TWI644472B - Battery electrode or separator coating film composition, battery electrode or separator with coating film obtained using the same, and battery having the battery electrode or separator - Google Patents

Battery electrode or separator coating film composition, battery electrode or separator with coating film obtained using the same, and battery having the battery electrode or separator Download PDF

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TWI644472B
TWI644472B TW103107419A TW103107419A TWI644472B TW I644472 B TWI644472 B TW I644472B TW 103107419 A TW103107419 A TW 103107419A TW 103107419 A TW103107419 A TW 103107419A TW I644472 B TWI644472 B TW I644472B
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particles
separator
coating film
battery electrode
meth
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TW103107419A
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TW201440293A (en
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清水嘉人
上村太一
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日商協立化學產業股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

本發明之課題為提供一種電池電極或分隔板塗布膜組成物，其係可抑制捲曲(curling)之發生，並可形成具有高耐熱性的塗布膜。本發明為包含黏結劑、溶劑及黏彈性粒子的電池電極或分隔板塗布膜組成物。 An object of the present invention is to provide a coating film composition for a battery electrode or a separator, which can suppress the occurrence of curling and can form a coating film having high heat resistance. The invention is a battery electrode or separator coating film composition containing a binder, a solvent and viscoelastic particles.

Description

電池電極或分隔板塗布膜組成物、具有使用其所得塗布膜的電池電極或分隔板、及具有此電池電極或分隔板的電池 Battery electrode or separator coating film composition, battery electrode or separator with coating film obtained using the same, and battery having the battery electrode or separator

本發明係關於電池電極或分隔板塗布膜組成物、其表面具有使用前述組成物所得塗布膜的電池電極或分隔板、及具有此電池電極或分隔板的電池。 The present invention relates to a battery electrode or separator coating film composition, a battery electrode or separator having a coating film obtained using the composition on its surface, and a battery having the battery electrode or separator.

輕量、高電壓且容量亦大的鋰離子蓄電池，已一部份被實用化於作為行動電話或筆記型電腦等的可移動式機器、電動工具或車等的動力工具用電源。然而，以往的電池因來自於差的耐熱性或耐壓潰性而安全性為低，又，於製造階段混入之導電性異物刺穿分隔板而導致短路之問題。又，鋰離子蓄電池之內部電阻高，於高速率之充電及放電特性在實用上並不充分，充電及放電容量亦不充分，於長期間使用時之活性物質層之劣化亦加劇。 Lightweight, high-voltage, and large-capacity lithium-ion batteries have been practically used as power sources for mobile devices such as mobile phones and notebook computers, power tools, and power tools for cars. However, conventional batteries have low safety due to poor heat resistance or crush resistance, and conductive foreign materials mixed in the manufacturing stage penetrate the separator and cause short circuits. In addition, the lithium ion battery has a high internal resistance, and the charging and discharging characteristics at high rates are insufficient in practice, and the charging and discharging capacity is also insufficient. The deterioration of the active material layer during long-term use is also intensified.

如上述般，作為鋰離子蓄電池之無法提供充分安全性之一理由，可列舉如導電性異物之混入、樹枝狀晶之發生、電池破損等之因分隔板之絕緣性遭破壞而短路 並發熱之際，用來防止於熱暴衝導致破壞進行之構造或耐熱性尚不充分。 As mentioned above, as one of the reasons that lithium-ion batteries cannot provide sufficient safety, there may be short circuits such as the incorporation of conductive foreign matter, the occurrence of dendrites, and battery damage due to the insulation of the separator being damaged. When heat is generated, the structure or heat resistance to prevent damage caused by thermal shock is not sufficient.

作為上述問題之改善對策，已思考出對塗布於集電體的活性物質塗布層形成由氧化鋁粉末或氧化矽粉末所成的多孔質膜，以保護活性物質之從電極脫落之方法(專利文獻1)。此種多孔性保護膜會發揮抑制樹枝狀晶的發生，或多孔質膜亦作為保持電解液之層的作用，藉由此多孔性保護膜成為離子供給源而使內部電阻降低亦有助於高速率下之放電特性提高。又，該多孔性保護膜可使因伴隨著電極表面之不均勻而使電極反應集中所致之局部劣化加速獲得緩衝並均勻化，藉此亦有防止長期間使用後之活性物質層劣化之效果。 As a countermeasure to the above problems, a method of forming a porous film made of alumina powder or silicon oxide powder on an active material coating layer applied to a current collector to protect the active material from falling off the electrode has been considered (Patent Literature) 1). Such a porous protective film can suppress the occurrence of dendritic crystals, or the porous film also serves as a layer that holds the electrolyte solution. The porous protective film can be used as an ion supply source to reduce internal resistance and contribute to high The discharge characteristics at the rate are improved. In addition, the porous protective film can accelerate the buffering and homogenization of the local deterioration caused by the concentration of the electrode reaction due to the unevenness of the electrode surface, thereby preventing the degradation of the active material layer after long-term use. .

另一方面，已思考出在以接著層來接著電極與分隔板的電池中，接著層為多孔性樹脂層，利用溶劑蒸散時之路徑來連續形成多孔質的保護層之方法(專利文獻2)。藉由使液體電解液保持於如此般的多孔性樹脂層之貫穿孔中，可確保電極電解質界面的良好離子傳導性。 On the other hand, in a battery in which an electrode and a separator are adhered with an adhesive layer, the adhesive layer is a porous resin layer, and a method for continuously forming a porous protective layer using a path during solvent evaporation (Patent Document 2) has been considered. ). By keeping the liquid electrolyte in the through holes of such a porous resin layer, it is possible to ensure good ion conductivity at the electrode-electrolyte interface.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Literature]

〔專利文獻1〕日本特開平7-220759 [Patent Document 1] Japanese Patent Laid-Open No. 7-220759

〔專利文獻2〕WO1999/026307 [Patent Document 2] WO1999 / 026307

然而，專利文獻1及2中，關於形成為電極或分隔板的多孔性樹脂層係具有捲曲(curling)之發生之問題。以專利文獻1中所記載之方法時，由於電極與多孔性保護膜之彈性率及線膨脹係數之差異，因產生應力而使捲曲發生。又，以專利文獻2中所記載之方法時，溶劑之蒸散之同時由於塗膜會收縮，因於分隔板及多孔性樹脂層間產生應力，而發生捲曲。此捲曲不僅會使組裝時之操作性變差，亦為皺褶產生之因素。當產生皺褶時，電極間距離會局部性改變。因而，具有所謂產生電氣化學反應之局部化，並使電池之充放電特性或壽命降低之問題。 However, in Patent Documents 1 and 2, the porous resin layer formed as an electrode or a separator has a problem that curling occurs. In the method described in Patent Document 1, curling occurs due to a difference in the elastic modulus and the coefficient of linear expansion between the electrode and the porous protective film. In the method described in Patent Document 2, the coating film shrinks at the same time as the solvent evaporates and curls due to stress generated between the separator and the porous resin layer. This curling not only deteriorates the operability during assembly, but also causes wrinkles. When wrinkles occur, the distance between the electrodes changes locally. Therefore, there is a problem that a so-called localization of an electrochemical reaction occurs and the charge-discharge characteristics or the life of a battery are reduced.

因此，本發明之課題為提供一種電池電極或分隔板塗布膜組成物，其係可抑制捲曲之發生，並可形成具有高耐熱性的塗布膜。 Therefore, an object of the present invention is to provide a coating film composition for a battery electrode or a separator, which can suppress the occurrence of curl and can form a coating film having high heat resistance.

本發明人對於以往技術所應解決的上述問題點進行檢討之結果，發現藉由使用黏彈性粒子來作為形成塗布膜的組成物中所包含的成分，可抑制塗布膜之捲曲之發生並具有高耐熱性，且具備具有使用該塗布膜組成物所得到的塗布膜的電池電極及/或分隔板的電池，耐熱性高、內部電阻低、充電及放電循環特性優異，充電及放電容量大，長期間經多次循環充電及放電後之活性物質層之劣化小，而為長壽命。 As a result of a review of the above-mentioned problems that the present inventors should solve, the inventors have found that by using viscoelastic particles as a component included in the coating film-forming composition, the occurrence of curling of the coating film can be suppressed and has high A battery having heat resistance and a battery electrode and / or a separator having a coating film obtained by using the coating film composition has high heat resistance, low internal resistance, excellent charge and discharge cycle characteristics, and large charge and discharge capacity. The degradation of the active material layer after a long period of charge and discharge for many cycles is small and the life is long.

本發明之要旨如同下述。 The gist of the present invention is as follows.

本發明1為一種電池電極或分隔板塗布膜組成物，其係包含黏結劑、溶劑及黏彈性粒子。 The invention 1 is a battery electrode or separator coating film composition, which comprises a binder, a solvent and viscoelastic particles.

本發明2係如本發明1之電池電極或分隔板塗布膜組成物，其中，黏彈性粒子之黏彈性率較黏結劑之黏彈性率為低。 The present invention 2 is a battery electrode or separator coating film composition according to the present invention 1, wherein the viscoelasticity of the viscoelastic particles is lower than that of the binder.

本發明3係如本發明1或2之電池電極或分隔板塗布膜組成物，其中，黏彈性粒子具有形狀異向性。 The third aspect of the present invention is the battery electrode or separator coating film composition according to the first or second aspect of the present invention, wherein the viscoelastic particles have shape anisotropy.

本發明4為一種電池電極或分隔板，其係具有使用本發明1~3中任一項之電池電極或分隔板塗布膜組成物所得塗布膜。 The present invention 4 is a battery electrode or a separator, which is a coating film obtained by applying the film composition using the battery electrode or the separator of any one of the present inventions 1 to 3.

本發明5係如本發明4之電池電極或分隔板，其中，黏彈性粒子具有形狀異向性，對電池電極或分隔板之基材之收縮方向而言，黏彈性粒子之最長軸係以平行配向。 The fifth aspect of the present invention is the battery electrode or separator of the fourth aspect, wherein the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is in the contraction direction of the substrate of the battery electrode or the separator. With parallel alignment.

本發明6為一種電池，其係具有本發明5之電池電極及/或分隔板。 The present invention 6 is a battery having the battery electrode and / or the separator of the present invention 5.

藉由本發明，可提供一種電池電極或分隔板塗布膜組成物，其係可抑制捲曲之發生，並可得到具有高耐熱性的電池電極或分隔板塗布膜。藉由將具有本發明塗布膜的電池電極或分隔板使用於電池，可防止伴隨著事故造成之電池之壓壞或導電性異物之混入或熱暴衝等造成之分隔板之熔解等所致之正負極之短路。 According to the present invention, it is possible to provide a battery electrode or separator coating film composition which can suppress the occurrence of curl and can obtain a battery electrode or separator coating film having high heat resistance. By using a battery electrode or a separator plate having the coating film of the present invention in a battery, it is possible to prevent the battery from being crushed due to an accident, the mixing of conductive foreign matter, or the melting of the separator plate caused by a thermal storm. Caused by the short circuit of the positive and negative poles.

又，本發明之塗布膜係藉由成為電極或分隔板表面之電解液之保持層或電解液中之離子之去溶劑化層而減低離子傳導電阻，故發揮所謂可以高速率來充電及放電，可防止長期間經多次循環充電及放電後或在充電狀態下高溫放置時之電池特性劣化之效果。因此，本發明之電池為耐熱性高、內部電阻低、充電及放電循環特性優異，充電及放電容量大，長期間經多次循環充電及放電後之活性物質層之劣化小，而為長壽命。 In addition, the coating film of the present invention reduces the ion conduction resistance by becoming a holding layer of an electrolytic solution on the surface of an electrode or a separator or a desolvating layer of ions in the electrolytic solution, so that it can be charged and discharged at a high rate. , It can prevent the battery characteristics from deteriorating after a long period of charging and discharging for many cycles or when stored at high temperature in a charged state. Therefore, the battery of the present invention has high heat resistance, low internal resistance, excellent charge and discharge cycle characteristics, large charge and discharge capacity, and small degradation of the active material layer after a long period of charge and discharge, and has a long life. .

另一方面，作為抑制捲曲發生之方法，亦有降低黏結劑之黏彈性率之方法。然而，黏結劑係藉由黏結粒子間而具有保持多孔質構造之構造。因此，相較於使粒子具緩和應力之機能之情形時，黏結劑之應力緩和能相對為弱，耐熱性亦低。相較於此，使用黏彈性粒子的本發明之方法，由於黏彈性粒子難以變形至黏彈性粒子之變形量以上，故相較於使黏結劑之黏彈性率降低之方法，可抑制捲曲之發生，且可得到耐熱性高的塗布膜。 On the other hand, as a method of suppressing the occurrence of curl, there is also a method of reducing the viscoelasticity of the adhesive. However, the binder has a structure that maintains a porous structure by bonding between particles. Therefore, the stress relaxation energy of the adhesive is relatively weak and the heat resistance is low compared to the case where the particles have a stress relaxation function. In contrast, the method of the present invention using viscoelastic particles, because it is difficult to deform the viscoelastic particles to more than the amount of deformation of the viscoelastic particles, can reduce the occurrence of curling compared to the method of reducing the viscoelasticity of the adhesive In addition, a coating film having high heat resistance can be obtained.

又，本發明之塗布膜係藉由使具有離子傳導性的固體或凝膠含浸於多孔質構造中，亦可作為固體電解質膜或凝膠電解質膜使用。 The coating film of the present invention can be used as a solid electrolyte membrane or a gel electrolyte membrane by impregnating a porous structure with a solid or gel having ion conductivity.

1‧‧‧電池電極或分隔板塗布膜 1‧‧‧ Battery electrode or separator coating film

2‧‧‧活性物質層 2‧‧‧ active material layer

3‧‧‧集電體 3‧‧‧ current collector

4‧‧‧分隔板 4‧‧‧ divider

5‧‧‧基材之搬送方向 5‧‧‧ Transport direction of substrate

〔圖1〕圖1為具有電池電極或分隔板塗布膜的電池用電極之剖面圖。 [FIG. 1] FIG. 1 is a cross-sectional view of a battery electrode having a battery electrode or a separator coating film.

〔圖2〕圖2為具有電池電極或分隔板塗布膜的分隔板之剖面圖。 [Fig. 2] Fig. 2 is a sectional view of a separator having a battery electrode or a separator coating film.

〔圖3〕圖3為具有實施例8的塗布膜的分隔板之光學顯微鏡照片。箭頭表示基材之搬送方向。 [Fig. 3] Fig. 3 is an optical microscope photograph of a partition plate having a coating film of Example 8. [Fig. The arrows indicate the direction of transport of the substrate.

〔實施發明之的最佳形態〕 [Best Mode for Implementing Invention]

電池電極或分隔板塗布膜組成物為具有(1)黏彈性粒子、(2)黏結劑、及(3)溶劑。 The battery electrode or separator coating film composition has (1) viscoelastic particles, (2) a binder, and (3) a solvent.

〔黏彈性粒子〕 〔Viscoelastic particles〕

對於本發明之(1)黏彈性粒子進行說明。本發明中所謂「黏彈性粒子」，指具有對於應力為不可逆塑性變形之性質、與可逆彈性變形之性質之粒子。藉由使電池電極或分隔板塗布膜組成物包含黏彈性粒子，在塗布膜中，該粒子可不可逆變形，使所得到的塗布膜之黏彈性率下降。藉此，可降低與電池電極或分隔板基材之應力。在電池之製造中使用凹版塗布器等，並以捲繞式(roll to roll)來進行塗布之際，基材係以被施加張力之狀態下塗布，使乾燥之同時進行捲取。將此捲取的基材以在後續步驟裁切時，由於塗布時之張力會被放開，而亦成為捲曲之原因。塗布膜中的黏彈性粒子藉由緩和與基材之應力而可降低捲曲之發生，故即使是藉由捲繞式手段來製造電池之情形，操作性亦為良好，又，可抑制皺褶之發生。藉此，可提供 高品位的電池。 (1) The viscoelastic particles of the present invention will be described. The "viscoelastic particles" in the present invention refer to particles having properties of irreversible plastic deformation with respect to stress and properties of reversible elastic deformation. By making the battery electrode or separator coating film composition contain viscoelastic particles, the particles can be irreversibly deformed in the coating film, and the viscoelasticity of the obtained coating film is reduced. This can reduce the stress on the battery electrode or the separator substrate. When a gravure coater or the like is used in the production of a battery, and the coating is performed by a roll-to-roll method, the base material is coated in a state where tension is applied, and the substrate is wound while being dried. When the rolled substrate is cut in subsequent steps, the tension during coating will be released, which will also cause curling. The viscoelastic particles in the coating film can reduce the occurrence of curl by reducing the stress with the substrate. Therefore, even when the battery is manufactured by a winding method, the operability is good, and the wrinkle can be suppressed. occur. With this, you can provide High-grade battery.

作為黏彈性粒子之材質，可示例各種聚合物，例如聚乙烯、聚丙烯、聚苯乙烯、聚碳酸酯、聚縮醛、聚苯硫醚、液晶聚合物、聚氯乙烯、賽璐珞(celluloid)、聚乙烯醇、聚酯、聚乙酸乙烯酯、具有聚乙二醇構造的高分子、具有碳酸酯基的高分子、聚偏二氟乙烯、聚四氟乙烯、苯乙烯‧丁二烯橡膠、聚異戊二烯、氯丁二烯橡膠、丙烯酸橡膠、具有氰基的高分子、胺基甲酸酯橡膠、乙烯丙烯橡膠、表氯醇橡膠、丁二烯橡膠、氟橡膠、乙烯-乙烯醇共聚物、丙烯酸-乙烯醇共聚物、環氧樹脂、氧雜環丁烷樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、多糖類、聚醯亞胺、聚醯胺醯亞胺、聚矽氧、具有羰基的高分子(例如，具有β-二酮構造的高分子)及該等共聚物。 As the material of the viscoelastic particles, various polymers can be exemplified, such as polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celloid, Polyvinyl alcohol, polyester, polyvinyl acetate, polymer with polyethylene glycol structure, polymer with carbonate group, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, poly Isoprene, chloroprene rubber, acrylic rubber, polymers with cyano groups, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, butadiene rubber, fluorine rubber, ethylene-vinyl alcohol copolymerization Polymer, acrylic-vinyl alcohol copolymer, epoxy resin, oxetane resin, urethane resin, acrylic resin, polysaccharides, polyimide, polyimide, polysiloxane, polysiloxane Polymers having a carbonyl group (for example, polymers having a β-diketone structure) and such copolymers.

作為具有氰基的高分子衍生物，具體而言可示例如氰乙基化乙烯醇、氰乙基化羧甲基纖維素、氰乙基化聚三葡萄糖、氰乙基化纖維素、氰乙基化澱粉、氰乙基化酯化澱粉、氰乙基化糊精、氰乙基化膠原蛋白、及腈橡膠等。作為具有聚乙二醇構造的高分子衍生物，具體而言可示例如聚乙二醇丙烯酸醯胺苯乙烯共聚物、聚乙二醇聚乳酸共聚物、將聚乙二醇鏈作為側鏈的聚乙烯醇等。作為具有羰基的高分子之例，可示例如JAPAN VAM & POVAL製的D聚合物(具有羰基的PVA)、Kuraray(股)製的Isoban等。作為具有β-二酮構造的高分子， 具體而言可示例如，將乙醯乙酸烯丙酯等具有β-二酮構造的乙烯基化合物與丙烯酸酯，藉由自由基共聚合而可製作的具有β-二酮構造的聚丙烯酸酯共聚物，或進而與乙酸乙烯酯共聚合的聚乙烯醇等。作為具有碳酸酯基的高分子，具體而言可示例如聚碳酸酯、CO2-philic Co-polymer(CO2兩親分子共聚物)等。作為黏彈性粒子之材質，較佳為胺基甲酸酯樹脂及聚乙烯。 Specific examples of the polymer derivative having a cyano group include cyanoethylated vinyl alcohol, cyanoethylated carboxymethyl cellulose, cyanoethylated polytriglucose, cyanoethylated cellulose, and cyanoethyl Basic starch, cyanoethylated starch, cyanoethylated dextrin, cyanoethylated collagen, and nitrile rubber. Specific examples of the polymer derivative having a polyethylene glycol structure include a polyethylene glycol acrylamide styrene copolymer, a polyethylene glycol polylactic acid copolymer, and a polyethylene glycol chain as a side chain. Polyvinyl alcohol and so on. Examples of the polymer having a carbonyl group include a D polymer (PVA having a carbonyl group) made by JAPAN VAM & POVAL, and Isoban made by Kuraray. Specific examples of the polymer having a β-diketone structure include a vinyl compound having a β-diketone structure, such as allyl acetoacetate, and acrylate, which can be produced by radical copolymerization. A polyacrylate copolymer having a β-diketone structure, or polyvinyl alcohol copolymerized with vinyl acetate, and the like. As the polymer having a carbonate group, and specific examples may be such as polycarbonate, CO 2 -philic Co-polymer ( CO 2 molecules of amphiphilic copolymer). The material of the viscoelastic particles is preferably a urethane resin and polyethylene.

黏彈性粒子可單獨使用，亦可組合複數種使用。又，黏彈性粒子亦可為分散於分散媒(例如，水)中的分散液狀態。 Viscoelastic particles can be used alone or in combination. The viscoelastic particles may be in a state of a dispersion liquid dispersed in a dispersion medium (for example, water).

黏彈性粒子之平均粒徑，較佳為0.001~100μm之範圍，又較佳為0.01~50μm之範圍，更佳為0.05~10μm之範圍。由於可更提高塗布膜之空隙率，故黏彈性粒子之粒度分布以狹窄者為佳。即，相對於黏彈性粒子之平均粒徑，將該1/5倍設為A，該5倍設為B時，較佳為黏彈性粒子中80體積%以上為具有A~B範圍粒徑之粒子，又較佳為90體積%以上。平均粒徑及粒度分布，可例如使用雷射繞射/散射式粒度分布測定裝置來測定，具體而言可使用(股)堀場製作所製的LA-920等。黏彈性粒子可以各種習知方法來生產，可使粉碎、乳化聚合、再結晶、噴霧、或使用強制薄膜微反應器來製作。 The average particle diameter of the viscoelastic particles is preferably in the range of 0.001 to 100 μm, more preferably in the range of 0.01 to 50 μm, and more preferably in the range of 0.05 to 10 μm. Since the porosity of the coating film can be further increased, the particle size distribution of the viscoelastic particles is preferably narrow. That is, with respect to the average particle diameter of the viscoelastic particles, when the 1/5 times is set to A and the 5 times is set to B, it is preferable that 80% by volume or more of the viscoelastic particles have a particle size ranging from A to B. The particles are more preferably 90% by volume or more. The average particle diameter and particle size distribution can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device, and specifically, LA-920 manufactured by Horiba, etc. can be used. Viscoelastic particles can be produced by various conventional methods, such as pulverization, emulsion polymerization, recrystallization, spraying, or using a forced thin film microreactor.

黏彈性粒子之形狀未特別限定。黏彈性粒子，可舉例具有形狀等向性或形狀異向性的黏彈性粒子。本發明中，黏彈性粒子以具有形狀異向性者為佳。 The shape of the viscoelastic particles is not particularly limited. Examples of the viscoelastic particles include viscoelastic particles having shape isotropy or shape anisotropy. In the present invention, the viscoelastic particles are preferably those having shape anisotropy.

當黏彈性粒子具有形狀異向性時，將包含具有形狀異向性的黏彈性粒子的電極電池或分隔板塗布膜組成物予以塗布至電池電極或分隔板之基材之際，藉由塗布時的剪切力，可使具有形狀異向性的黏彈性粒子朝塗布之流動方向配向。又，外加磁場或電場等，可使黏彈性粒子之最長軸，以對電池電極或分隔板之基材之收縮方向而言為平行之方式來配向。藉此，可使伴隨於該粒子之變形之應力緩和能更為提高，同時可使塗布層中的細孔配向，而可進而提高電池特性。 When the viscoelastic particles have shape anisotropy, an electrode cell or separator coating film composition containing viscoelastic particles having shape anisotropy is applied to the base material of the battery electrode or the separator. The shearing force during coating can align the viscoelastic particles with shape anisotropy in the flow direction of coating. In addition, by applying a magnetic field or an electric field, the longest axis of the viscoelastic particles can be aligned so as to be parallel to the contraction direction of the substrate of the battery electrode or the separator. Thereby, the stress relaxation accompanying the deformation of the particles can be further improved, and at the same time, the pores in the coating layer can be aligned, thereby further improving the battery characteristics.

作為具有形狀等向性的黏彈性粒子之形狀，可舉例立方體狀、球狀等。作為具有形狀異向性的黏彈性粒子之形狀，可舉例扁平形狀(例如，直方體的板狀)、纖維狀、彎折的纖維狀、線圈狀等。當分隔板具有易收縮方向之情形時，可使用黏彈性粒子朝對於緩和收縮應力為有效之方向來配向。扁平形狀的黏彈性粒子之中，板狀的黏彈性粒子係可藉由將粒子輕叩、破壞、或將纖維切成薄片等，以自我組織化使成為板狀之方式來製作。纖維狀粒子係可藉由將紡絲的高分子切短、或以靜電紡絲法來製作。藉由將此纖維狀粒子切短、或於靜電紡絲法進行紡絲之際，以電場之開關控制(on-off)來製作短纖維，可製作能利用來作為具有形狀異向性粒子的短纖維。 Examples of the shape of the viscoelastic particles having an isotropic shape include a cubic shape and a spherical shape. Examples of the shape of the viscoelastic particles having shape anisotropy include a flat shape (for example, a plate shape of a cuboid), a fibrous shape, a bent fibrous shape, and a coil shape. When the partition plate has an easy-to-shrink direction, the viscoelastic particles can be aligned in a direction that is effective for reducing shrinkage stress. Among the flat-shaped viscoelastic particles, plate-shaped viscoelastic particles can be produced by flicking, destroying particles, or cutting fibers into thin sheets, and self-organizing them into a plate shape. The fibrous particle system can be produced by short-cutting a spinning polymer or by an electrospinning method. When the fibrous particles are cut short, or when the electrospinning method is used for spinning, the short fibers are produced by on-off control of an electric field, and it is possible to produce a fiber that can be used as a shape anisotropic particle. short fibre.

黏彈性粒子之進行彈性變形之性質之程度，可以藉由下述測定方法1所求得的彈性率：h3表示。本發明中的黏彈性粒子之h3，較佳為0.95以下，又較佳為 0.9以下。又，黏彈性粒子之h3未特別限定，可為0.5以上，較佳為0.6以上。黏彈性粒子之進行塑性變形之性質之程度，可以藉由下述測定方法2所求得的塑性變形率：h6表示。本發明中的h6，較佳為0.85以下，又較佳為0.75以下。又，黏彈性粒子之h6未特別限定，較佳為0.5以上，又較佳為0.6以上。黏彈性粒子之h3及h6只要是前述上限值以下，應力緩和能會變高並可有效抑制捲曲。黏彈性粒子之h3及h6只要是前述下限值以上，可更提高耐熱性。h3及h6皆為表示易變形之程度之參數，當數值越小時，皆表示越容易變形。因此，當h3及h6為更小時，可更抑制捲曲。然而，因彈性變形所致的變形，會殘留變形應力。另一方面，因塑性變形所致的變形，不會殘留變形應力。在此，變形應力係成為可產生捲曲之力。因此，相較於彈性變形率：h3為小之情形，塑性變形率：h6為小者可更抑制捲曲之發生。 The degree of elastic deformation properties of viscoelastic particles can be expressed by the elastic modulus obtained by the following measurement method 1: h3. H3 of the viscoelastic particles in the present invention is preferably 0.95 or less, and more preferably 0.9 or less. In addition, h3 of the viscoelastic particles is not particularly limited, but may be 0.5 or more, and preferably 0.6 or more. The degree of the plastic deformation property of the viscoelastic particles can be expressed by the plastic deformation rate obtained by the following measurement method 2: h6. H6 in the present invention is preferably 0.85 or less, and more preferably 0.75 or less. In addition, h6 of the viscoelastic particles is not particularly limited, but is preferably 0.5 or more, and more preferably 0.6 or more. As long as h3 and h6 of the viscoelastic particles are below the aforementioned upper limit, the stress relaxation energy will be high and curling can be effectively suppressed. As long as h3 and h6 of the viscoelastic particles are at least the aforementioned lower limit value, heat resistance can be further improved. h3 and h6 are parameters indicating the degree of easy deformation. The smaller the value, the easier it is to deform. Therefore, when h3 and h6 are smaller, curling can be more suppressed. However, deformation due to elastic deformation leaves deformation stress. On the other hand, deformation due to plastic deformation does not leave deformation stress. Here, the deformation stress is a force capable of generating curl. Therefore, compared with the case where the elastic deformation rate: h3 is small, the plastic deformation rate: h6 is small, the occurrence of curl can be more suppressed.

