JP2012204244A - Binder resin composition for nonaqueous secondary battery electrode - Google Patents
Binder resin composition for nonaqueous secondary battery electrode Download PDFInfo
- Publication number
- JP2012204244A JP2012204244A JP2011069463A JP2011069463A JP2012204244A JP 2012204244 A JP2012204244 A JP 2012204244A JP 2011069463 A JP2011069463 A JP 2011069463A JP 2011069463 A JP2011069463 A JP 2011069463A JP 2012204244 A JP2012204244 A JP 2012204244A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- meth
- ethylenically unsaturated
- resin composition
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011230 binding agent Substances 0.000 title claims abstract description 37
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
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- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 3
- 230000020169 heat generation Effects 0.000 abstract description 3
- -1 nickel metal hydride Chemical class 0.000 description 72
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- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
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- 239000007773 negative electrode material Substances 0.000 description 4
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- OGRPJZFGZFQRHZ-UHFFFAOYSA-M sodium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O OGRPJZFGZFQRHZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000011029 spinel Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、結着性、耐電解液性に優れた非水二次電池電極用バインダー樹脂組成物に関する。更には充放電サイクル特性、高容量化に優れた非水系二次電池、更にはリチウムイオン二次電池を得ることができる非水二次電池電極用バインダー樹脂組成物に関する。 The present invention relates to a binder resin composition for a non-aqueous secondary battery electrode that is excellent in binding and electrolytic solution resistance. Furthermore, it is related with the binder resin composition for non-aqueous secondary battery electrodes which can obtain the non-aqueous secondary battery excellent in charge / discharge cycle characteristics and high capacity | capacitance, and also a lithium ion secondary battery.
近年、電子技術の進歩により、電子機器の性能が向上して小型化、ポータブル化が進み、その電源としてエネルギー密度の高い二次電池の需要が高まっている。二次電池としては、例えば、ニッケル水素二次電池、リチウムイオン二次電池などが挙げられ、これら二次電池も機器の小型化、軽量化から、高容量かつ高寿命品の開発が進められている。
二次電池の電極は、電極活物質、導電助剤、更にはこれらを集電体に結着するバインダーより構成される。二次電池電極用バインダー樹脂には従来、正極、負極共にポリフッ化ビニリデンなどのフッ素樹脂をN−メチルピロリドン等の有機溶剤に溶解させて使用されてきた(非特許文献1、2)。この有機溶媒系バインダー組成物に活物質を分散させたスラリーを電極基体に塗布して、有機溶媒を除去して製造した電極を用いると電池の初期容量を大きくすることができるが、この電極を用いた電池で充放電を繰り返すと電極に固定された活物質が脱落しやすいという問題がある。また、電極作製時の臭気等、人体や環境に対する悪影響も懸念されている。このような問題を解決するために、特許文献1〜3では、乳化重合法により水を溶媒として製造されたスチレン・ブタジエン共重合ゴムのエマルジョン水分散液に、増粘剤としてカルボキシルメチルセルロースを添加した水系バインダー樹脂組成物が開示されている。この水系バインダー樹脂組成物は、有機溶剤系バインダー樹脂組成物に対して、活物質の密着性に優れているが、遊離してくる界面活性剤成分が電極の耐電解液性や電池の充放電サイクル特性を低下させる問題がある。そこで、特許文献4では、エチレン性不飽和カルボン酸を含むエチレン性不飽和単量体を共重合して得られる高酸価の樹脂を乳化剤として、乳化重合したエマルジョンを含む水系バインダー組成物が開示されている。このエマルジョンを水系バインダー樹脂として使用する事で、電池特性に悪影響を及ぼす遊離成分が減少し、電池の充放電サイクル特性が確かに向上するがまだ十分とは言いがたい。
In recent years, due to advances in electronic technology, the performance of electronic devices has improved, and miniaturization and portability have progressed, and the demand for secondary batteries with high energy density as the power source has increased. Secondary batteries include, for example, nickel metal hydride secondary batteries, lithium ion secondary batteries, etc. These secondary batteries are also being developed for high-capacity and long-life products due to the miniaturization and weight reduction of equipment. Yes.
The electrode of the secondary battery is composed of an electrode active material, a conductive additive, and a binder that binds these to a current collector. Conventionally, a binder resin for a secondary battery electrode has been used by dissolving a fluorine resin such as polyvinylidene fluoride in an organic solvent such as N-methylpyrrolidone for both the positive electrode and the negative electrode (Non-patent Documents 1 and 2). When an electrode manufactured by applying a slurry in which an active material is dispersed in this organic solvent binder composition to an electrode substrate and removing the organic solvent can be used, the initial capacity of the battery can be increased. When charging and discharging are repeated in the used battery, there is a problem that the active material fixed to the electrode is easily dropped. There are also concerns about adverse effects on human bodies and the environment, such as odor during electrode fabrication. In order to solve such a problem, in Patent Documents 1 to 3, carboxymethyl cellulose was added as a thickener to an emulsion aqueous dispersion of styrene / butadiene copolymer rubber produced using water as a solvent by an emulsion polymerization method. An aqueous binder resin composition is disclosed. This water-based binder resin composition is superior in the adhesion of the active material to the organic solvent-based binder resin composition, but the free surfactant component is resistant to the electrolytic solution of the electrode and the charge / discharge of the battery. There is a problem of deteriorating cycle characteristics. Therefore, Patent Document 4 discloses an aqueous binder composition containing an emulsion-polymerized emulsion using, as an emulsifier, a high acid value resin obtained by copolymerizing an ethylenically unsaturated monomer containing an ethylenically unsaturated carboxylic acid. Has been. By using this emulsion as an aqueous binder resin, free components that adversely affect battery characteristics are reduced, and the charge / discharge cycle characteristics of the battery are certainly improved, but it is still not sufficient.
本発明は、集電体との密着性に優れ、充放電の繰り返しや、発熱による高温環境下にあっても高放電容量を保持した非水系二次電池を提供することが可能な非水二次電池電極用バインダー樹脂組成物の提供を目的とする。更に、電極活物質に対する影響が少なくかつ、集電性を確保し、その利用効率を向上させ、電池の充放電サイクル特性、高容量化を達成することが可能な非水系二次電池電極、及び該電極を用いた非水系二次電池の提供を目的とする。 The present invention provides a non-aqueous secondary battery that is excellent in adhesiveness with a current collector and that can provide a non-aqueous secondary battery that retains a high discharge capacity even in a high temperature environment due to repeated charge and discharge or heat generation. It aims at provision of the binder resin composition for secondary battery electrodes. Furthermore, a non-aqueous secondary battery electrode that has little influence on the electrode active material, secures current collection, improves its utilization efficiency, and can achieve battery charge / discharge cycle characteristics, high capacity, and An object is to provide a non-aqueous secondary battery using the electrode.
第1の発明は、ウレタン樹脂(A)の存在下、ラジカル重合可能なエチレン性不飽和単量体(B)を水性溶媒中で乳化重合してなる非水二次電池電極用バインダー樹脂組成物に関する。 1st invention is the binder resin composition for non-aqueous secondary battery electrodes formed by emulsion-polymerizing the ethylenically unsaturated monomer (B) which can be radically polymerized in an aqueous solvent in presence of urethane resin (A). About.
又、第2の発明は、ウレタン樹脂(A)の重量平均分子量が1000〜50000であることを特徴とする第1の発明の非水二次電池電極用バインダー樹脂組成物に関する。 The second invention relates to the binder resin composition for non-aqueous secondary battery electrodes according to the first invention, wherein the urethane resin (A) has a weight average molecular weight of 1,000 to 50,000.
又、第3の発明は、ウレタン樹脂(A)の酸価が50〜400mgKOH/gであることを特徴とする第1または第2の発明の非水二次電池電極用バインダー樹脂組成物に関する。 The third invention relates to the binder resin composition for nonaqueous secondary battery electrodes according to the first or second invention, wherein the acid value of the urethane resin (A) is 50 to 400 mgKOH / g.
又、第4の発明は、ラジカル重合可能なエチレン性不飽和単量体(B)が、アルコキシシリル基含有エチレン性不飽和単量体(c)、N−メチロール基含有エチレン性不飽和単量体(d)、及び1分子中に2つ以上のエチレン性不飽和基を有する単量体(e)からなる群より選ばれる少なくとも1種類の単量体を、エチレン性不飽和単量体全体の合計100重量%中に0.1〜10重量%含むことを特徴とする第1〜第3いずれかの発明の非水二次電池電極用バインダー樹脂組成物に関する。 Further, the fourth invention is that the ethylenically unsaturated monomer (B) capable of radical polymerization is an alkoxysilyl group-containing ethylenically unsaturated monomer (c), an N-methylol group-containing ethylenically unsaturated monomer. And at least one monomer selected from the group consisting of a body (d) and a monomer (e) having two or more ethylenically unsaturated groups in one molecule. It is related with the binder resin composition for non-aqueous secondary battery electrodes of any one of the 1st-3rd invention characterized by including 0.1 to 10weight% in 100 weight% in total.
又、第5の発明は、第1〜4いずれかの発明の非水二次電池電極用バインダー樹脂組成物を用いてなる非水系二次電池電極に関する。 Moreover, 5th invention is related with the nonaqueous secondary battery electrode which uses the binder resin composition for nonaqueous secondary battery electrodes of the invention in any one of 1-4.
又、第6の発明は、第5の発明の非水系二次電池電極を用いてなる非水系二次電池に関する。 The sixth invention also relates to a non-aqueous secondary battery using the non-aqueous secondary battery electrode of the fifth invention.
又、第7の発明は、リチウムイオン二次電池であることを特徴とする第6の発明の非水系二次電池に関する。 The seventh invention relates to a non-aqueous secondary battery according to the sixth invention, which is a lithium ion secondary battery.
本発明の非水二次電池電極用バインダー樹脂組成物は、耐電解液性、集電体との密着性、可とう性に優れており、本発明の非水二次電池電極用バインダー樹脂組成物を用いることにより、発熱による高温環境下にあっても充放電サイクルにおける放電容量低下の低減が可能となる長寿命の非水系二次電池を提供できる。 The binder resin composition for non-aqueous secondary battery electrodes of the present invention is excellent in electrolytic solution resistance, adhesion to a current collector, and flexibility, and the binder resin composition for non-aqueous secondary battery electrodes of the present invention. By using the product, it is possible to provide a long-life non-aqueous secondary battery capable of reducing a decrease in discharge capacity in a charge / discharge cycle even in a high temperature environment due to heat generation.
