TWI805210B - Aqueous polyurethane dispersion and composition comprising such - Google Patents
Aqueous polyurethane dispersion and composition comprising such Download PDFInfo
- Publication number
- TWI805210B TWI805210B TW111104193A TW111104193A TWI805210B TW I805210 B TWI805210 B TW I805210B TW 111104193 A TW111104193 A TW 111104193A TW 111104193 A TW111104193 A TW 111104193A TW I805210 B TWI805210 B TW I805210B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyols
- polyurethane dispersion
- weight
- polyurethane
- acid
- Prior art date
Links
Abstract
Description
本發明是關於一種水性聚氨酯分散體(aqueous polyurethane dispersion，PUD)；特定而言，本發明是關於一種陽離子型水性聚氨酯分散體(cationic aqueous polyurethane dispersion，CAPUD)。該水性聚氨酯分散體尤其有利於改良聚氨酯發泡體、真皮、合成皮或織物的機械性質。The present invention relates to an aqueous polyurethane dispersion (aqueous polyurethane dispersion, PUD); specifically, the present invention relates to a cationic aqueous polyurethane dispersion (cationic aqueous polyurethane dispersion, CAPUD). The aqueous polyurethane dispersions are especially advantageous for improving the mechanical properties of polyurethane foams, genuine leather, synthetic leather or textiles.
聚氨酯因其軟硬度可調範圍廣、耐低溫、柔韌性好、附著力強等優點被廣泛應用於皮革塗飾劑、木器漆、塗料、黏著劑、塑件、鋼鐵、紡織、製鞋、紙張等領域。已知一般溶劑型聚氨酯使用大量有機溶劑，其衍生的揮發性有機物(VOC)對環境及人體造成不良影響。隨著世界各國環保法規日趨嚴厲，近年對於水性聚氨酯的需求及性質要求漸增。Polyurethane is widely used in leather finishing agents, wood lacquers, coatings, adhesives, plastic parts, steel, textiles, shoemaking, and paper because of its wide range of softness and hardness, low temperature resistance, good flexibility, and strong adhesion. and other fields. It is known that general solvent-based polyurethanes use a large amount of organic solvents, and the volatile organic compounds (VOCs) derived from them have adverse effects on the environment and human body. With the increasingly stringent environmental protection regulations around the world, the demand and property requirements for water-based polyurethane have been increasing in recent years.
在水性聚氨酯的製備過程中，為獲得穩定分散的聚氨酯乳液，一般需在聚氨酯寡聚物（預聚物）的分子中引入親水基團，使其在水中乳化。根據所引入基團的帶電性，水性聚氨酯可區分為陽離子型水性聚氨酯(CAPUD)、陰離子型水性聚氨酯、非離子型水性聚氨酯、以及混合型水性聚氨酯。In the preparation process of waterborne polyurethane, in order to obtain a stable and dispersed polyurethane emulsion, it is generally necessary to introduce hydrophilic groups into the molecules of polyurethane oligomers (prepolymers) to emulsify them in water. According to the chargeability of the introduced groups, waterborne polyurethane can be divided into cationic waterborne polyurethane (CAPUD), anionic waterborne polyurethane, nonionic waterborne polyurethane, and mixed waterborne polyurethane.
一般常見的水性聚氨酯分散體多屬陰離子型的水性聚氨酯分散體。對於陽離子型水性聚氨酯(CAPUD)而言，由於聚氨酯本身具有胺基甲酸酯結構，再加上形成CAPUD所需的季銨鹽離子中心，使得CAPUD易黃變且在高溫下黃變情況更加嚴重，故CAPUD的商品化過程仍存在相當困難。Generally, the common water-based polyurethane dispersions are mostly anionic water-based polyurethane dispersions. For cationic waterborne polyurethane (CAPUD), because polyurethane itself has a urethane structure, coupled with the quaternary ammonium salt ion center required to form CAPUD, CAPUD is prone to yellowing and the yellowing is more serious at high temperatures , so the commercialization process of CAPUD is still quite difficult.
水性聚氨酯分散體若在塗料中作為色漆應用，一般需於色漆上施作保護性清漆，惟清漆通常含有有機溶劑，若基於水性聚氨酯分散體的色漆塗膜的耐溶劑性不佳，則清漆所含的有機溶劑即會侵蝕塗膜表面，導致最終外觀失光或色相不均勻等問題。If the water-based polyurethane dispersion is used as a paint in paint, it is generally necessary to apply a protective varnish on the paint, but the varnish usually contains organic solvents. If the solvent resistance of the paint film based on water-based polyurethane dispersion is not good, The organic solvent contained in the varnish will erode the surface of the coating film, resulting in problems such as loss of gloss or uneven hue in the final appearance.
水性聚氨酯分散體若作為表面處理劑，或是在塗料中作為最外層的面漆應用，在終端產品應用會遇到溶劑(例如酒精)清洗或擦拭的情形，對於耐溶劑性要求更加嚴苛。If the water-based polyurethane dispersion is used as a surface treatment agent or as the outermost topcoat in the coating, it will encounter solvent (such as alcohol) cleaning or wiping in the end product application, and the requirements for solvent resistance are more stringent.
因此，所屬技術領域中亟需一種具有製備方法簡單、改善前述缺點（如：改良在高溫下的耐黃變性（下稱「耐熱黃變性」）及/或耐溶劑性的新穎CAPUD。Therefore, there is an urgent need in the technical field for a novel CAPUD that has a simple preparation method, improves the aforementioned shortcomings (eg, improves yellowing resistance at high temperature (hereinafter referred to as "heat yellowing resistance") and/or solvent resistance.
有鑒於上述的問題，本發明首先提供一種水性聚氨酯分散體，其中該聚氨酯由包含以下各項的成分反應而得：至少二種多元醇，多異氰酸酯，擴鏈劑，及中和劑；其中該至少二種多元醇包含具有叔胺基的多元醇。In view of the above-mentioned problems, the present invention firstly provides a water-based polyurethane dispersion, wherein the polyurethane is obtained by reacting components comprising the following: at least two polyols, polyisocyanates, chain extenders, and neutralizing agents; wherein the The at least two polyols comprise polyols having tertiary amine groups.
本發明另提供一種塗料組合物，其包含如本發明的水性聚氨酯分散體及色料。The present invention further provides a coating composition, which comprises the aqueous polyurethane dispersion of the present invention and a colorant.
本發明另提供一種黏著劑組合物，其包含如本發明的水性聚氨酯分散體及樹脂。The present invention further provides an adhesive composition, which comprises the aqueous polyurethane dispersion and resin of the present invention.
為便於理解本文所陳述的揭示內容，茲於以下定義若干術語。To facilitate understanding of the disclosure set forth herein, several terms are defined below.
在本說明書及申請專利範圍中所使用的表達含量、比例、物理特徵等的所有數位應理解為在所有情況下經術語「約」修飾。本文中，術語「約」意謂如由一般熟習此項技術者所測定的特定值的可接受誤差，其部分地視如何量測或測定該值而定。All numbers expressing amounts, ratios, physical characteristics, etc. used in this specification and claims should be understood as being modified by the term "about" in all cases. Herein, the term "about" means an acceptable error for a particular value, as determined by one of ordinary skill in the art, depending in part on how the value was measured or determined.
本文中，除非特別限定，單數形「一」和「該」亦包括其複數形。本文中任何和所有實施例和例示性用語（「例如」和「如」）目的僅為了更加突顯本揭露，並非針對本發明的範圍構成限制，本案說明書中的用語不應被視為暗示任何未請求的方法及條件可構成實施本發明時的必要特徵。Herein, unless otherwise specified, the singular forms "a" and "the" also include their plural forms. Any and all examples and illustrative language ("such as" and "such as") herein are for the purpose of highlighting the present disclosure only and are not intended to limit the scope of the present invention, and the language in this case specification should not be taken to imply any The claimed methods and conditions may constitute essential features in the practice of the invention.
關於兩項或超過兩項的清單的「或」一詞涵蓋所有以下詞的解釋：清單中的任一項、清單中的所有項，及清單中各項的任何組合。The term "or" in reference to a list of two or more includes all interpretations of any of the items in the list, all of the items in the list, and any combination of items in the list.
本文中所揭示的所有範圍均應理解為涵蓋其中所包含的任何及所有次範圍。舉例而言，「1至10」的範圍應視為包含最小值1與最大值10之間的任何及所有次範圍且包含最大值1及最大值10；亦即，以1或大於1的最小值開始且以10或小於10的最大值結束的所有次範圍，例如：1至6.7、3.2至8.1或5.5至10，以及該範圍內的任何數位，例如：2.6、4.7或7.3。All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a range of "1 to 10" should be considered to include any and all subranges between and including a minimum value of 1 and a maximum value of 10; All subranges that begin with a value and end with a maximum value of 10 or less, eg: 1 to 6.7, 3.2 to 8.1, or 5.5 to 10, and any digits within that range, eg: 2.6, 4.7, or 7.3.