〔測定方法1〕 [Measurement method 1]

(1)得到試驗粒子之步驟、(2)於內徑10mm、外徑110mm、高150mm的丙烯酸製筒中，以成為高100mm之方式來填裝步驟(1)所得到的試驗粒子，使用萬能試驗機(autograph)壓入外徑10mm、長200mm的鐵製棒之步驟、(3)測定以1kgf壓入時的高h1，及之後鬆緩壓入力，測定以0.5kgf壓入時的高h2之步驟、(4)藉由h1/h2=h3而求得黏彈性粒子之彈性率：h3之步驟。 (1) Steps for obtaining test particles, (2) Filling the test particles obtained in step (1) in an acrylic cylinder with an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to be 100 mm high, and using a universal test The step of pressing an autograph into an iron rod with an outer diameter of 10mm and a length of 200mm, (3) measuring the height h1 when it is pushed in at 1kgf, and then slowly pushing the force, and measuring the height h2 when it is pushed in at 0.5kgf Step, (4) Step of obtaining the elastic modulus of the viscoelastic particle by h1 / h2 = h3: h3.

〔測定方法2〕 [Measurement method 2]

(1)得到試驗粒子之步驟、(2)於內徑10mm、外徑110mm、高150mm的丙烯酸製筒中，以成為高100mm之方式來填裝試驗粒子，使用萬能試驗機壓入外徑10mm、長200mm的鐵製棒之步驟、(3)施加1kgf之荷重後，求得使荷重回復至0.5kgf為止的高h4，接著，以100kgf壓入鐵製棒後，求得使荷重回復至0.5kgf為止的高h5。(4)藉由h5/h4=h6而求得黏彈性粒子之塑性變形率：h6之步驟。 (1) Steps for obtaining test particles, (2) Filling test particles in an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to be 100 mm high, and using a universal testing machine to press the outer diameter of 10 mm, In the step of an iron rod with a length of 200 mm, (3) After applying a load of 1 kgf, a height h4 of 0.5 kgf is returned to the load, and then the iron rod is pressed at 100 kgf to recover the load to 0.5 kgf. Up to h5. (4) The step of determining the plastic deformation rate of the viscoelastic particles by h5 / h4 = h6: h6.

尚，當黏彈性粒子之平均粒徑為50μm以上時，將試驗對象的黏彈性粒子以篩孔距50μm之篩來過篩，使成為試驗粒子。又，容易網眼阻塞的粒子，藉由使成為水分散體並進行過濾，來使成為試驗粒子。 When the average particle diameter of the viscoelastic particles is 50 μm or more, the viscoelastic particles of the test object are sieved with a sieve having a sieve opening distance of 50 μm to make the test particles. In addition, particles that are prone to clogging of the mesh are made into test particles by filtering them into an aqueous dispersion.

黏彈性粒子之含有量，在除去溶劑後的塗布膜組成物中所包含的成分之中，以0.1~99.9重量%以上，較佳為0.5~99.5重量%，又較佳為1~99重量%。只要是如此般範圍，可使伴隨於黏彈性粒子之變形或低彈性率化之應力緩和能更為提高，並可有效抑制捲曲。尚，溶劑係包含用於後述黏結劑之溶劑、及黏彈性粒子為分散液形態情形時之分散媒。 The content of the viscoelastic particles is 0.1 to 99.9% by weight or more, preferably 0.5 to 99.5% by weight, and more preferably 1 to 99% by weight, among the components included in the coating film composition after the solvent is removed. . With such a range, the stress relaxation accompanied by the deformation or low elasticity of the viscoelastic particles can be further improved, and curl can be effectively suppressed. In addition, the solvent is a dispersion medium in the case where the viscoelastic particles are in the form of a dispersion liquid, including a solvent used in a binder described later.

〔黏結劑〕 [Binder]

對於本發明之(2)黏結劑進行說明。本發明之電池 電極或分隔板塗布膜組成物係包含黏結劑。作為黏結劑，可舉例固體(例如，粒子狀)黏結劑或液體黏結劑。黏結劑亦可為：分散於溶劑中之狀態、溶解於溶劑中之狀態、或分散於溶劑中之狀態及溶解於溶劑中之狀態。 The (2) adhesive of the present invention will be described. Battery of the invention The electrode or separator coating film composition contains a binder. As the adhesive, a solid (e.g., particulate) adhesive or a liquid adhesive can be exemplified. The binder may be in a state of being dispersed in a solvent, a state of being dissolved in a solvent, or a state of being dispersed in a solvent and a state of being dissolved in a solvent.

〔固體黏結劑〕 〔Solid adhesive】

作為固體黏結劑，可使用各種習知的固體黏結劑。固體黏結劑方面，可舉例熱塑性的有機物之粒子、有機物之結晶、及熱熔著時進行交聯的有機物之粒子。固體黏結劑之平均粒徑未特別限定，可使成為0.01~500μm。又，固體黏結劑中不包含對於應力為具有不可逆塑性變形之性質及可逆彈性變形之性質的粒子(即，黏彈性粒子)。 As the solid adhesive, various conventional solid adhesives can be used. As the solid binder, there can be mentioned thermoplastic organic particles, organic crystals, and organic particles that are crosslinked during thermal fusion. The average particle diameter of the solid binder is not particularly limited, and may be 0.01 to 500 μm. In addition, the solid binder does not include particles (that is, viscoelastic particles) having properties of irreversible plastic deformation and reversible elastic deformation with respect to stress.

熱塑性的有機物之粒子係以熱熔來使粒子熱熔著，只要是能使黏結者即可，未特別限定，舉例如熱塑性高分子之粒子。 The particles of the thermoplastic organic substance are thermally fused by thermal fusion, and are not particularly limited as long as they are capable of bonding, and examples thereof include particles of a thermoplastic polymer.

作為熱塑性高分子，可示例如黏彈性粒子之材質。熱塑性的有機物之粒子可單獨使用，亦可組合複數種使用。作為熱塑性的有機物之粒子，就與離子之容易相互作用性、離子傳導之觀點而言，較佳為：具有氰基的高分子衍生物之粒子、具有聚乙二醇構造的高分子衍生物之粒子、具有羰基的高分子衍生物之粒子(較佳為具有β-二酮構造的高分子之粒子)、及具有碳酸酯基的高分子之粒子；又較佳為：具有氰基的高分子衍生物之粒子、具有聚乙二醇構造的高分子之粒子、及具有碳酸酯基的高分子 之粒子。 Examples of the thermoplastic polymer include materials of viscoelastic particles. The thermoplastic organic particles can be used alone or in combination. As the particles of the thermoplastic organic substance, from the viewpoint of easy interaction with ions and ion conduction, the particles of a polymer derivative having a cyano group and the polymer derivative having a polyethylene glycol structure are preferred. Particles, particles of a polymer derivative having a carbonyl group (preferably particles of a polymer having a β-diketone structure), and particles of a polymer having a carbonate group; and more preferably: a polymer having a cyano group Particles of derivatives, particles of polymers with polyethylene glycol structure, and polymers with carbonate groups Of particles.

可將熱塑性的有機物之粒子，以於-40~300℃之範圍具有融點或軟化點之程度來調整該分子量或交聯密度。 The molecular weight or crosslinking density of the thermoplastic organic particles can be adjusted to such an extent that they have a melting point or a softening point in the range of -40 to 300 ° C.

熱塑性的有機物之粒子，亦可作為乾燥粉末來使用，亦可作為以界面活性劑或水溶性高分子使成為保護膠體粒子的水性乳液來使用。又，以調整融點為目的，亦可進而加入乙二醇、丙三醇、二乙二醇、N-甲基吡咯啶酮、二甲基亞碸、及異佛爾酮等之沸點為80℃以上之高沸點溶劑。 The thermoplastic organic particles can also be used as a dry powder or as an aqueous emulsion made of protective colloidal particles with a surfactant or a water-soluble polymer. In addition, for the purpose of adjusting the melting point, the boiling point of ethylene glycol, glycerol, diethylene glycol, N-methylpyrrolidone, dimethyl sulfene, and isophorone can be further added. High boiling point solvents above ℃.

〔有機物之結晶〕 [Crystal of Organic Matter]

作為有機物之結晶，可示例如醯肼結晶、酸酐結晶、胺結晶、咪唑結晶、及三嗪結晶、或該等之混晶。有機物之結晶之融點，以40℃以上為佳，又較佳為50~300℃。 Examples of the crystals of organic matter include hydrazine crystals, acid anhydride crystals, amine crystals, imidazole crystals, and triazine crystals, or mixed crystals thereof. The melting point of the crystals of organic matter is preferably above 40 ° C, and more preferably from 50 to 300 ° C.

作為醯肼結晶，可示例如己二酸二醯肼(融點177~180℃)、1,3-雙(醯肼碳乙基)-5-異丙基乙內醯脲(融點120℃)、7,11-十八碳二烯-1,18-二碳醯肼(融點160℃)等。作為酸酐結晶，可示例如馬來酸酐(融點53℃)、鄰苯二甲酸酐(融點131℃)、苯均四酸二酐(融點286℃)等。作為胺結晶，可示例如尿素(融點132℃)、二氰二醯胺(融點208℃)等。作為咪唑結晶，可示例如咪唑(融點89~91℃)、2-甲基咪唑(融點140~148℃)、苯基咪唑(融點174~184℃)等。作為三 嗪結晶，可示例如2,4-二胺基-6-乙烯基-S-三嗪(融點240℃)、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪(融點170℃)等。有機物之結晶，以調整融點或軟化點為目的，亦可混合2種以上成為固熔體使用。 Examples of the hydrazine crystals include dihydrazine adipate (melting point 177 to 180 ° C), 1,3-bis (hydrazinocarbonethyl) -5-isopropylhydantoin (melting point 120 ° C) ), 7,11-octadecadiene-1,18-dicarbohydrazine (melting point 160 ° C) and so on. Examples of the acid anhydride crystal include maleic anhydride (melting point: 53 ° C), phthalic anhydride (melting point: 131 ° C), pyromellitic dianhydride (melting point: 286 ° C), and the like. Examples of the amine crystal include urea (melting point: 132 ° C), dicyandiamide (melting point: 208 ° C), and the like. Examples of the imidazole crystal include imidazole (melting point: 89-91 ° C), 2-methylimidazole (melting point: 140-148 ° C), phenylimidazole (melting point: 174-184 ° C), and the like. As three Examples of hydrazine crystals include 2,4-diamino-6-vinyl-S-triazine (melting point 240 ° C), 2,4-diamino-6-methacryloxyethyl-S -Triazine (melting point 170 ° C), etc. The crystallization of organic substances is for the purpose of adjusting the melting point or softening point, and it is also possible to mix two or more types and use it as a solid solution.

〔熱熔著時進行交聯的有機物之粒子〕 [Particles of organic matter that are crosslinked during thermal fusion]

熱熔著時進行交聯的有機物之粒子係各種習知的潛在性硬化型之固形樹脂之粒子。作為潛在性硬化型之固形樹脂，舉例如環氧樹脂、環氧樹脂與環氧乙烷(oxirane)化合物之混合物、(甲基)丙烯酸酯、及具有活性氫基的預聚物。因此，作為熱熔著時進行交聯的有機物之粒子，舉例如：固形的環氧樹脂中調配有潛在性熱起始劑之粒子；固形的環氧樹脂與環氧乙烷化合物之混合物中調配有潛在性熱起始劑之粒子；包含固形的(甲基)丙烯酸酯、與硬化劑或起始劑的系之粒子；以及具有活性氫基的預聚物與交聯劑之組合之粒子。本發明中所謂的「(甲基)丙烯酸酯」，指丙烯酸酯及甲基丙烯酸酯。 The particles of an organic substance which is crosslinked during thermal fusion are particles of various conventionally-cured solid resins. Examples of the potentially hardening type solid resin include epoxy resins, mixtures of epoxy resins and oxirane compounds, (meth) acrylates, and prepolymers having an active hydrogen group. Therefore, as particles of an organic substance that is crosslinked during thermal fusion, for example: particles containing a potential thermal initiator in a solid epoxy resin; and mixtures of a solid epoxy resin and an ethylene oxide compound Particles with a potential thermal initiator; particles containing a solid (meth) acrylate, and a system of a hardener or initiator; and particles of a combination of a prepolymer having an active hydrogen group and a crosslinking agent. The "(meth) acrylate" as used in this invention means an acrylate and a methacrylate.

作為固形的環氧樹脂，可示例如DIC(股)製的EPICLON 1050(軟化點64~74℃的雙酚A型環氧樹脂)、DIC(股)製的EPICLON N-660(軟化點62~70℃的甲酚酚醛型環氧樹脂)、DIC(股)製的EPICLON N-770(軟化點65~75℃的酚酚醛型環氧樹脂)、DIC(股)製的HP-7200HH(軟化點88~98℃的二環戊二烯型環氧樹脂)、DIC(股)製的EPICLON HP-4700(軟化點85~95 ℃的萘型環氧樹脂)、Nagasechemtex(股)製的EX-721(融點94~96℃的單官能固形環氧鄰苯二甲醯亞胺骨架)、Nagasechemtex(股)製的EX-171(融點40℃的月桂醇(EO)15縮水甘油醚)等。尚，本說明書中所謂的「EO」，指環氧乙烷；「PO」指環氧丙烷。 Examples of the solid epoxy resin include EPICLON 1050 (softening point of bisphenol A type epoxy resin of 64 to 74 ° C.) made by DIC (strand), and EPICLON N-660 (softening point of 62 to 6) made of DIC (strand). 70 ° C cresol novolac epoxy resin), EPICLON N-770 (softening point 65-75 ° C phenol novolac epoxy resin) by DIC (HP), HP-7200HH (softening point by DIC) Dicyclopentadiene type epoxy resin at 88 ~ 98 ℃), EPICLON HP-4700 (softening point: 85 ~ 95) Naphthalene type epoxy resin at ℃), EX-721 made by Nagasechemtex (strand) (monofunctional solid epoxy phthalimide skeleton having a melting point of 94 to 96 ° C), EX-171 made by Nagasechemtex (strand) (Lauryl alcohol (EO) 15 glycidyl ether having a melting point of 40 ° C) and the like. In the present specification, "EO" means ethylene oxide; "PO" means propylene oxide.

作為環氧乙烷化合物，舉例如氧雜環丁烷化合物。環氧乙烷化合物，具體而言可示例如：3-乙基-3-羥基甲基氧雜環丁烷、3-(甲基)烯丙氧基甲基-3-乙基氧雜環丁烷、(3-乙基-3-氧雜環丁烷基甲氧基)甲基苯、4-氟-[1-(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、4-甲氧基-[1-(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、[1-(3-乙基-3-氧雜環丁烷基甲氧基)乙基]苯醚、異丁氧基甲基(3-乙基-3-氧雜環丁烷基甲基)醚、異冰片氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、異冰片基(3-乙基-3-氧雜環丁烷基甲基)醚、2-乙基己基(3-乙基-3-氧雜環丁烷基甲基)醚、乙基二乙二醇(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊二烯(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊烯氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊烯基(3-乙基-3-氧雜環丁烷基甲基)醚、四氫糠基(3-乙基-3-氧雜環丁烷基甲基)醚、四溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、三溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、2-羥基乙基(3-乙基-3-氧雜環丁烷基甲基) 醚、2-羥基丙基(3-乙基-3-氧雜環丁烷基甲基)醚、丁氧基乙基(3-乙基-3-氧雜環丁烷基甲基)醚、五氯苯基(3-乙基-3-氧雜環丁烷基甲基)醚、五溴苯基(3-乙基-3-氧雜環丁烷基甲基)醚、冰片基(3-乙基-3-氧雜環丁烷基甲基)醚、3,7-雙(3-氧雜環丁烷基)-5-氧雜壬烷、3,3’-(1,3-(2-甲烯基(methylenyl))丙烷二基雙(氧基亞甲基))雙-(3-乙基氧雜環丁烷)、1,4-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]苯、1,2-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]乙烷、1,3-雙[(3-乙基-3-氧雜環丁烷基甲氧基)甲基]丙烷、乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、二環戊烯基雙(3-乙基-3-氧雜環丁烷基甲基)醚、三乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、四乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、三環癸烷二基二亞甲基(3-乙基-3-氧雜環丁烷基甲基)醚、三羥甲基丙烷參(3-乙基-3-氧雜環丁烷基甲基)醚、1,4-雙(3-乙基-3-氧雜環丁烷基甲氧基)丁烷、1,6-雙(3-乙基-3-氧雜環丁烷基甲氧基)己烷、季戊四醇參(3-乙基-3-氧雜環丁烷基甲基)醚、季戊四醇肆(3-乙基-3-氧雜環丁烷基甲基)醚、聚乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、二季戊四醇陸(3-乙基-3-氧雜環丁烷基甲基)醚、二季戊四醇伍(3-乙基-3-氧雜環丁烷基甲基)醚、二季戊四醇肆(3-乙基-3-氧雜環丁烷基甲基)醚、己內酯改質二季戊四醇陸(3-乙基-3-氧雜環丁烷基甲基)醚、己內酯改質二季戊四醇伍(3-乙基-3-氧雜環丁烷基甲基)醚、雙三羥甲基 丙烷肆(3-乙基-3-氧雜環丁烷基甲基)醚、EO改質雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、PO改質雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、EO改質氫化雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、PO改質氫化雙酚A雙(3-乙基-3-氧雜環丁烷基甲基)醚、EO改質雙酚F(3-乙基-3-氧雜環丁烷基甲基)醚、氧雜環丁烷基倍半矽氧烷等。 Examples of the ethylene oxide compound include an oxetane compound. Specific examples of ethylene oxide compounds include: 3-ethyl-3-hydroxymethyloxetane, 3- (methyl) allyloxymethyl-3-ethyloxetane Alkane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl Yl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetan Butylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl- 3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxo Cyclobutanemethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetan Butylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxanyl) Cyclobutanemethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanyl) (Methyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) Ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, norbornyl (3 -Ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxononane, 3,3 '-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3- Oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentane Alkenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, tris Methylolpropane (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3- Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol (3-ethyl Methyl-3-oxetanylmethyl) ether, pentaerythritol (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxo Hexacyclylmethyl) ether, dipentaerythritol (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol (3-ethyl-3-oxetanylmethyl) ether Base) ether, dipentaerythritol (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol (3-ethyl-3-oxetanylmethyl) ) Ether, caprolactone modified dipentaerythritol (3-ethyl-3-oxetanylmethyl) ether, bistrimethylol Propane (3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified Bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol F (3-ethyl-3-oxetanylmethyl) Ether, oxetanylsilsesquioxane and the like.

對於環氧樹脂或環氧乙烷化合物之潛在性熱起始劑係陽離子聚合用觸媒，可示例如：二苯基錪‧六氟磷酸鹽、二苯基錪‧六氟銻酸鹽、二苯基錪‧四氟硼酸鹽、二苯基錪‧肆(五氟苯基)硼酸鹽、雙(十二烷基苯基)錪‧六氟磷酸鹽、雙(十二烷基苯基)錪‧六氟銻酸鹽、雙(十二烷基苯基)錪‧四氟硼酸鹽、雙(十二烷基苯基)錪‧肆(五氟苯基)硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪‧六氟磷酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪‧六氟銻酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪‧四氟硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪‧肆(五氟苯基)硼酸鹽、4-甲氧基二苯基錪‧六氟磷酸鹽、雙(4-甲基苯基)錪‧六氟磷酸鹽、雙(4-t-丁基苯基)錪‧六氟磷酸鹽、雙(十二烷基苯基)錪‧甲苯基枯烯基錪六氟磷酸鹽等之錪鹽；三烯丙基鋶六氟銻酸鹽等之鋶鹽；三苯基芘基甲基鏻鹽等之鏻鹽；(η6-苯)(η5-環戊二烯基)鐵(II)六氟銻酸鹽；o-硝基苄基矽烷醚與乙醯基丙酮酸鋁之組合；倍半矽氧烷與乙醯基丙酮酸鋁 之組合等。 Potential thermal initiators for epoxy resins or ethylene oxide compounds are catalysts for cationic polymerization. Examples include diphenylphosphonium‧hexafluorophosphate, diphenylphosphonium‧hexafluoroantimonate, Phenyl 錪 ‧Tetrafluoroborate, Diphenyl 錪, ‧ (Pentafluorophenyl) borate, Bis (dodecylphenyl) 錪, Hexafluorophosphate, Bis (dodecylphenyl) 錪‧Hexafluoroantimonate, bis (dodecylphenyl) 錪, tetrafluoroborate, bis (dodecylphenyl) 錪, (pentafluorophenyl) borate, 4-methylphenyl 4- (1-methylethyl) phenylphosphonium‧hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenylphosphonium‧hexafluoroantimonate, 4-methyl Phenyl-4- (1-methylethyl) phenylfluorene‧tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenylfluorene‧penta (pentafluorophenyl ) Borate, 4-methoxydiphenyl 錪 ‧hexafluorophosphate, bis (4-methylphenyl) 錪 ‧hexafluorophosphate, bis (4-t-butylphenyl) 錪 hexafluoro Phosphonium salts of phosphate, bis (dodecylphenyl) fluorene, tolylcumenyl, hexafluorophosphate, etc .; sulfonium salts of triallyl, hexafluoroantimonate, etc .; triphenylfluorenylmethyl Base salt And other phosphonium salts; (η6-benzene) (η5-cyclopentadienyl) iron (II) hexafluoroantimonate; a combination of o-nitrobenzylsilyl ether and aluminum ethyl pyruvate; silsesquioxane Oxane and aluminum acetopyruvate Combination and so on.

熱起始劑之調配量，相對於固形的環氧樹脂或前述固形的環氧樹脂與環氧乙烷化合物之混合物100重量份，較佳為0.001~50重量份，又較佳為0.01~20重量份，更佳為0.1~10重量份。 The blending amount of the thermal initiator is preferably 0.001 to 50 parts by weight, and more preferably 0.01 to 20 parts by weight relative to 100 parts by weight of the solid epoxy resin or the aforementioned mixture of the solid epoxy resin and the ethylene oxide compound. It is more preferably 0.1 to 10 parts by weight.

固形的環氧樹脂中為調配有潛在性熱起始劑者，及固形的環氧樹脂與環氧乙烷化合物之混合物中為調配有潛在性熱起始劑者，可進而含有羧酸、羧酸酐、胺、及醯肼等之硬化劑粒子。藉此，亦可使於熱熔著時進行交聯反應。藉由調配硬化劑粒子，可使熱熔著之同時進行交聯反應，可得到相互成為連續相且交聯之構造。硬化劑之調配量，相對於後述固形的預聚物之粒子100重量份，較佳為1~500重量份，又較佳為2~200重量份。 Solid epoxy resins are formulated with a latent thermal initiator, and solid epoxy resins and ethylene oxide compounds are formulated with a latent thermal initiator, which may further contain carboxylic acids and carboxylic acids. Hardener particles such as acid anhydride, amine, and hydrazine. Thereby, a crosslinking reaction can also be performed at the time of thermal fusion. By blending the hardener particles, a cross-linking reaction can be performed at the same time as heat fusion, and a continuous phase and cross-linked structure can be obtained. The blending amount of the curing agent is preferably 1 to 500 parts by weight, and more preferably 2 to 200 parts by weight with respect to 100 parts by weight of particles of the solid prepolymer described later.

固形的環氧樹脂中為調配有潛在性熱起始劑者之粒子、或固形的環氧樹脂與環氧乙烷化合物之混合物中為調配有潛在性熱起始劑者之粒子，係將前述固形的環氧樹脂或前述固形的環氧樹脂與環氧乙烷化合物之混合物、潛在性熱起始劑、及情況所調配的硬化劑混合，接著藉由進行粉碎，而可製造作為固形的預聚物之粒子。又，藉由將固形的環氧樹脂之粒子或前述固形的環氧樹脂與環氧乙烷化合物之混合物之粒子、起始劑粒子、及硬化劑粒子混合，亦可得到作為固形的預聚物之粒子。 The particles in the solid epoxy resin prepared with a latent thermal starter, or the particles in a mixture of solid epoxy resin and ethylene oxide compound prepared with a latent thermal starter are those described above. A solid epoxy resin or a mixture of the aforementioned solid epoxy resin and an ethylene oxide compound, a latent thermal initiator, and a hardening agent prepared according to the situation is mixed, and then pulverized to produce a solid preform. Polymer particles. In addition, a solid prepolymer can also be obtained by mixing solid epoxy particles or particles of a mixture of the solid epoxy resin and an ethylene oxide compound, initiator particles, and hardener particles. Of particles.

作為包含固形的(甲基)丙烯酸酯、與硬化劑或起始劑的系，熱硬化性的系方面，可示例如甲基丙烯 酸酯及熱起始劑之混合物(EBECRYL 767(Daicel‧cytec(股)製)：PerhexaHC(日油(股)製)=100：5混合物)；光硬化性的系方面，可示例如甲基丙烯酸酯及光起始劑之混合物(EBECRYL 740-40TP(Daicel‧cytec(股)製)：1-羥基-環己基-苯基-酮=100：5)等。 Examples of the system containing a solid (meth) acrylate, a curing agent or a starter, and a thermosetting system include methacrylic acid. Mixture of acid ester and thermal initiator (EBECRYL 767 (made by Daicel‧cytec): PerhexaHC (made by Nippon Oil (stock)) = 100: 5 mixture); for photohardenability, examples include methyl Mixture of acrylate and photoinitiator (EBECRYL 740-40TP (manufactured by Daicel ‧ Cytec): 1-hydroxy-cyclohexyl-phenyl-one = 100: 5) and the like.

具有活性氫基的預聚物與交聯劑之組合中，作為交聯劑可示例如羧酸或羧酸酐、金屬螯合物等。具有活性氫基的預聚物與交聯劑之組合方面，可示例如聚乙烯醇與聚羧酸及該等衍生物之混合物、聚乙烯醇或其衍生物與金屬螯合物或烷氧化物之混合物等、硼酸。作為聚羧酸之例，可示例如檸檬酸、丁烷四羧酸、3,3’,4,4’-聯苯四羧酸、六氫鄰苯二甲酸、1,3,3a,4,5,9b-六氫-5(四氫-2,5-二氧代-3-呋喃基)萘并[1,2-c]呋喃-1,3-二酮(酸酐)、丙三醇雙偏苯三酸酐單乙酸酯(酸酐)、3,3’,4,4’-二苯基碸四羧酸、乙二醇雙偏苯三酸酐酯(酸酐)、3,3’,4,4’-二苯基碸四羧酸、乙二醇雙偏苯三酸酐酯、甲基雙環[2.2.1]庚烷-2,3-二羧酸、雙環[2.2.1]庚烷-2,3-二羧酸、天門冬胺酸、均苯四酸、苯六甲酸、含磷酯基四羧酸、苯基乙炔基鄰苯二甲酸、氧基二鄰苯二甲酸、聚丙烯酸、聚甲基丙烯酸、及其衍生物等。之中，就反應性之觀點而言，以芳香族羧酸為佳，就反應性或交聯密度之觀點而言，以一分子中具有3個以上羧基者為佳。又，亦可使用示例之聚羧酸中之相當於酸酐者。作為金屬螯合物，可示例如四異丙氧化鈦、四正丁氧化鈦、二異丙氧基鈦雙(乙醯基丙酮酯)、 四乙醯基丙酮鈦、乳酸鈦銨鹽、二異丙氧基鈦雙(三乙醇胺化物)般的鈦螯合物或烷氧化物、四正丙氧化鋯、四乙醯基丙酮鋯、二丁氧基鋯雙(乙基乙醯基乙酸酯)、三丁氧基單硬脂酸鋯般的鋯螯合物或烷氧化物、異丙氧化鋁般的鋁螯合物等各種習知的金屬化合物。又，具有活性氫基的預聚物與交聯劑之組合，視情況可含有前述硬化劑及熱起始劑。具有活性氫基的預聚物與交聯劑之組合之粒子，將具有活性氫基的預聚物、交聯劑、以及視情況存在的硬化劑及起始劑進行混合之際，以不因熱而反應之方式，於對該等為良溶劑中混合，並將薄薄地澆鑄且在室溫使溶劑乾燥者邊冷卻邊粉碎，可製造作為於熱熔著時進行交聯的有機物粒子型之黏結劑使用。 In the combination of a prepolymer having an active hydrogen group and a cross-linking agent, examples of the cross-linking agent include a carboxylic acid or a carboxylic anhydride, a metal chelate, and the like. Examples of the combination of a prepolymer having an active hydrogen group and a cross-linking agent include, for example, a mixture of polyvinyl alcohol and polycarboxylic acid and derivatives thereof, polyvinyl alcohol or a derivative thereof, and a metal chelate compound or alkoxide Mixture, etc., boric acid. Examples of the polycarboxylic acid include citric acid, butanetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, hexahydrophthalic acid, 1,3,3a, 4, 5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furyl) naphtho [1,2-c] furan-1,3-dione (anhydride), glycerol bis Trimellitic anhydride monoacetate (anhydride), 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic acid, ethylene glycol bistrimellitic anhydride (anhydride), 3,3', 4,4'-diphenyl Perylenetetracarboxylic acid, ethylene glycol trimellitic anhydride ester, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, asparagus Amino acid, pyromellitic acid, pyromellitic acid, phosphorus ester-containing tetracarboxylic acid, phenylethynyl phthalic acid, oxydiphthalic acid, polyacrylic acid, polymethacrylic acid, and derivatives thereof, etc. . Among them, from the viewpoint of reactivity, an aromatic carboxylic acid is preferred, and from the viewpoint of reactivity or crosslink density, it is preferred to have three or more carboxyl groups in one molecule. In addition, those equivalent to acid anhydrides in the exemplified polycarboxylic acids may be used. Examples of the metal chelate compound include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium diisopropoxide bis (ethylacetone), Titanium tetraacetamidate, titanium ammonium lactate, titanium diisopropoxide bis (triethanolamine) titanium chelate or alkoxide, tetra-n-propionate zirconium oxide, zirconium tetraethylacetonate, dibutyl Zirconyl bis (ethylacetamidate), zirconium chelate like zirconium tributoxyzirconate or alkoxide, aluminum chelate like isopropyl aluminum oxide, etc. Metal compounds. The combination of a prepolymer having an active hydrogen group and a cross-linking agent may optionally contain the aforementioned hardener and thermal initiator. Particles of a combination of a prepolymer having an active hydrogen group and a cross-linking agent are mixed with a prepolymer having an active hydrogen group, a cross-linking agent, and optionally a hardener and an initiator, so that A method of reacting with heat, mixing them into a good solvent, and thinly casting and pulverizing the solvent while drying the solvent at room temperature, and can be produced as an organic particle type that is crosslinked during thermal fusion. Use of adhesive.

