TWI725089B - Dispersant composition for powder - Google Patents

Dispersant composition for powder Download PDF

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TWI725089B
TWI725089B TW105141773A TW105141773A TWI725089B TW I725089 B TWI725089 B TW I725089B TW 105141773 A TW105141773 A TW 105141773A TW 105141773 A TW105141773 A TW 105141773A TW I725089 B TWI725089 B TW I725089B
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composition
powder
dispersant
dispersant composition
copolymer
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TW105141773A
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TW201731885A (en
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石橋洋一
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日商花王股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/04—Anhydrides, e.g. cyclic anhydrides
    • C08F22/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/124—Treatment for improving the free-flowing characteristics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本發明在一個方式中，提供可提高漿料組合物之再分散性的分散劑組合物。在一個方式中，提供一種粉體用分散劑組合物，其含有聚合物組合物，該聚合物組合物含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽，該聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上。In one aspect of the present invention, a dispersant composition that can improve the redispersibility of a slurry composition is provided. In one aspect, there is provided a dispersant composition for powder, which contains a polymer composition containing a structural unit derived from (meth)acrylic acid and a structural unit derived from an unsaturated dibasic acid The organic amine salt or quaternary ammonium salt of the copolymer, the molar ratio (II) of all carboxyl groups (I) contained in the polymer composition and the carboxyl group (II) that forms a counterion with the organic amine or quaternary ammonium )/(I) is 0.33 or more.

Description

粉體用分散劑組合物Dispersant composition for powder

本發明係關於粉體用分散劑組合物、分散方法、漿料組合物之製造方法及漿料組合物。The present invention relates to a dispersant composition for powder, a dispersion method, a method for producing a slurry composition, and a slurry composition.

在製造層疊陶瓷電容器等電子零件時，使用漿料化之電子材料用粉體。舉例而言，介電質陶瓷粉末之漿料組合物用作層疊陶瓷電容器之介電質陶瓷層之形成材料。隨著以攜帶電話等為首之電子設備及其電子零件的高效能化及小型化，要求有進一步提高處置性之漿料組合物。舉例而言，在層疊陶瓷電容器之小型化時需要介電質陶瓷層之薄層化，要求有提高分散性及操作性之介電質陶瓷粉末之漿料組合物。 作為粉體之分散劑之一，可舉出聚羧酸系(共)聚合物。其中，作為藉由降低粉體之漿料組合物之黏度來提高分散性及操作性的分散劑，揭示含有包含以α，β－不飽和羧酸作為構成單元之(共)聚合物之中和物的顏料分散劑、分子量為25000～80000的(甲基)丙烯酸－不飽和二元酸共聚物之分散劑組合物等(例如專利文獻1～3)。 另外，電磁學-光學用構件精細陶瓷一旦混入Na、K、Mg等金屬離子，會給電磁學特性帶來弊病，因此其中所使用之試劑使用不含金屬離子之物質，例如將銨鹽作為分散劑使用(例如專利文獻4～6)。 現有技術文獻 專利文獻 專利文獻1：日本特開平7－308563號公報 專利文獻2：日本特開平10－110015號公報 專利文獻3：日本特開平11－217534號公報 專利文獻4：日本特開2004－123903號公報 專利文獻5：日本特開2005－288294號公報 專利文獻6：日本特開2005－290125號公報When manufacturing electronic components such as laminated ceramic capacitors, paste-formed powders for electronic materials are used. For example, a slurry composition of dielectric ceramic powder is used as a material for forming the dielectric ceramic layer of a laminated ceramic capacitor. With the increase in performance and miniaturization of electronic devices and their electronic components, such as mobile phones, there is a demand for slurry compositions that further improve handling properties. For example, in the miniaturization of laminated ceramic capacitors, thinning of the dielectric ceramic layer is required, and a slurry composition of dielectric ceramic powder with improved dispersibility and operability is required. As one of the powder dispersants, polycarboxylic acid-based (co)polymers can be cited. Among them, as a dispersant that improves the dispersibility and operability by reducing the viscosity of the powder slurry composition, it is disclosed that it contains a (co)polymer containing α, β-unsaturated carboxylic acid as a structural unit and neutralization The pigment dispersant of the product, the dispersant composition of the (meth)acrylic acid-unsaturated dibasic acid copolymer having a molecular weight of 25,000 to 80,000, etc. (for example, Patent Documents 1 to 3). In addition, once the metal ions such as Na, K, Mg, etc. are mixed into the fine ceramics for electromagnetic-optical components, it will bring disadvantages to the electromagnetic properties. Therefore, the reagents used