本文中，「聚氨酯」是指包括寡聚物(例如，預聚物)的聚合物，其含有胺基甲酸酯基「-O-C(=O)-NH-」。所屬技術領域已知，聚氨酯除胺基甲酸酯基之外，亦可含有其它的基團，例如但不限於：脲、脲甲酸酯、縮二脲、碳二醯亞胺、㗁唑啶基、異氰尿酸酯、脲二酮、酯、醚、碳酸酯、烴、氟碳化合物、醇、硫醇、胺、醯肼、矽氧烷、矽烷、酮、或烯烴等。Herein, "polyurethane" refers to a polymer including an oligomer (eg, a prepolymer) containing a urethane group "-O-C(=O)-NH-". It is known in the art that besides urethane groups, polyurethanes may also contain other groups, such as but not limited to: urea, alloformate, biuret, carbodiimide, oxazolidine group, isocyanurate, uretdione, ester, ether, carbonate, hydrocarbon, fluorocarbon, alcohol, thiol, amine, hydrazine, siloxane, silane, ketone, or olefin, etc.
本文中，「水性分散體」是指含有相當數量的水的分散體。在一些態樣中，以所有溶劑（包含水）的總重量計，水性分散體含有至少5重量%的水，例如但不限於：5重量%、10重量%、15重量%、20重量%、25重量%、30重量%、35重量%、40重量%、45重量%、50重量%、55重量%、60重量%、65重量%、70重量%、75重量%、80重量%、或90重量%，合適的含水量範圍可為以上數值的任意組合。水性分散體可含有其它成分，例如可與水相容的有機溶劑。舉例言之，本發明的水性聚氨酯分散體的含意可為：包含水及聚氨酯的分散體，其中聚氨酯分散於至少含有20重量%為水的水性介質中，且該分散體亦可含有可與水相容的有機材料（如醇及其它極性有機溶劑）。Herein, "aqueous dispersion" refers to a dispersion containing a substantial amount of water. In some aspects, the aqueous dispersion contains at least 5% by weight water based on the total weight of all solvents (including water), such as but not limited to: 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, or 90% by weight % by weight, the suitable range of water content can be any combination of the above values. Aqueous dispersions may contain other ingredients such as water-compatible organic solvents. For example, the meaning of the aqueous polyurethane dispersion of the present invention can be: a dispersion comprising water and polyurethane, wherein the polyurethane is dispersed in an aqueous medium containing at least 20% by weight of water, and the dispersion can also contain water-compatible Compatible organic materials (such as alcohols and other polar organic solvents).
在本發明中的水性聚氨酯分散體，其中該聚氨酯由包含以下各項的成分反應而得：至少二種多元醇，多異氰酸酯，擴鏈劑，及中和劑。該水性聚氨酯分散體是藉由在聚氨酯分子上引入離子型親水基團實現其在水中的穩定分散，離子型的親水基團根據中和類別不同可分為陰離子型(如二羥甲基丙酸和磺酸鹽類)和陽離子型(如N-甲基二乙醇胺)。在一些態樣中，該水性聚氨酯分散體是陽離子型水性聚氨酯分散體(CAPUD)。In the aqueous polyurethane dispersion of the present invention, the polyurethane is obtained by reacting components comprising at least two kinds of polyols, polyisocyanates, chain extenders, and neutralizing agents. The water-based polyurethane dispersion realizes its stable dispersion in water by introducing ionic hydrophilic groups on the polyurethane molecules. The ionic hydrophilic groups can be divided into anionic types (such as dimethylol propionic acid and sulfonates) and cationic (such as N-methyldiethanolamine). In some aspects, the aqueous polyurethane dispersion is a cationic aqueous polyurethane dispersion (CAPUD).
本發明的CAPUD中所含的聚氨酯可根據形成聚氨酯寡聚物、擴鏈及中和（季銨化）的順序製備。以下是搭配上述步驟，詳述本發明聚氨酯的組成及其製備方式。 形成聚氨酯寡聚物： The polyurethane contained in the CAPUD of the present invention can be prepared in the order of polyurethane oligomer formation, chain extension, and neutralization (quaternization). The following is a detailed description of the composition of the polyurethane of the present invention and its preparation method in conjunction with the above steps. Formation of polyurethane oligomers:
本發明所涉及的聚氨酯寡聚物是由多異氰酸酯及至少二種多元醇所形成。該至少二種多元醇包含具有叔胺基的多元醇，該具有叔胺基的多元醇具有親水性（可用作親水擴鏈劑），可提升聚氨酯在水中的分散性，使其外狀呈現透明且穩定分散於水中。多元醇可經由-NCO+H-X→-NH-C(=O)-X反應來提供與異氰酸酯基團進行反應的活性氫來源，在一些態樣中，除本文所述的具有叔胺基的多元醇之外，該至少二種多元醇另包含不同於該具有叔胺基的多元醇的其他多元醇（以下簡稱為「其他多元醇」）。The polyurethane oligomer involved in the present invention is formed of polyisocyanate and at least two kinds of polyols. The at least two kinds of polyols include polyols with tertiary amino groups, and the polyols with tertiary amino groups are hydrophilic (can be used as hydrophilic chain extenders), which can improve the dispersibility of polyurethane in water and make its appearance appear Transparent and stable dispersion in water. Polyols can provide a source of active hydrogen to react with isocyanate groups via the -NCO+H-X→-NH-C(=O)-X reaction. In addition to alcohols, the at least two polyols further include other polyols (hereinafter referred to as "other polyols") different from the polyols having tertiary amino groups.
在一些態樣中，多異氰酸酯可先與其他多元醇反應形成中間物，再將該中間物與具有叔胺基的多元醇反應形成聚氨酯寡聚物，反應方程示意如下：
- 形成中間物：
其中R 1、R 2、R 3、R 4及R 5各彼此獨立地表示飽和直鏈或支鏈飽和烴基，其可具有1至12個碳原子，較佳具有1至8個碳原子，更佳具有1至6個碳原子，尤佳具有1至4個碳原子，例如但不限於：甲基、乙基、丙基（例如，正丙基、異丙基）、丁基（例如，正丁基、異丁基、叔丁基）、戊基、己基及其類似基團。 I.1 多異氰酸酯 Wherein R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a saturated linear or branched saturated hydrocarbon group, which may have 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more Preferably have 1 to 6 carbon atoms, especially preferably have 1 to 4 carbon atoms, such as but not limited to: methyl, ethyl, propyl (for example, n-propyl, isopropyl), butyl (for example, n- butyl, isobutyl, tert-butyl), pentyl, hexyl and the like. I.1 Polyisocyanate
在一些態樣中，多異氰酸酯具有平均大於一個的異氰酸酯基；多異氰酸酯具有平均兩個以上的異氰酸酯基；多異氰酸酯具有平均三個以上的異氰酸酯基；多異氰酸酯具有平均四個以上的異氰酸酯基。In some aspects, the polyisocyanate has an average of more than one isocyanate group; the polyisocyanate has an average of more than two isocyanate groups; the polyisocyanate has an average of more than three isocyanate groups; the polyisocyanate has an average of more than four isocyanate groups.
在一些態樣中，多異氰酸酯包括脂肪族多異氰酸酯、芳香族多異氰酸酯及雜環族多異氰酸酯，及其寡聚反應的產物，多異氰酸酯可單獨使用或者是使用兩種以上的混合物。也可以使用上述多異氰酸酯的二聚物、三聚物及寡聚物。In some aspects, the polyisocyanate includes aliphatic polyisocyanate, aromatic polyisocyanate and heterocyclic polyisocyanate, and oligomerization products thereof, and the polyisocyanate may be used alone or in mixture of two or more. Dimers, trimers and oligomers of the above polyisocyanates can also be used.
合適的脂肪族多異氰酸酯可為鏈狀脂肪族多異氰酸酯或環狀脂肪族多異氰酸酯（以下簡稱為「環脂族多異氰酸酯」）。Suitable aliphatic polyisocyanate may be chain aliphatic polyisocyanate or cyclic aliphatic polyisocyanate (hereinafter referred to as "cycloaliphatic polyisocyanate").
合適的鏈狀脂肪族多異氰酸酯例如但不限於：具有5至20個碳原子的α,Ω-伸烷基二異氰酸酯，如六亞甲-1,6-二異氰酸酯、1,12-十二烷二異氰酸酯、2,2,4-三甲基-六亞甲二異氰酸酯、2,4,4-三甲基-六亞甲二異氰酸酯、2-甲基-1,5-五亞甲二異氰酸酯、離胺酸二異氰酸酯等。較佳的鏈狀脂肪族多異氰酸酯例如但不限於：六亞甲-1,6-二異氰酸酯、2,2,4-三甲基-六亞甲二異氰酸酯或2,4,4-三甲基-六亞甲二異氰酸酯。Suitable chain aliphatic polyisocyanates such as, but not limited to: α,Ω-alkylene diisocyanates having 5 to 20 carbon atoms, such as hexamethylene-1,6-diisocyanate, 1,12-dodecane Diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, Lysine diisocyanate, etc. Preferred chain aliphatic polyisocyanates such as but not limited to: hexamethylene-1,6-diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate or 2,4,4-trimethyl - hexamethylene diisocyanate.
合適的環脂族多異氰酸酯例如但不限於：二環己基甲烷二異氰酸酯(H 12MDI)、異佛酮二異氰酸酯(IPDI)、環己烷二異氰酸酯、雙-(異氰甲基)環己烷、甲基環己烷二異氰酸酯、環己烷三異氰酸酯、其異構物等。較佳的環脂族多異氰酸酯例如但不限於：二環己基甲烷二異氰酸酯或異佛酮二異氰酸酯。 Suitable cycloaliphatic polyisocyanates are such as, but not limited to: dicyclohexylmethane diisocyanate (H 12 MDI ), isophorone diisocyanate (IPDI), cyclohexane diisocyanate, bis-(isocyanomethyl)cyclohexane , Methylcyclohexane diisocyanate, cyclohexane triisocyanate, its isomers, etc. Preferred cycloaliphatic polyisocyanates are, for example but not limited to, dicyclohexylmethane diisocyanate or isophorone diisocyanate.