包含熱熔著時進行交聯的有機物粒子來作為黏結劑的電極電池或分隔板塗布膜組成物，於塗布組成物後，藉由使溶劑蒸散，並於組成物與電池電極或分隔板熔著之同時及/或熔著後，藉由加熱或照射能量線，可使交聯進行。藉此，可得到機械強度優異且耐熱性高的保護膜。 Coating film composition for electrode batteries or separators containing organic particles that are cross-linked during thermal fusion as a binder. After coating the composition, the solvent is evaporated and the composition is bonded to the battery electrodes or separators. At the same time and / or after the fusion, the crosslinking can be performed by heating or irradiating the energy rays. Thereby, a protective film having excellent mechanical strength and high heat resistance can be obtained.

〔液狀黏結劑〕 [Liquid adhesive]

作為本發明之黏結劑，亦可使用液狀黏結劑。 As the adhesive of the present invention, a liquid adhesive can also be used.

作為液狀黏結劑，可使用各種習知的液狀黏結劑。液狀黏結劑方面，具體而言舉例如：液狀預聚物與起始劑之混合物；使固形高分子物質溶解於溶劑中而成 者；藉由溶膠-凝膠反應成為固形的無機物者；及水玻璃。 As the liquid adhesive, various conventional liquid adhesives can be used. As for the liquid adhesive, specifically, for example: a mixture of a liquid prepolymer and an initiator; a solid polymer substance dissolved in a solvent Those who become solid inorganic substances through sol-gel reaction; and water glass.

(液狀預聚物與起始劑之混合物) (Mixture of liquid prepolymer and initiator)

作為液狀預聚物與起始劑之混合物，可示例如：光自由基起始劑或熱自由基產生劑與具有(甲基)丙烯酸基、烯丙基、乙烯基、馬來醯亞胺基等之化合物之組合；光陽離子起始劑或熱陽離子起始劑與具有環氧基、氧雜環丁烷環等之環氧乙烷環、乙烯醚、環狀乙縮醛等之化合物之組合；以及，光陰離子起始劑與具有環氧基之化合物及/或具有氰基丙烯酸酯基之化合物之組合。尚，(甲基)丙烯酸基係包含丙烯酸基及甲基丙烯酸基。 As a mixture of the liquid prepolymer and the initiator, examples thereof include a photo radical initiator or a thermal radical generator and a (meth) acrylic group, an allyl group, a vinyl group, and a maleimine. Combination of compounds such as radicals; photocationic or thermal cationic initiators and compounds having an epoxy group, an ethylene oxide ring, an ethylene oxide ring, a cyclic acetal, etc. A combination; and a combination of a photoanion initiator with a compound having an epoxy group and / or a compound having a cyanoacrylate group. The (meth) acrylic group includes an acrylic group and a methacrylic group.

對於光自由基起始劑或熱自由基產生劑與具有(甲基)丙烯酸基、烯丙基、乙烯基、馬來醯亞胺基等之化合物之組合進行說明。 A combination of a photo radical initiator or a thermal radical generator with a compound having a (meth) acrylic group, an allyl group, a vinyl group, a maleimide group, or the like will be described.

作為光自由基起始劑，可示例如4-苯氧基二氯苯乙酮、4-t-丁基-二氯苯乙酮、4-t-丁基-三氯苯乙酮、二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)-苯基(2-羥基-2-丙基)酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1等之苯乙酮系；苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚、苯偶姻異丁醚、苄基二甲基縮酮、α-烯丙基苯偶姻、α- 烯丙基苯偶姻芳醚等之苯偶姻系；二苯甲酮、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、3,3’-二甲基-4-甲氧基二苯甲酮等之二苯甲酮系；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、及2,4-二異丙基噻噸酮等之噻噸酮系；1-苯基-1,2-丙烷二酮-2(O-乙氧基羰基)肟、2,4,6-三甲基苯甲醯二苯基氧化膦、甲基苯基乙醛酸酯、9,10-菲醌(phenanthrenequinone)、樟腦醌(camphorquinone)、二苯并環庚酮(dibenzosuberone)、2-乙基蒽醌、4’,4”-二乙基間苯二苯甲酮(isophthalophenone)、3,3’,4,4’-四(t-丁基過氧基羰基)二苯甲酮、1-[4-(3-巰基丙硫基)苯基1-2-甲基-2-嗎啉-4-基-丙烷-1-酮、1-[4-(10-巰基癸硫基)苯基]-2-甲基-2-嗎啉-4-基-丙烷-1-酮、1-(4-{2-[2-(2-巰基-乙氧基)乙氧基]乙硫基}苯基)-2-甲基-2-嗎啉-4-基-丙烷-1-酮、1-[3-(巰基丙硫基)苯基]-2-二甲基胺基-2-苄基-丙烷-1-酮、1-[4-(3-巰基丙基胺基)苯基]-2-二甲基胺基-2-苄基-丙烷-1-酮、1-[4-(3-巰基-丙氧基)苯基]-2-甲基-2-嗎啉-4-基-丙烷-1-酮、雙(η5-2,4-環戊二烯-1-基)雙[2,6-二氟-3-(1H-吡咯-1-基)苯基]鈦、1,2-辛二酮、1-4-(苯硫基)-，2-(O-苯甲醯基肟)]、乙酮，1-[9-乙基-6-(2-甲基苯甲醯)-9H-咔唑-3-基]-，1-(O-乙醯基肟)、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、及1,3-雙(p-二 甲基胺基亞苄基)丙酮等。光自由基起始劑之中，對於如二苯甲酮、米其勒酮、二苯并環庚酮、2-乙基蒽醌、樟腦醌、異丁基噻噸酮般分子間奪氫型之光起始劑，可添加電子供體(供氫體)來作為起始助劑。作為如此般的電子供體，舉例如具有活性氫的脂肪族胺及芳香族胺。脂肪族胺方面，具體而言可示例如三乙醇胺、甲基二乙醇胺、三異丙醇胺。芳香族胺方面，具體而言可示例如4,4’-二甲基胺基二苯甲酮、4,4’-二乙基胺基二苯甲酮、2-二甲基胺基苯甲酸乙酯、及4-二甲基胺基苯甲酸乙酯。 Examples of the photo-radical initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, and diethyl Oxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl ) Ketones, acetophenones such as 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1; benzoin, Benzoin methyl ether, Benzoin ethyl ether, Benzoin isopropyl ether, Benzoin isobutyl ether, Benzyl dimethyl ketal, α-allyl benzoin, α- Benzoin series such as allyl benzoin aryl ether; benzophenone, benzophenone benzoic acid, methyl benzophenone benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic acid Benzophenones such as benzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4 -Thioxanthone based on diethylthioxanthone and 2,4-diisopropylthioxanthone; 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime , 2,4,6-trimethylbenzidine diphenylphosphine oxide, methylphenylglyoxylate, 9,10-phenanthrenequinone, camphorquinone, dibenzocycloheptanone (dibenzosuberone), 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetrakis (t-butylperoxycarbonyl) ) Benzophenone, 1- [4- (3-mercaptopropylthio) phenyl 1- 2-methyl-2-morpholin-4-yl-propane-1-one, 1- [4- (10 -Mercaptodecylthio) phenyl] -2-methyl-2-morpholin-4-yl-propane-1-one, 1- (4- {2- [2- (2-mercapto- Ethoxy) ethoxy] ethylthio} phenyl) -2-methyl-2-morpholin-4-yl-propane-1-one, 1- [3- (mercaptopropylthio) phenyl] 2-dimethylamino-2-benzyl-propane-1-one, 1- [4- (3-mercaptopropylamino) phenyl] -2-dimethylamino-2-benzyl -Propane-1-one, 1- [4- (3-mercapto-propoxy) phenyl] -2-methyl-2-morpholin-4-yl-propane-1-one, bis (η5-2 , 4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl] titanium, 1,2-octanedione, 1-4- ( Phenylthio)-, 2- (O-benzylideneoxime)], ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ]-, 1- (O-ethylamidoxime), bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, and 1,3-bis (p-di Methylaminobenzylidene) acetone and the like. Among the photo-radical initiators, intermolecular hydrogen abstraction type such as benzophenone, Michelin, dibenzocycloheptanone, 2-ethylanthraquinone, camphorquinone, isobutylthioxanthone As a light initiator, an electron donor (hydrogen donor) can be added as a starting aid. Examples of such an electron donor include aliphatic amines and aromatic amines having active hydrogen. Specific examples of the aliphatic amine include triethanolamine, methyldiethanolamine, and triisopropanolamine. Specific examples of the aromatic amine include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, and 2-dimethylaminobenzoic acid. Ethyl and 4-dimethylaminobenzoate.

作為熱自由基產生劑，可示例如4-疊氮苯胺鹽酸鹽、及4,4’-二硫代雙(1-疊氮苯)等之疊氮化物；4,4’-二乙基-1,2-二硫雜環戊烷、四甲基秋蘭姆二硫醚、及四乙基秋蘭姆二硫醚等之二硫醚；辛醯基過氧化物、3,5,5-三甲基己醯基過氧化物、癸醯基過氧化物、月桂醯基過氧化物、琥珀酸過氧化物、苯甲醯基過氧化物、2,4-二氯苯甲醯基過氧化物、m-甲苯甲醯基過氧化物般之二醯基過氧化物；二-n-丙基過氧基二碳酸酯、二異丙基過氧基二碳酸酯、二-2-乙基己基過氧基二碳酸酯、及二-(2-乙氧基乙基)過氧基二碳酸酯般之過氧基二碳酸酯；t-丁基過氧基異丁酸酯、t-丁基過氧基三甲基乙酸酯、t-丁基過氧基辛酸酯、辛基過氧基辛酸酯、t-丁基過氧基-3,5,5-三甲基己酸酯、t-丁基過氧基新十二烷酸酯、辛基過氧基新十二烷酸酯、t-丁基過氧基月桂酸酯、及t-丁基過氧基苯甲酸酯般之過氧基酯；二-t-丁基過氧化物、t-丁基異丙 苯基過氧化物、二異丙苯基過氧化物、2,5-二甲基-2,5-二(t-丁基過氧基)己烷、及2,5-二甲基-2,5-二(t-丁基)己炔-3之二烷基過氧化物；2,2-雙(t-丁基過氧基)丁烷、1,1-雙(t-丁基過氧基)環己烷、1,1-雙(t-丁基過氧基)-3,3,5-三甲基環己烷、及n-丁基-4,4-雙(t-丁基過氧基)戊酸酯般之過氧基縮酮；甲基乙基酮過氧化物般之酮過氧化物；p-薄荷烷過氧化氫、及異丙苯過氧化氫等之過氧化物；2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丙腈)、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-甲腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、及2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈等之偶氮腈類；2,2’-偶氮雙(2-甲基-N-苯基丙脒)二鹽酸鹽、2,2’-偶氮雙[N-(4-氯苯基)-2-甲基丙脒]二鹽酸鹽、2,2’-偶氮雙[N-(4-羥基苯基)-2-甲基丙脒]二鹽酸鹽、2,2’-偶氮雙[2-甲基-N-(4-苯基甲基)丙脒]二鹽酸鹽、2,2’-偶氮雙[2-甲基-N-(2-丙烯基)丙脒]二鹽酸鹽、2,2’-偶氮雙(2-甲基丙脒)二鹽酸鹽、2,2’-偶氮雙[N-(2-羥基乙基)-2-甲基丙脒]二鹽酸鹽、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2’-偶氮雙{2-[1-(2-羥基乙基)-2-咪唑啉-2-基]丙烷}二鹽酸鹽、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等之偶氮醯胺類；2,2’-偶氮雙(2,4,4-三甲基戊烷)、及2,2’-偶氮雙(2-甲基丙烷)等之烷基偶氮化合物類；以及，其他的二甲基-2,2’-偶氮雙(2-甲基丙酸酯)、2,2’- 偶氮雙(4-氰基戊酸)、及2,2’-偶氮雙[2-(羥基甲基)丙酸酯]等之偶氮化合物；吡啶；具有過渡金屬的起始劑(例如，氯化銅(I)及氯化銅(II))；甲基2-溴丙酸酯、乙基2-溴丙酸酯、乙基2-溴異丁酸酯等之鹵素化合物。 Examples of the thermal radical generator include 4-azideaniline hydrochloride and azides such as 4,4'-dithiobis (1-azidobenzene); 4,4'-diethyl -1,2-Dithiocyclopentane, tetramethylthiuram disulfide, and diethyl thiosulfate; octyl peroxide, 3,5,5-tris Methylhexyl fluorenyl peroxide, decyl fluorenyl peroxide, lauryl fluorenyl peroxide, succinic acid peroxide, benzamyl peroxide, 2,4-dichlorobenzyl peroxide , M-toluenyl peroxide-like difluorenyl peroxide; di-n-propylperoxy dicarbonate, diisopropylperoxy dicarbonate, di-2-ethylhexyl Peroxydicarbonate, and di- (2-ethoxyethyl) peroxydicarbonate-like peroxydicarbonate; t-butylperoxyisobutyrate, t-butyl Peroxytrimethylacetate, t-butylperoxycaprylate, octylperoxycaprylate, t-butylperoxy-3,5,5-trimethylhexanoate , T-butylperoxyneododecanoate, octylperoxyneododecanoate, t-butylperoxylaurate, and t-butylperoxybenzoate The peroxy esters like esters; two -t- butyl peroxide, t- butyl isopropyl Phenyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and 2,5-dimethyl-2 2,5-bis (t-butyl) hexyne-3 dialkyl peroxide; 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butyl peroxy) (Oxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis (t-butyl Peroxy) valerate-like peroxy ketals; methyl ethyl ketone peroxide-like ketone peroxides; p-menthane hydrogen peroxide, and cumene hydrogen peroxide, etc. Compounds; 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2 ,, 2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) , 1-[(1-cyano-1-methylethyl) azo] methaneamine, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile Nitriles; 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2 -Methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropamidine] dihydrochloride, 2,2'- Azobis [2-methyl-N- (4-phenylmethyl) propanyl] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propanyl) ] Dihydrochloride, 2,2'-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-Azobis [N- (2-hydroxyethyl) -2-methyl Propylamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis { 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) Propane] and other azoxamines; 2,2'-azobis (2,4,4-trimethylpentane), and 2,2'-azobis (2-methylpropane), etc. Alkyl azo compounds; and other dimethyl-2,2'-azobis (2-methylpropionate), 2,2'- Azo compounds such as azobis (4-cyanovaleric acid) and 2,2'-azobis [2- (hydroxymethyl) propionate]; pyridine; starters with transition metals (e.g. , Copper (I) chloride and copper (II) chloride); methyl 2-bromopropionate, ethyl 2-bromopropionate, halogen compounds such as ethyl 2-bromoisobutyrate.

對於上述熱自由基產生劑，可併用分解促進劑。作為分解促進劑，可示例如硫脲衍生物、有機金屬錯合物、胺化合物、磷酸酯化合物、甲苯胺衍生物、苯胺衍生物。 The thermal radical generator may be used in combination with a decomposition accelerator. Examples of the decomposition accelerator include thiourea derivatives, organometallic complexes, amine compounds, phosphate compounds, toluidine derivatives, and aniline derivatives.

作為硫脲衍生物，舉例如N,N’-二甲基硫脲、四甲基硫脲、N,N’-二乙基硫脲、N,N’-二丁基硫脲、苯甲醯基硫脲、乙醯基硫脲、亞乙基硫脲、N,N’-二亞乙基硫脲、N,N’-二苯基硫脲、及N,N’-二月桂基硫脲，較佳為四甲基硫脲或苯甲醯基硫脲。作為有機金屬錯合物，舉例如環烷酸鈷、環烷酸釩、環烷酸銅、環烷酸鐵、環烷酸錳、硬脂酸鈷、硬脂酸釩、硬脂酸銅、硬脂酸鐵、及硬脂酸錳等。作為胺化合物，可示例如以烷基或伸烷基之碳數為1~18之整數表示之1~3級之烷基胺類或烷二胺類、二乙醇胺、三乙醇胺、二甲基苄基胺、參-二甲基胺基甲基酚、參-二乙基胺基甲基酚、1,8-二氮雜雙環(5,4,0)十一碳烯-7、1,8-二氮雜雙環(5,4,0)十一碳烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一碳烯-7、2-甲基咪唑、及2-乙基-4-甲基咪唑等。作為磷酸酯化合物，可示例如甲基丙烯酸磷酸酯、 二甲基丙烯酸磷酸酯、單烷基酸式磷酸酯、二烷基磷酸酯、三烷基磷酸酯、二烷基亞磷酸酯、及三烷基亞磷酸酯等。作為甲苯胺衍生物，可示例如N,N-二甲基-p-甲苯胺、及N,N-二乙基-p-甲苯胺等。作為苯胺衍生物，可示例如N,N-二甲基苯胺、及N,N-二乙基苯胺等。 Examples of the thiourea derivative include N, N'-dimethylthiourea, tetramethylthiourea, N, N'-diethylthiourea, N, N'-dibutylthiourea, and benzamidine Thiourea, ethylthiourea, ethylenethiourea, N, N'-diethylenethiourea, N, N'-diphenylthiourea, and N, N'-dilaurylthiourea , Preferably tetramethylthiourea or benzamidinethiourea. Examples of the organometallic complex include cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, hard Iron stearate, and manganese stearate. Examples of the amine compound include alkylamines or alkyldiamines of the 1st to 3rd order represented by an alkyl group or an alkylene group having an integer of 1 to 18 carbons, diethanolamine, triethanolamine, and dimethylbenzyl. Methylamine, p-dimethylaminomethylphenol, p-diethylaminomethylphenol, 1,8-diazabicyclo (5,4,0) undecene-7,1,8 -Diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) -nonene-5,6-dibutylamino-1, 8-diazabicyclo (5,4,0) -undecene-7, 2-methylimidazole, and 2-ethyl-4-methylimidazole. Examples of the phosphate compound include phosphate methacrylate, Dimethacrylate phosphate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphite, and trialkyl phosphite. Examples of the toluidine derivative include N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine. Examples of the aniline derivative include N, N-dimethylaniline and N, N-diethylaniline.

具有(甲基)丙烯酸基、烯丙基、乙烯基、或馬來醯亞胺基之化合物為液狀預聚物。作為具有(甲基)丙烯酸基的化合物，可示例如丁二醇單(甲基)丙烯酸酯、(甲基)丙烯酸t-丁基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸n-己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸2-甲氧基乙酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇400二(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、四氫糠醇(甲基)丙烯酸酯、(甲基)丙烯醯氧基乙基苯二甲酸酯、N-(甲基)丙烯醯氧基-N-羧基哌啶、N-(甲基)丙烯醯氧基-N,N-二羧甲基-p-苯二胺、羥基萘氧基丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧基乙基磷酸苯酯、4-(甲基)丙烯醯氧基乙基偏苯三酸酯、(甲基)丙烯醯氧基乙基磷酸鹽、長鏈脂肪族(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸丁氧基乙酯、丁二醇單(甲基)丙烯酸酯、丁氧基 三乙二醇(甲基)丙烯酸酯、ECH改質丁基(甲基)丙烯酸酯、(甲基)丙烯酸t-丁基胺基乙酯、己內酯(甲基)丙烯酸酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸2-氰基乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、脂環式改質新戊二醇(甲基)丙烯酸酯、(甲基)丙烯酸2,3-二溴丙酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸2-乙基己酯、丙三醇(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸十五氟癸酯、(甲基)丙烯酸2-羥基乙酯、己內酯改質(甲基)丙烯酸2-羥基乙酯、氯化2-羥基-3-(甲基)丙烯醯氧基丙基三甲基銨、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯酸2-甲氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基四乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇1000(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、甲氧基化環癸三烯(甲基)丙烯酸酯、嗎啉(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸苯氧基羥基 丙酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基四乙二醇(甲基)丙烯酸酯、苯氧基六乙二醇(甲基)丙烯酸酯、EO改質苯氧基化磷酸(甲基)丙烯酸酯、苯氧基(甲基)丙烯酸酯、EO改質磷酸(甲基)丙烯酸酯、EO改質磷酸(甲基)丙烯酸酯、EO改質鄰苯二甲酸(甲基)丙烯酸酯、EO、PO改質鄰苯二甲酸(甲基)丙烯酸酯、聚乙二醇90(甲基)丙烯酸酯、聚乙二醇200(甲基)丙烯酸酯、聚乙二醇400(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、聚丙二醇500(甲基)丙烯酸酯、聚丙二醇800(甲基)丙烯酸酯、聚乙二醇/聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸硬脂基酯、EO改質琥珀酸(甲基)丙烯酸酯、磺酸鈉乙氧基(甲基)丙烯酸酯、(甲基)丙烯酸四氟丙酯、四氫糠基(甲基)EO改質雙酚A二(甲基)丙烯酸酯、丙烯酸酯、己內酯改質四氫糠基(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、烯丙基化環己基二(甲基)丙烯酸酯、(甲基)丙烯酸化異氰尿酸酯、雙(丙烯醯氧基新戊二醇)己二酸酯、EO改質雙酚A二(甲基)丙烯酸酯、EO改質雙酚S二(甲基)丙烯酸酯、雙酚F二(甲基)丙烯酸酯、EO改質雙酚AD二(甲基)丙烯酸酯、EO改質雙酚AF二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二(甲基) 丙烯酸二環戊酯、二乙二醇二(甲基)丙烯酸酯、ECH(環氧氯丙烷)改質二乙二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、倍半矽氧烷(甲基)丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、丙三醇(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甲氧基化環己基二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二丙烯酸酯、己內酯改質羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、硬脂酸改質季戊四醇二(甲基)丙烯酸酯、EO改質磷酸二(甲基)丙烯酸酯、EO改質磷酸三(甲基)丙烯酸酯、聚乙二醇200二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四溴雙酚A二(甲基)丙烯酸酯、三乙二醇(甲基)丙烯酸酯、三丙三醇二(甲基)丙烯酸酯、新戊二醇改質三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、EO改質三羥甲基丙烷三(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、參(丙烯醯氧基乙基)異氰尿酸酯、己內酯改質參(丙烯醯氧基乙基)異氰尿酸酯、參(甲基丙烯醯氧基乙基)異氰尿酸酯、二(甲基)丙烯酸鋅、異氰酸酯基乙基丙烯酸酯、氯菌酸(chlorendic acid)二(甲基)丙烯 酸酯、甲氧醚(甲基)丙烯酸酯、及2-(甲基丙烯醯氧基)乙基三甲基鋁‧雙(三氟甲基磺醯基)胺陰離子等。 A compound having a (meth) acrylic group, an allyl group, a vinyl group, or a maleimide group is a liquid prepolymer. Examples of the compound having a (meth) acrylic group include butanediol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, and N, N-dimethylmethacrylate Aminoaminoethyl, N, N-diethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, new Pentylene glycol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, tetrahydrofurfuryl alcohol ( (Meth) acrylate, (meth) acryloxyethyl phthalate, N- (meth) acryloxy-N-carboxypiperidine, N- (meth) acryloxy- N, N-Dicarboxymethyl-p-phenylenediamine, hydroxynaphthyloxypropyl (meth) acrylate, (meth) acrylic acid oxyethyl phenyl phosphate, 4- (meth) acrylic acid Oxyethyl trimellitate, (meth) acrylic acid oxyethyl phosphate, long chain aliphatic (meth) acrylic acid Ester, (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl acrylate, butanediol mono (meth) acrylate, butoxyethyl Triethylene glycol (meth) acrylate, ECH modified butyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, caprolactone (meth) acrylate, (meth) ) 3-chloro-2-hydroxypropyl acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, alicyclic modified neopentyl Diol (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, (methyl ) N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid 2- (2-ethoxyethoxy) ethyl ester, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, (meth) Pentafluorodecyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate modified, 2-hydroxy-3- (meth) acrylic acid oxychloride Propyltrimethylammonium, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, ( (Isyl) isooctyl acrylate, lauryl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethyl Glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol 1000 (meth) acrylic acid Ester, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecadiene (meth) acrylate, morpholine (meth) acrylate, nonylphenoxy polyethylene glycol (methyl ) Acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, phenoxyhydroxy (meth) acrylate Propyl ester, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol ( (Meth) acrylate, EO modified phenoxylated phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, EO modified phosphate (meth) acrylate, EO modified phosphate (meth) Acrylate, EO modified phthalate (meth) acrylate, EO, PO modified phthalate (meth) acrylate, polyethylene glycol 90 (meth) acrylate, polyethylene glycol 200 (Meth) acrylate, polyethylene glycol 400 (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene glycol 500 (meth) acrylate, polypropylene glycol 800 (meth) acrylate, polyethylene Glycol / polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO modified succinate (meth) acrylate, sodium sulfonate ethoxy (meth) acrylate, (meth) ) Tetrafluoropropyl acrylate, tetrahydrofurfuryl (meth) EO modified bisphenol A di (meth) acrylate, acrylate, caprolactone modified tetrahydrofuryl (meth) acrylate, (formyl) Base) trifluoroethyl acrylate , Allyl cyclohexyl di (meth) acrylate, (meth) acrylic isocyanurate, bis (propylene ethoxy neopentyl glycol) adipate, EO modified bisphenol A di (Meth) acrylate, EO modified bisphenol S di (meth) acrylate, bisphenol F di (meth) acrylate, EO modified bisphenol AD di (meth) acrylate, EO modified bis Phenol AF di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate Base) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, di (meth) Dicyclopentyl acrylate, diethylene glycol di (meth) acrylate, ECH (epoxychloropropane) modified diethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, two Pentaerythritol monohydroxypenta (meth) acrylate, silsesquioxane (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylic acid Ester, bistrimethylolpropane tetra (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol diacrylate Ester, caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di ( (Meth) acrylate, EO modified phosphoric acid di (meth) acrylate, EO modified phosphoric acid tri (meth) acrylate, polyethylene glycol 200 di (meth) acrylic acid Acrylate, tetraethylene glycol di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triethylene glycol (meth) acrylate, triglycerol di (meth) acrylic acid Ester, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, Tripropylene glycol di (meth) acrylate, ginseng (propenyloxyethyl) isocyanurate, caprolactone modified ginseng (propyleneoxyethyl) isocyanurate, ginseng (methacrylic acid) (Ethoxyethyl) isocyanurate, zinc di (meth) acrylate, isocyanate ethyl acrylate, chlorendic acid di (meth) propylene Acid esters, methoxy ether (meth) acrylates, and 2- (methacryloxy) ethyltrimethylaluminum bis (trifluoromethylsulfonyl) amine anions.

