JP7502859B2 - Polymer composition for non-aqueous secondary battery, non-aqueous secondary battery, and method for producing polymer composition for non-aqueous secondary battery - Google Patents
Polymer composition for non-aqueous secondary battery, non-aqueous secondary battery, and method for producing polymer composition for non-aqueous secondary battery Download PDFInfo
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- JP7502859B2 JP7502859B2 JP2019234370A JP2019234370A JP7502859B2 JP 7502859 B2 JP7502859 B2 JP 7502859B2 JP 2019234370 A JP2019234370 A JP 2019234370A JP 2019234370 A JP2019234370 A JP 2019234370A JP 7502859 B2 JP7502859 B2 JP 7502859B2
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- 125000002704 decyl 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])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910000687 transition metal group alloy Inorganic materials 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、非水系二次電池用重合体組成物、非水系二次電池及び非水系二次電池用重合体組成物の製造方法に関する。 The present invention relates to a polymer composition for non-aqueous secondary batteries, a non-aqueous secondary battery, and a method for producing a polymer composition for non-aqueous secondary batteries.
従来、リチウムイオン二次電池などの電気化学的デバイスに用いられる電極を製造する方法としては、電極活物質にバインダーや増粘剤等を添加した液状の組成物を、集電体表面に塗布して乾燥することによって、当該集電体の上に電極層を形成させる方法が挙げられる。ここで、集電体を構成する金属との接着力が高く、しかも、柔軟性が高い電極層を形成することができるバインダーとして、スチレン－ブタジエン系共重合体ラテックスが知られている。なお、バインダーは、活物質を含む電極層と、集電体又はセパレータとの密着性を向上させるために機能するものであるが、上記の共重合体ラテックスは、集電体との密着性が不十分となる場合がある。電極層と集電体又はセパレータとの密着性が十分でない場合、二次電池の充放電サイクル特性を損ねる傾向にある。 Conventionally, a method for manufacturing electrodes used in electrochemical devices such as lithium ion secondary batteries includes a method in which a liquid composition in which a binder, a thickener, etc. is added to an electrode active material is applied to the surface of a current collector and dried to form an electrode layer on the current collector. Styrene-butadiene copolymer latex is known as a binder that can form an electrode layer that has high adhesion to the metal constituting the current collector and is also highly flexible. Note that the binder functions to improve the adhesion between the electrode layer containing the active material and the current collector or separator, but the above-mentioned copolymer latex may have insufficient adhesion to the current collector. If the adhesion between the electrode layer and the current collector or separator is insufficient, the charge-discharge cycle characteristics of the secondary battery tend to be impaired.
上記に鑑み、特許文献１では、特定のポリマーに対して、その曇点が所定の数値範囲内にある化合物を特定の割合で添加・混合した二次電池電極用バインダー組成物が提案されている。 In view of the above, Patent Document 1 proposes a binder composition for secondary battery electrodes in which a compound whose cloud point is within a specified numerical range is added and mixed in a specific ratio with a specific polymer.
特許文献１に記載の二次電池電極用バインダー組成物によれば、集電体との密着性に優れ、降温及び昇温の温度変化を繰り返す条件下で充放電を行う場合にあっても、充放電サイクル特性に優れるとされている。一方、本発明者らが検討したところ、組成物としての取り扱い性や当該組成物を適用して得られる二次電池の電池特性において、未だ改善の余地があることが判明している。 The binder composition for secondary battery electrodes described in Patent Document 1 is said to have excellent adhesion to the current collector and excellent charge/discharge cycle characteristics even when charging/discharging is performed under conditions of repeated temperature changes of lowering and raising the temperature. However, the inventors' investigations have revealed that there is still room for improvement in the handleability of the composition and the battery characteristics of the secondary battery obtained by applying the composition.
本発明は、上記の従来技術が有する課題に鑑みてなされたものであり、取り扱い性に優れると共に良好な電池特性を発現できる非水系二次電池用重合体組成物、非水系二次電池及び非水系二次電池用重合体組成物の製造方法を提供することを目的とする。 The present invention has been made in consideration of the problems associated with the above-mentioned conventional techniques, and aims to provide a polymer composition for non-aqueous secondary batteries that is easy to handle and exhibits good battery characteristics, a non-aqueous secondary battery, and a method for producing a polymer composition for non-aqueous secondary batteries.
本発明者らは、鋭意研究した結果、動的光散乱法により測定された重合体粒子の平均粒子径と、ＴＥＭ観察により測定された当該重合体粒子の平均粒子径ＤＢとの比が特定の範囲にある非水系二次電池用重合体組成物により、上記課題を達成できることを見出し、本発明を完成するに至った。 As a result of intensive research, the inventors have found that the above object can be achieved by a polymer composition for non-aqueous secondary batteries in which the ratio of the average particle diameter of the polymer particles measured by dynamic light scattering to the average particle diameter DB of the polymer particles measured by TEM observation is within a specific range, and have thus completed the present invention.
すなわち、本発明は以下の態様を包含する。
［１］
重合体粒子を含む非水系二次電池用重合体組成物であって、
前記重合体粒子の動的光散乱法により測定された平均粒子径ＤＡと、前記重合体粒子のＴＥＭ観察により測定された平均粒子径ＤＢとの比が、ＤＡ／ＤＢとして、中和度４０モル％において、１０以上５０以下である、非水系二次電池用重合体組成物。
［２］
前記ＤＡ／ＤＢが、未中和において、２以上１０以下である、［１］に記載の非水系二次電池用重合体組成物。
［３］
前記ＤＡが、中和度４０モル％において、２．５μｍ以上である、［１］又は［２］に記載の非水系二次電池用重合体組成物。
［４］
前記ＤＡが、未中和において、１μｍ以上２μｍ以下である、［１］～［３］のいずれかに記載の非水系二次電池用重合体組成物。
［５］
エチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１と、
前記Ｕ１と共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２と、
Ｎ原子含有エチレン性不飽和単量体に由来する単位Ｕ３と、
を分子中に有する重合体粒子を含む、非水系二次電池用重合体組成物であって、
前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、前記Ｕ１の含有量が２５質量％以上５０質量％以下であり、かつ、前記Ｕ２の含有量が３０質量％以上６０質量％以下であり、かつ、前記Ｕ３の含有量が１０質量％以上３０質量％以下であり、
前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、アルキレンオキサイド構造の含有量が０．１質量部以下であり、かつ、スルホン酸又はその塩の含有量が０．３質量部以下である、非水系二次電池用重合体組成物。
［６］
前記重合体粒子１００質量部に対して０．０００１質量部以上１．０質量部以下のイソチアゾリン系化合物を更に含む、［１］～［５］のいずれかに記載の非水系二次電池用重合体組成物。
［７］
［１］～［６］のいずれかに記載の非水系二次電池用重合体組成物を含む、非水系二次電池。
［８］
［１］～［６］のいずれかに記載の非水系二次電池用重合体組成物を製造するための方法であって、
Ｎ原子含有エチレン性不飽和単量体と重合開始剤とが溶解した溶液を調製する工程と、
前記溶液に対して、エチレン性不飽和カルボン酸又はそのアルカリ金属塩と、これらと共重合可能なエチレン性不飽和カルボン酸エステルとを添加して重合し、前記重合体粒子を得る工程と、
を有する、非水系二次電池用重合体組成物の製造方法。
That is, the present invention includes the following aspects.
[1]
A polymer composition for a non-aqueous secondary battery comprising polymer particles,
a ratio of an average particle diameter DA of the polymer particles measured by a dynamic light scattering method to an average particle diameter DB of the polymer particles measured by TEM observation, expressed as DA/DB, of 10 to 50 at a degree of neutralization of 40 mol%.
[2]
The polymer composition for a nonaqueous secondary battery according to [1], wherein the DA/DB is 2 or more and 10 or less before neutralization.
[3]
The polymer composition for a non-aqueous secondary battery according to [1] or [2], wherein the DA is 2.5 μm or more at a degree of neutralization of 40 mol %.
[4]
The polymer composition for a non-aqueous secondary battery according to any one of [1] to [3], wherein the DA is 1 μm or more and 2 μm or less before neutralization.
[5]
A unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof;
a unit U2 derived from an ethylenically unsaturated carboxylic acid ester copolymerizable with U1;
Units U3 derived from N-atom-containing ethylenically unsaturated monomers;
A polymer composition for a non-aqueous secondary battery, comprising polymer particles having in their molecules:
In the polymer particles, when the total amount of units derived from all ethylenically unsaturated monomers is taken as 100 mass%, the content of U1 is 25 mass% or more and 50 mass% or less, the content of U2 is 30 mass% or more and 60 mass% or less, and the content of U3 is 10 mass% or more and 30 mass% or less,
the polymer particles have an alkylene oxide structure content of 0.1 parts by mass or less and a sulfonic acid or a salt thereof content of 0.3 parts by mass or less, when the total number of units derived from ethylenically unsaturated monomers is 100 parts by mass.
[6]
The polymer composition for a non-aqueous secondary battery according to any one of [1] to [5], further comprising 0.0001 parts by mass or more and 1.0 parts by mass or less of an isothiazolinone compound relative to 100 parts by mass of the polymer particles.
[7]
A non-aqueous secondary battery comprising the polymer composition for non-aqueous secondary batteries according to any one of [1] to [6].
[8]
A method for producing the polymer composition for a nonaqueous secondary battery according to any one of [1] to [6],
A step of preparing a solution in which an N-atom-containing ethylenically unsaturated monomer and a polymerization initiator are dissolved;
a step of adding an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, and an ethylenically unsaturated carboxylic acid ester copolymerizable therewith to the solution and polymerizing them to obtain the polymer particles;
The present invention relates to a method for producing a polymer composition for a non-aqueous secondary battery.
本発明によれば、取り扱い性に優れると共に良好な電池特性を発現できる非水系二次電池用重合体組成物、非水系二次電池及び非水系二次電池用重合体組成物の製造方法を提供することができる。 According to the present invention, it is possible to provide a polymer composition for a non-aqueous secondary battery, which is easy to handle and exhibits good battery characteristics, a non-aqueous secondary battery, and a method for producing the polymer composition for a non-aqueous secondary battery.
以下、本発明の実施の形態（以下、「本実施形態」ともいう。）について詳細に説明する。なお、本発明は、以下の本実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 The following describes in detail an embodiment of the present invention (hereinafter, also referred to as the "present embodiment"). Note that the present invention is not limited to the present embodiment, and can be modified in various ways within the scope of the gist of the present invention.
［非水系二次電池用重合体組成物］
本実施形態の一態様に係る非水系二次電池用重合体組成物（以下、「第１の組成物」ともいう。）は、重合体粒子を含む非水系二次電池用重合体組成物であって、前記重合体粒子の動的光散乱法により測定された平均粒子径ＤＡと、前記重合体粒子のＴＥＭ観察により測定された平均粒子径ＤＢとの比が、ＤＡ／ＤＢとして、中和度４０モル％において、１０以上５０以下である。このように構成されているため、第１の組成物は、取り扱い性に優れると共に良好な電池特性を発現できる。
[Nonaqueous polymer composition for secondary batteries]
The polymer composition for non-aqueous secondary batteries according to one aspect of this embodiment (hereinafter also referred to as "first composition") is a polymer composition for non-aqueous secondary batteries containing polymer particles, in which the ratio of an average particle diameter DA of the polymer particles measured by dynamic light scattering to an average particle diameter DB of the polymer particles measured by TEM observation, as DA/DB, is 10 or more and 50 or less at a degree of neutralization of 40 mol%. Because of this configuration, the first composition is excellent in handleability and can exhibit good battery characteristics.