合適的芳香族多異氰酸酯例如但不限於：4,4'-二苯基亞甲二異氰酸酯(MDI)、甲苯二異氰酸酯、伸苯基二異氰酸酯、萘二異氰酸酯、四氫萘二異氰酸酯、二伸苯基二異氰酸酯、二甲基二伸苯基二異氰酸酯、二氯二伸苯基二異氰酸酯、三苯基甲烷三異氰酸酯、間-四甲基苯二甲基二異氰酸酯、對-四甲基苯二甲基二異氰酸酯、1,4-苯二甲基二異氰酸酯、1,3-苯二甲基二異氰酸酯、其異構物等。較佳的芳香族多異氰酸酯例如但不限於：4,4'-二苯基亞甲二異氰酸酯或甲苯二異氰酸酯。Suitable aromatic polyisocyanates such as but not limited to: 4,4'-diphenylmethylene diisocyanate (MDI), toluene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate, diphenylene diisocyanate, diisocyanate, dimethyldiphenylene diisocyanate, dichlorodiphenylene diisocyanate, triphenylmethane triisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, isomers thereof, etc. Preferred aromatic polyisocyanates are, for example but not limited to: 4,4'-diphenylmethylene diisocyanate or toluene diisocyanate.
合適的雜環族異氰酸酯例如但不限於：5,5'-亞甲雙呋喃異氰酸酯、5,5'-亞異丙基雙呋喃異氰酸酯、其異構物等。 I.2 至少二種多元醇 Suitable heterocyclic isocyanates are, for example but not limited to, 5,5'-methylene bisfuran isocyanate, 5,5'-isopropylidene bisfuran isocyanate, their isomers, and the like. I.2 At least two polyols
本文中，至少二種多元醇包含具有叔胺基的多元醇及「其他多元醇」。Herein, at least two kinds of polyols include polyols having tertiary amino groups and "other polyols".
本文中，「多元醇」是分子中具有兩個或兩個以上的羥基或可還原成羥基並與NCO-基團反應的官能基的材料。Herein, "polyol" is a material having two or more hydroxyl groups or functional groups that are reducible to hydroxyl groups and react with NCO-groups in the molecule.
本發明所用的多元醇是長鏈多元醇（例如，數量平均分子量(Mn)為80 g/mol至10,000 g/mol者），每分子平均具有兩個或兩個以上的羥基或可還原成羥基並與NCO-基團反應的官能基。該多元醇具有可與多異氰酸酯反應的活性氫，可經由以下反應與異氰酸酯基進行反應：-NCO+H-X→-NH-C(=O)-X。較高分子量的多元醇有助於聚氨酯形成軟鏈段；較低分子量的多元醇有助於聚氨酯形成硬鏈段。The polyols used in the present invention are long-chain polyols (e.g., those with a number average molecular weight (Mn) of 80 g/mol to 10,000 g/mol) having an average of two or more hydroxyl groups per molecule or being reducible to hydroxyl groups and a functional group that reacts with NCO-groups. The polyol has active hydrogens that can react with polyisocyanates and can react with isocyanate groups via the following reaction: -NCO+H-X→-NH-C(=O)-X. Higher molecular weight polyols help polyurethane form soft segments; lower molecular weight polyols help polyurethane form hard segments.
在一些態樣中，以形成聚氨酯反應物的總重量計，該至少二種多元醇用量的下限為25重量%，該至少二種多元醇用量的上限為55重量%，合適的至少二種多元醇用量例如但不限於：25重量%、26重量%、27重量%、28重量%、29重量%、30重量%、31重量%、32重量%、33重量%、34重量%、35重量%、36重量%、37重量%、38重量%、39重量%、40重量%、41重量%、42重量%、43重量%、44重量%、45重量%、46重量%、47重量%、48重量%、49重量%、50重量%、51重量%、52重量%、53重量%、54重量%或55重量%，其範圍可為以上數值的任意組合。 I.2.1 具有叔胺基的多元醇 In some aspects, based on the total weight of polyurethane-forming reactants, the lower limit of the amount of the at least two polyols is 25% by weight, and the upper limit of the amount of the at least two polyols is 55% by weight. Suitable at least two polyols The amount of alcohol used is for example but not limited to: 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight , 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight % by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight or 55% by weight, the range can be any combination of the above values. I.2.1 Polyols with tertiary amino groups
在本發明中，具有叔胺基的多元醇是以其活性氫經由-NCO+H-X→-NH-C(=O)-X反應，反應後位於聚氨酯寡聚物的主鏈上，以在主鏈上提供可經季銨化處理的氮原子，因此，該具有叔胺基的多元醇不但具有擴鏈劑的作用且能提升聚氨酯寡聚物的親水性，對CAPUD之外觀及分散穩定性的改良程度有重要影響。本案發明人發現若聚氨酯於水中分散性不佳，容易導致CAPUD呈現乳白色外觀、甚至發生分層現象，相對於此，本發明藉由導入具有叔胺基的多元醇的親水性基團於聚氨酯主鏈上，可有效改善聚氨酯於水中的分散性，所得CAPUD呈現透明外觀且安定不分層。In the present invention, the polyhydric alcohol with tertiary amino group is reacted by its active hydrogen via -NCO+H-X→-NH-C(=O)-X, and is located on the main chain of the polyurethane oligomer after the reaction, so that The chain provides nitrogen atoms that can be treated by quaternization. Therefore, the polyol with tertiary amino groups not only acts as a chain extender but also improves the hydrophilicity of polyurethane oligomers. The degree of improvement has a significant effect. The inventors of this case found that if the dispersibility of polyurethane in water is not good, it is easy to cause CAPUD to present a milky white appearance, or even delamination. On the chain, it can effectively improve the dispersibility of polyurethane in water, and the obtained CAPUD has a transparent appearance and is stable without delamination.
在一些態樣中，具有叔胺基的多元醇的數量平均分子量(Mn)下限為80 g/mol，具有叔胺基的多元醇的Mn上限為500 g/mol，合適的Mn例如但不限於：80、90、100、110、120、130、140、150、160、170、180、190、200、220、240、250、260、280、300、350、400、450或500 g/mol，其範圍可為以上數值的任意組合。在一些態樣中，具有叔胺基的多元醇例如但不限於：N-甲基二乙醇胺(N-MDEA)、N-乙基二乙醇胺(EDEA)、N-丙基二乙醇胺(PDEA)、N-丁基二乙醇胺(BDEA)、或3-(二甲胺基)-1,2-丙二醇。具有叔胺基的多元醇可單獨使用或者是使用兩者以上的混合物。In some aspects, the lower limit of the number average molecular weight (Mn) of polyols with tertiary amino groups is 80 g/mol, and the upper limit of Mn of polyols with tertiary amino groups is 500 g/mol. Suitable Mn is such as but not limited to : 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 250, 260, 280, 300, 350, 400, 450 or 500 g/mol, Its range can be any combination of the above numerical values. In some aspects, polyols with tertiary amine groups such as but not limited to: N-methyldiethanolamine (N-MDEA), N-ethyldiethanolamine (EDEA), N-propyldiethanolamine (PDEA), N-butyldiethanolamine (BDEA), or 3-(dimethylamino)-1,2-propanediol. The polyols having tertiary amino groups can be used alone or in combination of two or more.
在一些態樣中，以所有多元醇及多異氰酸酯的總重量計，該具有叔胺基的多元醇的用量為6至15重量%，合適的具有叔胺基的多元醇用量例如但不限於：6重量%、6.5重量%、7重量%、7.5重量%、8重量%、8.5重量%、9重量%、9.5重量%、10重量%、10.5重量%、11重量%、11.5重量%、12重量%、12.5重量%、13重量%、13.5重量%、14重量%、14.5重量%或15重量%。 I.2.2 「其他多元醇」 In some aspects, based on the total weight of all polyols and polyisocyanates, the amount of polyols with tertiary amino groups is 6 to 15% by weight. Suitable amounts of polyols with tertiary amino groups are for example but not limited to: 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, 10% by weight, 10.5% by weight, 11% by weight, 11.5% by weight, 12% by weight %, 12.5% by weight, 13% by weight, 13.5% by weight, 14% by weight, 14.5% by weight or 15% by weight. I.2.2 "Other polyols"
在一些態樣中，其他多元醇包含：聚醚多元醇、聚酯多元醇或聚碳酸酯多元醇。In some aspects, the other polyols include: polyether polyols, polyester polyols, or polycarbonate polyols.
在一些態樣中，其他多元醇的數量平均分子量(Mn)的下限為500 g/mol，多元醇的數量平均分子量(Mn)的上限為10,000 g/mol，合適的數量平均分子量(Mn)例如但不限於：500、1,000、1,500、2,000、2,500、3,000、3,500、4,000、4,500、5,000、5,500、6,000、6,500、7,000、7,500、8,000、8,500、9,000、9,500、或10,000，其範圍可為以上數值的任意組合。In some aspects, the lower limit of the number average molecular weight (Mn) of other polyols is 500 g/mol, the upper limit of the number average molecular weight (Mn) of polyols is 10,000 g/mol, suitable number average molecular weights (Mn) such as But not limited to: 500, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, or 10,00 0, its range can be above Any combination of values.