therein use substances that do not contain metal ions, such as ammonium salt as a dispersion. Agent is used (for example, Patent Documents 4 to 6). Prior Art Literature Patent Literature Patent Literature 1: Japanese Patent Application Publication No. 7-308563 Patent Literature 2: Japanese Patent Application Publication No. 10-110015 Patent Literature 3: Japanese Patent Application Publication No. 11-217534 Patent Literature 4: Japanese Patent Application Publication No. 2004- 123903 Patent Document 5: Japanese Patent Application Publication No. 2005-288294 Patent Document 6: Japanese Patent Application Publication No. 2005-290125

發明所要解決之問題 但是，藉由使用以往之分散劑組合物使粉體分散於水系溶劑中而得之漿料組合物在乾燥後的再分散性不足。舉例而言，若將漿料組合物以附著於容器或配管等的內壁之狀態置放，則隨著時間經過，漿料組合物會變成硬塊狀物(乾燥物)而牢固地附著於內壁，從而存在即使加水亦難以使粉體(乾燥物)再分散於水系溶劑中之問題。 因而，本發明在一個方式中，提供一種可提高漿料組合物之再分散性的分散劑組合物。 用於解決問題之方法 本發明在一個方式中，係關於一種粉體用分散劑組合物，其含有聚合物組合物，該聚合物組合物含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽，該聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上。 本發明在另一個方式中，係關於一種粉體用分散劑組合物之製造方法，其包括如下中和步驟，亦即，將包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物與有機胺或四級銨(鹽)混合，以使該共聚物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上的方式，將該共聚物用有機胺或四級銨(鹽)中和而得到聚合物組合物。 本發明在另一個方式中，係關於一種分散方法，其包括使用本發明之分散劑組合物使粉體分散於水系溶劑中之步驟。 本發明在另一個方式中，係關於一種漿料組合物之製造方法，其包括將本發明之分散劑組合物、粉體以及水系溶劑混合且使該粉體分散的步驟。 本發明在另一個方式中，係關於一種漿料組合物，其含有本發明之分散劑組合物、粉體以及水系溶劑。 發明效果 根據本發明，可在一或多個實施方式中，提供可提高漿料組合物之再分散性的粉體用分散劑組合物。Problems to be Solved by the Invention However, a slurry composition obtained by dispersing a powder in an aqueous solvent using a conventional dispersant composition has insufficient redispersibility after drying. For example, if the slurry composition is placed in a state attached to the inner wall of a container or piping, the slurry composition will become a hard lumpy (dry matter) and firmly adhere to it as time passes. The inner wall has the problem that it is difficult to redisperse the powder (dried substance) in the aqueous solvent even if water is added. Therefore, in one aspect of the present invention, a dispersant composition that can improve the redispersibility of a slurry composition is provided. Means for Solving the Problems In one aspect of the present invention, it relates to a dispersant composition for powders, which contains a polymer composition containing structural units derived from (meth)acrylic acid and The organic amine salt or quaternary ammonium salt of the copolymer of the constituent unit of unsaturated dibasic acid, all the carboxyl groups (I) contained in the polymer composition and the carboxyl group which forms a counterion with the organic amine or quaternary ammonium The molar ratio (II)/(I) of (II) is 0.33 or more. In another aspect of the present invention, it relates to a method for producing a dispersant composition for powders, which includes the following neutralization step, that is, a structural unit derived from (meth)acrylic acid and a The copolymer of the structural unit of the basal acid is mixed with the organic amine or the quaternary ammonium (salt), so that all the carboxyl groups (I) contained in the copolymer and the carboxyl group (II) which form the counterion with the organic amine or the quaternary ammonium (salt) When the molar ratio (II)/(I) of) is 0.33 or more, the copolymer is neutralized with an organic amine or a quaternary ammonium (salt) to obtain a polymer composition. In another aspect of the present invention, it relates to a dispersion method, which includes the step of using the dispersant composition of the present invention to disperse powder in an aqueous solvent. In another aspect of the present invention, it relates to a method for producing a slurry composition, which includes the steps of mixing the dispersant composition of the present invention, a powder, and an aqueous solvent, and dispersing the powder. In another aspect of the present invention, it relates to a slurry composition containing the dispersant composition, powder, and water-based solvent of the present invention. Effects of the Invention According to the present invention, in one or more embodiments, it is possible to provide a dispersant composition for powder that can improve the redispersibility of a slurry composition.