本発明の非水二次電池電極用バインダー樹脂組成物は、ウレタン樹脂(A)の存在下、ラジカル重合可能なエチレン性不飽和単量体(B)を水性溶媒中で乳化重合してなる樹脂微粒子分散体であることを特徴とする。分子量の高いウレタン樹脂(A)を乳化剤として用いるため、低分子量の界面活性剤を乳化剤に用いる場合に比べ、電池特性に悪影響を及ぼす遊離成分が大幅に低減される。さらに、ウレタン樹脂の持つ強度や柔軟な骨格から活物質や集電体への密着性、ならびに電極の可とう性にも優れ、電池の充放電サイクル特性が飛躍的に向上する。ウレタン樹脂は水性溶媒中で分散していても、溶解していても良いが、乳化重合の安定性の点からは溶解している方が好ましい。 The binder resin composition for nonaqueous secondary battery electrodes of the present invention is a resin obtained by emulsion polymerization of an ethylenically unsaturated monomer (B) capable of radical polymerization in an aqueous solvent in the presence of a urethane resin (A). It is a fine particle dispersion. Since the urethane resin (A) having a high molecular weight is used as an emulsifier, free components that adversely affect battery characteristics are greatly reduced as compared with the case where a low molecular weight surfactant is used as an emulsifier. Furthermore, the strength and flexibility of the urethane resin, the adhesiveness to the active material and the current collector, and the flexibility of the electrode are excellent, and the charge / discharge cycle characteristics of the battery are dramatically improved. The urethane resin may be dispersed or dissolved in an aqueous solvent, but is preferably dissolved from the viewpoint of stability of emulsion polymerization.
まず本発明のおけるウレタン樹脂(A)について説明する。
本発明のおけるウレタン樹脂(A)は、特に限定はされないが、従来既知の方法に従いポリオールとポリイソシアネートとを反応させて得ることができる。
First, the urethane resin (A) in the present invention will be described.
The urethane resin (A) in the present invention is not particularly limited, but can be obtained by reacting a polyol and a polyisocyanate according to a conventionally known method.
ポリオールとしては、代表的なものとして例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールなどが挙げられる。 Typical examples of the polyol include polyester polyol, polyether polyol, and polycarbonate polyol.
ポリエステルポリオールとしては、例えば、ポリオール成分と二塩基酸成分とが縮合反応したポリエステルポリオールがある。ポリオールのうちジオールとしては、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3’−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、1,3−ブタンジオール、1,4−ブタンジオール、ネオペンチルグリコール、オクタンジオール、ブチルエチルペンタンジオール、2−エチル−1,3−ヘキサンジオール、シクロヘキサンジオール、ビスフェノールA等が挙げられ、3個以上の水酸基を有するポリオールとしては、グリセリン、トリメチロールプロパン、ペンタエリスリトール等が挙げられ、二塩基酸成分としてテレフタル酸、アジピン酸、アゼライン酸、セバチン酸、無水フタル酸、イソフタル酸、トリメリット酸等の脂肪族あるいは芳香族二塩基酸、およびそれらの無水物が挙げられる。また、ε−カプロラクトン、ポリ(β−メチル−γ−バレロラクトン)、ポリバレロラクトン等のラクトン類等の環状エステル化合物の開環重合により得られるポリエステルポリオールが挙げられる。 Examples of the polyester polyol include a polyester polyol obtained by condensation reaction of a polyol component and a dibasic acid component. Among the polyols, diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene. Methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, and the like as dibasic acid components. Terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, aliphatic or aromatic dibasic acids such as trimellitic acid, and anhydrides thereof. Moreover, the polyester polyol obtained by ring-opening polymerization of cyclic ester compounds, such as lactones, such as (epsilon) -caprolactone, poly ((beta) -methyl-gamma-valerolactone), and polyvalerolactone, is mentioned.
ポリエーテルポリオールとしては、例えば、テトラヒドロフラン、あるいはエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等のアルキレンオキサイドの重合体、共重合体あるいはグラフト共重合体、またはヘキサンジオール、メチルヘキサンジオール、ヘプタンジオール、オクタンジオールあるいはこれらの混合物の縮合によるポリエーテルポリオール類、プロポキシル化またはエトキシル化されたポリエーテルポリオール類等の水酸基が2個以上のものを用いることができる。 Examples of the polyether polyol include tetrahydrofuran, or a polymer, copolymer or graft copolymer of alkylene oxide such as tetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide, hexanediol, methylhexanediol, heptanediol, octanediol, or Those having two or more hydroxyl groups, such as polyether polyols obtained by condensation of these mixtures and polyether polyols which are propoxylated or ethoxylated, can be used.
ポリカーボネートポリオールとしては、例えば、ポリオールとジアルキルカーボネート、アルキレンカーボネート、ジアリールカーボネートなどのカーボネート化合物との反応により得られるものを挙げることができる。ポリカーボネートポリオールを構成するポリオールとしては、ポリエステルポリオールの構成成分として先に例示したポリオールを用いることができる。また、ジアルキルカーボネートとしてはジメチルカーボネート、ジエチルカーボネートなどを、アルキレンカーボネートとしてはエチレンカーボネートなどを、ジアリールカーボネートとしてはジフェニルカーボネートなどを挙げることができる。 Examples of the polycarbonate polyol include those obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate, alkylene carbonate, and diaryl carbonate. As a polyol which comprises a polycarbonate polyol, the polyol illustrated previously as a structural component of a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.
上記のポリオールの内、ポリエーテルポリオールは、サイクリックボルタンメトリー法、分子軌道計算法などの耐酸化性評価の結果から、ポリエステルポリオール、ポリカーボネートポリオールより酸化耐性の点で劣っているため、正極よりも負極に用いることが好ましい。 Among the above polyols, polyether polyol is inferior in oxidation resistance to polyester polyol and polycarbonate polyol from the results of evaluation of oxidation resistance such as cyclic voltammetry method and molecular orbital calculation method. It is preferable to use for.
この他、ポリブタジエンポリオール、アクリルポリオール、ポリシロキサンポリオール、ひまし油なども挙げられる。 In addition, polybutadiene polyol, acrylic polyol, polysiloxane polyol, castor oil, and the like are also included.
これらのポリオールは、1種だけを用いてもよいし、あるいは、複数種を併用してもよい。 These polyols may use only 1 type, or may use multiple types together.
また、これらのポリオールにアニオン基を有するポリオールを使用し、該アニオン基を塩基性化合物で中和するとウレタン樹脂(A)を水性媒体中に溶解ないし分散しやすくなる。
アニオン基としては、カルボキシル基、スルホニル基などが挙げられ、集電体への密着性の観点ではカルボキシル基が好ましい。
Further, when a polyol having an anionic group is used for these polyols and the anionic group is neutralized with a basic compound, the urethane resin (A) is easily dissolved or dispersed in an aqueous medium.
Examples of the anionic group include a carboxyl group and a sulfonyl group, and the carboxyl group is preferable from the viewpoint of adhesion to the current collector.
カルボキシル基を有するポリオール成分としては、例えば、
ジメチロール酢酸、ジメチロールプロピオン酸、ジメチロールブタン酸、2,2−ジメチロール酪酸、2,2−ジメチロールペンタン酸等のジメチロールアルカン酸や、ジヒドロキシコハク酸、ジヒドロキシプロピオン酸、ジヒドロキシ安息香酸等が挙げられ、ジメチロールアルカン酸が好ましい。本発明では、これらのようなアニオン基含有ポリオールを単独、または複数使用できる。
As a polyol component having a carboxyl group, for example,
Examples include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, dihydroxybenzoic acid, etc. And dimethylolalkanoic acid is preferred. In the present invention, these anionic group-containing polyols can be used alone or in combination.
中和に使用する塩基性化合物としては、水酸化ナトリウム、水酸化カリウムのような無機塩基、アンモニア、トリエチルアミン、トリブチルアミン、N,N-ジエチルアミノエタノール、ジメチルエタノールアミン、ジイソプロパノールアミン、モルホリンなどの有機アミン等が挙げられる。 Basic compounds used for neutralization include inorganic bases such as sodium hydroxide and potassium hydroxide, organic substances such as ammonia, triethylamine, tributylamine, N, N-diethylaminoethanol, dimethylethanolamine, diisopropanolamine, and morpholine. An amine etc. are mentioned.
更に、同一分子中に少なくとも2個の水酸基と1個の不飽和基を有するエチレン性不飽和単量体を用いることで、ウレタンとアクリルがグラフト化され、遊離のウレタン樹脂を低減することができる。 Furthermore, by using an ethylenically unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule, urethane and acrylic can be grafted and free urethane resin can be reduced. .
同一分子中に少なくとも2個の水酸基と1個の不飽和基を有するエチレン性不飽和単量体としては、例えば、グリシドールとアクリル酸の反応物、トリオール、ジイソシアネートと2−ヒドロキシメタアクリレートとの反応物等が挙げられる。 Examples of the ethylenically unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule include a reaction product of glycidol and acrylic acid, a reaction of triol, diisocyanate and 2-hydroxymethacrylate. Thing etc. are mentioned.
本発明では、ポリオールと反応させるポリイソシアネートとして、芳香族、脂肪族、脂環式のポリイソシアネートが用いられる。 In the present invention, aromatic, aliphatic, and alicyclic polyisocyanates are used as the polyisocyanate to be reacted with the polyol.
芳香族ポリイソシアネートとしては、例えば、
2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、m−フェニレンジイソシアネート、p−フェニレンジイソシアネート、4,4'−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、リジンジイソシアネート、3,3'−ジメチル−4,4'−ビフェニレンジイソシアネート、3,3'−ジメトキシ−4,4'−ビフェニレンジイソシアネート、3,3' −ジクロロ−4,4'−ビフェニレンジイソシアネート、1,5−ナフタレンジイソシアネート、1,5−テトラヒドロナフタレンジイソシアネート
等が挙げられる。
As an aromatic polyisocyanate, for example,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, lysine diisocyanate, 3,3'-dimethyl-4, 4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate Etc.
脂肪族ポリイソシアネートとしては、例えば、
テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート
等が挙げられる。
Examples of aliphatic polyisocyanates include:
Examples include tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
脂環式ポリイソシアネートとしては、例えば、イソホロンジイソシアネート、1,4−シクロヘキシレンジイソシアネート、4,4'−ジシクロヘキシルメタンジイソシアネート
等が挙げられるが、特にこれらに限定されるものではない。これらは、1種だけを用いてもよいし、あるいは、複数種を併用してもよい。
Examples of the alicyclic polyisocyanate include, but are not limited to, isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and the like. These may use only 1 type or may use multiple types together.
イソシアネートと水酸基の反応に用いられる触媒としては、ジブチルすずジラウレート、オクトエ酸すず、ジブチルすずジ(2−エチルヘキソエート)、2−エチルヘキソエート鉛、チタン酸2−エチルヘキシル、2−エチルヘキソエート鉄、2−エチルヘキソエートコバルト、ナフテン酸亜鉛、ナフテン酸コバルト、テトラ−n−ブチルすず、塩化第一すず、塩化第二すず、塩化鉄等が挙げられる。 Catalysts used for the reaction between isocyanate and hydroxyl group include dibutyltin dilaurate, octoate tin, dibutyltin di (2-ethylhexoate), 2-ethylhexoate lead, 2-ethylhexyl titanate, 2-ethylhexanoate. Examples include iron xoxoate, cobalt 2-ethylhexoate, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, stannous chloride, stannous chloride, and iron chloride.
