TW202234734A

TW202234734A - Electrode binder and slurry compositions for lithium ion electrical storage devices

Info

Publication number: TW202234734A
Application number: TW110105386A
Authority: TW
Inventors: 章鵬飛; 宏英周; 史都華 D 西勒倫; 吳方暉; 王偉民
Original assignee: 美商片片堅俄亥俄州工業公司
Priority date: 2021-02-17
Filing date: 2021-02-17
Publication date: 2022-09-01

Abstract

The present invention provides a binder composition comprising (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, the secondary fluoropolymer comprising at least one perfluoropolyether segment, at least one non-fluorinated segment, and a linking group that links the perfluoropolyether segment and the non-fluorinated segment. The invention further provides slurry compositions, electrodes, and electrical storage devices.

Description

用於鋰離子蓄電裝置之電極黏合劑及漿料組合物Electrode binder and slurry composition for lithium ion storage device

本發明係關於可用於製造用於蓄電裝置（諸如電池）之電極的含氟聚合物黏合劑及漿料組合物。The present invention relates to fluoropolymer binder and slurry compositions useful in the manufacture of electrodes for electrical storage devices such as batteries.

電子行業中存在著生產由較小及較輕電池供電之較小裝置的趨勢。具有負電極（諸如含碳材料）及正電極（諸如鋰金屬氧化物）的電池可提供相對較高的電力及較低的重量。There is a trend in the electronics industry to produce smaller devices powered by smaller and lighter batteries. Batteries with negative electrodes (such as carbonaceous materials) and positive electrodes (such as lithium metal oxides) can provide relatively high power and low weight.

諸如聚偏二氟乙烯之含氟聚合物由於其極佳電化學阻抗已被認為係形成用於蓄電裝置之電極的適用黏合劑。典型地，含氟聚合物溶解於有機溶劑中且電極材料與PVDF溶液組合以形成漿料，該漿料施加至金屬箔或網以形成電極。有機溶劑之作用在於溶解含氟聚合物，以便在蒸發有機溶劑後於電極材料粒子與金屬箔或網之間提供良好黏著力。目前，所選有機溶劑為N-甲基-2-吡咯啶酮（NMP）。溶解於NMP中之PVDF黏合劑提供優良黏著力及電極組合物中之所有活性成分的互連性。黏合之成分能夠容許充電及放電循環期間之大體積膨脹及收縮，而不會失去電極內之互連性。電極中之活性成分的互連性對於電池效能極其重要，尤其在充電及放電循環期間，因為電子必須移動穿過電極，且鋰離子遷移率要求電極內的粒子之間具有互連性。令人遺憾的是，NMP為毒性材料且存在健康及環境問題。Fluoropolymers such as polyvinylidene fluoride have been recognized as suitable binders for forming electrodes for electrical storage devices due to their excellent electrochemical impedance. Typically, the fluoropolymer is dissolved in an organic solvent and the electrode material is combined with the PVDF solution to form a slurry that is applied to a metal foil or mesh to form the electrode. The function of the organic solvent is to dissolve the fluoropolymer in order to provide good adhesion between the electrode material particles and the metal foil or mesh after evaporation of the organic solvent. Currently, the organic solvent of choice is N-methyl-2-pyrrolidone (NMP). The PVDF binder dissolved in NMP provides excellent adhesion and interconnectivity of all active ingredients in the electrode composition. The adhesive composition is able to tolerate large volume expansions and contractions during charge and discharge cycles without loss of interconnectivity within the electrodes. The interconnectivity of the active components in the electrodes is extremely important to battery performance, especially during charge and discharge cycles, because electrons must move across the electrodes, and lithium ion mobility requires interconnectivity between particles within the electrodes. Unfortunately, NMP is a toxic material and has health and environmental concerns.

已研發出針對NMP的替代技術。然而，為了使替代技術變得適用，其必須與當前製造實踐相容且提供中間物及最終產物之所需特性。一些常見準則包括：a）具有足夠儲存期限之含氟聚合物分散液的穩定性，b）在摻合電化學活性及/或導電粉末與分散液之後漿料的穩定性，c）用以促進良好施加特性之漿料的適當黏度，d）電極內之充足互連性，及e）用於所得電極塗層之黏合劑對電池中之電解質的充足耐久性。Alternative technologies for NMP have been developed. However, in order for an alternative technology to be applicable, it must be compatible with current manufacturing practices and provide the desired properties of the intermediate and final product. Some common criteria include: a) stability of fluoropolymer dispersions with adequate shelf life, b) stability of slurries after blending electrochemically active and/or conductive powders with dispersions, c) use to facilitate Adequate viscosity of the paste for good application characteristics, d) sufficient interconnectivity within the electrodes, and e) sufficient durability of the binder for the resulting electrode coating to the electrolyte in the cell.

因此，本發明之一目標為使用符合此等準則之N-甲基-2-吡咯啶酮的替代物提供穩定含氟聚合物黏合劑組合物分散液。黏合劑組合物可用於製備形成電極的漿料組合物，以用於製造供電池及其他蓄電裝置中用的具有互連性及耐久性之高品質電極。Accordingly, it is an object of the present invention to provide stable dispersions of fluoropolymer adhesive compositions using alternatives to N-methyl-2-pyrrolidone that meet these criteria. The binder composition can be used to prepare an electrode-forming slurry composition for use in the manufacture of high-quality electrodes with interconnectivity and durability for use in batteries and other electrical storage devices.

本發明提供一種包含以下之黏合劑組合物：（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。 The present invention provides an adhesive composition comprising: (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, the secondary fluoropolymer comprising at least A perfluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment.

本發明亦提供一種包含黏合劑組合物之漿料組合物，該黏合劑組合物包含（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團；電化學活性材料；及液體介質。 The present invention also provides a slurry composition comprising an adhesive composition comprising (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer , the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment; an electrochemically active material; and liquid medium.

本發明進一步提供一種包含黏合劑組合物之漿料組合物，該黏合劑組合物包含（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團；導電試劑；及液體介質。The present invention further provides a slurry composition comprising an adhesive composition comprising (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer , the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment; a conductive agent; and a liquid medium .

本發明亦提供一種包含以下之電極：（a）集電器；及（b）形成於該集電器上之膜，其中該膜自包含黏合劑組合物之漿料組合物沈積，該黏合劑組合物包含（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，其中該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團；電化學活性材料；及液體介質。The present invention also provides an electrode comprising: (a) a current collector; and (b) a film formed on the current collector, wherein the film is deposited from a slurry composition comprising a binder composition, the binder composition comprising (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, wherein the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one a non-fluorinated segment and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment; an electrochemically active material; and a liquid medium.

本發明進一步提供一種包含以下之蓄電裝置：（a）本發明之電極；（b）相對電極；及（c）電解質。The present invention further provides an electrical storage device comprising: (a) the electrode of the present invention; (b) a counter electrode; and (c) an electrolyte.

政府支持公告Government Support Announcement

本發明是藉由在由能源部（Department of Energy）授與之政府合同第DE-EE0006250號下之政府支持完成的。美國政府具有本發明之某些權利。This invention was made with government support under Government Contract No. DE-EE0006250 awarded by the Department of Energy. The US Government has certain rights in this invention.

本發明係關於一種包含以下之黏合劑組合物：（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。The present invention relates to an adhesive composition comprising: (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, the secondary fluoropolymer comprising At least one perfluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment.

本發明之黏合劑組合物可用於調配漿料組合物，該漿料組合物包含除其他視情況選用之組分以外的黏合劑組合物。黏合劑組合物之組分可充當漿料組合物之黏合劑。The adhesive composition of the present invention can be used to formulate a slurry composition comprising the adhesive composition in addition to other optional components. The components of the binder composition can act as binders for the paste composition.

根據本發明，黏合劑組合物包含主要含氟聚合物。主要含氟聚合物可包含含有偏二氟乙烯之殘基的(共)聚合物。含有偏二氟乙烯之殘基的(共)聚合物之非限制性實例為聚偏二氟乙烯聚合物（PVDF）。如本文所用，「聚偏二氟乙烯聚合物」包括均聚物、共聚物（諸如二元共聚物）及三聚物，包括高分子量均聚物、共聚物及三聚物。此等(共)聚合物包括含有至少50莫耳%，諸如至少75莫耳%及至少80莫耳%及至少85莫耳%之偏二氟乙烯（亦已知為偏二氟乙烯（vinylidene difluoride））之殘基的彼等。偏二氟乙烯單體可與至少一種選自由以下組成之群的共聚單體共聚合：四氟乙烯、三氟乙烯、三氟氯乙烯、六氟丙烯、氟乙烯、五氟丙烯、四氟丙烯、全氟甲基乙烯基醚、全氟丙基乙烯基醚及將容易地與偏二氟乙烯共聚合以便產生本發明之主要含氟聚合物的任何其他單體。主要含氟聚合物亦可包含PVDF均聚物。According to the present invention, the adhesive composition comprises primarily a fluoropolymer. The primary fluoropolymer may comprise a (co)polymer containing residues of vinylidene fluoride. A non-limiting example of a (co)polymer containing residues of vinylidene fluoride is polyvinylidene fluoride polymer (PVDF). As used herein, "polyvinylidene fluoride polymer" includes homopolymers, copolymers (such as dipolymers), and terpolymers, including high molecular weight homopolymers, copolymers, and terpolymers. These (co)polymers include vinylidene fluoride (also known as vinylidene fluoride) containing at least 50 mol %, such as at least 75 mol % and at least 80 mol % and at least 85 mol % )) of the residues of them. The vinylidene fluoride monomer is copolymerizable with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, pentafluoropropylene, tetrafluoropropylene , perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and any other monomer that will readily copolymerize with vinylidene fluoride to yield the primary fluoropolymer of the present invention. The primary fluoropolymer may also include PVDF homopolymers.

主要含氟聚合物可包含重量平均分子量為至少50,000 g/mol（諸如至少100,000 g/mol）的高分子量PVDF，且可在50,000 g/mol至1,500,000 g/mol（諸如100,000 g/mol至1,000,000 g/mol）之範圍內。PVDF可例如以商標KYNAR自Arkema、以商標HYLAR自Solvay及自Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd商購。The primary fluoropolymer may comprise high molecular weight PVDF having a weight average molecular weight of at least 50,000 g/mol (such as at least 100,000 g/mol), and may range from 50,000 g/mol to 1,500,000 g/mol (such as 100,000 g/mol to 1,000,000 g) /mol) range. PVDF is commercially available, for example, from Arkema under the trademark KYNAR, from Solvay under the trademark HYLAR, and from Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd.

主要含氟聚合物可包含奈米粒子。如本文所用，術語「奈米粒子」係指粒徑低於1,000 nm之粒子。主要含氟聚合物之粒徑可為至少50 nm，諸如至少100 nm，諸如至少250 nm，諸如至少300 nm，且不超過900 nm，諸如不超過600 nm，諸如不超過450 nm，諸如不超過400 nm，諸如不超過300 nm，諸如不超過200 nm。主要含氟聚合物奈米粒子之粒徑可為50 nm至900 nm，諸如100 nm至600 nm，諸如250 nm至450 nm，諸如300 nm至400 nm，諸如100nm至400 nm，諸如100 nm至300 nm，諸如100 nm至200 nm。如本文所用，術語「粒徑」係指主要含氟聚合物粒子之平均直徑。本發明中提及之粒徑藉由以下程序確定：藉由將主要含氟聚合物分散至一段附接到鋁掃描電子顯微鏡（SEM）短線之碳帶上來製備樣品。用壓縮空氣吹掉碳帶上之過量粒子。隨後用Au/Pd濺塗樣品20秒，且隨後在高真空下於Quanta 250 FEG SEM（場發射槍掃描電子顯微鏡）中進行分析。將加速電壓設定為20.00 kV，且將光斑尺寸設定為3.0。收集來自所製備樣品上之三個不同區域的影像，且使用ImageJ軟體量測來自每一區域之10個主要含氟聚合物粒子的直徑，得到總共30個粒徑量測值，將該等量測值一起求平均以確定平均粒徑。The primary fluoropolymer may contain nanoparticles. As used herein, the term "nanoparticles" refers to particles with a particle size below 1,000 nm. The particle size of the primary fluoropolymer may be at least 50 nm, such as at least 100 nm, such as at least 250 nm, such as at least 300 nm, and not more than 900 nm, such as not more than 600 nm, such as not more than 450 nm, such as not more than 450 nm 400 nm, such as not more than 300 nm, such as not more than 200 nm. The particle size of the primary fluoropolymer nanoparticles may be from 50 nm to 900 nm, such as 100 nm to 600 nm, such as 250 nm to 450 nm, such as 300 nm to 400 nm, such as 100 nm to 400 nm, such as 100 nm to 100 nm to 300 nm, such as 100 nm to 200 nm. As used herein, the term "particle size" refers to the average diameter of the primary fluoropolymer particles. The particle sizes referred to in the present invention were determined by the following procedure: A sample was prepared by dispersing the main fluoropolymer onto a length of carbon tape attached to an aluminum scanning electron microscope (SEM) stub. Use compressed air to blow off excess particles from the ribbon. The samples were then sputter coated with Au/Pd for 20 seconds and then analyzed in a Quanta 250 FEG SEM (Field Emission Gun Scanning Electron Microscope) under high vacuum. The accelerating voltage was set to 20.00 kV, and the spot size was set to 3.0. Images were collected from three different areas on the prepared sample, and the diameters of 10 primary fluoropolymer particles from each area were measured using ImageJ software, resulting in a total of 30 particle size measurements. The measured values are averaged together to determine the average particle size.

以黏合劑固體之總重量計，主要含氟聚合物可以至少30重量%、諸如至少40重量%、諸如至少50重量%、諸如至少65重量%、諸如至少70重量%、諸如至少80重量%、諸如至少85重量%、諸如至少90重量%、諸如至少95重量%、諸如至少98重量%之量存在於黏合劑中。以黏合劑固體之總重量計，主要含氟聚合物可以不超過98重量%、諸如不超過95重量%、諸如不超過90重量%、諸如不超過85重量%、諸如不超過70重量%、諸如不超過60重量%、諸如不超過50重量%之量存在。以黏合劑固體之總重量計，主要含氟聚合物可以以下量存在於黏合劑中：30%至98重量%、諸如30%至95重量%、諸如30%至90重量%、諸如30%至85重量%、諸如30%至70重量%、諸如30%至60重量%、諸如30%至50重量%、諸如40%至98重量%、諸如40%至95重量%、諸如40%至90重量%、諸如40%至85重量%、諸如40%至70重量%、諸如40%至60重量%、諸如40%至50重量%、諸如50%至98重量%、諸如50%至95重量%、諸如50%至90重量%、諸如50%至85重量%、諸如50%至70重量%、諸如50%至60重量%、諸如65%至98重量%、諸如65%至95重量%、諸如65%至90重量%、諸如65%至85重量%、諸如65%至70重量%、諸如70%至98重量%、諸如70%至95重量%、諸如70%至90重量%、諸如70%至85重量%、諸如80%至98重量%、諸如80%至95重量%、諸如80%至90重量%、諸如80%至85重量%、諸如85%至98重量%、諸如85%至95重量%、諸如85%至90重量%、諸如90%至98重量%、諸如90%至95重量%、諸如95%至98%重量。主要含氟聚合物可溶解或分散於有機介質中。The primary fluoropolymer may be at least 30% by weight, such as at least 40% by weight, such as at least 50% by weight, such as at least 65% by weight, such as at least 70% by weight, such as at least 80% by weight, based on the total weight of the binder solids. An amount such as at least 85% by weight, such as at least 90% by weight, such as at least 95% by weight, such as at least 98% by weight, is present in the binder. Based on the total weight of the binder solids, the primary fluoropolymer may be no more than 98% by weight, such as no more than 95% by weight, such as no more than 90% by weight, such as no more than 85% by weight, such as no more than 70% by weight, such as It is present in an amount of not more than 60% by weight, such as not more than 50% by weight. The primary fluoropolymer may be present in the adhesive in an amount from 30% to 98% by weight, such as 30% to 95% by weight, such as 30% to 90% by weight, such as 30% to 90% by weight, based on the total weight of the adhesive solids. 85% by weight, such as 30% to 70% by weight, such as 30% to 60% by weight, such as 30% to 50% by weight, such as 40% to 98% by weight, such as 40% to 95% by weight, such as 40% to 90% by weight %, such as 40% to 85% by weight, such as 40% to 70% by weight, such as 40% to 60% by weight, such as 40% to 50% by weight, such as 50% to 98% by weight, such as 50% to 95% by weight, such as 50% to 90% by weight, such as 50% to 85% by weight, such as 50% to 70% by weight, such as 50% to 60% by weight, such as 65% to 98% by weight, such as 65% to 95% by weight, such as 65% by weight % to 90% by weight, such as 65% to 85% by weight, such as 65% to 70% by weight, such as 70% to 98% by weight, such as 70% to 95% by weight, such as 70% to 90% by weight, such as 70% to 90% by weight 85% by weight, such as 80% to 98% by weight, such as 80% to 95% by weight, such as 80% to 90% by weight, such as 80% to 85% by weight, such as 85% to 98% by weight, such as 85% to 95% by weight %, such as 85% to 90% by weight, such as 90% to 98% by weight, such as 90% to 95% by weight, such as 95% to 98% by weight. Primary fluoropolymers are soluble or dispersible in organic media.

根據本發明，黏合劑組合物可包含與該主要含氟聚合物不同之次要含氟聚合物，該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。According to the present invention, the adhesive composition may comprise a secondary fluoropolymer different from the primary fluoropolymer, the secondary fluoropolymer comprising at least one perfluoropolyether segment, at least one non-fluorinated segment and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment.

如本文所用，術語「全氟聚醚鏈段」係指具有「-C(F)(F)-C(F)(F)-O-」之重複單元的化合物或聚合物鏈段。全氟聚醚鏈段可包含具有結構R-O-[C(F)(F)-C(F)(F)-O-] _nR之鏈段，其中R為經取代或未經取代之伸烷基、伸芳基、伸環烷基或伸環芳基，且n為1或更大之整數，諸如1至500。全氟聚醚鏈段可作為具有反應性官能基之全氟聚醚的殘基存在於次要含氟聚合物中。舉例而言，全氟聚醚可包含活性氫官能基（如本文所定義之術語），諸如羥基、一級或二級胺基、羧酸基及/或硫醇基，及/或可包含可與活性氫官能基（諸如異氰酸酯基或環氧官能基）反應之官能基，且此等官能基可與另一反應物（諸如不同全氟聚醚或非氟化化合物）之官能基反應，以形成次要含氟聚合物。全氟聚醚可為單官能性、雙官能性、三官能性、四官能性或更高官能性全氟聚醚。 As used herein, the term "perfluoropolyether segment" refers to a compound or polymer segment having repeating units of "-C(F)(F)-C(F)(F)-O-". The perfluoropolyether segment may comprise a segment having the structure RO-[C(F)(F)-C(F)(F)-O-] _nR , where R is a substituted or unsubstituted alkylene group, aryl-extended group, cyclo-extended alkyl group, or ring-extended aryl group, and n is an integer of 1 or greater, such as 1 to 500. The perfluoropolyether segment may be present in the secondary fluoropolymer as the residue of the perfluoropolyether with reactive functional groups. For example, perfluoropolyethers may contain active hydrogen functional groups (as the term is defined herein), such as hydroxyl groups, primary or secondary amine groups, carboxylic acid groups, and/or thiol groups, and/or may contain groups that may interact with Functional groups that react with active hydrogen functional groups (such as isocyanate groups or epoxy functional groups), and these functional groups can react with functional groups of another reactant (such as various perfluoropolyethers or non-fluorinated compounds) to form Secondary fluoropolymer. The perfluoropolyethers can be monofunctional, difunctional, trifunctional, tetrafunctional or higher functional perfluoropolyethers.

如本文所用，術語「非氟化鏈段」係指不含氟原子之有機鏈段。非氟化鏈段可包含經取代或未經取代之烷基、伸烷基、環烷基、伸環烷基、芳基、伸芳基、環芳基或伸環芳基。非氟化鏈段可包含官能基或可不含官能基。非氟化鏈段可作為具有反應性官能基之非氟化化合物的殘基存在於次要含氟聚合物中。舉例而言，非氟化化合物可包含活性氫官能基，諸如羥基、一級或二級胺基、羧酸基及/或硫醇基，及/或可包含可與活性氫官能基（諸如異氰酸酯或環氧官能基）反應之官能基，且此等官能基可與另一反應物之官能基反應，以形成次要含氟聚合物。非氟化化合物之官能基可選擇為可與全氟聚醚之官能基反應。As used herein, the term "non-fluorinated segment" refers to an organic segment that does not contain fluorine atoms. The non-fluorinated segment can comprise substituted or unsubstituted alkyl, alkylene, cycloalkyl, cycloalkyl, aryl, aryl, cycloaryl, or cycloextended aryl. The non-fluorinated segment may or may not contain functional groups. The non-fluorinated segment may be present in the secondary fluoropolymer as the residue of a non-fluorinated compound with reactive functional groups. For example, non-fluorinated compounds may contain active hydrogen functional groups, such as hydroxyl groups, primary or secondary amine groups, carboxylic acid groups, and/or thiol groups, and/or may contain active hydrogen functional groups, such as isocyanate or epoxy functional groups) reactive functional groups, and these functional groups can react with functional groups of another reactant to form a secondary fluoropolymer. The functional groups of the non-fluorinated compound may be selected to be reactive with the functional groups of the perfluoropolyether.

次要含氟聚合物之非氟化鏈段不受限制且可包含任何適合的非氟化化合物之殘基。非氟化化合物可包含可與全氟聚醚反應之單官能性、雙官能性、三官能性、四官能性或更高官能性化合物。舉例而言，非氟化化合物可包含單或聚異氰酸酯化合物，諸如二異氰酸酯、三異氰酸酯或更高官能性異氰酸酯。The non-fluorinated segment of the secondary fluoropolymer is not limited and may comprise residues of any suitable non-fluorinated compound. Non-fluorinated compounds may include monofunctional, difunctional, trifunctional, tetrafunctional, or higher functional compounds that are reactive with perfluoropolyethers. For example, the non-fluorinated compound may comprise a mono- or polyisocyanate compound, such as a diisocyanate, triisocyanate, or higher functional isocyanates.

如本文所用，術語「鍵聯基團」係指形成於兩個反應性化合物之間以產生將兩個化合物鍵聯在一起以形成次要含氟聚合物之共價鍵的部分。鍵聯基團不受限制且可包含可藉由使形成次要含氟聚合物之構成化合物之官能基反應形成的任何部分。舉例而言，鍵聯基團可包含由使活性氫官能基與可與活性氫官能基反應之官能基反應產生的任何化學部分。鍵聯基團之非限制性實例尤其包括胺基甲酸酯基、脲基、硫代胺基甲酸酯基、醚基、硫醚基。As used herein, the term "linking group" refers to a moiety formed between two reactive compounds to create a covalent bond linking the two compounds together to form a secondary fluoropolymer. The linking group is not limited and can include any moiety that can be formed by reacting functional groups of the constituent compounds that form the secondary fluoropolymer. For example, the linking group can comprise any chemical moiety that results from reacting an active hydrogen functional group with a functional group that can react with the active hydrogen functional group. Non-limiting examples of linking groups include carbamate groups, urea groups, thiocarbamate groups, ether groups, thioether groups, among others.

視情況，次要含氟聚合物可進一步包含多氟化聚醚鏈段。如本文所用，術語「多氟化聚醚鏈段」係指具有連接至醚氧之碳鏈的化合物或聚合物，該碳鏈具有至少兩個氟原子取代氫但未經氟原子完全飽和。此結構之一個非限制性實例包括FEVE聚合物。FEVE聚合物由氟乙烯（FE）及乙烯醚（VE）組成且在產品名稱LUMIFLON下由AGC化學物質商業地供應。Optionally, the secondary fluoropolymer may further comprise polyfluorinated polyether segments. As used herein, the term "polyfluorinated polyether segment" refers to a compound or polymer having a carbon chain attached to an ether oxygen, the carbon chain having at least two fluorine atoms in place of hydrogen but not fully saturated with fluorine atoms. A non-limiting example of this structure includes FEVE polymers. FEVE polymers are composed of vinyl fluoride (FE) and vinyl ether (VE) and are commercially supplied by AGC Chemicals under the product name LUMIFLON.