聚醚多元醇可藉由已知的方式獲得，製備方式是使含有反應性氫原子的起始化合物(如水或用來製備聚酯多元醇的二醇)與環氧烷，例如但不限於：環氧乙烷、環氧丙烷、環氧丁烷、環氧乙基苯、四氫呋喃、表氯醇、或其混合物發生反應。較佳的聚醚包括聚四氫呋喃(PTHF)和聚(丙二醇)(PPG)。Polyether polyols can be obtained in a known manner by reacting a starting compound containing reactive hydrogen atoms, such as water or diols used to prepare polyester polyols, with alkylene oxides, such as but not limited to: Ethylene oxide, propylene oxide, butylene oxide, ethyl oxide benzene, tetrahydrofuran, epichlorohydrin, or mixtures thereof react. Preferred polyethers include polytetrahydrofuran (PTHF) and poly(propylene glycol) (PPG).
聚酯多元醇通常為有機羧酸與超化學計量的二醇進行反應所製備的酯化產物。適合用於反應中的多元醇例如但不限於：聚乙二醇己二酸酯、聚對酞酸乙二酯多元醇、聚己內酯多元醇、鄰苯二甲酸多元醇、磺化多元醇、或其混合物。Polyester polyols are generally esterification products prepared by reacting organic carboxylic acids with superstoichiometric diols. Polyols suitable for use in the reaction such as but not limited to: polyethylene glycol adipate, polyethylene terephthalate polyols, polycaprolactone polyols, phthalate polyols, sulfonated polyols , or a mixture thereof.
在一些態樣中，用於製造聚酯多元醇的有機羧酸包括二羧酸和三羧酸以及酸酐，例如順丁烯二酸、順丁烯二酸酐、琥珀酸、戊二酸、戊二酸酐、己二酸、辛二酸、庚二酸、壬二酸、癸二酸、氯橋酸、1,2,4-丁烷-三羧酸、酞酸、酞酸的異構物、酞酸酐、反丁烯二酸、四溴酞酸酐及酸、二聚脂肪酸，如油酸等，及其混合物。用於製造聚酯多元醇的較佳多羧酸包括脂肪或芳香二元酸。In some aspects, organic carboxylic acids used to make polyester polyols include dicarboxylic and tricarboxylic acids and anhydrides such as maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric acid, Acid anhydride, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorobridge acid, 1,2,4-butane-tricarboxylic acid, phthalic acid, isomers of phthalic acid, phthalein Anhydrides, fumaric acid, tetrabromophthalic anhydride and acids, dimerized fatty acids such as oleic acid, etc., and mixtures thereof. Preferred polycarboxylic acids for use in making polyester polyols include aliphatic or aromatic dibasic acids.
用於製造聚酯多元醇的二醇可為脂肪族二醇、環脂族二醇或芳香族二醇，例如但不限於：伸烷基二醇，如乙二醇、1,2-和1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、己二醇、新戊二醇、1,6-己二醇、1,8-辛二醇；其它二醇，如雙酚-A、環己二醇、環己二甲醇(1,4-雙-羥甲基環己烷)、2-甲基-1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、2-丁基-2-乙基丙烷-1,3-二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇、聚丁二醇、己內酯二醇、二聚酸酯二醇、羥基化雙酚、聚醚二醇、鹵化二醇、或其混合物。較佳的二醇包括乙二醇、丁二醇、己二醇及新戊二醇。The diols used to make polyester polyols can be aliphatic, cycloaliphatic or aromatic, such as but not limited to: alkylene glycols such as ethylene glycol, 1,2- and 1- ,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, hexanediol, neopentyl glycol, 1,6- Hexylene glycol, 1,8-octanediol; other diols such as bisphenol-A, cyclohexanediol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl -1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethylpropane-1,3-diol, triethylene glycol, tetraethylene Diol, Polyethylene Glycol, Dipropylene Glycol, Polypropylene Glycol, Dibutylene Glycol, Polytetramethylene Glycol, Caprolactone Diol, Dipolyester Diol, Hydroxylated Bisphenol, Polyether Diol, Halogenated Diol , or a mixture thereof. Preferred diols include ethylene glycol, butanediol, hexylene glycol and neopentyl glycol.
在一些態樣中，聚酯多元醇為聚酯二醇，例如但不限於：己二醇新戊二醇、己二酸聚酯二醇、丙二醇順丁烯二酸酐己二酸聚酯二醇、己二醇新戊二醇、反丁烯二酸聚酯二醇。In some aspects, the polyester polyol is a polyester diol, such as but not limited to: hexanediol neopentyl glycol, adipate polyester diol, propylene glycol maleic anhydride adipate polyester diol , Hexylene glycol neopentyl glycol, fumaric acid polyester diol.
在一些態樣中，聚碳酸酯多元醇可為二醇與碳酸二芳酯（例如但不限於：碳酸二苯酯）的反應所獲得的化合物。在一些態樣中，用於製造聚碳酸酯多元醇的二醇可例如但不限於：1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、三乙二醇、四乙二醇、或其混合物。In some aspects, the polycarbonate polyol may be a compound obtained by reacting a diol with a diaryl carbonate such as but not limited to diphenyl carbonate. In some aspects, the diols used to make polycarbonate polyols can be, for example but not limited to: 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, or mixtures thereof.
本案發明人另發現，在本發明中，相對於使用聚酯多元醇和/或聚醚多元醇作為其他多元醇而言，使用聚碳酸酯多元醇可使CAPUD具有更佳的耐溶劑性，有利於所得CAPUD於抗指紋漆樹脂的應用。The inventors of this case have also found that in the present invention, compared with using polyester polyol and/or polyether polyol as other polyols, using polycarbonate polyol can make CAPUD have better solvent resistance, which is beneficial to The obtained CAPUD is used in the application of anti-fingerprint paint resin.
在一些態樣中，其他多元醇另包含例如但不限於：聚己內酯多元醇、聚醯胺多元醇、聚酯醯胺多元醇、聚縮醛多元醇、聚硫醚多元醇、聚矽氧烷多元醇、乙氧化聚矽氧烷多元醇、鹵化聚酯多元醇、鹵化聚醚多元醇、聚丁二烯多元醇、氫化聚丁二烯多元醇、聚異戊二烯多元醇、聚異丁烯多元醇、醇酸-改質多元醇、聚硫醚多元醇、含羥基的丙烯酸及甲基丙烯酸聚合物和共聚物、或含羥基環氧化物等。In some aspects, other polyols include, for example but not limited to, polycaprolactone polyols, polyamide polyols, polyesteramide polyols, polyacetal polyols, polythioether polyols, polysilicon Oxane polyol, ethoxylated polysiloxane polyol, halogenated polyester polyol, halogenated polyether polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, poly Isobutylene polyols, alkyd-modified polyols, polythioether polyols, hydroxyl-containing acrylic and methacrylic polymers and copolymers, or hydroxyl-containing epoxides, etc.
上述的其他多元醇可單獨使用或者是使用兩者以上的混合物。The above-mentioned other polyols may be used alone or as a mixture of two or more.
在一些態樣中，以所有多元醇及多異氰酸酯的總重量計，其他多元醇的用量下限為28重量%，其他多元醇的用量上限為50重量%，合適的其他多元醇用量例如但不限於：28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49或50重量%，其範圍可為以上數值的任意組合。In some aspects, based on the total weight of all polyols and polyisocyanates, the lower limit of the amount of other polyols is 28% by weight, and the upper limit of the amount of other polyols is 50% by weight. Suitable amounts of other polyols are such as but not limited to : 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50% by weight, which Ranges can be any combination of the above values.
如前文的反應方程所示，所產生的聚氨酯寡聚物是以異氰酸酯基(NCO)封端。在一些態樣中，以莫耳計，本發明所用多異氰酸酯的異氰酸酯基(NCO)對於所有多元醇的羥基(OH)的莫耳用量比率為1.5至2。合適的比率例如但不限於：1.5、1.55、1.6、1.65、1.7、1.75、1.8、1.85、1.9、1.95或2，其範圍可為以上數值的任意組合。As shown in the previous reaction equation, the resulting polyurethane oligomer is terminated with isocyanate groups (NCO). In some aspects, the polyisocyanate used in the present invention has a molar ratio of isocyanate groups (NCO) to hydroxyl groups (OH) of all polyols of 1.5 to 2 on a molar basis. A suitable ratio is, for example but not limited to: 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95 or 2, and the range can be any combination of the above values.
視需要，可在形成聚氨酯寡聚物的過程中添加受阻酚，受阻酚可捕捉過氧化自由基及/或烷氧自由而抑制聚氨酯的氧化反應，進而獲得改善耐熱黃變性的功效。較佳的受阻酚例如但不限於：2,6-叔丁基-4-甲基苯酚、雙(3,5-叔丁基-4-羥基苯基)硫醚、四[β-(3,5-二叔丁基-4-羥苯基)丙酸]季戊四醇酯(Ciba Irganox ®1010)、或其組合。 If necessary, hindered phenols can be added during the formation of polyurethane oligomers. The hindered phenols can capture peroxide free radicals and/or alkoxy free radicals to inhibit the oxidation reaction of polyurethane, thereby obtaining the effect of improving heat yellowing resistance. Preferred hindered phenols such as but not limited to: 2,6-tert-butyl-4-methylphenol, bis(3,5-tert-butyl-4-hydroxyphenyl)sulfide, tetrakis[β-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol (Ciba Irganox ® 1010), or a combination thereof.