本発明で使用されるウレタン樹脂(A)は、必要に応じて鎖延長を行ってもよい。鎖延長には、ヒドラジン、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ノナメチレンジアミン、キシリレンジアミン、イソホロンジアミン、ピペラジンおよびその誘導体、フェニレンジアミン、トリレンジアミン、キシレンジアミン、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジドなどのジアミン類;
ジエチレントリアミンなどのトリアミン類;
エチレングリコール、プロピレングリコール、1,4−ブタンジオール、1,6−ヘキサンジオール、1,4−ビス(β−ヒドロキシエトキシ)ベンゼン、1,4−シクロヘキサンジオール、ビス(β−ヒドロキシエチル)テレフタレート、キシリレングリコールなどのジオール類;
トリメチロールプロパンなどのトリオール類;
ペンタエリスリトールなどのペンタオール類;
アミノエチルアルコール、アミノプロピルアルコールなどのアミノアルコール類
などの公知の鎖延長剤を使用できる。単官能のモノアミンまたはモノオールを併用すれば、鎖延長の停止による分子量の制御も可能である。
The urethane resin (A) used in the present invention may be subjected to chain extension as necessary. For chain extension, hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, etc. Diamines of
Triamines such as diethylenetriamine;
Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate, xylyl Diols such as lenglycol;
Triols such as trimethylolpropane;
Pentaols such as pentaerythritol;
Known chain extenders such as amino alcohols such as aminoethyl alcohol and aminopropyl alcohol can be used. When a monofunctional monoamine or monool is used in combination, the molecular weight can be controlled by stopping the chain extension.
ウレタン樹脂(A)の重量平均分子量は1000〜50000、好ましくは2000〜30000である。重量平均分子量が50000より大きいと、粘度が高くなりすぎて、乳化重合の安定性が損なわれたりする。分子量が1000より小さいと、ウレタン樹脂の持つ強度や密着性が十分に発揮されない恐れがある。 The weight average molecular weight of the urethane resin (A) is 1000 to 50000, preferably 2000 to 30000. When the weight average molecular weight is larger than 50000, the viscosity becomes too high, and the stability of emulsion polymerization is impaired. If the molecular weight is less than 1000, the strength and adhesion of the urethane resin may not be sufficiently exhibited.
本発明のウレタン樹脂(A)はポリオールの説明で述べたようなカルボキシル基、スルホニル基などのアニオン基を有するポリオールを使用し、該アニオン基を塩基性化合物で中和することでウレタン樹脂(A)を水性媒体中に溶解ないし分散することが出来るが、これらのアニオン基導入によって付与されるウレタン樹脂(A)の酸価は50〜400mgKOH/gの範囲であることが好ましい。より好ましくは80〜200mgKOH/gである。酸価が400mgKOH/gより大きいと、中和した際の粘度が高すぎて乳化が不安定となり、合成が困難となる恐れがある。また、酸価が50mgKOH/gより小さいと水分散の際に不安定となり、凝集してしまう恐れがある。酸価とは、樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのmg数の事をいう。 The urethane resin (A) of the present invention uses a polyol having an anion group such as a carboxyl group and a sulfonyl group as described in the description of the polyol, and the anion group is neutralized with a basic compound to obtain a urethane resin (A ) Can be dissolved or dispersed in an aqueous medium, but the acid value of the urethane resin (A) imparted by introduction of these anionic groups is preferably in the range of 50 to 400 mgKOH / g. More preferably, it is 80-200 mgKOH / g. When the acid value is larger than 400 mgKOH / g, the viscosity at the time of neutralization is too high, the emulsification becomes unstable, and the synthesis may be difficult. On the other hand, if the acid value is less than 50 mgKOH / g, the aqueous dispersion may become unstable and agglomerate. The acid value refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin.
本発明に用いられる水性媒体としては、水が挙げられる。また、親水性の有機溶剤も本発明の目的を損なわない範囲で使用することができる。 Water is mentioned as an aqueous medium used for this invention. A hydrophilic organic solvent can also be used as long as the object of the present invention is not impaired.
次に本発明に用いられるラジカル重合可能なエチレン性不飽和単量体(B)について説明する。
エチレン性不飽和単量体(B)としては、例えば、
メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、tーブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘプチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、トリデシル(メタ)アクリレート、テトラデシル(メタ)アクリレート等の直鎖または分岐アルキル基含有エチレン性不飽和単量体;
シクロヘキシル(メタ)アクリレート、イソボニル(メタ)アクリレート等の脂環式アルキル基含有エチレン性不飽和単量体;
トリフルオロエチル(メタ)アクリレート、ヘプタデカフルオロデシル(メタ)アクリレート等のフッ素化アルキル基含有エチレン性不飽和単量体;
ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェニル(メタ)アクリレート、スチレン、α−メチルスチレン、o−メチルスチレン、p−メチルスチレン、m−メチルスチレン、ビニルナフタレン等の芳香族エチレン性不飽和単量体;
(メタ)アクリロニトリルなどのニトリル基含有エチレン性不飽和単量体;
(メタ)アクリルアミド、N−メトキシメチル−(メタ)アクリルアミド、N−エトキシメチル−(メタ)アクリルアミド、N−プロポキシメチル−(メタ)アクリルアミド、N−ブトキシメチル−(メタ)アクリルアミド、N−ペントキシメチル−(メタ)アクリルアミド、N,N−ジ(メトキシメチル)アクリルアミド、N−エトキシメチル−N−メトキシメチルメタアクリルアミド、N,N−ジ(エトキシメチル)アクリルアミド、N−エトキシメチル−N−プロポキシメチルメタアクリルアミド、N,N−ジ(プロポキシメチル)アクリルアミド、N−ブトキシメチル−N−(プロポキシメチル)メタアクリルアミド、N,N−ジ(ブトキシメチル)アクリルアミド、N−ブトキシメチル−N−(メトキシメチル)メタアクリルアミド、N,N−ジ(ペントキシメチル)アクリルアミド、N−メトキシメチル−N−(ペントキシメチル)メタアクリルアミド、N,N−ジメチルアミノプロピルアクリルアミド、N,N−ジエチルアミノプロピルアクリルアミド、N,N−ジメチルアクリルアミド、N,N−ジエチルアクリルアミド、ダイアセトン(メタ)アクリルアミド等のアミド基含有エチレン性不飽和単量体;
2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、グリセロールモノ(メタ)アクリレート、4−ヒドロキシビニルベンゼン、1−エチニル−1−シクロヘキサノール、アリルアルコール等のヒドロキシル基含有エチレン性不飽和単量体;
スチレンスルホン酸、スチレンスルホン酸ナトリウム、スチレンスルホン酸アンモニウム、2−アクリルアミド2−メチルプロパンスルホン酸、2−アクリルアミド2−メチルプロパンスルホン酸ナトリウム、メタリルスルホン酸、メタリルスルホン酸、メタリルスルホン酸ナトリウム、アリルスルホン酸、アリルスルホン酸ナトリウム、アリルスルホン酸アンモニウム、ビニルスルホン酸、アリルオキシベンゼンスルホン酸、アリルオキシベンゼンスルホン酸ナトリウム、アリルオキシベンゼンスルホン酸アンモニウム等のスルホン酸基含有エチレン性不飽和単量体;
ポリエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレート、プロポキシポリエチレングリコール(メタ)アクリレート、n−ブトキシポリエチレングリコール(メタ)アクリレート、n−ペンタキシポリエチレングリコール(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、エトキシポリプロピレングリコール(メタ)アクリレート、プロポキシポリプロピレングリコール(メタ)アクリレート、n−ブトキシポリプロピレングリコール(メタ)アクリレート、n−ペンタキシポリプロピレングリコール(メタ)アクリレート、フェノキシポリプロピレングリコール(メタ)アクリレート、ポリテトラメチレングリコール(メタ)アクリレート、メトキシポリテトラメチレングリコール(メタ)アクリレート、フェノキシテトラエチレングリコール(メタ)アクリレート、ヘキサエチレングリコール(メタ)アクリレート、メトキシヘキサエチレングリコール(メタ)アクリレートなどのポリエーテル鎖を有するエチレン性不飽和単量体;
γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリブトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシメチルトリメトキシシラン、γ−アクリロキシメチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン等のアルコキシシリル基含有エチレン性不飽和単量体;
N−メチロール(メタ)アクリルアミド、N,N−ジメチロール(メタ)アクリルアミド、アルキルエーテル化N−メチロール(メタ)アクリルアミド等のメチロール基含有エチレン性不飽和単量体;
グリシジル(メタ)アクリレート、3,4−エポキシシクロヘキシル(メタ)アクリレート等のエポキシ基含有エチレン性不飽和単量体;
アリル(メタ)アクリレート、ビニル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、1,10−デカンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、グリセリンジメタクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリストールテトラ(メタ)アクリレート、ジビニルベンゼン、アジピン酸ジビニル、イソフタル酸ジアリル、フタル酸ジアリル、マレイン酸ジアリル等の2個以上のエチレン性不飽和基を有するエチレン性不飽和単量体が挙げられるが、特にこれらに限定されるものではない。これらは1種類または2種以上を併用して用いることができる。
Next, the radically polymerizable ethylenically unsaturated monomer (B) used in the present invention will be described.
As the ethylenically unsaturated monomer (B), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate Linear or branched alkyl group-containing ethylenically unsaturated monomers such as
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
Aromatic ethylenic polymers such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene Saturated monomers;
Nitrile group-containing ethylenically unsaturated monomers such as (meth) acrylonitrile;
(Meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmeta Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylic net N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N-dimethyl Amide group-containing ethylenically unsaturated monomers such as acrylamide, N, N-diethylacrylamide, diacetone (meth) acrylamide;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Hydroxyl group-containing ethylenically unsaturated monomers such as alcohol;
Styrene sulfonic acid, sodium styrene sulfonate, ammonium styrene sulfonate, 2-acrylamide 2-methylpropane sulfonic acid, sodium 2-acrylamide 2-methylpropane sulfonate, methallyl sulfonic acid, methallyl sulfonic acid, sodium methallyl sulfonate Allyl sulfonic acid, sodium allyl sulfonate, ammonium allyl sulfonate, vinyl sulfonic acid, allyloxybenzene sulfonic acid, sodium allyloxybenzene sulfonate, ammonium allyloxybenzene sulfonate, etc. body;
Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, n-butoxypolyethylene glycol (meth) acrylate, n-pentoxypolyethylene glycol (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate N-Pentoxypolypropylene Recall (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, An ethylenically unsaturated monomer having a polyether chain such as methoxyhexaethylene glycol (meth) acrylate;
γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Alkoxysilyl group-containing ethylenically unsaturated monomers such as vinyltributoxysilane and vinylmethyldimethoxysilane;
Methylol group-containing ethylenically unsaturated monomers such as N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, alkyletherified N-methylol (meth) acrylamide;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
Allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Glycerin dimethacrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( A) ethylenically unsaturated monomers having two or more ethylenically unsaturated groups such as acrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, diallyl maleate, etc. It is not limited. These can be used alone or in combination of two or more.