如上文所論述，次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。非氟化鏈段與全氟聚醚鏈段之比率可為至少0.5:1，諸如至少1:1，諸如至少1.5:1，諸如至少2:1，諸如至少2.5:1，諸如至少3:1，諸如至少4:1，諸如至少5:1，諸如至少100:1。非氟化鏈段與全氟聚醚鏈段之比率可不超過100:1，諸如不超過5:1，諸如不超過4:1，諸如不超過3:1，諸如不超過2.5:1，諸如不超過2:1，諸如不超過1.5:1，諸如不超過1:1。非氟化鏈段與全氟聚醚鏈段之比率可為0.5:1至100:1，諸如0.5:1至5:1，諸如0.5:1至4:1，諸如0.5:1至3:1，諸如0.5:1至2.5:1，諸如0.5:1至2:1，諸如0.5:1至1.5:1，諸如0.5:1至1:1，諸如1:1至100:1，諸如1:1至5:1，諸如1:1至4:1，諸如1:1至3:1，諸如1:1至2.5:1，諸如1:1至2:1，諸如1:1至1.5:1，諸如諸如1.5:1至100:1，諸如1.5:1至5:1，諸如1.5:1至4:1，諸如1.5:1至3:1，諸如1.5:1至2.5:1，諸如1.5:1至2:1，諸如2:1至100:1，諸如2:1至5:1，諸如2:1至4:1，諸如2:1至3:1，諸如2:1至2.5:1，諸如2.5:1至100:1，諸如2.5:1至5:1，諸如2.5:1至4:1，諸如2.5:1至3:1，諸如3:1至100:1，諸如3:1至5:1，諸如3:1至4:1，諸如4:1至100:1，諸如4:1至5:1，諸如5:1至100:1。鍵聯基團將存在於次要含氟聚合物鏈段之間。As discussed above, the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment. The ratio of non-fluorinated segments to perfluoropolyether segments may be at least 0.5:1, such as at least 1:1, such as at least 1.5:1, such as at least 2:1, such as at least 2.5:1, such as at least 3:1 , such as at least 4:1, such as at least 5:1, such as at least 100:1. The ratio of non-fluorinated segments to perfluoropolyether segments may be no more than 100:1, such as no more than 5:1, such as no more than 4:1, such as no more than 3:1, such as no more than 2.5:1, such as no more than more than 2:1, such as not more than 1.5:1, such as not more than 1:1. The ratio of non-fluorinated segments to perfluoropolyether segments may be from 0.5:1 to 100:1, such as 0.5:1 to 5:1, such as 0.5:1 to 4:1, such as 0.5:1 to 3:1 , such as 0.5:1 to 2.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.5:1, such as 0.5:1 to 1:1, such as 1:1 to 100:1, such as 1:1 to 5:1, such as 1:1 to 4:1, such as 1:1 to 3:1, such as 1:1 to 2.5:1, such as 1:1 to 2:1, such as 1:1 to 1.5:1, such as 1.5:1 to 100:1, such as 1.5:1 to 5:1, such as 1.5:1 to 4:1, such as 1.5:1 to 3:1, such as 1.5:1 to 2.5:1, such as 1.5:1 to 2:1, such as 2:1 to 100:1, such as 2:1 to 5:1, such as 2:1 to 4:1, such as 2:1 to 3:1, such as 2:1 to 2.5:1, such as 2.5:1 to 100:1, such as 2.5:1 to 5:1, such as 2.5:1 to 4:1, such as 2.5:1 to 3:1, such as 3:1 to 100:1, such as 3:1 to 5:1, such as 3:1 to 4:1, such as 4:1 to 100:1, such as 4:1 to 5:1, such as 5:1 to 100:1. Linking groups will be present between the secondary fluoropolymer segments.

次要含氟聚合物亦包含至少一個全氟聚醚之殘基及至少一個非氟化化合物之殘基。非氟化化合物與全氟聚醚之殘基的比率可與如上文關於非氟化鏈段與全氟聚醚鏈段之比率所論述相同。舉例而言，非氟化化合物與全氟聚醚之殘基的比率可為0.5:1至100:1，諸如0.5:1至5:1，諸如0.5:1至4:1，諸如0.5:1至3:1，諸如0.5:1至2.5:1，諸如0.5:1至2:1，諸如0.5:1至1.5:1，諸如0.5:1至1:1，諸如1:1至100:1，諸如1:1至5:1，諸如1:1至4:1，諸如1:1至3:1，諸如1:1至2.5:1，諸如1:1至2:1，諸如1:1至1.5:1，諸如諸如1.5:1至100:1，諸如1.5:1至5:1，諸如1.5:1至4:1，諸如1.5:1至3:1，諸如1.5:1至2.5:1，諸如1.5:1至2:1，諸如2:1至100:1，諸如2:1至5:1，諸如2:1至4:1，諸如2:1至3:1，諸如2:1至2.5:1，諸如2.5:1至100:1，諸如2.5:1至5:1，諸如2.5:1至4:1，諸如2.5:1至3:1，諸如3:1至100:1，諸如3:1至5:1，諸如3:1至4:1，諸如4:1至100:1，諸如4:1至5:1，諸如5:1至100:1。鍵聯基團將存在於除末端殘基以外的次要含氟聚合物之非氟化化合物之各殘基或全氟聚醚之殘基之間。The secondary fluoropolymer also contains at least one residue of a perfluoropolyether and at least one residue of a non-fluorinated compound. The ratio of residues of non-fluorinated compound to perfluoropolyether may be the same as discussed above with respect to the ratio of non-fluorinated segments to perfluoropolyether segments. For example, the ratio of residues of non-fluorinated compound to perfluoropolyether may be 0.5:1 to 100:1, such as 0.5:1 to 5:1, such as 0.5:1 to 4:1, such as 0.5:1 to 3:1, such as 0.5:1 to 2.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.5:1, such as 0.5:1 to 1:1, such as 1:1 to 100:1, such as 1:1 to 5:1, such as 1:1 to 4:1, such as 1:1 to 3:1, such as 1:1 to 2.5:1, such as 1:1 to 2:1, such as 1:1 to 1.5:1, such as 1.5:1 to 100:1, such as 1.5:1 to 5:1, such as 1.5:1 to 4:1, such as 1.5:1 to 3:1, such as 1.5:1 to 2.5:1, such as 1.5:1 to 2:1, such as 2:1 to 100:1, such as 2:1 to 5:1, such as 2:1 to 4:1, such as 2:1 to 3:1, such as 2:1 to 2.5:1, such as 2.5:1 to 100:1, such as 2.5:1 to 5:1, such as 2.5:1 to 4:1, such as 2.5:1 to 3:1, such as 3:1 to 100:1, such as 3:1 to 5:1, such as 3:1 to 4:1, such as 4:1 to 100:1, such as 4:1 to 5:1, such as 5:1 to 100:1. Linking groups will be present between each residue of the non-fluorinated compound of the secondary fluoropolymer or the residue of the perfluoropolyether other than the terminal residues.

次要含氟聚合物之重量平均分子量可為至少100 g/mol，諸如至少500 g/mol，諸如至少1,000 g/mol，諸如至少1,200 g/mol。次要含氟聚合物之重量平均分子量可為不超過10,000 g/mol，諸如不超過9,000 g/mol，諸如不超過7,500 g/mol，諸如不超過6,000 g/mol，諸如不超過3,000 g/mol，諸如不超過1,800 g/mol。次要含氟聚合物之重量平均分子量可為100至10,000 g/mol，諸如100至9,000 g/mol，諸如100至7,500 g/mol，諸如100至6,000 g/mol，諸如500至10,000 g/mol，諸如500至9,000 g/mol，諸如500至7,500 g/mol，諸如500至6,000 g/mol，諸如500至3,000 g/mol，諸如500至1,800 g/mol，諸如1,000至10,000 g/mol，諸如1,000至9,000 g/mol，諸如1,000至7,500 g/mol，諸如1,000至6,000 g/mol，諸如1,000至3,000 g/mol，諸如1,000至1,800 g/mol，諸如1,200至10,000 g/mol，諸如1,200至9,000 g/mol，諸如1,200至7,500 g/mol，諸如1,200至6,000 g/mol，諸如1,200至3,000 g/mol，諸如1,200至1,800 g/mol。The weight average molecular weight of the secondary fluoropolymer may be at least 100 g/mol, such as at least 500 g/mol, such as at least 1,000 g/mol, such as at least 1,200 g/mol. The weight average molecular weight of the secondary fluoropolymer may be up to 10,000 g/mol, such as up to 9,000 g/mol, such as up to 7,500 g/mol, such as up to 6,000 g/mol, such as up to 3,000 g/mol , such as not more than 1,800 g/mol. The weight average molecular weight of the secondary fluoropolymer may be from 100 to 10,000 g/mol, such as 100 to 9,000 g/mol, such as 100 to 7,500 g/mol, such as 100 to 6,000 g/mol, such as 500 to 10,000 g/mol , such as 500 to 9,000 g/mol, such as 500 to 7,500 g/mol, such as 500 to 6,000 g/mol, such as 500 to 3,000 g/mol, such as 500 to 1,800 g/mol, such as 1,000 to 10,000 g/mol, such as 1,000 to 9,000 g/mol, such as 1,000 to 7,500 g/mol, such as 1,000 to 6,000 g/mol, such as 1,000 to 3,000 g/mol, such as 1,000 to 1,800 g/mol, such as 1,200 to 10,000 g/mol, such as 1,200 to 9,000 g/mol, such as 1,200 to 7,500 g/mol, such as 1,200 to 6,000 g/mol, such as 1,200 to 3,000 g/mol, such as 1,200 to 1,800 g/mol.

次要含氟聚合物之非限制性實例根據以下結構：

其中各R獨立地包含烷基、芳基、環烷基或環芳基，諸如C ₁至C ₆、烷基、芳基、環烷基或環芳基，n為1至500之整數，諸如1至200，諸如1至100，諸如1至84，諸如5-30，諸如8-20，諸如9-16，且各R _F獨立地為(CF ₂) _m，其中m為1或2。R基團可包含例如1至18個碳，諸如1至10個碳，諸如1至8個碳，諸如1至6個碳，諸如1至3個碳或更多。 Non-limiting examples of secondary fluoropolymers are according to the following structures:

wherein each R independently comprises an alkyl, aryl, cycloalkyl or cycloaryl, such as _C1 to _C6 , alkyl, aryl, cycloalkyl or cycloaryl, and n is an integer from 1 to 500, such as 1 to 200, such as 1 to 100, such as 1 to 84, such as 5-30, such as 8-20, such as 9-16, and each _RF is independently ( _CF2 ) _m , where m is 1 or 2. The R group may comprise, for example, 1 to 18 carbons, such as 1 to 10 carbons, such as 1 to 8 carbons, such as 1 to 6 carbons, such as 1 to 3 carbons or more.

次要含氟聚合物之另一非限制性實例根據以下結構：

其中各R獨立地包含烷基、芳基、環烷基或環芳基，諸如C ₁至C ₆、烷基、芳基、環烷基或環芳基，n為1至500之整數，諸如1至200，諸如1至100，諸如1至84，諸如5至30，諸如8至20，諸如9至16。 Another non-limiting example of a secondary fluoropolymer is according to the following structure:

wherein each R independently comprises an alkyl, aryl, cycloalkyl or cycloaryl, such as _C1 to _C6 , alkyl, aryl, cycloalkyl or cycloaryl, and n is an integer from 1 to 500, such as 1 to 200, such as 1 to 100, such as 1 to 84, such as 5 to 30, such as 8 to 20, such as 9 to 16.

次要含氟聚合物之非限制性實例可藉由下文說明之反應合成製備。舉例而言，二羥基官能性全氟聚醚可與兩當量之二異氰酸酯反應，產生具有中心全氟聚醚鏈段（二羥基官能性全氟聚醚之殘基）之聚合物，該中心全氟聚醚鏈段藉由胺基甲酸酯鍵聯基團彼此連接至兩個二異氰酸酯鏈段（二異氰酸酯之殘基），產生兩個末端異氰酸酯基官能基。異氰酸酯基官能基隨後可與醇（諸如丁醇）反應，以將異氰酸酯基官能基封端。

Non-limiting examples of secondary fluoropolymers can be prepared synthetically by the reactions described below. For example, a dihydroxy-functional perfluoropolyether can be reacted with two equivalents of diisocyanate to produce a polymer having a central perfluoropolyether segment (residue of a dihydroxy-functional perfluoropolyether) that is fully The fluoropolyether segments are linked to each other by urethane linking groups to two diisocyanate segments (residues of diisocyanates), resulting in two terminal isocyanate functional groups. The isocyanate functional group can then be reacted with an alcohol, such as butanol, to cap the isocyanate functional group.

用以產生次要含氟聚合物之反應合成的第二非限制性實例說明如下。舉例而言，二異氰酸酯可與兩當量之二羥基官能性全氟聚醚反應，產生具有中心二異氰酸酯鏈段（二羥基官能性全氟聚醚之殘基）之聚合物，該中心二異氰酸酯鏈段藉由胺基甲酸酯鍵聯基團彼此連接至兩個全氟聚醚鏈段（二羥基官能性全氟聚醚之殘基），產生兩個末端羥基官能基及羥基官能性次要含氟聚合物。

A second non-limiting example of a reactive synthesis to produce a secondary fluoropolymer is illustrated below. For example, a diisocyanate can be reacted with two equivalents of a dihydroxy-functional perfluoropolyether to produce a polymer having a central diisocyanate segment (residue of a dihydroxy-functional perfluoropolyether), the central diisocyanate chain The segments are linked to each other by urethane linking groups to two perfluoropolyether segments (residues of a dihydroxy-functional perfluoropolyether), resulting in two terminal hydroxyl functional groups and a hydroxyl functional secondary Fluoropolymer.

以黏合劑固體之總重量計，次要含氟聚合物可以以下量存在於黏合劑中：至少0.1重量%，諸如至少0.5重量%、諸如至少1重量%、諸如至少2重量%、諸如至少5重量%、諸如至少7.5重量%、諸如至少10重量%、諸如至少15重量%、諸如至少20重量%、諸如至少25重量%、諸如至少30重量%、諸如至少35重量%。以黏合劑固體之總重量計，次要含氟聚合物可以以下量存在於黏合劑中：不超過35重量%，諸如不超過25重量%、諸如不超過20重量%、諸如不超過15重量%、諸如不超過10重量%、諸如不超過7.5重量%、諸如不超過5重量%、諸如不超過3重量%、諸如不超過2重量%、諸如不超過1重量%。以黏合劑固體之總重量計，次要含氟聚合物可以以下量存在於黏合劑中：0.1%至35重量%，諸如0.1%至25重量%、諸如0.1%至20重量%、諸如0.1%至15重量%、諸如0.1%至10重量%、諸如0.1%至7.5重量%、諸如0.1%至5重量%、諸如0.1%至3重量%、諸如0.1%至2重量%、諸如0.1%至1重量%、諸如0.5%至35重量%、諸如0.5%至25重量%、諸如0.5%至20重量%、諸如0.5%至15重量%、諸如0.5%至10重量%、諸如0.5%至7.5重量%、諸如0.5%至5重量%、諸如0.5%至3重量%、諸如0.5%至2重量%、諸如0.5%至1重量%、諸如1%至35重量%、諸如1%至25重量%、諸如1%至20重量%、諸如1%至15重量%、諸如1%至10重量%、諸如1%至7.5重量%、諸如1%至5重量%、諸如1%至3重量%、諸如1%至2重量%、諸如2%至35重量%、諸如2%至25重量%、諸如2%至20重量%、諸如2%至15重量%、諸如2%至10重量%、諸如2%至7.5重量%、諸如2%至5重量%、諸如2%至3重量%、諸如諸如5%至35重量%、諸如5%至25重量%、諸如5%至20重量%、諸如5%至15重量%、諸如5%至10重量%、諸如5%至7.5重量%、諸如7.5%至35重量%、諸如7.5%至25重量%、諸如7.5%至20重量%、諸如7.5%至15重量%、諸如7.5%至10重量%、諸如10%至35重量%、諸如10%至25重量%、諸如15%至35重量%、諸如15%至25重量%、諸如20%至35重量%、諸如20%至25重量%、諸如25%至35重量%、諸如30%至35重量%。次要含氟聚合物可溶解或分散於有機介質中。The secondary fluoropolymer may be present in the binder in an amount based on the total weight of binder solids: at least 0.1 wt%, such as at least 0.5 wt%, such as at least 1 wt%, such as at least 2 wt%, such as at least 5 wt% % by weight, such as at least 7.5% by weight, such as at least 10% by weight, such as at least 15% by weight, such as at least 20% by weight, such as at least 25% by weight, such as at least 30% by weight, such as at least 35% by weight. The secondary fluoropolymer may be present in the binder in an amount of not more than 35% by weight, such as not more than 25% by weight, such as not more than 20% by weight, such as not more than 15% by weight, based on the total weight of the binder solids , such as not more than 10% by weight, such as not more than 7.5% by weight, such as not more than 5% by weight, such as not more than 3% by weight, such as not more than 2% by weight, such as not more than 1% by weight. The secondary fluoropolymer may be present in the binder in an amount from 0.1% to 35% by weight, such as 0.1% to 25% by weight, such as 0.1% to 20% by weight, such as 0.1%, based on the total weight of the binder solids to 15% by weight, such as 0.1% to 10% by weight, such as 0.1% to 7.5% by weight, such as 0.1% to 5% by weight, such as 0.1% to 3% by weight, such as 0.1% to 2% by weight, such as 0.1% to 1 % by weight, such as 0.5% to 35% by weight, such as 0.5% to 25% by weight, such as 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 7.5% by weight , such as 0.5% to 5% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1% by weight, such as 1% to 35% by weight, such as 1% to 25% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 7.5% by weight, such as 1% to 5% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 2% to 35% by weight, such as 2% to 25% by weight, such as 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 2% to 7.5% % by weight, such as 2% to 5% by weight, such as 2% to 3% by weight, such as such as 5% to 35% by weight, such as 5% to 25% by weight, such as 5% to 20% by weight, such as 5% to 15% by weight %, such as 5% to 10% by weight, such as 5% to 7.5% by weight, such as 7.5% to 35% by weight, such as 7.5% to 25% by weight, such as 7.5% to 20% by weight, such as 7.5% to 15% by weight, such as 7.5% to 10% by weight, such as 10% to 35% by weight, such as 10% to 25% by weight, such as 15% to 35% by weight, such as 15% to 25% by weight, such as 20% to 35% by weight, such as 20% % to 25% by weight, such as 25% to 35% by weight, such as 30% to 35% by weight. The secondary fluoropolymer can be dissolved or dispersed in the organic medium.

主要含氟聚合物與次要含氟聚合物之比率可為至少5:1，諸如至少10:1，諸如至少20:1，諸如至少25:1，諸如至少30:1，諸如至少35:1，諸如至少40:1，諸如至少50:1，諸如至少55:1。主要含氟聚合物與次要含氟聚合物之比率可為不超過65:1，諸如不超過60:1，諸如不超過55:1，諸如不超過50:1，諸如不超過40:1，諸如不超過35:1，諸如不超過30:1，諸如不超過25:1，諸如不超過20:1，諸如不超過15:1，諸如不超過10:1。主要含氟聚合物與次要含氟聚合物之比率可為5:1至65:1，諸如5:1至60:1，諸如5:1至55:1，諸如5:1至50:1，諸如5:1至40:1，諸如5:1至35:1，諸如5:1至30:1，諸如5:1至25:1，諸如5:1至20:1，諸如5:1至15:1，諸如5:1至10:1，諸如10:1至65:1，諸如10:1至60:1，諸如10:1至55:1，諸如10:1至50:1，諸如10:1至40:1，諸如10:1至35:1，諸如10:1至30:1，諸如10:1至25:1，諸如10:1至20:1，諸如10:1至15:1，諸如20:1至65:1，諸如20:1至60:1，諸如20:1至55:1，諸如20:1至50:1，諸如20:1至40:1，諸如20:1至35:1，諸如20:1至30:1，諸如20:1至25:1，諸如25:1至65:1，諸如25:1至60:1，諸如25:1至55:1，諸如25:1至50:1，諸如25:1至40:1，諸如25:1至35:1，諸如25:1至30:1，諸如25:1至25:1，諸如25:1至20:1，諸如25:1至15:1，諸如25:1至10:1，諸如30:1至65:1，諸如30:1至60:1，諸如30:1至55:1，諸如30:1至50:1，諸如30:1至40:1，諸如30:1至35:1，諸如35:1至65:1，諸如35:1至60:1，諸如35:1至55:1，諸如35:1至50:1，諸如35:1至40:1，諸如40:1至65:1，諸如40:1至60:1，諸如40:1至55:1，諸如40:1至50:1，諸如50:1至65:1，諸如50:1至60:1，諸如55:1至65:1，諸如55:1至60:1。The ratio of primary fluoropolymer to secondary fluoropolymer may be at least 5:1, such as at least 10:1, such as at least 20:1, such as at least 25:1, such as at least 30:1, such as at least 35:1 , such as at least 40:1, such as at least 50:1, such as at least 55:1. The ratio of primary fluoropolymer to secondary fluoropolymer may be no more than 65:1, such as no more than 60:1, such as no more than 55:1, such as no more than 50:1, such as no more than 40:1, Such as not more than 35:1, such as not more than 30:1, such as not more than 25:1, such as not more than 20:1, such as not more than 15:1, such as not more than 10:1. The ratio of primary fluoropolymer to secondary fluoropolymer may be 5:1 to 65:1, such as 5:1 to 60:1, such as 5:1 to 55:1, such as 5:1 to 50:1 , such as 5:1 to 40:1, such as 5:1 to 35:1, such as 5:1 to 30:1, such as 5:1 to 25:1, such as 5:1 to 20:1, such as 5:1 to 15:1, such as 5:1 to 10:1, such as 10:1 to 65:1, such as 10:1 to 60:1, such as 10:1 to 55:1, such as 10:1 to 50:1, such as 10:1 to 40:1, such as 10:1 to 35:1, such as 10:1 to 30:1, such as 10:1 to 25:1, such as 10:1 to 20:1, such as 10:1 to 15:1, such as 20:1 to 65:1, such as 20:1 to 60:1, such as 20:1 to 55:1, such as 20:1 to 50:1, such as 20:1 to 40:1, such as 20:1 to 35:1, such as 20:1 to 30:1, such as 20:1 to 25:1, such as 25:1 to 65:1, such as 25:1 to 60:1, such as 25:1 to 55 :1, such as 25:1 to 50:1, such as 25:1 to 40:1, such as 25:1 to 35:1, such as 25:1 to 30:1, such as 25:1 to 25:1, such as 25 :1 to 20:1, such as 25:1 to 15:1, such as 25:1 to 10:1, such as 30:1 to 65:1, such as 30:1 to 60:1, such as 30:1 to 55:1 1, such as 30:1 to 50:1, such as 30:1 to 40:1, such as 30:1 to 35:1, such as 35:1 to 65:1, such as 35:1 to 60:1, such as 35:1 1 to 55:1, such as 35:1 to 50:1, such as 35:1 to 40:1, such as 40:1 to 65:1, such as 40:1 to 60:1, such as 40:1 to 55:1 , such as 40:1 to 50:1, such as 50:1 to 65:1, such as 50:1 to 60:1, such as 55:1 to 65:1, such as 55:1 to 60:1.

根據本發明，黏合劑組合物及/或漿料組合物可包含液體介質。液體介質可包含有機介質。如本文所用，術語「有機介質」係指包含以有機介質之總重量計低於50重量%水之液體介質。此類有機介質可包含以有機介質之總重量計低於40重量%水、或低於30重量%水、或低於20重量%水、或低於10重量%水、或低於5重量%水、或低於1重量%水、或低於0.1重量%水或可不含水。有機溶劑包含以有機介質之總重量計超過50重量%有機介質，諸如至少70重量%、諸如至少80重量%、諸如至少90重量%、諸如至少95重量%、諸如至少99重量%、諸如至少99.9重量%、諸如100重量%。有機溶劑可包含以有機介質之總重量計50.1%至100重量%、諸如70%至100重量%、諸如80%至100重量%、諸如90%至100重量%、諸如95%至100重量%、諸如99%至100重量%、諸如99.9%至100重量%。According to the present invention, the adhesive composition and/or the slurry composition may comprise a liquid medium. The liquid medium may comprise an organic medium. As used herein, the term "organic medium" refers to a liquid medium comprising less than 50 wt % water, based on the total weight of the organic medium. Such organic medium may comprise less than 40 wt% water, or less than 30 wt% water, or less than 20 wt% water, or less than 10 wt% water, or less than 5 wt% water, based on the total weight of the organic medium Water, or less than 1 wt% water, or less than 0.1 wt% water or may be free of water. The organic solvent comprises more than 50% by weight of the organic medium, such as at least 70% by weight, such as at least 80% by weight, such as at least 90% by weight, such as at least 95% by weight, such as at least 99% by weight, such as at least 99.9% by weight, based on the total weight of the organic medium % by weight, such as 100% by weight. The organic solvent may comprise 50.1% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 95% to 100% by weight, based on the total weight of the organic medium. Such as 99% to 100% by weight, such as 99.9% to 100% by weight.