作為具有乙烯基的化合物，可示例如乙酸乙烯酯、氯乙烯、乙烯基三甲氧基矽烷、1-乙烯基-3,4-環氧環己烷、乙烯乙酸酯等。作為烯丙基的化合物，可示例如烯丙基醇、3-胺基丙烯、溴化烯丙基、氯化烯丙基、二烯丙醚、二烯丙基硫醚、蒜精、二硫化烯丙基、烯丙基異硫氰酸酯等。作為具有馬來醯亞胺基的化合物，可示例如馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、4,4’-二苯基甲烷馬來醯亞胺、m-苯馬來醯亞胺、雙酚A二苯醚雙馬來醯亞胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-苯雙馬來醯亞胺、及1,6’-雙馬來醯亞胺-(2,2,4-三甲基)己烷等。該等化合物之中，較佳為具有(甲基)丙烯酸基、及乙烯基的化合物。該等化合物，即使是在光自由基起始劑之不存在下，亦能以電子線使其硬化。 Examples of the compound having a vinyl group include vinyl acetate, vinyl chloride, vinyltrimethoxysilane, 1-vinyl-3,4-epoxycyclohexane, ethylene acetate, and the like. Examples of the allyl compound include allyl alcohol, 3-aminopropylene, brominated allyl, chlorinated allyl, diallyl ether, diallyl sulfide, garlic, disulfide Allyl, allyl isothiocyanate, etc. Examples of the compound having a maleimidine group include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and 4,4'-diphenylmethane. Lymeimide, m-phenylmaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanebismaleimide, 4-methyl-1,3-phenylbismaleimide, and 1,6'-bismaleimide- (2,2,4-trimethyl Group) hexane and the like. Among these compounds, compounds having a (meth) acrylic group and a vinyl group are preferred. These compounds can be hardened by electron rays even in the absence of a photo-radical initiator.

光自由基起始劑及熱自由基產生劑，亦可組合2種以上使用。該等光自由基起始劑及熱自由基產生劑，相對於液狀預聚物的具有(甲基)丙烯酸基、烯丙基、乙烯基、或馬來醯亞胺基之化合物100重量份，較佳為添加0.01~50重量份，又較佳為0.1~20重量份，更佳為1~10重量份。當併用光自由基起始劑及熱自由基產生劑時，上述含有量為光自由基起始劑及熱自由基產生劑之合計含有量。又，電子供體之含有量，相對於光自由基起始 劑100重量份，較佳為10~500重量份。分解促進劑之含有量，相對於熱自由基產生劑100重量份，較佳為1~500重量份。 The photo radical initiator and the thermal radical generator may be used in combination of two or more kinds. These photo radical initiators and thermal radical generators are 100 parts by weight of the liquid prepolymer having a (meth) acrylic group, an allyl group, a vinyl group, or a maleimide group. It is preferable to add 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight. When a photo radical initiator and a thermal radical generator are used in combination, the above-mentioned content is the total content of the photo radical initiator and the thermal radical generator. In addition, the content of the electron donor is relative to the photo radical initiation. The agent is 100 parts by weight, preferably 10 to 500 parts by weight. The content of the decomposition accelerator is preferably 1 to 500 parts by weight based on 100 parts by weight of the thermal radical generator.

對於光陽離子起始劑、熱陽離子起始劑或光陰離子起始劑，與具有環氧基、氧雜環丁烷環等之環氧乙烷環、乙烯醚、環狀乙縮醛等之化合物之組合進行說明。 For photocationic initiators, thermal cationic initiators or photoanionic initiators, and compounds with ethylene oxide rings, vinyl ethers, cyclic acetals, etc. having epoxy groups, oxetane rings, etc. The combination will be described.

作為光陽離子起始劑，舉例在前述對於環氧樹脂或環氧乙烷化合物之潛在性熱起始劑中，倍半矽氧烷與乙醯基丙酮酸鋁之組合以外之化合物。 Examples of the photocationic initiator include compounds other than the combination of silsesquioxane and aluminum acetopyruvate among the aforementioned potential thermal initiators for epoxy resins or ethylene oxide compounds.

光陽離子起始劑中可併用增感劑。作為如此般的增感劑，可示例如9,10-丁氧基蒽、吖啶橙(acridine orange)、吖啶黃、苯并黃素(benzoflavin)、硫代磺素(Setoflavine)T、苝、芘、蒽、吩噻嗪、1,2-苯并蒽、蔻、噻噸酮、茀酮、二苯甲酮、及蒽醌等。 A photocationic initiator may be used in combination with a sensitizer. Examples of such a sensitizer include 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, thioflavin (Setoflavine) T, and pyrene , Pyrene, anthracene, phenothiazine, 1,2-benzoanthracene, succinyl, thioxanthone, fluorenone, benzophenone, and anthraquinone.

作為熱陽離子起始劑，舉例如前述的對於環氧樹脂或環氧乙烷化合物之潛在性熱起始劑。 As the thermal cationic initiator, for example, the aforementioned potential thermal initiator for epoxy resins or ethylene oxide compounds.

作為光陰離子起始劑，可示例如於o-硝基苄基醇化合物使二官能基以上之異氰酸酯封端而成之2-硝基苄基胺基甲酸酯化合物、及喹啉疊氮磺酸酯化合物與N-烷基氮丙啶化合物之組合等。光陰離子起始劑係使用於使具有環氧基之化合物，具有氰基丙烯酸酯基的化合聚合之用途。 Examples of the photoanion initiator include 2-nitrobenzylcarbamate compounds in which o-nitrobenzyl alcohol compounds block isocyanates having more than two functional groups, and quinoline azidesulfonic acid. A combination of an acid ester compound and an N-alkylaziridine compound, and the like. The photoanion initiator is used for the polymerization polymerization of a compound having an epoxy group and a cyanoacrylate group.

具有環氧基、氰基丙烯酸酯基、環硫化物(episulfide)、氧雜環丁烷環、螺原碳酸酯、或乙烯醚基 的化合物為液狀預聚物，係具有藉由光陽離子起始劑、熱陽離子起始劑及/或光陰離子起始劑進行交聯的反應性取代基之化合物。 With epoxy, cyanoacrylate, episulfide, oxetane ring, spiro orthocarbonate, or vinyl ether group The compound is a liquid prepolymer, and is a compound having a reactive substituent that is crosslinked by a photocationic initiator, a thermal cationic initiator, and / or a photoanionic initiator.

具有環氧基的化合物，可示例如(3’,4’-環氧基環己烷)甲基3,4-環氧基環己烷羧酸酯、4-乙烯基環己烯氧化物、1-甲基-4-(2-甲基環氧乙基)-7-氧雜雙環[4.1.0]庚烷、環氧化丁烷四羧酸肆-(3-環己烯基甲基)修飾之ε-己內酯、環氧化之聚丁二烯、2,2-雙(羥基甲基)-1-丁醇之1,2-環氧基-4-(2-環氧乙基)環己烷加成物、2,2-雙(羥基甲基)-1-丁醇之1,2-環氧基-4-(2-環氧乙基)環己烷加成物、3,4-環氧基環己烯基甲基-3’,4’-環氧基環己烯基羧酸酯、甲基丙烯酸3,4-環氧基環己基甲基酯、α-烯烴環氧化物、苯乙烯-丁二烯嵌段共聚物之環氧化物、苯乙烯-丁二烯嵌段共聚物之環氧化物、雙酚A型環氧樹脂、雙酚AD型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、酚酚醛型環氧樹脂、甲酚酚醯型環氧樹脂、α-萘酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、四溴雙酚A型環氧樹脂、四縮水甘油基二胺基二苯基甲烷、二羥基萘‧二縮水甘油醚、聯苯型環氧樹脂、倍半矽氧烷型環氧樹脂、異戊二烯型環氧樹脂、異莰基骨架、雙酚S型環氧樹脂、氫化雙酚A型環氧樹脂、環氧丙烷加成之雙酚A型環氧樹脂、間苯二酚型環氧樹脂、環氧改質之聚矽氧、及環氧改質之倍半矽氧烷等。 Examples of the compound having an epoxy group include (3 ', 4'-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene oxide, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, epoxidized butane tetracarboxylic acid- (3-cyclohexenylmethyl) Modified ε-caprolactone, epoxidized polybutadiene, 1,2-epoxy-4- (2-epoxyethyl) of 2,2-bis (hydroxymethyl) -1-butanol Cyclohexane adduct, 1,2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenylcarboxylate, 3,4-epoxycyclohexylmethyl methacrylate, α-olefin epoxy Compounds, epoxy of styrene-butadiene block copolymer, epoxy of styrene-butadiene block copolymer, bisphenol A epoxy resin, bisphenol AD epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, four Bromobisphenol A epoxy resin, tetraglycidyl Diaminodiphenylmethane, dihydroxynaphthalene‧diglycidyl ether, biphenyl epoxy resin, silsesquioxane epoxy resin, isoprene epoxy resin, isofluorenyl skeleton, bis Phenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, epoxy modified polysiloxane, and ring Oxygen-modified sesquioxane and so on.

具有氰基丙烯酸酯基的化合物，可示例如氰 基丙烯酸甲酯、及氰基丙烯酸乙酯。 Examples of compounds having a cyanoacrylate group include cyanide Methyl acrylate, and ethyl cyanoacrylate.

具有環硫化物的化合物，其係上述具有環氧基的化合物之氧原子經硫原子所取代的化合物，可示例如環硫乙烷、環硫丙烷、1-丁烯硫醚、2-丁烯硫醚、環硫異丁烷、1-戊烯硫醚、2-戊烯硫醚、1-己烯硫醚、1-辛烯硫醚、1-十二碳烯硫醚、環戊烯硫醚、環己烯硫醚、苯乙烯硫醚、乙烯基環己烯硫醚、3-苯基環硫丙烷、3,3,3-三氟環硫丙烷、3-萘基環硫丙烷、3-苯氧基環硫丙烷、3-萘氧基環硫丙烷、丁二烯單硫醚、3-三甲基矽烷基氧基環硫丙烷等。 The compound having an episulfide is a compound in which the oxygen atom of the above-mentioned compound having an epoxy group is substituted with a sulfur atom, and examples thereof include episulfide, episulfide, 1-butene sulfide, and 2-butene. Sulfide, epithioisobutane, 1-pentene sulfide, 2-pentene sulfide, 1-hexene sulfide, 1-octene sulfide, 1-dodecene sulfide, cyclopentene sulfide Ether, cyclohexene sulfide, styrene sulfide, vinyl cyclohexene sulfide, 3-phenyl epithiopropane, 3,3,3-trifluoroepanethiopropane, 3-naphthyl epithiopropane, 3 -Phenoxy epithiopropane, 3-naphthyloxy epithiopropane, butadiene monosulfide, 3-trimethylsilyloxy epithiopropane, and the like.

作為具有氧雜環丁烷環的化合物，舉例如前述氧雜環丁烷化合物。 Examples of the compound having an oxetane ring include the aforementioned oxetane compounds.

作為具有螺原碳酸酯的化合物，可示例如螺二醇二烯丙醚、雙環原酯等。 Examples of the compound having a spiro orthocarbonate include a spirodiol diallyl ether, a bicyclic orthoester, and the like.

作為具有乙烯醚的化合物，可示例如n-丙基乙烯醚、異丙基乙烯醚、n-丁基乙烯醚、異丁基乙烯醚、2-乙基己基乙烯醚、十八烷基乙烯醚、環己基乙烯醚、烯丙基乙烯醚、羥基乙基乙烯醚、羥基丁基乙烯醚、9-羥基壬基乙烯醚、4-羥基環己基乙烯醚、環己烷二甲醇單乙烯醚、三乙二醇單乙烯醚、三乙二醇二乙烯醚、1,4-丁二醇二乙烯醚、壬二醇二乙烯醚、環己二醇二乙烯醚、環己烷二甲醇二乙烯醚、三乙二醇二乙烯醚、三甲基丙烷三乙烯醚、及季戊四醇四乙烯醚等。 Examples of the compound having a vinyl ether include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and octadecyl vinyl ether. , Cyclohexyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, three Ethylene glycol monovinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, Triethylene glycol divinyl ether, trimethylpropane trivinyl ether, and pentaerythritol tetravinyl ether.

具有環氧基、氰基丙烯酸酯基、環硫化物、 氧雜環丁烷環、螺原碳酸酯、或乙烯醚基的化合物，以具有氧雜環丁烷環的化合物為佳。 With epoxy, cyanoacrylate, episulfide, The compound having an oxetane ring, a spiro orthocarbonate, or a vinyl ether group is preferably a compound having an oxetane ring.

光陽離子起始劑、熱陽離子起始劑及光陰離子起始劑，亦可組合2種以上使用。該等光陽離子起始劑、熱陽離子起始劑及光陰離子起始劑，相對於液狀預聚物的具有環氧基、氰基丙烯酸酯基、環硫化物、氧雜環丁烷環、螺原碳酸酯、或乙烯醚基的化合物100重量份，較佳為添加0.01~50重量份，又較佳為0.1~20重量份，更佳為1~10重量份。當併用光陽離子起始劑、熱陽離子起始劑及光陰離子起始劑時，上述含有量為光陽離子起始劑、熱陽離子起始劑及光陰離子起始劑之合計含有量。又，增感劑之含有量，相對於光陽離子起始劑100重量份，較佳為5~500重量份。 A photocationic initiator, a thermal cationic initiator, and a photoanionic initiator may be used in combination of two or more. These photocationic initiators, thermal cationic initiators, and photoanionic initiators have epoxy groups, cyanoacrylate groups, episulfides, oxetane rings, and Spiro orthocarbonate or vinyl ether-based compound is 100 parts by weight, preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight. When a photocationic initiator, a thermal cationic initiator, and a photoanionic initiator are used in combination, the above-mentioned content is the total content of the photocationic initiator, the thermal cationic initiator, and the photoanionic initiator. The content of the sensitizer is preferably 5 to 500 parts by weight based on 100 parts by weight of the photocationic initiator.

(將固形的高分子物質溶解於溶劑中的液狀黏結劑) (Liquid adhesive in which a solid polymer substance is dissolved in a solvent)

作為將固形的高分子物質溶解於溶劑中的液狀黏結劑，可示例如將前述高分子之粒子溶解於溶劑中者，及懸浮於溶劑中者。作為溶劑，可自能將固形高分子溶解的溶劑中適當選擇，亦可混合2種以上使用。 Examples of the liquid adhesive in which a solid polymer substance is dissolved in a solvent include those in which the aforementioned polymer particles are dissolved in a solvent, and those in which the particles are suspended in a solvent. The solvent may be appropriately selected from solvents capable of dissolving the solid polymer, and two or more kinds may be used in combination.

作為固形的高分子物質，可將完全皂化之聚乙烯醇(Kuraray(股)製的Kuraray Poval PVA-124，JAPAN VAM & POVAL(股)製的JC-25等)、部分皂化之聚乙烯醇(Kuraray(股)製的Kuraray Poval PVA-235，JAPAN VAM & POVAL(股)製的JP-33等)、改 質之聚乙烯醇(Kuraray(股)製的Kuraray K Polymer KL-118，Kuraray C Polymer CM-318，Kuraray R Polymer R-1130，Kuraray LM Polymer LM-10HD，JAPAN VAM & POVAL(股)製的D Polymer DF-20，陰離子改質之PVA AF-17、烷基改質之PVA ZF-15、羧基甲基纖維素(Daicel工業(股)製的H-CMC、DN-100L、1120、2200，日本製紙化學(股)製的MAC200HC等)、羥基乙基纖維素(Daicel工業(股)製的SP-400等)、聚丙烯醯胺(MT Aqua Polymer(股)製的Accofloc A-102)、聚氧乙烯(明成化學工業(股)製的ALKOX E-30)、環氧樹脂(Nagasechemtex(股)製的EX-614，Japan ChemTech(股)製的EPICOTE 5003-W55等)、聚伸乙亞胺(日本觸媒(股)製的EPOMIN P-1000)、聚丙烯酸酯(MT Aqua Polymer(股)製的Accofloc C-502等)、以及糖類及其衍生物(和光純藥工業(股)的甲聚糖5，日澱化學(股)製的酯化澱粉乳華，Glyco(股)製的曇狀糊精)、聚苯乙烯磺酸(TOSOH有機化學(股)製的BOLINAS PS-100等)等水溶性高分子，以溶解於水中之狀態來使用。 As the solid polymer material, fully saponified polyvinyl alcohol (Kuraray Poval PVA-124 manufactured by Kuraray Co., Ltd., JC-25 manufactured by JAPAN VAM & POVAL, etc.), partially saponified polyvinyl alcohol ( Kuraray Poval PVA-235 made by Kuraray (stock), JP-33 made by Japan VAM & POVAL (stock), etc.) High-quality polyvinyl alcohol (Kuraray K Polymer KL-118, Kuraray C Polymer CM-318, Kuraray R Polymer R-1130, Kuraray LM Polymer LM-10HD, D made by JAPAN VAM & POVAL (stock) Polymer DF-20, anionic modified PVA AF-17, alkyl modified PVA ZF-15, carboxymethyl cellulose (H-CMC, manufactured by Daicel Industries, Ltd., DN-100L, 1120, 2200, Japan Paper Chemical (MAC200HC, etc.), Hydroxyethyl Cellulose (SP-400, etc. by Daicel Industries, Inc.), Polyacrylamide (Acofloc A-102, MT Aqua Polymer), Oxyethylene (ALKOX E-30 manufactured by Mingcheng Chemical Industry Co., Ltd.), epoxy resin (EX-614 manufactured by Nagasechemtex Co., Ltd., EPICOTE 5003-W55 manufactured by Japan ChemTech Co., Ltd., etc.), polyethyleneimine (EPOMIN P-1000 made by Japan Catalysts Co., Ltd.), polyacrylate (Acofloc C-502 made by MT Aqua Polymer, etc.), and sugars and their derivatives (Wako Pure Chemical Industries, Ltd.) Glycan 5, Esterified Starch Glue from Nitto Chemical Co., Ltd., Glyco Dextrin from Glyco Co., Ltd.), Polystyrene Sulfonic Acid (BOLINAS PS-100 from TOSOH Organic Chemistry Co., Ltd., etc.) And other water-soluble polymers to dissolve The state water use.

作為固形的高分子物質，可將丙烯酸酯聚合乳液(昭和電工(股)製的Polysol F-361、F-417、S-65、SH-502)、及乙烯‧乙酸乙烯酯共聚合乳液((股)Kuraray製的PANFLEX OM-4000NT、OM-4200NT、OM-28NT、OM-5010NT)等之乳液，以懸浮於水中之狀態來 使用。又，作為固形的高分子物質，可將聚偏二氟乙烯(Kureha(股)製的Kureha KF Polymer#1120、Kureha KF Polymer#9130)、改質聚乙烯醇(信越化學工業(股)製的氰基樹脂CR-V)、改質聚三葡萄糖(信越化學工業(股)製的氰基氰基樹脂CR-S)等的高分子，以溶解於N-甲基吡咯啶酮中之狀態來使用。 As solid polymer materials, acrylic polymer emulsions (Polysol F-361, F-417, S-65, SH-502, manufactured by Showa Denko Corporation), and ethylene-vinyl acetate copolymer emulsions (( (E.g., PANFLEX OM-4000NT, OM-4200NT, OM-28NT, OM-5010NT) made by Kuraray, suspended in water use. As solid polymer materials, polyvinylidene fluoride (Kureha KF Polymer # 1120, Kureha KF Polymer # 9130, manufactured by Kureha Co., Ltd.), and modified polyvinyl alcohol (made by Shin-Etsu Chemical Industry Co., Ltd.) can be used. Polymers such as cyano resin CR-V) and modified polytriglucose (cyano cyano resin CR-S manufactured by Shin-Etsu Chemical Industry Co., Ltd.) are dissolved in N-methylpyrrolidone use.

作為將固形的高分子物質溶解於溶劑中的液狀黏結劑，較佳為將水溶性高分子溶解於水中的液狀黏結劑、及將乳液懸浮於水中的黏結劑。 As the liquid adhesive in which a solid polymer substance is dissolved in a solvent, a liquid adhesive in which a water-soluble polymer is dissolved in water, and an adhesive in which an emulsion is suspended in water are preferred.

將固形的高分子物質溶解於溶劑中的液狀黏結劑，可藉由加熱及/或減壓來除去溶劑並使其固化。如此般的黏結劑，藉由將電解液含浸於塗布膜中使成為凝膠電解層，亦可提高塗布膜之離子傳導性。 The liquid adhesive in which a solid polymer substance is dissolved in a solvent can be removed and solidified by heating and / or reducing the pressure. Such a binder can also improve the ion conductivity of the coating film by impregnating the electrolytic solution into the coating film to form a gel electrolytic layer.

(藉由溶膠-凝膠反應使成為固形的無機物的液狀黏結劑) (Liquid adhesive that becomes a solid inorganic substance by sol-gel reaction)

作為藉由溶膠-凝膠反應使成為固形的無機物的液狀黏結劑，具體可示例如下述各種偶合劑等：三乙氧基矽烷、三甲氧基矽烷、異丙氧化鋁、四異丙氧化鈦、四正丁氧化鈦、丁氧化鈦二聚物、四-2-乙基己氧化鈦、二異丙氧基鈦雙(乙醯基丙酮酸鹽)、四乙醯基丙銅酸鈦、二辛氧基鈦雙(辛二醇酸酯)、二異丙氧基鈦雙(乙基乙醯基乙酸酯)、二異丙氧基鈦雙(三乙醇胺化物)、乳酸鈦、聚羥基硬脂酸鈦、四正丙氧化鋯、四正丁氧化鋯、四乙醯 基丙酮酸鋯、三丁氧基單乙醯基丙酮酸鋯、單丁氧基乙醯基丙酮酸鋯雙(乙基乙醯基乙酸酯)、二丁氧基鋯雙(乙基乙醯基乙酸酯)、四乙醯基丙酮酸鋯、三丁氧基單硬脂酸鋯。又，該等可添加溶膠-凝膠反應用的觸媒。作為溶膠-凝膠反應用的觸媒，只要是用於使無機成分水解並縮聚合之反應的觸媒即可，未特別限定。作為如此般的觸媒，可舉例如：如鹽酸之酸；如氫氧化鈉之鹼；胺；或者二丁基錫二乙酸鹽、二丁基錫二辛酸鹽、二丁基錫二月桂酸鹽、二丁基錫二馬來酸鹽、二辛基錫二月桂酸鹽、二辛基錫二馬來酸鹽、辛酸錫等之有機錫化合物；異丙基三異硬脂醯基鈦酸酯、異丙基參(二辛基焦磷酸酯)鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、四烷基鈦酸酯等之有機鈦酸酯化合物；四丁基鋯酸酯、肆(乙醯基丙酮酸)鋯、四異丁基鋯、丁氧基參(乙醯基丙酮酸)鋯、環烷酸鋯等之有機鋯化合物；參(乙基乙醯基乙酸)鋁、參(乙醯基丙酮酸)鋁等之有機鋁化合物；環烷酸鋅、環烷酸鈷、辛酸鈷等之有機金屬觸媒等。該等之中，作為市售品可具體舉例二丁基錫化合物(三共有機化學(股)製之SCAT-24)。該等化合物可使用1種，或組合2種以上使用。 Specific examples of the liquid adhesive that is made into a solid inorganic substance by a sol-gel reaction include various coupling agents such as triethoxysilane, trimethoxysilane, isopropyl aluminum oxide, and tetraisopropyl titanium oxide. , Tetra-n-butoxide, titanate dimer, tetra-2-ethylhexyl titanium oxide, titanium diisopropoxide bis (ethylpyruvate), titanium tetraethylpropionate propionate, two Titanium octyloxy bis (octanediol ester), Titanium diisopropoxy bis (ethylacetamidoacetate), Titanium diisopropoxy bis (triethanolamine), Titanate lactate, Polyhydroxy rigid Titanium stearate, tetra-n-propyl zirconia, tetra-n-butyl zirconia, tetraethylpyrene Zirconylpyruvate, Zirconium tributoxymonoethylfluorenylpyruvate, Zirconium monobutoxyacetamidopyruvate bis (ethylethylfluorenylacetate), Zirconium dibutoxybis (ethylethylfluorene) Acetic acid ester), tetraethylfluorenyl zirconate, zirconium tributoxy monostearate. In addition, a catalyst for a sol-gel reaction may be added to these. The catalyst for the sol-gel reaction is not particularly limited as long as it is a catalyst for a reaction for hydrolysis and condensation polymerization of an inorganic component. Examples of such catalysts include: acids such as hydrochloric acid; bases such as sodium hydroxide; amines; or dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin dimaleate Organotin compounds such as sodium salt, dioctyltin dilaurate, dioctyltin dimaleate, tin octoate, etc .; isopropyltriisostearylphosphonium titanate, isopropyl ginseng (dioctyl Organic titanate compounds such as dibasic pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate, etc .; tetrabutyl zirconate, Organic zirconium compounds such as zirconium acetoacetate) zirconium, tetraisobutyl zirconium, zirconium butoxide (ethylpyruvate) zirconium, zirconium naphthenate, etc. Organoaluminum compounds such as acetopyruvate) aluminum; organometallic catalysts such as zinc naphthenate, cobalt naphthenate, cobalt octoate, etc. Among these, as a commercially available product, a dibutyltin compound (SCAT-24 by Sankyo Organic Chemicals Co., Ltd.) is mentioned specifically. These compounds can be used singly or in combination of two or more kinds.

當電池電極或分隔板塗布膜組成物包含後述的界面活性劑時，界面活性劑有形成微胞(micelle)之情形。此時，以微胞為鑄模，可使固形的無機物成為無機多孔質體。作為用以形成無機多孔質體的界面活性劑，較佳 為第四級銨鹽，具體可舉例如：丁基三甲基氯化銨、己基三甲基氯化銨、二丁基二甲基氯化銨、二己基二甲基氯化銨等。 When a battery electrode or a separator coating film composition contains a surfactant described later, the surfactant may form micelles. In this case, using the cells as a mold, the solid inorganic substance can be made into an inorganic porous body. As a surfactant for forming an inorganic porous body, it is preferable The fourth-order ammonium salt includes, for example, butyltrimethylammonium chloride, hexyltrimethylammonium chloride, dibutyldimethylammonium chloride, and dihexyldimethylammonium chloride.

(水玻璃) (Water glass)

藉由溶膠-凝膠反應使成為固形的無機物的液狀黏結劑以外，作為固形的無機物所得到的液狀黏結劑，可示例如水玻璃。具體而言可使用JIS規格表K1408之1號水玻璃、2號水玻璃、3號水玻璃、或偏矽酸鈉1種、偏矽酸鈉2種、1號矽酸鉀、2號矽酸鉀、矽酸鋰等。 Examples of the liquid adhesive obtained as a solid inorganic substance other than the liquid adhesive made into a solid inorganic substance by a sol-gel reaction include water glass. Specifically, JIS specification table K1408 No. 1 water glass, No. 2 water glass, No. 3 water glass, or 1 type of sodium metasilicate, 2 types of sodium metasilicate, 1 type of potassium silicate, and 2 type of silicate Potassium, lithium silicate, etc.

黏結劑之進行彈性變形之性質之程度及進行塑性變形之性質之程度，與黏彈性粒子為相同地，可以彈性率(h3)及塑性變形率(h6)來表示。本發明中，黏結劑之h3較佳為0.95以下，又較佳為0.9以下。又，黏結劑之h3未特別限定，但可為0.5以上，較佳為0.6以上。本發明中，黏結劑之h6較佳為0.90以下，又較佳為0.85以下。又，h6未特別限定，但較佳為0.5以上，又較佳為0.6以上。黏結劑之h3及h6只要是前述上限值以下，應力緩和能為優異，且將基材彎曲時之密著力為優異。黏結劑之h3及h6只要前述下限值以上，可更提高機械強度或耐熱性。 The degree of elastic deformation and the degree of plastic deformation of the adhesive are the same as those of the viscoelastic particles, and can be expressed in terms of elasticity (h3) and plastic deformation rate (h6). In the present invention, h3 of the binder is preferably 0.95 or less, and more preferably 0.9 or less. In addition, h3 of the binder is not particularly limited, but may be 0.5 or more, and preferably 0.6 or more. In the present invention, h6 of the binder is preferably 0.90 or less, and more preferably 0.85 or less. H6 is not particularly limited, but is preferably 0.5 or more, and more preferably 0.6 or more. As long as h3 and h6 of the adhesive are below the aforementioned upper limit values, the stress relaxation energy can be excellent, and the adhesion when the substrate is bent is excellent. As long as h3 and h6 of the adhesive are above the aforementioned lower limit values, mechanical strength or heat resistance can be further improved.

