organometallic compounds (ES CAT-100E, Seho Tech Inc., Korea ) is better.
此外，應注意的是，上述水性聚氨酯阻燃性材料中包含的離子(即陰離子基團及中和劑)，於該水性聚氨酯阻燃性材料中係形成恰當數量的離子中心，以進一步提升聚氨酯阻燃性材料與水相溶劑之間的交互作用，增加該聚氨酯阻燃性材料之親水性及促進分散液的穩定。 In addition, it should be noted that the ions (ie, an anionic group and a neutralizing agent) contained in the above-mentioned aqueous polyurethane flame-retardant material form an appropriate number of ion centers in the water-based polyurethane flame-retardant material to further enhance the polyurethane. The interaction between the flame retardant material and the aqueous phase solvent increases the hydrophilicity of the polyurethane flame retardant material and promotes the stability of the dispersion.
第一圖 本發明之水性聚氨酯(BHEOPF/WPU)分散液之粒徑分布圖。 First Figure The particle size distribution of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.
第二圖 本發明之水性聚氨酯(BHEOPF/WPU)分散液之平均粒徑圖。 Second Figure Average particle size diagram of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.
第三圖 本發明之水性聚氨酯(BHEOPF/WPU)分散液之黏度圖。 Third Fig. Viscosity diagram of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.
第四圖 本發明之水性聚氨酯(BHEOPF/WPU)分散液之zeta電位隨BHEOPF含量之變化圖。 Fig. 4 is a graph showing the change of zeta potential with BHEOPF content of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention.
第五圖 本發明之水性聚氨酯(BHEOPF/WPU)薄膜之膨潤度圖。 Fig. 5 is a graph showing the swelling degree of the aqueous polyurethane (BHEOPF/WPU) film of the present invention.
第六圖 本發明之阻燃性試驗圖，(A)純棉布；(B)織物含浸一般純水性聚氨酯分散液；(C)織物含浸本發明之(BHEOPF/WPU)阻燃材料。 Figure 6 is a flame retardancy test chart of the present invention, (A) a pure cotton cloth; (B) a fabric impregnated with a generally pure aqueous polyurethane dispersion; (C) a fabric impregnated with the (BHEOPF/WPU) flame retardant material of the present invention.
以下，根據實施例以詳細說明本發明，但本發明並非僅限於此等。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
水性聚氨酯阻燃性材料之製備 Preparation of waterborne polyurethane flame retardant material
實施例 配方表中(BHEOPF/WPU 3) Example Formulation Table (BHEOPF/WPU 3)
1、加入9,9-雙酚4-(2-羥乙氧基)芴(9,9-bis(4-hydroxyphenyl)fluorine,BHEOPF)2.1925g N-甲基吡喀烷酮(N-methyl-2-pyrrolidone,NMP)12.5682g二羥甲基丙酸(dimethylol propionic acid,DMPA)2.4203g聚(四亞甲基醚)二醇(polytetramethylene ether glycol,PTMEG；分子量1000g/mole)26.9354g異佛爾酮二異氰酸酯(Isophorone diisocyanate,IPDI)20g以轉速300rpm攪拌均勻，之後添加觸媒二月桂酸二丁基錫(T12)數滴，開始升溫至75℃維持2小時，之後降溫至51℃。 1. Add 9,9-bis(4-hydroxyphenyl)fluorine (BHEOPF) 2.1925g N-methyl-2-pyrrolidone (NMP) 12.5682 g dimethylol propionic acid (DMPA) 2.4203 g polytetramethylene ether glycol , PTMEG; molecular weight 1000g / mole) 26.9354g Isophorone diisocyanate (IPDI) 20g stirred at 300rpm, then add a few drops of catalyst dibutyltin dilaurate (T12), began to heat up to 75 ° C to maintain After 2 hours, then cool to 51 °C.
2、上述反應物添加1.8391g三乙基胺(triethylamine,TEA)中和，以轉速500rpm攪拌10分鐘。 2. The above reactant was neutralized by adding 1.8391 g of triethylamine (TEA) and stirred at 500 rpm for 10 minutes.