また、本実施形態の他の態様に係る非水系二次電池用重合体組成物（以下、「第２の組成物」ともいう。）は、エチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１と、前記Ｕ１と共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２と、Ｎ原子含有エチレン性不飽和単量体に由来する単位Ｕ３と、を分子中に有する重合体粒子を含む、非水系二次電池用重合体組成物であって、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、前記Ｕ１の含有量が２５質量％以上５０質量％以下であり、かつ、前記Ｕ２の含有量が３０質量％以上６０質量％以下であり、かつ、前記Ｕ３の含有量が１０質量％以上３０質量％以下であり、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、アルキレンオキサイド構造の含有量が０．１質量部以下であり、かつ、スルホン酸又はその塩の含有量が０．３質量部以下である。このように構成されているため、第２の組成物も、取り扱い性に優れると共に良好な電池特性を発現できる。 In addition, a polymer composition for a non-aqueous secondary battery according to another aspect of this embodiment (hereinafter also referred to as the "second composition") is a polymer composition for a non-aqueous secondary battery comprising polymer particles having in the molecule a unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, a unit U2 derived from an ethylenically unsaturated carboxylic acid ester copolymerizable with the U1, and a unit U3 derived from an N-atom-containing ethylenically unsaturated monomer, wherein, in the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 mass%, the content of the U1 is 25 mass% or more and 50 mass% or less, the content of the U2 is 30 mass% or more and 60 mass% or less, and the content of the U3 is 10 mass% or more and 30 mass% or less, and when the units derived from all ethylenically unsaturated monomers are taken as 100 mass parts in the polymer particles, the content of the alkylene oxide structure is 0.1 mass parts or less, and the content of the sulfonic acid or a salt thereof is 0.3 mass parts or less. Because of this configuration, the second composition also has excellent handleability and can exhibit good battery characteristics.
上記のとおり、第１の組成物及び第２の組成物の双方が取り扱い性に優れると共に良好な電池特性を発現できる。以下、「本実施形態の組成物」と称するときは、「第１の組成物」と「第２の組成物」を包含するものとして本実施形態を説明する。同様に、「本実施形態における重合体粒子」と称するときは、「第１の組成物における重合体粒子」と「第２の組成物における重合体粒子」を包含するものとして本実施形態を説明する。 As described above, both the first composition and the second composition are easy to handle and can exhibit good battery characteristics. Hereinafter, when the term "composition of the present embodiment" is used, this embodiment will be described as including the "first composition" and the "second composition". Similarly, when the term "polymer particles in the present embodiment" is used, this embodiment will be described as including the "polymer particles in the first composition" and the "polymer particles in the second composition".
（重合体粒子）
第１の組成物における重合体粒子は、動的光散乱法により測定された平均粒子径ＤＡと、前記重合体粒子のＴＥＭ観察により測定された平均粒子径ＤＢとの比が、ＤＡ／ＤＢとして、中和度４０モル％において、１０以上５０以下であるものとして特定される。ここで、ＤＡは湿潤状態にて、ＤＢは乾燥状態にて、それぞれ重合体粒子の平均粒子径を評価しているが、ＤＡ／ＤＢが大きいほど湿潤状態での膨潤が顕著となる。すなわち、ＤＡ／ＤＢが１０以上であることにより、組成物としての粘度が高くなり、結果として塗工性に優れるものとなる。また、ＤＡ／ＤＢが５０以下であることにより、ダイラタント流体のようなせん断力の増加に対する異常な粘度挙動を抑制することができ、取扱い性に優れる。かかる観点から、ＤＡ／ＤＢは１１以上２０以下であることが好ましく、より好ましくは１２以上１８以下である。
中和度４０モル％におけるＤＡ／ＤＢは、後述する実施例に記載の方法により測定することができる。
また、後述する本実施形態の組成物の好ましい製造方法を採用すること等により、中和度４０モル％におけるＤＡ／ＤＢを上記範囲に調整できる。
なお、後述する第２の組成物における重合体粒子についても、その組成ゆえ、中和度４０モル％におけるＤＡ／ＤＢが上記範囲を満たす傾向にある。すなわち、第２の組成物における重合体粒子に関しても、上述した観点より、中和度４０モル％におけるＤＡ／ＤＢが１０以上５０以下であることが好ましく、より好ましくは１１以上２０以下であり、さらに好ましくは１２以上１８以下である。
(Polymer particles)
The polymer particles in the first composition are specified as a ratio of the average particle diameter DA measured by dynamic light scattering to the average particle diameter DB measured by TEM observation of the polymer particles, DA/DB, of 10 to 50 at a neutralization degree of 40 mol%. Here, DA is the average particle diameter of the polymer particles evaluated in a wet state, and DB is the average particle diameter of the polymer particles evaluated in a dry state, and the larger DA/DB, the more significant the swelling in the wet state becomes. That is, when DA/DB is 10 or more, the viscosity of the composition is increased, resulting in excellent coatability. In addition, when DA/DB is 50 or less, abnormal viscosity behavior against an increase in shear force such as a dilatant fluid can be suppressed, and the handling is excellent. From this viewpoint, DA/DB is preferably 11 to 20, more preferably 12 to 18.
The DA/DB at a degree of neutralization of 40 mol % can be measured by the method described in the Examples below.
Furthermore, by employing a preferred production method for the composition of this embodiment, which will be described later, the DA/DB at a degree of neutralization of 40 mol % can be adjusted to fall within the above range.
In addition, the polymer particles in the second composition described later also tend to have a DA/DB ratio at a neutralization degree of 40 mol% that satisfies the above range due to their composition. That is, from the above-mentioned viewpoint, the polymer particles in the second composition also preferably have a DA/DB ratio at a neutralization degree of 40 mol% of 10 or more and 50 or less, more preferably 11 or more and 20 or less, and even more preferably 12 or more and 18 or less.
第１の組成物において、ＤＡ／ＤＢが、未中和において、２以上１０以下であることが好ましく、より好ましくは４以上１０以下であり、さらに好ましくは５以上１０以下である。上記範囲を満たす場合、ヒステリシスな粘度挙動を抑制でき、取扱い性により優れる傾向にある。
未中和におけるＤＡ／ＤＢは、後述する実施例に記載の方法により測定することができる。
また、後述する本実施形態の組成物の好ましい製造方法を採用すること等により、未中和におけるＤＡ／ＤＢを上記範囲に調整できる。
なお、後述する第２の組成物における重合体粒子についても、その組成ゆえ、未中和におけるＤＡ／ＤＢが上記範囲を満たす傾向にある。すなわち、第２の組成物における重合体粒子に関しても、上述した観点より、未中和におけるＤＡ／ＤＢが２以上１０以下であることが好ましく、より好ましくは４以上１０以下であり、さらに好ましくは５以上１０以下である。
In the first composition, DA/DB, before neutralization, is preferably 2 or more and 10 or less, more preferably 4 or more and 10 or less, and even more preferably 5 or more and 10 or less. When the above range is satisfied, hysteretic viscosity behavior can be suppressed, and the handleability tends to be more excellent.
The unneutralized DA/DB can be measured by the method described in the Examples below.
Furthermore, the DA/DB ratio before neutralization can be adjusted to fall within the above range by employing a preferred method for producing the composition of the present embodiment, which will be described later.
In addition, the polymer particles in the second composition described later also tend to have a DA/DB ratio in the unneutralized state that satisfies the above range due to their composition. That is, from the above-mentioned viewpoint, the polymer particles in the second composition also preferably have a DA/DB ratio in the unneutralized state that is 2 or more and 10 or less, more preferably 4 or more and 10 or less, and even more preferably 5 or more and 10 or less.
第１の組成物において、ＤＡが、中和度４０モル％において、２．５μｍ以上であることが好ましく、より好ましくは２．７μｍ以上５．０μｍ以下であり、さらに好ましくは２．９μｍ以上４．０μｍ以下である。上記範囲を満たす場合、組成物としての粘度が高くなり、塗工性により優れる傾向にある。
中和度４０モル％におけるＤＡは、後述する実施例に記載の方法により測定することができる。
また、後述する本実施形態の組成物の好ましい製造方法を採用すること等により、中和度４０モル％におけるＤＡを上記範囲に調整できる。
なお、後述する第２の組成物における重合体粒子についても、その組成ゆえ、中和度４０モル％におけるＤＡが上記範囲を満たす傾向にある。すなわち、第２の組成物における重合体粒子に関しても、上述した観点より、中和度４０モル％におけるＤＡ／ＤＢが２．５μｍ以上であることが好ましく、より好ましくは２．７μｍ以上５．０μｍ以下であり、さらに好ましくは２．９μｍ以上４．０μｍ以下である。
In the first composition, DA is preferably 2.5 μm or more, more preferably 2.7 μm or more and 5.0 μm or less, and even more preferably 2.9 μm or more and 4.0 μm or less, at a degree of neutralization of 40 mol %. When the above range is satisfied, the viscosity of the composition becomes high, and the coatability tends to be more excellent.
The DA at a degree of neutralization of 40 mol % can be measured by the method described in the Examples below.
Furthermore, by employing a preferred production method for the composition of this embodiment described below, the DA at a degree of neutralization of 40 mol % can be adjusted to fall within the above range.
In addition, the polymer particles in the second composition described later also tend to have a DA at a neutralization degree of 40 mol% that satisfies the above range due to their composition. That is, from the above-mentioned viewpoint, the polymer particles in the second composition also preferably have a DA/DB at a neutralization degree of 40 mol% of 2.5 μm or more, more preferably 2.7 μm or more and 5.0 μm or less, and even more preferably 2.9 μm or more and 4.0 μm or less.
第１の組成物において、ＤＡが、未中和において、１μｍ以上２μｍ以下であることが好ましく、より好ましくは１．１μｍ以上２μｍ以下であり、さらに好ましくは１．２μｍ以上２μｍ以下である。上記範囲を満たす場合、ヒステリシスな粘度挙動を抑制でき、取扱い性により優れる傾向にある。
未中和におけるＤＡは、後述する実施例に記載の方法により測定することができる。
また、後述する本実施形態の組成物の好ましい製造方法を採用すること等により、未中和におけるＤＡを上記範囲に調整できる。
なお、後述する第２の組成物における重合体粒子についても、その組成ゆえ、未中和におけるＤＡが上記範囲を満たす傾向にある。すなわち、第２の組成物における重合体粒子に関しても、上述した観点より、未中和におけるＤＡ／ＤＢが１μｍ以上２μｍであることが好ましく、より好ましくは１．１μｍ以上２μｍ以下であり、さらに好ましくは１．２μｍ以上２μｍ以下である。
In the first composition, the DA is preferably 1 μm or more and 2 μm or less, more preferably 1.1 μm or more and 2 μm or less, and even more preferably 1.2 μm or more and 2 μm or less, when not neutralized. When the above range is satisfied, hysteretic viscosity behavior can be suppressed, and the handling property tends to be more excellent.