本發明中，以黏彈性粒子之黏彈性率較黏結劑之黏彈性率為低者為佳。本發明中所謂的「黏彈性粒子之黏彈性率較黏結劑之黏彈性率為低」，意味著黏彈性粒子 之h3及h6較黏結劑之h3及h6為小。當黏彈性粒子之黏彈性率較黏結劑之黏彈性率為低時，黏結劑可應力緩和加熱時的強度，且黏彈性粒子可應力緩和加熱時的捲曲。因此，可得到耐熱性為更高，且可更抑制捲曲之發生的塗布膜。黏彈性粒子與黏結劑之h3之差(△h3=h3黏結劑-h3黏彈性粒子)，較佳為0.01~0.3，又較佳為0.05~0.2。只要黏彈性粒子與黏結劑之h3之差為0.01以上，可有效率地兼具提高耐熱性與抑制捲曲之發生；只要為0.3以下，可更提高耐熱性，且可更抑制捲曲之發生。又，黏彈性粒子與黏結劑之h6之差(△h6=h6黏結劑-h6黏彈性粒子)，較佳為0.01~0.3，又較佳為0.05~0.2。只要黏彈性粒子與黏結劑之h6之差為0.01以上，可有效率地兼具提高耐熱性與抑制捲曲之發生；只要為0.3以下，可更提高耐熱性，且可更抑制捲曲之發生。尚，對於抑制捲曲之發生而言，以表示塑性變形量的△h6為具支配性。 In the present invention, it is preferable that the viscoelasticity of the viscoelastic particles is lower than that of the binder. The so-called "the viscoelasticity of the viscoelastic particles is lower than the viscoelasticity of the adhesive" in the present invention, which means that the h3 and h6 of the viscoelastic particles are smaller than the h3 and h6 of the adhesive. When the viscoelasticity of the viscoelastic particles is lower than the viscoelasticity of the adhesive, the adhesive can reduce the stress during heating and the viscoelastic particles can reduce the curl during heating. Therefore, a coating film having higher heat resistance and further suppressing occurrence of curl can be obtained. The difference in h3 between the viscoelastic particles and the binder (△ h3 = h3 binder- h3 viscoelastic particles ) is preferably 0.01 to 0.3, and more preferably 0.05 to 0.2. As long as the difference between h3 of the viscoelastic particles and the binder is 0.01 or more, it can effectively improve both heat resistance and suppress the occurrence of curl; as long as it is 0.3 or less, the heat resistance can be improved and the occurrence of curl can be more suppressed. In addition, the difference between h6 of the viscoelastic particles and the binder (△ h6 = h6 binder- h6 viscoelastic particles ) is preferably 0.01 to 0.3, and more preferably 0.05 to 0.2. As long as the difference between h6 of the viscoelastic particles and the binder is 0.01 or more, it can effectively improve the heat resistance and suppress the occurrence of curl; as long as it is 0.3 or less, the heat resistance can be improved and the occurrence of curl can be more suppressed. To suppress the occurrence of curl, Δh6, which represents the amount of plastic deformation, is dominant.

黏結劑之h3及h6，可與黏彈性粒子相同地進行測定。即，以使用黏結劑之條件下，使固化成厚度50μm的膜狀後，以液體氮冷卻，之後使用磨機(IKA製的M20汎用磨機)並藉由粉碎，而可得到黏結劑粒子。可使此黏結劑粒子設為[測定方法1]及[測定方法2]之步驟(1)的試驗對象之粒子。藉此，可求得黏結劑之h3及h6。 H3 and h6 of the binder can be measured in the same way as viscoelastic particles. That is, under the conditions using a binder, a 50 μm thick film is solidified, and then cooled with liquid nitrogen, and then a mill (M20 universal mill manufactured by IKA) is used for pulverization to obtain binder particles. This adhesive particle can be made into the particle | grains of the test object of step (1) of [measurement method 1] and [measurement method 2]. With this, h3 and h6 of the adhesive can be obtained.

黏結劑之含有量，以不填埋產生於粒子間之空隙，並進而以實用上為充分的量之添加量為佳。本發明 之組成物中，黏結劑之含有量，相對於前述黏彈性粒子100重量份，較佳為0.01~49重量份，又較佳為0.5~30重量份，更佳為1~20重量份。 The content of the binder is preferably such that the voids generated between the particles are not filled, and further, a practically sufficient amount is added. this invention The content of the binder in the composition is preferably 0.01 to 49 parts by weight, more preferably 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight relative to 100 parts by weight of the aforementioned viscoelastic particles.

〔溶劑〕 [Solvent]

對於本發明之(3)溶劑進行說明。本發明之電池電極或分隔板塗布膜組成物係用以產生伴隨於蒸散的空隙，又，用以調整流動性而具有溶劑。溶劑之蒸散，可藉由加熱乾燥、真空乾燥、凍結乾燥，或組合該等來進行。當黏結劑為利用光或電子線進行硬化的樹脂時，於凍結乾燥後，藉由以光或電子線來使其硬化，亦可利用著霜形狀而多孔質化。又，將使用於電池的電解液溶劑予以事先添加，亦可協助電解質之含浸。作為溶劑，可示例如：烴(丙烷、n-丁烷、n-戊烷、異己烷、環己烷、n-辛烷、異辛烷、苯、甲苯、二甲苯、乙基苯、戊基苯、萜烯油、蒎烯(pinene)等)、鹵系烴(甲基氯、氯仿、四氯化碳、二氯乙烷、甲基溴、乙基溴、氯苯、氯溴甲烷、溴苯、氟二氯甲烷、二氯二氟甲烷、二氟氯乙烷等)、醇(甲醇、乙醇、n-丙醇、異丙醇、n-戊醇、異戊醇、n-己醇、n-庚醇、2-辛醇、n-十二烷醇、壬醇、環己醇、環氧丙醇等)、醚、乙縮醛(***、二氯***、異丙醚、n-丁醚、二異戊醚、甲基苯醚、乙基苄醚、呋喃、糠醛(furfural)、2-甲基呋喃、桉油酚(cineol)、甲縮醛(methylal))、酮(丙酮、甲基乙基酮、甲基-n-丙基 酮、甲基-n-戊基酮、二異丁基酮、佛爾酮、異氟爾酮、環己酮、苯乙酮等)、酯(甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸-n-戊酯、乙酸甲基環己酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、硬脂酸丁酯等、碳酸伸丙酯、碳酸二乙酯、碳酸伸乙酯、碳酸伸乙烯酯等)、多元醇與其衍生物(乙二醇、乙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單***、甲氧基甲氧基乙醇、乙二醇單乙酸酯、二乙二醇、二乙二醇單甲醚、丙二醇、丙二醇單***等)、脂肪酸及酚(甲酸、乙酸、乙酸酐、丙酸、丙酸酐、丁酸、異戊酸、苯酚、甲酚、o-甲酚、苯二甲酚等)、氮化合物(硝基甲烷、硝基乙烷、1-硝基丙烷、硝基苯、單甲基胺、二甲基胺、三甲基胺、單乙基胺、二戊基胺、苯胺、單甲基苯胺、o-甲苯胺、o-氯苯胺、二氯己基胺、二環己基胺、單乙醇胺、甲醯胺、N,N-二甲基甲醯胺、乙醯胺、乙腈、吡啶、α-甲基吡啶、2,4-二甲基吡啶、喹啉、嗎啉等)、硫、磷、其他化合物(二硫化碳、二甲基亞碸、4,4-二乙基-1,2-二硫雜環戊烷、二甲基硫醚、二甲基二硫醚、甲硫醇、丙烷磺內酯、磷酸三乙酯、磷酸三苯酯、碳酸二乙酯、碳酸伸乙酯、硼酸戊酯等)、無機溶劑(液體氨、聚矽氧油等)、水等之液體。 The (3) solvent of the present invention will be described. The battery electrode or separator coating film composition of the present invention is used to generate voids accompanying evapotranspiration, and to have a solvent to adjust fluidity. Evaporation of the solvent can be performed by heat drying, vacuum drying, freeze drying, or a combination of these. When the adhesive is a resin hardened by light or electron beams, after freeze-drying, the light or electron beams can be used to harden the resin, or it can be made porous by frosting. In addition, the electrolyte solution used in the battery is added in advance, which can also help impregnate the electrolyte. Examples of the solvent include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, pentyl Benzene, terpene oil, pinene, etc.), halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, dichloroethane, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene , Fluoromethylene chloride, dichlorodifluoromethane, difluorochloroethane, etc.), alcohols (methanol, ethanol, n-propanol, isopropanol, n-pentanol, isoamyl alcohol, n-hexanol, n -Heptanol, 2-octanol, n-dodecanol, nonanol, cyclohexanol, propylene oxide, etc.), ether, acetal (ether, dichloroether, isopropyl ether, n-butyl ether , Diisoamyl ether, methyl phenyl ether, ethyl benzyl ether, furan, furfural, 2-methylfuran, cineol, methylal), ketone (acetone, methyl Ethyl ketone, methyl-n-propyl Ketones, methyl-n-pentyl ketones, diisobutyl ketones, phorone, isoflurone, cyclohexanone, acetophenone, etc.), esters (methyl formate, ethyl formate, propyl formate, Methyl acetate, ethyl acetate, propyl acetate, -n-pentyl acetate, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, etc. Propyl ester, diethyl carbonate, ethylene carbonate, ethylene carbonate, etc.), polyols and their derivatives (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, etc.), fatty acids and phenols (formic acid, acetic acid, acetic anhydride) , Propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrate Phenylbenzene, monomethylamine, dimethylamine, trimethylamine, monoethylamine, dipentylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, dichlorohexylamine, Dicyclohexylamine, monoethanol Amine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-methylpyridine, 2,4-dimethylpyridine, quinoline, morpholine, etc.), sulfur, Phosphorus, other compounds (carbon disulfide, dimethyl sulfene, 4,4-diethyl-1,2-dithiocyclopentane, dimethyl sulfide, dimethyl disulfide, methyl mercaptan, propane Liquids such as sultone, triethyl phosphate, triphenyl phosphate, diethyl carbonate, ethylene carbonate, pentyl borate, etc., inorganic solvents (liquid ammonia, silicone oil, etc.), water

電池電極或分隔板塗布膜組成物中，為了配合塗布裝置而調整黏度，可以任意比率來添加溶劑。就塗布性之觀點而言，電池電極或分隔板塗布膜組成物之黏度 以1~10,000mPa‧s為佳，又較佳為2~5000mPa‧s之黏度，更佳為3~1,000mPa‧s之黏度，將剪切速度20秒-1時之黏度設為C，剪切速度200秒-1時之黏度設為D之情形時，黏度較佳為C/D=E時的1<E<3之範圍。可適當決定溶劑之種類及含有量以達如此般之黏度。本發明中，黏度為藉由圓錐-平板式回轉黏度計所求得之值。 In the battery electrode or separator coating film composition, in order to adjust the viscosity in accordance with the coating device, a solvent may be added at an arbitrary ratio. From the viewpoint of coatability, the viscosity of the coating film composition of the battery electrode or separator is preferably 1 to 10,000 mPa · s, more preferably 2 to 5000 mPa · s, and more preferably 3 to 1,000 mPa‧ when the viscosity of the s, the viscosity when the shear rate of 20 seconds -1 is C, when the viscosity of a shear rate of 200 seconds -1 to D of the case, the viscosity is preferably 1 C / D = E <E <3 range. The type and content of the solvent can be appropriately determined to achieve such a viscosity. In the present invention, the viscosity is a value obtained by a cone-plate type rotary viscometer.

在不損及本發明之目的範圍內，電池電極或分隔板塗布膜組成物亦可包含其他粒子、蕊殼(core shell)型之發泡劑、鹽、具有離子性的液體、偶合劑、安定劑、防腐劑、及界面活性劑。 To the extent that the purpose of the present invention is not impaired, the battery electrode or separator coating film composition may also contain other particles, core shell-type foaming agents, salts, ionic liquids, coupling agents, Stabilizers, preservatives, and surfactants.

〔其他粒子〕 [Other particles]

電池電極或分隔板塗布膜組成物，可進而包含選自由有機填料、碳系填料及無機填料所構成之群之1種以上的粒子來作為其他粒子。其他粒子中不包含對於應力為具有不可逆塑性變形之性質及可逆彈性變形之性質的粒子(即，黏彈性粒子)。 The battery electrode or separator coating film composition may further include, as other particles, one or more particles selected from the group consisting of an organic filler, a carbon-based filler, and an inorganic filler. The other particles do not include particles (that is, viscoelastic particles) that have properties of irreversible plastic deformation and reversible elastic deformation with respect to stress.

作為有機填料之具體例，舉例如丙烯酸樹脂或環氧樹脂、聚醯亞胺等之高分子當中，經三次元交聯亦實質上未塑性變形的高分子或纖維素之粒子、聚矽氧粒子、或聚烯烴粒子，或該等之纖維、薄片等。有機填料可使用1種，或組合2種以上使用。 As specific examples of the organic filler, for example, among polymers such as acrylic resin, epoxy resin, and polyimide, polymer or cellulose particles and polysiloxane particles that are not substantially plastically deformed after three-dimensional cross-linking. Or polyolefin particles, or such fibers, flakes, etc. The organic filler may be used singly or in combination of two or more kinds.

作為碳系填料之具體例，舉例如石墨、乙炔黑、及奈米碳管。碳系填料可使用1種，或組合2種以上 使用。碳系填料係以不損及絕緣性之程度而可添加之粒子。 Specific examples of the carbon-based filler include graphite, acetylene black, and carbon nanotubes. One type of carbon-based filler can be used, or two or more types can be combined use. Carbon-based fillers are particles that can be added to such an extent that the insulation properties are not impaired.

作為無機填料之具體例，舉例如：氧化鋁、氧化矽、氧化鋯、氧化鈹、氧化鎂、氧化鈦、及氧化鐵等之金屬氧化物之粉末；膠質氧化矽或氧化鈦溶膠、氧化鋁溶膠等之溶膠、滑石、高嶺石、及膨潤石等之黏土礦物；碳化矽、及碳化鈦等之碳化物；氮化矽、氮化鋁、及氮化鈦等之氮化物；氮化硼、硼化鈦、及氧化硼等之硼化物；莫來石(Mullite)等之複合氧化物；氫氧化鋁、氫氧化鎂、及氫氧化鐵等之氫氧化物；鈦酸鋇、碳酸鍶、矽酸鎂、矽酸鋰、矽酸鈉、矽酸鉀、及玻璃等。又，作為不損及絕緣性之程度而可添加的無機填料，舉例如鈷酸鋰、橄欖石型磷酸鐵鋰。無機填料可使用1種，或適當組合2種以上使用。 Specific examples of the inorganic filler include powders of metal oxides such as alumina, silica, zirconia, beryllia, magnesia, titania, and iron oxide; colloidal silica, titania sol, and alumina sol Clay minerals such as sol, talc, kaolinite, and bentonite; carbides such as silicon carbide and titanium carbide; nitrides such as silicon nitride, aluminum nitride, and titanium nitride; boron nitride and boron Borides such as titanium oxide and boron oxide; composite oxides such as mullite; hydroxides of aluminum hydroxide, magnesium hydroxide, and iron hydroxide; barium titanate, strontium carbonate, and silicic acid Magnesium, lithium silicate, sodium silicate, potassium silicate, and glass. In addition, examples of the inorganic filler that can be added to the extent that the insulation is not impaired include lithium cobaltate and olivine-type lithium iron phosphate. One type of inorganic filler may be used, or two or more types may be used in combination.

為使表面之活性氫基活性化，無機填料較佳以200℃左右之高溫乾燥約1小時。藉由使活性氫基活性化，可提高對有機物粒子之密著性，提高機械強度或耐熱性，且藉由使電解質中之離子安定化而提高離子傳導性。 In order to activate the active hydrogen groups on the surface, the inorganic filler is preferably dried at a high temperature of about 200 ° C for about 1 hour. By activating an active hydrogen group, adhesion to organic particles can be improved, mechanical strength or heat resistance can be improved, and ion conductivity can be improved by stabilizing ions in an electrolyte.

無機填料可使用粉體，亦可以如氧化矽溶膠或氧化鋁溶膠般之水分散膠體之形態或如有機溶膠般之分散於有機溶劑中之狀態使用。該等亦可含於前述經熱熔著之有機物粒子中，亦可以密著於前述經熱熔著之有機物粒子表面之狀態使用，亦可以與前述經熱熔著之有機物粒子為獨立之狀態添加。 The inorganic filler can be used in the form of powder, or in the form of a water-dispersed colloid such as silica sol or alumina sol, or in the state of being dispersed in an organic solvent like an organic sol. These can also be contained in the thermally fused organic particles, can also be used in a state of being closely adhered to the surface of the thermally fused organic particles, or can be added in a separate state from the thermally fused organic particles. .

其他粒子之大小，較佳為0.001~100μm之範圍，更佳為0.005~10μm之範圍。更，就提升空隙率之觀點而言，亦以使用多孔質體的其他粒子為宜，具體而言，作為其他粒子亦可使用氧化矽凝膠或多孔質氧化鋁、各種沸石等的無機填料。 The size of other particles is preferably in the range of 0.001 to 100 μm, and more preferably in the range of 0.005 to 10 μm. Furthermore, from the viewpoint of increasing the porosity, it is also preferable to use other particles of a porous body. Specifically, inorganic fillers such as silica gel, porous alumina, and various zeolites may be used as the other particles.

其他粒子之表面，可經各種偶合劑予以修飾。作為偶合劑，舉例如矽烷系偶合劑及鈦系偶合劑。 The surface of other particles can be modified by various coupling agents. Examples of the coupling agent include a silane-based coupling agent and a titanium-based coupling agent.

作為矽烷系偶合劑，氟系的矽烷偶合劑方面，舉例如(十三氟-1,1,2,2-四氫辛基)三乙氧基矽烷；溴系的矽烷偶合劑方面，舉例如(2-溴-2-甲基)丙醯氧基丙基三乙氧基矽烷；氧雜環丁烷改質矽烷偶合劑方面，舉例如：東亞合成(股)製偶合劑(商品名：TESOX)，或者乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷(市售品方面有KBM-403(信越化學工業(股)製))、β-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、氰醇矽烷醚等之矽烷偶合劑。 As a silane-based coupling agent, for example, a fluorine-based silane coupling agent may include (tridecylfluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane; for a bromine-based silane coupling agent, for example, (2-bromo-2-methyl) propanyloxypropyltriethoxysilane; oxetane modified silane coupling agents, for example: a coupling agent (trade name: TESOX) ), Or vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidyloxypropyltrimethoxysilane ( Commercially available products include KBM-403 (by Shin-Etsu Chemical Industry Co., Ltd.)), β-glycidyloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, Silane coupling agents such as γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and cyanohydrin silane.

作為鈦系偶合劑，可舉例如：三乙醇胺鈦酸酯、乙醯基丙酮酸鈦、乙基乙醯基乙酸鈦、乳酸鈦、乳酸鈦銨鹽、四硬脂基鈦酸酯、異丙基三異丙苯基苯基鈦酸 酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、二異丙苯基苯基氧基乙酸酯鈦酸酯、異丙基三辛醇鈦酸酯、異丙基二甲基丙烯酸基異硬脂醯基鈦酸酯、乳酸鈦乙酯、辛二醇鈦酸酯、異丙基三異硬脂醯基鈦酸酯、三異硬脂基異丙基鈦酸酯、異丙基三-十二烷基苯磺醯基鈦酸酯、肆(2-乙基己基)鈦酸酯、丁基鈦酸酯二聚物、異丙基異硬脂醯基二丙烯酸基鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、異丙基參(二辛基焦磷酸酯)鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯、四辛基雙(二-十三烷基亞磷酸酯)鈦酸酯、肆(2,2-二烯丙氧基甲基-1-丁基)雙(二-十三烷基)亞磷酸酯鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、雙(二辛基焦磷酸酯)伸乙基鈦酸酯、四-i-丙基鈦酸酯、四-n-丁基鈦酸酯、二異硬脂醯基伸乙基鈦酸酯等。 Examples of the titanium-based coupling agent include triethanolamine titanate, titanium ethionylpyruvate, titanium ethylacetonyl acetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, and isopropyl group. Tricumylphenyl titanic acid Ester, isopropyltris (N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, isopropyltrioctanol titanate, isopropyl Propyl dimethacrylate isostearyl fluorenyl titanate, titanium lactate, octyl glycol titanate, isopropyl triisostearyl fluorenyl titanate, triisostearyl isopropyl titanium Acid esters, isopropyltris-dodecylbenzenesulfonyl titanate, bis (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl isostearyl diyl Acrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, tetraisopropylbis (dioctyl phosphite) Titanate, tetraoctylbis (di-tridecyl phosphite) titanate, (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) ) Phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetra-i-propyl titanate Esters, tetra-n-butyl titanates, diisostearyl acetoethyl titanates, and the like.

作為偶合劑，較佳為：鈦系偶合劑、及乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、β-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、及氰醇矽烷醚。矽烷系偶合劑及鈦系偶合劑可使用1種，或組合2種以上使用。 As the coupling agent, a titanium-based coupling agent, and vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-aminopropyltriethoxysilane are preferable. , N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and cyanohydrin silane. The silane-based coupling agent and the titanium-based coupling agent may be used singly or in combination of two or more kinds.

如此般的偶合劑，可藉由引起與電池電極表面或分隔板表面之相互作用而提高密著力。又，亦可藉由該等偶合劑來被覆其他粒子之表面，以偶合劑分子造成之排斥效果，可在其他粒子間產生間隙，於其間傳導離子藉而提高離子傳導性。又，藉由以偶合劑來被覆無機填料、聚矽氧粒子或聚烯烴粒子等之表面，可使該等粒子疏水化，因此，可更提高消泡性。又，藉由以矽烷偶合劑來取代其他粒子之表面之活性氫，可使表面吸附水之量減少，因此，可降低成為非水系電池內特性降低之原因的水分之量。又，其他粒子，以表面藉由接枝聚合所形成的高分子鏈被覆的粒子為佳。高分子鏈且包含其較佳者，可示例如在本發明之黏彈性粒子中所說明者。 Such a coupling agent can improve adhesion by causing interaction with the surface of a battery electrode or the surface of a separator. In addition, the surface of other particles can also be covered by these coupling agents, and the repulsive effect caused by the coupling agent molecules can create a gap between other particles, thereby conducting ions between them to improve ion conductivity. In addition, by coating the surface of the inorganic filler, polysiloxane particles, or polyolefin particles with a coupling agent, the particles can be made hydrophobic, and therefore, the defoaming property can be further improved. In addition, by replacing active hydrogen on the surface of other particles with a silane coupling agent, the amount of water adsorbed on the surface can be reduced, and therefore, the amount of moisture that can cause a decrease in characteristics in a non-aqueous battery can be reduced. The other particles are preferably particles whose surface is covered with a polymer chain formed by graft polymerization. The polymer chain that includes the preferred ones can be exemplified as described in the viscoelastic particles of the present invention.

同樣的效果亦可調配樹枝狀聚合物而獲得。離子傳導性之提高，較佳導入具有與介電率高之氰基或離子之相互作用強之聚氧乙烯等構造。對於等電點之pH為7以上之無機粒子可更好地應用鈦系的偶合劑，對於等電點之pH未達7之無機粒子則可更好地應用矽烷偶合劑。無機粒子之等電點之pH可使用例如等電點為以JIS R1638「微細陶瓷粉末之等電點之測定方法」中規定之方法測定之數值，可示例如：氧化矽(pH約1.8)、高嶺土(pH約5.1)、莫來石(pH約6.3；改變矽與鋁之比率可某種程度的控制等電點之pH)、氧化鈦(銳鈦礦型)(pH約6.2)、氧化錫(pH約6.9)、軟水鋁石(Boehmite)(pH約7.7)、γ-氧化鋁(pH約7.9)、α-氧化鋁(pH 約9.1)、氧化鈹(pH約10.1)、氫氧化鐵；Fe(OH)2(pH約12.0)、氫氧化錳(pH約12.0)、氫氧化鎂(pH約12.4)等。 The same effect can also be obtained by blending a dendrimer. To improve the ion conductivity, it is preferable to introduce a structure such as polyoxyethylene having a strong interaction with a cyano group or an ion having a high dielectric constant. For inorganic particles with an isoelectric point pH of 7 or higher, a titanium-based coupling agent can be better used, and for inorganic particles whose isoelectric point has a pH of less than 7, a silane coupling agent can be better applied. The pH of the isoelectric point of the inorganic particles can be, for example, a value measured by a method specified in JIS R1638 "Method for Measuring the Isoelectric Point of Fine Ceramic Powders". Examples include: silicon oxide (pH about 1.8), Kaolin (pH about 5.1), mullite (pH about 6.3; changing the ratio of silicon to aluminum can control the pH of the isoelectric point to some extent), titanium oxide (anatase type) (pH about 6.2), tin oxide (pH about 6.9), Boehmite (pH about 7.7), γ-alumina (pH about 7.9), α-alumina (pH about 9.1), beryllium oxide (pH about 10.1), iron hydroxide; Fe (OH) 2 (pH about 12.0), manganese hydroxide (pH about 12.0), magnesium hydroxide (pH about 12.4), and the like.

在不使空隙率或空隙之連續性降低之範圍內，本發明之電池電極或分隔板塗布膜組成物可添加上述其他粒子，較佳相對於黏彈性粒子100重量份，可使含有0~90重量份，又較佳為含有0~50重量份。又，本發明之組成物中，不損及絕緣性之程度而可添加的碳系填料及無機填料之含有量，相對於黏彈性粒子100重量份，較佳為0.01~10重量份，又較佳為0.1~5重量份。 As long as the porosity and the continuity of the voids are not reduced, the battery electrode or separator coating film composition of the present invention may include the above-mentioned other particles, and it is preferable to contain 0 to 100 parts by weight of the viscoelastic particles. 90 parts by weight, and preferably 0 to 50 parts by weight. In addition, in the composition of the present invention, the content of the carbon-based filler and the inorganic filler that can be added without impairing the degree of insulation is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the viscoelastic particles. It is preferably 0.1 to 5 parts by weight.

其他粒子，可使用2種以上。等電點之pH差異大的無機填料之組合，容易引起酸鹼基相互作用，但以使一方的活性氫增多之方式調配者，可提高另一方的活性氫之活性，故宜。具體而言較佳為，等電點之pH較小之氧化矽與等電點之pH較大之無機填料，如γ-氧化鋁、α-氧化鋁、氧化鈹、氫氧化鐵、氫氧化錳、氫氧化鎂之組合；又較佳為，氧化矽與α-氧化鋁之組合，或氧化矽與氫氧化鎂之組合。於Li離子電池時，等電點之pH較小之氧化矽之添加量，相對於等電點之pH較大之無機填料，較佳為0.1~100重量%之範圍，又較佳為1~10重量%之範圍。 For other particles, two or more kinds can be used. Combinations of inorganic fillers with large differences in isoelectric point pH are likely to cause acid-base interactions. However, those formulated in such a way as to increase the active hydrogen on one side can increase the activity of the active hydrogen on the other side. Specifically, preferably, silicon oxide having a low isoelectric point pH and inorganic filler having a high isoelectric point pH, such as γ-alumina, α-alumina, beryllium oxide, iron hydroxide, and manganese hydroxide And a combination of magnesium hydroxide; and more preferably, a combination of silicon oxide and α-alumina, or a combination of silicon oxide and magnesium hydroxide. In Li-ion batteries, the addition amount of silicon oxide with a low isoelectric point pH is preferably in the range of 0.1 to 100% by weight, and more preferably 1 to 100% of the inorganic filler with a higher isoelectric point pH. A range of 10% by weight.

〔蕊殼型之發泡劑〕 [Core-shell type foaming agent]

本發明之電池電極或分隔板塗布膜組成物，可包含蕊 殼型之發泡劑。作為如此般的發泡劑，可使用EXPANCEL(日本FILLITE(股)製)等。殼由於為有機物故對電解液缺乏長期信賴性。因此，可使用以無機物進一步被覆該蕊殼型發泡劑而成者。作為如此般的無機物，可示例如：氧化鋁、氧化矽、氧化鋯、氧化鈹、氧化鎂、氧化鈦、及氧化鐵等之金屬氧化物；膠質氧化矽或氧化鈦溶膠、氧化鋁溶膠等之溶膠；氧化矽凝膠、及活性氧化鋁等之凝膠；莫來石等之複合氧化物；氫氧化鋁、氫氧化鎂、氫氧化鐵等之氫氧化物、以及鈦酸鋇。該等無機物可藉由溶膠-凝膠反應或加熱而被覆於黏彈性粒子表面。又，無機物被覆前，表面經鉻酸鹽處理或電漿處理、添加PVA或羧基甲基纖維素、澱粉等水溶性高分子及該等前述之聚羧酸，以經酯交聯之調配物進行表面處理，可提高密著性。 The battery electrode or separator coating film composition of the present invention may include a core Shell-type foaming agent. As such a foaming agent, EXPANCEL (made by Japan FILLITE) can be used. Because the shell is organic, it lacks long-term reliability in the electrolyte. Therefore, the core-shell type foaming agent can be further coated with an inorganic substance. Examples of such inorganic substances include metal oxides such as alumina, silica, zirconia, beryllia, magnesia, titania, and iron oxide; colloidal silica, titania sol, and alumina sol. Sol; silica gel, and gels of activated alumina; composite oxides of mullite; hydroxides of aluminum hydroxide, magnesium hydroxide, iron hydroxide; and barium titanate. These inorganic substances can be coated on the surface of the viscoelastic particles by sol-gel reaction or heating. In addition, before the inorganic substance is coated, the surface is treated with chromate treatment or plasma treatment, and water-soluble polymers such as PVA or carboxymethyl cellulose, starch, and the aforementioned polycarboxylic acid are added, and the preparation is performed by ester-crosslinking preparation. Surface treatment can improve adhesion.