受阻酚的用量可視需要調整。在一些態樣中，以所有多元醇及多異氰酸酯的總重量計，受阻酚的用量下限為0.5 wt.%，受阻酚的用量上限為1 wt.%，較佳的受阻酚的用量例如但不限於：0.5、0.6、0.7、0.8、0.9或1 wt.% ，其範圍可為以上數值的任意組合。 II. 聚氨酯寡聚物的擴鏈： II.1 擴鏈劑 The amount of hindered phenol can be adjusted as needed. In some aspects, based on the total weight of all polyols and polyisocyanates, the lower limit of the amount of hindered phenol is 0.5 wt.%, and the upper limit of the amount of hindered phenol is 1 wt.%. The preferred amount of hindered phenol is such as but not Limited to: 0.5, 0.6, 0.7, 0.8, 0.9 or 1 wt.%, the range can be any combination of the above values. II. Chain extension of polyurethane oligomers: II.1 Chain extenders
本發明進一步使用擴鏈劑以提高聚氨酯寡聚物的分子量。本發明所用的擴鏈劑可包含二或多官能醇或二或多官能胺，較佳為短鏈的二或多官能醇或二或多官能胺（即，短鏈多元醇或短鏈多元胺）。當擴鏈劑包含多元胺時，因多元胺能與異氰酸酯基形成極性較氨酯鍵（-NHCOO-）強的脲鍵（-NHCONH-），故使用包含多元胺的擴鏈劑所得的聚氨酯具有改良的機械強度、機械模數，及耐熱性質。The present invention further uses a chain extender to increase the molecular weight of the polyurethane oligomer. The chain extender used in the present invention can comprise two or polyfunctional alcohols or two or polyfunctional amines, preferably short-chain di or polyfunctional alcohols or two or polyfunctional amines (that is, short-chain polyols or short-chain polyamines ). When the chain extender contains polyamines, because polyamines can form urea bonds (-NHCONH-) with isocyanate groups that are more polar than urethane bonds (-NHCOO-), the polyurethane obtained by using chain extenders containing polyamines has Improved mechanical strength, mechanical modulus, and heat resistance properties.
在一些態樣中，多元胺包含具有平均2個以上的伯胺基、仲胺基、或其組合的無機胺。在一些態樣中，多元胺包含具有平均2個以上的伯胺基、仲胺基、或其組合的有機聚胺。In some aspects, the polyamine comprises an inorganic amine having an average of 2 or more primary amine groups, secondary amine groups, or combinations thereof. In some aspects, the polyamine comprises an organic polyamine having an average of 2 or more primary amino groups, secondary amino groups, or combinations thereof.
在一些較佳態樣中，多元胺擴鏈劑為有機聚胺擴鏈劑例如但不限於：乙二胺(EDA)、二乙三胺(DETA)、三乙四胺(TETA)、間-苯二甲基二胺(MXDA)、2-甲基戊烷二胺、丙二胺、丁二胺、二亞乙基三胺、六亞甲基二胺、環己二胺、苯二胺、甲苯二胺、3,3-二氯聯苯胺、4,4'-亞甲基-雙-(2-氯苯胺)、3,3-二氯-4,4-二胺基二苯基甲烷、或其混合物。一些較佳態樣中，多元胺擴鏈劑為無機聚胺擴鏈劑例如但不限於：肼（H 2N-NH 2）、經取代的肼和水合肼（H 2N-NH 2･H 2O）、或其混合物。 In some preferred aspects, the polyamine chain extender is an organic polyamine chain extender such as but not limited to: ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), m- Xylylenediamine (MXDA), 2-methylpentanediamine, propylenediamine, butylenediamine, diethylenetriamine, hexamethylenediamine, cyclohexanediamine, phenylenediamine, Toluenediamine, 3,3-dichlorobenzidine, 4,4'-methylene-bis-(2-chloroaniline), 3,3-dichloro-4,4-diaminodiphenylmethane, or a mixture thereof. In some preferred aspects, the polyamine chain extender is an inorganic polyamine chain extender such as but not limited to: hydrazine (H 2 N-NH 2 ), substituted hydrazine and hydrazine hydrate (H 2 N-NH 2 ･H 2 O), or mixtures thereof.
在一些態樣中，為使本發明的聚氨酯寡聚物擴鏈，可在聚氨酯寡聚物形成後，加入溶劑（例如但不限於：酮溶劑，如：丙酮或丁酮）稀釋並分散聚氨酯寡聚物，再於經稀釋的聚氨酯寡聚物分散體中加入擴鏈劑。In some aspects, in order to extend the polyurethane oligomer of the present invention, after the polyurethane oligomer is formed, a solvent (such as but not limited to: a ketone solvent, such as: acetone or butanone) can be added to dilute and disperse the polyurethane oligomer polymer, and then add a chain extender to the diluted polyurethane oligomer dispersion.
在一些態樣中，聚氨酯寡聚物與多元胺擴鏈劑的具體反應方程如下：
其中R 1、R 2、R 3、R 4及R 5各彼此獨立地具有如前文所述的含意，R 6表示具有1至20個碳原子的直鏈飽和烴基、支鏈飽和烴基或芳香烴基；m=0或1。在上述反應方程中，m=0即使用肼作為擴鏈劑的態樣。 wherein R 1 , R 2 , R 3 , R 4 and R 5 each independently have the meanings as described above, and R 6 represents a straight-chain saturated hydrocarbon group, a branched-chain saturated hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms ;m=0 or 1. In the above reaction equation, m=0 means that hydrazine is used as the chain extender.
在一些態樣中，擴鏈劑的數量平均分子量(Mn)下限為18 g/mol，上限為500 g/mol，合適的數量平均分子量(Mn)例如但不限於：18、50、100、150、200、250、300、350、400、450或500，其範圍可為以上數值的任意組合。In some aspects, the lower limit of the number average molecular weight (Mn) of the chain extender is 18 g/mol, and the upper limit is 500 g/mol. Suitable number average molecular weights (Mn) are such as but not limited to: 18, 50, 100, 150 , 200, 250, 300, 350, 400, 450 or 500, the range can be any combination of the above values.
在一些態樣中，以莫耳計，多元胺擴鏈劑的胺基對多異氰酸酯的NCO基團的用量比率的下限為0.5；多元胺擴鏈劑的胺基對多異氰酸酯的NCO基團的用量比率的上限為1，合適的用量比率例如但不限於：0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、或1，其範圍可為以上數值的任意組合。In some aspects, in terms of moles, the lower limit of the ratio of the amount of the amine group of the polyamine chain extender to the NCO group of the polyisocyanate is 0.5; The upper limit of the dosage ratio is 1. Suitable dosage ratios are, for example, but not limited to: 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1, and the range can be any combination of the above values.
前揭擴鏈劑可單獨使用或者是使用兩者以上的混合物。 III. 季銨化處理形成陽離子型聚氨酯： III.1 中和劑 The chain extenders can be used alone or as a mixture of two or more. III. Quaternization treatment to form cationic polyurethane: III.1 Neutralizer
為提高聚氨酯的親水性以形成穩定分散的CAPUD，本發明的聚氨酯可添加中和劑，使得聚氨酯主鏈上對應的氮原子經中和劑處理，藉由酸中和/季銨化方式賦予氮原子陽離子電荷以形成銨陽離子中心。在一些態樣中，酸中和/季銨化聚氨酯的反應方程示意如下：
其中R 1、R 2、R 3、R 4、R 5、R 6及m各彼此獨立地具有如前文所述的含意。 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and m each independently have the meanings as described above.
以使用肼作為擴鏈劑為例，酸中和/季銨化聚氨酯的反應為上述方程中m=0的態樣。Taking hydrazine as an example as a chain extender, the reaction of acid neutralization/quaternization of polyurethane is in the form of m=0 in the above equation.
理論上，聚氨酯主鏈上的叔胺基可被任何已知的中和劑季銨化。然而，在本發明中，本案發明人出乎意料之外的發現，使用特定多元酸組合作為中和劑時，除可增加聚氨酯分子內離子鍵及/或氫鍵的數目，導致分子間交聯密度增加，進而改善CAPUD耐溶劑性之外，可顯著地改善所得CAPUD的耐熱黃變性。Theoretically, the tertiary amine groups on the polyurethane backbone can be quaternized with any known neutralizing agent. However, in the present invention, the inventors of this case unexpectedly found that when using a specific polybasic acid combination as a neutralizing agent, in addition to increasing the number of ionic bonds and/or hydrogen bonds in the polyurethane molecule, resulting in intermolecular crosslinking In addition to increasing the density and thus improving the solvent resistance of the CAPUD, the thermal yellowing resistance of the obtained CAPUD can be significantly improved.