3、將轉速提升至1000rpm加入128.2504g去離子水，攪拌至冒小氣泡。 3. Increase the rotation speed to 1000 rpm and add 128.2504 g of deionized water. Stir to a small bubble.
4、加入1.6611g之3-胺基丙基三乙氧基矽烷(3-aminopropyltriethoxysilane,APTES)與5g丙酮混合液攪拌5分鐘。 4. A mixture of 1.6611 g of 3-aminopropyltriethoxysilane (APTES) and 5 g of acetone was added and stirred for 5 minutes.
5、加入2.4035g乙二胺(ethylenediamine,EDA)與10g去離子水混合液，攪拌1小時，完成本發明之水性聚氨酯阻燃性材料。 5. A mixture of 2.4035 g of ethylenediamine (EDA) and 10 g of deionized water was added and stirred for 1 hour to complete the water-based polyurethane flame retardant material of the present invention.
阻燃性試驗 Flame retardancy test
取棉布靜泡至水性聚氨酯阻燃性材料溶液中，待布濕後取出放置60℃烘箱3小時，乾燥後取出棉布分別由酒精噴燈燃燒2秒與5秒觀察其形貌，結果顯示如第六圖，其中，由燒黑之面積大小顯示含有雙酚芴結構之水性聚氨酯阻燃性材料具有優於純水性聚氨酯材料之阻燃性。 The cotton cloth was bubbled into the water-based polyurethane flame retardant material solution. After being wetted, the oven was taken out and placed in a 60 ° C oven for 3 hours. After drying, the cotton cloth was taken out and burned by an alcohol burner for 2 seconds and 5 seconds, and the appearance was as shown. In the figure, the water-based polyurethane flame-retardant material containing the bisphenol fluorene structure has a flame retardancy superior to that of the pure water-based polyurethane material.
水性聚氨酯阻燃性薄膜之製備 Preparation of waterborne polyurethane flame retardant film
將上述水性聚氨酯阻燃性材料到至鐵氟容版靜置一天後，隔天將溫度 設定為30℃，之後每天同一時間升溫5℃直到75℃當天將薄膜取出。 After the above-mentioned water-based polyurethane flame-retardant material is allowed to stand for one day until the iron-fluorine-filled plate is placed, the temperature is set every other day. The temperature was set to 30 ° C, and then the temperature was raised by 5 ° C at the same time every day until the film was taken out on the day of 75 ° C.
本發明之一具體水性聚氨酯合成例反應方程式 One specific waterborne polyurethane synthesis example reaction equation of the present invention
水性聚氨酯阻燃性材料配方表，表4 Waterborne polyurethane flame retardant material formula table, Table 4
本發明之聚氨酯(BHEOPF/WPU)阻燃性材料之物理特性及安定性測試 Physical properties and stability test of the polyurethane (BHEOPF/WPU) flame retardant material of the present invention
粒徑分析 Particle size analysis
在實驗所用配方條件，BHEOPF/WPU分散液沒有沉澱物，其粒徑分佈不隨BHEOPF含量增加而變寬，參考第一圖，但其體積平均粒徑(DLS)會隨著BHEOPF含量增加而上升，如表5，本發明之水性聚氨酯(BHEOPF/WPU)分散液之平均粒徑圖如第二圖。 In the formulation conditions used in the experiment, the BHEOPF/WPU dispersion has no precipitate, and its particle size distribution does not widen with the increase of BHEOPF content. Referring to the first figure, its volume average particle size (DLS) will increase with the increase of BHEOPF content. As shown in Table 5, the average particle size of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention is as shown in the second figure.
黏度分析 Viscosity analysis
本發明之水性聚氨酯(BHEOPF/WPU)分散液之黏度測量時，所得黏度隨轉子之轉速的變化，隨著轉速增加，分散液黏度上升，在X軸為剪切變率是隨時間變化，Y軸為剪切應力是與受力面成正切應力，剪切變率與剪切應力成正比是牛頓流體。第三圖為以轉速250rpm時的黏度對不同BHEOPF含量作圖，結果顯示水性聚氨酯(BHEOPF/WPU)分散液之黏度維持在5~7cps。 When the viscosity of the waterborne polyurethane (BHEOPF/WPU) dispersion of the present invention is measured, the viscosity of the dispersion increases with the rotation speed of the rotor, and as the rotation speed increases, the viscosity of the dispersion increases, and the shear variability on the X axis changes with time, Y The shear stress of the shaft is tangent to the force surface, and the shear variability is proportional to the shear stress is Newtonian fluid. The third graph is a plot of viscosity at 250 rpm versus different BHEOPF levels. The results show that the viscosity of the aqueous polyurethane (BHEOPF/WPU) dispersion is maintained at 5-7 cps.