藉由使用組合在一定溫度下軟化之殼與由藉加熱而蒸發等之體積會膨脹之材料所成之蕊而成之蕊殼型發泡劑，在電池熱暴衝時，可因發泡劑之發泡使電極間之距離擴大，藉此可發揮斷電機能。更，藉由使殼部大幅膨脹，可使電極間距離擴大，藉此可防止短路等。又，即使發熱結束膨脹的殼部亦可維持其形狀，因此亦可防止電極間再度變窄的再度短路。又，藉由以無機物來被覆蕊殼型發泡劑，可降低充放電時電分解之影響，進而亦可藉由使無機物表面之活性氫基成為離子傳導之相對離子(counter ion)而效率良好地提高離子傳導性。 By using a core-shell type foaming agent formed by combining a shell that softens at a certain temperature and a core made of a material that expands by heating and evaporating, the foaming agent can be used when the battery is bursting. The foaming expands the distance between the electrodes, so that the interrupting power can be exerted. Furthermore, by greatly expanding the case portion, the distance between the electrodes can be increased, thereby preventing short circuits and the like. In addition, the shape of the case can be maintained even if the expansion is completed after the heat generation, so that the short circuit between the electrodes can be prevented from narrowing again. In addition, by covering the core-shell type foaming agent with an inorganic substance, the effect of electrolysis during charge and discharge can be reduced, and the active hydrogen group on the surface of the inorganic substance can also be used as an ion-conducting counter ion to improve efficiency. To improve ion conductivity.

本發明之電池電極或分隔板塗布膜組成物，相對於黏彈性粒子及黏結劑之合計100重量份，較佳含有上述蕊殼型發泡劑1~99重量份，又較佳為含有10~98重量份，更佳為含有20~97重量份。 The battery electrode or separator coating film composition of the present invention preferably contains 1 to 99 parts by weight of the core-shell type foaming agent described above with respect to 100 parts by weight of the total of the viscoelastic particles and the binder, and further preferably contains 10 ~ 98 parts by weight, more preferably 20 to 97 parts by weight.

〔鹽〕 〔salt〕

本發明之電池電極或分隔板保護膜組成物，可調配成為各種離子源之鹽。據此，可提高離子傳導性。亦可添加所使用之電池之電解質。在鋰離子電池之情況下，作為電解質可示例如：氫氧化鋰、矽酸鋰、六氟化磷酸鋰、四氟化硼酸鋰、過氯酸鋰、雙(三氟甲烷磺醯基)醯亞胺鋰、雙(五氟乙烷磺醯基)醯亞胺鋰、及三氟甲烷磺酸鋰等，在鈉離子電池之情況下，可示例如：氫氧化鈉、及過氯酸鈉等。在鈣離子電池之情況下，作為電解質可示例如：氫氧化鈣、及過氯酸鈣等。在鎂離子電池之情況下，作為電解質可示例如：過氯酸鎂。在電雙層電容器之情況下，作為電解質可示例如：四氟化硼酸四乙基銨、三乙基甲基銨雙(三氟甲烷磺醯基)醯亞胺、及四乙基銨雙(三氟甲烷磺醯基)醯亞胺等。 The battery electrode or separator protective film composition of the present invention can be adjusted to form salts of various ion sources. Thereby, ion conductivity can be improved. The electrolyte of the battery used can also be added. In the case of a lithium ion battery, examples of the electrolyte include lithium hydroxide, lithium silicate, lithium hexafluoride phosphate, lithium tetrafluoride borate, lithium perchlorate, and bis (trifluoromethanesulfonyl) fluorene. In the case of a sodium ion battery, lithium amine, lithium bis (pentafluoroethanesulfonyl) fluorenimide, and lithium trifluoromethanesulfonate can be exemplified by sodium hydroxide and sodium perchlorate. In the case of a calcium ion battery, examples of the electrolyte include calcium hydroxide and calcium perchlorate. In the case of a magnesium ion battery, examples of the electrolyte include magnesium perchlorate. In the case of an electric double-layer capacitor, examples of the electrolyte include tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethanesulfonyl) sulfonium imine, and tetraethylammonium bis ( Trifluoromethanesulfonyl) fluorenimine and the like.

本發明之電池電極或分隔板塗布膜組成物，相對於黏彈性粒子及黏結劑之合計100重量份，較佳含有上述鹽0.1~300重量份，又較佳含有0.5~200重量份，更佳含有1~100重量份。上述鹽可以粉體添加，或成為多孔質添加，亦可溶解於調配成分中使用。 The battery electrode or separator coating film composition of the present invention preferably contains 0.1 to 300 parts by weight of the above salt, and more preferably 0.5 to 200 parts by weight, with respect to 100 parts by weight of the total of the viscoelastic particles and the binder. It preferably contains 1 to 100 parts by weight. The above-mentioned salt may be added as a powder, or may be added as a porous material, or it may be dissolved in a preparation component and used.

〔具有離子性的液體〕 [Ionic liquid]

本發明之電池電極或分隔板塗布膜組成物，可包含具有離子性的液體。具有離子性的液體可為使前述鹽溶解於溶劑中之溶液或離子性液體。作為使鹽溶解於溶劑中之溶液，可示例如六氟化磷酸鋰或硼氟化四乙基銨等之鹽溶解於碳酸二甲酯等之溶劑中之溶液。 The battery electrode or separator coating film composition of the present invention may contain a liquid having an ionic property. The ionic liquid may be a solution or an ionic liquid in which the aforementioned salt is dissolved in a solvent. Examples of the solution in which a salt is dissolved in a solvent include a solution in which a salt such as lithium hexafluorophosphate or tetraethylammonium borofluoride is dissolved in a solvent such as dimethyl carbonate.

作為離子性液體之例，可示例如：1,3-二甲基咪唑鎓甲基硫酸鹽、1-乙基-3-甲基咪唑鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓溴化物等之咪唑鎓鹽衍生物；3-甲基-1-丙基吡啶鎓雙(三氟甲基磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺等之吡啶鎓鹽衍生物；四丁基銨十七氟辛烷磺酸鹽、四苯基銨甲烷磺酸鹽等之烷基銨衍生物；四丁基鏻甲烷磺酸鹽等之鏻鹽衍生物；聚烷撐二醇與過氯酸鋰等之複合物等之複合化導電性賦予劑等。 Examples of the ionic liquid include 1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) fluorenimine, Imidazolium salt derivatives such as 1-ethyl-3-methylimidazolium bromide; 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-butyl Pyridinium salt derivatives such as 3-methylpyridinium bis (trifluoromethylsulfonyl) sulfonium imine; tetrabutylammonium heptafluorooctane sulfonate, tetraphenylammonium methane sulfonate, etc. Alkylammonium derivatives; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; composite conductivity imparting agents such as a complex of polyalkylene glycol and lithium perchlorate; and the like.

具有離子性的液體之含有量，相對於黏彈性粒子100重量份，較佳為0.01~40重量份，又較佳為0.1~30重量份，更佳為0.5~5重量份。 The content of the ionic liquid is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the viscoelastic particles.

〔偶合劑〕 [Coupling agent]

本發明之電池電極或分隔板塗布膜組成物，可進而包含偶合劑。偶合劑且包含其較佳者，可示例如前述所示例的偶合劑。偶合劑之含有量，相對於黏彈性粒子100重量 份，較佳包含0.001~10重量份，又較佳包含0.01~5重量份。 The battery electrode or separator coating film composition of the present invention may further include a coupling agent. As the coupling agent, and the preferred ones are included, the coupling agents as exemplified above can be exemplified. Coupling agent content, relative to 100 weight of viscoelastic particles Parts, preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight.

〔安定劑〕 〔Stabilizer〕

本發明之電池電極或分隔板塗布膜組成物，可選擇並含有安定劑。作為如此般的安定劑，具體而言可舉例如：以2,6-二-tert-丁基酚、2,4-二-tert-丁基酚、2,6-二-tert-丁基-4-乙基酚、2,4-雙-(n-辛硫基)-6-(4-羥基-3,5-二-tert-丁基苯胺基)-1,3,5-三嗪等所示例之酚系抗氧化劑；以烷基二苯基胺、N,N’-二苯基-p-苯二胺、6-乙氧基-2,2,4-三甲基-1,2-二氫喹啉、N-苯基-N’-異丙基-p-苯二胺等所示例之芳香族胺系抗氧化劑；以二月桂基-3,3’-硫代二丙酸酯、二-十三烷基-3,3’-硫代二丙酸酯、雙[2-甲基-4-{3-n-烷基硫代丙醯氧基}-5-tert-丁基-苯基]硫醚、2-巰基-5-甲基-苯并咪唑等所示例之硫醚系過氧化氫分解劑；以參(異癸基)亞磷酸酯、苯基二異辛基亞磷酸酯、二苯基異辛基亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、3,5-二-tert-丁基-4-羥基-苄基磷酸二乙酯、雙(4-tert-丁基苯基)磷酸鈉等所示例之磷系過氧化氫分解劑；以水楊酸苯酯、4-tert-辛基苯基水楊酸酯等所示例之水楊酸酯系光安定劑；以2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮-5-磺酸等所示例之二苯甲酮系光安定劑；以2-(2’-羥基-5’-甲基苯基)苯并***、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2N-苯并***-2-基)酚]等所 示例之苯并***系光安定劑；以苯基-4-哌啶基碳酸酯、癸二酸雙-[2,2,6,6-四甲基-4-哌啶基]酯等所示例之受阻胺系光安定劑；以[2,2’-硫基-雙(4-tert-辛基酚酸酯)]-2-乙基己基胺-鎳-(II)所示例之Ni系光安定劑；氰基丙烯酸酯系光安定劑；草酸醯胺苯系光安定劑；富勒烯、氫化富勒烯、氫氧化富勒烯之富勒烯系光安定劑等。該等安定劑可使用1種或組合2種以上使用。 The battery electrode or separator coating film composition of the present invention can be selected and contains a stabilizer. Specific examples of such stabilizers include 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, and 2,6-di-tert-butyl- 4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylaniline) -1,3,5-triazine, etc. Illustrative phenolic antioxidant; alkyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2 -Dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, and other examples of aromatic amine antioxidants; dilauryl-3,3'-thiodipropionate , Di-tridecyl-3,3'-thiodipropionate, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl -Phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole, and other examples of thioether-based hydrogen peroxide decomposing agents; ginseng (isodecyl) phosphite, phenyldiisooctyl Phosphate, diphenyl isooctyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl diethyl phosphate, bis ( Phosphorus-based hydrogen peroxide decomposing agents such as 4-tert-butylphenyl) sodium phosphate; phenyl salicylate, 4-tert-octylphenyl water Salicylate light stabilizers such as salicylate; exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc. Benzophenone-based light stabilizers; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] Exemplary benzotriazole light stabilizers; phenyl-4-piperidinyl carbonate, sebacate bis- [2,2,6,6-tetramethyl-4-piperidinyl] ester, etc. Exemplary hindered amine light stabilizers; Ni based on [2,2'-thio-bis (4-tert-octylphenolate)]-2-ethylhexylamine-nickel- (II) Light stabilizers; cyanoacrylate-based light stabilizers; ammonium oxalate benzene-based light stabilizers; fullerenes, hydrogenated fullerenes, fullerene hydroxide-based light stabilizers, and the like. These stabilizers can be used singly or in combination of two or more kinds.

安定劑之含有量，相對於黏彈性粒子100重量份，較佳為0.01~10重量份，又較佳為0.05~5重量份，更佳為0.1~1重量份。 The content of the stabilizer is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 1 part by weight based on 100 parts by weight of the viscoelastic particles.

〔防腐劑〕 〔preservative〕

本發明之電池電極或分隔板塗布膜組成物，可進而包含防腐劑，藉此，可調節該組成物之保存安定性。 The battery electrode or separator coating film composition of the present invention may further contain a preservative, whereby the storage stability of the composition can be adjusted.

作為防腐劑，可舉例：如苯甲酸、水楊酸、去氫乙酸、山梨酸般的酸；如苯甲酸鈉、水楊酸鈉、去氫乙酸鈉、及山梨酸鉀般的鹽；如2-甲基-4-異噻唑啉-3-酮、及1,2-苯并異噻唑啉-3-酮般的異噻唑啉系防腐劑；甲醇、乙醇、異丙醇、及乙二醇等的醇類；對羥基苯甲酸酯類、苯氧基乙醇、羥基氯苯胺、鹽酸克羅希西定(chlorhexidine hydrochloride)等。 Examples of the preservative include acids such as benzoic acid, salicylic acid, dehydroacetic acid, and sorbic acid; salts such as sodium benzoate, sodium salicylate, sodium dehydroacetate, and potassium sorbate; such as 2- Methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one-like isothiazoline preservatives; methanol, ethanol, isopropanol, and ethylene glycol Alcohols; parabens, phenoxyethanol, hydroxychloroaniline, chlorhexidine hydrochloride, etc.

該等防腐劑可使用1種，或組合2種以上使用。 These preservatives can be used singly or in combination of two or more kinds.

防腐劑之含有量，相對於黏彈性粒子100重 量份，較佳為0.0001~1重量份，又較佳為0.0005~0.5重量份。 The content of preservative is 100 heavier than viscoelastic particles The amount is preferably 0.0001 to 1 part by weight, and more preferably 0.0005 to 0.5 part by weight.

〔界面活性劑〕 〔Surface active agent〕

本發明之電池電極或分隔板塗布膜組成物，以調節組成物之潤濕性或消泡性為目的，可進而包含界面活性劑。又，本發明之電池電極或分隔板塗布膜組成物進而以提高離子傳導性為目的，可包含離子性的界面活性劑。 The battery electrode or separator coating film composition of the present invention may further contain a surfactant for the purpose of adjusting the wettability or defoaming property of the composition. The battery electrode or separator coating film composition of the present invention may further include an ionic surfactant for the purpose of improving ion conductivity.

作為界面活性劑，陰離子界面活性劑方面，可舉例如：皂、月桂基硫酸鹽、聚氧乙烯烷基醚硫酸鹽、烷基苯磺酸鹽(例如，十二烷基苯磺酸鹽)、聚氧乙烯烷基醚磷酸鹽、聚氧乙烯烷基苯基醚磷酸鹽、N-醯基胺基酸鹽、α-烯烴磺酸鹽、烷基硫酸酯鹽、烷基苯基醚硫酸酯鹽、甲基牛磺酸鹽、三氟甲烷磺酸鹽、五氟乙烷磺酸鹽、七氟丙烷磺酸鹽、九氟丁烷磺酸鹽等；相對陽離子(counter cation)方面，可使用鈉離子或鋰離子等。鋰離子電池中更好為鋰離子類型的界面活性劑，鈉離子電池中更好為鈉離子類的界面活性劑。 As the surfactant, for the anionic surfactant, for example, soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate (for example, dodecylbenzenesulfonate), Polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate, N-fluorenylamino acid salt, α-olefin sulfonate, alkyl sulfate, alkylphenyl ether sulfate , Methyl taurate, trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, etc .; in terms of counter cation, sodium ions or Lithium ions, etc. The lithium ion battery is more preferably a lithium ion type surfactant, and the sodium ion battery is more preferably a sodium ion type surfactant.

作為兩性界面活性劑，舉例如：鹽酸烷基二胺基乙基甘胺酸、2-烷基-N-羧基甲基-N-羥基乙基咪唑鎓甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、椰子油脂肪酸醯胺丙基甜菜鹼、脂肪酸烷基甜菜鹼、磺基甜菜鹼、醯胺氧化物(amioxide)等。 Examples of the amphoteric surfactant include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, and lauryldimethylaminoacetic acid. Betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amioxide and the like.

作為非離子(nonion)型界面活性劑，舉例 如：聚乙二醇或乙炔二醇(acetylenic glycol)等之烷基酯型化合物、三乙二醇單丁醚等之烷基醚型化合物、聚氧山梨醇酐酯等之酯型化合物、烷基酚型化合物、氟型化合物、聚矽氧型化合物等。 Examples of nonionic surfactants For example: alkyl ester compounds such as polyethylene glycol or acetylenic glycol, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxy sorbitan esters, alkyl Phenol-based compounds, fluorine-based compounds, polysiloxane compounds, and the like.

界面活性劑可使用1種，或組合2種以上使用。 The surfactant can be used singly or in combination of two or more kinds.

界面活性劑之含有量，相對於黏彈性粒子100重量份，較佳為0.01~50重量份，又較佳為0.05~20重量份，更佳為0.1~10重量份。 The content of the surfactant is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the viscoelastic particles.

本發明之電池電極或分隔板塗布膜組成物係使用用來保護電池電極或分隔板。即，本發明之組成物係作為用來形成於電池電極或分隔板之至少表面的塗布膜之組成物使用，且該一部份亦可進入電池電極或分隔板之內部。 The battery electrode or separator coating film composition of the present invention is used to protect the battery electrode or separator. That is, the composition of the present invention is used as a composition for forming a coating film on at least the surface of a battery electrode or a separator, and this part can also enter the inside of a battery electrode or a separator.

〔電池電極或分隔板塗布膜組成物之製造〕 [Manufacture of battery electrode or separator coating film composition]

本發明之電池電極或分隔板塗布膜組成物，可藉由混合上述成分並攪拌而製作。尚，本發明之黏彈性粒子能以分散於溶劑中之狀態來混合。攪拌可使用葉片式混練機、行星式混練機、混合式混練機、捏合機、乳化用均質機、及超音波均質機等之攪拌裝置來進行。又，亦可視需要邊加熱或冷卻邊攪拌。 The battery electrode or separator coating film composition of the present invention can be produced by mixing the above components and stirring them. However, the viscoelastic particles of the present invention can be mixed in a state of being dispersed in a solvent. Stirring can be performed by using a stirring device such as a blade kneader, a planetary kneader, a hybrid kneader, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. If necessary, stirring may be performed while heating or cooling.

本發明中，表面經接枝聚合形成的高分子所被覆的黏彈性粒子，其製造方法包含下述步驟：將本發明 之黏彈性粒子與具有反應性取代基的偶合劑混合，而得到經表面修飾的黏彈性粒子之步驟；及，將經表面修飾的黏彈性粒子、與聚合性化合物(其係與經表面修飾的黏彈性粒子所具有的反應性取代基為能反應者)混合，並藉由接枝聚合，而得到表面經接枝聚合形成的高分子所被覆的黏彈性粒子之步驟。 In the present invention, the manufacturing method of the viscoelastic particles covered with a polymer formed on the surface by graft polymerization includes the following steps: Mixing viscoelastic particles with a coupling agent having a reactive substituent to obtain surface-modified viscoelastic particles; and, combining surface-modified viscoelastic particles with a polymerizable compound (which is similar to a surface-modified The reactive substituents of the viscoelastic particles are those capable of reacting), and then graft polymerization is performed to obtain the viscoelastic particles covered by the polymer formed on the surface by graft polymerization.

藉由得到經表面修飾的黏彈性粒子之步驟，具有反應性取代基的矽烷偶合劑係固定化於黏彈性粒子之表面。前述接枝聚合可將固定化於表面修飾後表面的該反應性取代基作為反應起點來進行。尚，所謂的「固定化」，指化學性鍵結於黏彈性粒子表面之狀態或物理性吸附於黏彈性粒子表面之狀態之意思。 By the step of obtaining the surface-modified viscoelastic particles, the silane coupling agent having a reactive substituent is immobilized on the surface of the viscoelastic particles. The aforementioned graft polymerization can be performed using the reactive substituent immobilized on the surface after surface modification as a starting point of the reaction. Still, the so-called "immobilization" means the state of being chemically bonded to the surface of the viscoelastic particle or the state of being physically adsorbed on the surface of the viscoelastic particle.

作為一端具有反應性取代基的偶合劑，舉例如前述矽烷系偶合劑及鈦系偶合劑，較佳為氟系的矽烷偶合劑及溴系的矽烷偶合劑；特佳為(2-溴-2-甲基)丙醯氧基丙基三乙氧基矽烷。 Examples of the coupling agent having a reactive substituent at one end include the aforementioned silane-based coupling agent and titanium-based coupling agent, preferably a fluorine-based silane coupling agent and a bromine-based silane coupling agent; particularly preferred is (2-bromo-2 -Methyl) propanyloxypropyltriethoxysilane.

一端具有反應性取代基的偶合劑之使用量，相對於黏彈性粒子之固形分100重量份，較佳為0.1~200重量份，又較佳為1~150重量份。 The amount of the coupling agent having a reactive substituent at one end is preferably 0.1 to 200 parts by weight, and more preferably 1 to 150 parts by weight, relative to 100 parts by weight of the solid content of the viscoelastic particles.

本發明中，在得到經表面修飾的黏彈性粒子之步驟後，可包含使用前述溶劑來洗淨黏彈性粒子之步驟。藉此，可除去未反應的偶合劑等之反應殘渣。在洗淨黏彈性粒子之步驟中所使用的溶劑，只要是可溶解反應殘渣且不使表面修飾的高分子剝離者即可，未特別限定；使 用的溶劑之量，只要是可除去反應殘渣之量即可，未特別限定。 In the present invention, after the step of obtaining the surface-modified viscoelastic particles, the step of washing the viscoelastic particles with the aforementioned solvent may be included. Thereby, reaction residues such as an unreacted coupling agent can be removed. The solvent used in the step of washing the viscoelastic particles is not particularly limited as long as it dissolves the reaction residue and does not peel off the surface-modified polymer; The amount of the solvent used is not particularly limited as long as it can remove the reaction residue.

作為與經表面修飾的黏彈性粒子所具有的反應性取代基為能反應的聚合性化合物，舉例如前述的具有(甲基)丙烯酸基、烯丙基、乙烯基、馬來醯亞胺基之化合物、具有環氧基、氧雜環丁烷環等之環氧乙烷環、乙烯醚、環狀乙縮醛等之化合物，可選擇能與經表面修飾的黏彈性粒子所具有的反應性取代基反應並鍵結者。作為如此般的組合，例如反應性取代基為(2-溴-2-甲基)丙醯氧基時，作為聚合性化合物係舉例如具有(甲基)丙烯酸基、烯丙基、及乙烯基之化合物。聚合性化合物之量，只要是可得到經所希望的聚合物所被覆的黏彈性粒子之量即可，未特別限定，相對於原料的黏彈性粒子100重量份，較佳為100~300重量份。 The reactive substituents with the surface-modified viscoelastic particles are polymerizable compounds that can react, such as those having a (meth) acrylic group, an allyl group, a vinyl group, or a maleimide group. Compounds, compounds with ethylene oxide rings such as epoxy groups, oxetane rings, vinyl ethers, cyclic acetals, etc., can be selected to be reactively substituted with surface-modified viscoelastic particles Radicals react and bond. As such a combination, for example, when the reactive substituent is (2-bromo-2-methyl) propanyloxy, examples of the polymerizable compound include a (meth) acrylic group, an allyl group, and a vinyl group. Of compounds. The amount of the polymerizable compound is not particularly limited as long as it can obtain viscoelastic particles coated with a desired polymer, and is preferably 100 to 300 parts by weight relative to 100 parts by weight of the viscoelastic particles of the raw material. .

聚合可在起始劑之存在下進行。起始劑可因應前述聚合性化合物之種類使用。作為如此般的起始劑，舉例如前述的潛在性熱起始劑、光陽離子起始劑、及熱陽離子起始劑，可因應所使用的聚合性化合物之種類使用。該等起始劑可單獨使用，亦可組合複數種使用。起始劑之使用量，可示例如前述潛在性熱起始劑、光陽離子起始劑、及熱陽離子起始劑之含有量。 Polymerization can be performed in the presence of an initiator. The initiator can be used in accordance with the type of the polymerizable compound. As such an initiator, for example, the aforementioned latent thermal initiator, photocationic initiator, and thermal cationic initiator can be used depending on the type of the polymerizable compound used. These initiators may be used singly or in combination. The amount of the initiator used may be exemplified by the aforementioned content of a latent thermal initiator, a photocationic initiator, and a thermal cationic initiator.

在得到表面經接枝聚合形成的高分子所被覆的黏彈性粒子之步驟後，亦可包含洗淨以前述高分子所被覆的黏彈性粒子之步驟。洗淨可使用前述溶劑。 After the step of obtaining the viscoelastic particles covered with the polymer formed on the surface by graft polymerization, the step of washing the viscoelastic particles covered with the polymer may be included. The aforementioned solvents can be used for washing.

〔電池電極或分隔板表面保護方法〕 [Method for protecting the surface of a battery electrode or a separator]

本發明之電池電極或分隔板表面保護方法包含下述步驟，其係在電池電極或分隔板表面形成1層以上如上述之電池電極或分隔板塗布膜組成物之層，並藉由使前述溶劑蒸散以形成具有空隙的塗布膜。藉由本發明之電池電極或分隔板塗布膜來保護電池電極或分隔板之表面。 The method for protecting the surface of a battery electrode or a separator according to the present invention includes the following steps. One or more layers of the above-mentioned battery electrode or separator coating film composition layer are formed on the surface of the battery electrode or the separator. The aforementioned solvent is evaporated to form a coating film having voids. The surface of a battery electrode or a separator is protected by the battery electrode or separator coating film of the present invention.

〔電池電極或分隔板塗布膜之製造方法〕 [Manufacturing method of battery electrode or separator coating film]

本發明亦有關在前述電池電極或分隔板表面保護方法中，使用本發明之電池電極或分隔板塗布膜組成物所得到的塗布膜。即，使用本發明之電池電極或分隔板塗布膜組成物以得到塗布膜之製造方法，當黏結劑為溶解於溶劑中之狀態時，包含下述步驟：於電池電極或分隔板表面形成至少1層以上前述電池電極或分隔板塗布膜組成物之塗布層之步驟；及，使溶劑蒸散之步驟。又，當黏結劑為不溶於溶劑的固體時，包含下述步驟：於電池電極或分隔板表面形成至少1層以上前述電池電極或分隔板塗布膜組成物之塗布層之步驟；使溶劑蒸散之步驟；及，在前述使溶劑蒸散之溫度條件下而固體黏結劑為未熱熔著之情形時，使前述固體黏結劑加熱熔著之步驟。 The present invention also relates to a coating film obtained by coating the film composition with the battery electrode or the separator of the present invention in the method for protecting the surface of a battery electrode or the separator. That is, the method for producing a coating film by using the battery electrode or the separator of the present invention to obtain a coating film, when the adhesive is in a state of being dissolved in a solvent, includes the following steps: forming on the surface of the battery electrode or the separator A step of coating at least one of the foregoing battery electrodes or separators with a coating layer of a film composition; and a step of evaporating a solvent. In addition, when the adhesive is a solid that is insoluble in a solvent, the method includes the steps of: forming a coating layer of at least one layer of the foregoing battery electrode or separator coating film composition on the surface of a battery electrode or a separator; The step of evapotranspiration; and the step of heating and melting the solid adhesive when the solid adhesive is not thermally fused under the temperature conditions for the solvent to evaporate.