本發明基於如下見解，亦即，在包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽中所含之全部羧基當中，特定與有機胺或四級銨形成抗衡離子之羧基的比例，由此可提高漿料組合物之再分散性。 雖然可提高漿料組合物之再分散性的理由並不確定，然而可如下所示進行考慮。亦即，可認為，在將該共聚物之銨(NH4 ＋ )鹽作為分散劑使用的情況下，隨著漿料組合物之乾燥，銨(NH4 ＋ )發生氣化，作為使分散劑表面疏水化而凝固至粉體上的糊劑發揮作用，經乾燥之漿料殘渣變為硬的塊狀物而固著在容器等的內壁。另一方面可認為，在將以特定比例具有與有機胺或四級銨形成抗衡離子之羧基的該共聚物的有機胺鹽或四級銨鹽作為分散劑使用的情況下，即使漿料組合物進一步乾燥，有機胺或四級銨亦不會氣化(或難以氣化)，因此會殘留於分散劑中。由此可認為，可抑制漿料組合物之乾燥物變為硬的塊狀物，抑制向容器等的內壁固著，當向漿料組合物之乾燥物中添加水時，會再次分散於水中。但是，此等均為推測，本發明並不限定於此等機理。 亦即，本發明在一個方式中，係關於一種粉體用分散劑組合物(以下亦稱作「本發明之分散劑組合物」)，該粉體用分散劑組合物含有聚合物組合物，該聚合物組合物含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽，該聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上。根據本發明之分散劑組合物，可提高漿料組合物之再分散性。由此，可將漿料組合物之乾燥物再次分散於水系溶劑中，因此使得容器、配管等內的清洗變得容易。此外，對於藉由使得附著於容器、配管等的內壁之漿料組合物的乾燥物再次分散於水系溶劑中而得的物質，可將其作為漿料組合物再次利用。 本發明中所謂「漿料組合物之再分散性」，係指漿料組合物之乾燥物重新與水系溶劑接觸時會分散於該水系溶劑中。漿料組合物之再分散性可利用後述實施例中記載之方法測定。 本發明中，作為構成容器、配管等的內壁之材料，不特別限定，然而在一或多個實施方式中，可舉出金屬材料，具體而言，可舉出不鏽鋼。 (分散劑組合物) 本發明之分散劑組合物在一或多個實施方式中，含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽(以下亦稱作「聚合物組合物」)。本發明中，「聚合物組合物」在一或多個實施方式中，為包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物(以下亦簡稱為「共聚物」)的至少一部分用有機胺或四級銨(鹽)中和而得的物質。在一或多個實施方式中，該共聚物之至少一部分亦可用有機胺或四級銨以外之中和劑(銨(鹽)等)中和。本發明中「有機胺或四級銨(鹽)」在一或多個實施方式中，表示選自有機胺、有機胺鹽、四級銨以及四級銨鹽中之至少1種。本發明中「銨(鹽)」在一或多個實施方式中，表示銨及銨鹽之至少一者。 本發明之分散劑組合物在一或多個實施方式中，可含有水系溶劑。作為水系溶劑，可舉出離子交換水、超純水等水，或水與水溶性有機溶劑(乙醇、乙二醇等)的混合溶劑等。此外，本發明之分散劑組合物在一或多個實施方式中，亦可在上述聚合物組合物及水系溶劑以外，還含有添加劑等任意成分。 作為本發明之分散劑組合物的形態，在一或多個實施方式中，可舉出粉末狀或水溶液。本發明之分散劑組合物在一或多個實施方式中，亦可為該聚合物組合物本身。 本發明的所謂「共聚物」，為包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物，在一或多個實施方式中，可包含其他構成單元。在一或多個實施方式中，構成共聚物之全部構成單元中來自於(甲基)丙烯酸之構成單元與來自於不飽和二元酸之構成單元的合計量較佳為70質量%以上，更佳為85質量%以上，進一步較佳實質上為100質量%。作為「其他構成單元」，例如可舉出α－烯烴、磺酸單體、苯乙烯、烯丙醇等。 