電極の耐電解液性の観点から、エチレン性不飽和単量体(B)は、エチレン性不飽和単量体(B)の合計100重量%中、上記で挙げたアルコキシシリル基含有エチレン性不飽和単量体(c)、N−メチロール基含有エチレン性不飽和単量体(d)、及び1分子中に2つ以上のエチレン性不飽和基を有する単量体(e)からなる群より選ばれる少なくとも1種の架橋性エチレン性不飽和単量体0.1〜10重量%を含む事が好ましい。架橋性エチレン性不飽和単量体の量が0.1重量%未満であると電解液への溶出が大きくなり、電池特性が悪化する恐れがある。架橋性エチレン性不飽和単量体の量が10重量%を超えると十分な柔軟性が得られず密着性・可とう性が低下し、電極の活物質が欠落しやすくなる場合がある。 From the viewpoint of the electrolytic solution resistance of the electrode, the ethylenically unsaturated monomer (B) is an ethylenically unsaturated monomer containing the alkoxysilyl group mentioned above in a total of 100% by weight of the ethylenically unsaturated monomer (B). From the group consisting of a saturated monomer (c), an N-methylol group-containing ethylenically unsaturated monomer (d), and a monomer (e) having two or more ethylenically unsaturated groups in one molecule. It is preferable to contain 0.1 to 10% by weight of at least one crosslinkable ethylenically unsaturated monomer selected. If the amount of the crosslinkable ethylenically unsaturated monomer is less than 0.1% by weight, elution into the electrolytic solution is increased, and battery characteristics may be deteriorated. If the amount of the crosslinkable ethylenically unsaturated monomer exceeds 10% by weight, sufficient flexibility may not be obtained, and adhesion and flexibility may be reduced, and the active material of the electrode may be easily lost.
本発明で使用するエチレン性不飽和単量体を乳化重合するのに用いられる重合開始剤としては、ラジカル重合を開始する能力を有するものであれば特に制限はなく、公知の油溶性重合開始剤や水溶性重合開始剤を使用することができる。油溶性重合開始剤としては特に限定されず、例えば、ベンゾイルパーオキサイド、tert−ブチルパーオキシベンゾエート、tert−ブチルハイドロパーオキサイド、tert−ブチルパーオキシ(2−エチルヘキサノエート)、tert−ブチルパーオキシ−3,5,5−トリメチルヘキサノエート、ジ−tert−ブチルパーオキサイドなどの有機過酸化物;
2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−2,4−ジメチルバレロニトリル、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、1,1’−アゾビス−シクロヘキサン−1−カルボニトリルなどのアゾビス化合物を挙げることができる。これらは1種類又は2種類以上を混合して使用することができる。これら重合開始剤は、エチレン性不飽和単量体100重量部に対して、0.1〜10.0重量部の量を用いるのが好ましい。
The polymerization initiator used for emulsion polymerization of the ethylenically unsaturated monomer used in the present invention is not particularly limited as long as it has the ability to initiate radical polymerization, and is a known oil-soluble polymerization initiator. Alternatively, a water-soluble polymerization initiator can be used. The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Mention may be made of azobis compounds such as' -azobis-cyclohexane-1-carbonitrile. These may be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
本発明においては水溶性重合開始剤を使用することが好ましく、水溶性重合開始剤としては、例えば、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、2,2’−アゾビス(2−メチルプロピオンアミジン)ジハイドロクロライドなど、従来既知のものを好適に使用することができる。又、乳化重合を行うに際して、所望により重合開始剤とともに還元剤を併用することができる。これにより、乳化重合速度を促進したり、低温において乳化重合を行ったりすることが容易になる。このような還元剤としては、例えば、アスコルビン酸、エルソルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラートなどの金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウムなどの還元性無機化合物、塩化第一鉄、ロンガリット、二酸化チオ尿素などを例示できる。これら還元剤は、全エチレン性不飽和単量体100重量部に対して、0.05〜5.0重量部の量を用いるのが好ましい。なお、前記した重合開始剤によらずとも、光化学反応や、放射線照射等によっても重合を行うことができる。重合温度は各重合開始剤の重合開始温度以上とする。例えば、過酸化物系重合開始剤では、通常70℃程度とすればよい。重合時間は特に制限されないが、通常2〜24時間である。 In the present invention, it is preferable to use a water-soluble polymerization initiator. Examples of the water-soluble polymerization initiator include ammonium persulfate, potassium persulfate, hydrogen peroxide, and 2,2′-azobis (2-methylpropionamidine). Conventionally known ones such as dihydrochloride can be preferably used. Moreover, when performing emulsion polymerization, a reducing agent can be used together with a polymerization initiator if desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature. Examples of such a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, Examples include reducing inorganic compounds such as sodium bisulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the total ethylenically unsaturated monomer. In addition, it can superpose | polymerize also by a photochemical reaction, radiation irradiation, etc. irrespective of an above described polymerization initiator. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 70 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.
さらに必要に応じて、緩衝剤として、酢酸ナトリウム、クエン酸ナトリウム、重炭酸ナトリウムなどが、また、連鎖移動剤としてのオクチルメルカプタン、チオグリコール酸2−エチルヘキシル、チオグリコール酸オクチル、ステアリルメルカプタン、ラウリルメルカプタン、t−ドデシルメルカプタンなどのメルカプタン類が適量使用できる。 Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate, etc. as a buffering agent, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan as a chain transfer agent A suitable amount of mercaptans such as t-dodecyl mercaptan can be used.
また、本発明には界面活性剤を使用しないことが好ましいが、水分散体の安定性、あるいは該分散体を重合してなる複合分散体の機械的安定性を改良する目的で、少量の界面活性剤の併用も可能である。 In the present invention, it is preferable not to use a surfactant. However, in order to improve the stability of the aqueous dispersion or the mechanical stability of the composite dispersion obtained by polymerizing the dispersion, a small amount of the interface is not used. A combination of activators is also possible.
本発明において乳化重合の際に必要に応じて用いられる界面活性剤としては、エチレン性不飽和基を有する反応性界面活性剤やエチレン性不飽和基を有しない非反応性界面活性剤など、従来公知のものを任意に使用することができる。 In the present invention, as the surfactant used as necessary during the emulsion polymerization, a reactive surfactant having an ethylenically unsaturated group, a non-reactive surfactant having no ethylenically unsaturated group, and the like are conventionally used. A well-known thing can be used arbitrarily.
エチレン性不飽和基を有する反応性界面活性剤は更に大別して、アニオン系、非イオン系のノニオン系のものが例示できる。特にエチレン性不飽和基を有するアニオン系反応性界面活性剤若しくはノニオン性反応性界面活性剤を用いると、共重合体の分散粒子径が微細となるとともに粒度分布が狭くなるため、非水系二次電池電極用バインダーとして使用した際に耐電解液性を向上することができ好ましい。このエチレン性不飽和基を有するアニオン系反応性界面活性剤若しくはノニオン性反応性界面活性剤は、1種を単独で使用しても、複数種を混合して用いても良い。 Reactive surfactants having an ethylenically unsaturated group can be further broadly classified into anionic and nonionic nonionic ones. In particular, when an anionic reactive surfactant or a nonionic reactive surfactant having an ethylenically unsaturated group is used, the dispersion particle size of the copolymer becomes fine and the particle size distribution becomes narrow. When used as a binder for battery electrodes, it is possible to improve the resistance to electrolytic solution, which is preferable. This anionic reactive surfactant or nonionic reactive surfactant having an ethylenically unsaturated group may be used singly or in combination.
エチレン性不飽和基を有するアニオン系反応性界面活性剤の一例として、以下にその具体例を例示するが、本願発明において使用可能とする界面活性剤は、以下に記載するもののみを限定するものではない。前記界面活性剤としては、アルキルエーテル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンKH−05、KH−10、KH−20、株式会社ADEKA製アデカリアソープSR−10N、SR−20N、花王株式会社製ラテムルPD−104など);
スルフォコハク酸エステル系(市販品としては、例えば、花王株式会社製ラテムルS−120、S−120A、S−180P、S−180A、三洋化成株式会社製エレミノールJS−2など);
アルキルフェニルエーテル系もしくはアルキルフェニルエステル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンH−2855A、H−3855B、H−3855C、H−3856、HS−05、HS−10、HS−20、HS−30、株式会社ADEKA製アデカリアソープSDX−222、SDX−223、SDX−232、SDX−233、SDX−259、SE−10N、SE−20N、など);
(メタ)アクリレート硫酸エステル系(市販品としては、例えば、日本乳化剤株式会社製アントックスMS−60、MS−2N、三洋化成工業株式会社製エレミノールRS−30など);
リン酸エステル系(市販品としては、例えば、第一工業製薬株式会社製H−3330PL、株式会社ADEKA製アデカリアソープPP−70など)が挙げられる。
Specific examples of the anionic reactive surfactant having an ethylenically unsaturated group are shown below, but the surfactants that can be used in the present invention are limited to those described below. is not. Examples of the surfactant include alkyl ethers (commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA rear soap SR-10N, SR manufactured by ADEKA Corporation. -20N, LATEMUL PD-104 manufactured by Kao Corporation), etc .;
Sulfosuccinic acid ester-based (for example, LATEMUL S-120, S-120A, S-180P, S-180A, Sanyo Chemical Co., Ltd., Elemiol JS-2, etc., manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -20, HS-30, Adeka Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc. manufactured by ADEKA Corporation);
(Meth) acrylate sulfate-based (commercially available products include, for example, Antox MS-60, MS-2N, Sanyo Chemical Industries Co., Ltd., Elemiol RS-30, manufactured by Nippon Emulsifier Co., Ltd.);
Examples of the phosphoric acid ester (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap PP-70 manufactured by ADEKA Co., Ltd.), and the like.
本発明で用いることのできるノニオン系反応性界面活性剤としては、例えばアルキルエーテル系(市販品としては、例えば、株式会社ADEKA製アデカリアソープER−10、ER−20、ER−30、ER−40、花王株式会社製ラテムルPD−420、PD−430、PD−450など);
アルキルフェニルエーテル系もしくはアルキルフェニルエステル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンRN−10、RN−20、RN−30、RN−50、株式会社ADEKA製アデカリアソープNE−10、NE−20、NE−30、NE−40など);
(メタ)アクリレート硫酸エステル系(市販品としては、例えば、日本乳化剤株式会社製RMA−564、RMA−568、RMA−1114など)が挙げられる。
Nonionic reactive surfactants that can be used in the present invention include, for example, alkyl ethers (commercially available products such as Adeka Soap ER-10, ER-20, ER-30, and ER- manufactured by ADEKA Corporation). 40, Latemu PD-420, PD-430, PD-450, etc. manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA rear soap NE- manufactured by ADEKA Co., Ltd. 10, NE-20, NE-30, NE-40, etc.);
(Meth) acrylate sulfate esters (commercially available products include, for example, RMA-564, RMA-568, and RMA-1114 manufactured by Nippon Emulsifier Co., Ltd.).
本発明の樹脂微粒子を乳化重合により得るに際しては、前記したエチレン性不飽和基を有する反応性界面活性剤とともに、必要に応じエチレン性不飽和基を有しない非反応性界面活性剤を併用することができる。非反応性界面活性剤は、非反応性アニオン系界面活性剤と非反応性カチオン系界面活性剤と非反応性ノニオン系界面活性剤とに大別することができる。 When the resin fine particles of the present invention are obtained by emulsion polymerization, a non-reactive surfactant having no ethylenically unsaturated group may be used in combination with the reactive surfactant having an ethylenically unsaturated group as described above. Can do. Non-reactive surfactants can be broadly classified into non-reactive anionic surfactants, non-reactive cationic surfactants, and non-reactive nonionic surfactants.