〔塗布膜組成物之塗布層之形成方法〕 [Method for Forming Coating Layer of Coating Film Composition]

本發明之電池電極或分隔板塗布膜之製造方法中，可 利用凹版塗布器或狹長模嘴塗布器、噴霧塗布器、浸漬塗布器等來對於電池電極或分隔板形成塗布膜組成物之塗布層。塗布層之厚度較佳為0.01~100μm之範圍，就電特性及密著性之觀點而言，更佳為0.05~50μm之範圍。亦可為本發明之電池電極或分隔板塗布膜組成物之至少一部份含浸於電池電極或分隔板之內部之構造。藉由使本發明之電池電極或分隔板塗布膜組成物之至少一部份含浸於電池電極或分隔板之內部，可更抑制製程或加熱時的捲曲或變形。本發明中，塗布層之乾燥厚度(即，塗布膜之厚度)較佳為0.01~100μm之範圍，更佳為0.05~50μm之範圍。只要塗布膜之厚度為0.01μm以上，對於電子導電的絕緣性為良好，可抑制短路之危險性。只要塗布膜之厚度為100μm以下，由於電阻與厚度成比例增加，故相對於離子傳導的電阻為低，電池之充放電特性會提高。 In the method for producing a battery electrode or a separator coating film of the present invention, A gravure coater or a slit die coater, a spray coater, a dip coater, or the like is used to form a coating layer of a coating film composition for a battery electrode or a separator. The thickness of the coating layer is preferably in the range of 0.01 to 100 μm, and in terms of electrical characteristics and adhesion, more preferably in the range of 0.05 to 50 μm. It is also possible to impregnate at least a part of the coating film composition of the battery electrode or the separator of the present invention with the inside of the battery electrode or the separator. By impregnating at least a part of the battery electrode or the separator coating film composition of the present invention with the inside of the battery electrode or the separator, it is possible to further suppress curling or deformation during manufacturing or heating. In the present invention, the dry thickness of the coating layer (that is, the thickness of the coating film) is preferably in the range of 0.01 to 100 μm, and more preferably in the range of 0.05 to 50 μm. As long as the thickness of the coating film is 0.01 μm or more, the insulating property for electronic conduction is good, and the danger of short circuit can be suppressed. As long as the thickness of the coating film is 100 μm or less, since the resistance increases in proportion to the thickness, the resistance to ion conduction is low, and the charge and discharge characteristics of the battery are improved.

當本發明之電池電極或分隔板塗布膜組成物之至少一部份為含浸於電池電極或分隔板之內部時，該組成物之含浸量，以不完全填埋電極或分隔板之細孔構造之量，即，以電極或分隔板之空隙率超過0%之量為佳，又較佳為電極或分隔板之空隙率為50%以上之量，更佳為電極或分隔板之空隙率為75%以上之量。 When at least a part of the coating film composition of the battery electrode or the separator of the present invention is impregnated inside the battery electrode or the separator, the impregnation amount of the composition is such that the electrode or the separator is not completely filled. The amount of the pore structure, that is, an amount in which the porosity of the electrode or the separator exceeds 0% is more preferable, and the amount of the porosity in the electrode or the separator is more than 50%. The void ratio of the separator is an amount of 75% or more.

當黏彈性粒子為具有形狀異向性之粒子時，可藉由塗布時的剪切力來使具有形狀異向性之粒子朝塗布方向配向。例如，來自於將塗布時的分隔板之張力放開之際的收縮的捲曲，藉由將纖維狀粒子的長軸方向以平行於分隔板 的長軸方向之方式來進行塗布，相較於使相同長軸方向配向的纖維狀粒子呈無秩序般存在之情形，可更有效率地緩和應力。 When the viscoelastic particles are particles having shape anisotropy, the particles having shape anisotropy can be aligned in a coating direction by a shearing force during coating. For example, the curl caused by the shrinkage when the tension of the separator is released at the time of coating is applied, and the long axis direction of the fibrous particles is parallel to the separator. Compared with the case where the fibrous particles aligned in the same major axis direction exist in an disorderly manner, the stress can be more efficiently relieved.

〔溶劑之蒸散方法〕 [Solvent evaporation method]

溶劑可藉由加熱乾燥、真空乾燥、凍結乾燥、或該等之組合來進行。加熱乾燥可使用熱風爐、紅外線加熱器、加熱輥等來進行。真空乾燥可藉由將塗布膜組成物之塗膜置入於反應室內並使成為真空來進行。凍結乾燥可於使用具有昇華性的溶劑之情形時採用。加熱乾燥的加熱溫度及加熱時間，只要是溶劑為蒸散之溫度及時間即可，未特別限定，可設為例如以80~120℃、0.1小時~2小時。藉由使溶劑蒸散，電池電極或分隔板塗布膜組成物之溶劑以外之成分會與電池電極或分隔板密著，當黏結劑為熱熔粒子時，藉由進行熱熔著而可形成本發明之塗布膜。 The solvent can be performed by heat drying, vacuum drying, freeze drying, or a combination thereof. The heating and drying can be performed using a hot blast stove, an infrared heater, a heating roller, and the like. Vacuum drying can be performed by putting the coating film of a coating film composition in a reaction chamber and making it vacuum. Freeze-drying can be used when a sublimating solvent is used. The heating temperature and heating time for the heating and drying are not particularly limited as long as the solvent is the temperature and time during which the solvent is evaporated. For example, the heating temperature and the heating time can be set at 80 to 120 ° C. for 0.1 to 2 hours. By evaporating the solvent, components other than the solvent of the battery electrode or the separator coating film composition will adhere to the battery electrode or the separator. When the adhesive is hot-melt particles, it can be formed by thermal fusion. The coating film of the present invention.

〔加熱方法〕 [Heating method]

本發明之電池電極或分隔板塗布膜之製造方法中，當使用粒子狀的黏結劑時，使黏結劑彼此熱熔著而可使其固化。此情形時，可在使粒子完全熔融之溫度下予以熱熔著並固化，亦可僅使有機物粒子之表面熱熔解而以熔著且以相互密著之狀態冷卻，使粒子彼此以點密著且空出間隙之狀態固化。依據前者之熱熔著固化，成為連續相之部分較多，離子傳導性或機械強度及耐熱性較高。依據後者之熱 熔著固化，成為連續相之部分較少，通過熔著之有機物粒子之離子傳導性或機械強度及耐熱性差，但藉由使電解液含浸於粒子間之空隙，可提高離子傳導性。又，後者由於成為無規空開間隙之構造，故在產生樹枝狀晶之情況下，藉由阻礙其直線的成長亦可提高防止短路之效果。熱熔時之加熱熔著方法可使用熱風或加熱板、烘箱、紅外線、超音波熔著等各種習知之方法，亦可在加熱時以壓製而提高保護劑層之密度。又，冷卻除了自然冷卻以外，亦可使用冷卻氣體、壓向放熱板等各種習知之方法。又，黏結劑為加熱至熔融溫度之情形時，黏結劑能以熔融溫度加熱0.1~1000秒。 In the method for manufacturing a battery electrode or a separator coating film of the present invention, when a particulate adhesive is used, the adhesives are thermally fused to each other to be cured. In this case, the particles can be thermally fused and solidified at a temperature at which the particles are completely melted, or only the surface of the organic particles can be thermally fused and cooled in a fused and closely-closed state, so that the particles are closely adhered to each other. And the state of the vacant gap is solidified. According to the former, heat-melting and solidification, there are many parts that become a continuous phase, and ion conductivity or mechanical strength and heat resistance are high. According to the latter's heat Fusing and solidifying, there are fewer parts that become a continuous phase. The ionic conductivity, mechanical strength, and heat resistance of the fused organic particles are poor. However, the ionic conductivity can be improved by impregnating the electrolyte with voids between the particles. Moreover, since the latter has a structure of randomly open gaps, when dendritic crystals are generated, the effect of preventing a short circuit can be improved by hindering the growth of the straight lines. The heating and melting method during hot melting can use various conventional methods such as hot air or hot plate, oven, infrared, and ultrasonic welding, and can also increase the density of the protective agent layer by pressing during heating. In addition to the natural cooling, various conventional methods such as cooling gas and pressure on a heat radiation plate can be used. When the adhesive is heated to the melting temperature, the adhesive can be heated at the melting temperature for 0.1 to 1000 seconds.

〔磁場及/或電場配向〕 [Magnetic and / or electric field alignment]

本發明之電池電極或分隔板塗布膜之製造方法可使用磁場及/或電場，來使調配之材料以配向之狀態下固化。藉此，可形成離子傳導性或機械強度及耐熱性具有異向性之塗布膜。使用磁場及/或電場，藉由將黏彈性粒子以朝向易應力緩和之方向配向之狀態下固定時，可提高應力緩和能。前述高分子材料之情形時，可藉由延伸而對磁化率及/或介電率賦與異向性，故可利用磁場及/或電場予以配向。又，亦可使用纖維素等具有異向性之纖維。使如此般的高分子延伸而製作之纖維或纖維粉碎而成之粒子，可藉由使長軸方向以垂直於電極面立起之方式配向而提高離子傳導性。關於有機物結晶，可以磁場及/或電場使具有結 晶磁性及/或介電率異向性者配向，可發揮如前述之效果。磁場及/或電場可為靜磁場及/或電場，亦可為如旋轉磁場及/或電場之隨時間變動之磁場及/或電場，亦可同時施加磁場與電場。 The manufacturing method of the battery electrode or the separator coating film of the present invention can use a magnetic field and / or an electric field to cure the prepared material in an aligned state. Thereby, a coating film having an anisotropy of ion conductivity, mechanical strength, and heat resistance can be formed. When a magnetic field and / or an electric field are used, and the viscoelastic particles are fixed in a state of being oriented toward the direction of easy stress relaxation, the stress relaxation energy can be improved. In the case of the aforementioned polymer material, anisotropy can be imparted to the magnetic susceptibility and / or the permittivity by extension, and thus magnetic field and / or electric field can be used for alignment. Also, anisotropic fibers such as cellulose can be used. The fibers produced by stretching such a polymer or the particles obtained by pulverizing the fibers can be oriented by raising the long axis direction perpendicular to the electrode surface to improve ion conductivity. With regard to the crystallization of organic matter, the The crystal magnetic and / or dielectric anisotropy alignment can exert the effects as described above. The magnetic field and / or electric field may be a static magnetic field and / or an electric field, and may also be a magnetic field and / or an electric field that varies with time, such as a rotating magnetic field and / or an electric field, and a magnetic field and an electric field may be applied simultaneously.

藉由包含上述步驟的本發明之電池電極或分隔板塗布膜之製造方法，可得到其表面為具有塗布膜的電池電極或分隔板。尚，塗布膜之至少一部份亦可形成為進入電池電極或分隔板之內部。塗布膜之空隙率為40%以上，較佳為41~90%，又較佳為41~80%。 By the method for manufacturing a battery electrode or a separator coating film of the present invention including the above steps, a battery electrode or a separator having a coating film on the surface thereof can be obtained. Still, at least a part of the coating film may be formed to enter the inside of a battery electrode or a separator. The void ratio of the coating film is 40% or more, preferably 41 to 90%, and more preferably 41 to 80%.

〔電池電極及/或分隔板〕 [Battery electrode and / or separator]

本發明係有關以上述電池電極或分隔板塗布膜所保護，或具有藉由上述電池電極或分隔板塗布膜之製造方法所製造的塗布膜的電池電極及/或分隔板。 The present invention relates to a battery electrode and / or a separator that is protected by the above-mentioned battery electrode or separator coating film, or has a coating film manufactured by the above-mentioned method for manufacturing a battery electrode or separator coating film.

以本發明之電池電極或分隔板塗布膜所保護的電池電極或分隔板，可藉由將本發明之組成物塗布於電池電極或分隔板上，接著，使溶劑蒸散而製造。作為電池電極，可示例如各種習知的電池或電雙層型電容器之正極及/或負極，且可於該等之至少一面上塗布或含浸電池電極或分隔板塗布膜組成物。作為分隔板，可示例如聚丙烯或聚乙烯製之多孔質材料或纖維素製之聚丙烯、聚乙烯、聚酯製之不織布等，可塗布並含浸於該等之兩面或一面上。本發明之電池電極或分隔板塗布膜組成物可以密著於對向之分隔板或電極上之狀態下使用，亦可於溶劑未蒸散之前將分隔 板與電極密著，之後，藉由乾燥或電池組裝後以進行熱壓製，來使該等構件密著。 The battery electrode or separator protected by the battery electrode or separator coating film of the present invention can be produced by coating the composition of the present invention on a battery electrode or separator, and then evaporating the solvent. Examples of the battery electrode include positive electrodes and / or negative electrodes of various conventional batteries or electric double-layer capacitors, and a battery electrode or a separator coating film composition can be coated on or impregnated on at least one of these surfaces. Examples of the partition plate include a porous material made of polypropylene or polyethylene, or a nonwoven fabric made of cellulose, polypropylene, polyethylene, or polyester, which can be coated and impregnated on both or one of these surfaces. The coating film composition of the battery electrode or the separator of the present invention can be used in a state of being closely adhered to the opposite separator or electrode, or the separator can be separated before the solvent is evaporated. The plate is closely adhered to the electrode, and then these components are adhered by drying or hot pressing after the battery is assembled.

電極或分隔板會因為電極活性物質層之塗布方向或分隔板之延伸及捲取方向等，而彈性率或線膨脹係數、加熱時之收縮量有產生異向性之情形。例如，經單軸延伸的聚乙烯製分隔板，當加熱時，延伸時之應力會被緩和，而於延伸方向之收縮量會變大，其結果，與塗布膜間之應力之異向性會變大，此情形時，較佳為具有使用本發明之電池電極或分隔板塗布膜組成物所得塗布膜的電池電極或分隔板，本發明之電池電極或分隔板塗布膜組成物係黏彈性粒子具有形狀異向性，對電池電極或分隔板之基材之收縮方向(即，延伸方向)而言，黏彈性粒子之最長軸係以平行配向。在此，所謂的「黏彈性粒子之最長軸」，指將黏彈性粒子之任意2點之端部以最短直線連接時，該最長之線。又，所謂的「電池電極或分隔板之基材」，指具有塗布膜的電池電極或分隔板中，該塗布膜以外之部分。對電池電極或分隔板之基材之收縮方向而言，當黏彈性粒子之最長軸係以平行配向時，塗布膜中的黏彈性粒子之變形量係以對延伸方向而言為變大之方式配向。因此，具有塗布膜的電池電極或分隔板中，塗布膜與電池電極或分隔板之基材之間之應力緩和能會變大，可抑制捲曲之發生，耐熱性會更提高。例如，將經延伸的聚乙烯纖維切短並作為黏彈性粒子，藉由使纖維之配向方向與分隔板之延伸方向成為一致，可提高應力緩和能，可更抑制捲曲之發 生，並可更提高耐熱性。 The electrode or the separator may have anisotropy due to the coating direction of the electrode active material layer, the extension and winding direction of the separator, and the elastic modulus, the coefficient of linear expansion, and the amount of shrinkage during heating. For example, when a uniaxially stretched polyethylene separator is heated, the stress during stretching will be relaxed, and the amount of shrinkage in the direction of stretching will increase. As a result, the stress anisotropy with the coating film will be reduced. In this case, a battery electrode or a separator having a coating film obtained by using the battery electrode or a separator coating film composition of the present invention is preferred, and a battery electrode or a separator coating film composition of the present invention is preferred. The viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is aligned in parallel with respect to the contraction direction (that is, the extension direction) of the substrate of the battery electrode or the separator. Here, the "longest axis of the viscoelastic particle" refers to the longest line when the ends of any two points of the viscoelastic particle are connected by the shortest straight line. The "base material of a battery electrode or a separator" refers to a portion of the battery electrode or separator having a coating film other than the coating film. For the contraction direction of the substrate of the battery electrode or the separator, when the longest axis of the viscoelastic particles is aligned in parallel, the amount of deformation of the viscoelastic particles in the coating film becomes larger in the direction of extension. Way alignment. Therefore, in a battery electrode or a separator having a coating film, the stress relaxation energy between the coating film and the base material of the battery electrode or the separator is increased, the occurrence of curling is suppressed, and the heat resistance is further improved. For example, by shortening the stretched polyethylene fibers and using them as viscoelastic particles, the alignment direction of the fibers and the extension direction of the partition plate can be made consistent, which can improve the stress relaxation energy and further suppress the curling. Health, and can improve heat resistance.

〔電池〕 〔battery〕

本發明係有關包含以本發明之電池電極或分隔板塗布膜組成物所保護的電池電極及/或分隔板的電池。電池之製造可藉由習知的方法來進行。又，可使電解液含浸於塗布膜中，使用賦予有離子傳導性的塗布膜來製造電池。更，亦可使塗布膜組成物本身具有離子傳導性，以作為固體電解質膜而組入於電池中。使電解液含浸於塗布膜中時，將對於黏彈性粒子之黏結劑之量設為20重量%以下，並藉由使電解液含浸於以粒子之排外體積之效果所生成的空隙中，而可賦予離子傳導性。當設為無空隙之構造時，藉由以電解液來使黏結劑膨潤，而可賦予離子傳導性。 The present invention relates to a battery including a battery electrode and / or a separator protected by a battery electrode or a separator coating film composition of the present invention. The manufacturing of the battery can be performed by a conventional method. Moreover, a battery can be manufactured by impregnating an electrolytic solution with a coating film and using a coating film provided with ion conductivity. Furthermore, the coating film composition itself may have ion conductivity, and may be incorporated into a battery as a solid electrolyte membrane. When the electrolytic solution is impregnated in the coating film, the amount of the binder for the viscoelastic particles is set to 20% by weight or less, and the electrolytic solution is impregnated into the voids generated by the effect of the volume of the particles. Imparts ion conductivity. When the structure is void-free, ion-conductivity can be imparted by swelling the binder with an electrolytic solution.

〔實施例〕 [Example]

以下使用實施例具體的說明本發明，但本發明並不限於該等。添加量之表示若無指明時為重量份或重量%。 The following specifically describes the present invention using examples, but the present invention is not limited thereto. The amount of addition is expressed in parts by weight or% by weight unless otherwise specified.

〔試驗例1〕 [Test Example 1]

對於在後述實施例及比較例使用的黏彈性粒子及黏結劑，以下述之方法來評價彈性率與塑性變形率。在此，關於黏彈性粒子係將使用的黏彈性粒子之分散液過濾並使乾 燥，而得到試驗粒子。關於黏結劑係以使用的條件，來將使用的黏結劑以固化成厚度50μm的膜狀，之後，以液體氮冷卻後使用磨機(IKA製的M20汎用磨機)粉碎，使用篩孔距50μm的篩進行過篩，而得到試驗粒子。 For the viscoelastic particles and the binder used in the examples and comparative examples described later, the elastic modulus and the plastic deformation rate were evaluated by the following methods. Here, regarding the viscoelastic particle system, the dispersion liquid of the viscoelastic particles used is filtered and dried. Dry to obtain test particles. Regarding the binder, the used binder was solidified into a film thickness of 50 μm under the conditions of use, and then cooled with liquid nitrogen and pulverized with a mill (M20 universal mill made by IKA), using a screen distance of 50 μm The sieve was sieved to obtain test particles.

(彈性率之測定) (Measurement of elasticity)

於內徑10mm、外徑110mm、高150mm的丙烯酸製筒中，以成為高100mm之方式來填裝試驗粒子，使用萬能試驗機壓入外徑10mm、長200mm的鐵製棒。測定以1kgf壓入時的高h1，及之後鬆緩壓入力，測定以0.5kgf壓入時的高h2，將該比h1/h2=h3設為彈性率。 An acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm was filled with test particles so as to have a height of 100 mm, and an iron rod having an outer diameter of 10 mm and a length of 200 mm was pressed using a universal testing machine. The height h1 at the time of indentation at 1 kgf was measured, and then the indentation force was loosened. The height h2 at the time of indentation at 0.5 kgf was measured, and this ratio h1 / h2 = h3 was used as the modulus of elasticity.

(塑性變形率之測定) (Measurement of plastic deformation rate)

於上述測定施加1kgf之荷重後，求得使荷重回復至0.5kgf為止的高h4，接著，以100kgf壓入鐵製棒後，求得使荷重回復至0.5kgf為止的高h5，將該比h5/h4=h6設為塑性變形率。 After applying a load of 1 kgf in the above measurement, the height h4 until the load was restored to 0.5 kgf was obtained. Next, after pressing the iron rod at 100 kgf, the height h5 until the load was restored to 0.5 kgf was obtained. The ratio h5 was determined. / h4 = h6 is set as the plastic deformation rate.

〔試驗例2〕 [Test Example 2]

對於在後述實施例及比較例所製造的鋰離子蓄電池，測定下述特性。 The following characteristics were measured for lithium ion batteries manufactured in Examples and Comparative Examples described later.

(初期容量測定) (Initial capacity measurement)

為了測出初期容量，以0.005mA的恆定電流充電至電 壓達到4.2V，接著以4.2V的恆定電壓充電2小時。之後，以0.005mA的恆定電流放電至電壓達到3.5V。重複該等三次，以第三次之放電容量設為初期容量。 In order to measure the initial capacity, charge the battery with a constant current of 0.005mA. The voltage reached 4.2V, followed by charging at a constant voltage of 4.2V for 2 hours. After that, it was discharged at a constant current of 0.005 mA until the voltage reached 3.5V. Repeat these three times, and set the third discharge capacity as the initial capacity.

(初期內部電阻) (Initial internal resistance)

使測定了初期容量的電池晶胞處為4.2V之電位，以該電位為中心，在±15mV之電壓變化下測定1kHz之阻抗(impedance)。 The cell with the initial capacity measured at a potential of 4.2 V, with this potential as the center, the impedance at 1 kHz was measured with a voltage change of ± 15 mV.

(速率特性) (Rate characteristics)

由初期容量求得放電速率，對各放電速率的放電容量進行測定。充電係在每次花費10小時以恆定電流使電壓上升至4.2V後，以4.2V之恆定電壓充電2小時。隨後，花費10小時以恆定電流放電至3.5V，以此時之放電容量設為0.1C之放電容量。接著經同樣之充電後，自以0.1C求得之放電容量後，求得以1小時放電結束之電流值放電之該時之放電容量作為1C時之放電容量。同樣的，求得3C、10C、30C時之放電容量，算出以0.1C時之放電容量作為100%時之容量維持率。 The discharge rate was determined from the initial capacity, and the discharge capacity at each discharge rate was measured. After charging for 10 hours at a constant current to increase the voltage to 4.2V, charging was performed at a constant voltage of 4.2V for 2 hours. Subsequently, it took 10 hours to discharge to 3.5V at a constant current, and the discharge capacity at this time was set to a discharge capacity of 0.1C. Then, after the same charging, the discharge capacity at the time when the current value at the end of the 1-hour discharge can be obtained from the discharge capacity obtained at 0.1C is taken as the discharge capacity at 1C. Similarly, the discharge capacity at 3C, 10C, and 30C was obtained, and the capacity retention rate when the discharge capacity at 0.1C was taken as 100% was calculated.

(循環壽命) (Cycle life)

實施以1C充電至4.2V，以4.2V之恆定電壓充電2小時及以1C放電至3.5V之充電及放電試驗。此時，計算放電容量對於最初第一次放電成為多少%，以容量成為 80%時之充電及放電次數作為壽命。 Charging and discharging tests were performed with 1C charging to 4.2V, charging at a constant voltage of 4.2V for 2 hours, and discharging at 1C to 3.5V. At this time, calculate how much the discharge capacity becomes for the first discharge, and take the capacity as The charging and discharging times at 80% are regarded as the life.

(耐熱絕緣性試驗) (Heat resistance insulation test)

以1C充電至4.2V，且以4.2V之恆定電壓充電2小時成為充滿電之狀態下，實施以平均1小時10℃自25℃升溫至260℃，隨後以平均1小時20℃冷卻至25℃之試驗，以前述(初期內部電阻)之測定法確認耐久試驗後之電阻。評價基準如下。 Charge at 1C to 4.2V, and charge at a constant voltage of 4.2V for 2 hours to become fully charged. The temperature is raised from 25 ° C to 260 ° C at an average of 1 hour at 10 ° C, and then cooled to 25 ° C at an average of 1 hour 20 ° C In the test, the resistance after the endurance test was confirmed by the aforementioned (initial internal resistance) measurement method. The evaluation criteria are as follows.

1kHz之阻抗為 1kHz impedance is

◎：10MΩ以上 ◎: Above 10MΩ

○：100kΩ~未達10MΩ ○: 100kΩ to less than 10MΩ

△：1kΩ~未達100kΩ △: 1kΩ ~ less than 100kΩ

×：未達1kΩ ×: Less than 1kΩ

(耐熱外觀試驗) (Heat resistance appearance test)

試驗法係與前述耐熱絕緣試驗相同，分解試驗後之電池並確認內部之樣態。評價基準如下。 The test method is the same as the aforementioned heat-resistant insulation test. The battery after the test is disassembled and the internal condition is confirmed. The evaluation criteria are as follows.

◎：正極與負極未直接接觸並保持絕緣狀態，且電池電極保護層密著於電極及/或分隔板上。 ◎: The positive electrode and the negative electrode are not in direct contact and remain insulated, and the battery electrode protective layer is closely adhered to the electrode and / or the separator.

○：正極與負極未直接接觸並保持絕緣狀態，但發現電池電極保護層部分***但並未剝離。 ○: The positive electrode and the negative electrode were not in direct contact and remained in an insulated state, but the battery electrode protective layer portion was found to be bulged but not peeled.

△：脫離進行，且正負極之一部份露出。 △: Detachment proceeds, and part of the positive and negative electrodes is exposed.

×：正負極接觸且為短路狀態。 ×: The positive and negative electrodes are in a short-circuited state.

〔試驗例3〕 [Test Example 3]

在以後述實施例及比較例所製造的電極或分隔板中，測定下述特性。 The following characteristics were measured in the electrodes or separators produced in Examples and Comparative Examples described later.

(捲曲試驗) (Curl test)

將形成有塗布膜的電極或分隔板裁切成50mm方形，來確認捲曲狀態。評價基準如下。 The electrode or separator on which the coating film was formed was cut into a 50 mm square to confirm the curled state. The evaluation criteria are as follows.

◎：完全未捲曲。 ：: No curl at all.

○：端部捲起高度未達1mm。 ○: The end rolled up height is less than 1 mm.

△：端部捲起高度為1~5mm。 △: The end rolled height is 1 to 5 mm.

×：捲曲至輥上。 ×: Curl onto the roll.

〔實施例1〕 [Example 1]

實施例1為說明使用具有一塗布膜的負極來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於負極並使溶劑蒸散而得到。 Example 1 is a method for manufacturing a lithium-ion battery using a negative electrode having a coating film. The coating film is formed by coating a battery electrode or separator coating film composition made of a solvent, a binder, and viscoelastic particles. It is obtained by evaporating the solvent on the negative electrode.

(組成物之製造) (Manufacture of composition)

(黏彈性粒子漿料1之製作) (Production of viscoelastic particle slurry 1)

於100L聚丙烯製槽中添加離子交換水10L與胺基甲酸酯粒子(根上工業(股)製的低彈性率胺基甲酸酯2μm粒子之60%水混合物；Art Pearl MM-120TW)50kg，攪拌12小時製作50%分散液。將分散液以篩孔距20μm的尼龍 篩孔過濾，進而以2T的電磁石除去磁性異物，添加在步驟中所失去的水，來製作包含黏彈性粒子50%的分散液。 50 kg of ion-exchanged water and urethane particles (60% water mixture of low-elasticity urethane 2 μm particles manufactured by Genjo Industrial Co., Ltd .; Art Pearl MM-120TW) were added to a 100-liter polypropylene tank. , Stir for 12 hours to make a 50% dispersion. Nylon with a sieve spacing of 20 μm It is filtered through a sieve, and magnetic foreign matter is removed with 2T magnetite, and water lost in the step is added to prepare a dispersion liquid containing 50% of viscoelastic particles.

(組成物之調配) (Composition of composition)

於前述分散液50kg中添加水20kg，進而加入聚氧乙烯(明成化學工業(股)製的ALKOX E-30)200g並攪拌6小時使溶解，得到電池電極或分隔板塗布膜組成物。尚，組成物中，除去溶劑後成分之中黏彈性粒子之含有量為99.2重量%。 20 kg of water was added to 50 kg of the dispersion, and 200 g of polyoxyethylene (ALKOX E-30 manufactured by Meisei Chemical Industries, Ltd.) was added and stirred for 6 hours to dissolve to obtain a battery electrode or separator coating film composition. In the composition, the content of the viscoelastic particles in the components after removing the solvent was 99.2% by weight.

(正極之製造) (Manufacture of positive electrode)

於加裝冷卻套筒之10L行星式混練機中添加PVdF(聚偏二氟乙烯)之15% NMP(N-甲基吡咯啶酮)溶液((股)Kureha製的Kureha KF Polymer #1120)520份、鈷酸鋰(簡稱=LCO)(日本化學工業(股)製的Cellseed C-5H)1140份、乙炔黑(電氣化學工業(股)製的Denka Black HS-100)120份、NMP 5400份，以不使液溫超過30℃之方式邊冷卻邊攪拌至均勻。將該等以寬度180mm、厚度200μm塗布於壓延之鋁集電體(日本製箔(股)製造的寬度300mm，厚度20μm)上，以130℃之溫風爐乾燥30秒。將其以線壓530kgf/cm輥壓。壓製後之正極活性物質層之厚度為22μm。 Add a 15% NMP (N-methylpyrrolidone) solution of PVdF (polyvinylidene fluoride) to a 10L planetary mixer equipped with a cooling sleeve (Kureha KF Polymer # 1120 made by Kureha) 520 1,140 parts of lithium cobaltate (abbreviation = LCO) (Cellseed C-5H manufactured by Japan Chemical Industry Co., Ltd.), 120 parts of acetylene black (Denka Black HS-100 manufactured by Denki Chemical Industry Co., Ltd.), 5400 parts of NMP , Stir until the liquid temperature does not exceed 30 ° C while cooling until homogeneous. These were coated with a width of 180 mm and a thickness of 200 μm on a rolled aluminum current collector (300 mm in width and 20 μm in thickness manufactured by Japan Foil Co., Ltd.), and dried in a hot air oven at 130 ° C. for 30 seconds. It was rolled at a linear pressure of 530 kgf / cm. The thickness of the positive electrode active material layer after pressing was 22 μm.