The unneutralized DA can be measured by the method described in the Examples below.
Moreover, the unneutralized DA can be adjusted to fall within the above range by, for example, employing a preferred method for producing the composition of the present embodiment, which will be described later.
In addition, the polymer particles in the second composition described later also tend to have a DA in the unneutralized state that satisfies the above range due to their composition. That is, from the above-mentioned viewpoint, the polymer particles in the second composition also preferably have a DA/DB in the unneutralized state that is 1 μm or more and 2 μm or less, more preferably 1.1 μm or more and 2 μm or less, and even more preferably 1.2 μm or more and 2 μm or less.
第２の組成物における重合体粒子は、エチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１と、前記Ｕ１と共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２と、Ｎ原子含有エチレン性不飽和単量体に由来する単位Ｕ３と、を分子中に有するものであって、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、前記Ｕ１の含有量が２５質量％以上５０質量％以下であり、かつ、前記Ｕ２の含有量が３０質量％以上６０質量％以下であり、かつ、前記Ｕ３の含有量が１０質量％以上３０質量％以下であり、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、アルキレンオキサイド構造の含有量が０．１質量部以下であり、かつ、スルホン酸又はその塩の含有量が０．３質量部以下であるものとして特定される。各単位の含有量については、重合体粒子を常法により分析して特定することもできるが、各単量体の仕込み比として特定することもできる。
なお、前述した観点より、第１の組成物における重合体粒子についても、エチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１と、前記Ｕ１と共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２と、Ｎ原子含有エチレン性不飽和単量体に由来する単位Ｕ３と、を分子中に有するものであって、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、前記Ｕ１の含有量が２５質量％以上５０質量％以下であり、かつ、前記Ｕ２の含有量が３０質量％以上６０質量％以下であり、かつ、前記Ｕ３の含有量が１０質量％以上３０質量％以下であり、前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、アルキレンオキサイド構造の含有量が０．１質量部以下であり、かつ、スルホン酸又はその塩の含有量が０．３質量部以下であることが好ましい。
The polymer particles in the second composition have a unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, a unit U2 derived from an ethylenically unsaturated carboxylic acid ester copolymerizable with the U1, and a unit U3 derived from an N-atom-containing ethylenically unsaturated monomer in the molecule, and in the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 mass%, the content of the U1 is 25 mass% or more and 50 mass% or less, and the content of the U2 is 30 mass% or more and 60 mass% or less, and the content of the U3 is 10 mass% or more and 30 mass% or less, and in the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 parts by mass, the content of the alkylene oxide structure is 0.1 parts by mass or less, and the content of the sulfonic acid or its salt is 0.3 parts by mass or less. The content of each unit can be specified by analyzing the polymer particles by a conventional method, but it can also be specified as the charge ratio of each monomer.
From the above-mentioned viewpoint, the polymer particles in the first composition also have a unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, a unit U2 derived from an ethylenically unsaturated carboxylic acid ester copolymerizable with the U1, and a unit U3 derived from an N-atom-containing ethylenically unsaturated monomer in the molecule, and in the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 mass%, the content of the U1 is 25 mass% or more and 50 mass% or less, and the content of the U2 is 30 mass% or more and 60 mass% or less, and the content of the U3 is 10 mass% or more and 30 mass% or less, and in the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 parts by mass, it is preferable that the content of the alkylene oxide structure is 0.1 parts by mass or less, and the content of the sulfonic acid or a salt thereof is 0.3 parts by mass or less.
本実施形態の組成物において、重合体粒子を構成しうるエチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１は、組成物の粘度、集電体への密着力及び電池特性の向上に寄与し、これらのバランスを確保する観点から、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、Ｕ１の含有量が２５質量％以上４８質量％以下であることが好ましく、より好ましくは２５質量％以上４５質量％以下である。 In the composition of this embodiment, the unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof that can constitute the polymer particles contributes to improving the viscosity of the composition, adhesion to the current collector, and battery characteristics. From the viewpoint of ensuring a balance between these, when the units derived from all ethylenically unsaturated monomers are taken as 100% by mass, the content of U1 is preferably 25% by mass or more and 48% by mass or less, and more preferably 25% by mass or more and 45% by mass or less.
本実施形態の組成物において、重合体粒子を構成しうる共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２は、重合体粒子の安定性及び集電体への密着力の向上に寄与し、これらのバランスを確保する観点から、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、Ｕ２の含有量が３０質量％以上５８質量％以下であることが好ましく、より好ましくは３０質量％以上５５質量％以下である。 In the composition of this embodiment, the unit U2 derived from a copolymerizable ethylenically unsaturated carboxylic acid ester capable of constituting the polymer particles contributes to improving the stability of the polymer particles and the adhesion to the current collector, and from the viewpoint of ensuring a balance between these, when the units derived from all ethylenically unsaturated monomers are taken as 100% by mass, the content of U2 is preferably 30% by mass or more and 58% by mass or less, and more preferably 30% by mass or more and 55% by mass or less.
本実施形態の組成物において、重合体粒子を構成しうるＮ原子含有エチレン性不飽和単量体に由来する単位Ｕ３は、取り扱い性の向上に寄与し、塗工性をより良好なものとする観点から、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、Ｕ３の含有量が１２質量％以上３０質量％以下であることが好ましく、より好ましくは１５質量％以上３０質量％以下である。 In the composition of this embodiment, the unit U3 derived from the N-atom-containing ethylenically unsaturated monomer capable of constituting the polymer particles contributes to improved handleability and from the viewpoint of improving coatability, when the units derived from all ethylenically unsaturated monomers are taken as 100% by mass, the content of U3 is preferably 12% by mass or more and 30% by mass or less, and more preferably 15% by mass or more and 30% by mass or less.
本実施形態の組成物において、重合体粒子に含まれうるアルキレンオキサイド構造は、重合体粒子の分散性に寄与するものであるが、一方で脱泡性を損ねる傾向にあり、十分な脱泡性を確保する観点から、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、アルキレンオキサイド構造の含有量が０．０８質量部以下であることが好ましく、より好ましくは０．０５質量部以下である。アルキレンオキサイド構造の含有量としては、少ない方が好ましく、特に下限値は限定されないが、例えば、０．０２質量部含んでいてもよく、０．０１質量部含んでいてもよい。 In the composition of this embodiment, the alkylene oxide structure that may be contained in the polymer particles contributes to the dispersibility of the polymer particles, but on the other hand tends to impair defoaming properties. From the viewpoint of ensuring sufficient defoaming properties, when the units derived from all ethylenically unsaturated monomers are taken as 100 parts by mass, the content of the alkylene oxide structure is preferably 0.08 parts by mass or less, and more preferably 0.05 parts by mass or less. The content of the alkylene oxide structure is preferably low, and there is no particular lower limit, but it may contain, for example, 0.02 parts by mass or 0.01 parts by mass.
本実施形態の組成物において、重合体粒子を構成しうるスルホン酸又はその塩は、重合体粒子の分散性に寄与するものであるが、一方で脱泡性を損ねる傾向にあり、十分な脱泡性を確保する観点から、全エチレン性不飽和単量体に由来する単位を１００質量部としたとき、スルホン酸又はその塩の含有量が０．２質量部以下であることが好ましく、より好ましくは０．１質量部以下である。スルホン酸又はその塩の含有量としては、少ない方が好ましく、特に下限値は限定されないが、例えば、０．０５質量部含んでいてもよく、０．０３質量部含んでいてもよい。 In the composition of this embodiment, the sulfonic acid or its salt that can constitute the polymer particles contributes to the dispersibility of the polymer particles, but on the other hand tends to impair defoaming properties. From the viewpoint of ensuring sufficient defoaming properties, the content of sulfonic acid or its salt is preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less, when the units derived from all ethylenically unsaturated monomers are taken as 100 parts by mass. The content of sulfonic acid or its salt is preferably low, and there is no particular lower limit, but it may contain, for example, 0.05 parts by mass or 0.03 parts by mass.
本実施形態の組成物において、重合体粒子の単量体（原料モノマー）として用いうるエチレン性不飽和カルボン酸としては、特に限定されないが、例えば、フマル酸、イタコン酸、アクリル酸、メタクリル酸等を挙げられる。これらは１種単独または２種以上を組み合わせて用いることができる。
上記した中でも、重合体粒子の安定性の観点から、メタクリル酸が好ましい。
In the composition of the present embodiment, the ethylenically unsaturated carboxylic acid that can be used as a monomer (raw material monomer) for the polymer particles is not particularly limited, but examples thereof include fumaric acid, itaconic acid, acrylic acid, methacrylic acid, etc. These can be used alone or in combination of two or more.
Among the above, methacrylic acid is preferred from the viewpoint of the stability of the polymer particles.
本実施形態の組成物において、原料モノマーとして用いうるＵ１と共重合可能なエチレン性不飽和カルボン酸エステルとしては、特に限定されないが、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、ｎ－プロピル(メタ)アクリレート、i－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、i－ブチル（メタ）アクリレート、ｎ－アミル（メタ）アクリレート、i－アミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、i－ノニル（メタ）アクリレート、デシル（メタ）アクリレート、２－エチルヘキシルアクリレート、ヒドロキシメチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート等が挙げられる。これらは１種単独または２種以上を組み合わせて用いることができる。
上記した中でも、重合体粒子の安定性の観点から、エチルアクリレートが好ましい。
In the composition of the present embodiment, the ethylenically unsaturated carboxylic acid ester copolymerizable with U1 that can be used as a raw material monomer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, n-amyl (meth)acrylate, i-amyl (meth)acrylate, hexyl (meth)acrylate, 2-hexyl (meth)acrylate, octyl (meth)acrylate, i-nonyl (meth)acrylate, decyl (meth)acrylate, 2-ethylhexyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. These can be used alone or in combination of two or more.
Among the above, ethyl acrylate is preferred from the viewpoint of the stability of the polymer particles.
本実施形態の組成物において、原料モノマーとして用いうるＮ原子含有エチレン性不飽和単量体としては、特に限定されないが、例えば、アクリル酸アミノエチル、アクリル酸ジメチルアミノエチル、アクリル酸ジエチルアミノエチル、２－ビニルピリジン、４－ビニルピリジンアクリルアミド、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、グリシジルメタクリルアミド、Ｎ,Ｎ－ブトキシメチルアクリルアミド等が挙げられる。これらは１種単独または２種以上を組み合わせて用いることができる。
上記した中でも、重合体粒子の安定性の観点から、アクリルアミドが好ましい。
In the composition of the present embodiment, the N-atom-containing ethylenically unsaturated monomer that can be used as a raw material monomer is not particularly limited, and examples thereof include aminoethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, 2-vinylpyridine, 4-vinylpyridine acrylamide, acrylamide, methacrylamide, N-methylolacrylamide, glycidyl methacrylamide, N,N-butoxymethylacrylamide, etc. These can be used alone or in combination of two or more.