作為本發明之「(甲基)丙烯酸」，在一或多個實施方式中，可舉出選自丙烯酸及甲基丙烯酸中之至少1種。 本發明的所謂「不飽和二元酸」，在一或多個實施方式中，可舉出選自碳原子數4～6之脂肪族不飽和二元酸中之至少1種。作為具體不飽和二元酸，在一或多個實施方式中，可舉出選自馬來酸酐、馬來酸以及衣康酸中之至少1種。 作為本發明之「有機胺」，在一或多個實施方式中，可舉出一級、二級或三級烷基胺或烷醇胺。作為有機胺，在一或多個實施方式中，可舉出選自單烷基(烷基之碳原子數1～3)胺、二烷基(烷基之碳原子數1～3)胺、三烷基(烷基之碳原子數1～3)胺、單烷醇(烷醇之碳原子數1～3)胺、二烷醇(烷醇之碳原子數1～3)胺、以及三烷醇(烷醇之碳原子數1～3)胺中之至少1種。作為具體有機胺，在一或多個實施方式中，可舉出選自單乙醇胺、二乙醇胺、三乙醇胺、乙二胺、二亞乙三胺、三乙胺及三丁胺中之至少1種。作為本發明之「四級銨」，在一或多個實施方式中，可舉出四低碳烷基銨，然而較佳不含有金屬之四級銨。作為具體四級銨，在一或多個實施方式中，可舉出四甲基銨。 本發明之分散劑組合物中，對於聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)，在一或多個實施方式中，為0.33以上，自提高漿料組合物之再分散性的觀點考慮，較佳為0.4以上，更佳為0.45以上，進一步較佳為0.5以上。此外，對於該莫耳比(II)/(I)，在一或多個實施方式中，自本來的作為分散劑之效能的觀點考慮，較佳為2.5以下，更佳為2.0以下，進一步較佳為1.5以下。對於該莫耳比(II)/(I)，在一或多個實施方式中，自本來的作為分散劑之效能的觀點考慮，較佳為1.0以下，更佳為0.95以下，進一步較佳為0.9以下。本發明的所謂「全部羧基」，係指構成共聚物或聚合物組合物之全部構成單元中所含的全部羧基，亦包括經中和之羧基以及開環後變為羧基之基團。本發明的所謂「莫耳比(II)/(I)」，為該共聚物中所含之全部羧基當中的與有機胺或四級銨形成抗衡離子之羧基的比例。對於「莫耳比(II)/(I)」之算出方法，例如在製作丙烯酸與馬來酸之共聚物(單體組成比：AA/MA＝83/17)的鹽(聚合物組合物)時，在使用單乙醇胺：72莫耳%(相對於共聚物中之全部單體)進行中和的情況下，由於相對於共聚物中之全部單體而言，來自於丙烯酸之羧基數為83莫耳%，來自於馬來酸(二元酸)之羧基數為17莫耳%×2＝34莫耳%，因此莫耳比(II)/(I)＝72/(83＋34)＝0.62。本發明之分散劑組合物亦可含有不與該共聚物之羧基形成抗衡離子的選自有機胺及四級銨中之至少1種(以下亦簡稱為「過量胺」)。在本發明之分散劑組合物含有過量胺的情況下，對於聚合物組合物中所含之全部羧基(Ⅰ)與分散劑組合物中所含之有機胺及四級銨(III)的莫耳比(III)/(I)，自提高漿料組合物之再分散性的觀點考慮，較佳為2.5以下，更佳為2.0以下，進一步較佳為1.5以下。本發明中「分散劑組合物中所含之有機胺及四級銨」包括與共聚物之羧基形成抗衡離子的有機胺及四級銨，以及不與共聚物之羧基形成抗衡離子的有機胺及四級銨。 本發明之分散劑組合物中，對於聚合物組合物之中和度，在一或多個實施方式中，自提高分散劑之分散效能的觀點考慮，相對於共聚物或聚合物組合物中所含之全部羧基100莫耳%，較佳為40莫耳%以上且100莫耳%以下，更佳為50莫耳%以上且95莫耳%以下，進一步較佳為60莫耳%以上且90莫耳%以下。對於該聚合物組合物之中和度，在一或多個實施方式中，自提高分散劑之分散效能的觀點考慮，相對於共聚物或聚合物組合物中所含之全部羧基100莫耳%，較佳為40莫耳%以上，更佳為50莫耳%以上，進一步較佳為60莫耳%以上，此外，自相同之觀點考慮，較佳為100莫耳%以下，更佳為95莫耳%以下，進一步較佳為90莫耳%以下。本發明中所謂「中和度」，係指在共聚物或聚合物組合物中所含之全部羧基(100莫耳%)中，經中和步驟中所用之全部中和劑所中和之羧基的比例(莫耳%)。本發明中「中和度」以［經中和之羧基的莫耳當量/可中和之全部羧基的莫耳當量］×100(莫耳%)表示。