非反応性ノニオン系乳化剤界面活性剤の例としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテルなどのポリオキシエチレンアルキルエーテル類;
ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類;
ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエートなどのソルビタン高級脂肪酸エステル類;
ポリオキシエチレンソルビタンモノラウレートなどのポリオキシエチレンソルビタン高級脂肪酸エステル類;
ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレートなどのポリオキシエチレン高級脂肪酸エステル類;
オレイン酸モノグリセライド、ステアリン酸モノグリセライドなどのグリセリン高級脂肪酸エステル類;
ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー、ポリオキシエチレンジスチレン化フェニルエーテルなどを例示することができる。
Examples of non-reactive nonionic emulsifier surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether;
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether;
Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate;
Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate;
Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate;
Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride;
Examples include polyoxyethylene / polyoxypropylene / block copolymer, polyoxyethylene distyrenated phenyl ether, and the like.
又、非反応性アニオン系乳化剤の例としては、オレイン酸ナトリウムなどの高級脂肪酸塩類;
ドデシルベンゼンスルホン酸ナトリウムなどのアルキルアリールスルホン酸塩類;
ラウリル硫酸ナトリウムなどのアルキル硫酸エステル塩類;
ポリエキシエチレンラウリルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルエーテル硫酸エステル塩類;
ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類;
モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウムなどのアルキルスルホコハク酸エステル塩及びその誘導体類;
ポリオキシエチレンジスチレン化フェニルエーテル硫酸エステル塩類などを例示することができる。
非反応性カチオン系界面活性剤の例としては、
例えばR−N(CH3)3X〔R=ステアリル・セチル・ラウリル・オレイル・ドデシル・ヤシ・大豆・牛脂等/X=ハロゲン・アミン等〕で表されるアルキルトリメチルアミン系4級アンモニウム塩類;
テトラメチルアミン系塩、テトラブチルアミン塩等の4級アンモニウム塩類;
(RNH3)(CH3COO)〔R=ステアリル・セチル・ラウリル・オレイル・ドデシル・ヤシ・大豆・牛脂等〕で表される酢酸塩類;
ラウリルジメチルベンジルアンモニウム塩(ハロゲン・アミン塩等)、ステアリルジメチルベンジルアンモニウム塩(ハロゲン・アミン塩等)、ドデシルジメチルベンジルアンモニウム塩(ハロゲン・アミン塩等)等のベンジルアミン系4級アンモニウム塩類;
R(CH3)N(C2H4O)mH(C2H4O)n・X〔R=ステアリル・セチル・ラウリル・オレイル・ドデシル・ヤシ・大豆・牛脂等/X=ハロゲン・アミン等、mおよびnは、0以上の整数〕で表されるポリオキシアルキレン系4級アンモニウム塩類を使用することができる。
Examples of non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate;
Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate;
Alkyl sulfate salts such as sodium lauryl sulfate;
Polyoxyethylene alkyl ether sulfate esters such as sodium polyoxyethylene lauryl ether sulfate;
Polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate;
Alkyl sulfosuccinic acid ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof;
Examples thereof include polyoxyethylene distyrenated phenyl ether sulfate salts.
Examples of non-reactive cationic surfactants include
For example, alkyltrimethylamine-based quaternary ammonium salts represented by RN (CH 3 ) 3 X [R = stearyl, cetyl, lauryl, oleyl, dodecyl, palm, soybean, beef tallow etc./X=halogen, amine, etc.];
Quaternary ammonium salts such as tetramethylamine salts and tetrabutylamine salts;
Acetates represented by (RNH 3 ) (CH 3 COO) [R = stearyl, cetyl, lauryl, oleyl, dodecyl, palm, soybean, beef tallow, etc.];
Benzylamine quaternary ammonium salts such as lauryldimethylbenzylammonium salt (halogen / amine salt, etc.), stearyldimethylbenzylammonium salt (halogen / amine salt, etc.), dodecyldimethylbenzylammonium salt (halogen / amine salt, etc.);
R (CH 3) N (C 2 H 4 O) mH (C 2 H 4 O) n · X [R = stearyl cetyl lauryl oleyl dodecyl coconut, soybean beef tallow / X = halogen amine , M, and n are integers of 0 or more], and polyoxyalkylene-based quaternary ammonium salts can be used.
本発明において、エチレン性不飽和単量体(B)の合計100重量部に対する、ウレタン樹脂(A)の量は、5〜150重量部である事が好ましい。ウレタン樹脂(A)の量が5重量部未満であると、粒子核が不安定化して、安定な樹脂微粒子分散体を得る事ができない場合がある。ウレタン樹脂(A)の量が150重量部を超えると耐電解液性が低下して電池特性に悪影響を及ぼしてしまう場合がある。 In this invention, it is preferable that the quantity of a urethane resin (A) with respect to a total of 100 weight part of an ethylenically unsaturated monomer (B) is 5-150 weight part. If the amount of the urethane resin (A) is less than 5 parts by weight, the particle nuclei may become unstable and a stable resin fine particle dispersion may not be obtained. When the amount of the urethane resin (A) exceeds 150 parts by weight, the electrolytic solution resistance may be lowered and the battery characteristics may be adversely affected.
本発明の非水二次電池電極用バインダー樹脂組成物は樹脂の物理的架橋をより強固にする目的、又は集電体との密着性を向上させる目的、更にはバインダーの機械強度調整の目的で、バインダー組成物に添加剤を添加することができる。集電体との密着性を向上させるための添加剤としては、集電体が主に金属化合物であることから、一般的に金属密着性を向上させる成分、例えばリン酸、イミダゾールシラン系化合物などを添加することができる。又、バインダーの機械強度を調整するための添加剤として、ポリエステル樹脂、ポリウレタン樹脂といった樹脂をブレンドすることも可能である。これら添加剤は、上記目的を満たすものであればこれに限らない。 The binder resin composition for non-aqueous secondary battery electrodes of the present invention is for the purpose of strengthening the physical crosslinking of the resin, or for improving the adhesion with the current collector, and for the purpose of adjusting the mechanical strength of the binder. An additive can be added to the binder composition. As an additive for improving the adhesion with the current collector, since the current collector is mainly a metal compound, components that generally improve the metal adhesion, such as phosphoric acid, imidazole silane compounds, etc. Can be added. Further, as an additive for adjusting the mechanical strength of the binder, it is possible to blend a resin such as a polyester resin or a polyurethane resin. These additives are not limited to these as long as they satisfy the above purpose.
更に本発明の非水二次電池電極用バインダー樹脂組成物には、成膜助剤、消泡剤、レベリング剤、防腐剤、pH調整剤、粘性調整剤などを必要に応じて配合できる。 Furthermore, the binder resin composition for a non-aqueous secondary battery electrode of the present invention can contain a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjusting agent, a viscosity adjusting agent, and the like as required.
成膜助剤は、塗膜の形成を助け、塗膜が形成された後においては比較的速やかに蒸発揮散して塗膜の強度を向上させる一時的な可塑化機能を担うものであり、沸点が110〜200℃の溶媒が好適に用いられる。具体的には、プロピレングリコールモノブチルエーテル、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノプロピルエーテル、カルビトール、ブチルカルビトール、ジブチルカルビトール、ベンジルアルコールなどが挙げられる。中でも、エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルは少量で高い成膜助剤効果を有するため特に好ましい。これら成膜助剤は、二次電池電極用組成物中に0.5〜15重量%含まれることが好ましい。 The film-forming aid is responsible for the temporary plasticization function that helps the formation of the coating film and evaporates relatively quickly after the coating film is formed, thereby improving the strength of the coating film. Is preferably a solvent having a temperature of 110 to 200 ° C. Specifically, propylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monopropyl ether, carbitol, butyl carbitol, dibutyl carbitol, benzyl alcohol, etc. Is mentioned. Among these, ethylene glycol monobutyl ether and propylene glycol monobutyl ether are particularly preferable because they have a high film forming auxiliary effect in a small amount. These film-forming aids are preferably contained in the secondary battery electrode composition in an amount of 0.5 to 15% by weight.
粘性調整剤は、樹脂微粒子分散体100重量部に対して1〜100重量部用いるのが好ましい。粘性調整剤としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸(及びその塩)、酸化スターチ、リン酸化スターチ、カゼインなどが挙げられる。 The viscosity modifier is preferably used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the resin fine particle dispersion. Examples of the viscosity modifier include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (and its salt), oxidized starch, phosphorylated starch, and casein.
本発明の非水二次電池電極用バインダー樹脂組成物は、二次電池の正極、及び負極に使用することができる。その他、エネルギーデバイス、即ち、キャパシタ、太陽電池などにも使用することができる。 The binder resin composition for nonaqueous secondary battery electrodes of the present invention can be used for a positive electrode and a negative electrode of a secondary battery. In addition, it can also be used for energy devices, that is, capacitors, solar cells, and the like.
ウレタン樹脂を乳化剤として乳化重合して得た樹脂微粒子分散体、すなわち本発明の非水二次電池電極用バインダー樹脂組成物と電極活物質と導電助剤とを配合することにより、二次電池電極用組成物を得ることができる。この二次電池電極用組成物を集電体に塗布し、乾燥することにより、非水系二次電池電極を製造することができる。 A resin fine particle dispersion obtained by emulsion polymerization using a urethane resin as an emulsifier, that is, a secondary battery electrode by blending the binder resin composition for a non-aqueous secondary battery electrode of the present invention, an electrode active material, and a conductive additive. The composition for use can be obtained. A nonaqueous secondary battery electrode can be produced by applying the composition for a secondary battery electrode to a current collector and drying it.
本発明において、樹脂微粒子は、固形分として、電極活物質100重量部に対して、通常0.1〜20重量部、好ましくは0.5〜10重量部用いられる。樹脂微粒子の添加量が0.1重量部未満であると、電極活物質を集電体に結着させる力が不十分であり、電極活物質が脱落し電池の容量が低下する場合がある。一方、樹脂微粒子の添加量が20重量部を超えると、電池内の抵抗が増して電池の容量が低下する場合がある。 In the present invention, the resin fine particles are generally used in a solid content of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the electrode active material. When the addition amount of the resin fine particles is less than 0.1 parts by weight, the force for binding the electrode active material to the current collector is insufficient, and the electrode active material may fall off and the battery capacity may be reduced. On the other hand, if the amount of resin fine particles added exceeds 20 parts by weight, the resistance in the battery may increase and the battery capacity may decrease.