Among the above, acrylamide is preferred from the viewpoint of the stability of the polymer particles.
重合体粒子には、単位Ｕ１と共重合可能な単量体に由来する単位であって、単位Ｕ２に該当しない単位が含まれていてもよい。このような単位としては、特に限定されないが、例えば、芳香族ビニル化合物、シアン化ビニル化合物等が挙げられる。
芳香族ビニル化合物としては、特に限定されないが、例えば、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、クロルスチレン、ジビニルベンゼン等が挙げられ、１種単独または２種以上を組み合わせて用いることができる。
シアン化ビニル系化合物としては、特に限定されないが、例えば、アクリロニトリル、メタアクリロニトリル、α－クロルアクリロニトリル等が挙げられ、これらの単量体を１種単独または２種以上を組み合わせて用いることができる。
The polymer particles may contain a unit derived from a monomer copolymerizable with the unit U1, but not corresponding to the unit U2. Examples of such a unit include, but are not limited to, an aromatic vinyl compound, a vinyl cyanide compound, and the like.
The aromatic vinyl compound is not particularly limited, but examples thereof include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like. One type may be used alone, or two or more types may be used in combination.
The vinyl cyanide compound is not particularly limited, but examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and these monomers can be used alone or in combination of two or more.
（用途）
本実施形態の組成物は、その用途に応じ、本実施形態における重合体粒子の他、種々公知の任意成分を含むことができる。本実施形態の組成物の用途としては、非水系二次電池の一材料として使用されるものであれば特に限定されず、負極用材料、正極用材料及びセパレータ用材料等として用いることができるが、負極用材料として用いることがとりわけ好ましい。
(Application)
The composition of the present embodiment may contain various known optional components in addition to the polymer particles of the present embodiment depending on the application. The application of the composition of the present embodiment is not particularly limited as long as it is used as one material of a non-aqueous secondary battery, and may be used as a negative electrode material, a positive electrode material, a separator material, etc., but is particularly preferably used as a negative electrode material.
以下、本実施形態の組成物を、負極、正極又はセパレータの製造用に用いる場合は特に「電池材料製造用組成物」と称するものとする。ここで、電池材料製造用組成物により負極を製造する場合、電池材料製造用組成物は、本実施形態における重合体粒子と、負極活物質と、必要に応じて任意成分とを含むものとすることができる。また、電池材料製造用組成物により正極を製造する場合、電池材料製造用組成物は、本実施形態における重合体粒子と、正極活物質と、必要に応じて任意成分とを含むものとすることができる。さらに、電池材料製造用組成物によりセパレータを製造する場合、電池材料製造用組成物は、本実施形態における重合体粒子と、セパレータ原料と、必要に応じて任意成分とを含むものとすることができる。
一方、本実施形態の組成物が、負極活物質、正極活物質及びセパレータ原料のいずれも含まない場合、電池材料製造用の添加剤として適用することができる。すなわち、本実施形態の組成物をバインダー用途に用いる場合は「バインダー用組成物」と、増粘剤用途に用いる場合は「増粘剤用組成物」と、それぞれ称するものとする。
上記のとおり、「本実施形態の組成物」との用語は、「電池材料製造用組成物」、「バインダー用組成物」及び「増粘剤用組成物」を包含するものということができ、いずれの用途においても、本実施形態における重合体粒子が含まれているという点において共通する。また、いずれの用途においても、本実施形態の組成物が任意成分を含む場合、その種類や配合割合等は特に限定されず、用途に応じて適宜決定すればよい。
Hereinafter, when the composition of the present embodiment is used for producing a negative electrode, a positive electrode, or a separator, it will be referred to as a "battery material manufacturing composition". Herein, when a negative electrode is produced using the battery material manufacturing composition, the battery material manufacturing composition may contain the polymer particles of the present embodiment, a negative electrode active material, and optional components as required. When a positive electrode is produced using the battery material manufacturing composition, the battery material manufacturing composition may contain the polymer particles of the present embodiment, a positive electrode active material, and optional components as required. Furthermore, when a separator is produced using the battery material manufacturing composition, the battery material manufacturing composition may contain the polymer particles of the present embodiment, a separator raw material, and optional components as required.
On the other hand, when the composition of the present embodiment does not contain any of the negative electrode active material, the positive electrode active material, and the separator raw material, it can be used as an additive for manufacturing battery materials. That is, when the composition of the present embodiment is used as a binder, it is called a "binder composition", and when it is used as a thickener, it is called a "thickener composition".
As described above, the term "composition of the present embodiment" can be said to include "composition for manufacturing battery materials,""composition for binder," and "composition for thickener," and all of these applications have in common the fact that they contain the polymer particles of the present embodiment. In addition, in all applications, when the composition of the present embodiment contains an optional component, the type, blending ratio, etc. of the optional component are not particularly limited, and may be appropriately determined depending on the application.
電池材料製造用組成物により負極を製造する場合、用いうる負極活物質としては、特に限定されないが、例えば、炭素系活物質やシリコン系活物質が挙げられる。
炭素系活物質としては、特に限定されないが、例えば、黒鉛、炭素繊維、コークス、ハードカーボン、メソカーボンマイクロビーズ（ＭＣＭＢ）、フルフリルアルコール樹脂焼成体（ＰＦＡ）、導電性高分子（ポリ－ｐ－フェニレン等）等が挙げられる。
シリコン系活物質としては、特に限定されないが、例えば、ケイ素、ＳｉＯｘ（０．０１≦ｘ＜２）、ケイ素と遷移金属との合金等が挙げられる。
When a negative electrode is produced from the composition for producing a battery material, the negative electrode active material that can be used is not particularly limited, but examples thereof include carbon-based active materials and silicon-based active materials.
The carbon-based active material is not particularly limited, but examples thereof include graphite, carbon fiber, coke, hard carbon, mesocarbon microbeads (MCMB), baked furfuryl alcohol resin (PFA), conductive polymers (poly-p-phenylene, etc.), and the like.
The silicon-based active material is not particularly limited, but examples thereof include silicon, SiO x (0.01≦x<2), and alloys of silicon and transition metals.
電池材料製造用組成物により正極を製造する場合、用いうる正極活物質としては、特に限定されないが、例えば、リチウム含有複合酸化物や遷移金属酸化物、遷移金属フッ化物、遷移金属硫化物等が挙げられる。
リチウム含有複合酸化物としては、特に限定されないが、例えば、ＬｉＣｏＯ２、ＬｉＭｎＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４、ＬｉＸＣｏＹＳｎＺＯ２、ＬｉＦｅＰＯ４、ＬｉＸＣｏＹＳｎＺＯ２等が挙げられる。
遷移金属酸化物としては、特に限定されないが、例えば、ＭｎＯ２、ＭｏＯ３、Ｖ２Ｏ５、Ｖ６Ｏ１３、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４等が挙げられる。
遷移金属フッ化物としては、特に限定されないが、例えば、ＣｕＦ２、ＮｉＦ２等が挙げられる。
遷移金属硫化物としては、特に限定されないが、例えば、ＴｉＳ２、ＴｉＳ３、ＭｏＳ３、ＦｅＳ２等が挙げられる。
When a positive electrode is manufactured using the composition for manufacturing a battery material, the positive electrode active material that can be used is not particularly limited, but examples thereof include lithium-containing composite oxides, transition metal oxides, transition metal fluorides, and transition metal sulfides.
The lithium-containing composite oxide is not particularly limited, but examples thereof include LiCoO2 , LiMnO2 , LiNiO2 , LiMn2O4 , LiXCoYSnZO2 , LiFePO4 , LiXCoYSnZO2 , and the like.
The transition metal oxide is not particularly limited, but examples thereof include MnO2 , MoO3 , V2O5 , V6O13 , Fe2O3 , and Fe3O4 .
The transition metal fluoride is not particularly limited, but examples thereof include CuF 2 and NiF 2 .
The transition metal sulfide is not particularly limited, but examples thereof include TiS 2 , TiS 3 , MoS 3 , FeS 2 and the like.
本実施形態において、バインダー用組成物は、本実施形態における重合体粒子と、当該重合体粒子１００質量部に対して０．０００１質量部以上１．０質量部以下のイソチアゾリン系化合物とを含むことが好ましい。上記範囲を満たす場合、せん断力に対するヒステリシスな粘度挙動を抑制でき、より安定した塗工性を発現できる傾向にある。イソチアゾリン系化合物としては、特に限定されず、種々公知のものを採用でき、例えば、２－メチル－４－イソチアゾリン－３－オン、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、１，２－ベンゾイソチアゾリン－３－オン、２－ｎ－オクチル４－イソチアゾリン－３－オン、４，５－ジクロロ－２－ｎ－オクチル－４－イソチアゾリン－３－オン、２－エチル－４－イソチアゾリン－３－オン、４，５－ジクロロ－２－シクロヘキシル－４－イソチアゾリン－３－オン、５－クロロ－２－エチル－４－イソチアゾリン－３－オン、５－クロロ－２－ｔ－オクチル－４－イソチアゾリン－３－オン、４－クロロ－２－ｎ－オクチル－４－イソチアゾリン－３－オン、５－クロロ－２－ｎ－オクチル－４－イソチアゾリン－３－オン、Ｎ－ｎ－ブチル－１，２－ベンゾイソチアゾリン－３－オン、Ｎ－ブチルベンゾイソチアゾリン－３－オン、Ｎ－メチルベンゾイソチアゾリン－３－オン、Ｎ－エチルベンゾイソチアゾリン－３－オン、Ｎ－プロピルベンゾイソチアゾリン－３－オン、Ｎ－イソブチルベンゾイソチアゾリン－３－オン、Ｎ－ペンチルベンゾイソチアゾリン－３－オン、Ｎ－イソペンチルベンゾイソチアゾリン－３－オン、Ｎ－ヘキシルベンゾイソチアゾリン－３－オン、Ｎ－アリルベンゾイソチアゾリン－３－オン、Ｎ－（２－ブテニル）ベンゾイソチアゾリン－３－オン等が挙げられる。これらの中でも、２－メチル－４－イソチアゾリン－３－オンが好ましい。
その他、本実施形態のバインダー用組成物は、任意成分として消泡剤や乳化剤を含んでいてもよい。
消泡剤としては、ミネラルオイル系、シリコーン系、アクリル系、ポリエーテル系の各種消泡剤が挙げられる。消泡剤を含む場合、より脱泡性に優れる傾向にある。
また、乳化剤は、脱泡性への影響が顕在化しない範囲で使用することができ、乳化剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、反応性界面活性剤などが単独で、あるいは２種以上を併用して使用できる。
アニオン界面活性剤としては例えば高級アルコールの硫酸エステル、アルキルベンゼン
スルホン酸塩、脂肪族スルホン酸塩、ポリエチレングリコールアルキルエーテルの硫酸塩
エステルなどが挙げられる。アルキルベンゼンスルホン酸塩としてはドデシルベンゼンス
ルホン酸ナトリウムが好ましい。
ノニオン性界面活性剤としてはポリエチレングリコールのアルキルエステル型、アルキ
ルエーテル型、アルキルフェニルエーテル型などが用いられる。
両性界面活性剤としてはラウリルベタイン、ステアリルベタインなどのベタイン類、ラ
ウリル－β－アラニン、ステアリル－β－アラニン、ラウリルジ（アミノエチル）グリシ
ンなどのアミノ酸タイプのものなどが用いられる。
反応性界面活性剤としては例えばポリオキシエチレンアルキルプロペニルフェニルエー
テル、α－〔１－〔（アリルオキシ）メチル〕－２－（ノニルフェノキシ）エチル〕－ω
－ヒドロキシポリオキシエチレンなどが挙げられる。
In the present embodiment, the binder composition preferably contains the polymer particles of the present embodiment and 0.0001 part by mass or more and 1.0 part by mass or less of an isothiazolinone compound relative to 100 parts by mass of the polymer particles. When the above range is satisfied, hysteretic viscosity behavior against shear force can be suppressed, and more stable coatability tends to be achieved. The isothiazoline compound is not particularly limited, and various known compounds can be used. For example, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, Azolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, N-n-butyl-1,2-benzisothiazolin-3-one, N-butylbenzisothiazolin-3-one, N-methylbenzisothiazolin-3-one, N-ethylbenzisothiazolin-3-one, N-propylbenzisothiazolin-3-one, N-isobutylbenzisothiazolin-3-one, N-pentylbenzisothiazolin-3-one, N-isopentylbenzisothiazolin-3-one, N-hexylbenzisothiazolin-3-one, N-allylbenzisothiazolin-3-one, N-(2-butenyl)benzisothiazolin-3-one, etc. Among these, 2-methyl-4-isothiazolin-3-one is preferred.