有機介質可視情況具有在分散於有機介質中之主要含氟聚合物的溶解溫度下低於10 g/min m ²之蒸發速率。蒸發速率可使用ASTM D3539（1996）來量測。根據本發明，分散於有機介質中之主要含氟聚合物的溶解溫度可藉由量測混合物之複數黏度隨溫度變化來確定。此技術可應用於混合於有機介質中之含氟聚合物（外加其他類型聚合物），其中此類混合物之非揮發性固體含量的總質量為混合物之總質量的44%至46%，諸如45%。複數黏度可用Anton-Paar MCR301流變儀使用50毫米錐及溫度受控板量測。在20℃至至少75℃之溫度範圍內以10℃/分鐘之升溫速率、1 Hz之振盪頻率及90 Pa之應力幅度設定點來量測含氟聚合物混合物之複數黏度。主要含氟聚合物在有機介質中之溶解藉由複數黏度隨溫度升高而急劇增大來指示。溶解溫度經定義為隨溫度升高之黏度變化速率最高時的溫度，且藉由確定複數黏度之Log ₁₀相對於溫度的第一導數達到最大時的溫度來計算。下表說明根據此方法使用來自Inner Mongolia 3F Wanhao Fluorochemical Co. Ltd.之PVDF T-1 （PVDF T-1具有約330至380 nm之粒徑及約130,000至160,000 g/mol之重量平均分子量）確定的在所列舉之各種溶劑或溶劑混合物中之溶解溫度。溶劑有機介質之溶劑質量% 輔溶劑有機介質之輔溶劑質量% 混合物之PVDF質量% 溶解溫度（℃）溶解溫度下之蒸發速率（mg/min m ²） N-丁基吡咯啶酮 100 - - 45 48 - γ-丁內酯 100 - - 45 51 9.31 異佛爾酮 100 - - 45 72 16.59 三乙酸甘油酯 100 - - 45 76 0.69 乙醯乙酸乙酯 100 - - 45 76 37.76 磷酸三乙酯 80 乙醯乙酸乙酯 20 45 46 - 磷酸三乙酯 80 Dowanol™ PM ¹ 20 45 58 - ¹丙二醇甲醚可購自陶氏化學公司。 The organic medium may optionally have an evaporation rate below 10 g/min m ² at the dissolution temperature of the primary fluoropolymer dispersed in the organic medium. Evaporation rate can be measured using ASTM D3539 (1996). According to the present invention, the dissolution temperature of the main fluoropolymer dispersed in the organic medium can be determined by measuring the complex viscosity of the mixture as a function of temperature. This technique can be applied to fluoropolymers (plus other types of polymers) mixed in organic media where the total mass of the non-volatile solids content of such a mixture is 44% to 46% of the total mass of the mixture, such as 45 %. Complex viscosity can be measured with an Anton-Paar MCR301 rheometer using a 50 mm cone and temperature controlled plate. The complex viscosity of the fluoropolymer mixture was measured over a temperature range of 20°C to at least 75°C with a ramp rate of 10°C/min, an oscillation frequency of 1 Hz, and a stress amplitude set point of 90 Pa. Dissolution of the main fluoropolymer in organic media is indicated by a sharp increase in complex viscosity with increasing temperature. The dissolution temperature is defined as the temperature at which the rate of viscosity change with increasing temperature is highest, and is calculated by determining the temperature at which the first derivative of the Log ₁₀ of the complex viscosity with respect to temperature is at a maximum. The following table illustrates the determination according to this method using PVDF T-1 from Inner Mongolia 3F Wanhao Fluorochemical Co. Ltd. (PVDF T-1 has a particle size of about 330 to 380 nm and a weight average molecular weight of about 130,000 to 160,000 g/mol) The dissolution temperature in each of the listed solvents or solvent mixtures. solvent Solvent mass % of organic medium cosolvent Cosolvent mass% of organic medium PVDF mass % of mixture Dissolution temperature (℃) Evaporation rate at dissolution temperature (mg/min m ² ) N-butylpyrrolidone 100 - - 45 48 - gamma-butyrolactone 100 - - 45 51 9.31 isophorone 100 - - 45 72 16.59 Triacetin 100 - - 45 76 0.69 Ethyl Acetate 100 - - 45 76 37.76 Triethyl Phosphate 80 Ethyl Acetate 20 45 46 - Triethyl Phosphate 80 Dowanol™ PM ¹ 20 45 58 - ¹ Propylene glycol methyl ether is available from The Dow Chemical Company.

分散於有機介質中之主要含氟聚合物的溶解溫度可低於77℃，諸如低於70℃，諸如低於65℃，諸如低於60℃，諸如低於55℃，諸如低於50℃。分散於有機介質中之主要含氟聚合物的溶解溫度可在以下範圍內：30℃至77℃，諸如30℃至70℃，諸如30℃至65℃，諸如30℃至60℃，諸如30℃至55℃，諸如30℃至50℃。溶解溫度可根據上文所論述之方法量測。The dissolution temperature of the primary fluoropolymer dispersed in the organic medium may be below 77°C, such as below 70°C, such as below 65°C, such as below 60°C, such as below 55°C, such as below 50°C. The dissolution temperature of the primary fluoropolymer dispersed in the organic medium may be in the following range: 30°C to 77°C, such as 30°C to 70°C, such as 30°C to 65°C, such as 30°C to 60°C, such as 30°C to 55°C, such as 30°C to 50°C. The dissolution temperature can be measured according to the methods discussed above.

有機介質可包含例如丁基吡咯啶酮、磷酸三烷基酯、磷酸三芳基酯、1,2,3-三乙醯氧基丙烷、3-甲氧基-N,N-二甲基丙醯胺、乙醯乙酸乙酯、γ-丁內酯、丙二醇甲醚、環己酮、碳酸伸丙酯、己二酸二甲酯、丙二醇甲醚乙酸酯、二元酯（DBE）、二元酯5（DBE-5）、4-羥基-4-甲基-2-戊酮（二丙酮醇）、丙二醇二乙酸酯、鄰苯二甲酸二甲酯、甲基異戊基酮、丙酸乙酯、1-乙氧基-2-丙醇、二丙二醇二甲醚、飽和及不飽和線性酮及環酮（可以其混合物形式以Eastman™ C-11 Ketone自Eastman化學公司商購）、二異丁酮、乙酸酯（可以Exxate™ 1000形式自Hallstar商購）、三丙二醇甲醚、二乙二醇乙基醚乙酸酯或其組合。磷酸三烷基酯可包含例如磷酸三甲酯、磷酸三乙酯、磷酸三丙酯、磷酸三丁酯或類似物。磷酸三芳基酯可包含例如磷酸參(鄰甲苯酯)。The organic medium may contain, for example, butylpyrrolidone, trialkyl phosphate, triaryl phosphate, 1,2,3-triacetoxypropane, 3-methoxy-N,N-dimethylpropane Amine, Ethyl Acetate, γ-Butyrolactone, Propylene Glycol Methyl Ether, Cyclohexanone, Propylene Glycol Carbonate, Dimethyl Adipate, Propylene Glycol Methyl Ether Acetate, Dibasic Ester (DBE), Dibasic Ester 5 (DBE-5), 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycol diacetate, dimethyl phthalate, methyl isoamyl ketone, propionic acid Ethyl esters, 1-ethoxy-2-propanol, dipropylene glycol dimethyl ether, saturated and unsaturated linear and cyclic ketones (commercially available as Eastman™ C-11 Ketone from Eastman Chemical Company as a mixture thereof), dimethicone Isobutyl ketone, acetate (commercially available from Hallstar as Exxate™ 1000), tripropylene glycol methyl ether, diethylene glycol ethyl ether acetate, or combinations thereof. Trialkyl phosphates may include, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, or the like. Triaryl phosphates can include, for example, ginsenoside (o-cresol) phosphate.

有機介質可基本上由以下組成或由以下組成：例如丁基吡咯啶酮、磷酸三烷基酯、1,2,3-三乙醯氧基丙烷、3-甲氧基-N,N-二甲基丙醯胺、乙醯乙酸乙酯、γ-丁內酯、環己酮、碳酸伸丙酯、己二酸二甲酯、丙二醇甲醚乙酸酯、二元酯（DBE）、二元酯5（DBE-5）、4-羥基-4-甲基-2-戊酮（二丙酮醇）、丙二醇二乙酸酯、鄰苯二甲酸二甲酯、甲基異戊基酮、丙酸乙酯、1-乙氧基-2-丙醇、飽和及不飽和線性酮及環酮（可以其混合物形式以Eastman™ C-11 Ketone自Eastman化學公司商購）、二異丁酮、乙酸酯（可以Exxate™ 1000形式自Hallstar商購）、二乙二醇乙基醚乙酸酯或其組合。The organic medium may consist essentially of or consist of, for example, butylpyrrolidone, trialkyl phosphate, 1,2,3-triacetoxypropane, 3-methoxy-N,N-di Methylpropionamide, Ethyl Acetate, γ-Butyrolactone, Cyclohexanone, Propylene Carbonate, Dimethyl Adipate, Propylene Glycol Methyl Ether Acetate, Dibasic Ester (DBE), Dibasic Ester 5 (DBE-5), 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycol diacetate, dimethyl phthalate, methyl isoamyl ketone, propionic acid Ethyl esters, 1-ethoxy-2-propanol, saturated and unsaturated linear and cyclic ketones (commercially available as Eastman™ C-11 Ketone from Eastman Chemical Company as a mixture thereof), diisobutyl ketone, acetic acid ester (commercially available from Hallstar as Exxate™ 1000), diethylene glycol ethyl ether acetate, or a combination thereof.

有機介質可包含與作為分散相之主要含氟聚合物一起形成均質連續相的主要溶劑及輔溶劑。主要溶劑及輔溶劑以及其相關量可經選擇以在室溫（亦即約23℃）下提供主要含氟聚合物於有機介質中之分散液。主要溶劑及輔溶劑兩者可包含有機溶劑。主要含氟聚合物可在單獨使用時可溶於主要溶劑中，但與主要溶劑一起使用輔溶劑可允許主要含氟聚合物穩定分散於有機介質中。主要溶劑可包含以下、基本上由以下組成或由以下組成：例如丁基吡咯啶酮、磷酸三烷基酯、3-甲氧基-N,N-二甲基丙醯胺、1,2,3-三乙醯氧基丙烷或其組合。輔溶劑可包含以下、基本上由以下組成或由以下組成：例如乙醯乙酸乙酯、γ-丁內酯及/或二醇醚，諸如丙二醇甲醚、二丙二醇甲醚、丙二醇單丙醚、二乙二醇單丁醚、乙二醇單己醚及類似物。以有機介質之總重量計，主要溶劑可以至少50重量%、諸如至少65重量%、諸如至少75重量%之量存在，且可以不超過99重量%、諸如不超過90重量%、諸如不超過85重量%之量存在。以有機介質之總重量計，主要溶劑可以50%至99重量%、諸如65%至90重量%、諸如75%至85重量%之量存在。輔溶劑可以至少1重量%、諸如至少10重量%、諸如至少15重量%之量存在，且可以不超過50重量%、諸如不超過35重量%、諸如不超過25重量%之量存在。以有機介質之總重量計，輔溶劑可以1%至50重量%、諸如10%至35重量%、諸如15%至25重量%之量存在。The organic medium may contain a primary solvent and a secondary solvent that form a homogeneous continuous phase with the primary fluoropolymer as the dispersed phase. The primary and co-solvents and their relative amounts can be selected to provide a dispersion of the primary fluoropolymer in an organic medium at room temperature (ie, about 23°C). Both the main solvent and the auxiliary solvent may comprise organic solvents. The primary fluoropolymer may be soluble in the primary solvent when used alone, but the use of a cosolvent with the primary solvent may allow the primary fluoropolymer to be stably dispersed in the organic medium. The primary solvent may comprise, consist essentially of, or consist of, for example, butylpyrrolidone, trialkyl phosphate, 3-methoxy-N,N-dimethylpropionamide, 1,2, 3-Triacetoxypropane or a combination thereof. The co-solvent may comprise, consist essentially of, or consist of, for example, ethyl acetate, gamma-butyrolactone, and/or glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol monopropyl ether, Diethylene glycol monobutyl ether, ethylene glycol monohexyl ether and the like. The primary solvent may be present in an amount of at least 50% by weight, such as at least 65% by weight, such as at least 75% by weight, and may be no more than 99% by weight, such as no more than 90% by weight, such as no more than 85% by weight, based on the total weight of the organic medium. The amount is present in % by weight. The primary solvent may be present in an amount of 50% to 99% by weight, such as 65% to 90% by weight, such as 75% to 85% by weight, based on the total weight of the organic medium. The co-solvent may be present in an amount of at least 1 wt %, such as at least 10 wt %, such as at least 15 wt %, and may be present in an amount of no more than 50 wt %, such as no more than 35 wt %, such as no more than 25 wt %. The co-solvent may be present in an amount of 1% to 50% by weight, such as 10% to 35% by weight, such as 15% to 25% by weight, based on the total weight of the organic medium.

有機介質亦可具有在180℃下大於80 g/min m ²，諸如在180℃下大於90 g/min m ²，諸如在180℃下大於100 g/min m ²之蒸發速率。 The organic medium may also have an evaporation rate of greater than 80 ^g /min m2 at 180°C, such as greater than 90 ^g /min m2 at 180°C, such as greater than 100 ^g /min m2 at 180°C.

以黏合劑組合物及/或漿料組合物之總重量計，有機介質可以至少10重量%，諸如至少15重量%、諸如至少20重量%、諸如至少30重量%、諸如至少35重量%、諸如至少40重量%之量存在，且可以不超過80重量%，諸如不超過70重量%、諸如不超過60重量%、諸如不超過50重量%、諸如不超過45重量%、諸如不超過45重量%、諸如不超過40重量%、諸如不超過35重量%、諸如不超過29重量%、諸如不超過25重量%之量存在。以黏合劑組合物及/或漿料組合物之總重量計，有機介質可以諸如20%至80重量%、10%至70重量%、諸如30%至70重量%、諸如35%至60重量%、諸如40%至50重量%、15%至60重量%、15%至50重量%、15%至45重量%、15%至40重量%、15%至35重量%、15%至29重量%、15%至25重量%之量存在。The organic medium may be at least 10% by weight, such as at least 15% by weight, such as at least 20% by weight, such as at least 30% by weight, such as at least 35% by weight, such as at least 35% by weight, based on the total weight of the adhesive composition and/or the slurry composition is present in an amount of at least 40% by weight, and may not exceed 80% by weight, such as not more than 70% by weight, such as not more than 60% by weight, such as not more than 50% by weight, such as not more than 45% by weight, such as not more than 45% by weight , such as not more than 40% by weight, such as not more than 35% by weight, such as not more than 29% by weight, such as not more than 25% by weight. Based on the total weight of the binder composition and/or the slurry composition, the organic medium may be such as 20% to 80% by weight, 10% to 70% by weight, such as 30% to 70% by weight, such as 35% to 60% by weight , such as 40% to 50% by weight, 15% to 60% by weight, 15% to 50% by weight, 15% to 45% by weight, 15% to 40% by weight, 15% to 35% by weight, 15% to 29% by weight , present in an amount of 15% to 25% by weight.

黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含N-甲基-2-吡咯啶酮（NMP）。如本文所用，若NMP以按黏合劑組合物及/或漿料組合物之總重量計低於5重量%之量存在（若有的話），則黏合劑組合物及/或漿料組合物「實質上不含」NMP。如本文所用，若NMP以按黏合劑組合物及/或漿料組合物之總重量計低於0.3重量%之量存在（若有的話），則黏合劑組合物及/或漿料組合物「基本上不含」NMP。如本文所用，若NMP以黏合劑組合物及/或漿料組合物之總重量計不存在於黏合劑組合物及/或漿料組合物中，亦即0.000重量%，則漿料組合物「完全不含」NMP。The adhesive composition and/or the slurry composition may be substantially free, substantially free, or completely free of N-methyl-2-pyrrolidone (NMP). As used herein, if NMP is present in an amount less than 5% by weight, if any, based on the total weight of the adhesive composition and/or slurry composition, the adhesive composition and/or slurry composition "Substantially free" of NMP. As used herein, if NMP is present in an amount (if any) of less than 0.3% by weight, based on the total weight of the adhesive composition and/or slurry composition, the adhesive composition and/or slurry composition "Basically free" of NMP. As used herein, if NMP is not present in the adhesive composition and/or the slurry composition based on the total weight of the adhesive composition and/or the Completely free of "NMP.

黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含酮類，諸如甲基乙基酮、環己酮、異佛爾酮、苯乙酮。The adhesive composition and/or the slurry composition may be substantially free, substantially free or completely free of ketones, such as methyl ethyl ketone, cyclohexanone, isophorone, acetophenone.

黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含醚類，諸如乙二醇或丙二醇之C ₁至C ₄烷基醚。 The adhesive composition and/or the slurry composition may be substantially free, substantially free, or completely free of ethers, such as _C1 to _C4 alkyl ethers of ethylene glycol or propylene glycol.

黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含氟乙烯，諸如四氟乙烯。The adhesive composition and/or the slurry composition may be substantially free, substantially free, or completely free of vinyl fluoride, such as tetrafluoroethylene.

主要含氟聚合物、次要含氟聚合物、黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含氟界面活性劑。The primary fluoropolymer, secondary fluoropolymer, adhesive composition, and/or slurry composition may be substantially free, substantially free, or completely free of fluorosurfactant.

黏合劑組合物及/或漿料組合物可實質上不含、基本上不含或完全不含矽氧烷。The adhesive composition and/or the slurry composition may be substantially free, substantially free or completely free of siloxane.

黏合劑組合物及/或漿料組合物可視情況進一步包含分散劑。分散劑可幫助使含氟聚合物及/或（若存在）導電試劑及/或電化學活性材料分散於有機介質中。存在時，分散劑可為漿料組合物黏合劑之組分。該分散劑可包含與主要含氟聚合物及/或漿料組合物之其他組分（若存在，諸如導電試劑或電化學活性材料）相容的至少一個相，且可進一步包含與有機介質相容的至少一個相。漿料組合物可包含一種、二種、三種、四種或更多種不同分散劑，且每一種分散劑可幫助分散漿料組合物之不同組分。該分散劑可包含具有與主要含氟聚合物、次要含氟聚合物及/或（若存在）導電試劑或電化學活性材料以及有機介質中之每一者相容之相的任何材料。如本文所用，術語「相容」意謂材料與其他材料形成摻混物之能力，該摻混物係實質上均質的且隨時間推移將保持實質上均質的。主要含氟聚合物及分散劑可不藉由共價鍵結合。舉例而言，該分散劑可包含含有此類相之聚合物。聚合物可呈嵌段聚合物、無規聚合物或梯度聚合物形式，其中存在於該聚合物之不同嵌段中之相分別無規地包括於整個聚合物中，或漸進地越來越密集地或越來越不密集地沿聚合物主鏈存在。該分散劑可包含任何適合聚合物以提供此用途。舉例而言，該聚合物可包含藉由使烯系不飽和單體、聚環氧化物聚合物、聚醯胺聚合物、聚氨酯聚合物、聚脲聚合物、聚醚聚合物、多元酸聚合物及聚酯聚合物等等聚合來產生之加成聚合物。該分散劑亦可充當黏合劑組合物或漿料組合物之黏合劑的額外組分。The adhesive composition and/or the slurry composition may optionally further contain a dispersant. The dispersing agent can help disperse the fluoropolymer and/or, if present, the conductive agent and/or the electrochemically active material in the organic medium. When present, the dispersant can be a component of the binder of the slurry composition. The dispersant may comprise at least one phase compatible with the primary fluoropolymer and/or other components of the slurry composition (if present, such as conductive agents or electrochemically active materials), and may further comprise a phase with an organic medium contain at least one phase. The slurry composition can contain one, two, three, four or more different dispersants, and each dispersant can help disperse the different components of the slurry composition. The dispersant may comprise any material having a phase compatible with each of the primary fluoropolymer, the secondary fluoropolymer and/or, if present, the conductive agent or electrochemically active material and the organic medium. As used herein, the term "compatible" means the ability of a material to form a blend with other materials that is substantially homogeneous and will remain substantially homogeneous over time. The primary fluoropolymer and dispersant may not be bound by covalent bonds. For example, the dispersant may comprise a polymer containing such a phase. The polymer may be in the form of a block polymer, a random polymer or a gradient polymer in which the phases present in different blocks of the polymer are included randomly throughout the polymer, respectively, or progressively denser and denser exist either more or less densely along the polymer backbone. The dispersant may contain any suitable polymer to provide this purpose. For example, the polymer can include ethylenically unsaturated monomers, polyepoxide polymers, polyamide polymers, polyurethane polymers, polyurea polymers, polyether polymers, polyacid polymers Addition polymers produced by the polymerization of polyester polymers, etc. The dispersant may also serve as an additional component of the binder of the binder composition or slurry composition.

該分散劑可包含官能基。該官能基可包含例如活性氫官能基、雜環基及其組合。如本文所用，術語「活性氫官能基」係指如藉由描述於JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 第49卷, 第3181頁（1927）中之Zerewitinoff測試確定的可與異氰酸鹽反應且包括例如羥基、一級或二級胺基、羧酸基及硫醇基的彼等基團。如本文所用，術語「雜環基」係指在其環中含有至少兩種不同元素之環基，諸如在環結構中具有至少一個除碳以外之原子（諸如氧、氮或硫）的環狀部分。雜環基之非限制性實例包括環氧化物、氮丙啶、硫環氧化物、內醯胺及內酯。另外，當加成聚合物上存在環氧化物官能基時，分散劑上之環氧化物官能基可與β-羥基官能性酸後反應。β-羥基官能性酸之非限制性實例包括檸檬酸、酒石酸及/或芳族酸，諸如3-羥基-2-萘甲酸。環氧化物官能基之開環反應將在分散劑上產生羥基官能基。The dispersant may contain functional groups. The functional groups can include, for example, active hydrogen functional groups, heterocyclic groups, and combinations thereof. As used herein, the term "active hydrogen functional group" means reactive with isocyanates as determined by the Zerewitinoff test described in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, p. 3181 (1927) and includes Such groups as hydroxyl, primary or secondary amine groups, carboxylic acid groups and thiol groups. As used herein, the term "heterocyclyl" refers to a cyclic group containing at least two different elements in its ring, such as a cyclic group having at least one atom other than carbon (such as oxygen, nitrogen, or sulfur) in the ring structure part. Non-limiting examples of heterocyclyl groups include epoxides, aziridines, sulfur epoxides, lactamides, and lactones. Additionally, when epoxide functional groups are present on the addition polymer, the epoxide functional groups on the dispersant can be post-reacted with the beta-hydroxy functional acid. Non-limiting examples of beta-hydroxy functional acids include citric acid, tartaric acid, and/or aromatic acids such as 3-hydroxy-2-naphthoic acid. The ring-opening reaction of the epoxide functional groups will produce hydroxyl functional groups on the dispersant.

當存在酸官能基時，分散劑可具有至少350 g/酸當量，諸如至少878 g/酸當量，諸如至少1,757 g/酸當量之理論酸當量，且可不超過17,570 g/酸當量，諸如不超過12,000 g/酸當量，諸如不超過7,000 g/酸當量。分散劑可具有350至17,570 g/酸當量，諸如878至12,000 g/酸當量，諸如1,757至7,000 g/酸當量之理論酸當量。When acid functional groups are present, the dispersant may have a theoretical acid equivalent of at least 350 g/acid equivalent, such as at least 878 g/acid equivalent, such as at least 1,757 g/acid equivalent, and may not exceed 17,570 g/acid equivalent, such as not more than 12,000 g/acid equivalent, such as not more than 7,000 g/acid equivalent. The dispersant may have a theoretical acid equivalent of 350 to 17,570 g/acid equivalent, such as 878 to 12,000 g/acid equivalent, such as 1,757 to 7,000 g/acid equivalent.