(負極之製造) (Manufacturing of negative electrode)

於加裝冷卻套筒之10L行星式混練機中添加PVdF之15% NMP溶液((股)Kureha製的Kureha KF Polymer #9130)530份、石墨(日本石墨(股)製的GR-15)1180份、NMP 4100份，以不使液溫超過30℃之方式邊冷卻邊攪拌至均勻。將其以寬度180mm、厚度200μm塗布於壓延之銅箔集電體(日本製箔(股)製的寬度300mm、厚度20μm)上，以100℃之溫風爐乾燥2分鐘。將其以線壓360kgf/cm輥壓。壓製後之負極活性物質層之厚度為28μm。 In a 10L planetary mixer equipped with a cooling sleeve, 530 parts of PVdF 15% NMP solution (Kureha KF Polymer # 9130 manufactured by Kureha), graphite (GR-15 manufactured by Japan Graphite Corporation) 1180 Parts, 4100 parts NMP, and stir until the liquid temperature does not exceed 30 ° C while stirring until homogeneous. This was coated on a rolled copper foil current collector (300 mm width and 20 μm thickness made by Japan Foil Co., Ltd.) with a width of 180 mm and a thickness of 200 μm, and dried in a hot air oven at 100 ° C. for 2 minutes. It was rolled at a linear pressure of 360 kgf / cm. The thickness of the negative electrode active material layer after pressing was 28 μm.

(具有塗布膜的負極之製造) (Manufacture of negative electrode with coating film)

使用凹版塗布器((股)康井精機製μcoater，圓筒(cylinder)# 100、搬送速度1m/min、圓筒/搬送速度比=1)，將前述組成物以乾燥厚度成為5μm之方式塗布於前述負極上，加熱100℃×60秒，來製作電池電極或分隔板塗布膜之厚度為5μm的具有塗布膜的負極。 Using a gravure coater ((Co.) Kangjing Seiki μcoater, cylinder # 100, conveying speed 1m / min, cylinder / conveying speed ratio = 1), the foregoing composition was applied so as to have a dry thickness of 5 μm. The negative electrode was heated at 100 ° C. for 60 seconds to prepare a negative electrode having a coating film with a thickness of 5 μm for a battery electrode or a separator coating film.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

將正極及塗布有塗布膜之負極，以包含於短邊10mm之寬度於兩端未塗布活性物質層之區域之方式，切成40mm×50mm，在金屬露出之部分，以電阻熔接，於正極接合鋁之接片，於負極接合鎳之接片。將分隔板(Celgard(股)製的# 2400)切成寬度45mm、長度120mm，且反折成三折，於其間以使成對向之方式夾入正 極及負極，且以將寬度50mm長度100mm之鋁層合電池晶胞對折而成者將其予以夾持，在相當於接片之部分夾入密封劑，使密封劑部分及與其直行之邊進行熱層合作成袋狀。將其置於100℃真空烘箱中真空乾燥24小時，接著在乾燥手套箱中注入六氟化磷酸鋰/EC：DEC=1：1 1M電解液(KISHIDA化學(股)製的LBG-96533)，經真空含浸後，吸出多餘的電解液，以真空封口機接合密封，製造鋰離子蓄電池。 The positive electrode and the negative electrode coated with a coating film were cut into a size of 40 mm × 50 mm so as to include a width of 10 mm on a short side and a region where an active material layer was not coated on both ends. The exposed part of the metal was welded with resistance and bonded to the positive electrode The aluminum tab is connected to the nickel tab at the negative electrode. Cut the divider plate (# 2400 made by Celgard) into a width of 45mm and a length of 120mm, and fold it back into three folds, and sandwich it in a positive direction. The electrode and the negative electrode are folded by folding the aluminum laminated battery cell with a width of 50mm and a length of 100mm, and then clamp it, sandwich the sealant in the part equivalent to the tab, and make the sealant part and the straight line The thermal layer cooperates into a bag shape. Put it in a vacuum oven at 100 ° C for 24 hours and vacuum dry, and then inject lithium hexafluoride phosphate / EC: DEC = 1: 1 1M electrolyte (LBG-96533 made by KISHIDA Chemical Co., Ltd.) into a dry glove box, After vacuum impregnation, the excess electrolyte was sucked out, and sealed with a vacuum sealer to manufacture a lithium ion battery.

〔實施例2〕 [Example 2]

實施例2為說明使用具有一塗布膜的正極來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於正極並使溶劑蒸散而得到。 Example 2 is a method for manufacturing a lithium-ion battery using a positive electrode having a coating film. The coating film is formed by coating a battery electrode or separator coating film composition made of a solvent, a binder, and viscoelastic particles. It is obtained by evaporating the solvent on the positive electrode.

(組成物之製造) (Manufacture of composition)

與實施例1以相同之方法來製造。 It was manufactured in the same manner as in Example 1.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的正極之製造) (Manufacture of a positive electrode with a coating film)

以實施例1之方法對於正極來製造。 The positive electrode was manufactured by the method of Example 1.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例3〕 [Example 3]

實施例3為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Example 3 is a method for manufacturing a lithium ion battery using a separator having a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(組成物之製造) (Manufacture of composition)

與實施例1以相同之方法來製造。 It was manufactured in the same manner as in Example 1.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

與實施例1以相同方法對於分隔板來製造。 A separator was manufactured in the same manner as in Example 1.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例4〕 [Example 4]

實施例4為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Embodiment 4 is a method for manufacturing a lithium ion battery using a separator having a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(組成物之製造) (Manufacture of composition)

(黏彈性粒子漿料1之製作) (Production of viscoelastic particle slurry 1)

於100L聚丙烯製槽中添加離子交換水10L與胺基甲酸酯粒子(根上工業(股)製的低彈性率胺基甲酸酯2μm粒子之60%水混合物；Art Pearl MM-120TW)50kg，攪拌12小時製作50%分散液。將分散液以篩孔距20μm的尼龍篩孔過濾，進而以2T的電磁石除去磁性異物，添加在步驟中所失去的水，來製作包含黏彈性粒子50%的分散液(黏彈性粒子漿料1)。 50 kg of ion-exchanged water and urethane particles (60% water mixture of low-elasticity urethane 2 μm particles manufactured by Genjo Industrial Co., Ltd .; Art Pearl MM-120TW) were added to a 100-liter polypropylene tank. , Stir for 12 hours to make a 50% dispersion. The dispersion was filtered through a nylon sieve with a sieve spacing of 20 μm, and then magnetic foreign matter was removed with 2T magnetite, and the water lost in the step was added to make a dispersion containing 50% of viscoelastic particles (Viscoelastic particle slurry 1 ).

(組成物之調配) (Composition of composition)

於前述分散液12kg中添加水2kg，進而加入乙烯‧乙酸乙烯酯共聚合乳液((股)Kuraray製的PANFLEX OM-4000NT)0.1kg並攪拌6小時使溶解，接著添加十二烷基苯磺酸鋰之55%水溶液0.01kg，進而攪拌2小時，得 到電池電極或分隔板塗布膜組成物。尚，組成物中，除去溶劑後成分之中黏彈性粒子之含有量為99.2重量%。 To 12 kg of the dispersion was added 2 kg of water, and then 0.1 kg of an ethylene-vinyl acetate copolymer emulsion (PANFLEX OM-4000NT manufactured by Kuraray) was added and stirred for 6 hours to dissolve, and then dodecylbenzenesulfonic acid was added. 0.01kg of 55% lithium aqueous solution, and stir for 2 hours to obtain The film composition is applied to a battery electrode or a separator. In the composition, the content of the viscoelastic particles in the components after removing the solvent was 99.2% by weight.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

以實施例3之方法來製造。 It was manufactured by the method of Example 3.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例5〕 [Example 5]

實施例5為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Example 5 is a method for manufacturing a lithium ion battery using a separator with a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(組成物之製造) (Manufacture of composition)

(黏彈性粒子漿料2之製作) 於100L聚丙烯製槽中添加離子交換水10L與聚乙烯 (Production of viscoelastic particle slurry 2) Add 10L of ion-exchanged water and polyethylene to a 100L polypropylene tank

粒子(Unitika(股)製的聚乙烯0.2μm粒子之60%水混合物；CD-1200)50kg，攪拌12小時製作50%分散液。將分散液以篩孔距20μm的尼龍篩孔過濾，進而以2T的電磁石除去磁性異物，添加在步驟中所失去的水，來製作包含黏彈性粒子50%的分散液(黏彈性粒子漿料2)。 50 kg of particles (60% water mixture of polyethylene 0.2 μm particles made by Unitika (strand); CD-1200), and stirred for 12 hours to prepare a 50% dispersion. The dispersion was filtered through a nylon sieve with a mesh spacing of 20 μm, and then magnetic foreign matter was removed with 2T magnetite, and the water lost in the step was added to make a dispersion containing 50% of viscoelastic particles (viscoelastic particle slurry 2 ).

(組成物之調配) (Composition of composition)

於前述分散液12kg中添加水2kg，進而加入乙烯‧乙酸乙烯酯共聚合乳液((股)Kuraray製的PANFLEX OM-4000NT)0.1kg並攪拌6小時使溶解，接著添加十二烷基苯磺酸鋰之55%水溶液0.01kg，進而攪拌2小時，得到電池電極或分隔板塗布膜組成物。尚，組成物中，除去溶劑後成分之中黏彈性粒子之含有量為99.2重量%。 To 12 kg of the dispersion was added 2 kg of water, and then 0.1 kg of an ethylene-vinyl acetate copolymer emulsion (PANFLEX OM-4000NT manufactured by Kuraray) was added and stirred for 6 hours to dissolve, and then dodecylbenzenesulfonic acid was added. 0.01 kg of a 55% aqueous solution of lithium was further stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of the viscoelastic particles in the components after removing the solvent was 99.2% by weight.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

以實施例3之方法來製造。 It was manufactured by the method of Example 3.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例6〕 [Example 6]

實施例6為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Example 6 is a method for manufacturing a lithium-ion battery using a separator having a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(組成物之製造) (Manufacture of composition)

(無機粒子分散漿料之製作) (Production of inorganic particle dispersion slurry)

於100L聚丙烯製槽中添加離子交換水50L與金剛砂(昭和電工(股)製的A-50-F)100kg，攪拌12小時製作67%分散液。將此邊冷卻邊使用容器容積20L的珠磨機(0.3mm氧化鋯珠粒80%充填，周速10m/s)循環粉碎1星期，來製作微粉碎漿料。將前述微粉碎漿料以篩孔距5μm的尼龍篩孔過濾，並滯留於100L聚丙烯製槽內靜置2天後，使用泵浦除去容積的1/5的上清液層，之後以泵浦分離殘餘的3/5作為中間層並滯留於100L聚丙烯製槽中，將殘留於容器底部的1/5作為沈降層而除去。對於已分離的3/5補足失去的水份使成為67%後，進而滯留於50L聚丙烯製槽內靜置2天，之後，相同地除去上清液層與沈降層。將此分離中間層之操作變更為在容量20L之聚丙烯製槽中進行，之後重複進行三次後，從最終分離的中間層中進而以2T的電磁石除去磁性異物，添加在步驟中 所失去的離子交換水，來製作包含金剛砂粒子67%的無機粒子分散漿料。 50 L of ion-exchanged water and 100 kg of emery (A-50-F manufactured by Showa Denko Corporation) were added to a 100 L polypropylene tank, and stirred for 12 hours to prepare a 67% dispersion. This was cooled while using a bead mill with a container volume of 20 L (filled with 0.3 mm zirconia beads at 80%, and the peripheral speed was 10 m / s). The powder was pulverized for one week to prepare a finely pulverized slurry. The finely pulverized slurry was filtered through a nylon sieve with a sieve spacing of 5 μm, and was allowed to stand in a 100 L polypropylene tank for 2 days. The supernatant liquid layer with a volume of 1/5 was removed using a pump. The remaining 3/5 of the PU separation was used as an intermediate layer and was retained in a 100L polypropylene tank. The 1/5 remaining on the bottom of the container was removed as a sink layer. The separated 3/5 made up the lost water to 67%, and then remained in a 50L polypropylene tank for 2 days. After that, the supernatant layer and the sink layer were similarly removed. The operation of separating the intermediate layer was changed to a polypropylene tank with a capacity of 20 L, and then repeated three times. Then, the magnetic layer was removed from the finally separated intermediate layer with 2T magnetite and added in the step. The lost ion-exchanged water was used to produce an inorganic particle dispersion slurry containing 67% of diamond particles.

(組成物之調配) (Composition of composition)

於前述無機粒子分散漿料3kg中添加水1kg，進而加入聚氧乙烯(明成化學工業(股)製的ALKOX E-30)0.03kg並攪拌6小時使溶解，接著添加100g的CD-1200，進而攪拌2小時，得到電池電極或分隔板塗布膜組成物。尚，組成物中，除去溶劑後成分之中黏彈性粒子之含有量為2.9重量%。 To 3 kg of the inorganic particle dispersion slurry, 1 kg of water was added, and then 0.03 kg of polyoxyethylene (ALKOX E-30 manufactured by Meisei Chemical Industries, Ltd.) was added and stirred for 6 hours to dissolve, and then 100 g of CD-1200 was added, and further After stirring for 2 hours, a battery electrode or separator coating film composition was obtained. In the composition, the content of the viscoelastic particles in the components after removing the solvent was 2.9% by weight.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

以實施例3之方法來製造。 It was manufactured by the method of Example 3.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例7〕 [Example 7]

實施例7為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Example 7 is a method for manufacturing a lithium-ion battery using a separator having a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(纖維狀彈性粒子之製造) (Manufacture of fibrous elastic particles)

將聚乙烯製釣魚線(YKG YOZ-AMI製的G-soul Pe 0.3號)切成1mm寬度後，使50g分散於水5kg中，將此邊冷卻邊使用容器容積0.6L的珠磨機(0.3mm氧化鋯珠粒80%充填，周速10m/s)循環分散1天，來製作漿料。之後，以80℃加熱攪拌前述漿料來使水分揮發，使濃度提高至60%。 A polyethylene fishing line (G-soul Pe 0.3, manufactured by YKG YOZ-AMI) was cut into a width of 1 mm, and 50 g was dispersed in 5 kg of water. This was cooled while using a bead mill with a container volume of 0.6 L (0.3 mm zirconia beads were filled at 80%, and the peripheral speed was 10 m / s) for 1 day to circulate and disperse to make a slurry. Thereafter, the slurry was heated and stirred at 80 ° C. to evaporate water and increase the concentration to 60%.

(組成物之製造) (Manufacture of composition)

除了放入上述漿料來取代實施例6中的CD-1200以外，與實施例6以相同之方法來製作組成物。 A composition was prepared in the same manner as in Example 6 except that the above slurry was put in place of CD-1200 in Example 6.

(正極之製造) (Manufacture of positive electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(負極之製造) (Manufacturing of negative electrode)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

以實施例3之方法來製造。 It was manufactured by the method of Example 3.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔實施例8〕 [Example 8]

實施例8為說明使用具有一塗布膜的分隔板來製造鋰離子蓄電池之方法，該塗布膜係藉由將由溶劑、黏結劑、與黏彈性粒子所成之電池電極或分隔板塗布膜組成物塗布於分隔板並使溶劑蒸散而得到。 Example 8 is a method for manufacturing a lithium-ion battery using a separator having a coating film. The coating film is composed of a battery electrode or a separator coating film composed of a solvent, a binder, and viscoelastic particles. The product is obtained by coating the separator and evaporating the solvent.

(具有塗布膜的分隔板之製造) (Manufacture of a separator with a coating film)

除了將圓筒/搬送速度比設為2，使圓筒成為搬送速度之2倍，使纖維藉由圓筒與基材之剪切力而平行配向於基材之搬送方向之方式進行塗布以外，以實施例3之方法來製造。纖維配向之樣態為使用光學顯微鏡來觀察。 Except that the cylinder / conveying speed ratio is set to 2, the cylinder is twice the conveying speed, and the fibers are coated in such a manner that the fibers are aligned in parallel to the conveying direction of the substrate by the shearing force of the cylinder and the substrate, It was manufactured by the method of Example 3. The state of fiber alignment was observed using an optical microscope.

(鋰離子蓄電池之製造) (Manufacture of lithium ion battery)

以實施例1之方法來製造。 It was manufactured by the method of Example 1.

〔比較例1〕 [Comparative Example 1]

除了使用不具有電池電極或分隔板塗布膜的電極及分隔板以外，與實施例1以相同方法來製造鋰離子蓄電池。 A lithium ion secondary battery was produced in the same manner as in Example 1 except that an electrode and a separator without a battery electrode or a separator coating film were used.

〔比較例2〕 [Comparative Example 2]

除了未使用黏彈性粒子以外，與實施例6以相同方法來製造鋰離子蓄電池。 A lithium ion secondary battery was produced in the same manner as in Example 6 except that no viscoelastic particles were used.

將結果表示於表1~表3中。 The results are shown in Tables 1 to 3.

〔產業利用性〕 [Industrial availability]

藉由本發明之電池電極或分隔板塗布膜組成物，即使是塗布塗布膜，基材的電極或分隔板中亦可抑制捲曲之發生，且由於具有高耐熱性，故製程適切性為優異，由於未有伴隨於基材之皺褶的電氣化學的耐久性之劣化，故可提供長期間信頼性優異的電池。 With the battery electrode or separator coating film composition of the present invention, even if it is a coating film, the occurrence of curling can be suppressed in the electrode or separator of the substrate, and because of its high heat resistance, the process suitability is excellent. Since there is no deterioration in the electrochemical durability accompanying wrinkles of the substrate, a battery having excellent long-term reliability can be provided.

Claims (5)

一種電池電極或分隔板塗布膜組成物，其係包含黏結劑、溶劑及黏彈性粒子，且黏彈性粒子之黏彈性率較黏結劑之黏彈性率為低，黏彈性粒子之材質係選自由聚乙烯、聚丙烯、聚苯乙烯、聚碳酸酯、聚縮醛、聚苯硫醚、液晶聚合物、聚氯乙烯、賽璐珞、聚乙烯醇、聚乙酸乙烯酯、具有聚乙二醇構造的高分子、具有碳酸酯基的高分子(但不包括前述聚碳酸酯)、聚偏二氟乙烯、聚四氟乙烯、苯乙烯‧丁二烯橡膠、聚異戊二烯、氯丁二烯橡膠、丙烯酸橡膠、具有氰基的高分子、胺基甲酸酯橡膠、乙烯丙烯橡膠、表氯醇橡膠、丁二烯橡膠、氟橡膠、乙烯-乙烯醇共聚物、丙烯酸-乙烯醇共聚物、環氧樹脂、氧雜環丁烷樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、多糖類、聚醯亞胺、聚醯胺醯亞胺、聚矽氧及該等共聚物所構成之群之1種以上，黏結劑係固體黏結劑或液體黏結劑，固體黏結劑係熱塑性的高分子之粒子、有機物之結晶、或熱熔著時進行交聯的有機物之粒子，熱塑性的高分子之粒子之材質係與前述黏彈性粒子之材質為同義，有機物之結晶係醯肼結晶、酸酐結晶、胺結晶、咪唑結晶、三嗪結晶、或該等之混晶，熱熔著時進行交聯的有機物之粒子係：固形的環氧樹脂中調配有潛在性熱起始劑之粒子；固形的環氧樹脂與氧雜環丁烷化合物之混合物中調配有潛在性熱起始劑之粒子；包含固形的(甲基)丙烯酸酯、與硬化劑或起始劑的系之粒子；或，具有活性氫基的預聚物與交聯劑之組合之粒子，具有活性氫基的預聚物與交聯劑之組合係：聚乙烯醇與聚羧酸或其衍生物之混合物；或，聚乙烯醇或其衍生物與金屬螯合物或烷氧化物之混合物，液狀黏結劑係：液狀預聚物與起始劑之混合物；使固形高分子物質溶解於溶劑中而成者；藉由溶膠-凝膠反應成為固形的無機物者；或，水玻璃，液狀預聚物與起始劑之混合物係：光自由基起始劑或熱自由基產生劑與具有(甲基)丙烯酸基、烯丙基、乙烯基、或馬來醯亞胺基之化合物之組合；光陽離子起始劑或熱陽離子起始劑與具有環氧基、氧雜環丁烷環、乙烯醚、或環狀乙縮醛之化合物之組合；或，光陰離子起始劑與具有環氧基之化合物及/或具有氰基丙烯酸酯基之化合物之組合，固形的高分子物質係完全皂化之聚乙烯醇、部分皂化之聚乙烯醇、改質之聚乙烯醇、羧基甲基纖維素、羥基乙基纖維素、聚丙烯醯胺、聚氧乙烯、環氧樹脂、聚伸乙亞胺、聚丙烯酸酯、糖類、糖類之衍生物、聚苯乙烯磺酸、丙烯酸酯聚合乳液、乙烯‧乙酸乙烯酯共聚合乳液、聚偏二氟乙烯、或改質聚三葡萄糖，藉由溶膠-凝膠反應成為固形的無機物者係三乙氧基矽烷、三甲氧基矽烷、異丙氧化鋁、四異丙氧化鈦、四正丁氧化鈦、丁氧化鈦二聚物、四-2-乙基己氧化鈦、二異丙氧基鈦雙(乙醯基丙酮酸鹽)、四乙醯基丙銅酸鈦、二辛氧基鈦雙(辛二醇酸酯)、二異丙氧基鈦雙(乙基乙醯基乙酸酯)、二異丙氧基鈦雙(三乙醇胺化物)、乳酸鈦、聚羥基硬脂酸鈦、四正丙氧化鋯、四正丁氧化鋯、四乙醯基丙酮酸鋯、三丁氧基單乙醯基丙酮酸鋯、單丁氧基乙醯基丙酮酸鋯雙(乙基乙醯基乙酸酯)、二丁氧基鋯雙(乙基乙醯基乙酸酯)、四乙醯基丙酮酸鋯、或三丁氧基單硬脂酸鋯，溶劑係烴、鹵系烴、一元醇、醚、乙縮醛、酮、酯、多元醇、多元醇之衍生物、脂肪酸、酚氮化合物、硫化合物、磷化合物、硼酸戊酯、或無機溶劑(但不包括前述氮化合物、前述硫化合物及前述磷化合物)，前述黏彈性粒子之含有量，在除去溶劑後的塗布膜組成物中所包含的成分之中係0.1~99.9重量%，前述黏結劑之含有量，相對於前述黏彈性粒子100重量份係0.01~49重量份，液狀黏結劑之黏彈性率係液狀黏結劑固化後的黏彈性率。A battery electrode or separator coating film composition includes a binder, a solvent, and viscoelastic particles, and the viscoelasticity of the viscoelastic particles is lower than that of the adhesive. The material of the viscoelastic particles is selected from the group consisting of Polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celluloid, polyvinyl alcohol, polyvinyl acetate, high polyethylene glycol structure Molecules, polymers with carbonate groups (but not the aforementioned polycarbonates), polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, polyisoprene, chloroprene rubber, Acrylic rubber, polymer with cyano group, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, butadiene rubber, fluorine rubber, ethylene-vinyl alcohol copolymer, acrylic acid-vinyl alcohol copolymer, epoxy Resins, oxetane resins, urethane resins, acrylic resins, polysaccharides, polyimide, polyimide, imide, polysiloxane, and these copolymers , The adhesive is a solid adhesive or liquid Binders, solid binders are thermoplastic polymer particles, organic crystals, or organic particles that are crosslinked during thermal fusion. The material of the thermoplastic polymer particles is synonymous with the aforementioned viscoelastic particles. Crystals of organics are hydrazine crystals, acid anhydride crystals, amine crystals, imidazole crystals, triazine crystals, or mixed crystals of these. The particles of organic substances that are crosslinked during thermal fusion: solid epoxy resins are formulated with a potential Particles of thermostable thermal initiators; particles formulated with a latent thermal initiator in a mixture of solid epoxy resins and oxetane compounds; containing solid (meth) acrylates, and hardeners or initiators Particles of an agent system; or particles of a combination of a prepolymer having an active hydrogen group and a crosslinking agent, and a combination of a prepolymer having an active hydrogen group and a crosslinking agent: polyvinyl alcohol and polycarboxylic acid or A mixture of derivatives; or, a mixture of polyvinyl alcohol or a derivative thereof and a metal chelate or an alkoxide, a liquid binder system: a mixture of a liquid prepolymer and a starter; a solid polymer substance is dissolved Yu Rong Those who have become successful; those who have become solid inorganic substances through sol-gel reaction; or, water glass, liquid prepolymers and starter mixtures: photo radical initiators or thermal radical generators with (Meth) acrylic, allyl, vinyl, or maleimide-based compounds; photocationic or thermal cationic initiators with epoxy, oxetane, A combination of vinyl ether or cyclic acetal compounds; or a combination of a photoanion initiator and a compound having an epoxy group and / or a compound having a cyanoacrylate group, the solid polymer material is completely saponified Polyvinyl alcohol, partially saponified polyvinyl alcohol, modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polypropylene amidamine, polyoxyethylene, epoxy resin, polyethyleneimine, Polyacrylates, saccharides, saccharide derivatives, polystyrene sulfonic acid, acrylate polymer emulsions, ethylene · vinyl acetate copolymer emulsions, polyvinylidene fluoride, or modified polytriglucose through sol-gel Those who react to become solid inorganic Triethoxysilane, trimethoxysilane, isopropyl aluminum oxide, tetraisopropyl titanium oxide, tetra-n-butyl titanium oxide, titanium dibutyl dimer, tetra-2-ethylhexyl titanium oxide, diisopropyloxy Titanium bis (acetamidopyruvate), Tetraethylfluorenyl propionate, Dioctyloxytitanium bis (octanoate), Diisopropoxytitanium bis (ethylacetamidoacetic acid) (Ester), titanium diisopropoxy bis (triethanolamine), titanium lactate, titanium polyhydroxystearate, tetra-n-propionate zirconium oxide, tetra-n-butyrate zirconium oxide, zirconyl acetonylpyruvate, tributoxyl Zirconium monoethylpyruvate, zirconium monobutoxyethylpyruvate bis (ethylethylfluorenyl acetate), zirconium dibutoxy bis (ethylethylfluorenyl acetate), tetraethylfluorene Zirconyl pyruvate, or tributoxy zirconium stearate, solvent based hydrocarbons, halogenated hydrocarbons, monohydric alcohols, ethers, acetals, ketones, esters, polyols, derivatives of polyols, fatty acids, phenol nitrogen Compounds, sulfur compounds, phosphorus compounds, pentyl borate, or inorganic solvents (but not including the aforementioned nitrogen compounds, the aforementioned sulfur compounds, and the aforementioned phosphorus compounds). Among the components contained in the coating film composition, the content is 0.1 to 99.9% by weight. The content of the binder is 0.01 to 49 parts by weight relative to 100 parts by weight of the viscoelastic particles. The viscosity of the liquid binder is The rate is the viscoelasticity of the liquid adhesive after curing. 如請求項1之電池電極或分隔板塗布膜組成物，其中，黏彈性粒子具有形狀異向性。For example, the coating electrode composition for a battery electrode or a separator of claim 1, wherein the viscoelastic particles have shape anisotropy. 一種電池電極或分隔板，其係具有使用請求項1或2之電池電極或分隔板塗布膜組成物所得塗布膜。A battery electrode or separator comprising a coating film obtained by coating a film composition using the battery electrode or separator of claim 1 or 2. 如請求項3之電池電極或分隔板，其中，黏彈性粒子具有形狀異向性，對電池電極或分隔板之基材之收縮方向而言，黏彈性粒子之最長軸係以平行配向。For example, the battery electrode or separator of claim 3, wherein the viscoelastic particles have anisotropy in shape, and the longest axis of the viscoelastic particles is aligned in parallel with respect to the contraction direction of the base material of the battery electrode or separator. 一種電池，其係具有請求項3或4之電池電極及/或分隔板。A battery having a battery electrode and / or a separator plate of claim 3 or 4.
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