In addition, the binder composition of the present embodiment may contain an antifoaming agent and an emulsifier as optional components.
Examples of the defoaming agent include various defoaming agents based on mineral oil, silicone, acrylic, and polyether. When a defoaming agent is contained, the defoaming property tends to be more excellent.
The emulsifier can be used within a range in which the effect on defoaming property is not significant. As the emulsifier, anionic surfactants, nonionic surfactants, amphoteric surfactants, reactive surfactants, etc. can be used alone or in combination of two or more kinds.
Examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ethers, etc. As the alkylbenzene sulfonate, sodium dodecylbenzene sulfonate is preferred.
As the nonionic surfactant, alkyl ester type, alkyl ether type, alkyl phenyl ether type, etc. of polyethylene glycol are used.
As the amphoteric surfactant, betaines such as lauryl betaine and stearyl betaine, and amino acid surfactants such as lauryl-β-alanine, stearyl-β-alanine, and lauryl di(aminoethyl)glycine can be used.
Examples of reactive surfactants include polyoxyethylene alkylpropenyl phenyl ether, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω
-hydroxypolyoxyethylene and the like.
本実施形態において、増粘剤用組成物は、脱泡性の観点から、本実施形態における重合体粒子と、防腐剤と消泡剤とを含むことが好ましい。前述したイソチアゾリン系化合物は防腐剤として機能し得るが、本実施形態の増粘剤用組成物は、当該イソチアゾリン系化合物以外の防腐剤として、例えば、フェノール類およびこれらのアルカリ金属塩類、塩化キノン類、ニトロ基含有化合物類、アミン類、アミド類、ヨウ素含有化合物、チアゾール類、チオシアネート類等を含んでいてもよい。 In this embodiment, from the viewpoint of defoaming properties, the thickener composition preferably contains the polymer particles of this embodiment, a preservative, and an antifoaming agent. The above-mentioned isothiazolinone compound can function as a preservative, but the thickener composition of this embodiment may contain preservatives other than the isothiazolinone compound, such as phenols and their alkali metal salts, quinone chlorides, nitro group-containing compounds, amines, amides, iodine-containing compounds, thiazoles, thiocyanates, etc.
（非水系二次電池用重合体組成物の製造方法）
本実施形態の組成物を製造するための方法としては、特に限定されないが、次の製造方法（以下、「本実施形態の製法」ともいう。）にて好ましく製造することができる。すなわち、本実施形態の組成物の製造方法は、Ｎ原子含有エチレン性不飽和単量体と重合開始剤とが溶解した溶液を調製する工程（以下、「工程１」ともいう。）と、前記溶液に対して、エチレン性不飽和カルボン酸又はそのアルカリ金属塩と、これらと共重合可能なエチレン性不飽和カルボン酸エステルとを添加して重合し、前記重合体粒子を得る工程（以下、「工程２」ともいう。）と、を有することが好ましい。
(Method for producing polymer composition for non-aqueous secondary battery)
The method for producing the composition of the present embodiment is not particularly limited, but the composition can be preferably produced by the following production method (hereinafter also referred to as the "production method of the present embodiment"). That is, the production method of the composition of the present embodiment preferably includes a step of preparing a solution in which an N-atom-containing ethylenically unsaturated monomer and a polymerization initiator are dissolved (hereinafter also referred to as "step 1"), and a step of adding an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof and an ethylenically unsaturated carboxylic acid ester copolymerizable therewith to the solution, and polymerizing the resulting polymer particles (hereinafter also referred to as "step 2").
本実施形態の製法では、工程１により先にＮ原子含有エチレン性不飽和単量体を含有する溶液を調製し、次いで工程２によりエチレン性不飽和カルボン酸又はそのアルカリ金属塩と、これらと共重合可能なエチレン性不飽和カルボン酸エステルとを添加して重合を実施する。そのため、Ｎ原子含有エチレン性不飽和単量体と、エチレン性不飽和カルボン酸又はそのアルカリ金属塩と、これらと共重合可能なエチレン性不飽和カルボン酸エステルとを同時に添加して重合する場合に比べ、Ｎ原子含有エチレン性不飽和単量体が重合体粒子の外側に局在化される傾向にある。これにより、得られる組成物の粘度が高くなり、ヒステリシスが良好となりため、結果として取り扱い性が向上する。 In the manufacturing method of this embodiment, a solution containing an N-atom-containing ethylenically unsaturated monomer is first prepared in step 1, and then an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof and an ethylenically unsaturated carboxylic acid ester copolymerizable therewith are added in step 2 to carry out polymerization. Therefore, compared to the case where an N-atom-containing ethylenically unsaturated monomer, an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, and an ethylenically unsaturated carboxylic acid ester copolymerizable therewith are simultaneously added and polymerized, the N-atom-containing ethylenically unsaturated monomer tends to be localized on the outside of the polymer particles. This increases the viscosity of the resulting composition and improves hysteresis, resulting in improved handleability.
本実施形態の製法における重合方法としては、乳化重合を採用することができる。重合時には適当なシード粒子を用いることができ、シード粒子も通常の乳化重合により得ることができる。また、乳化重合に際しては公知の方法を採用することができ、水性媒体中で重合開始剤、分子量調整剤、キレート化剤、ｐＨ調整剤、乳化剤等を適宜用いて製造することができる。 As the polymerization method in the manufacturing method of this embodiment, emulsion polymerization can be adopted. Appropriate seed particles can be used during polymerization, and the seed particles can also be obtained by normal emulsion polymerization. In addition, a known method can be adopted for emulsion polymerization, and the polymer can be manufactured by appropriately using a polymerization initiator, a molecular weight regulator, a chelating agent, a pH regulator, an emulsifier, etc. in an aqueous medium.
乳化剤としては、特に限定されないが、例えば、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、反応性界面活性剤などを単独で、あるいは２種以上を併用して使用できる。 The emulsifier is not particularly limited, but for example, anionic surfactants, nonionic surfactants, amphoteric surfactants, reactive surfactants, etc. can be used alone or in combination of two or more.
アニオン界面活性剤としては、特に限定されないが、例えば、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、脂肪族スルホン酸塩、ポリエチレングリコールアルキルエーテルの硫酸塩エステルなどが挙げられる。 Anionic surfactants are not particularly limited, but examples include sulfate esters of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, and sulfate esters of polyethylene glycol alkyl ethers.
ノニオン性界面活性剤としては、特に限定されないが、例えば、ポリエチレングリコールのアルキルエステル型、アルキルエーテル型、アルキルフェニルエーテル型などが用いられる。 Nonionic surfactants are not particularly limited, but examples include alkyl esters, alkyl ethers, and alkyl phenyl ethers of polyethylene glycol.
両性界面活性剤としては、特に限定されないが、例えば、ラウリルベタイン、ステアリルベタインなどのベタイン類、ラウリル－β－アラニン、ステアリル－β－アラニン、ラウリルジ（アミノエチル）グリシンなどのアミノ酸タイプのものなどが用いられる。 Although there is no particular limitation on amphoteric surfactants, examples of amphoteric surfactants that can be used include betaines such as lauryl betaine and stearyl betaine, and amino acid surfactants such as lauryl-β-alanine, stearyl-β-alanine, and lauryl di(aminoethyl)glycine.
反応性界面活性剤としては、特に限定されないが、例えば、ポリオキシエチレンアルキルプロペニルフェニルエーテル、α－〔１－〔（アリルオキシ）メチル〕－２－（ノニルフェノキシ）エチル〕－ω－ヒドロキシポリオキシエチレンなどが挙げられる。 Reactive surfactants are not particularly limited, but examples include polyoxyethylene alkylpropenylphenyl ether, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene, etc.
重合開始剤としては、特に限定されないが、例えば、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの水溶性重合開始剤、過酸化ベンゾイル、ラウリルパーオキサイドなどの油溶性重合開始剤、還元剤との組み合わせによるレドックス系重合開始剤などを、単独であるいは組み合わせて使用できる。 The polymerization initiator is not particularly limited, but examples thereof include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate, oil-soluble polymerization initiators such as benzoyl peroxide and lauryl peroxide, and redox-based polymerization initiators in combination with a reducing agent, which can be used alone or in combination.
本実施形態の製法において、攪拌速度、重合温度、反応（重合）時間等の条件は、本実施形態の組成物が得られる限り、特に限定されない。典型的には、攪拌速度は通常５０ｒｐｍ以上５００ｒｐｍ以下とすることができ、重合温度は通常５０℃以上１００℃以下とすることができ、反応時間は通常３時間以上７２時間以下とすることができる。 In the manufacturing method of this embodiment, the conditions such as the stirring speed, polymerization temperature, and reaction (polymerization) time are not particularly limited as long as the composition of this embodiment is obtained. Typically, the stirring speed can be usually 50 rpm or more and 500 rpm or less, the polymerization temperature can be usually 50° C. or more and 100° C. or less, and the reaction time can be usually 3 hours or more and 72 hours or less.
本実施形態の製法においては、上記のようにして重合体粒子を得た後、必要に応じて、当該重合体粒子を分散媒に分散させ、任意成分を加えることにより、本実施形態の組成物を得ることができる。分散媒としては水を用いることができ、また、必要に応じて活物質に適した有機系溶媒を用いることもできる。 In the manufacturing method of this embodiment, after obtaining the polymer particles as described above, the polymer particles are dispersed in a dispersion medium as necessary, and optional components are added to obtain the composition of this embodiment. Water can be used as the dispersion medium, and an organic solvent suitable for the active material can also be used as necessary.