電極活物質としては、以下のものが挙げられる。
正極活物質としては、特に限定はされないが、リチウムイオンをドーピングまたはインターカレーション可能な金属酸化物、金属硫化物等の金属化合物、および導電性高分子等を使用することができる。例えば、Fe、Co、Ni、Mn等の遷移金属の酸化物、リチウムとの複合酸化物、遷移金属硫化物等の無機化合物等が挙げられる。具体的には、MnO、V2O5、V6O13、TiO2等の遷移金属酸化物粉末、層状構造のニッケル酸リチウム、コバルト酸リチウム、マンガン酸リチウム、スピネル構造のマンガン酸リチウムなどのリチウムと遷移金属との複合酸化物粉末、オリビン構造のリン酸化合物であるリン酸鉄リチウム系材料、TiS2、FeSなどの遷移金属硫化物粉末等が挙げられる。また、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン等の導電性ポリマーを使用することもできる。また、上記の無機化合物や有機化合物を混合して用いてもよい。
負極活物質としては、リチウムイオンをドーピングまたはインターカレーション可能なものであれば特に限定されない。例えば、金属Li、その合金であるスズ合金、シリコン合金、鉛合金等の合金系、LiXFe2O3、LiXFe3O4、LiXWO2、チタン酸リチウム、バナジウム酸リチウム、ケイ素酸リチウム等の金属酸化物系、ポリアセチレン、ポリ−p−フェニレン等の導電性高分子系、ソフトカーボンやハードカーボンといった、アモルファス系炭素質材料や、高黒鉛化炭素材料等の人造黒鉛、あるいは天然黒鉛等の炭素質粉末、カーボンブラック、メソフェーズカーボンブラック、樹脂焼成炭素材料、気層成長炭素繊維、炭素繊維などの炭素系材料が挙げられる。
これら負極活物質は、1種または複数を組み合わせて使用することも出来る。
Examples of the electrode active material include the following.
The positive electrode active material is not particularly limited, and metal oxides that can be doped or intercalated with lithium ions, metal compounds such as metal sulfides, conductive polymers, and the like can be used. Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc. Examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, transition metal sulfide powders such as TiS 2 and FeS, and the like. In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.
The negative electrode active material is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloys thereof such as tin alloy, silicon alloy, lead alloy, Li X Fe 2 O 3 , Li X Fe 3 O 4 , Li X WO 2 , lithium titanate, lithium vanadate, silicon Metal oxides such as lithium oxide, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers.
These negative electrode active materials can be used alone or in combination.
電極活物質と併用する導電性材料としては、例えば、ニッケル粉末、酸化コバルト、酸化チタン、カーボンなどを挙げることができる。カーボンとしては、アセチレンブラック、ファーネスブラック、黒鉛、炭素繊維、フラーレン類を挙げることができる。導電性材料の使用量は、電極活物質100重量部に対して0.5〜10重量部が好ましい。0.5重量部未満では導電性が低く、二次電池の高いレートで充放電した場合の容量が低下する場合がある。集電体としては、二次電池電極に通常用いられているものであれば特に限定されず、例えば、パンチングメタル、エキスパンドメタル、金網、発泡金属、網状金属繊維焼結体などを挙げることができる。 Examples of the conductive material used in combination with the electrode active material include nickel powder, cobalt oxide, titanium oxide, and carbon. Examples of carbon include acetylene black, furnace black, graphite, carbon fiber, and fullerenes. As for the usage-amount of an electroconductive material, 0.5-10 weight part is preferable with respect to 100 weight part of electrode active materials. If the amount is less than 0.5 parts by weight, the conductivity is low, and the capacity may be reduced when charging / discharging at a high rate of the secondary battery. The current collector is not particularly limited as long as it is usually used for a secondary battery electrode, and examples thereof include punching metal, expanded metal, wire mesh, foam metal, and reticulated metal fiber sintered body. .
非水系二次電池電極を形成するには、前記二次電池電極用組成物を、スラリー状にして集電体に塗布、加熱し、乾燥する。二次電池電極用組成物の塗布方法としては、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法など任意のコーターヘッドを用いることができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できる。 In order to form a non-aqueous secondary battery electrode, the composition for a secondary battery electrode is applied to a current collector in the form of a slurry, heated and dried. As a coating method for the secondary battery electrode composition, any coater head such as a reverse roll method, a comma bar method, a gravure method, an air knife method, etc. can be used. A dryer, an infrared heater, a far infrared heater, etc. can be used.
本発明の非水系二次電池は、前記非水二次電池電極用バインダー樹脂組成物を用いて製作された二次電池用電極を具えている。上記のようにして得られた非水系二次電池電極を用いて、非水系二次電池を作製する場合、例えば、電解液にエチレンカーボネート、プロピレンカーボネートなどのカーボネート系溶剤を用い、電解質としてLiPF6などのリチウムイオン化合物を用いるリチウムイオン二次電池として使用するのが好ましい。更に、セパレーター、集電体、端子、絶縁板などの部品を用いて電池が構成される。セパレーターとしては、例えば、ポリエチレン不織布、ポリプロピレン不織布、ポリアミド不織布及びそれらに親水性処理を施したものが挙げられる。 The non-aqueous secondary battery of the present invention comprises a secondary battery electrode manufactured using the binder resin composition for a non-aqueous secondary battery electrode. When producing a non-aqueous secondary battery using the non-aqueous secondary battery electrode obtained as described above, for example, a carbonate solvent such as ethylene carbonate or propylene carbonate is used as the electrolyte, and LiPF 6 is used as the electrolyte. It is preferable to use it as a lithium ion secondary battery using a lithium ion compound such as. Furthermore, a battery is configured using components such as a separator, a current collector, a terminal, and an insulating plate. Examples of the separator include polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyamide nonwoven fabric, and those obtained by subjecting them to hydrophilic treatment.
以下に、実施例により本発明を更に具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例における「部」は「重量部」、「%」は「重量%」を表す。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
<ウレタン樹脂(A)の合成>
[製造例1]
還流冷却管、滴下漏斗、ガス導入管、攪拌装置、温度計を備えた四ツ口の1000mlフラスコにPEG#2000(日油株式会社製 ポリエチレングリコール)26.1部、ジメチロールブタン酸13.4部、メチルエチルケトン39.8部を仕込み、乾燥窒素で置換し、攪拌しながら60℃まで昇温した。攪拌下、イソホロンジイソシアネート20.7部、ジブチルすずジラウレート0.01部を加え80℃まで昇温し、4時間反応させた。得られたウレタン樹脂の重量平均分子量は9304、酸価は138mgKOH/gであった。反応物を50℃まで冷却し、25%アンモニア水10.0部、水230.8部を加えた後に昇温して、メチルエチルケトンを脱溶剤し、固形分20%となるように水を加え、ウレタン樹脂水溶液を得た。
<Synthesis of urethane resin (A)>
[Production Example 1]
In a four-neck 1000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer, 26.1 parts of PEG # 2000 (polyethylene glycol manufactured by NOF Corporation) and dimethylolbutanoic acid 13.4 And 39.8 parts of methyl ethyl ketone were charged, replaced with dry nitrogen, and heated to 60 ° C. with stirring. Under stirring, 20.7 parts of isophorone diisocyanate and 0.01 part of dibutyltin dilaurate were added and the temperature was raised to 80 ° C. and reacted for 4 hours. The resulting urethane resin had a weight average molecular weight of 9304 and an acid value of 138 mgKOH / g. The reaction product was cooled to 50 ° C., 10.0 parts of 25% aqueous ammonia and 230.8 parts of water were added, and the temperature was raised to remove the methyl ethyl ketone, and water was added to a solid content of 20%. A urethane resin aqueous solution was obtained.
[製造例2〜9]
表1に示す配合組成で、製造例1と同様の方法で合成し、ウレタン樹脂(A)を得た。
[Production Examples 2 to 9]
The compounding composition shown in Table 1 was synthesized in the same manner as in Production Example 1 to obtain a urethane resin (A).
[製造例10]
還流冷却管、滴下漏斗、ガス導入管、攪拌装置、温度計を備えた四ツ口の1000mlフラスコにPEG#2000(日油株式会社製 ポリエチレングリコール)14.8部、ジメチロールブタン酸10.5部、メチルエチルケトン39.8部を仕込み、乾燥窒素で置換し、攪拌しながら60℃まで昇温した。攪拌下、イソホロンジイソシアネート34.9部、ジブチルすずジラウレート0.01部を加え80℃まで昇温し、4時間反応させた。反応物を50℃まで冷却し、イソプロピルアルコールに溶解したイソホロンジアミンを滴下し、重量平均分子量が50000に達するまで鎖延長を行った。その後IRでイソシアネートのピークがなくなるまでイソプロピルアルコールに溶解したジブチルアミンを滴下し、鎖延長を終了した。得られたウレタン樹脂の重量平均分子量は52430、酸価は132mgKOH/gであった。25%アンモニア水10.0部、水200部を加えた後に昇温して、メチルエチルケトンを脱溶剤し、固形分20%となるように水を加え、ウレタン樹脂水溶液を得た。
[Production Example 10]
In a four-neck 1000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer, 14.8 parts of PEG # 2000 (manufactured by NOF Corporation, polyethylene glycol), dimethylolbutanoic acid 10.5 And 39.8 parts of methyl ethyl ketone were charged, replaced with dry nitrogen, and heated to 60 ° C. with stirring. Under stirring, 34.9 parts of isophorone diisocyanate and 0.01 part of dibutyltin dilaurate were added and the temperature was raised to 80 ° C. and reacted for 4 hours. The reaction product was cooled to 50 ° C., isophoronediamine dissolved in isopropyl alcohol was added dropwise, and chain extension was performed until the weight average molecular weight reached 50000. Thereafter, dibutylamine dissolved in isopropyl alcohol was dropped until the isocyanate peak disappeared by IR to complete chain extension. The resulting urethane resin had a weight average molecular weight of 52430 and an acid value of 132 mgKOH / g. After adding 10.0 parts of 25% ammonia water and 200 parts of water, the temperature was raised to remove methyl ethyl ketone, and water was added so that the solid content was 20% to obtain an aqueous urethane resin solution.
<樹脂微粒子分散体の合成>
[製造例11]
攪拌器、温度計、2つの滴下ロート、還流器を備えた別の反応容器に、製造例1で得た固形分20%のウレタン樹脂水溶液500.0部、イオン交換水56.7部を加えて、攪拌しながら、窒素還流下で温度70℃まで昇温した。別途、スチレン60.4部、2−エチルヘキシルアクリレート37.6部、3−メタクリロキシプロピルトリメトキシシラン2.0部を滴下槽1に、又、過硫酸カリウム10%水溶液15.0部を滴下槽2に仕込んだ。滴下槽1、2の内容物を2時間かけて滴下し、重合を行った。滴下終了後、内温を70℃に保ったまま1時間攪拌を続け、固形分測定にて転化率が98%超えたことを確認後、温度を室温まで冷却し、樹脂微粒子分散体を得た。得られた樹脂微粒子分散体の固形分は30.0%であった。
<Synthesis of resin fine particle dispersion>
[Production Example 11]
In another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, add 500.0 parts of a 20% solid urethane resin aqueous solution obtained in Production Example 1 and 56.7 parts of ion-exchanged water. While stirring, the temperature was raised to 70 ° C. under nitrogen reflux. Separately, 60.4 parts of styrene, 37.6 parts of 2-ethylhexyl acrylate, 2.0 parts of 3-methacryloxypropyltrimethoxysilane are added to the dropping tank 1, and 15.0 parts of a 10% aqueous solution of potassium persulfate are added to the dropping tank. 2 was charged. The contents of the dropping tanks 1 and 2 were dropped over 2 hours to perform polymerization. After completion of the dropping, stirring was continued for 1 hour while maintaining the internal temperature at 70 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to room temperature to obtain a resin fine particle dispersion. . The obtained resin fine particle dispersion had a solid content of 30.0%.