界面電位分析 Interface potential analysis
分散液之穩定性可用界面電位來分析，一般而言電雙層是膠體粒子表 面所吸附的一固定層(稱為Stern層)，當膠體粒子與外界做相對運動時，會將固定層一起帶著運動，因此固定層表面與外界擴散層之間的電位差稱為Zeta電位。而當具有表面電荷的膠體粒子在外加電場的環境中，相對於固定不動的液體而有移動的現象，稱之為電泳動，藉由膠體粒子的電泳動行為可獲得粒子表面的電位，即界面電位。通常Zeta電位絕對值越大，粒子和粒子之間的排斥力越大，則粒子分散效果越好，越不易產生團聚的現象，溶液的穩定性越好。 The stability of the dispersion can be analyzed by the interface potential. Generally, the electric double layer is a colloidal particle table. A fixed layer (called a Stern layer) adsorbed by the surface, when the colloidal particles move relative to the outside, will move the fixed layer together, so the potential difference between the surface of the fixed layer and the external diffusion layer is called the Zeta potential. When a colloidal particle having a surface charge moves in an environment where an electric field is applied, relative to a stationary liquid, it is called electrophoresis, and the potential of the surface of the particle can be obtained by the electrophoretic behavior of the colloidal particle, that is, the interface. Potential. Generally, the larger the absolute value of the zeta potential, the larger the repulsive force between the particles and the particles, the better the particle dispersion effect, the less prone to agglomeration, and the better the stability of the solution.
第四圖為本發明水性聚氨酯(BHEOPF/WPU)分散液之zeta電位隨BHEOPF含量之變化圖，不含BHEOPF的WPU分散液之zeta電位絕對值為-19.97±2mV，而含BHEOPF的WPU分散液之zeta電位為-18~-20mV之間。本發明水性聚氨酯(BHEOPF/WPU)分散液之zeta電位值不隨BHEOPF含量增高而改變，其顯示電位均為穩定。 The fourth figure is a graph showing the change of zeta potential with BHEOPF content of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention. The absolute value of the zeta potential of the WPU dispersion without BHEOPF is -19.97±2 mV, and the WPU dispersion containing BHEOPF. The zeta potential is between -18 and -20 mV. The zeta potential value of the aqueous polyurethane (BHEOPF/WPU) dispersion of the present invention does not change with the increase of the BHEOPF content, and the display potential is stable.
接觸角測量 Contact angle measurement
由於薄膜表面可能帶有親水基團，或者本身表面就是疏水，為了探討此特性必須藉由接觸角量測儀來檢測膜的親疏水性，這項性能是重要的，因為膜如果可以呈現疏水相對應用性廣，呈現較親水則是耐久度低易分解。本發明將水性聚氨酯(BHEOPF/WPU)分散液乾燥成製成薄膜，薄膜經由接觸角測量儀分析，測試結果列於表5，一般之水性聚氨酯接觸角為67°左右，而隨雙酚芴的含量愈多，所測得的角度有變大之趨勢，表示有偏向愈疏水的性質。 Since the surface of the film may have a hydrophilic group, or the surface itself is hydrophobic, in order to investigate this property, it is necessary to measure the hydrophilicity of the film by a contact angle meter. This property is important because the film can exhibit hydrophobicity. Sexually broad, and more hydrophilic, it is low in endurance and easy to decompose. The invention dries the aqueous polyurethane (BHEOPF/WPU) dispersion into a film, and the film is analyzed by a contact angle measuring instrument. The test results are listed in Table 5. The general aqueous polyurethane contact angle is about 67°, and the bisphenol quinone is used. The more the content, the greater the tendency of the measured angle, indicating the more hydrophobic nature.