（非水系二次電池）
本実施形態の非水系二次電池は、本実施形態の組成物を用いて製造することができる。換言すると、本実施形態の非水系二次電池は、本実施形態の組成物を含むものである。
本実施形態の非水系二次電池がリチウムイオン二次電池である場合、その典型的な構成部材としては、負極、負極集電体、正極、正極集電体、セパレータ及び電解液を挙げることができ、本実施形態の非水系二次電池は、その主要部材（負極、正極及びセパレータ）の少なくとも１つが本実施形態の組成物を用いて得られたもの、すなわち、その主要部材の少なくとも１つが、本実施形態の組成物を含むものであればよい。
各部材が本実施形態の組成物を含むことについては、本実施形態における重合体粒子が当該部材に含まれているか否かにより特定することができる。
(Non-aqueous secondary battery)
The nonaqueous secondary battery of the present embodiment can be manufactured using the composition of the present embodiment. In other words, the nonaqueous secondary battery of the present embodiment contains the composition of the present embodiment.
When the nonaqueous secondary battery of the present embodiment is a lithium ion secondary battery, typical components thereof include a negative electrode, a negative electrode current collector, a positive electrode, a positive electrode current collector, a separator, and an electrolyte. The nonaqueous secondary battery of the present embodiment may have at least one of its main components (negative electrode, positive electrode, and separator) obtained using the composition of the present embodiment, that is, at least one of its main components contains the composition of the present embodiment.
Whether each component contains the composition of this embodiment can be specified based on whether the component contains the polymer particles of this embodiment.
本実施形態の非水系二次電池の製造方法としては、特に限定されないが、リチウムイオン二次電池を例にすると、本実施形態の組成物を、集電体に塗布し、加熱し、乾燥することによって対応する電極を形成し、セパレータを介して正極及び負極を対向させ、電解液を注入して密封すること等が挙げられる。負極集電体としては、特に限定されないが、例えば、銅箔が用いられ、正極集電体としては、特に限定されないが、例えば、アルミ箔が用いられる。電解液としては、特に限定されないが、例えば、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６等の電解質を有機溶媒に溶解したものを使用できる。有機溶媒としては、特に限定されないが、例えば、エーテル類、ケトン類、ラクトン類、ニトリル類、アミン類、アミド類、カーボネート類、塩素化炭化水素類などが挙げられ、代表例としてはテトラヒドロフラン、アセトニトリル、ブチロニトリル、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート等を挙げることができ、１種類または２種類以上の混合物として使用される。 The method for producing the non-aqueous secondary battery of this embodiment is not particularly limited. For example, in the case of a lithium ion secondary battery, the composition of this embodiment is applied to a current collector, heated, and dried to form a corresponding electrode, and the positive and negative electrodes are opposed to each other via a separator, and an electrolyte is injected and sealed. The negative electrode current collector is not particularly limited, but for example, copper foil is used, and the positive electrode current collector is not particularly limited, but for example, aluminum foil is used. The electrolyte is not particularly limited, but for example, an electrolyte such as LiClO 4 , LiBF 4 , or LiPF 6 dissolved in an organic solvent can be used. The organic solvent is not particularly limited, but for example, ethers, ketones, lactones, nitriles, amines, amides, carbonates, and chlorinated hydrocarbons can be used. Representative examples include tetrahydrofuran, acetonitrile, butyronitrile, propylene carbonate, ethylene carbonate, and diethyl carbonate, and is used as one or a mixture of two or more types.
塗布方法としては、特に限定されないが、例えば、リバースロールコーター、コンマバーコーター、グラビヤコーター、エア－ナイフコーターなど任意のコーターヘッドを用いることができる。乾燥方法としても、特に限定されず、例えば、放置乾燥、送風乾燥、温風乾燥、赤外線加熱機、遠赤外過熱機などが使用できる。乾燥温度は、特に限定されないが、例えば、６０℃～１５０℃で行うことができる。 The coating method is not particularly limited, but any coater head can be used, such as a reverse roll coater, a comma bar coater, a gravure coater, or an air knife coater. The drying method is also not particularly limited, but for example, drying by leaving it to dry, drying by blowing air, drying by hot air, an infrared heater, or a far-infrared heater can be used. The drying temperature is not particularly limited, but for example, the drying can be performed at 60°C to 150°C.
以下に実施例を挙げて本実施形態をより具体的に説明するが、本実施形態はこれらの実施例により何ら限定されるものではない。なお、説明の便宜上、以下の実施例では「組成物」や「塗工液」といった文言を使用するが、いずれも本実施形態の組成物に包含される概念である。 The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to these examples. For ease of explanation, the following examples use terms such as "composition" and "coating liquid," but both are concepts that are included in the composition of the present embodiment.
［実施例１］
反応器に、イオン交換水を加え、撹拌しながら６５℃に昇温して保持した。ここへ、重合開始剤として過硫酸ナトリウム（以下、「ＮＰＳ」ともいう。）を加えた後に、単量体（以下、「モノマー」ともいう。）成分として、アクリルアミド水溶液（イオン交換水及びアクリルアミド（以下、「ＡＡｍ」ともいう。））、及び、ｐ-スチレンスルホン酸ナトリウム（以下、「ＮａＳＳ」ともいう。）を溶解させた。このようにして得られた溶液に対し、更なる単量体成分として、メタクリル酸（以下、「ＭＡＡ」ともいう。）及びエチルアクリレート（以下、「ＥＡ」ともいう。）を同時に滴下し、温度を６５℃に保ちながら３時間で滴下を終了した後、２．５時間重合を継続させた。このときの各成分の配合量としては、単量体成分の合計（全エチレン性不飽和単量体に由来する単位：ＭＡＡ、ＥＡ、ＡＡｍ）を１００質量部としたとき、ＮＰＳは０．３質量部、ＭＡＡは３０質量部、ＥＡは５５質量部、ＡＡｍは１５質量部及びＮａＳＳは０．３質量部となるように配合し、イオン交換水の配合量は８９９．７質量部であった。
その後、温度を６５℃から８０℃へ昇温し、１．５時間保持して重合を完結させた。
得られた組成物は、重合率が９８％、ｐＨ５、固形分（重合体粒子）が９．８％であった。なお、重合率は、全仕込み成分量に対する残渣量の比率に固形分率を加えて算出した。
また、この組成物を固形分濃度が２質量％となるように水で希釈した。さらに、２５質量％濃度の水酸化ナトリウム水溶液を滴下することで、中和度４０モル％（ｐＨ７）とした組成物を得た。中和度は、重合体粒子を重合する際の仕込み比より算出した。具体的には、重合に用いたエチレン性不飽和カルボン酸又はそのアルカリ金属塩を１００モル％とした際、重合に用いたエチレン性不飽和カルボン酸のアルカリ金属塩と中和により生成したエチレン性不飽和カルボン酸のアルカリ金属塩のモル比が４０モル％になるように水酸化ナトリウム水溶液を滴下した。中和度４０モル％（ｐＨ７）の組成物を用い、次のとおり二次電池負極を作成した。具体的には以下のように作製した。
[Example 1]
Ion-exchanged water was added to the reactor, and the temperature was raised to 65° C. while stirring and maintained. Sodium persulfate (hereinafter also referred to as “NPS”) was added as a polymerization initiator, and then an aqueous acrylamide solution (ion-exchanged water and acrylamide (hereinafter also referred to as “AAm”)) and sodium p-styrenesulfonate (hereinafter also referred to as “NaSS”) were dissolved as monomer (hereinafter also referred to as “monomer”) components. Methacrylic acid (hereinafter also referred to as “MAA”) and ethyl acrylate (hereinafter also referred to as “EA”) were simultaneously added dropwise to the solution thus obtained as further monomer components, and the dropwise addition was completed in 3 hours while maintaining the temperature at 65° C., after which polymerization was continued for 2.5 hours. The amounts of each component blended in this case were such that, when the total of the monomer components (units derived from all ethylenically unsaturated monomers: MAA, EA, AAm) was taken as 100 parts by mass, NPS was 0.3 parts by mass, MAA was 30 parts by mass, EA was 55 parts by mass, AAm was 15 parts by mass, and NaSS was 0.3 parts by mass, and the amount of ion-exchanged water blended was 899.7 parts by mass.
Thereafter, the temperature was raised from 65° C. to 80° C. and maintained at that temperature for 1.5 hours to complete the polymerization.
The resulting composition had a polymerization rate of 98%, a pH of 5, and a solid content (polymer particles) of 9.8%. The polymerization rate was calculated by adding the solid content rate to the ratio of the amount of residue to the amount of all charged components.
This composition was diluted with water so that the solid content concentration was 2% by mass. Furthermore, a composition with a neutralization degree of 40 mol% (pH 7) was obtained by dropping an aqueous sodium hydroxide solution with a concentration of 25% by mass. The neutralization degree was calculated from the charge ratio when polymerizing the polymer particles. Specifically, when the ethylenically unsaturated carboxylic acid or its alkali metal salt used in the polymerization was 100 mol%, an aqueous sodium hydroxide solution was dropped so that the molar ratio of the alkali metal salt of the ethylenically unsaturated carboxylic acid used in the polymerization and the alkali metal salt of the ethylenically unsaturated carboxylic acid produced by neutralization was 40 mol%. A secondary battery negative electrode was prepared using a composition with a neutralization degree of 40 mol% (pH 7) as follows. Specifically, it was prepared as follows.
＜二次電池負極用塗工液の作製＞
中和度４０モル％（ｐＨ７）の組成物（重合体粒子２質量％の組成物）１固形分質量部に対して、バインダーとしてスチレンブタジエンラテックス１．５固形分質量部と、さらに負極活物質として天然黒鉛１００質量部を加え、そこへイオン交換水を添加し、メカニカルスターラーで攪拌して総固形分が６０％になるように調製した。これをプレミックスとし、その後、薄膜旋回型高速ミキサー（ＰＲＩＭＩＸ社製、Ｔ．Ｋ．フィルミックス ＦＭ５６－Ｌ型（製品名）」）を用いて周速２０ｍ/秒にて３０秒分散し、二次電池負極用の塗工液とした。
<Preparation of coating solution for secondary battery negative electrode>
To 1 part by mass of a composition with a neutralization degree of 40 mol% (pH 7) (composition with 2% by mass of polymer particles), 1.5 parts by mass of a styrene butadiene latex as a binder and 100 parts by mass of natural graphite as a negative electrode active material were added, and ion-exchanged water was added thereto, and the mixture was stirred with a mechanical stirrer so that the total solid content was 60%. This was used as a premix, and then dispersed for 30 seconds at a peripheral speed of 20 m/s using a thin film swirling high-speed mixer (T.K. Filmix FM56-L type (product name) manufactured by PRIMIX Corporation) to obtain a coating liquid for a secondary battery negative electrode.