在一些較佳態樣中，本發明的中和劑包含至少兩種酸，具有穩定性好等優點。此外，申請人發現，當中和劑包含有機酸及無機酸，更具有優異的耐黃變性的優點。在一些態樣中，以莫耳計，該有機酸對於無機酸的用量比率為35至50。合適的有機酸對於無機酸的莫耳用量比率例如但不限於：35、35.5、36、36.5、37、37.5、38、38.5、39、39.5、40、40.5、41、41.5、42、42.5、43、43.5、44、44.5、45、45.5、46、46.5、47、47.5、48、48.5、49、49.5或50，其範圍可為以上數值的任意組合。In some preferred aspects, the neutralizing agent of the present invention contains at least two acids, which has the advantages of good stability and the like. In addition, the applicant found that the neutralizer contains organic acid and inorganic acid, which has the advantage of excellent yellowing resistance. In some aspects, the ratio of organic acid to inorganic acid is 35 to 50 on a molar basis. Suitable molar ratios of organic acid to inorganic acid are for example, but not limited to: 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43 , 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5 or 50, and its range can be any combination of the above values.
可用於本發明的有機酸包含甲酸。可用於本發明的無機酸包含多元無機酸。在一些態樣中，可用於本發明的多元無機酸包含磷酸或硫酸。Organic acids useful in the present invention include formic acid. Mineral acids useful in the present invention include polybasic mineral acids. In some aspects, polybasic mineral acids useful in the present invention comprise phosphoric or sulfuric acid.
在一較佳態樣中，本發明所使用的中和劑包含甲酸和選自由磷酸及硫酸所組成之群的多元無機酸。在一些較佳態樣中，中和劑包含甲酸及磷酸，或甲酸及硫酸，或甲酸、磷酸及硫酸。In a preferred aspect, the neutralizing agent used in the present invention includes formic acid and a polybasic inorganic acid selected from the group consisting of phosphoric acid and sulfuric acid. In some preferred aspects, the neutralizing agent includes formic acid and phosphoric acid, or formic acid and sulfuric acid, or formic acid, phosphoric acid and sulfuric acid.
在一些態樣中，以莫耳計，該中和劑對於該含叔胺基的多元醇的用量比率為1.1至1.7，合適的中和劑對於含叔胺基的多元醇的莫耳用量比率例如但不限於：1.1、1.15、1.2、1.25、1.3、1.35、1.4、1.45、1.5、1.55、1.6、1.65、或1.7，其範圍可為以上數值的任意組合。已發現，使用包含甲酸和選自由磷酸及硫酸所組成之群的無機酸的中和劑，較佳使用包含甲酸和磷酸的中和劑。由於甲酸具備醛基，醛基具有抗氧化的特性，因此可改善聚氨酯的耐熱黃變性，磷酸增加分子內離子鍵及/或氫鍵，具有提升耐溶劑效果，可製得具有良好穩定性、不分層、良好耐熱黃變性等優點的CAPUD。另外，申請人已發現，當甲酸對於磷酸的莫耳用量比率為35至50，且中和劑對於含叔胺基的多元醇的莫耳用量比率為1.1至1.7，甲酸及磷酸兩者發生協同效應，所獲致的CAPUD的耐熱黃變性及耐溶劑性為更佳。In some aspects, the molar ratio of the neutralizing agent to the tertiary amino-containing polyol is 1.1 to 1.7, and a suitable molar ratio of the neutralizing agent to the tertiary amino-containing polyol For example but not limited to: 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, or 1.7, the range can be any combination of the above values. It has been found that using a neutralizing agent comprising formic acid and an inorganic acid selected from the group consisting of phosphoric acid and sulfuric acid, preferably using a neutralizing agent comprising formic acid and phosphoric acid. Because formic acid has aldehyde groups, aldehyde groups have anti-oxidation properties, so it can improve the heat yellowing resistance of polyurethane, and phosphoric acid increases intramolecular ionic bonds and/or hydrogen bonds, which has the effect of improving solvent resistance. CAPUD with advantages such as delamination and good heat yellowing resistance. Additionally, applicants have discovered that when the molar ratio of formic acid to phosphoric acid is 35 to 50 and the molar ratio of neutralizer to polyol containing tertiary amino groups is 1.1 to 1.7, both formic and phosphoric acid synergistically Effect, the heat yellowing resistance and solvent resistance of the obtained CAPUD are better.
在一些態樣中，將經中和/季銨化處理後的聚氨酯分散於水中，以形成CAPUD。In some aspects, the neutralized/quaternized polyurethane is dispersed in water to form CAPUD.
在一些態樣中，聚氨酯主鏈上的叔胺基是在將聚氨酯分散於水中之前經酸部份地中和。在一些態樣中，聚氨酯主鏈上的叔胺基是在將聚氨酯分散於水中之期間經酸部份地中和。在一些態樣中，聚氨酯主鏈上的叔胺基的中和程度的下限為10莫耳%，聚氨酯主鏈上的叔胺基的中和程度的上限為100莫耳%，合適的叔胺基中和程度例如但不限於：10莫耳%、15莫耳%、20莫耳%、25莫耳%、30莫耳%、35莫耳%、40莫耳%、45莫耳%、50莫耳%、55莫耳%、60莫耳%、65莫耳%、70莫耳%、75莫耳%、80莫耳%、85莫耳%、90莫耳%、95莫耳%、96莫耳%、97莫耳%、98莫耳%、98.5莫耳%、99莫耳%、99.5莫耳%、或100莫耳%，其範圍可為以上數值的任意組合。本文中，聚氨酯主鏈上的叔胺基的中和程度是指將在聚氨酯主鏈上一或多個氮原子經中和/季銨化的比例。在一些實施態樣中，可以使用超過聚氨酯主鏈上氮原子當量的過量酸。In some aspects, the tertiary amine groups on the polyurethane backbone are partially neutralized with an acid prior to dispersing the polyurethane in water. In some aspects, the tertiary amine groups on the polyurethane backbone are partially neutralized with an acid during dispersion of the polyurethane in water. In some aspects, the lower limit of the neutralization degree of the tertiary amine groups on the polyurethane main chain is 10 mol%, and the upper limit of the neutralization degree of the tertiary amine groups on the polyurethane main chain is 100 mol%. The degree of neutralization is for example but not limited to: 10 mol %, 15 mol %, 20 mol %, 25 mol %, 30 mol %, 35 mol %, 40 mol %, 45 mol %, 50 mol % Mole %, 55 Mole %, 60 Mole %, 65 Mole %, 70 Mole %, 75 Mole %, 80 Mole %, 85 Mole %, 90 Mole %, 95 Mole %, 96 Mole %, 97 Mole %, 98 Mole %, 98.5 Mole %, 99 Mole %, 99.5 Mole %, or 100 Mole %, the range can be any combination of the above values. Herein, the degree of neutralization of the tertiary amine groups on the polyurethane backbone refers to the proportion of one or more nitrogen atoms on the polyurethane backbone to be neutralized/quaternized. In some embodiments, an excess of acid over equivalents of nitrogen atoms on the polyurethane backbone may be used.
在一些態樣中，視需要可移除前文所述用於分散聚氨酯寡聚物的溶劑。In some aspects, the solvent previously described for dispersing the polyurethane oligomer can be removed if desired.
在一些態樣中，本發明的CAPUD可以依照已知的聚氨酯技術與各種不同的其它成分和特色一起製造。此類添加劑包括介面活性劑、安定劑、消泡劑、抗菌劑、抗氧化劑、流變調整劑、或其混合物。可以在將CAPUD處理成最終產品之前及/或期間，依照本技術領域所習知的方式，視需要選擇性地使用以上添加劑。In some aspects, the CAPUD of the present invention can be manufactured according to known polyurethane technology with various other ingredients and features. Such additives include surfactants, stabilizers, defoamers, antimicrobials, antioxidants, rheology modifiers, or mixtures thereof. The above additives may optionally be used in a manner known in the art before and/or during processing of the CAPUD into a final product.
本發明的CAPUD的固含量上限為40%，固含量下限為20%，合適的固含量例如但不限於：20、22、24、25、26、28、30、32、34、35、36、38或40% ，其範圍可為以上數值的任意組合。The upper limit of the solid content of the CAPUD of the present invention is 40%, and the lower limit of the solid content is 20%. Suitable solid content is for example but not limited to: 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38 or 40%, and its range can be any combination of the above values.
本發明的CAPUD的pH值上限為6，合適的pH值例如但不限於：0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5或6，其範圍可為以上數值的任意組合。已發現，若pH值大於6將導致聚氨酯季銨化程度不足及/或親水性不足，故聚氨酯不易分散於水中，不利於儲存穩定性。The upper limit of pH value of CAPUD of the present invention is 6, suitable pH value is for example but not limited to: 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 or 6, and its range can be the above values any combination of . It has been found that if the pH value is greater than 6, the degree of quaternization and/or hydrophilicity of the polyurethane is insufficient, so the polyurethane is not easily dispersed in water, which is not conducive to storage stability.
本發明的CAPUD的黏度可視實際應用需求選擇，合適的黏度上限為500cps，黏度下限為10cps，合適的黏度例如但不限於：10、50、100、150、200、250、300、350、400、450或500cps ，其範圍可為以上數值的任意組合。The viscosity of the CAPUD of the present invention can be selected according to the actual application requirements. The upper limit of the suitable viscosity is 500cps, and the lower limit of the viscosity is 10cps. The suitable viscosity is for example but not limited to: 10, 50, 100, 150, 200, 250, 300, 350, 400, 450 or 500cps, the range can be any combination of the above values.