膨潤度分析 Swelling analysis
進行膨潤度試驗，將薄膜浸入水中靜置，分別由時間1、2、4、8、 12、15分鐘之後每15分鐘作為間隔，隨每個時間將膜取出擦乾秤重，第五圖為BHEOPF/WPU薄膜膨潤度曲線圖，其中含水率(公式求得)值為Y軸，時間為X軸，結果顯示隨時間變化量薄膜之吸水率是緩慢上升，而大約100分鐘後薄膜之吸水量到達飽和，之後的曲線呈現水平狀，由圖中WPU曲線顯示吸水最多，接著依序為BHEOPF/WPU1曲線至BHEOPF/WPU5，可知由於雙酚芴含量越多越不容易吸水，在接觸角試驗可得之雙酚芴含量越多，角度越大也越趨向疏水，而此特性相對在膨潤試驗中也有所呼應，隨雙酚芴含量越多則可以降低吸水性質和改善薄膜之親水現象。 Perform a swelling test and immerse the film in water for a time of 1, 2, 4, 8, respectively. After 12 and 15 minutes, every 15 minutes as the interval, the film was taken out and weighed with each time. The fifth figure is the BHEOPF/WPU film swelling degree curve, in which the water content (formula) is the Y-axis, time For the X-axis, the results show that the water absorption of the film changes slowly with time, and the water absorption of the film reaches saturation after about 100 minutes, and the subsequent curve is horizontal. The WPU curve shows the most water absorption, followed by BHEOPF/WPU1 curve to BHEOPF/WPU5, it is known that the more bisphenol bismuth content is, the less water absorbing, the more bisphenol quinone content can be obtained in the contact angle test, the larger the angle, the more hydrophobic, and the characteristic is relatively swelled. There is also a response in the test, as the content of bisphenol quinone is reduced, the water absorption property can be lowered and the hydrophilicity of the film can be improved.
聚氨酯(BHEOPF/WPU)分散液之物理特性，表5 Physical properties of polyurethane (BHEOPF/WPU) dispersions, Table 5
耐燃測試 Flame resistance test
取棉布靜泡至水性聚氨酯阻燃性材料溶液中，待布濕後取出放置60℃烘箱3小時，乾燥後取出棉布分別由酒精噴燈燃燒2秒與5秒觀察其形貌，結果顯示如第六圖(A)、(B)、(C)，其中，由燒黑之面積大小顯示含有雙酚芴結構之水性聚氨酯阻燃性材料具有優於純水性聚氨酯材料之阻燃性。 The cotton cloth was bubbled into the water-based polyurethane flame retardant material solution. After being wetted, the oven was taken out and placed in a 60 ° C oven for 3 hours. After drying, the cotton cloth was taken out and burned by an alcohol burner for 2 seconds and 5 seconds, and the appearance was as shown. Figs. (A), (B), and (C), wherein the water-based polyurethane flame-retardant material containing the bisphenol fluorene structure has a flame retardancy superior to that of the pure water-based polyurethane material.