＜二次電池負極の作製＞
上記塗工液を用いて、乾燥後の厚みが１００μｍになるように銅箔の片面にダイコーターで塗布した後、６０℃で６０分乾燥した。１２０℃で３分間乾燥後、ロールプレス機で圧縮成形した。負極活物質塗布量は１０６ｇ／ｍ２、負極活物質嵩密度は１．３５ｇ／ｃｍ３になるようにした。
<Preparation of secondary battery negative electrode>
The coating solution was applied to one side of a copper foil using a die coater so that the thickness after drying was 100 μm, and then dried for 60 minutes at 60° C. After drying for 3 minutes at 120° C., compression molding was performed using a roll press machine. The amount of negative electrode active material applied was 106 g/m 2 , and the bulk density of the negative electrode active material was 1.35 g/cm 3 .
上記のようにして得られた組成物（未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７））及び二次電池負極を用い、後述する各種物性評価に供した。結果を表１に示す。 The composition obtained as described above (unneutralized (pH 5) or neutralized to 40 mol% (pH 7)) and the secondary battery negative electrode were used to evaluate various physical properties as described below. The results are shown in Table 1.
［実施例２～４］
界面活性剤の種類と配合量を表１に示すとおりに変更したことを除き、実施例１と同様に組成物を調製し、二次電池負極を作成した。なお、界面活性剤として、実施例３及び４では、それぞれ、日本乳化剤株式会社製のアルキレンオキサイド「ニューコール２３２７」及び「ＡＮＴＯＸ ＬＭＡ－２７」を使用した。このようにして得られた組成物（未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７））及び二次電池負極を用い、後述する各種物性評価に供した。結果を表１に示す。
[Examples 2 to 4]
Except for changing the type and amount of the surfactant as shown in Table 1, compositions were prepared in the same manner as in Example 1, and secondary battery negative electrodes were produced. In Examples 3 and 4, alkylene oxides "Newcol 2327" and "ANTOX LMA-27" manufactured by Nippon Nyukazai Co., Ltd. were used as the surfactants. The compositions (unneutralized (pH 5) or neutralized to 40 mol% (pH 7)) and secondary battery negative electrodes thus obtained were used for various physical property evaluations described later. The results are shown in Table 1.
［実施例５～９］
界面活性剤を使用せず、各モノマーの配合量を表１に示すとおりに変更したことを除き、実施例１と同様に組成物を調製し、二次電池負極を作成した。このようにして得られた組成物（未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７））及び二次電池負極を用い、後述する各種物性評価に供した。結果を表１に示す。
[Examples 5 to 9]
A composition was prepared and a secondary battery negative electrode was produced in the same manner as in Example 1, except that no surfactant was used and the blending amount of each monomer was changed as shown in Table 1. The composition (unneutralized (pH 5) or neutralization degree 40 mol% (pH 7)) and the secondary battery negative electrode thus obtained were used to evaluate various physical properties as described below. The results are shown in Table 1.
［比較例１］
反応器に、イオン交換水、アルキルジフェニルエーテルスルホン酸ナトリウム、ニューコール２３２７を加え、撹拌しながら６５℃に昇温して保持した。ここへ、ＮＰＳと、ＡＡｍ水溶液と、ＭＡＡと、ＥＡの４成分を同時に滴下し、温度を６５℃に保ちながら３時間で滴下を終了した。その後、２．５時間重合を継続させた。このときの各成分の配合量としては、単量体成分の合計（全エチレン性不飽和単量体に由来する単位：ＭＡＡ、ＥＡ、ＡＡｍ）を１００質量部としたとき、アルキルジフェニルエーテルスルホン酸ナトリウム０．８質量部、ニューコール２３２７を０．２質量部、ＮＰＳは０．３質量部、ＭＡＡは３０質量部、ＥＡは５５質量部、ＡＡｍは１５質量部となるように配合し、イオン交換水の配合量は８９９質量部であった。
その後、温度を６５℃から８０℃へ昇温し、１．５時間保持して重合を完結させた。
得られた組成物は、重合率が９８％、ｐＨ５、固形分（重合体粒子）が９．８％であった。この組成物のｐＨを実施例１と同様に調整し、中和度４０モル％（ｐＨ７）とした組成物を得た。さらに、実施例１と同様に二次電池負極を作成した。
このようにして得られた組成物（未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７））及び二次電池負極を用い、後述する各種物性評価に供した。結果を表１に示す。
[Comparative Example 1]
Ion-exchanged water, sodium alkyl diphenyl ether sulfonate, and Newcol 2327 were added to the reactor, and the temperature was raised to 65° C. and maintained while stirring. Four components, NPS, an aqueous AAm solution, MAA, and EA, were added dropwise at the same time, and the dropwise addition was completed in 3 hours while maintaining the temperature at 65° C. Then, polymerization was continued for 2.5 hours. The amount of each component was 0.8 parts by mass of sodium alkyl diphenyl ether sulfonate, 0.2 parts by mass of Newcol 2327, 0.3 parts by mass of NPS, 30 parts by mass of MAA, 55 parts by mass of EA, and 15 parts by mass of AAm, when the total of the monomer components (units derived from all ethylenically unsaturated monomers: MAA, EA, AAm) was 100 parts by mass, and the amount of ion-exchanged water was 899 parts by mass.
Thereafter, the temperature was raised from 65° C. to 80° C. and maintained at that temperature for 1.5 hours to complete the polymerization.
The obtained composition had a polymerization rate of 98%, pH 5, and a solid content (polymer particles) of 9.8%. The pH of this composition was adjusted in the same manner as in Example 1 to obtain a composition with a neutralization degree of 40 mol% (pH 7). Furthermore, a secondary battery negative electrode was produced in the same manner as in Example 1.
The thus obtained composition (unneutralized (pH 5) or neutralized to 40 mol % (pH 7)) and the secondary battery negative electrode were used to evaluate various physical properties as described below. The results are shown in Table 1.
［比較例２～９］
界面活性剤を使用せず、各モノマーの配合量を表１に示すとおりに変更したことを除き、実施例１と同様に組成物を調製し、二次電池負極を作成した。このようにして得られた組成物（未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７））及び二次電池負極を用い、後述する各種物性評価に供した。結果を表１に示す。
[Comparative Examples 2 to 9]
A composition was prepared and a secondary battery negative electrode was produced in the same manner as in Example 1, except that no surfactant was used and the blending amount of each monomer was changed as shown in Table 1. The composition (unneutralized (pH 5) or neutralization degree 40 mol% (pH 7)) and the secondary battery negative electrode thus obtained were used to evaluate various physical properties as described below. The results are shown in Table 1.
（動的光散乱法による平均粒子径）
未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７）にそれぞれ調整した組成物中の重合体粒子の平均粒子径を、粒子径測定装置（日機装株式会社製、Ｍｉｃｒｏｔｒａｃ ＵＰＡ１５０）を使用して測定した。測定条件としては、ローディングインデックス＝０．１５～０．３、測定時間３００秒とし、得られたデータにおける５０％粒子径の数値を動的光散乱法による平均粒子径（ＤＡ）とした。
(Average particle size measured by dynamic light scattering)
The average particle size of the polymer particles in each composition adjusted to unneutralized (pH 5) or to a degree of neutralization of 40 mol% (pH 7) was measured using a particle size measuring device (Microtrac UPA150, manufactured by Nikkiso Co., Ltd.) The measurement conditions were a loading index of 0.15 to 0.3 and a measurement time of 300 seconds, and the numerical value of the 50% particle size in the obtained data was taken as the average particle size (DA) by dynamic light scattering.
（ＴＥＭ観察による平均粒子径）
未中和（ｐＨ５）又は中和度４０モル％（ｐＨ７）にそれぞれ調整した組成物中の重合体粒子１００個を、常法に従ってコロジオン膜状に載せ、透過型電子顕微鏡（ＴＥＭ）により粒子画像を撮影し、画像上の粒子径（５０個）を計測することにより平均粒子径（ＤＢ）を求めた。
(Average particle size by TEM observation)
100 polymer particles in each composition, which was unneutralized (pH 5) or adjusted to a degree of neutralization of 40 mol% (pH 7), were placed on a collodion film in a conventional manner, and particle images were taken with a transmission electron microscope (TEM). The particle diameters (50 particles) on the images were measured to determine the average particle diameter (DB).
（残渣量）
未中和（ｐＨ５）の組成物を２５０μｍメッシュを用いて濾過した後、メッシュに残った残渣を６０℃、１日で乾燥させた。得られた残渣を計量し、以下の式にて重量分率を算出した。
残渣量＝（得られた残渣）／（仕込みのモノマー量）×１００
次いで、以下の基準に基づき残渣量を評価した。
◎：０．２％未満
〇：０．２％以上０．５％未満
△：０．５％以上１．０％未満
×：１．０％以上
(Amount of Residue)
The unneutralized (pH 5) composition was filtered using a 250 μm mesh, and the residue remaining on the mesh was dried for one day at 60° C. The resulting residue was weighed, and the weight fraction was calculated using the following formula.
Residue amount=(residue obtained)/(amount of monomer charged)×100
The amount of residue was then evaluated based on the following criteria.
◎: Less than 0.2% ◯: 0.2% or more and less than 0.5% △: 0.5% or more and less than 1.0% ×: 1.0% or more
（粘度）
得られた塗工液をＢ型粘度計にて、６０ｒｐｍで１分攪拌した後の２５℃下の粘度を測定し、以下の基準に基づき評価した。
◎：２０００ｍＰａ・ｓ以上
〇：１５００ｍＰａ・ｓ以上・２０００ｍＰａ・ｓ未満
△：１０００ｍＰａ・ｓ以上・１５００ｍＰａ・ｓ未満
×：１０００ｍＰａ・ｓ未満
(viscosity)
The obtained coating liquid was stirred at 60 rpm for 1 minute and then the viscosity at 25° C. was measured using a Brookfield viscometer, and the viscosity was evaluated according to the following criteria.
◎: 2000 mPa.s or more 〇: 1500 mPa.s or more, but less than 2000 mPa.s △: 1000 mPa.s or more, but less than 1500 mPa.s ×: Less than 1000 mPa.s
（ヒステリシス）
得られた塗工液をレオメーター（ＭＣＲ１０２、Ａｎｔｏｎ－Ｐａａｒ社製）を用いて測定した。すなわち、せん断速度を０[１／ｓ]から１００[１／ｓ]に上昇する時と１００[１／ｓ]から０[１／ｓ]へ下降する際の１０[１／ｓ]における粘度の差からヒステリシスを算出した。
ヒステリシス＝｜せん断速度上昇時の１０[１／ｓ]における粘度－せん断速度下降時の１０[１／ｓ]における粘度｜／せん断速度上昇時の１０[１／ｓ]における粘度×１００
以下の基準に基づき評価した。
◎：５％未満
〇：５％以上１０％未満
△：１０％以上１５％未満
×：１５％以上
(Hysteresis)
The obtained coating liquid was measured using a rheometer (MCR102, manufactured by Anton-Paar). That is, the hysteresis was calculated from the difference in viscosity at 10 [1/s] when the shear rate was increased from 0 [1/s] to 100 [1/s] and when the shear rate was decreased from 100 [1/s] to 0 [1/s].