如上文所提及，分散劑可包含加成聚合物。加成聚合物可衍生自且包含含有一或多種諸如下文所論述之彼等α,β-烯系不飽和單體之殘基的組成單元，且可藉由使此類單體之反應混合物聚合來製備。單體之混合物可包含一或多種含活性氫基團之烯系不飽和單體。反應混合物亦可包含含有雜環基之烯系不飽和單體。如本文所用，包含雜環基之烯系不飽和單體係指具有至少一個α, β烯系不飽和基團及至少一個環狀部分的單體，該至少一個環狀部分在環結構中具有至少一個除碳之外的原子，諸如氧、氮或硫。含有雜環基之烯系不飽和單體的非限制性實例包括環氧基官能性烯系不飽和單體、乙烯基吡咯啶酮及乙烯基己內醯胺等等。反應混合物可額外包含其他烯系不飽和單體，諸如(甲基)丙烯酸之烷基酯及下文所述之其他烯系不飽和單體。As mentioned above, the dispersant may comprise an addition polymer. Addition polymers can be derived from and comprise constituent units containing residues of one or more α,β-ethylenically unsaturated monomers such as those discussed below, and can be obtained by polymerizing a reaction mixture of such monomers to prepare. The mixture of monomers may contain one or more ethylenically unsaturated monomers containing active hydrogen groups. The reaction mixture may also contain ethylenically unsaturated monomers containing heterocyclyl groups. As used herein, an ethylenically unsaturated monomer system comprising a heterocyclyl group refers to a monomer having at least one alpha, beta ethylenically unsaturated group and at least one cyclic moiety having in the ring structure At least one atom other than carbon, such as oxygen, nitrogen or sulfur. Non-limiting examples of heterocyclyl-containing ethylenically unsaturated monomers include epoxy functional ethylenically unsaturated monomers, vinylpyrrolidone, vinylcaprolactam, and the like. The reaction mixture may additionally contain other ethylenically unsaturated monomers, such as alkyl (meth)acrylic acid esters and other ethylenically unsaturated monomers described below.

加成聚合物可包含(甲基)丙烯酸聚合物，其包含含有一或多種(甲基)丙烯酸單體之殘基的組成單元。(甲基)丙烯酸聚合物可藉由使包含一或多種(甲基)丙烯酸單體及視情況存在之其他烯系不飽和單體之α,β-烯系不飽和單體之反應混合物聚合來製備。如本文所用，術語「(甲基)丙烯酸單體」係指丙烯酸、甲基丙烯酸及自其衍生之單體，包括丙烯酸及甲基丙烯酸之烷基酯及類似物。如本文所用，術語「(甲基)丙烯酸聚合物」係指衍生自一或多種(甲基)丙烯酸單體或包含含有一或多種(甲基)丙烯酸單體之殘基之組成單元的聚合物。單體之混合物可包含一或多種含活性氫基團之(甲基)丙烯酸單體、含有雜環基之烯系不飽和單體及其他烯系不飽和單體。(甲基)丙烯酸聚合物亦可使用反應混合物中之環氧基官能性烯系不飽和單體（諸如甲基丙烯酸縮水甘油酯）來製備，且所得聚合物上之環氧基官能基可與β-羥基官能性酸（諸如檸檬酸、酒石酸及/或3-羥基-2-萘甲酸）後反應以產生(甲基)丙烯酸聚合物上之羥基官能基。Addition polymers may comprise (meth)acrylic polymers comprising constituent units containing residues of one or more (meth)acrylic monomers. (Meth)acrylic polymers can be obtained by polymerizing a reaction mixture of α,β-ethylenically unsaturated monomers comprising one or more (meth)acrylic monomers and, optionally, other ethylenically unsaturated monomers preparation. As used herein, the term "(meth)acrylic monomer" refers to acrylic acid, methacrylic acid and monomers derived therefrom, including alkyl esters of acrylic acid and methacrylic acid and the like. As used herein, the term "(meth)acrylic polymer" refers to a polymer derived from one or more (meth)acrylic monomers or comprising constituent units containing residues of one or more (meth)acrylic monomers . The mixture of monomers may include one or more active hydrogen group-containing (meth)acrylic monomers, heterocyclic group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers. (Meth)acrylic polymers can also be prepared using epoxy functional ethylenically unsaturated monomers such as glycidyl methacrylate in the reaction mixture, and the epoxy functional groups on the resulting polymer can be combined with Beta-hydroxy functional acids such as citric acid, tartaric acid, and/or 3-hydroxy-2-naphthoic acid are post-reacted to produce hydroxyl functional groups on the (meth)acrylic polymer.

加成聚合物可包含含有α,β-烯系不飽和羧酸之殘基的組成單元。α,β-烯系不飽和羧酸之非限制性實例包括含有至多10個碳原子之彼等，諸如丙烯酸及甲基丙烯酸。其他不飽和酸之非限制性實例為α,β-烯系不飽和二羧酸，諸如順丁烯二酸或其酸酐、反丁烯二酸及伊康酸。又，可採用此等二羧酸之半酯。以加成聚合物之總重量計，包含α,β-烯系不飽和羧酸之殘基的組成單元可佔至少1重量%、諸如至少2重量%、諸如至少5重量%，且可不超過50重量%、諸如不超過20重量%、諸如不超過10重量%、諸如不超過5重量%。以加成聚合物之總重量計，包含α,β-烯系不飽和羧酸之殘基的組成單元可佔1%至50重量%、2%至50重量%、諸如2%至20重量%、諸如2%至10重量%、諸如2%至5重量%、諸如1%至5重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以1%至50重量%、2%至50重量%，諸如2%至20重量%、諸如2%至10重量%、諸如2%至5重量%、諸如1%至5重量%之量包含α,β-烯系不飽和羧酸。在分散劑中包括包含α,β-烯系不飽和羧酸之殘基的組成單元產生包含至少一個羧酸基之分散劑，其可有助於為分散液提供穩定性。The addition polymer may contain a constituent unit containing a residue of an α,β-ethylenically unsaturated carboxylic acid. Non-limiting examples of α,β-ethylenically unsaturated carboxylic acids include those containing up to 10 carbon atoms, such as acrylic acid and methacrylic acid. Non-limiting examples of other unsaturated acids are α,β-ethylenically unsaturated dicarboxylic acids such as maleic acid or its anhydride, fumaric acid, and itonic acid. Also, half esters of these dicarboxylic acids can be used. The constituent units comprising residues of α,β-ethylenically unsaturated carboxylic acids may account for at least 1 wt %, such as at least 2 wt %, such as at least 5 wt %, and may not exceed 50 wt %, based on the total weight of the addition polymer. % by weight, such as not more than 20% by weight, such as not more than 10% by weight, such as not more than 5% by weight. The constituent unit comprising the residue of the α,β-ethylenically unsaturated carboxylic acid may account for 1% to 50% by weight, 2% to 50% by weight, such as 2% to 20% by weight, based on the total weight of the addition polymer , such as 2% to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% by weight. The addition polymer can be derived from the reaction mixture at 1% to 50% by weight, 2% to 50% by weight, such as 2% to 20% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture The α,β-ethylenically unsaturated carboxylic acid is included in an amount such as 2% to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% by weight. Inclusion of the constituent unit containing the residue of the α,β-ethylenically unsaturated carboxylic acid in the dispersant results in a dispersant containing at least one carboxylic acid group, which can help to provide stability to the dispersion liquid.

加成聚合物可包含組成單元，該等組成單元包含(甲基)丙烯酸之烷基酯的殘基，該烷基酯在烷基中含有1至3個碳原子。在烷基中含有1至3個碳原子之(甲基)丙烯酸之烷基酯的非限制性實例包括(甲基)丙烯酸甲酯及(甲基)丙烯酸乙酯。以加成聚合物之總重量計，包含在烷基中含有1至3個碳原子之(甲基)丙烯酸之烷基酯的殘基的組成單元可佔至少20重量%，諸如至少30重量%、諸如至少40重量%、諸如至少45重量%、諸如至少50重量%，且可不超過98重量%，諸如不超過96重量%、諸如不超過90重量%、諸如不超過80重量%、諸如不超過75重量%。以加成聚合物之總重量計，包含在烷基中含有1至3個碳原子之(甲基)丙烯酸之烷基酯的殘基的組成單元可佔20至98重量%、諸如30至96重量%、諸如30至90重量%、40至90重量%、諸如40至80重量%、諸如45至75重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以20至98重量%，諸如30至96重量%、諸如30至90重量%、40至90重量%、諸如40至80重量%、諸如45至75重量%之量包含在烷基中含有1至3個碳原子之(甲基)丙烯酸之烷基酯。The addition polymer may comprise constituent units comprising residues of alkyl esters of (meth)acrylic acid containing 1 to 3 carbon atoms in the alkyl group. Non-limiting examples of alkyl esters of (meth)acrylic acid containing 1 to 3 carbon atoms in the alkyl group include methyl (meth)acrylate and ethyl (meth)acrylate. The constituent units comprising the residue of an alkyl ester of (meth)acrylic acid having 1 to 3 carbon atoms in the alkyl group may constitute at least 20% by weight, such as at least 30% by weight, based on the total weight of the addition polymer , such as at least 40% by weight, such as at least 45% by weight, such as at least 50% by weight, and may not exceed 98% by weight, such as not more than 96% by weight, such as not more than 90% by weight, such as not more than 80% by weight, such as not more than 90% by weight 75% by weight. The constituent unit comprising the residue of an alkyl ester of (meth)acrylic acid having 1 to 3 carbon atoms in the alkyl group may account for 20 to 98% by weight, such as 30 to 96% by weight, based on the total weight of the addition polymer. % by weight, such as 30 to 90% by weight, 40 to 90% by weight, such as 40 to 80% by weight, such as 45 to 75% by weight. The addition polymer can be derived from the reaction mixture at 20 to 98% by weight, such as 30 to 96% by weight, such as 30 to 90% by weight, 40% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture. The alkyl ester of (meth)acrylic acid having 1 to 3 carbon atoms in the alkyl group is contained in an amount of to 90% by weight, such as 40 to 80% by weight, such as 45 to 75% by weight.

加成聚合物可包含含有(甲基)丙烯酸之烷基酯之殘基的組成單元，該烷基酯在烷基中含有4至18個碳原子。在烷基中含有4至18個碳原子之(甲基)丙烯酸之烷基酯的非限制性實例包括(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸癸酯及(甲基)丙烯酸十二酯。以加成聚合物之總重量計，包含在烷基中含有4至18個碳原子之(甲基)丙烯酸之烷基酯的殘基的組成單元可佔至少2重量%，諸如至少5重量%、諸如至少10重量%、諸如至少15重量%、諸如至少20重量%，且可不超過70重量%，諸如不超過60重量%、諸如不超過50重量%、諸如不超過40重量%、諸如不超過35重量%。以加成聚合物之總重量計，包含在烷基中含有4至18個碳原子之(甲基)丙烯酸之烷基酯之殘基的組成單元可佔2至70重量%、諸如2至60重量%、諸如5至50重量%、10至40重量%、諸如15至35重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以2至70重量%，諸如2至60重量%、諸如5至50重量%、10至40重量%、諸如15至35重量%之量包含在烷基中含有4至18個碳原子之(甲基)丙烯酸的烷基酯。The addition polymer may contain a constituent unit containing a residue of an alkyl ester of (meth)acrylic acid, the alkyl ester having 4 to 18 carbon atoms in the alkyl group. Non-limiting examples of alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group include butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate , Isodecyl (meth)acrylate, octadecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate and dodecyl (meth)acrylate. The constituent units comprising the residue of an alkyl (meth)acrylic acid having 4 to 18 carbon atoms in the alkyl group may constitute at least 2% by weight, such as at least 5% by weight, based on the total weight of the addition polymer , such as at least 10% by weight, such as at least 15% by weight, such as at least 20% by weight, and may not exceed 70% by weight, such as not more than 60% by weight, such as not more than 50% by weight, such as not more than 40% by weight, such as not more than 40% by weight 35% by weight. The constituent unit comprising the residue of an alkyl ester of (meth)acrylic acid having 4 to 18 carbon atoms in the alkyl group may account for 2 to 70% by weight, such as 2 to 60% by weight, based on the total weight of the addition polymer. % by weight, such as 5 to 50% by weight, 10 to 40% by weight, such as 15 to 35% by weight. The addition polymer can be derived from the reaction mixture at 2 to 70% by weight, such as 2 to 60% by weight, such as 5 to 50% by weight, 10% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture. The alkyl ester of (meth)acrylic acid having 4 to 18 carbon atoms in the alkyl group is contained in an amount of to 40% by weight, such as 15 to 35% by weight.

加成聚合物可包含含有羥基烷基酯之殘基的組成單元。羥基烷基酯之非限制性實例包括(甲基)丙烯酸羥乙酯及(甲基)丙烯酸羥丙酯。以加成聚合物之總重量計，包含羥基烷基酯之殘基的組成單元可佔至少0.5重量%，諸如至少1重量%、諸如至少2重量%，且可不超過30重量%，諸如不超過20重量%、諸如不超過10重量%、諸如不超過5重量%。以加成聚合物之總重量計，包含羥基烷基酯之殘基的組成單元可佔0.5%至30重量%，諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以0.5%至30重量%，諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5重量%之量包含羥基烷基酯。在分散劑中包括包含羥基烷基酯之殘基的組成單元產生包含至少一個羥基之分散劑（儘管羥基可藉由其他方法被包括）。由包括羥基烷基酯（或藉由其他手段併入）產生的羥基可與單獨添加之包含可與羥基反應之官能基的交聯劑（諸如胺基塑膠、酚醛塑膠、聚環氧化物及封端聚異氰酸酯）反應，或在將具有可與羥基反應之基團的自交聯單體併入加成聚合物中時可與存在於加成聚合物中之N-烷氧基甲基醯胺基或封端異氰酸酯基反應。The addition polymer may contain constituent units containing residues of hydroxyalkyl esters. Non-limiting examples of hydroxyalkyl esters include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. The constituent units comprising residues of hydroxyalkyl esters may constitute at least 0.5% by weight, such as at least 1% by weight, such as at least 2% by weight, and may not exceed 30% by weight, such as not more than 30% by weight, based on the total weight of the addition polymer 20% by weight, such as not more than 10% by weight, such as not more than 5% by weight. Based on the total weight of the addition polymer, the constituent units comprising the residues of hydroxyalkyl esters may account for 0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight, 2% to 10% by weight % by weight, such as 2% to 5% by weight. The addition polymer can be derived from the reaction mixture at 0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture %, 2% to 10% by weight, such as 2% to 5% by weight, comprise the hydroxyalkyl ester. Inclusion of a constituent unit comprising a residue of a hydroxyalkyl ester in a dispersant results in a dispersant comprising at least one hydroxyl group (although the hydroxyl group may be included by other methods). Hydroxyl groups resulting from the inclusion of hydroxyalkyl esters (or incorporation by other means) can be combined with separately added crosslinkers containing functional groups reactive with polyisocyanates), or with N-alkoxymethylamides present in the addition polymer when a self-crosslinking monomer having a hydroxyl-reactive group is incorporated into the addition polymer or blocked isocyanate groups.

加成聚合物可包含組成單元，該等組成單元包含含有雜環基之烯系不飽和單體的殘基。含有雜環基之烯系不飽和單體的非限制性實例包含環氧基官能性烯系不飽和單體，諸如(甲基)丙烯酸縮水甘油酯、乙烯基吡咯啶酮及乙烯基己內醯胺等等。以加成聚合物之總重量計，包含含有雜環基之烯系不飽和單體之殘基的組成單元可佔至少0.5重量%，諸如至少1重量%、諸如至少5重量%、諸如至少8重量%，且可不超過99重量%，諸如不超過50重量%、諸如不超過40重量%、諸如不超過30重量%、諸如不超過27重量%。以加成聚合物之總重量計，包含含有雜環基之烯系不飽和單體之殘基的組成單元可佔0.5%至99重量%，諸如0.5%至50重量%、諸如1%至40重量%、諸如5%至30重量%、8%至27重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以0.5%至50重量%、諸如1%至40重量%、諸如5%至30重量%、8%至27重量%之量包含含有雜環基之烯系不飽和單體。The addition polymer may comprise constituent units comprising residues of heterocyclic group-containing ethylenically unsaturated monomers. Non-limiting examples of heterocyclyl-containing ethylenically unsaturated monomers include epoxy functional ethylenically unsaturated monomers such as glycidyl (meth)acrylate, vinylpyrrolidone, and vinylcaprolactone Amines, etc. The constituent units comprising the residue of the heterocyclic group-containing ethylenically unsaturated monomer may account for at least 0.5% by weight, such as at least 1% by weight, such as at least 5% by weight, such as at least 8% by weight, based on the total weight of the addition polymer. % by weight, and may not exceed 99% by weight, such as not more than 50% by weight, such as not more than 40% by weight, such as not more than 30% by weight, such as not more than 27% by weight. The constituent unit comprising the residue of the heterocyclic group-containing ethylenically unsaturated monomer may account for 0.5% to 99% by weight, such as 0.5% to 50% by weight, such as 1% to 40%, based on the total weight of the addition polymer. % by weight, such as 5% to 30% by weight, 8% to 27% by weight. The addition polymer can be derived from the reaction mixture at 0.5% to 50% by weight, such as 1% to 40% by weight, such as 5% to 30% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture %, 8% to 27% by weight include the heterocyclic group-containing ethylenically unsaturated monomer.

如上文所指出，加成聚合物可包含含有自交聯單體之殘基的組成單元，且加成聚合物可包含自交聯加成聚合物。如本文所用，術語「自交聯單體」係指併有可與存在於分散劑上之其他官能基反應以在分散劑或多於一種分散劑之間交聯之官能基的單體。自交聯單體之非限制性實例包括：N-烷氧基甲基(甲基)丙烯醯胺單體，諸如(甲基)丙烯醯胺及N-異丙氧基甲基(甲基)丙烯醯胺；以及含有封端異氰酸酯基之自交聯單體，諸如(甲基)丙烯酸異氰酸乙酯，其中異氰酸酯基與在固化溫度下解封之化合物反應（「封端」）。適合封端劑之實例包括ε-己內酯及甲基乙基酮肟。以加成聚合物之總重量計，包含自交聯單體之殘基的組成單元可佔至少0.5重量%，諸如至少1重量%、諸如至少2重量%，且可不超過30重量%，諸如不超過20重量%、諸如不超過10重量%、諸如不超過5重量%。以加成聚合物之總重量計，包含自交聯單體之殘基的組成單元可佔0.5%至30重量%，諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以0.5%至30重量%、諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5重量%之量包含自交聯單體。As noted above, the addition polymer may comprise constituent units containing residues of self-crosslinking monomers, and the addition polymer may comprise a self-crosslinking addition polymer. As used herein, the term "self-crosslinking monomer" refers to a monomer incorporating functional groups that can react with other functional groups present on the dispersant to crosslink between the dispersant or more than one dispersant. Non-limiting examples of self-crosslinking monomers include: N-alkoxymethyl(meth)acrylamide monomers such as (meth)acrylamide and N-isopropoxymethyl(methyl) acrylamide; and self-crosslinking monomers containing blocked isocyanate groups, such as ethyl isocyanate (meth)acrylate, in which the isocyanate groups react with compounds that unblock at the curing temperature ("blocking"). Examples of suitable capping agents include ε-caprolactone and methyl ethyl ketoxime. The constituent units comprising residues of self-crosslinking monomers may comprise at least 0.5% by weight, such as at least 1% by weight, such as at least 2% by weight, and may not exceed 30% by weight, such as not more than 30% by weight, based on the total weight of the addition polymer. More than 20% by weight, such as not more than 10% by weight, such as not more than 5% by weight. The constituent units comprising residues of self-crosslinking monomers may account for 0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight, 2% to 20% by weight, based on the total weight of the addition polymer. 10% by weight, such as 2% to 5% by weight. The addition polymer can be derived from the reaction mixture at 0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture %, 2% to 10% by weight, such as 2% to 5% by weight, comprise self-crosslinking monomers.

加成聚合物可包含組成單元，該等組成單元包含其他α,β-烯系不飽和單體之殘基。其他α,β-烯系不飽和單體之非限制性實例包括：乙烯基芳族化合物，諸如苯乙烯、α-甲基苯乙烯、α-氯苯乙烯及乙烯基甲苯；有機腈，諸如丙烯腈及甲基丙烯腈；烯丙基單體，諸如氯丙烯及氰化丙烯及單體二烯，諸如1,3-丁二烯及2-甲基-1,3-丁二烯；及(甲基)丙烯酸乙醯乙醯氧基烷基酯，諸如甲基丙烯酸乙醯乙酸乙酯（AAEM）（其可為自交聯的）。以加成聚合物之總重量計，包含其他α,β-烯系不飽和單體之殘基的組成單元可佔至少0.5重量%，諸如至少1重量%、諸如至少2重量%，且可不超過30重量%、諸如不超過20重量%、諸如不超過10重量%、諸如不超過5重量%。以加成聚合物之總重量計，包含其他α,β-烯系不飽和單體之殘基的組成單元可佔0.5%至30重量%、諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5重量%。加成聚合物可衍生自反應混合物，該反應混合物按用於反應混合物中之可聚合單體的總重量計以0.5至30重量%，諸如1%至20重量%、諸如2%至20重量%、2%至10重量%、諸如2%至5%之量包含其他α,β-烯系不飽和單體。The addition polymer may comprise constituent units comprising residues of other α,β-ethylenically unsaturated monomers. Non-limiting examples of other α,β-ethylenically unsaturated monomers include: vinyl aromatics such as styrene, α-methylstyrene, α-chlorostyrene, and vinyltoluene; organic nitriles such as propylene Nitriles and methacrylonitrile; allyl monomers, such as allyl chloride and allyl cyanide, and monomeric dienes, such as 1,3-butadiene and 2-methyl-1,3-butadiene; and ( Acetylacetoxyalkyl meth)acrylates, such as ethyl acetoacetate methacrylate (AAEM) (which may be self-crosslinking). Constituent units comprising residues of other α,β-ethylenically unsaturated monomers may account for at least 0.5% by weight, such as at least 1% by weight, such as at least 2% by weight, based on the total weight of the addition polymer, and may not exceed 30% by weight, such as not more than 20% by weight, such as not more than 10% by weight, such as not more than 5% by weight. The constituent units comprising residues of other α,β-ethylenically unsaturated monomers may account for 0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20%, based on the total weight of the addition polymer. % by weight, 2% to 10% by weight, such as 2% to 5% by weight. The addition polymer can be derived from the reaction mixture at 0.5 to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight, based on the total weight of the polymerizable monomers used in the reaction mixture , 2% to 10% by weight, such as 2% to 5%, contain other α,β-ethylenically unsaturated monomers.

該等單體及相對量可經選擇使得所得加成聚合物具有100℃或更低之Tg，通常為-50℃至+70℃，諸如-50℃至0℃。0℃以下之Tg可為確保在低溫下之可接受電池效能所需。The monomers and relative amounts can be selected such that the resulting addition polymer has a Tg of 100°C or less, typically -50°C to +70°C, such as -50°C to 0°C. A Tg below 0°C may be required to ensure acceptable cell performance at low temperatures.

加成聚合物可藉由習知自由基引發溶液聚合技術製備，其中將可聚合單體溶解於包含溶劑或溶劑混合物之第二有機介質中且在自由基引發劑存在下聚合，直至完全轉化。用於製備加成聚合物之第二有機介質可與存在於黏合劑組合物及/或漿料組合物中之有機介質相同，使得有機介質之組成不因添加加成聚合物溶液而改變。舉例而言，第二有機介質可與黏合劑組合物及/或漿料組合物之有機介質以相同比率包含相同主要溶劑及輔溶劑。或者，用於製備加成聚合物之第二有機介質可與黏合劑組合物及/或漿料組合物之有機介質不同且相異。用於產生加成聚合物之第二有機介質可包含任何適合有機溶劑或溶劑之混合物，包括上文關於有機介質所論述的彼等，諸如磷酸三乙酯。Addition polymers can be prepared by conventional free radical initiated solution polymerization techniques in which polymerizable monomers are dissolved in a second organic medium comprising a solvent or solvent mixture and polymerized in the presence of a free radical initiator until complete conversion. The second organic medium used to prepare the addition polymer can be the same as the organic medium present in the binder composition and/or the slurry composition, so that the composition of the organic medium is not altered by the addition of the addition polymer solution. For example, the second organic medium may comprise the same main solvent and co-solvent in the same ratio as the organic medium of the binder composition and/or the slurry composition. Alternatively, the second organic medium used to prepare the addition polymer can be different and distinct from the organic medium of the binder composition and/or the slurry composition. The second organic medium used to generate the addition polymer may comprise any suitable organic solvent or mixture of solvents, including those discussed above with respect to organic medium, such as triethyl phosphate.

自由基引發劑之實例為可溶於單體的混合物中的彼等引發劑，諸如偶氮二異丁腈、偶氮雙(α,γ-甲基戊腈)、過苯甲酸三級丁酯、過乙酸三級丁酯、過氧化苯甲醯、二三級丁基過氧化物及過氧化2-乙基己基碳酸三級戊酯。Examples of free radical initiators are those which are soluble in the mixture of monomers, such as azobisisobutyronitrile, azobis(α,γ-methylvaleronitrile), tertiary butyl perbenzoate , tertiary butyl peracetate, benzyl peroxide, two tertiary butyl peroxide and tertiary amyl peroxide 2-ethylhexyl carbonate.