出乎發明人的意料，由於本發明的聚氨酯主鏈上含有經優化處理後的銨陽離子基團，因此本發明的CAPUD尤其適用於聚氨酯發泡體、真皮、合成皮或織物等，從而改良其機械性質。在一些態樣中，相較於陰離子型水性聚氨酯分散體，本發明的聚氨酯主鏈上帶正電荷，對所施用的基材具有良好的浸潤性。在一些態樣中，本發明的CAPUD對水的硬度具低敏性，可於酸性環境下使用。Contrary to the inventor's expectation, since the polyurethane main chain of the present invention contains ammonium cationic groups after optimized treatment, the CAPUD of the present invention is especially suitable for polyurethane foams, genuine leather, synthetic leather or fabrics, etc., thereby improving its Mechanical properties. In some aspects, compared to anionic aqueous polyurethane dispersions, the polyurethane backbone of the present invention is positively charged and has good wettability to the substrate to which it is applied. In some aspects, the CAPUD of the present invention is hyposensitive to water hardness and can be used in acidic environments.
在一些實施態樣中，本發明的CAPUD實質上不包含游離胺。在一些實施態樣中，本發明的CAPUD實質上揮發性有機物(VOC)含量極低(＜0.5%)。In some embodiments, the CAPUDs of the present invention comprise substantially no free amines. In some embodiments, the CAPUD of the present invention is substantially low in volatile organic compounds (VOC) (<0.5%).
在一些實施態樣中，本發明的CAPUD賦予皮革改良的鍵合力，可提供皮革柔軟、自然及豐滿之外觀/手感。In some embodiments, the CAPUD of the present invention imparts improved bonding to leather, which can provide a soft, natural, and voluptuous appearance/handle to leather.
在一些實施態樣中，本發明的CAPUD賦予織物改良的撕裂強度、耐磨性、抗皺性及/或回彈性。在一些實施態樣中，本發明的CAPUD賦予化學纖維織物改良的抗靜電性。In some embodiments, the CAPUDs of the present invention impart improved tear strength, abrasion resistance, wrinkle resistance, and/or resilience to fabrics. In some embodiments, the CAPUD of the present invention imparts improved antistatic properties to manmade fabrics.
在一些實施態樣中，本發明的CAPUD賦予金屬表面或金屬扣件改良的密著度、機械強度及/或耐水性。In some embodiments, the CAPUD of the present invention imparts improved adhesion, mechanical strength, and/or water resistance to metal surfaces or metal fasteners.
在一些實施態樣中，本發明的CAPUD適用於紙張、布料的印刷表面處理。在一些實施態樣中，本發明的CAPUD適用於織物的反撥彈性或永久免燙洗處理。In some embodiments, the CAPUD of the present invention is suitable for printing surface treatment of paper and cloth. In some embodiments, the CAPUD of the present invention is suitable for washback elastic or permanent wash-out treatments of fabrics.
在一些實施態樣中，本發明的CAPUD可與任何已知的色料並同使用以作為塗料組合物。In some embodiments, the CAPUD of the present invention can be used together with any known colorant as a coating composition.
在一些實施態樣中，本發明的CAPUD可與任何已知的樹脂並同使用以作為黏著劑組合物。 實施例 In some embodiments, the CAPUD of the present invention can be used together with any known resin as an adhesive composition. Example
以下透過實施例對本發明進行進一步的具體描述。有必要在此指出的是以下實施例只用於對本發明做進一步的說明，不能理解為對本發明保護範圍的限制，本領域技術人員根據上述本發明內容對本發明做出一些非本質的改進和調整，仍屬於本發明的保護範圍。在討論本發明的若干非限制性實施例之前，應理解，本發明在其申請上不限於本文中所示及所論述的特定非限制性實施例的細節，因為本發明可具有其他實施例。此外，在本文中用於論述本發明的術語是出於描述而非限制的目的。再此外，除非另外指明，否則以下類似數字的論述是指類似要素。 實例 1 ： CAPUD 樣品的製備 The present invention is further described in detail through the following examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and cannot be interpreted as limiting the protection scope of the present invention. Those skilled in the art make some non-essential improvements and adjustments to the present invention according to the above-mentioned content of the present invention , still belong to the protection scope of the present invention. Before discussing several non-limiting embodiments of the invention, it is to be understood that the invention is not limited in its application to the details of the particular non-limiting embodiments shown and discussed herein, as the invention is capable of other embodiments. Furthermore, the terminology used herein to discuss the present invention is for the purpose of description rather than limitation. Furthermore, the discussion of like numbers below refers to like elements unless otherwise indicated. Example 1 : Preparation of CAPUD samples
以下各CAPUD樣品所使用的試劑原料說明如下表1：
表1
以下各CAPUD樣品所使用的各試劑用量記載於表2：
表2
形成聚氨酯寡聚物：在設有電動攪拌器、溫控器及回流冷凝管的四口燒瓶中加入ETEROL 5650-1000 180g及ETEROL 5650-3000 67.5g，接著於120°C的溫度下真空除水1小時。待降溫至65°C，將IPDI 96.5g、H 12MDI 228g及Ciba Irganox ®1010 3.54g加入四口燒瓶中，在80°C的溫度下反應1小時。接著將N-MDEA 70.65g加入四口燒瓶中，並升溫至90°C並持溫3小時，以產生經NCO封端的聚氨酯寡聚物。 Form polyurethane oligomers: add ETEROL 5650-1000 180g and ETEROL 5650-3000 67.5g in a four-necked flask equipped with an electric stirrer, a thermostat and a reflux condenser, and then remove water under vacuum at a temperature of 120°C 1 hour. After cooling down to 65°C, 96.5g of IPDI, 228g of H 12 MDI and 3.54g of Ciba Irganox ® 1010 were added into a four-necked flask, and reacted at 80°C for 1 hour. Next, 70.65 g of N-MDEA was added into a four-necked flask, and the temperature was raised to 90° C. and maintained for 3 hours to produce NCO-terminated polyurethane oligomers.
聚氨酯寡聚物的擴鏈：待混合物降溫至70°C後，將丙酮 372g加入四口燒瓶中稀釋聚氨酯寡聚物，再降溫至45°C。將水合肼(80%) 26.7g及去離子水 27g充分混合，於10分鐘內滴加至四口燒瓶中，接著持續攪拌15分鐘。 Chain extension of polyurethane oligomers: After the mixture was cooled to 70°C, 372g of acetone was added into a four-necked flask to dilute the polyurethane oligomers, and then cooled to 45°C. 26.7 g of hydrazine hydrate (80%) and 27 g of deionized water were thoroughly mixed, and were added dropwise into the four-necked flask within 10 minutes, followed by continuous stirring for 15 minutes.
季銨化處理形成陽離子型聚氨酯：在25°C下，將表2所示各CAPUD樣品對應的甲酸、乙酸及/或磷酸用量及去離子水 1143g在轉水槽中充分混合。再將四口燒瓶內經丙酮稀釋的聚氨酯寡聚物於10分鐘內加入包含甲酸、乙酸及/或磷酸的轉水槽，快速攪拌混合30分鐘。最後加入消泡劑TEGO® Foamex 800 0.5g，並進行抽氣以移除丙酮，製得各CAPUD樣品。 實例 2 ：耐熱黃變性及耐溶劑性測試樣品的製備 Quaternization treatment to form cationic polyurethane: at 25°C, the amount of formic acid, acetic acid and/or phosphoric acid corresponding to each CAPUD sample shown in Table 2 and 1143 g of deionized water were fully mixed in a water transfer tank. Then, the polyurethane oligomer diluted with acetone in the four-neck flask was added into the water transfer tank containing formic acid, acetic acid and/or phosphoric acid within 10 minutes, and stirred and mixed rapidly for 30 minutes. Finally, 0.5 g of antifoaming agent TEGO® Foamex 800 was added, and air was pumped to remove acetone to prepare each CAPUD sample. Example 2 : Preparation of heat yellowing resistance and solvent resistance test samples
將實例1所得的CAPUD樣品1~9塗布於鍍鋅鋼板表面以形成塗層，於150°C下烘烤1分鐘後乾燥成膜，得到乾膜厚度為1 μm的CAPUD鍍鋅鋼板對應試樣。 實例 3 ：各 CAPUD 樣品的物理特性 Coat the CAPUD samples 1-9 obtained in Example 1 on the surface of galvanized steel sheet to form a coating, bake at 150°C for 1 minute and then dry to form a film to obtain the corresponding sample of CAPUD galvanized steel sheet with a dry film thickness of 1 μm . Example 3 : Physical properties of each CAPUD sample
表3顯示各CAPUD樣品的物理特性：
表3
表3中，各性質的量測方式如下。In Table 3, the measurement methods of each property are as follows.
固含量的量測：首先將空鋁皿秤重並記錄，接著秤取CAPUD樣品1-2g置於鋁皿中，待其流平，再放置於加熱板上，以150°C烘烤15分鐘，最後再秤重(烘烤樣品+鋁皿)的重量，並計算其固含量。 固含量%=（烘烤樣品+鋁皿-空鋁皿）/未烘乾樣品重 Measurement of solid content : First weigh and record the empty aluminum dish, then weigh 1-2g of the CAPUD sample and place it in the aluminum dish, wait for it to level off, then place it on a heating plate, and bake at 150°C for 15 minutes , and finally weigh the weight of (baked sample+aluminum pan) and calculate its solid content. Solid content% = (baked sample + aluminum dish - empty aluminum dish) / undried sample weight
pH 值的量測：將CAPUD樣品於溫度25°C下恆溫1小時，再以pH計進行量測。 Measurement of pH value: Keep the CAPUD sample at a temperature of 25°C for 1 hour, and then measure it with a pH meter.