[製造例12〜24]
表2に示す配合組成で、製造例11と同様の方法で合成し、樹脂微粒子分散体を得た。あらかじめ反応容器に仕込んでおくイオン交換水の量は、樹脂微粒子分散体の仕上がり固形分が30.0%なるように調整して加えた。
[Production Examples 12 to 24]
The compounding composition shown in Table 2 was synthesized in the same manner as in Production Example 11 to obtain a resin fine particle dispersion. The amount of ion-exchanged water charged in the reaction vessel in advance was adjusted and added so that the finished solid content of the resin fine particle dispersion was 30.0%.
[製造例25]
攪拌器、温度計、滴下ロート、還流器を備えた反応容器に、イオン交換水194.6部と界面活性剤としてドデシルベンゼンスルホン酸ナトリウム0.2部とを仕込み、別途、スチレン120.8部、2−エチルヘキシルアクリレート75.2部、3−メタクリロキシプロピルトリメトキシシラン4.0部、イオン交換水87.0部及び界面活性剤としてドデシルベンゼンスルホン酸ナトリウム3.8部をあらかじめ混合しておいたプレエマルジョンのうちの5%を更に加えた。内温を70℃に昇温し十分に窒素置換した後、過硫酸カリウムの5%水溶液24.0部の10%を添加し重合を開始した。反応系内を70℃で5分間保持した後、内温を70℃に保ちながらプレエマルジョンの残りと過硫酸カリウムの5%水溶液の残りを3時間かけて滴下し、更に2時間攪拌を継続した。固形分測定にて転化率が98%超えたことを確認後、温度を室温まで冷却し、樹脂微粒子水分散体を得た。得られた樹脂微粒子分散体の固形分は45.1%であった。
[Production Example 25]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a refluxing vessel was charged with 194.6 parts of ion-exchanged water and 0.2 part of sodium dodecylbenzenesulfonate as a surfactant, and separately, 120.8 parts of styrene. , 75.2 parts of 2-ethylhexyl acrylate, 4.0 parts of 3-methacryloxypropyltrimethoxysilane, 87.0 parts of ion-exchanged water, and 3.8 parts of sodium dodecylbenzenesulfonate as a surfactant are mixed in advance. An additional 5% of the pre-emulsion was added. After raising the internal temperature to 70 ° C. and sufficiently purging with nitrogen, 10% of 24.0 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization. After maintaining the reaction system at 70 ° C. for 5 minutes, the remaining pre-emulsion and the remaining 5% aqueous solution of potassium persulfate were added dropwise over 3 hours while maintaining the internal temperature at 70 ° C., and stirring was further continued for 2 hours. . After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to room temperature to obtain an aqueous dispersion of resin fine particles. The solid content of the obtained resin fine particle dispersion was 45.1%.
[製造例26]
攪拌器、温度計、2つの滴下ロート、還流器を備えた別の反応容器に、水溶性のスチレンアクリル樹脂であるジョンクリル61J(BASF社製、酸価213、固形分30%水溶液)500部、イオン交換水56.7部を加えて、攪拌しながら、窒素還流下で温度70℃まで昇温した。
別途、スチレン60.4部、2−エチルヘキシルアクリレート37.6部、3−メタクリロキシプロピルトリメトキシシラン2.0部を滴下槽1に、又、過硫酸アンモニウム10%水溶液15.0部を滴下槽2に仕込んだ。滴下槽1、2の内容物を2時間かけて滴下し、重合を行った。滴下終了後、内温を70℃に保ったまま1時間攪拌を続け、固形分測定にて転化率が98%超えたことを確認後、温度を室温まで冷却し、樹脂微粒子分散体を得た。得られた樹脂微粒子分散体の固形分は30.0%であった。
[Production Example 26]
In another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a reflux condenser, 500 parts of water-soluble styrene acrylic resin, Jonkrill 61J (manufactured by BASF, acid value 213, solid content 30% aqueous solution) Then, 56.7 parts of ion-exchanged water was added, and the temperature was raised to 70 ° C. under nitrogen reflux with stirring.
Separately, 60.4 parts of styrene, 37.6 parts of 2-ethylhexyl acrylate, 2.0 parts of 3-methacryloxypropyltrimethoxysilane are added to the dropping tank 1, and 15.0 parts of a 10% aqueous solution of ammonium persulfate are added to the dropping tank 2. Was charged. The contents of the dropping tanks 1 and 2 were dropped over 2 hours to perform polymerization. After completion of the dropping, stirring was continued for 1 hour while maintaining the internal temperature at 70 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to room temperature to obtain a resin fine particle dispersion. . The obtained resin fine particle dispersion had a solid content of 30.0%.
<二次電池電極用組成物及び非水系二次電池電極の作成>
[実施例1]
(正極の作製)
正極活物質であるリン酸鉄リチウム(LiFePO4)90部、導電性材料としてアセチレンブラック5部、増粘剤としてカルボキシメチルセルロース2部、製造例11で得られた樹脂微粒子水分散体を固形分として3部に、イオン交換水を固形分50%となるように加えた後、混練して二次電池電極用組成物を調整した。この二次電池電極用組成物を集電体となる厚さ20μmのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、ロールプレスによる圧延処理を行い、厚さ50μmの正極合剤層を有する正極を作製した。
<Creation of secondary battery electrode composition and non-aqueous secondary battery electrode>
[Example 1]
(Preparation of positive electrode)
90 parts of lithium iron phosphate (LiFePO 4 ) as a positive electrode active material, 5 parts of acetylene black as a conductive material, 2 parts of carboxymethyl cellulose as a thickener, and the resin fine particle aqueous dispersion obtained in Production Example 11 as a solid content To 3 parts, ion exchange water was added so as to have a solid content of 50%, and then kneaded to prepare a composition for a secondary battery electrode. This secondary battery electrode composition was applied onto a 20 μm-thick aluminum foil serving as a current collector using a doctor blade, dried under reduced pressure, and subjected to a rolling process using a roll press to form a 50 μm-thick positive electrode composite. A positive electrode having an agent layer was produced.
(負極の作製)
負極活物質としてメソフェーズカーボン97部、増粘剤としてカルボキシメチルセルロース1部、製造例11で得られた樹脂微粒子水分散体を固形分として2部に、イオン交換水を固形分50%となるように加えた後、混練して二次電池電極用組成物を調整した。この二次電池電極用組成物を集電体となる厚さ20μmの銅箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、ロールプレスによる圧延処理を行い、厚さ50μmの負極合剤層を有する負極を作製した。
(Preparation of negative electrode)
97 parts of mesophase carbon as the negative electrode active material, 1 part of carboxymethyl cellulose as the thickener, 2 parts of the resin fine particle water dispersion obtained in Production Example 11 as a solid content, and ion exchange water to a solid content of 50% After the addition, the composition for a secondary battery electrode was prepared by kneading. This secondary battery electrode composition was applied onto a 20 μm thick copper foil serving as a current collector using a doctor blade, dried under reduced pressure, and subjected to a rolling process using a roll press to form a negative electrode composite having a thickness of 50 μm. A negative electrode having an agent layer was produced.
[実施例2〜14、比較例1〜3]
表3に示す樹脂微粒子分散体を用い、実施例1と同様の方法で調製し、二次電池電極用組成物(正極用及び負極用)及び、正・負極電池電極を得た。尚、比較例3では、樹脂微粒子分散体にBM−400B(日本ゼオン株式会社製 SBRエマルジョン)を使用した。
[Examples 2-14, Comparative Examples 1-3]
Using the resin fine particle dispersion shown in Table 3, it was prepared in the same manner as in Example 1 to obtain a secondary battery electrode composition (for positive electrode and negative electrode) and positive and negative electrode batteries. In Comparative Example 3, BM-400B (SBR emulsion manufactured by Nippon Zeon Co., Ltd.) was used as the resin fine particle dispersion.
[比較例4]
(正極の作製)
正極活物質であるリン酸鉄リチウム(LiFePO4)を90部、導電性材料としてアセチレンブラック5部、KFポリマーW#1100(株式会社クレハ製 ポリフッ化ビニリデン)を固形分として5部に、N−メチル−2−ピロリドンを固形分50%となるように加えた後、混練して二次電池電極用組成物を調整した。この二次電池電極用組成物を集電体となる厚さ20μmのアルミ箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、ロールプレスによる圧延処理を行い、厚さ50μmの正極合剤層を有する正極を作製した。
[Comparative Example 4]
(Preparation of positive electrode)
90 parts of lithium iron phosphate (LiFePO 4 ) as a positive electrode active material, 5 parts of acetylene black as a conductive material, 5 parts of KF polymer W # 1100 (polyvinylidene fluoride manufactured by Kureha Co., Ltd.) as solids, N— Methyl-2-pyrrolidone was added to a solid content of 50%, and then kneaded to prepare a secondary battery electrode composition. This secondary battery electrode composition was applied onto a 20 μm-thick aluminum foil serving as a current collector using a doctor blade, dried under reduced pressure, and subjected to a rolling process using a roll press to form a 50 μm-thick positive electrode composite. A positive electrode having an agent layer was produced.
(負極の作製)
負極活物質としてメソフェーズカーボン97部、KFポリマーW#1100(株式会社クレハ製 ポリフッ化ビニリデン)を固形分として3部に、N−メチル−2−ピロリドンを固形分50%となるように加えた後、混練して二次電池電極用組成物を調整した。この二次電池電極用組成物を集電体となる厚さ20μmの銅箔上にドクターブレードを用いて塗布した後、減圧加熱乾燥し、ロールプレスによる圧延処理を行い、厚さ50μmの負極合剤層を有する負極を作製した。
(Preparation of negative electrode)
After adding 97 parts of mesophase carbon as the negative electrode active material, 3 parts of KF polymer W # 1100 (polyvinylidene fluoride manufactured by Kureha Co., Ltd.) as solids, and N-methyl-2-pyrrolidone to a solid content of 50% Kneaded to prepare a composition for a secondary battery electrode. This secondary battery electrode composition was applied onto a 20 μm thick copper foil serving as a current collector using a doctor blade, dried under reduced pressure, and subjected to a rolling process using a roll press to form a negative electrode composite having a thickness of 50 μm. A negative electrode having an agent layer was produced.
<リチウム二次電池正極評価用セルの組み立て>
実施例1〜14及び比較例1〜4で得られた正極を、直径16mmに打ち抜き作用極とし、金属リチウム箔を対極として、作用極及び対極の間に多孔質ポリプロピレンフィルムからなるセパレーターを挿入積層し、電解液(エチレンカーボネートとジエチルカーボネートを1:1(体積比)の割合で混合した混合溶媒にLiPF6を1Mの濃度で溶解させた非水電解液)を満たしてコインセルを組み立てた。コインセルの組み立てはアルゴンガス置換したグロ−ブボックス内で行い、セル組み立て後、所定の電池特性評価を行った。
<Assembly of lithium secondary battery positive electrode evaluation cell>
The positive electrodes obtained in Examples 1 to 14 and Comparative Examples 1 to 4 were punched to a diameter of 16 mm, the metallic lithium foil was the counter electrode, and a separator made of a porous polypropylene film was inserted between the working electrode and the counter electrode. Then, the coin cell was assembled by filling an electrolytic solution (a nonaqueous electrolytic solution in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio)). The coin cell was assembled in a glove box substituted with argon gas, and a predetermined battery characteristic evaluation was performed after the cell assembly.