視情況，可使用可溶於單體之混合物中的鏈轉移劑，諸如烷基硫醇，例如第三十二烷基硫醇；酮類，諸如甲基乙基酮；氯烴，諸如氯仿。鏈轉移劑提供對分子量之控制，得到具有用於各種塗層施加之所需黏度的產物。第三十二烷基硫醇較佳，因為其促成單體至聚合產物之高度轉化。Optionally, chain transfer agents that are soluble in the mixture of monomers can be used, such as alkyl mercaptans, such as thirty-dodecyl mercaptan; ketones, such as methyl ethyl ketone; chlorohydrocarbons, such as chloroform. Chain transfer agents provide control over molecular weight, resulting in products with the desired viscosity for various coating applications. Thirty-dodecyl mercaptan is preferred because it promotes a high degree of conversion of monomer to polymer product.

為了製備加成聚合物，可首先將溶劑加熱至回流，且可將含有自由基引發劑之可聚合單體的混合物緩慢添加至回流溶劑。隨後將反應混合物保持在聚合溫度下以便降低游離單體含量，諸如以可聚合單體之混合物之總重量計低於1.0%及通常低於0.5%。To prepare the addition polymer, the solvent can first be heated to reflux, and the mixture of polymerizable monomers containing the free radical initiator can be slowly added to the refluxing solvent. The reaction mixture is then maintained at the polymerization temperature in order to reduce the free monomer content, such as below 1.0% and usually below 0.5% based on the total weight of the mixture of polymerizable monomers.

對於用於本發明之黏合劑組合物及/或漿料組合物，如上文所述製備之分散劑通常具有約5000至500,000 g/mol，諸如10,000至100,000 g/mol及25,000至50,000 g/mol之重量平均分子量。For adhesive compositions and/or slurry compositions used in the present invention, dispersants prepared as described above typically have about 5000 to 500,000 g/mol, such as 10,000 to 100,000 g/mol and 25,000 to 50,000 g/mol the weight average molecular weight.

以黏合劑固體之總重量計，分散劑可以至少2重量%，諸如至少5重量%、諸如至少10重量%之量存在於黏合劑中。以黏合劑固體之總重量計，分散劑可以不超過20重量%，諸如不超過15重量%、諸如不超過10重量%、諸如不超過5重量%之量存在於黏合劑中。以黏合劑固體之總重量計，分散劑可以2%至20重量%，諸如2%至15重量%、諸如2%至10重量%、諸如2%至5重量%、諸如5%至20重量%、諸如5%至15重量%、諸如5%至10重量%、諸如10%至20重量%、諸如10%至15重量%之量存在於黏合劑中。The dispersant may be present in the binder in an amount of at least 2 wt%, such as at least 5 wt%, such as at least 10 wt%, based on the total weight of binder solids. The dispersant may be present in the binder in an amount of not more than 20% by weight, such as not more than 15% by weight, such as not more than 10% by weight, such as not more than 5% by weight, based on the total weight of the binder solids. The dispersant may be 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 2% to 5% by weight, such as 5% to 20% by weight, based on the total weight of the binder solids , such as 5% to 15% by weight, such as 5% to 10% by weight, such as 10% to 20% by weight, such as 10% to 15% by weight is present in the binder.

如上文所指出，黏合劑組合物及/或漿料組合物可視情況進一步包含用於與分散劑反應之單獨添加的交聯劑。交聯劑應可溶於或可分散於有機介質中，且可與分散劑之活性氫基團反應，諸如羧酸基及羥基（若存在）。適合交聯劑之非限制性實例包括胺基塑膠樹脂、封端聚異氰酸酯及聚環氧化物。As noted above, the adhesive composition and/or slurry composition may optionally further comprise a separately added crosslinking agent for reaction with the dispersing agent. The crosslinking agent should be soluble or dispersible in the organic medium and reactive with the active hydrogen groups of the dispersant, such as carboxylic acid groups and hydroxyl groups (if present). Non-limiting examples of suitable crosslinking agents include aminoplast resins, blocked polyisocyanates, and polyepoxides.

用作交聯劑之胺基塑膠樹脂之實例為藉由使諸如三聚氰胺或苯并胍胺之三

與甲醛反應所形成的彼等。該等反應產物含有反應性N-羥甲基。通常，該等反應基用甲醇、乙醇、丁醇（包括其混合物）醚化以使其反應性適中。關於胺基塑膠樹脂的化學製備及使用，參見「The Chemistry and Applications of Amino Crosslinking Agents or Aminoplast」,第V卷, 第II部分, 第21頁及以下, 由Oldring博士編輯; John Wiley & Sons/Cita Technology Limited, London, 1998。該等樹脂可以商標MAPRENAL ^®（諸如MAPRENAL MF980）及以商標CYMEL ^®（諸如CYMEL 303及CYMEL 1128，可購自Cytec Industries）商購。 Examples of amine-based plastic resins used as cross-linking agents are the

Those formed by reaction with formaldehyde. These reaction products contain reactive N-hydroxymethyl groups. Typically, these reactive groups are etherified with methanol, ethanol, butanol (including mixtures thereof) to moderate their reactivity. For the chemical preparation and use of aminoplast resins, see "The Chemistry and Applications of Amino Crosslinking Agents or Aminoplast", Vol. V, Part II, pp. 21 et seq., edited by Dr. Oldring; John Wiley & Sons/Cita Technology Limited, London, 1998. Such resins are commercially available under the trademark ^MAPRENAL® , such as MAPRENAL MF980, and under the trademark ^CYMEL® , such as CYMEL 303 and CYMEL 1128, available from Cytec Industries.

封端聚異氰酸酯交聯劑通常為二異氰酸酯，諸如二異氰酸甲苯酯、1,6-六亞甲基二異氰酸酯及異佛爾酮二異氰酸酯，包括其異氰酸酯基二聚體及三聚體，其中異氰酸酯基與諸如ε-己內酯及甲基乙基酮肟之物質反應（經該物質「封端」）。在固化溫度下，封端劑解封，從而暴露對與(甲基)丙烯酸聚合物相關之羥基官能性具反應性的異氰酸酯官能性。封端聚異氰酸酯交聯劑可以DESMODUR BL商購自Covestro。Blocked polyisocyanate crosslinkers are usually diisocyanates such as tolyl diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate, including their isocyanate-based dimers and trimers, where the isocyanate groups are reacted with ("capped" by) species such as ε-caprolactone and methyl ethyl ketoxime. At the curing temperature, the blocking agent deblocks, exposing isocyanate functionalities that are reactive towards the hydroxyl functionalities associated with the (meth)acrylic polymer. Blocked polyisocyanate crosslinkers are commercially available from Covestro as DESMODUR BL.

碳化二亞胺交聯劑可呈單體或聚合形式，或其混合物。碳化二亞胺交聯劑係指具有以下結構之化合物： R - N = C = N – R' 其中R及R'可各自個別地包含脂族、芳族、烷基芳族、羧酸或雜環基。市售碳化二亞胺交聯劑之實例包括例如以商標名CARBODILITE可購自Nisshinbo Chemical Inc.之交聯劑，諸如CARBODILITE V-02-L2、CARBODILITE SV-02、CARBODILITE E-02、CARBODILITE SW-12G、CARBODILITE V-10及CARBODILITE E-05。 The carbodiimide crosslinker can be in monomeric or polymeric form, or mixtures thereof. Carbodiimide crosslinking agent refers to a compound with the following structure: R - N = C = N - R' wherein R and R' may each individually comprise an aliphatic, aromatic, alkylaromatic, carboxylic acid or heterocyclic group. Examples of commercially available carbodiimide crosslinkers include, for example, those available from Nisshinbo Chemical Inc. under the tradename CARBODILITE such as CARBODILITE V-02-L2, CARBODILITE SV-02, CARBODILITE E-02, CARBODILITE SW- 12G, CARBODILITE V-10 and CARBODILITE E-05.

聚環氧化物交聯劑之實例為：含有環氧基之(甲基)丙烯酸聚合物，諸如由與其他乙烯系單體共聚合之甲基丙烯酸縮水甘油酯製備的彼等；多元酚之聚縮水甘油醚，諸如雙酚A之二縮水甘油醚；以及環脂族聚環氧化物，諸如3,4-環氧環己基甲基-3,4-環氧環己烷甲酸酯及雙(3,4-環氧基-6-甲基環己基-甲基)己二酸酯。Examples of polyepoxide crosslinkers are: (meth)acrylic polymers containing epoxy groups, such as those prepared from glycidyl methacrylate copolymerized with other vinyl monomers; polymers of polyhydric phenols Glycidyl ethers, such as the diglycidyl ether of bisphenol A; and cycloaliphatic polyepoxides, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis( 3,4-Epoxy-6-methylcyclohexyl-methyl)adipate.

除促進分散劑之交聯以外，交聯劑（包括與交聯單體及單獨添加之交聯劑相關聯的彼等交聯劑）與親水性基團（諸如分散劑之活性氫官能基）反應，從而防止該等基團吸收濕氣，此在鋰離子電池中可能係成問題的。In addition to facilitating cross-linking of the dispersant, the cross-linking agent (including those associated with the cross-linking monomers and separately added cross-linking agents) interacts with hydrophilic groups (such as the active hydrogen functionality of the dispersing agent) react, thereby preventing the groups from absorbing moisture, which can be problematic in lithium-ion batteries.

單獨添加之交聯劑可以至多15重量%，諸如1%至15重量%之量存在於黏合劑中，該重量%係以黏合劑固體之總重量計。The crosslinking agent added alone may be present in the adhesive in an amount of up to 15 wt%, such as 1% to 15 wt%, based on the total weight of the adhesive solids.

黏合劑組合物及/或漿料組合物可視情況進一步包含助黏劑。助黏劑可包含不同於上文所述之主要含氟聚合物及次要含氟聚合物的聚偏二氟乙烯共聚物、酸官能性聚烯烴或熱塑性材料。The adhesive composition and/or the slurry composition may optionally further comprise an adhesion promoter. The adhesion promoter may comprise polyvinylidene fluoride copolymers other than the primary and secondary fluoropolymers described above, acid functional polyolefins or thermoplastics.

聚偏二氟乙烯共聚物助黏劑包含含有偏二氟乙烯及以下中之至少一者之殘基的組成單元：（i）(甲基)丙烯酸；及/或（ii）(甲基)丙烯酸羥基烷基酯。(甲基)丙烯酸可包含丙烯酸、甲基丙烯酸或其組合。(甲基)丙烯酸羥基烷基酯可包含(甲基)丙烯酸C ₁至C ₅羥基烷基酯，諸如(甲基)丙烯酸羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯或其組合。此加成聚合物之可商購實例包括可購自Solvay之SOLEF 5130。聚偏二氟乙烯共聚物可分散或溶解於黏合劑組合物及/或漿料組合物之有機介質中。 The polyvinylidene fluoride copolymer adhesion promoter comprises a constituent unit containing vinylidene fluoride and residues of at least one of the following: (i) (meth)acrylic acid; and/or (ii) (meth)acrylic acid Hydroxyalkyl esters. (Meth)acrylic acid may comprise acrylic acid, methacrylic acid, or a combination thereof. The hydroxyalkyl (meth)acrylate may comprise a _C1 to _C5 hydroxyalkyl (meth)acrylate, such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate ) 2-hydroxybutyl acrylate or a combination thereof. A commercially available example of such an addition polymer includes SOLEF 5130 available from Solvay. The polyvinylidene fluoride copolymer can be dispersed or dissolved in the organic medium of the adhesive composition and/or the slurry composition.

酸官能性聚烯烴助黏劑包含乙烯-(甲基)丙烯酸共聚物，諸如乙烯-丙烯酸共聚物或乙烯-甲基丙烯酸共聚物。乙烯-丙烯酸共聚物可包含組成單元，該等組成單元包含以乙烯-丙烯酸共聚物之總重量計10至50重量%丙烯酸，諸如15至30重量%、諸如17至25重量%、諸如約20重量%及以乙烯-丙烯酸共聚物之總重量計50至90重量%乙烯，諸如70至85重量%、諸如75至83重量%、諸如80重量%。此加成聚合物之可商購實例包括可購自陶氏化學公司之PRIMACOR 5980i。Acid-functional polyolefin adhesion promoters include ethylene-(meth)acrylic acid copolymers, such as ethylene-acrylic acid copolymers or ethylene-methacrylic acid copolymers. The ethylene-acrylic acid copolymer may comprise constituent units comprising 10 to 50% by weight of acrylic acid, such as 15 to 30% by weight, such as 17 to 25% by weight, such as about 20% by weight, based on the total weight of the ethylene-acrylic acid copolymer % and 50 to 90 wt % ethylene, such as 70 to 85 wt %, such as 75 to 83 wt %, such as 80 wt %, based on the total weight of the ethylene-acrylic acid copolymer. Commercially available examples of such addition polymers include PRIMACOR 5980i available from The Dow Chemical Company.

以黏合劑固體之總重量計，助黏劑可以10%至60重量%、20%至60重量%，諸如30%至60重量%、諸如10%至50重量%、諸如15%至40重量%、諸如20%至30重量%、諸如35重量%之量存在於黏合劑組合物及/或漿料組合物中。The adhesion promoter may be 10% to 60%, 20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50% by weight, such as 15% to 40% by weight, based on the total weight of the adhesive solids , such as 20% to 30% by weight, such as 35% by weight, is present in the adhesive composition and/or the slurry composition.

由包含助黏劑之本發明之黏合劑組合物及/或漿料組合物產生的塗佈膜可具有相較於由不包括助黏劑之黏合劑組合物及/或漿料組合物產生的塗佈膜對集電器之改進的黏著力。舉例而言，使用由包含助黏劑之黏合劑組合物及/或漿料組合物產生的塗佈膜相較於由不包括助黏劑之黏合劑組合物及/或漿料組合物產生的塗佈膜可使黏著力改進至少50%，諸如至少100%、諸如至少200%、諸如至少300%、諸如至少400%。Coating films produced from the adhesive and/or slurry compositions of the present invention that include an Improved adhesion of the coating film to the current collector. For example, the use of a coated film produced from an adhesive composition and/or a slurry composition that includes an adhesion promoter is compared to that produced from an adhesive composition and/or a slurry composition that does not The coating film may improve adhesion by at least 50%, such as at least 100%, such as at least 200%, such as at least 300%, such as at least 400%.

黏合劑組合物通常具有以黏合劑組合物之總重量計30%至80重量%，諸如40%至70重量%之樹脂固體含量。如本文所用，術語「樹脂固體」可與「黏合劑固體」同義使用且包括主要含氟聚合物、次要含氟聚合物及（若存在）分散劑、助黏劑及單獨添加之交聯劑。如本文所用，術語「黏合劑組合物」係指黏合劑固體於有機介質中之分散液。主要含氟聚合物可以以下量存在於黏合劑組合物及/或漿料組合物中：30%至98重量%，諸如30%至95重量%、諸如30%至90重量%、諸如30%至85重量%、諸如30%至70重量%、諸如30%至60重量%、諸如30%至50重量%、諸如40%至98重量%、諸如40%至95重量%、諸如40%至90重量%、諸如40%至85重量%、諸如40%至70重量%、諸如40%至60重量%、諸如40%至50重量%、諸如50%至98重量%、諸如50%至95重量%、諸如50%至90重量%、諸如50%至85重量%、諸如50%至70重量%、諸如50%至60重量%、諸如65%至98重量%、諸如65%至95重量%、諸如65%至90重量%、諸如65%至85重量%、諸如65%至70重量%、諸如70%至98重量%、諸如70%至95重量%、諸如70%至90重量%、諸如70%至85重量%、諸如80%至98重量%、諸如80%至95重量%、諸如80%至90重量%、諸如80%至85重量%、諸如85%至98重量%、諸如85%至95重量%、諸如85%至90重量%、諸如90%至98重量%、諸如90%至95重量%、諸如95%至98重量%；次要含氟聚合物可以以下量存在：0.1%至35重量%，諸如0.1%至25重量%、諸如0.1%至20重量%、諸如0.1%至15重量%、諸如0.1%至10重量%、諸如0.1%至7.5重量%、諸如0.1%至5重量%、諸如0.1%至3重量%、諸如0.1%至2重量%、諸如0.1%至1重量%、諸如0.5%至35重量%、諸如0.5%至25重量%、諸如0.5%至20重量%、諸如0.5%至15重量%、諸如0.5%至10重量%、諸如0.5%至7.5重量%、諸如0.5%至5重量%、諸如0.5%至3重量%、諸如0.5%至2重量%、諸如0.5%至1重量%、諸如1%至35重量%、諸如1%至25重量%、諸如1%至20重量%、諸如1%至15重量%、諸如1%至10重量%、諸如1%至7.5重量%、諸如1%至5重量%、諸如1%至3重量%、諸如1%至2重量%、諸如2%至35重量%、諸如2%至25重量%、諸如2%至20重量%、諸如2%至15重量%、諸如2%至10重量%、諸如2%至7.5重量%、諸如2%至5重量%、諸如2%至3重量%、諸如諸如5%至35重量%、諸如5%至25重量%、諸如5%至20重量%、諸如5%至15重量%、諸如5%至10重量%、諸如5%至7.5重量%、諸如7.5%至35重量%、諸如7.5%至25重量%、諸如7.5%至20重量%、諸如7.5%至15重量%、諸如7.5%至10重量%、諸如10%至35重量%、諸如10%至25重量%、諸如15%至35重量%、諸如15%至25重量%、諸如20%至35重量%、諸如20%至25重量%、諸如25%至35重量%、諸如30%至35重量%；分散劑可視情況以以下量存在：2%至20重量%，諸如2%至15重量%、諸如2%至10重量%、諸如2%至5重量%、諸如5%至20重量%、諸如5%至15重量%、諸如5%至10重量%、諸如10%至20重量%、諸如10%至15重量%；助黏劑可視情況以以下量存在於黏合劑組合物及/或漿料組合物中：10%至60重量%、20%至60重量%，諸如30%至60重量%、諸如10%至50重量%、諸如15%至40重量%、諸如20%至30重量%、諸如35%至35重量%；且單獨添加之交聯劑可視情況以至多15重量%，諸如1%至15重量%之量存在於黏合劑中，該重量%係以黏合劑固體之總重量計。以黏合劑組合物及/或漿料組合物之總重量計，有機介質可以10%至70重量%，諸如10%至65重量%、諸如15%至60重量%、諸如15%至40重量%、諸如30%至60重量%之量存在於黏合劑組合物及/或漿料組合物中。The adhesive composition typically has a resin solids content of 30% to 80% by weight, such as 40% to 70% by weight, based on the total weight of the adhesive composition. As used herein, the term "resin solids" may be used synonymously with "binder solids" and includes primary fluoropolymer, secondary fluoropolymer and, if present, dispersants, adhesion promoters, and separately added crosslinking agents . As used herein, the term "binder composition" refers to a dispersion of binder solids in an organic medium. The primary fluoropolymer may be present in the adhesive composition and/or the slurry composition in an amount of 30% to 98% by weight, such as 30% to 95% by weight, such as 30% to 90% by weight, such as 30% to 90% by weight 85% by weight, such as 30% to 70% by weight, such as 30% to 60% by weight, such as 30% to 50% by weight, such as 40% to 98% by weight, such as 40% to 95% by weight, such as 40% to 90% by weight %, such as 40% to 85% by weight, such as 40% to 70% by weight, such as 40% to 60% by weight, such as 40% to 50% by weight, such as 50% to 98% by weight, such as 50% to 95% by weight, such as 50% to 90% by weight, such as 50% to 85% by weight, such as 50% to 70% by weight, such as 50% to 60% by weight, such as 65% to 98% by weight, such as 65% to 95% by weight, such as 65% by weight % to 90% by weight, such as 65% to 85% by weight, such as 65% to 70% by weight, such as 70% to 98% by weight, such as 70% to 95% by weight, such as 70% to 90% by weight, such as 70% to 90% by weight 85% by weight, such as 80% to 98% by weight, such as 80% to 95% by weight, such as 80% to 90% by weight, such as 80% to 85% by weight, such as 85% to 98% by weight, such as 85% to 95% by weight %, such as 85% to 90% by weight, such as 90% to 98% by weight, such as 90% to 95% by weight, such as 95% to 98% by weight; the secondary fluoropolymer may be present in the following amounts: 0.1% to 35% by weight %, such as 0.1% to 25% by weight, such as 0.1% to 20% by weight, such as 0.1% to 15% by weight, such as 0.1% to 10% by weight, such as 0.1% to 7.5% by weight, such as 0.1% to 5% by weight, such as 0.1% to 3% by weight, such as 0.1% to 2% by weight, such as 0.1% to 1% by weight, such as 0.5% to 35% by weight, such as 0.5% to 25% by weight, such as 0.5% to 20% by weight, such as 0.5 % to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 7.5% by weight, such as 0.5% to 5% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1% by weight, such as 1% to 35% by weight, such as 1% to 25% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 7.5% by weight %, such as 1% to 5% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 2% to 35% by weight, such as 2% to 25% by weight, such as 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 2% to 7.5% by weight, such as 2% to 5% by weight, such as 2% to 3% by weight, such as 5% to 35% by weight, such as 5% to 25% by weight, such as 5% to 20% by weight, such as 5% to 15% by weight, such as 5% to 1 0% by weight, such as 5% to 7.5% by weight, such as 7.5% to 35% by weight, such as 7.5% to 25% by weight, such as 7.5% to 20% by weight, such as 7.5% to 15% by weight, such as 7.5% to 10% by weight %, such as 10% to 35% by weight, such as 10% to 25% by weight, such as 15% to 35% by weight, such as 15% to 25% by weight, such as 20% to 35% by weight, such as 20% to 25% by weight, such as 25% to 35% by weight, such as 30% to 35% by weight; the dispersant may optionally be present in the following amounts: 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 2% % to 5% by weight, such as 5% to 20% by weight, such as 5% to 15% by weight, such as 5% to 10% by weight, such as 10% to 20% by weight, such as 10% to 15% by weight; is present in the adhesive composition and/or the slurry composition in the following amounts: 10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50% by weight, such as 15% to 40% by weight, such as 20% to 30% by weight, such as 35% to 35% by weight; and the cross-linking agent added separately may be present in the adhesive in an amount of up to 15% by weight, such as 1% to 15% by weight In the formulation, the wt% is based on the total weight of the binder solids. The organic medium may be 10% to 70% by weight, such as 10% to 65% by weight, such as 15% to 60% by weight, such as 15% to 40% by weight, based on the total weight of the binder composition and/or the slurry composition , is present in the adhesive composition and/or the slurry composition in an amount such as 30% to 60% by weight.

以漿料之總固體重量計，黏合劑固體可以0.1%至20重量%，諸如1%至10重量%、諸如0.5%至5.5%，諸如5%至10重量%、諸如1% 4重量%、諸如1%至3重量%、諸如1%至2重量%之量存在於漿料組合物中。Based on the total solids weight of the slurry, the binder solids may be 0.1% to 20% by weight, such as 1% to 10% by weight, such as 0.5% to 5.5%, such as 5% to 10% by weight, such as 1% 4% by weight, An amount such as 1% to 3% by weight, such as 1% to 2% by weight, is present in the slurry composition.

以漿料組合物之總固體重量計，主要含氟聚合物可以至少0.1重量%，諸如至少1重量%、諸如至少1.3重量%、諸如1.9重量%之量存在於漿料組合物中。以漿料組合物之總固體重量計，主要含氟聚合物可以不超過10重量%，諸如不超過6重量%、諸如不超過4.5重量%、諸如不超過2.9重量%之量存在於漿料組合物中。以漿料組合物之總固體重量計，主要含氟聚合物可以0.1%至10重量%，諸如0.1%至6重量%、諸如0.1%至4.5重量%、諸如0.1%至2.9重量%、諸如1%至10重量%、諸如1%至6重量%、諸如1%至4.5重量%、諸如1%至2.9重量%、諸如1.3%至10重量%、諸如1.3%至6重量%、諸如1.3%至4.5重量%、諸如1.3%至2.9重量%、諸如1.9%至10重量%、諸如1.9%至6重量%、諸如1.9%至4.5重量%、諸如1.9%至2.9重量%之量存在於漿料組合物中。The primary fluoropolymer may be present in the slurry composition in an amount of at least 0.1 wt%, such as at least 1 wt%, such as at least 1.3 wt%, such as 1.9 wt%, based on the total solids weight of the slurry composition. The primary fluoropolymer may be present in the slurry composition in an amount of not more than 10% by weight, such as not more than 6% by weight, such as not more than 4.5% by weight, such as not more than 2.9% by weight, based on the total solids weight of the slurry composition thing. The primary fluoropolymer may be from 0.1% to 10% by weight, such as 0.1% to 6% by weight, such as 0.1% to 4.5% by weight, such as 0.1% to 2.9% by weight, such as 1 % by weight, based on the total solids weight of the slurry composition % to 10% by weight, such as 1% to 6% by weight, such as 1% to 4.5% by weight, such as 1% to 2.9% by weight, such as 1.3% to 10% by weight, such as 1.3% to 6% by weight, such as 1.3% to 4.5% by weight, such as 1.3% to 2.9% by weight, such as 1.9% to 10% by weight, such as 1.9% to 6% by weight, such as 1.9% to 4.5% by weight, such as 1.9% to 2.9% by weight is present in the slurry combination thing.