經由酒精燈測試棉布之阻燃性質，由於高分子材料本身耐熱效果並不優良，藉此以預聚合物混合法製備出具有芴結構(Cardo)之水性聚氨酯 (WPU)以提升水性聚氨酯之耐熱溫度，因雙酚芴含有苯環結構能提升材料之耐熱度，相對將無機材料像二氧化矽粒子的添加，以提高耐熱。經由酒精燈測試其阻燃性質如第六圖(A)棉布之阻燃性驗圖觀察在燃燒2秒和5秒時焦黑的面積大小，5秒較2秒面積大且焦黑，再使用一塊棉布塗沾上一般純水性聚氨酯分散液如第六圖(B)塗有水性聚氨酯分散液之棉布阻燃測試圖，在酒精燈燃燒分別2秒與5秒試驗下得知2秒呈現微黃現象相較於純棉布顏色來淡也無焦黑現象，5則是焦黑面積變小，可得知沾染水性聚氨酯分散液之棉布有阻燃效果，再與塗有含有雙酚芴之水性聚氨酯分散液之棉布比較，如第六圖(C)發現在2秒時塗有含有雙酚芴之水性聚氨酯分散液之棉布焦黃面積又比塗有水性聚氨酯分散液之棉布來的更小，5秒焦黑程度與面積都較於水性聚氨酯分散液之棉布來的小。 The flame retardant property of the cotton cloth is tested by the alcohol lamp, and the water-repellent polyurethane having the enamel structure (Cardo) is prepared by the prepolymer mixing method because the heat resistance effect of the polymer material itself is not excellent. (WPU) to improve the heat-resistant temperature of water-based polyurethane, because bisphenol hydrazine contains a benzene ring structure can improve the heat resistance of the material, and the addition of inorganic materials like cerium oxide particles to improve heat resistance. Test the flame retardant properties of the cotton lamp by the alcohol lamp. Figure 6 (A) The flame retardancy of the cotton cloth is observed. The area of the coke black is burned at 2 seconds and 5 seconds. The area is 5 seconds larger than 2 seconds and the focus is black. Then use a piece of cotton cloth. Apply a general pure waterborne polyurethane dispersion as shown in Figure 6 (B). A flame retardant test chart of cotton coated with an aqueous polyurethane dispersion. Under the test of 2 seconds and 5 seconds of burning of the alcohol lamp, it is known that the yellow color is 2 seconds. Compared with the color of pure cotton cloth, there is no blackening phenomenon, and 5 is that the area of blackened black is small. It can be known that the cotton cloth contaminated with water-based polyurethane dispersion has a flame retardant effect, and is coated with an aqueous polyurethane dispersion containing bisphenolphthalein. Compared with the cotton cloth, as shown in the sixth figure (C), the area of the brown fabric coated with the aqueous polyurethane dispersion containing bisphenolphthalein at 2 seconds is smaller than that of the cotton coated with the aqueous polyurethane dispersion, and the degree of blackening is 5 seconds. The area is smaller than that of the cotton cloth of the aqueous polyurethane dispersion.
產業上之可利用性 Industrial availability
本發明所製備之水性聚氨酯阻燃性材料，為含雙酚芴結構之水性聚氨酯，具有優異之阻燃性質。可應用於聚氨基甲酸酯(PU)樹脂既有之各項用途，例如塗料、接著劑、油墨、纖維處理劑。 The water-based polyurethane flame-retardant material prepared by the invention is an aqueous polyurethane containing a bisphenol fluorene structure and has excellent flame retardant properties. It can be applied to various applications of polyurethane (PU) resins, such as coatings, adhesives, inks, and fiber treatment agents.
本發明之水性聚氨酯阻燃性材料，它具有良好的抗化學性，抗溶劑性，耐磨性，優異的彈性和耐熱變形性質，可被廣泛應用於防火塗料、黏著劑、難燃傢俱、床椅墊、襯裡、建築之絕緣體、電纜線、冰箱絕熱層、合成皮、防水材、車輛烤漆、耐磨胎、防水建材、耐磨傢俱、密封劑、填空劑、防水劑、彈性纖維品、纖維織物處理劑、發泡體、IC製程、印電路板、皮革表面處理劑及各種添加劑上之用途，應用於各電子IC工廠和化學廠，改善了人們的生活品質。 The water-based polyurethane flame-retardant material of the invention has good chemical resistance, solvent resistance, wear resistance, excellent elasticity and heat deformation resistance, and can be widely applied to fireproof coatings, adhesives, flame-retardant furniture, beds. Seat cushions, linings, building insulation, cable, refrigerator insulation, synthetic leather, waterproofing materials, vehicle paint, wear-resistant tires, waterproof building materials, wear-resistant furniture, sealants, fillers, waterproofing agents, elastic fibers, fibers Fabric treatment agents, foams, IC processes, printed circuit boards, leather surface treatment agents and various additives are used in various electronic IC factories and chemical plants to improve people's quality of life.
雖然本發明以數個較佳實施例揭露如上，然其非用以限制本發明，任何在所屬技術領域中具有通常知識者，於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 present invention has been described above in terms of several preferred embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. The scope of the present invention is defined by the scope of the appended claims.
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| CN113150671B (en) * | 2021-05-07 | 2022-09-23 | 华阳新材料科技集团有限公司 | Non-ionic water-based polyurethane-based expansion type steel structure fireproof coating and preparation method thereof |
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