<リチウム二次電池負極評価用セルの組み立て>
実施例1〜14及び比較例1〜4で得られた負極を、直径16mmに打ち抜き作用極とし、金属リチウム箔を対極として、作用極及び対極の間に多孔質ポリプロピレンフィルムからなるセパレーターを挿入積層し、電解液(エチレンカーボネートとジエチルカーボネートを1:1(体積比)の割合で混合した混合溶媒にLiPF6 を1Mの濃度で溶解させた非水電解液)を満たしてコインセルを組み立てた。コインセルの組み立てはアルゴンガス置換したグロ−ブボックス内で行い、セル組み立て後、所定の電池特性評価を行った。
<Assembly of lithium secondary battery negative electrode evaluation cell>
The negative electrodes obtained in Examples 1 to 14 and Comparative Examples 1 to 4 were punched to a diameter of 16 mm, the working electrode was a metallic lithium foil, and a separator made of a porous polypropylene film was inserted between the working electrode and the counter electrode. Then, the coin cell was assembled by filling an electrolytic solution (a nonaqueous electrolytic solution in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio)). The coin cell was assembled in a glove box substituted with argon gas, and a predetermined battery characteristic evaluation was performed after the cell assembly.
上記の方法で得られた二次電池電極及びリチウム二次電池電極評価用セルを用いて、密着性、耐電解液性、電池特性を評価した。評価結果を表4に示す。 Using the secondary battery electrode and lithium secondary battery electrode evaluation cell obtained by the above method, adhesion, resistance to electrolytic solution, and battery characteristics were evaluated. The evaluation results are shown in Table 4.
(密着性)
電極表面にナイフを用いて、合剤層から集電体に達する深さまでの切込みを2mm間隔で縦横それぞれ6本入れて碁盤目の切込みを入れた。この切り込みに粘着テープを貼り付けて直ちに引き剥がし、活物質の脱落の程度を目視判定で判定した。評価基準を下記に示す。
◎:「剥離なし」
○:「わずかに剥離(実用上問題のないレベル)」
○△:「半分程度剥離(問題はあるが使用可能レベル)」
△:「ほとんどの部分で剥離」
×:「完全に剥離」
(Adhesion)
Using a knife on the electrode surface, 6 incisions were made from the mixture layer to the depth reaching the current collector, both vertically and horizontally at intervals of 2 mm, to make a grid cut. An adhesive tape was applied to the cut and immediately peeled off, and the degree of the active material falling off was determined by visual judgment. The evaluation criteria are shown below.
A: “No peeling”
○: “Slightly peeled off (a level with no practical problem)”
○ △: About half peel (problem but usable level)
Δ: “Peeling at most parts”
×: “Completely peeled”
(耐電解液性)
作成した電極をエチレンカーボネートとジエチルカーボネートを1:1(体積比)の割合で混合した混合溶媒に60℃、24時間浸漬し、浸漬前後での膜の膨潤状態、樹脂の溶出状態を下記の通り算出し、比較評価した。
(Electrolytic solution resistance)
The prepared electrode was immersed in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio) at 60 ° C. for 24 hours, and the swelling state of the film and the elution state of the resin before and after immersion were as follows: Calculation and comparative evaluation were performed.
膨潤率 (%)=〔(浸漬後重量)/(浸漬前重量)〕×100
溶出率 (%)=〔1−(浸漬乾燥後重量)/(浸漬前重量)〕×100
膨潤率はその値が100%に近いほど、溶出率は0%に近いほど耐電解液性が高いことを示す。
○:「膨潤率が110%未満。全く問題なし。」
△:「膨潤率が110%以上、120%未満。実用上使用可。」
×:「膨潤率が120%以上。実用上問題あり。」
Swelling ratio (%) = [(weight after immersion) / (weight before immersion)] × 100
Dissolution rate (%) = [1- (weight after immersion drying) / (weight before immersion)] × 100
As the swelling rate is closer to 100% and the dissolution rate is closer to 0%, the resistance to electrolytic solution is higher.
○: “Swelling rate is less than 110%. No problem at all”
Δ: “The swelling rate is 110% or more and less than 120%. Practical use is possible.”
X: “Swelling rate is 120% or more.
○:「溶出率が1.0%未満。全く問題なし。」
△:「溶出率が1.0%以上、3.0%未満。実用上使用可。」
×:「溶出率が3.0%以上。実用上問題あり。」
○: “Elution rate is less than 1.0%. No problem”
Δ: “Elution rate is 1.0% or more and less than 3.0%. Practical use is possible.”
×: “Elution rate is 3.0% or more. There is a problem in practical use.”
(電池特性評価)
上記で作製したリチウム二次電池電極評価用セルの充放電サイクル試験を行った。1回目の放電容量を100%として70℃、100時間後の放電容量を測定し変化率とした(100%に近いほど良好)。
◎:「変化率が99%以上。特に優れている。」
○:「変化率が95%以上、99%未満。全く問題なし。」
○△:「変化率が90%以上、95%未満。実用上問題なし。」
△:「変化率が80%以上、90%未満。実用上問題はあるが使用可。」
×:「変化率が80%未満。実用上問題あり、使用不可。」
(Battery characteristics evaluation)
The charge / discharge cycle test of the lithium secondary battery electrode evaluation cell produced above was performed. The discharge capacity at the first time was set to 100%, and the discharge capacity after 100 hours at 70 ° C. was measured to obtain the rate of change (the closer to 100%, the better).
A: “Change rate is 99% or more. Particularly excellent.”
○: “Change rate is 95% or more and less than 99%. No problem at all”
○: “Change rate is 90% or more and less than 95%. No practical problem”
Δ: “Change rate is 80% or more and less than 90%.
X: “Change rate is less than 80%.
表4に示すように、製造例11〜24で合成した樹脂微粒子分散体を含む二次電池電極用組成物を用いた場合、耐電解液性、密着性のバランスが取れ、電池特性においても、70℃、100時間後も放電容量の低下が抑制されている(実施例1〜14)。一方、比較例1〜4においては、耐電解液性、密着性、電池特性の低下がみられてしまう。 As shown in Table 4, when the composition for a secondary battery electrode including the resin fine particle dispersion synthesized in Production Examples 11 to 24 is used, the balance between the electrolytic solution resistance and the adhesiveness can be obtained. The decrease in the discharge capacity is suppressed even after 100 hours at 70 ° C. (Examples 1 to 14). On the other hand, in Comparative Examples 1-4, the electrolyte solution resistance, adhesion, and battery characteristics are degraded.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013152955A (en) * | 2013-04-30 | 2013-08-08 | Nippon Zeon Co Ltd | Secondary battery positive electrode binder composition, secondary battery positive electrode slurry composition, method for manufacturing secondary battery positive electrode, secondary battery positive electrode, and secondary battery |
WO2015008619A1 (en) * | 2013-07-18 | 2015-01-22 | 第一工業製薬株式会社 | Binder for electrode of lithium secondary cell |
EP2811561A4 (en) * | 2012-02-02 | 2015-10-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Binder for electrodes of lithium secondary batteries, and lithium secondary battery which uses electrode produced using binder for electrodes of lithium secondary batteries |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06325752A (en) * | 1993-03-16 | 1994-11-25 | Dainippon Printing Co Ltd | Plate for nonaqueous electrolytic secondary battery and its manufacture |
JPH1021927A (en) * | 1996-06-28 | 1998-01-23 | Nippon Polyurethane Ind Co Ltd | Electrode for lithium ion secondary battery, manufacture thereof, lithium ion secondary battery using the electrode |
JPH113712A (en) * | 1997-06-11 | 1999-01-06 | Sony Corp | Nonaqueous electrolyte secondary battery |
JP2002256129A (en) * | 2000-11-10 | 2002-09-11 | Sanyo Chem Ind Ltd | Binder for electrode of electrochemical element and production method for electrode |
JP2005044681A (en) * | 2003-07-24 | 2005-02-17 | Nippon Synthetic Chem Ind Co Ltd:The | Binder composition for lithium secondary battery electrode, electrode for lithium secondary battery, and lithium secondary battery and manufacturing method thereof |
WO2010114119A1 (en) * | 2009-04-03 | 2010-10-07 | 東洋インキ製造株式会社 | Binder composition for non-aqueous secondary battery electrode |
-
2011
- 2011-03-28 JP JP2011069463A patent/JP5703891B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06325752A (en) * | 1993-03-16 | 1994-11-25 | Dainippon Printing Co Ltd | Plate for nonaqueous electrolytic secondary battery and its manufacture |
JPH1021927A (en) * | 1996-06-28 | 1998-01-23 | Nippon Polyurethane Ind Co Ltd | Electrode for lithium ion secondary battery, manufacture thereof, lithium ion secondary battery using the electrode |
JPH113712A (en) * | 1997-06-11 | 1999-01-06 | Sony Corp | Nonaqueous electrolyte secondary battery |
JP2002256129A (en) * | 2000-11-10 | 2002-09-11 | Sanyo Chem Ind Ltd | Binder for electrode of electrochemical element and production method for electrode |
JP2005044681A (en) * | 2003-07-24 | 2005-02-17 | Nippon Synthetic Chem Ind Co Ltd:The | Binder composition for lithium secondary battery electrode, electrode for lithium secondary battery, and lithium secondary battery and manufacturing method thereof |
WO2010114119A1 (en) * | 2009-04-03 | 2010-10-07 | 東洋インキ製造株式会社 | Binder composition for non-aqueous secondary battery electrode |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2811561A4 (en) * | 2012-02-02 | 2015-10-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Binder for electrodes of lithium secondary batteries, and lithium secondary battery which uses electrode produced using binder for electrodes of lithium secondary batteries |
JP2013152955A (en) * | 2013-04-30 | 2013-08-08 | Nippon Zeon Co Ltd | Secondary battery positive electrode binder composition, secondary battery positive electrode slurry composition, method for manufacturing secondary battery positive electrode, secondary battery positive electrode, and secondary battery |
WO2015008619A1 (en) * | 2013-07-18 | 2015-01-22 | 第一工業製薬株式会社 | Binder for electrode of lithium secondary cell |
JP2015022857A (en) * | 2013-07-18 | 2015-02-02 | 第一工業製薬株式会社 | Binding agent for lithium secondary battery electrode |
CN105324873A (en) * | 2013-07-18 | 2016-02-10 | 第一工业制药株式会社 | Binder for electrode of lithium secondary cell |
KR20160032017A (en) * | 2013-07-18 | 2016-03-23 | 다이이치 고교 세이야쿠 가부시키가이샤 | Binder for electrode of lithium secondary cell |
KR102233321B1 (en) | 2013-07-18 | 2021-03-26 | 다이이치 고교 세이야쿠 가부시키가이샤 | Binder for electrode of lithium secondary cell |
WO2016132589A1 (en) * | 2015-02-20 | 2016-08-25 | 第一工業製薬株式会社 | Binder for electrodes of lithium secondary batteries, electrode produced using said binder, and lithium secondary battery using said electrode |
JPWO2016132589A1 (en) * | 2015-02-20 | 2017-11-30 | 第一工業製薬株式会社 | Binder for electrode of lithium secondary battery, electrode manufactured using the binder, and lithium secondary battery using the electrode |
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