以漿料組合物之總固體重量計，次要含氟聚合物可以至少0.01重量%，諸如至少0.1重量%、諸如至少0.13重量%、諸如0.19重量%之量存在於漿料組合物中。以漿料組合物之總固體重量計，次要含氟聚合物可以不超過1重量%，諸如不超過0.6重量%、諸如不超過0.45重量%、諸如不超過0.29重量%之量存在於漿料組合物中。以漿料組合物之總固體重量計，次要含氟聚合物可以0.01%至1重量%，諸如0.01%至0.6重量%、諸如0.01%至0.45重量%、諸如0.01%至0.29重量%、諸如0.1%至1重量%、諸如0.1%至0.6重量%、諸如0.1%至0.45重量%、諸如0.1%至0.29重量%、諸如0.13%至1重量%、諸如0.13%至0.6重量%、諸如0.13%至0.45重量%、諸如0.13%至0.29重量%、諸如0.19%至1重量%、諸如0.19%至0.6重量%、諸如0.19%至0.45重量%、諸如0.19%至0.29重量%之量存在於漿料組合物中。The secondary fluoropolymer may be present in the slurry composition in an amount of at least 0.01 wt%, such as at least 0.1 wt%, such as at least 0.13 wt%, such as 0.19 wt%, based on the total solids weight of the slurry composition. The secondary fluoropolymer may be present in the slurry in an amount of not more than 1% by weight, such as not more than 0.6% by weight, such as not more than 0.45% by weight, such as not more than 0.29% by weight, based on the total solids weight of the slurry composition in the composition. The secondary fluoropolymer may be from 0.01% to 1% by weight, such as 0.01% to 0.6% by weight, such as 0.01% to 0.45% by weight, such as 0.01% to 0.29% by weight, such as 0.01% to 0.29% by weight, based on the total solids weight of the slurry composition. 0.1% to 1% by weight, such as 0.1% to 0.6% by weight, such as 0.1% to 0.45% by weight, such as 0.1% to 0.29% by weight, such as 0.13% to 1% by weight, such as 0.13% to 0.6% by weight, such as 0.13% is present in the slurry in an amount of from 0.45% by weight, such as from 0.13% to 0.29% by weight, such as from 0.19% to 1% by weight, such as from 0.19% to 0.6% by weight, such as from 0.19% to 0.45% by weight, such as from 0.19% to 0.29% by weight in the composition.

以漿料組合物之總固體重量計，分散劑（若存在）可以0.1%至10重量%，諸如1%至6重量%、諸如1.3%至4.5重量%、諸如1.9%至2.9重量%之量存在於漿料組合物中。The dispersant, if present, may be in an amount of 0.1% to 10% by weight, such as 1% to 6% by weight, such as 1.3% to 4.5% by weight, such as 1.9% to 2.9% by weight, based on the total solids weight of the slurry composition present in the slurry composition.

以漿料組合物之總固體重量計，單獨添加之交聯劑可以0.001%至5重量%，諸如0.002%至2重量%、諸如0.002至1重量%、諸如0.005至0.5重量%、諸如0.005至0.3重量%、諸如0.1%至5重量%之量存在於漿料組合物中。Based on the total solids weight of the slurry composition, the crosslinking agent may be added separately at 0.001% to 5% by weight, such as 0.002% to 2% by weight, such as 0.002% to 1% by weight, such as 0.005% to 0.5% by weight, such as 0.005% to An amount of 0.3% by weight, such as 0.1% to 5% by weight, is present in the slurry composition.

漿料組合物可視情況進一步包含電化學活性材料。構成漿料中所含之電化學活性材料的材料不受特別限制，且可根據所關注蓄電裝置之類型選擇適合材料。The slurry composition may optionally further comprise an electrochemically active material. The material constituting the electrochemically active material contained in the slurry is not particularly limited, and a suitable material can be selected according to the type of the electricity storage device concerned.

電化學活性材料可包含用作用於正電極之活性材料的材料。電化學活性材料可包含能夠併有鋰（包括經由鋰嵌入/脫嵌併入）的材料、能夠進行鋰轉化的材料或其組合。能夠併有鋰之電化學活性材料的非限制性實例包括LiCoO ₂、LiNiO ₂、LiFePO ₄、LiCoPO ₄、LiMnO ₂、LiMn ₂O ₄、Li(NiMnCo)O ₂、Li(NiCoAl)O ₂、碳塗佈LiFePO ₄及其組合。能夠鋰轉化之材料的非限制性實例包括硫、LiO ₂、FeF ₂及FeF ₃、Si、鋁、錫、SnCo、Fe ₃O ₄及其組合。 Electrochemically active materials may include materials used as active materials for positive electrodes. The electrochemically active material may comprise a material capable of incorporating lithium (including incorporation via lithium intercalation/deintercalation), a material capable of lithium conversion, or a combination thereof. Non-limiting examples of electrochemically active materials capable of incorporating lithium include LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiCoPO ₄ , LiMnO ₂ , LiMn ₂ O ₄ , Li(NiMnCo)O ₂ , Li(NiCoAl)O ₂ , carbon Coating LiFePO ₄ and combinations thereof. Non _- limiting examples of materials capable of lithium conversion include sulfur, LiO2, _FeF2 , and _FeF3 , Si, aluminum, tin, _SnCo , _Fe3O4 , and combinations thereof.

電化學活性材料可包含用作用於負電極之活性材料的材料。電化學活性材料可包含石墨、鈦酸鋰、矽化合物、錫、錫化合物、硫、硫化合物或其組合。Electrochemically active materials may include materials used as active materials for negative electrodes. The electrochemically active material may comprise graphite, lithium titanate, silicon compounds, tin, tin compounds, sulfur, sulfur compounds, or combinations thereof.

以漿料之總固體重量計，電化學活性材料可以以下量存在於漿料中：45%至99重量%，諸如50%至99重量%、諸如55%至99重量%、諸如60%至99重量%、諸如65%至99重量%、諸如85%至99重量%、諸如95%至99重量%、諸如97%至99重量%、諸如98%至99重量%、諸如55至98重量%、諸如65%至98重量%、諸如70%至98重量%、諸如80%至98重量%、諸如90%至98重量%、諸如91%至98重量%、諸如91%至95重量%、諸如94%至98重量%、諸如95%至98重量%、諸如96%至98重量%。Based on the total solids weight of the slurry, the electrochemically active material may be present in the slurry in an amount from 45% to 99% by weight, such as 50% to 99% by weight, such as 55% to 99% by weight, such as 60% to 99% by weight % by weight, such as 65% to 99% by weight, such as 85% to 99% by weight, such as 95% to 99% by weight, such as 97% to 99% by weight, such as 98% to 99% by weight, such as 55% to 98% by weight, such as 65% to 98% by weight, such as 70% to 98% by weight, such as 80% to 98% by weight, such as 90% to 98% by weight, such as 91% to 98% by weight, such as 91% to 95% by weight, such as 94% % to 98% by weight, such as 95% to 98% by weight, such as 96% to 98% by weight.

本發明之漿料組合物可視情況進一步包含導電試劑。導電試劑之非限制性實例包括含碳材料，諸如活性碳，諸如乙炔黑及爐法碳黑之碳黑、石墨、石墨烯、碳奈米管、碳纖維、富勒烯及其組合。導電材料亦可包含具有高表面積之任何活性碳，諸如大於100 m ²/g之BET表面積。如本文所用，術語「BET表面積」係指根據基於期刊「The Journal of the American Chemical Society」, 60, 309 （1938）中所述之布魯諾爾-艾米特-泰勒（Brunauer-Emmett-Teller）方法的ASTM D 3663-78標準，藉由氮吸附確定之比表面積。在一些實例中，導電碳可具有100 m ²/g至1,000 m ²/g，諸如150 m ²/g至600 m ²/g、諸如100 m ²/g至400 m ²/g、諸如200 m ²/g至400 m ²/g之BET表面積。在一些實例中，導電碳可具有約200 m ²/g之BET表面積。適合導電碳材料為可商購自Cabot Corporation之LITX 200。導電碳材料可按漿料之總固體重量計以2至20重量%、通常5至10重量%之量存在於漿料中。 The slurry composition of the present invention may optionally further contain a conductive agent. Non-limiting examples of conductive agents include carbonaceous materials, such as activated carbon, carbon blacks such as acetylene black and furnace black, graphite, graphene, carbon nanotubes, carbon fibers, fullerenes, and combinations thereof. The conductive material may also comprise any activated carbon with a high surface area, such as a BET surface area of greater than 100 m ² /g. As used herein, the term "BET surface area" refers to a method based on the Brunauer-Emmett-Teller method described in the journal "The Journal of the American Chemical Society", 60, 309 (1938). ASTM D 3663-78 standard, specific surface area determined by nitrogen adsorption. In some examples, the conductive carbon can have 100 m ² /g to 1,000 m ² /g, such as 150 m ² /g to 600 m ² /g, such as 100 m ² /g to 400 m ² /g, such as 200 m 2 BET surface area of ² /g to 400 m ² /g. In some examples, the conductive carbon can have a BET surface area of about 200 m ² /g. A suitable conductive carbon material is LITX 200 commercially available from Cabot Corporation. The conductive carbon material may be present in the slurry in an amount of 2 to 20 wt %, typically 5 to 10 wt %, based on the total solids weight of the slurry.

以漿料之總固體重量計，導電試劑可以1%至20重量%，諸如5%至10重量%之量存在於漿料中。The conductive agent may be present in the slurry in an amount of 1% to 20% by weight, such as 5% to 10% by weight, based on the total solids weight of the slurry.

漿料組合物可呈包含各自如上文所述之黏合劑、電化學活性材料及導電材料的電極漿料組合物形式。電極漿料可包含以上文所述之量存在於漿料組合物中的此類材料。舉例而言，電極漿料組合物可包含以45%至95重量%，諸如70%至98重量%之量存在的電化學活性材料；以1%至20重量%，諸如1%至10重量%、諸如5%至10重量%之量存在的來自黏合劑組合物之黏合劑固體；以及以1%至20重量%，諸如5%至10重量%之量存在的導電試劑，該重量%以電極漿料組合物之總固體重量計。The slurry composition may be in the form of an electrode slurry composition comprising a binder, an electrochemically active material, and a conductive material each as described above. The electrode paste may include such materials present in the paste composition in the amounts described above. For example, the electrode slurry composition may comprise the electrochemically active material in an amount of 45% to 95% by weight, such as 70% to 98% by weight; 1% to 20% by weight, such as 1% to 10% by weight , the binder solids from the binder composition present in an amount such as 5% to 10% by weight; and the conductive agent present in an amount of 1% to 20% by weight, such as 5% to 10% by weight in the electrode The total solids weight of the slurry composition.

包含有機介質、電化學活性材料、導電材料、黏合劑分散液（其可包括單獨添加之交聯劑）、額外有機介質（若需要）及視情況選用之成分的電極漿料組合物可藉由合併該等成分以形成漿料來製備。此等物質可藉由用已知手段，諸如攪拌器、砂磨機或高壓均質機攪動而混合在一起。Electrode slurry compositions comprising organic medium, electrochemically active material, conductive material, binder dispersion (which may include a separately added cross-linking agent), additional organic medium (if desired), and optional ingredients can be obtained by Prepare by combining the ingredients to form a slurry. These materials can be mixed together by stirring with known means, such as a stirrer, sand mill or high pressure homogenizer.

關於用於製造電極漿料組合物之混合及攪動，應選擇能夠攪拌該等組分之混合器以便滿足令人滿意的分散條件。分散程度可用粒子量規量測，且較佳地進行混合及分散以確保不存在100微米或更大之聚結物。符合此條件之混合器的實例包括球磨機、混砂機、顏料分散器、研磨機、擠壓機、轉子定子、捏泥機、超音波分散器、均質機、行星混合器、霍巴特混合器及其組合。Regarding the mixing and agitation used to make the electrode slurry composition, a mixer capable of agitation of the components should be selected so as to satisfy satisfactory dispersion conditions. The degree of dispersion can be measured with a particle gauge, and mixing and dispersion are preferably performed to ensure that there are no agglomerates of 100 microns or larger. Examples of mixers that meet this condition include ball mills, sand mixers, pigment dispersers, mills, extruders, rotor stators, kneaders, ultrasonic dispersers, homogenizers, planetary mixers, Hobart mixers, and its combination.

漿料組合物可具有至少30重量%，諸如至少40重量%、諸如至少50重量%、諸如至少55%、諸如至少60%、諸如至少65%、諸如至少71%、諸如至少75%，且可不超過90重量%，諸如不超過85重量%、諸如不超過75重量%之固體含量，該重量%以漿料組合物之總重量計。漿料組合物可具有按漿料組合物之總重量計30%至90重量%，諸如40%至85重量%、諸如50%至85重量%、諸如55%至85重量%、諸如60%至85重量%、諸如65%至85重量%、諸如71%至85重量%、諸如75%至85重量%之固體含量。The slurry composition may have at least 30% by weight, such as at least 40% by weight, such as at least 50% by weight, such as at least 55%, such as at least 60%, such as at least 65%, such as at least 71%, such as at least 75%, and may not Solids content in excess of 90 wt%, such as up to 85 wt%, such as up to 75 wt%, based on the total weight of the slurry composition. The slurry composition may have 30% to 90% by weight, such as 40% to 85% by weight, such as 50% to 85% by weight, such as 55% to 85% by weight, such as 60% to 85% by weight, based on the total weight of the slurry composition. Solids content of 85% by weight, such as 65% to 85% by weight, such as 71% to 85% by weight, such as 75% to 85% by weight.

使用本發明之有機介質及黏合劑可產生比先前採用之彼等更穩定的漿料組合物。舉例而言，相比使用N-甲基吡咯啶酮（NMP）之先前漿料組合物，該漿料組合物可將儲存期限穩定性維持更長時間段。改進的儲存期限穩定性可藉由在一段時間內定期量測漿料組合物之黏度來確定。舉例而言，當量漿料組合物可用使用本發明之有機介質之一種漿料組合物及使用NMP之第二漿料組合物來製備。Use of the organic medium and binder of the present invention can result in more stable slurry compositions than those previously employed. For example, the slurry composition may maintain shelf life stability for a longer period of time than previous slurry compositions using N-methylpyrrolidone (NMP). Improved shelf life stability can be determined by periodically measuring the viscosity of the slurry composition over a period of time. For example, equivalent slurry compositions can be prepared using one slurry composition using the organic medium of the present invention and a second slurry composition using NMP.

本發明亦係關於一種包含以下之電極：集電器；及形成於該集電器上之膜，其中該膜包含：（1）電化學活性材料；及（2）包含以下之黏合劑：（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，其中該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。黏合劑可包含且衍生自本文所述之黏合劑組合物中之任一者。膜可自上文所述之電極漿料組合物沈積。電極可為正電極或負電極，且可藉由將上文所述之漿料組合物施加至集電器之表面，以形成塗佈膜且隨後乾燥及/或固化塗佈膜來製造。塗佈膜之厚度可為至少1微米，諸如1至500微米（µm），諸如1至150 µm，諸如25至150 µm，諸如30至125 µm。塗佈膜可包含交聯塗層。集電器可包含導電材料，且導電材料可包含金屬，諸如鐵、銅、鋁、鎳及其合金；以及不鏽鋼。舉例而言，集電器可包含呈網、薄片或箔形式之鋁或銅。雖然集電器之形狀及厚度不受特定限制，但集電器可具有約0.001至0.5 mm之厚度，諸如具有約0.001至0.5 mm之厚度的網、薄片或箔。The present invention also relates to an electrode comprising: a current collector; and a film formed on the current collector, wherein the film comprises: (1) an electrochemically active material; and (2) a binder comprising: (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, wherein the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one non-fluorinated chain segment and the linking group connecting the perfluoropolyether segment and the non-fluorinated segment. The adhesive may comprise and be derived from any of the adhesive compositions described herein. Films can be deposited from the electrode paste compositions described above. The electrode can be a positive electrode or a negative electrode, and can be manufactured by applying the slurry composition described above to the surface of the current collector to form a coating film and then drying and/or curing the coating film. The thickness of the coating film may be at least 1 micrometer, such as 1 to 500 micrometers (µm), such as 1 to 150 µm, such as 25 to 150 µm, such as 30 to 125 µm. The coating film may contain a cross-linked coating. The current collectors can include conductive materials, and the conductive materials can include metals such as iron, copper, aluminum, nickel, and alloys thereof; and stainless steel. For example, the current collector may comprise aluminum or copper in the form of a mesh, sheet or foil. Although the shape and thickness of the current collector are not particularly limited, the current collector may have a thickness of about 0.001 to 0.5 mm, such as a mesh, sheet or foil having a thickness of about 0.001 to 0.5 mm.

另外，集電器可在沈積漿料組合物之前經預處理組合物預處理。如本文所用，術語「預處理組合物」係指在與集電器接觸後，與集電器表面反應並在化學上改變集電器表面且與其結合以形成保護層的組合物。預處理組合物可為包含IIIB族及/或IVB族金屬之預處理組合物。如本文所用，術語「IIIB族及/或IVB族金屬」係指如例如Handbook of Chemistry and Physics, 第63版（1983）中所示的CAS元素週期表之IIIB族或IVB族中的元素。適用時，可使用金屬本身，然而亦可使用第IIIB族及/或第IVB族金屬化合物。如本文所用，術語「IIIB族及/或IVB族金屬化合物」係指包括CAS元素週期表之IIIB族或IVB族中之至少一個元素的化合物。用於預處理集電器之合適的預處理組合物及方法描述於美國專利第9,273,399號第4欄第60行至第10欄第26行中，其引用部分以引用之方式併入本文中。預處理組合物可用以處理用於產生正電極或負電極之集電器。Additionally, the current collector may be pretreated with a pretreatment composition prior to depositing the slurry composition. As used herein, the term "pretreatment composition" refers to a composition that, upon contact with a current collector, reacts with the surface of the current collector and chemically alters and binds to the surface of the current collector to form a protective layer. The pretreatment composition may be a pretreatment composition comprising Group IIIB and/or Group IVB metals. As used herein, the term "Group IIIB and/or Group IVB metal" refers to an element in Group IIIB or Group IVB of the CAS Periodic Table of the Elements as shown, for example, in the Handbook of Chemistry and Physics, 63rd Edition (1983). Where applicable, the metal itself may be used, however Group IIIB and/or Group IVB metal compounds may also be used. As used herein, the term "Group IIIB and/or Group IVB metal compound" refers to a compound that includes at least one element from Group IIIB or Group IVB of the CAS Periodic Table of Elements. Suitable pretreatment compositions and methods for pretreatment of current collectors are described in US Pat. No. 9,273,399 at column 4, line 60 to column 10, line 26, the references of which are incorporated herein by reference. The pretreatment composition can be used to treat current collectors used to create positive or negative electrodes.

將漿料組合物施加至集電器之方法不受特別限制。漿料組合物可藉由刮刀塗佈、浸塗、反向滾塗、直接滾塗、凹版塗佈、擠壓塗佈、浸塗或刷塗來施加。儘管漿料組合物之施加量不受特別限制，但在移除有機介質之後形成的塗層之厚度可為25至150微米（µm），諸如30至125 µm。The method of applying the slurry composition to the current collector is not particularly limited. The slurry composition can be applied by knife coating, dip coating, reverse roll coating, direct roll coating, gravure coating, extrusion coating, dip coating, or brush coating. Although the applied amount of the slurry composition is not particularly limited, the thickness of the coating formed after removing the organic medium may be 25 to 150 micrometers (µm), such as 30 to 125 µm.

若適用，在施加之後乾燥及/或交聯塗佈膜可例如藉由在高溫下加熱進行，諸如至少50ºC，諸如至少60ºC，諸如在50-145ºC範圍內，諸如60-120ºC，諸如65-110ºC。加熱時間將或多或少視溫度而定。通常，較高溫度需要較少固化時間。通常，固化時間為至少5分鐘，諸如5至60分鐘。溫度及時間應足以使得經固化膜中之分散劑交聯（若適用），亦即使共價鍵形成於分散劑聚合物鏈上之共反應基之間，諸如羧酸基及羥基以及胺基塑膠之N-羥甲基及/或N-羥甲基醚基、封端聚異氰酸酯交聯劑之異氰酸酯基，或就自固化分散劑而言，N-烷氧基甲基醯胺或封端異氰酸酯基。固化或交聯程度可以對諸如甲基乙基酮（MEK）之溶劑的阻抗之形式量測。如ASTM D-540293中所述執行測試。報導雙重摩擦（一次來回運動）之數目。此測試常常被稱作「MEK阻抗」。因此，分散劑及交聯劑（包含自固化分散劑及具有單獨添加之交聯劑的分散劑）與黏合劑組合物分離、沈積成膜且以加熱黏合劑膜之溫度及時間加熱。隨後使用所報導數目之雙重摩擦量測膜的MEK阻抗。因此，交聯分散劑將具有至少50次雙重摩擦（諸如至少75次雙重摩擦）之MEK阻抗。又，交聯分散劑對於下文提及之電解質之溶劑可為實質上耐溶劑的。乾燥塗層膜之其他方法包括環境溫度乾燥、微波乾燥及紅外線乾燥，且固化塗層膜之其他方法包括電子束固化及UV固化。If applicable, drying and/or cross-linking the coated film after application may be carried out, for example, by heating at an elevated temperature, such as at least 50ºC, such as at least 60ºC, such as in the range of 50-145ºC, such as 60-120ºC, such as 65-110ºC . The heating time will be more or less temperature dependent. Generally, higher temperatures require less curing time. Typically, the curing time is at least 5 minutes, such as 5 to 60 minutes. The temperature and time should be sufficient to allow the dispersant in the cured film to crosslink (if applicable), i.e., covalent bonds are formed between co-reactive groups on the dispersant polymer chain, such as carboxylic acid groups and hydroxyl groups and aminoplasts N-methylol and/or N-methylol ether groups, isocyanate groups of blocked polyisocyanate crosslinking agents, or in the case of self-curing dispersants, N-alkoxymethyl amides or blocked isocyanates base. The degree of curing or crosslinking can be measured in the form of resistance to solvents such as methyl ethyl ketone (MEK). Testing was performed as described in ASTM D-540293. Reports the number of double rubs (a back-and-forth motion). This test is often referred to as "MEK impedance". Thus, the dispersants and crosslinkers (including self-curing dispersants and dispersants with separately added crosslinkers) are separated from the adhesive composition, deposited into a film, and heated at a temperature and time that heats the adhesive film. The MEK impedance of the membrane was then measured using the reported number of double rubs. Thus, the crosslinked dispersant will have a MEK resistance of at least 50 double rubs, such as at least 75 double rubs. Also, the cross-linking dispersant may be substantially solvent resistant to the solvent of the electrolyte mentioned below. Other methods of drying the coating film include ambient temperature drying, microwave drying, and infrared drying, and other methods of curing the coating film include electron beam curing and UV curing.

在鋰離子蓄電裝置之放電期間，鋰離子可自負電極釋放且將電流攜載至正電極。此過程可包括已知為脫嵌之過程。在充電期間，鋰離子自正電極中之電化學活性材料遷移至負電極，其在負電極處嵌入存在於負電極中之電化學活性材料中。此過程可包括已知為嵌入之過程。During discharge of the lithium ion storage device, lithium ions can be released from the negative electrode and carry current to the positive electrode. This process may include a process known as de-intercalation. During charging, lithium ions migrate from the electrochemically active material in the positive electrode to the negative electrode, where they intercalate in the electrochemically active material present in the negative electrode. This process may include a process known as embedding.

本發明亦係關於一種蓄電裝置。根據本發明之蓄電裝置可藉由使用由本發明之電極漿料組合物製備的以上電極來製造。蓄電裝置包含電極、相對電極及電解質。電極、相對電極或兩者可包含本發明之電極，只要一個電極為正電極且一個電極為負電極即可。根據本發明之蓄電裝置包括電池（cell/battery）、電池組、二次電池、電容器及超級電容器。The present invention also relates to a power storage device. The electricity storage device according to the present invention can be manufactured by using the above electrode prepared from the electrode slurry composition of the present invention. The electricity storage device includes an electrode, a counter electrode, and an electrolyte. The electrode, the opposing electrode, or both may comprise the electrodes of the present invention as long as one electrode is the positive electrode and one electrode is the negative electrode. The power storage device according to the present invention includes a cell/battery, a battery pack, a secondary battery, a capacitor, and a supercapacitor.