黏度的量測：將CAPUD樣品於溫度25°C下恆溫1小時，再以Brookfield，LVF #2，60rpm的條件進行量測。 Viscosity measurement : Keep the CAPUD sample at a temperature of 25°C for 1 hour, and then measure it under the conditions of Brookfield, LVF #2, 60rpm.
耐熱黃變性的量測：以CAPUD鍍鋅鋼板對應試樣於高溫烘烤前、後的色差程度作為判斷基準。在將實例2的CAPUD鍍鋅鋼板對應試樣置於烘箱前，先以色差儀測得各CAPUD鍍鋅鋼板對應試樣的b*
1值，將樣品置於150°C烘箱中烘烤30分鐘後取出，再次使用色差儀測得經烘烤後各CAPUD鍍鋅鋼板對應試樣的b*
2值，最後計算Δb值（即，b*
2- b*
1），以評估耐熱黃變性。
耐溶劑性的量測：用棉花沾取乙醇，接著使用耐磨試驗機(型號A20-339)以荷重1.0kg在實例2的各CAPUD鍍鋅鋼板對應試樣上，以含有乙醇的棉花來回進行擦拭5、10、15、20次，目視判斷有無失光。
如表3所示，CAPUD樣品1~5及7的耐熱黃變性測試Δb值皆小於3；CAPUD樣品1~6及9經耐溶劑性測試可來回擦拭超過10次，而不失光。在上述樣品中，CAPUD樣品1~3具有顯著更佳的耐熱黃變性（Δb值小於2）以及耐溶劑性表現（可來回擦拭超過20次）。As shown in Table 3, the Δb values of CAPUD samples 1~5 and 7 are all less than 3 in the heat yellowing test; CAPUD samples 1~6 and 9 can be wiped back and forth more than 10 times without loss of gloss after the solvent resistance test. Among the above samples, CAPUD samples 1~3 have significantly better heat yellowing resistance (Δb value is less than 2) and solvent resistance performance (can be wiped back and forth more than 20 times).
CAPUD樣品4有機酸/無機酸的莫耳比為83.34，非基於理論限制，已發現當有機酸/無機酸的莫耳比大於50時，聚氨酯分子間的離子鍵及/或氫鍵的強度減弱，因此耐溶劑性不若CAPUD樣品1~3；樣品5的有機酸/無機酸的莫耳比為18.62，非基於理論限制，已發現當有機酸/無機酸的莫耳比（特別是甲酸/無機酸的莫耳比；參下段有關樣品6的說明）小於35時，CAPUD的抗氧化力減弱，因此耐熱黃變性不若CAPUD樣品1~3。The molar ratio of organic acid/inorganic acid in CAPUD sample 4 is 83.34. It is not based on theoretical limitations. It has been found that when the molar ratio of organic acid/inorganic acid is greater than 50, the strength of ionic bonds and/or hydrogen bonds between polyurethane molecules is weakened. , so the solvent resistance is not as good as CAPUD samples 1~3; the molar ratio of organic acid/inorganic acid of sample 5 is 18.62, not based on theoretical limitations, it has been found that when the molar ratio of organic acid/inorganic acid (especially formic acid/ When the molar ratio of inorganic acid; refer to the description of sample 6 in the next paragraph) is less than 35, the antioxidant capacity of CAPUD is weakened, so the heat yellowing resistance is not as good as CAPUD samples 1~3.
相較於樣品1，樣品6使用乙酸取代甲酸，有機酸/無機酸的莫耳比維持37.86，但樣品6的耐熱黃變性表現較樣品1者差，非基於理論限制，咸信此是因乙酸不具抗氧化特性之故所致。Compared with sample 1, sample 6 uses acetic acid instead of formic acid, and the molar ratio of organic acid/inorganic acid is maintained at 37.86, but the thermal yellowing resistance of sample 6 is worse than that of sample 1. It is not based on theoretical limitations. It is believed that this is due to acetic acid Due to the lack of antioxidant properties.
相較於樣品1~3，樣品7的耐溶劑性不良。非基於理論限制，咸信此是因樣品7僅使用甲酸作為中和劑，而甲酸無法在聚氨酯分子之間提供離子鍵及/或氫鍵之故。Compared with samples 1-3, the solvent resistance of sample 7 was inferior. Without being bound by theory, it is believed that this is due to the fact that Sample 7 used only formic acid as a neutralizing agent, which is unable to provide ionic and/or hydrogen bonding between polyurethane molecules.
相較於樣品1~3，樣品8的耐熱黃變性及耐溶劑性二者均不良。非基於理論限制，咸信此是因樣品8僅使用乙酸作為中和劑，而乙酸無法在聚氨酯分子之間提供離子鍵及/或氫鍵且不具備抗氧化能力之故。Compared with samples 1 to 3, both of sample 8's thermal yellowing resistance and solvent resistance were inferior. Without being limited by theory, it is believed that this is because sample 8 only uses acetic acid as a neutralizing agent, and acetic acid cannot provide ionic bonds and/or hydrogen bonds between polyurethane molecules and has no antioxidant capacity.
相較於樣品1~3，樣品9的耐黃變性不良。非基於理論限制，咸信此是因樣品9僅使用磷酸作為中和劑，而磷酸不具備抗氧化能力之故。Compared with samples 1 to 3, the yellowing resistance of sample 9 was poor. Without being bound by theory, it is believed that this is due to the fact that sample 9 only used phosphoric acid as a neutralizing agent, which has no antioxidant capacity.
習此項技術者將明白在不脫離本發明的範疇或精神的情況下可對本發明作出各種修改及變化。鑒於前述內容，本發明意欲涵蓋本發明的修改及變化，限制條件為其屬於申請專利範圍及其等效物的範疇內。Those skilled in the art will recognize that various modifications and changes can be made to the present invention without departing from the scope or spirit of the invention. In view of the foregoing, the present invention is intended to cover modifications and variations of the present invention, provided that they fall within the scope of the patent application and its equivalents.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW111104193A TWI805210B (en) | 2022-01-28 | 2022-01-28 | Aqueous polyurethane dispersion and composition comprising such |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW111104193A TWI805210B (en) | 2022-01-28 | 2022-01-28 | Aqueous polyurethane dispersion and composition comprising such |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI805210B true TWI805210B (en) | 2023-06-11 |
| TW202330687A TW202330687A (en) | 2023-08-01 |
Family
ID=87802903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW111104193A TWI805210B (en) | 2022-01-28 | 2022-01-28 | Aqueous polyurethane dispersion and composition comprising such |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI805210B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335522C (en) * | 2005-09-29 | 2007-09-05 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101805438A (en) * | 2010-04-13 | 2010-08-18 | 江苏工业学院 | Preparation method and applications of cationic waterborne polyurethane surface sizing agent |
-
2022
- 2022-01-28 TW TW111104193A patent/TWI805210B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335522C (en) * | 2005-09-29 | 2007-09-05 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101805438A (en) * | 2010-04-13 | 2010-08-18 | 江苏工业学院 | Preparation method and applications of cationic waterborne polyurethane surface sizing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202330687A (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5170499B2 (en) | Emulsion composition containing blocked isocyanate, method for producing the same, and composition for baking type paint or adhesive | |
| JP5452794B2 (en) | Aqueous polyurethane resin emulsion coating composition and method for producing the same | |
| US6642303B2 (en) | Polyurethane-polyurea dispersions as coating compositions | |
| US6046295A (en) | Room temperature curable silane-terminated polyurethane dispersions | |
| US8758862B2 (en) | Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates | |
| US6359060B1 (en) | Oxidatively drying polyurethane dispersions | |
| CN105601879B (en) | Polyurethane urea for wood coatings | |
| AU2007253855A1 (en) | Polyurethane-urea polymers derived from cyclohexane dimethanol | |
| CN1910214A (en) | Coating composition | |
| TW201038602A (en) | Aqueous polyurethane resin dispersion and method for manufacturing the same | |
| JP6225979B2 (en) | Aqueous polyurethane resin dispersion composition and method for producing the same | |
| JPH08301964A (en) | Aqueous polyurethane dispersion based on polyether polyol oflow monool content | |
| CN102459383A (en) | Novel solvents for the production of polyutherane dispersions | |
| US20210363307A1 (en) | Aspartic acid ester-functional polysiloxanes, their preparation and use thereof | |
| JP5545954B2 (en) | Water-based polyurethane resin, paint film, artificial or synthetic leather | |
| TWI805210B (en) | Aqueous polyurethane dispersion and composition comprising such | |
| WO2017108872A1 (en) | Non-hazardous water-based polyurethane dispersion | |
| CN116425942A (en) | Aqueous polyurethane dispersion and composition containing same | |
| WO2022198046A1 (en) | Aqueous polyurethane dispersion | |
| JP7452096B2 (en) | Adhesive composition containing a polyurethane resin aqueous dispersion | |
| US20240158562A1 (en) | Aqueous polyurethane dispersion | |
| CN116715828A (en) | Water-based polyurethane-urea dispersion with enhanced hydrogen bond and ion interaction, and preparation method and application thereof | |
| JP2021134309A (en) | Adhesive composition containing polyurethane resin aqueous dispersion | |
| JP2021134310A (en) | Adhesive composition containing polyurethane resin aqueous dispersion | |
| CN104736582B (en) | For can delustred coating coating agent |