Hysteresis = | Viscosity at 10 [1/s] when shear rate is increasing - Viscosity at 10 [1/s] when shear rate is decreasing | / Viscosity at 10 [1/s] when shear rate is increasing x 100
The evaluation was based on the following criteria.
◎: Less than 5% 〇: 5% to less than 10% △: 10% to less than 15% ×: 15% or more
（脱泡性）
２００ｍＬのカップに調製した塗工液１００ｇを加えて、スリーワンモーター、アスピレーターを取り付けたドライボックスの中に入れた。塗工液を１００ｒｐｍ、０．０１ＭＰａ、１ｍｉｎで減圧しながら攪拌した後の状態で、目視にて、下記の基準で脱泡性を評価した。
◎：泡立たない
〇：水面が変わらない
△：水面が上昇するが容器から漏れない
×：容器から漏れる
(Defoaming ability)
100 g of the prepared coating liquid was added to a 200 mL cup, and the cup was placed in a dry box equipped with a three-one motor and an aspirator. The coating liquid was stirred at 100 rpm under reduced pressure at 0.01 MPa for 1 min, and then the defoaming property was evaluated by visual observation according to the following criteria.
◎: No foaming 〇: No change in water level △: Water level rises but does not leak from container ×: Leaks from container
（ピール強度）
得られた二次電池負極から幅２ｃｍ×長さ１２ｃｍの試験片を切り出し、この試験片の集電体側の表面を両面テープでアルミ板に貼り付けた。ＪＩＳ Ｚ １５２２に準拠し、試験片の電極層側に幅１８ｍｍのテープ（商品名「セロテープ（登録商標）」（ニチバン社製））を貼り付け、１８０°方向に１００ｍｍ／ｍｉｎの速度でテープを剥離したときの強度を６回測定し、その平均値（Ｎ／１８ｍｍ）をピール強度として算出した。この値が大きいほど集電体と電極層の接着強度が高く、集電体から電極層が剥離しがたいと評価でき、具体的には、以下の基準に基づきピール強度を評価した。
◎：４０Ｎ／ｍ以上
〇：３０Ｎ／ｍ以上４０Ｎ／ｍ未満
△：２０Ｎ／ｍ以上３０Ｎ／ｍ未満
×：２０Ｎ／ｍ未満
(Peel Strength)
A test piece measuring 2 cm wide x 12 cm long was cut out from the obtained secondary battery negative electrode, and the surface of the current collector side of this test piece was attached to an aluminum plate with double-sided tape. In accordance with JIS Z 1522, a tape measuring 18 mm wide (trade name "Cellotape (registered trademark)" (manufactured by Nichiban Co., Ltd.)) was attached to the electrode layer side of the test piece, and the strength when the tape was peeled off in a 180° direction at a speed of 100 mm/min was measured six times, and the average value (N/18 mm) was calculated as the peel strength. The larger this value, the higher the adhesive strength between the current collector and the electrode layer, and the more difficult it is to peel off the electrode layer from the current collector. Specifically, the peel strength was evaluated based on the following criteria.
◎: 40N/m or more 〇: 30N/m or more and less than 40N/m △: 20N/m or more and less than 30N/m ×: Less than 20N/m
（サイクル特性）
二次電池負極を使用し、次の方法にて製造した二次電池に関して、４５℃で４．２Ｖ－３Ｖの間１Ｃの定電流で充電を行ったのち、１Ｃの定電流で３Ｖまで放電を続けた。これを５００回繰り返した後、サイクル試験前後の１/３Ｃにおける容量の変化率を百分率で表し、サイクル特性を評価した。この値が大きい程サイクル特性が良いことを示す。
◎：８５％以上
〇：８２％以上８５％未満
△：８０％以上８２％未満
×：８０％未満
(Cycle characteristics)
A secondary battery produced by the following method using a secondary battery negative electrode was charged at a constant current of 1C between 4.2V and 3V at 45°C, and then discharged at a constant current of 1C to 3V. After repeating this 500 times, the rate of change in capacity at 1/3C before and after the cycle test was expressed as a percentage to evaluate the cycle characteristics. The higher this value, the better the cycle characteristics.
◎: 85% or more 〇: 82% or more but less than 85% △: 80% or more but less than 82% ×: Less than 80%
＜二次電池の作製＞
二次電池正極及び負極を円形に打抜き、当該正極と負極との活物質面が対向するよう、正極、セパレータ及び負極の順に積層した後に、蓋付きステンレス金属製容器に収納した。この容器と蓋とは絶縁されており、容器は負極の銅箔と、蓋は正極のアルミニウム箔と、それぞれ接するように配置した。そして、この容器内に電解液を注入して密閉し、その状態で室温にて１日放置して二次電池を作製した。
ここで使用した上記電解液には、エチレンカーボネート／エチルメチルカーボネート＝１／２（体積比）の混合溶媒に、溶質としてＬｉＰＦ６を濃度１．０ｍｏｌ／Ｌとなるように溶解させることにより調製したものを使用した。
また、上記セパレータには、ポリエチレン多孔膜製のものを使用し、上記二次電池負極には、上記実施例１～９及び比較例１～６で得られた二次電池負極を使用した。
さらに、上記二次電池正極には、以下のようにして作製されたものを使用した。
正極活物質としてリチウムコバルト複合酸化物（ＬｉＣｏＯ２）９２．２質量％、導電材としてリン片状グラファイトとアセチレンブラックそれぞれ２．３質量％、バインダーとしてポリフッ化ビニリデン（ＰＶＤＦ）３．２質量％を、Ｎ－メチルピロリドン（ＮＭＰ）中に分散させてスラリーを調製した。このスラリーを正極集電体となる厚さ２０μｍのアルミニウム箔の片面にダイコーターで塗布し、１３０℃で３分間乾燥後、ロールプレス機で圧縮成形した。この時、正極の活物質塗布量は２５０ｇ／ｍ２、活物質嵩密度は３．００ｇ／ｃｍ３になるようにした。このようにして得られた電極を二次電池正極として使用した。
<Preparation of secondary battery>
The positive and negative electrodes of the secondary battery were punched into a circle, and the positive electrode, separator, and negative electrode were laminated in this order so that the active material surfaces of the positive and negative electrodes faced each other, and then the laminate was placed in a stainless steel metal container with a lid. The container and the lid were insulated, and the container was placed so that the copper foil of the negative electrode was in contact with the copper foil of the negative electrode, and the lid was placed so that the aluminum foil of the positive electrode was in contact with the aluminum foil of the positive electrode. Then, the electrolyte was poured into the container, which was then sealed. The container was left at room temperature for one day in this state to prepare a secondary battery.
The electrolyte used here was prepared by dissolving LiPF6 as a solute in a mixed solvent of ethylene carbonate/ethyl methyl carbonate = 1/2 (volume ratio) to a concentration of 1.0 mol/L.
The separator used was made of a polyethylene porous film, and the secondary battery negative electrodes obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were used as the secondary battery negative electrodes.
The positive electrode of the secondary battery was prepared as follows.
A slurry was prepared by dispersing 92.2% by mass of lithium cobalt composite oxide (LiCoO 2 ) as a positive electrode active material, 2.3% by mass of flaky graphite and acetylene black as conductive materials, and 3.2% by mass of polyvinylidene fluoride (PVDF) as a binder in N-methylpyrrolidone (NMP). This slurry was applied to one side of an aluminum foil having a thickness of 20 μm as a positive electrode current collector with a die coater, dried at 130° C. for 3 minutes, and then compression molded with a roll press machine. At this time, the amount of active material applied to the positive electrode was 250 g/m 2 , and the bulk density of the active material was 3.00 g/cm 3. The electrode thus obtained was used as a secondary battery positive electrode.
Claims (8)
前記重合体粒子の動的光散乱法により測定された平均粒子径ＤＡと、前記重合体粒子のＴＥＭ観察により測定された平均粒子径ＤＢとの比が、ＤＡ／ＤＢとして、中和度４０モル％において、１０以上５０以下であり、
前記重合体粒子は、
エチレン性不飽和カルボン酸又はそのアルカリ金属塩に由来する単位Ｕ１と、
前記Ｕ１と共重合可能なエチレン性不飽和カルボン酸エステルに由来する単位Ｕ２と、
Ｎ原子含有エチレン性不飽和単量体に由来する単位Ｕ３と、
を分子中に有し、
前記重合体粒子において、全エチレン性不飽和単量体に由来する単位を１００質量％としたとき、前記Ｕ１の含有量が２５質量％以上５０質量％以下であり、かつ、前記Ｕ２の含有量が３０質量％以上６０質量％以下であり、かつ、前記Ｕ３の含有量が１０質量％以上３０質量％以下である、非水系二次電池用重合体組成物。 A polymer composition for a non-aqueous secondary battery comprising polymer particles,
the ratio of an average particle diameter DA of the polymer particles measured by a dynamic light scattering method to an average particle diameter DB of the polymer particles measured by TEM observation, expressed as DA/DB, is 10 or more and 50 or less at a degree of neutralization of 40 mol%,
The polymer particles are
A unit U1 derived from an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof;
a unit U2 derived from an ethylenically unsaturated carboxylic acid ester copolymerizable with U1;
Units U3 derived from N-atom-containing ethylenically unsaturated monomers;
in the molecule,
In the polymer particles, when the units derived from all ethylenically unsaturated monomers are taken as 100 mass%, the content of U1 is 25 mass% or more and 50 mass% or less, the content of U2 is 30 mass% or more and 60 mass% or less, and the content of U3 is 10 mass% or more and 30 mass% or less.
Ｎ原子含有エチレン性不飽和単量体と重合開始剤とが溶解した溶液を調製する工程と、
前記溶液に対して、エチレン性不飽和カルボン酸又はそのアルカリ金属塩と、これらと共重合可能なエチレン性不飽和カルボン酸エステルとを添加して重合し、前記重合体粒子を得る工程と、
を有する、非水系二次電池用重合体組成物の製造方法。 A method for producing the polymer composition for a non-aqueous secondary battery according to any one of claims 1 to 6, comprising the steps of:
A step of preparing a solution in which an N-atom-containing ethylenically unsaturated monomer and a polymerization initiator are dissolved;
a step of adding an ethylenically unsaturated carboxylic acid or an alkali metal salt thereof, and an ethylenically unsaturated carboxylic acid ester copolymerizable therewith to the solution and polymerizing them to obtain the polymer particles;
The present invention relates to a method for producing a polymer composition for a non-aqueous secondary battery.
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| WO2016039067A1 (en) | 2014-09-08 | 2016-03-17 | Jsr株式会社 | Binder composition for storage device electrode, slurry for storage device electrode, storage device electrode, and storage device |
| JP2019003962A (en) | 2018-10-16 | 2019-01-10 | 日本エイアンドエル株式会社 | Composition for battery electrode and binder composition for battery electrode |
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| WO2016039067A1 (en) | 2014-09-08 | 2016-03-17 | Jsr株式会社 | Binder composition for storage device electrode, slurry for storage device electrode, storage device electrode, and storage device |
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