蓄電裝置包括電解溶液，且可藉由使用諸如分隔件之部件，根據常用方法製造。作為更特定之製造方法，將負電極及正電極與其間之分隔件組裝在一起，根據電池之形狀捲起或彎曲所得總成且放入電池容器中，將電解溶液注入電池容器中，且密封電池容器。電池之形狀可如同硬幣、按鈕或薄片為圓柱形、方形或扁平的。The power storage device includes an electrolytic solution, and can be manufactured according to a common method by using a member such as a separator. As a more specific manufacturing method, the negative electrode and the positive electrode are assembled together with the separator therebetween, the resulting assembly is rolled or bent according to the shape of the battery and placed in a battery container, the electrolytic solution is injected into the battery container, and sealed battery container. The shape of the battery can be cylindrical, square or flat like a coin, button or sheet.

電解溶液可為液體或凝膠，且可有效地用於電池之電解溶液可根據負電極活性材料及正電極活性材料之類型選自用於蓄電裝置中之已知電解溶液之一。電解溶液可為含有溶解於適合溶劑中之電解質的溶液。電解質可為用於鋰離子二次電池之習知地已知鋰鹽。鋰鹽之實例包括：LiClO ₄、LiBF ₄、LiPF ₆、LiCF ₃CO ₂、LiAsF ₆、LiSbF ₆、LiB ₁₀Cl ₁₀、LiAlCl ₄、LiCl、LiBr、LiB(C ₂H ₅) ₄、LiB(C ₆H ₅) ₄、LiCF ₃SO ₃、LiCH ₃SO ₃、LiC ₄F ₉SO ₃、Li(CF ₃SO ₂) ₂N、LiB ₄CH ₃SO ₃Li及CF ₃SO ₃Li。用於溶解上文電解質之溶劑不受特定限制，且其實例包括：碳酸酯化合物，諸如碳酸伸丙酯、碳酸伸乙酯、碳酸伸丁酯、碳酸二甲酯、碳酸甲基乙酯及碳酸二乙酯；內酯化合物，諸如γ-丁基內酯；醚化合物，諸如三甲氧基甲烷、1,2-二甲氧基乙烷、二***、2-乙氧乙烷、四氫呋喃及2-甲基四氫呋喃；以及亞碸化合物，諸如二甲亞碸。電解質於電解溶液中之濃度可為0.5至3.0莫耳/公升，諸如0.7至2.0莫耳/公升。 The electrolytic solution may be a liquid or a gel, and an electrolytic solution that can be effectively used in batteries may be selected from one of known electrolytic solutions used in electrical storage devices according to the types of negative electrode active materials and positive electrode active materials. The electrolytic solution may be a solution containing an electrolyte dissolved in a suitable solvent. The electrolyte may be a conventionally known lithium salt used in lithium ion secondary batteries. Examples of lithium salts include: LiClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiB ₁₀ Cl ₁₀ , LiAlCl ₄ , LiCl , LiBr, LiB(C ₂ H ₅ ) ₄ , LiB(C ₆ H ₅ ) ₄ , LiCF ₃ SO ₃ , LiCH ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, LiB ₄ CH ₃ SO ₃ Li and CF ₃ SO ₃ Li. The solvent for dissolving the above electrolyte is not particularly limited, and examples thereof include carbonate compounds such as propylene carbonate, ethyl carbonate, butyl carbonate, dimethyl carbonate, methyl ethyl carbonate, and carbonic acid diethyl ester; lactone compounds such as γ-butyl lactone; ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and 2- Methyltetrahydrofuran; and sulfite compounds such as dimethyl sulfite. The concentration of the electrolyte in the electrolytic solution may be 0.5 to 3.0 mol/liter, such as 0.7 to 2.0 mol/liter.

如本文中所用，術語「聚合物」廣泛地指寡聚物以及均聚物及共聚物二者。術語「樹脂」可與「聚合物」互換使用。As used herein, the term "polymer" broadly refers to both oligomers and both homopolymers and copolymers. The term "resin" is used interchangeably with "polymer".

除非另有明確指示，否則術語「丙烯酸」及「丙烯酸酯」可互換使用（除非如此會改變預期含義），且包括丙烯酸、酸酐及其衍生物，諸如其C ₁-C ₅烷基酯、經低碳數烷基取代之丙烯酸（例如經C ₁-C ₂取代之丙烯酸，諸如甲基丙烯酸、2-乙基丙烯酸等）及其C ₁-C ₄烷基酯。術語「(甲基)丙烯酸」或「(甲基)丙烯酸酯」意欲涵蓋所指示材料之丙烯酸/丙烯酸酯及甲基丙烯酸/甲基丙烯酸脂形式兩者，例如(甲基)丙烯酸酯單體。術語「(甲基)丙烯酸聚合物」係指由一或多種(甲基)丙烯酸單體製備的聚合物。 Unless expressly indicated otherwise, the terms "acrylic acid" and "acrylate" are used interchangeably (unless the intended meaning would change as such), and include acrylic acid, anhydrides, and derivatives thereof, such as their _C1 - _C5 alkyl esters, via Lower alkyl substituted acrylic acids (eg C ₁ -C ₂ substituted acrylic acids such as methacrylic acid, 2-ethyl acrylic acid, etc.) and their C ₁ -C ₄ alkyl esters. The terms "(meth)acrylic" or "(meth)acrylate" are intended to encompass both the acrylic/acrylate and methacrylic/methacrylate forms of the indicated material, such as (meth)acrylate monomers. The term "(meth)acrylic polymer" refers to a polymer prepared from one or more (meth)acrylic monomers.

如本文所用，分子量係使用聚苯乙烯標準物藉由凝膠滲透層析法確定。除非另有指示，否則分子量係基於重量平均值。如本文所用，術語「重量平均分子量」或「（M _w）」意謂如使用具有Waters 410差分折射計（RI偵測器）之Waters 2695分離模組、具有580 Da至365,000 Da之分子量的線性聚苯乙烯標準、0.5 mL/min之流動速率下之作為溶離劑之二甲基甲醯胺（DMF）與0.05M溴化鋰（LiBr）及用於分離之一個Shodex Asahipak GF-510 HQ管柱（300×7.5 mm，5 µm）藉由凝膠滲透層析法（GPC）所確定的重量平均分子量（Mw）。 As used herein, molecular weight is determined by gel permeation chromatography using polystyrene standards. Molecular weights are based on weight averages unless otherwise indicated. As used herein, the term "weight average molecular weight" or "( _Mw )" means linearity with molecular weights of 580 Da to 365,000 Da as using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector). Polystyrene standards, dimethylformamide (DMF) as eluent and 0.05M lithium bromide (LiBr) at a flow rate of 0.5 mL/min, and a Shodex Asahipak GF-510 HQ column (300 M) for separation ×7.5 mm, 5 µm) weight average molecular weight (Mw) determined by gel permeation chromatography (GPC).

如本文所用，術語「玻璃轉移溫度」為根據T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956)及J. Brandrup, E. H. Immergut, Polymer Handbook 第3版, John Wiley, New York, 1989基於單體電荷之單體組成藉由Fox之方法計算的玻璃轉移溫度之理論值。As used herein, the term "glass transition temperature" is defined according to T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) and J. Brandrup, E. H. Immergut, Polymer Handbook 3rd Edition, John Wiley , New York, 1989 Theoretical value of the glass transition temperature calculated by the method of Fox based on the monomer composition of the monomer charge.

如本文所用，除非另外定義，否則術語實質上不含意謂組分以各別組合物之總重量計以低於5重量%之量存在（若有的話）。As used herein, unless otherwise defined, the term substantially free means that the components are present in an amount less than 5% by weight, if any, based on the total weight of the respective composition.

如本文所用，除非另外定義，否則術語基本上不含意謂組分以各別組合物之總重量計以低於1重量%之量存在（若有的話）。As used herein, unless otherwise defined, the term substantially free means that the components are present in an amount less than 1 wt%, if any, based on the total weight of the respective composition.

如本文所用，除非另外定義，否則術語完全不含意謂組分不存在於漿料組合物中，亦即以各別組合物之總重量計為0.00重量%。As used herein, unless otherwise defined, the term completely free means that the components are not present in the slurry composition, ie, 0.00% by weight, based on the total weight of the respective composition.

如本文所用，術語「總固體」係指本發明之漿料組合物的非揮發性組分且具體言之不包括有機介質。As used herein, the term "total solids" refers to the non-volatile components of the slurry composition of the present invention and specifically excludes organic media.

如本文所用，「基本上由……組成」包括所列舉材料或步驟以及不會實質上影響所要求的發明之基本及新穎特徵的彼等材料或步驟。As used herein, "consisting essentially of" includes the recited materials or steps as well as those materials or steps that do not materially affect the basic and novel characteristics of the claimed invention.

如本文所用，術語「由……組成」不包括未列舉之任何元素、步驟或成分。As used herein, the term "consisting of" does not include any element, step or ingredient not recited.

出於詳細描述之目的，除非其中明確相反地指定，否則應理解本發明可採用各種替代性變化形式及步驟順序。此外，除在任何操作實例中或另外指示外，所有數字（諸如表現值、量、百分比、範圍、子範圍及分數之彼等）可如同以詞「約」開始一般來閱讀，即使未明確地呈現術語亦如此。因此，除非有相反指示，否則以下說明書及隨附申請專利範圍中所闡述之數值參數為近似值，其可視藉由本發明獲得之所需特性而變化。至少，且不試圖將均等論之應用限於申請專利範圍之範疇，各數值參數至少應根據所報導之有效數位之個數且藉由應用普通捨入技術來解釋。當封閉式或開端式數值範圍描述於本文中時，數值範圍內或所涵蓋之所有數字、值、量、百分比、子範圍及分數應被視為專門包括在本申請案之初始揭示內容中且屬於該初始揭示內容，如同此等數字、值、量、百分比、子範圍及分數已在全文中明確寫出一般。For the purposes of the detailed description, unless explicitly stated to the contrary therein, it should be understood that the invention may employ various alternative modifications and sequences of steps. Furthermore, unless in any operational instance or otherwise indicated, all numbers (such as representation values, amounts, percentages, ranges, sub-ranges, and fractions, etc.) may be read as if beginning with the word "about," even if not explicitly The same goes for presentation terms. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties to be obtained by the present invention. At the very least, and without attempting to limit the application of egalitarianism to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. When closed or open numerical ranges are described herein, all numbers, values, amounts, percentages, sub-ranges, and fractions within or within the numerical range should be deemed to be specifically included in the initial disclosure of this application and pertain to this initial disclosure as if such numbers, values, amounts, percentages, subranges and fractions were expressly written throughout.

儘管闡述本發明之廣泛範疇的數值範圍及參數為近似值，但特定實施例中所闡述之數值應儘可能精確地報導。然而，任何數值均固有地含有某些必然由其各別測試量測值中發現之標凖偏差造成的誤差。Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

如本文所用，除非另有指示，否則複數術語可涵蓋其單數對應物且除非另有指示，否則反之亦然。舉例而言，儘管本文中提及「一」電化學活性材料、「一」含氟聚合物、「一」分散劑及「一」導電試劑，但可使用此等組分之組合（亦即複數個此等組分）。另外，在本申請案中，除非另外特定陳述，否則使用「或」意謂「及/或」，儘管「及/或」可明確地用於某些情況。As used herein, unless otherwise indicated, plural terms may encompass their singular counterparts and vice versa unless otherwise indicated. For example, although reference is made herein to "a" electrochemically active material, "a" fluoropolymer, "a" dispersant, and "a" conductive agent, a combination of these components (ie, a plurality of such components). Additionally, in this application, the use of "or" means "and/or" unless specifically stated otherwise, although "and/or" may be expressly used in certain circumstances.

如本文所用，「包括」、「含有」及類似術語在本申請案之上下文中理解為與「包含」同義，且因此為開端式的且並不排除額外未描述或未列舉之元素、材料、成分或方法步驟之存在。如本文所用，「由……組成」在本申請案之上下文中理解為排除任何未指定元素、成分或方法步驟之存在。如本文所用，「基本上由……組成」在本申請案之上下文中理解為包括指定元素、材料、成分或方法步驟，以及「不會實質上影響所述之以上各者的基本及新穎特徵的彼等」。儘管已以術語「包含」描述本發明之各種實施例，但基本上由……組成或由……組成之實施例亦在本發明之範疇內。As used herein, "comprising", "comprising" and similar terms are understood in the context of this application to be synonymous with "comprising" and are thus prescriptive and do not exclude additional undescribed or unrecited elements, materials, The presence of ingredients or method steps. As used herein, "consisting of" is understood in the context of this application to exclude the presence of any unspecified element, ingredient, or method step. As used herein, "consisting essentially of" is understood in the context of this application to include the specified elements, materials, components, or method steps, and "that does not materially affect the basic and novel characteristics of each of the foregoing. of them". While various embodiments of the invention have been described with the term "comprising," embodiments that consist essentially of or consist of are also within the scope of the invention.

如本文所用，術語「在……上」、「至……上」、「施加與……上」、「施加至……上」、「形成於……上」、「沈積於……上」、「沈積至……上」意謂形成、上覆、沈積或提供於表面上但不必接觸表面。舉例而言，組合物「沈積至基板上」不排除位於可電沈積塗佈組合物與基板之間的具有相同或不同組成之一或多個其他中間塗層之存在。As used herein, the terms "on", "on", "applied on", "applied on", "formed on", "deposited on" , "Deposited onto" means to form, overlie, deposit or provide on a surface without necessarily touching the surface. For example, "depositing onto a substrate" of a composition does not preclude the presence of one or more other intermediate coatings of the same or different composition between the electrodepositable coating composition and the substrate.

儘管已詳細地描述本發明之特定實例，但熟習此項技術者應瞭解，可根據本發明之全部教示對彼等細節做出各種修改及替代。因此，所揭示之特定佈置意謂僅係說明性的且並不限制本發明之範疇，本發明之範疇由隨附申請專利範圍之全部範圍及其任何及所有等效物給出。Although specific examples of the invention have been described in detail, it will be understood by those skilled in the art that various modifications and substitutions of these details can be made in light of the overall teachings of the invention. Therefore, the specific arrangements disclosed are meant to be illustrative only and not limiting of the scope of the invention, which is to be given the full scope of the appended claims and any and all equivalents thereof.

以下實例說明本發明，然而該等實例不應視為將本發明限於其細節。除非另有指示，否則以下實例中以及整個說明書中之所有份數及百分比均以重量計。實例實例 1 ：製備二羥基官能性次要含氟聚合物 The following examples illustrate the invention, however these examples should not be construed to limit the invention to its details. All parts and percentages in the following examples and throughout the specification are by weight unless otherwise indicated. EXAMPLES Example 1 : Preparation of a Dihydroxy Functional Secondary Fluoropolymer

次要含氟聚合物係由以下裝料製備：成分重量份裝料1號 TMXDI ¹ 16.9 Fluorolink E10H ² 24.8 磷酸三乙酯 ³ 208.3 裝料2號 DBTDL ⁴ 0.01 ¹TMXDI為四甲基二甲苯二異氰酸酯且可購自Allenex。 ²Fluorolink® E10H為可購自Solvay之二羥基官能性全氟聚醚。 ³磷酸三乙酯可購自Aceto公司。 ⁴DBTDL為二月桂酸二丁錫且可購自Arkema公司。 Secondary fluoropolymers were prepared from the following charges: Element parts by weight Charge No. 1 TMXDI ¹ 16.9 Fluorolink E10H ² 24.8 Triethyl Phosphate ³ 208.3 Charge No. 2 DBTDL ⁴ 0.01 ¹ TMXDI is tetramethylxylene diisocyanate and is available from Allenex. ² Fluorolink® E10H is a dihydroxy functional perfluoropolyether available from Solvay. ³ Triethyl phosphate is available from Aceto Corporation. ^4DBTDL is dibutyltin dilaurate and is available from Arkema Corporation.

將裝料1添加至1000 mL 4頸燒瓶中，該燒瓶配備有馬達驅動的不鏽鋼攪拌葉片、水冷凝器、氮氣層及帶有經由溫度回饋控制裝置連接的溫度計的加熱套。使反應混合物加熱至75℃。在75℃下，將裝料2逐滴添加至反應混合物中。添加後，將反應混合物保持在75℃下，直至IR光譜法顯示不存在特徵性NCO譜帶（2269 cm ^-1），其使用Thermo Scientific Nicolet iS5 FT-IR。在60℃下將反應產物倒出。實例 2 ：製備次要含氟聚合物 Charge 1 was added to a 1000 mL 4-neck flask equipped with a motor-driven stainless steel stirring blade, water condenser, nitrogen blanket, and heating mantle with a thermometer connected via a temperature feedback control. The reaction mixture was heated to 75°C. Charge 2 was added dropwise to the reaction mixture at 75°C. After addition, the reaction mixture was kept at 75 °C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm ⁻¹ ) using a Thermo Scientific Nicolet iS5 FT-IR. The reaction product was decanted at 60°C. Example 2 : Preparation of Secondary Fluoropolymer

次要含氟聚合物係由以下裝料製備：成分重量份裝料1號 TMXDI ¹ 91.6 磷酸三乙酯 ³ 133.69 裝料2號 DBTDL ⁴ 0.1 裝料3號 Fluorolink E10H ² 281.3 裝料4號丁醇 32.8 ¹TMXDI為四甲基二甲苯二異氰酸酯且可購自Allenex。 ²Fluorolink ® E10H可購自Solvay。 ³磷酸三乙酯可購自Aceto公司。 ⁴DBTDL為二月桂酸二丁錫且可購自Arkema公司。 Secondary fluoropolymers were prepared from the following charges: Element parts by weight Charge No. 1 TMXDI ¹ 91.6 Triethyl Phosphate ³ 133.69 Charge No. 2 DBTDL ⁴ 0.1 Charge No. 3 Fluorolink E10H ² 281.3 Charge No. 4 Butanol 32.8 ¹ TMXDI is tetramethylxylene diisocyanate and is available from Allenex. ² Fluorolink ® E10H is available from Solvay. ³ Triethyl phosphate is available from Aceto Corporation. ^4DBTDL is dibutyltin dilaurate and is available from Arkema Corporation.

將裝料1及2添加至1000 mL 4頸燒瓶中，該燒瓶配備有馬達驅動的不鏽鋼攪拌葉片、水冷凝器、氮氣層及帶有經由溫度回饋控制裝置連接的溫度計的加熱套。使反應混合物加熱至75℃。在75℃下，經30分鐘將裝料3逐滴添加至反應混合物中。添加後，使反應混合物保持在75℃下，直至停止異氰酸酯當量（NCO EQ WT=1145.30）。隨後經1小時將裝料4添加至反應混合物中。添加後，將反應混合物保持在95℃下，直至IR光譜法顯示不存在特徵性NCO譜帶（2269 cm ^-1），其使用Thermo Scientific Nicolet iS5 FT-IR。在70℃下將反應產物倒出。 製備分散劑 1 及 2 Charges 1 and 2 were added to a 1000 mL 4-neck flask equipped with a motor-driven stainless steel stirring blade, water condenser, nitrogen blanket, and heating mantle with a thermometer connected via a temperature feedback control. The reaction mixture was heated to 75°C. Charge 3 was added dropwise to the reaction mixture at 75°C over 30 minutes. After the addition, the reaction mixture was kept at 75°C until the isocyanate equivalents ceased (NCO EQ WT=1145.30). Charge 4 was then added to the reaction mixture over 1 hour. After addition, the reaction mixture was kept at 95 °C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm ⁻¹ ) using a Thermo Scientific Nicolet iS5 FT-IR. The reaction product was decanted at 70°C. Preparation of Dispersants 1 and 2

製備分散劑 1：使用下表中之成分如下製備(甲基)丙烯酸聚合物分散劑：成分量（公克（g））裝料1 丙二醇之甲醚 658.0 裝料2（預混合）甲基丙烯酸甲酯 784.8 丙烯酸2-乙基己酯 336.3 丙烯酸乙酯 435.9 丙烯酸羥基乙酯 33.2 甲基丙烯酸 33.15 裝料3（預混合）過氧化2-乙基己基碳酸三級戊酯 33.8 丙二醇之甲醚 169.6 裝料4（預混合）過氧化2-乙基己基碳酸三級戊酯 11.9 丙二醇之甲醚 169.6 裝料5 丙二醇之甲醚 584.6 Preparation of Dispersant 1 : A (meth)acrylic polymer dispersant was prepared as follows using the ingredients in the table below: Element Amount (grams (g)) Charge 1 Methyl ether of propylene glycol 658.0 Charge 2 (Premixed) methyl methacrylate 784.8 2-ethylhexyl acrylate 336.3 Ethyl acrylate 435.9 Hydroxyethyl acrylate 33.2 Methacrylate 33.15 Charge 3 (Premixed) 2-ethylhexyl peroxide tertiary amyl carbonate 33.8 Methyl ether of propylene glycol 169.6 Charge 4 (Premixed) 2-ethylhexyl peroxide tertiary amyl carbonate 11.9 Methyl ether of propylene glycol 169.6 Charge 5 Methyl ether of propylene glycol 584.6

在環境溫度下向裝備有攪拌器、回流冷凝器、溫度計、加熱套及氮入口之適合反應容器中添加裝料1。隨後使溫度升高至回流（約150℃），此時經185分鐘添加裝料3之催化劑預混合物。在裝料3開始之後五（5）分鐘，經180分鐘添加裝料2。在裝料2及3完成後，經60分鐘添加裝料4，之後在回流（約150℃）下再保持60分鐘。之後使反應溫度冷卻至40℃，且在後續30分鐘保持期內添加裝料5。由此形成之聚合產物具有52%之理論固體。Charge 1 was added to a suitable reaction vessel equipped with a stirrer, reflux condenser, thermometer, heating mantle and nitrogen inlet at ambient temperature. The temperature was then raised to reflux (about 150°C) at which time the catalyst premix of Charge 3 was added over 185 minutes. Five (5) minutes after the start of Charge 3, Charge 2 was added over 180 minutes. After Charges 2 and 3 were completed, Charge 4 was added over 60 minutes, followed by a further 60 minutes at reflux (about 150°C). The reaction temperature was then cooled to 40°C and Charge 5 was added during the subsequent 30 minute hold period. The polymer product thus formed had 52% theoretical solids.

製備分散劑 2：如下製備(甲基)丙烯酸共聚物分散劑：向四頸圓底燒瓶中添加375.4 g磷酸三乙酯（TEP），且燒瓶提供有機械攪拌葉片、熱電偶及回流冷凝器。將含有TEP溶劑之燒瓶在氮氣氛圍下加熱至120℃之設定點。使含有228.2 g甲基丙烯酸甲酯（MMA）、215.7 g丙烯酸2-乙基己酯（EHA）、58.4 g丙烯酸乙酯（EA）、58.4 g N-乙烯基吡咯啶酮（NVP）、11.5 g丙烯酸羥乙酯（HEA）及11.5 g甲基丙烯酸（MAA）之單體溶液在單獨的容器中充分混合。製備12.9 g過氧化2-乙基己基碳酸三級戊酯（Trigonox 131，可購自AkzoNobel）及61.1 g TEP的溶液且經185分鐘添加至燒瓶中。在開始添加引發劑溶液之後五分鐘，開始添加單體溶液且經180分鐘將單體溶液添加至燒瓶中。在引發劑及單體進料兩者完成後，用14.4 g TEP沖洗單體加料漏斗。隨後，經60分鐘添加4.3 g Trigonox 131及61.1 g TEP之另一溶液。在此第二引發劑進料完成後，用57.9 g TEP沖洗引發劑加料漏斗。隨後將反應混合物保持在120℃下60分鐘。在保持60分鐘後，將反應混合物冷卻且倒入適合容器中。反應產物之最終量測固體含量經確定為51.02重量%。 製備黏合劑組合物 Preparation of Dispersant 2 : A (meth)acrylic copolymer dispersant was prepared as follows: 375.4 g of triethyl phosphate (TEP) was added to a four neck round bottom flask, and the flask was provided with a mechanical stirring blade, thermocouple and reflux condenser. The flask containing TEP solvent was heated to a set point of 120°C under nitrogen atmosphere. Make contains 228.2 g methyl methacrylate (MMA), 215.7 g 2-ethylhexyl acrylate (EHA), 58.4 g ethyl acrylate (EA), 58.4 g N-vinylpyrrolidone (NVP), 11.5 g A monomer solution of hydroxyethyl acrylate (HEA) and 11.5 g of methacrylic acid (MAA) was mixed well in a separate vessel. A solution of 12.9 g of tertiary amyl peroxide 2-ethylhexyl carbonate (Trigonox 131, available from AkzoNobel) and 61.1 g of TEP was prepared and added to the flask over 185 minutes. Five minutes after the start of the addition of the initiator solution, the addition of the monomer solution began and was added to the flask over 180 minutes. After both initiator and monomer feeds were complete, the monomer addition funnel was flushed with 14.4 g of TEP. Subsequently, another solution of 4.3 g Trigonox 131 and 61.1 g TEP was added over 60 minutes. After this second initiator feed was complete, the initiator addition funnel was flushed with 57.9 g of TEP. The reaction mixture was then kept at 120°C for 60 minutes. After holding for 60 minutes, the reaction mixture was cooled and poured into suitable containers. The final measured solids content of the reaction product was determined to be 51.02 wt%. Preparing the Adhesive Composition

實例3至7之黏合劑組合物使用下表中之成分如下製備：對於各組合物，向塑膠杯中添加磷酸三乙酯（裝料1）、乙醯乙酸乙酯（裝料2）、(甲基)丙烯酸共聚物分散劑1（裝料3）、(甲基)丙烯酸共聚物分散劑2（裝料4）、實例1之次要含氟聚合物（裝料5）及/或實例2之次要含氟聚合物（裝料6）。用分散葉片攪拌混合物，直至分散劑及次要含氟聚合物完全併入溶劑中。隨後，經30至60分鐘緩慢添加聚偏二氟乙烯聚合物（裝料7，Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd.之PVDF T-1），同時用分散葉片攪拌直至PVDF完全併入混合物中。此漿料之經量測總非揮發物含量為45.00重量%。裝料成分比較實例3（g）實例4（g）實例5（g）實例6（g）實例7（g） 1 磷酸三乙酯 56.49 63.5 59.9 64.52 61.95 2 乙醯乙酸乙酯 16.5 17.83 16.5 17.83 16.5 3 分散劑1 13.26 6.63 0 6.63 0 4 分散劑2 6.7 6.7 6.7 6.7 6.7 5 實例1之次要含氟聚合物 0 0 0 3.91 7.81 6 實例2之次要含氟聚合物 0 4.93 9.85 0 0 7 PVDF T-1 57.04 57.04 57.04 57.04 57.04 The adhesive compositions of Examples 3 to 7 were prepared as follows using the ingredients in the table below: For each composition, add triethyl phosphate (charge 1), ethyl acetoacetate (charge 2), ( Meth)acrylic copolymer dispersant 1 (charge 3), (meth)acrylic copolymer dispersant 2 (charge 4), secondary fluoropolymer of example 1 (charge 5) and/or example 2 Next is the fluoropolymer (Charge 6). The mixture was stirred with a dispersing blade until the dispersant and secondary fluoropolymer were fully incorporated into the solvent. Subsequently, the polyvinylidene fluoride polymer (Charge 7, PVDF T-1 of Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd.) was slowly added over 30 to 60 minutes while stirring with a dispersing blade until the PVDF was completely incorporated into the mixture . The measured total nonvolatile content of this slurry was 45.00% by weight. charging Element Comparative Example 3 (g) Example 4 (g) Example 5 (g) Example 6 (g) Example 7 (g) 1 Triethyl Phosphate 56.49 63.5 59.9 64.52 61.95 2 Ethyl Acetate 16.5 17.83 16.5 17.83 16.5 3 Dispersant 1 13.26 6.63 0 6.63 0 4 Dispersant 2 6.7 6.7 6.7 6.7 6.7 5 Secondary Fluoropolymer of Example 1 0 0 0 3.91 7.81 6 Secondary Fluoropolymer of Example 2 0 4.93 9.85 0 0 7 PVDF T-1 57.04 57.04 57.04 57.04 57.04

黏合劑膜製備如下：向鋁箔盤中添加2 g各黏合劑組合物。隨後將盤放入溫度設定為120℃之烘箱中，且烘烤至少3小時以乾燥。 電解質浸泡 Adhesive films were prepared as follows: 2 g of each adhesive composition was added to an aluminum foil pan. The pan was then placed in an oven set at 120°C and baked for at least 3 hours to dry. Electrolyte Soak

隨後測試黏合劑膜對電解質的阻抗。如下進行電解質浸泡研究：在3:3:7比率下混合碳酸伸乙酯、碳酸伸丙酯及碳酸二甲酯，以製備電解質混合物。使用不鏽鋼葉片將黏合劑膜切割成3 mm球塊，以增大與電解質接觸之表面積。使用分析天平稱量出1 g黏合劑球塊且添加至含15 g電解質混合物之10 mL玻璃瓶中。用蓋密封瓶且將其在環境溫度下儲存1個月。The resistance of the adhesive film to the electrolyte was then tested. Electrolyte soaking studies were performed as follows: Ethylene carbonate, propylene carbonate, and dimethyl carbonate were mixed at a ratio of 3:3:7 to prepare electrolyte mixtures. The adhesive film was cut into 3 mm pellets using a stainless steel blade to increase the surface area in contact with the electrolyte. 1 g of binder pellets were weighed out using an analytical balance and added to a 10 mL glass vial containing 15 g of electrolyte mixture. The bottle was sealed with a cap and stored at ambient temperature for 1 month.

在一個月之後，自電解液混合物過濾黏合劑球塊且在烘箱中在120℃下乾燥至少3小時。隨後使用分析天平稱量黏合劑球塊且與添加至瓶中之前的球塊之原始重量相比，以確定在電解質中浸泡的重量損失。重量損失百分比藉由以下方式確定：自浸泡前球塊之重量減去浸泡後球塊之重量，將彼數值除以浸泡前球塊之重量且乘以100，確定重量損失百分比。實例3至7中之每一者的重量損失百分比提供於下表中。比較實例3 實例4 實例5 實例6 實例7 浸泡後之重量損失（%） 18.20% 11.90% 11.20% 9.70% 0.00% After one month, the binder pellets were filtered from the electrolyte mixture and dried in an oven at 120°C for at least 3 hours. The adhesive pellets were then weighed using an analytical balance and compared to the original weight of the pellets prior to addition to the bottle to determine the weight loss from soaking in the electrolyte. The percent weight loss was determined by subtracting the weight of the pellets after soaking from the weight of the pellets before soaking, dividing that value by the weight of the pellets before soaking and multiplying by 100 to determine the percent weight loss. The percent weight loss for each of Examples 3-7 is provided in the table below. Comparative Example 3 Example 4 Example 5 Example 6 Example 7 Weight loss after soaking (%) 18.20% 11.90% 11.20% 9.70% 0.00%

如上表中所示，當與不包括次要含氟聚合物之比較實例3相比時，包括本發明之次要含氟聚合物使得實例4至7中之每一者的重量損失百分比減小。As shown in the table above, the inclusion of the secondary fluoropolymer of the present invention resulted in a reduction in the percent weight loss of each of Examples 4-7 when compared to Comparative Example 3 which did not include the secondary fluoropolymer .

熟習此項技術者應瞭解，可在不脫離本文中所述及例示之寬泛的本發明概念的情況下根據上文揭示內容作出眾多修改及變化。因此，從而應理解，前述揭示內容僅為本申請案之各種例示性態樣之說明且熟習此項技術者可易於作出在本申請案及隨附申請專利範圍之精神及範疇內的眾多修改及變化。Those skilled in the art will appreciate that numerous modifications and variations can be made in light of the above disclosure without departing from the broad inventive concept described and exemplified herein. Therefore, it is thus to be understood that the foregoing disclosure is merely illustrative of various exemplary aspects of this application and that numerous modifications and variations within the spirit and scope of this application and the appended claims can be readily made by those skilled in the art. Variety.

Claims

一種黏合劑組合物，其包含：（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，其中該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。An adhesive composition comprising: (a) a primary fluoropolymer; and (b) a secondary fluoropolymer different from the primary fluoropolymer, wherein the secondary fluoropolymer comprises at least one A fluoropolyether segment, at least one non-fluorinated segment, and a linking group connecting the perfluoropolyether segment and the non-fluorinated segment.

如請求項1之黏合劑組合物，其中該鍵聯基團包含連接該全氟聚醚鏈段及該非氟化鏈段之胺基甲酸酯鍵聯基團。The adhesive composition of claim 1, wherein the linking group comprises a urethane linking group connecting the perfluoropolyether segment and the non-fluorinated segment.

如請求項1或2之黏合劑組合物，其中該次要含氟聚合物包含羥基官能性全氟聚醚之殘基及異氰酸酯基官能性非氟化化合物之殘基。The adhesive composition of claim 1 or 2, wherein the secondary fluoropolymer comprises residues of a hydroxy-functional perfluoropolyether and residues of an isocyanate-functional non-fluorinated compound.

如前述請求項中任一項之黏合劑組合物，其中該次要含氟聚合物包含至少一個活性氫官能基。The adhesive composition of any of the preceding claims, wherein the secondary fluoropolymer comprises at least one active hydrogen functional group.

如前述請求項中任一項之黏合劑組合物，其中該次要含氟聚合物包含至少一個羥基官能基。The adhesive composition of any of the preceding claims, wherein the secondary fluoropolymer comprises at least one hydroxyl functional group.

如前述請求項中任一項之黏合劑組合物，其中該次要聚合物進一步包含多氟化聚醚鏈段。The adhesive composition of any of the preceding claims, wherein the secondary polymer further comprises polyfluorinated polyether segments.

如前述請求項中任一項之黏合劑組合物，其中該次要含氟聚合物之重量平均分子量為100至10,000 g/mol，諸如100至9,000 g/mol、諸如100至7,500 g/mol，諸如100至6,000 g/mol，諸如500至10,000 g/mol，諸如500至9,000 g/mol，諸如500至7,500 g/mol，諸如500至6,000 g/mol，諸如500至3,000 g/mol，諸如500至1,800 g/mol，諸如1,000至10,000 g/mol，諸如1,000至9,000 g/mol，諸如1,000至7,500 g/mol，諸如1,000至6,000 g/mol，諸如1,000至3,000 g/mol，諸如1,000至1,800 g/mol，諸如1,200至10,000 g/mol，諸如1,200至9,000 g/mol，諸如1,200至7,500 g/mol，諸如1,200至6,000 g/mol，諸如1,200至3,000 g/mol，諸如1,200至1,800 g/mol。The adhesive composition of any of the preceding claims, wherein the secondary fluoropolymer has a weight average molecular weight of 100 to 10,000 g/mol, such as 100 to 9,000 g/mol, such as 100 to 7,500 g/mol, such as 100 to 6,000 g/mol, such as 500 to 10,000 g/mol, such as 500 to 9,000 g/mol, such as 500 to 7,500 g/mol, such as 500 to 6,000 g/mol, such as 500 to 3,000 g/mol, such as 500 to 1,800 g/mol, such as 1,000 to 10,000 g/mol, such as 1,000 to 9,000 g/mol, such as 1,000 to 7,500 g/mol, such as 1,000 to 6,000 g/mol, such as 1,000 to 3,000 g/mol, such as 1,000 to 1,800 g/mol, such as 1,200 to 10,000 g/mol, such as 1,200 to 9,000 g/mol, such as 1,200 to 7,500 g/mol, such as 1,200 to 6,000 g/mol, such as 1,200 to 3,000 g/mol, such as 1,200 to 1,800 g/mol mol.

如前述請求項中任一項之黏合劑組合物，其中非氟化鏈段與全氟聚醚鏈段之比率為0.5:1至100:1，諸如0.5:1至5:1，諸如0.5:1至4:1，諸如0.5:1至3:1，諸如0.5:1至2.5:1，諸如0.5:1至2:1，諸如0.5:1至1.5:1，諸如0.5:1至1:1，諸如1:1至100:1，諸如1:1至5:1，諸如1:1至4:1，諸如1:1至3:1，諸如1:1至2.5:1，諸如1:1至2:1，諸如1:1至1.5:1，諸如諸如1.5:1至100:1，諸如1.5:1至5:1，諸如1.5:1至4:1，諸如1.5:1至3:1，諸如1.5:1至2.5:1，諸如1.5:1至2:1，諸如2:1至100:1，諸如2:1至5:1，諸如2:1至4:1，諸如2:1至3:1，諸如2:1至2.5:1，諸如2.5:1至100:1，諸如2.5:1至5:1，諸如2.5:1至4:1，諸如2.5:1至3:1，諸如3:1至100:1，諸如3:1至5:1，諸如3:1至4:1，諸如4:1至100:1，諸如4:1至5:1，諸如5:1至100:1。The adhesive composition of any of the preceding claims, wherein the ratio of non-fluorinated segments to perfluoropolyether segments is from 0.5:1 to 100:1, such as 0.5:1 to 5:1, such as 0.5: 1 to 4:1, such as 0.5:1 to 3:1, such as 0.5:1 to 2.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.5:1, such as 0.5:1 to 1:1 , such as 1:1 to 100:1, such as 1:1 to 5:1, such as 1:1 to 4:1, such as 1:1 to 3:1, such as 1:1 to 2.5:1, such as 1:1 to 2:1, such as 1:1 to 1.5:1, such as such as 1.5:1 to 100:1, such as 1.5:1 to 5:1, such as 1.5:1 to 4:1, such as 1.5:1 to 3:1 , such as 1.5:1 to 2.5:1, such as 1.5:1 to 2:1, such as 2:1 to 100:1, such as 2:1 to 5:1, such as 2:1 to 4:1, such as 2:1 to 3:1, such as 2:1 to 2.5:1, such as 2.5:1 to 100:1, such as 2.5:1 to 5:1, such as 2.5:1 to 4:1, such as 2.5:1 to 3:1, such as 3:1 to 100:1, such as 3:1 to 5:1, such as 3:1 to 4:1, such as 4:1 to 100:1, such as 4:1 to 5:1, such as 5:1 to 100:1.

如前述請求項中任一項之黏合劑組合物，其中該次要含氟聚合物包含以下結構：

其中各R獨立地包含烷基、芳基、環烷基或環芳基，n為1至500之整數，且各R _F獨立地為(CF ₂) _m，其中m為1或2。 The adhesive composition of any preceding claim, wherein the secondary fluoropolymer comprises the structure:

wherein each R independently comprises an alkyl, aryl, cycloalkyl, or cycloaryl group, n is an integer from 1 to 500, and each R _F is independently ( _CF2 ) _m , where m is 1 or 2.

如前述請求項中任一項之黏合劑組合物，其中該主要含氟聚合物包含含有偏二氟乙烯之殘基的(共)聚合物。The adhesive composition of any of the preceding claims, wherein the primary fluoropolymer comprises a (co)polymer containing residues of vinylidene fluoride.

如前述請求項中任一項之黏合劑組合物，其中該主要含氟聚合物包含聚偏二氟乙烯聚合物。The adhesive composition of any of the preceding claims, wherein the primary fluoropolymer comprises a polyvinylidene fluoride polymer.

如前述請求項中任一項之黏合劑組合物，其進一步包含分散劑。The adhesive composition of any of the preceding claims, further comprising a dispersant.

如請求項12之黏合劑組合物，其中該分散劑包含加成聚合物。The adhesive composition of claim 12, wherein the dispersant comprises an addition polymer.

如請求項13之黏合劑組合物，其中該加成聚合物包含(甲基)丙烯酸聚合物，該(甲基)丙烯酸聚合物包含含有甲基丙烯酸甲酯之殘基的組成單元。The adhesive composition of claim 13, wherein the addition polymer comprises a (meth)acrylic polymer, and the (meth)acrylic polymer comprises a constituent unit containing a residue of methyl methacrylate.

如請求項14之黏合劑組合物，其中該(甲基)丙烯酸聚合物進一步包含含有含雜環基之烯系不飽和單體之殘基的組成單元。The adhesive composition of claim 14, wherein the (meth)acrylic polymer further comprises a constituent unit containing a residue of a heterocyclic group-containing ethylenically unsaturated monomer.

如前述請求項12至15中任一項之黏合劑組合物，其中該分散劑為自交聯的。The adhesive composition of any of the preceding claims 12 to 15, wherein the dispersant is self-crosslinking.

如前述請求項中任一項之黏合劑組合物，其中該漿料組合物進一步包含交聯劑。The adhesive composition of any of the preceding claims, wherein the slurry composition further comprises a crosslinking agent.

如前述請求項中任一項之黏合劑組合物，其進一步包含液體介質。The adhesive composition of any of the preceding claims, further comprising a liquid medium.

如請求項18之黏合劑組合物，其中該黏合劑分散於該液體介質中。The adhesive composition of claim 18, wherein the adhesive is dispersed in the liquid medium.

如請求項18或19之黏合劑組合物，其中該液體介質包含有機介質。The adhesive composition of claim 18 or 19, wherein the liquid medium comprises an organic medium.

如請求項20之黏合劑組合物，其中該有機介質具有在180℃下大於80 g/min m ²之蒸發速率。 The adhesive composition of claim 20, wherein the organic medium has an evaporation rate greater than 80 g/min m ² at 180°C.

如請求項20或21之黏合劑組合物，其中該有機介質包含丁基吡咯啶酮、磷酸三烷基酯、1,2,3-三乙醯氧基丙烷、3-甲氧基-N,N-二甲基丙醯胺、乙醯乙酸乙酯、γ-丁內酯、丙二醇甲醚、環己酮、碳酸伸丙酯、己二酸二甲酯、丙二醇甲醚乙酸酯、二元酯（DBE）、二元酯5、4-羥基-4-甲基-2-戊酮、丙二醇二乙酸酯、鄰苯二甲酸二甲酯、甲基異戊基酮、丙酸乙酯、1-乙氧基-2-丙醇、二丙二醇二甲醚、飽和及不飽和線性酮及環酮、二異丁酮、乙酸酯、三丙二醇甲醚、二乙二醇乙基醚乙酸酯或其組合。The adhesive composition of claim 20 or 21, wherein the organic medium comprises butylpyrrolidone, trialkyl phosphate, 1,2,3-triacetoxypropane, 3-methoxy-N, N-dimethylpropionamide, ethyl acetate, γ-butyrolactone, propylene glycol methyl ether, cyclohexanone, propylene carbonate, dimethyl adipate, propylene glycol methyl ether acetate, dibasic Ester (DBE), dibasic ester 5, 4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, dimethyl phthalate, methyl isoamyl ketone, ethyl propionate, 1-ethoxy-2-propanol, dipropylene glycol dimethyl ether, saturated and unsaturated linear and cyclic ketones, diisobutyl ketone, acetate, tripropylene glycol methyl ether, diethylene glycol ethyl ether acetic acid esters or combinations thereof.

如前述請求項中任一項之黏合劑組合物，其進一步包含助黏劑。The adhesive composition of any of the preceding claims, further comprising an adhesion promoter.

一種漿料組合物，其包含：如前述請求項中任一項之黏合劑組合物；電化學活性材料；及液體介質。A slurry composition comprising: the binder composition of any of the preceding claims; an electrochemically active material; and a liquid medium.

如請求項24之漿料組合物，其中該電化學活性材料包含能夠併有鋰之材料。The slurry composition of claim 24, wherein the electrochemically active material comprises a material capable of incorporating lithium.

如請求項24或25之漿料組合物，其中能夠併有鋰之材料包含LiCoO ₂、LiNiO ₂、LiFePO ₄、LiCoPO ₄、LiMnO ₂、LiMn ₂O ₄、Li(NiMnCo)O ₂、Li(NiCoAl)O ₂、碳塗佈LiFePO ₄或其組合。 The slurry composition of claim 24 or 25, wherein the material capable of incorporating lithium comprises LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiCoPO ₄ , LiMnO ₂ , LiMn ₂ O ₄ , Li(NiMnCo)O ₂ , Li(NiCoAl )O ₂ , carbon-coated LiFePO ₄ , or a combination thereof.

如請求項24之漿料組合物，其中該電化學活性材料包含能夠進行鋰轉化之材料。The slurry composition of claim 24, wherein the electrochemically active material comprises a material capable of lithium conversion.

如請求項24或27之漿料組合物，其中該能夠進行鋰轉化之材料包含硫、LiO ₂、FeF ₂、FeF ₃、鋁、Fe ₃O ₄或其組合。 The slurry composition of claim 24 or 27, wherein the material capable of lithium conversion comprises sulfur, LiO ₂ , FeF ₂ , FeF ₃ , aluminum, Fe ₃ O ₄ , or a combination thereof.

如請求項24之漿料組合物，其中該電化學活性材料包含石墨、矽化合物、錫、錫化合物、硫、硫化合物或其組合。The slurry composition of claim 24, wherein the electrochemically active material comprises graphite, silicon compounds, tin, tin compounds, sulfur, sulfur compounds, or a combination thereof.

如請求項24至28中任一項之漿料組合物，其進一步包含導電試劑。The slurry composition of any one of claims 24 to 28, further comprising a conductive agent.

如請求項30之漿料組合物，其中該導電試劑包含活性碳、乙炔黑、爐法碳黑、石墨、石墨烯、碳奈米管、碳纖維、富勒烯或其組合。The slurry composition of claim 30, wherein the conductive agent comprises activated carbon, acetylene black, furnace carbon black, graphite, graphene, carbon nanotubes, carbon fibers, fullerenes, or a combination thereof.

如請求項24至31中任一項之漿料組合物，其中該漿料實質上不含異佛爾酮。The slurry composition of any one of claims 24 to 31, wherein the slurry is substantially free of isophorone.

如請求項24至32中任一項之漿料組合物，其中該漿料實質上不含N-甲基-2-吡咯啶酮。The slurry composition of any one of claims 24 to 32, wherein the slurry is substantially free of N-methyl-2-pyrrolidone.

一種漿料組合物，其包含：如前述請求項1至23中任一項之黏合劑組合物；導電試劑；及液體介質。A slurry composition comprising: the adhesive composition according to any one of the preceding claims 1 to 23; a conductive agent; and a liquid medium.

一種電極，其包含：集電器；及形成於該集電器上之膜，其中該膜包含：（1）電化學活性材料；及（2）包含以下之黏合劑：（a）主要含氟聚合物；及（b）與該主要含氟聚合物不同之次要含氟聚合物，其中該次要含氟聚合物包含至少一個全氟聚醚鏈段、至少一個非氟化鏈段及連接該全氟聚醚鏈段及該非氟化鏈段之鍵聯基團。An electrode comprising: a current collector; and a film formed on the current collector, wherein the film comprises: (1) an electrochemically active material; and (2) a binder comprising: (a) a predominantly fluoropolymer and (b) a secondary fluoropolymer different from the primary fluoropolymer, wherein the secondary fluoropolymer comprises at least one perfluoropolyether segment, at least one non-fluorinated segment and linking the perfluoropolyether segment The fluoropolyether segment and the linking group of the non-fluorinated segment.

如請求項35之電極，其中該膜係自如請求項24至33中任一項之漿料組合物沈積。35. The electrode of claim 35, wherein the film is deposited from the slurry composition of any one of claims 24 to 33.

如請求項35或36之電極，其中該集電器（a）包含呈網、薄片或箔形式的銅或鋁。An electrode as claimed in claim 35 or 36, wherein the current collector (a) comprises copper or aluminium in the form of a mesh, sheet or foil.

如請求項35至37中任一項之電極，其中該電極包含正電極。The electrode of any one of claims 35 to 37, wherein the electrode comprises a positive electrode.

如請求項35至37中任一項之電極，其中該電極包含負電極。The electrode of any one of claims 35 to 37, wherein the electrode comprises a negative electrode.

如請求項35至39中任一項之電極，其中該膜經交聯。The electrode of any one of claims 35 to 39, wherein the membrane is cross-linked.

如請求項35至40中任一項之電極，其中該集電器經預處理組合物預處理。The electrode of any one of claims 35 to 40, wherein the current collector is pretreated with a pretreatment composition.

一種蓄電裝置，其包含：（a）如請求項35至41中任一項之電極；（b）相對電極；及（c）電解質。An electricity storage device comprising: (a) the electrode of any one of claims 35 to 41; (b) a counter electrode; and (c) an electrolyte.

如請求項42之蓄電裝置，其中該電解質（c）包含溶解於溶劑中之鋰鹽。The power storage device of claim 42, wherein the electrolyte (c) contains a lithium salt dissolved in a solvent.

如請求項43之蓄電裝置，其中該鋰鹽溶解於有機碳酸鹽中。The power storage device of claim 43, wherein the lithium salt is dissolved in an organic carbonate.

如請求項42至44中任一項之蓄電裝置，其中該蓄電裝置包含電池。The power storage device of any one of claims 42 to 44, wherein the power storage device comprises a battery.

如請求項42至44中任一項之蓄電裝置，其中該蓄電裝置包含電池組。The power storage device of any one of claims 42 to 44, wherein the power storage device comprises a battery pack.

如請求項42至44中任一項之蓄電裝置，其中該蓄電裝置包含二次電池。The power storage device of any one of claims 42 to 44, wherein the power storage device includes a secondary battery.

如請求項42至44中任一項之蓄電裝置，其中該蓄電裝置包含電容器。The power storage device of any one of claims 42 to 44, wherein the power storage device comprises a capacitor.

如請求項42至44中任一項之蓄電裝置，其中該蓄電裝置包含超級電容器。The power storage device of any one of claims 42 to 44, wherein the power storage device comprises a supercapacitor.