對於中和度之算出方法，例如在製作丙烯酸與馬來酸之共聚物(單體組成比：AA/MA＝83/17)的鹽(聚合物組合物)時，在使用銨鹽：8.3莫耳%(相對於共聚物中之全部單體)及單乙醇胺：72莫耳%(相對於共聚物中之全部單體)進行中和的情況下，由於相對於共聚物中之全部單體而言，來自於丙烯酸之羧基數為83莫耳%，來自於馬來酸(二元酸)之羧基數為17莫耳%×2＝34莫耳%，因此聚合物組合物之中和度＝100莫耳%×(8.3＋72)/(83＋34)＝68.6莫耳%。 對於該聚合物組合物之重量平均分子量(Mw)，在一或多個實施方式中，自提高漿料組合物之再分散性以及降低漿料組合物之黏度的觀點考慮，較佳為10000～90000，更佳為20000～75000，進一步較佳為30000～65000。對於該聚合物組合物之重量平均分子量(Mw)，在一或多個實施方式中，自提高漿料組合物之再分散性以及降低漿料組合物之黏度的觀點考慮，較佳為10000以上，更佳為20000以上，進一步較佳為30000以上，此外，自相同之觀點考慮，較佳為90000以下，更佳為75000以下，進一步較佳為65000以下。此處，重量平均分子量為利用GPC(凝膠滲透層析)測定之值，測定條件之詳情如實施例中所示。 對於該聚合物組合物中的來自於(甲基)丙烯酸之構成單元與來自於不飽和二元酸之構成單元的莫耳比，在一或多個實施方式中，自提高漿料組合物之再分散性以及降低漿料組合物之黏度的觀點考慮，較佳為50/50～95/5，更佳為55/45～90/10，進一步較佳為60/40～85/15。 在本發明之分散劑組合物的形態為水溶液的情況下，對於分散劑組合物之水溶液中聚合物組合物之含量，在一或多個實施方式中，自提高漿料組合物之再分散性以及降低漿料組合物之黏度的觀點考慮，較佳為20～60質量%，更佳為25～50質量%，進一步較佳為30～45質量%。本發明之分散劑組合物中聚合物組合物之含量例如可根據原材料之投料量求出，或者亦可藉由測定本發明之分散劑組合物中之固體成分量來求出。 在本發明之分散劑組合物之形態為水溶液的情況下，對於分散劑組合物之水溶液的pH，在一或多個實施方式中，自提高漿料組合物之再分散性以及粉體成分之耐化學分解性的觀點考慮，較佳為4.5～11.0，更佳為5.0～10.0，進一步較佳為5.5～9.0。 在將本發明之分散劑組合物用於電子材料用粉體之分散的情況下，對於與該共聚物中所含之羧基形成抗衡離子的物質，在一或多個實施方式中，較佳不含有金屬(鹽)。亦即，本發明之聚合物組合物在一或多個實施方式中，較佳不含有金屬(鹽)。本發明中「金屬(鹽)」在一或多個實施方式中，表示金屬及金屬鹽中之至少一者。 ［分散劑組合物之製造方法］ 本發明在其他方式中，係關於一種製造方法，為製造本發明之分散劑組合物的方法(以下亦稱作「本發明之分散劑組合物製造方法」)，包括如下中和步驟，亦即，將包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物與有機胺或四級銨(鹽)混合，以使該共聚物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上的方式，將該共聚物用有機胺或四級銨(鹽)中和而得到聚合物組合物。根據本發明之分散劑組合物製造方法，可製造能夠提高漿料組合物之再分散性的分散劑組合物。在該中和步驟中，亦可併用有機胺或四級銨(鹽)以外之中和劑(例如銨(鹽))。 本發明的包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物之製造方法無特別限定，然而例如可藉由在將不飽和二元酸用中和劑進行部分中和後，使之與(甲基)丙烯酸進行聚合反應而得到。聚合反應中，可以使用公知之聚合引發劑、鏈轉移劑等。作為聚合引發劑，可舉出過氧化氫等。作為鏈轉移劑，可舉出異丙醇等。作為部分中和中所用之中和劑，可使用有機胺(鹽)或銨(鹽)等，具體而言，可舉出選自單乙醇胺、二乙醇胺、三乙醇胺、乙二胺、二亞乙三胺、三乙胺、三丁胺、四甲基氫氧化銨、三乙基甲基氫氧化銨以及氨水溶液中之至少1種。 ［分散方法］ 本發明作為其他方式，可提供一種分散方法(以下亦稱作「本發明之分散方法」)，其包括使用本發明之分散劑組合物使粉體在水系溶劑中分散之步驟。根據本發明之分散方法，可製造提高粉體之再分散性的漿料組合物。 作為利用本發明之分散方法分散於水系溶劑中之粉體，在一或多個實施方式中，可舉出電子材料用粉體，具體而言，可舉出選自碳酸鹽、磷酸鹽、鈦酸鋇等鈦酸鹽、矽酸鹽、氧化鋅、氧化鐵、氧化鈦、氧化鋁(alumina)、二氧化矽(silica)、氧化鎂、氧化鋯、氧化鈰、碳黑及碳化矽中之至少1種。電子材料用粉體例如可用於IC封裝、佈線基板、絕緣體、傳感器、電極、磁性體、半導體、電容器、光纖等電子零件中。 作為本發明之分散方法中所用之水系溶劑，在一或多個實施方式中，可舉出水，或者水與乙醇、乙二醇等水溶性有機溶劑之混合溶液，較佳為水。作為水，例如可舉出蒸餾水、離子交換水、超純水等。 ［漿料組合物］ 本發明作為其他方式，可提供一種漿料組合物(以下亦稱作「本發明之漿料組合物」)，該漿料組合物含有水系溶劑、粉體以及分散劑組合物，該分散劑組合物為本發明之分散劑組合物。根據本發明之漿料組合物，可提高再分散性。作為本發明之漿料組合物中所用之粉體、水系溶劑，可使用與上述本發明之分散方法相同的物質。 本發明之漿料組合物中粉體之含量(固體成分)無特別規定，然而在一或多個實施方式中，自提高乾燥效率及生產率之觀點考慮，較佳為50質量%以上，更佳為55質量%以上，進一步較佳為60質量%以上。另一方面，對於該粉體之含量(固體成分)，在一或多個實施方式中，自流動性之觀點考慮，較佳為85質量%以下，更佳為80質量%以下。 對於本發明之漿料組合物中分散劑組合物之含量，在一或多個實施方式中，自降低漿料組合物之黏度的觀點考慮，以固體成分換算，相對於粉體100重量份，較佳為0.3～5.0重量份，更佳為0.4～4.0重量份，進一步較佳為0.5～3.0重量份。對於該分散劑組合物之含量，在一或多個實施方式中，自降低漿料組合物之黏度的觀點考慮，以固體成分換算，相對於粉體100重量份，較佳為0.3重量份以上，更佳為0.4重量份以上，進一步較佳為0.5重量份以上，此外，自相同的觀點考慮，較佳為5.0重量份以下，更佳為4.0重量份以下，進一步較佳為3.0重量份以下。 ［漿料組合物之製造方法］ 本發明作為其他方式，可提供一種漿料組合物之製造方法(以下亦稱作「本發明之漿料組合物之製造方法」)，該漿料組合物之製造方法包括將粉體、本發明之分散劑組合物以及水系溶劑混合且使該粉體分散的步驟。根據本發明，可以製造提高再分散性之漿料組合物。作為本發明之漿料組合物之製造方法中所用的粉體、水系溶劑，可使用與上述本發明之分散方法相同的物質。本發明之漿料組合物之製造方法中，可舉出將粉體及分散劑組合物以達到上述本發明漿料組合物之含量的方式混合的方法。 本發明還關於以下一或多個實施方式。 ＜1＞一種粉體用分散劑組合物，其含有聚合物組合物，該聚合物組合物含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽， 該聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上。 ＜2＞根據＜1＞中記載之粉體用分散劑組合物，其中，莫耳比(II)/(I)較佳為0.4以上，更佳為0.45以上，進一步較佳為0.5以上。 ＜3＞根據＜1＞或＜2＞中記載之粉體用分散劑組合物，其中，莫耳比(II)/(I)較佳為2.5以下，更佳為2.0以下，進一步較佳為1.5以下，或者較佳為1.0以下，更佳為0.95以下，進一步較佳為0.9以下。 ＜4＞根據＜1＞至＜3＞中任一項記載之粉體用分散劑組合物，其中，粉體為電子材料用粉體。 ＜5＞根據＜1＞至＜4＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之中和度相對於共聚物或聚合物組合物中所含之全部羧基100莫耳%，較佳為40莫耳%以上且100莫耳%以下，更佳為50莫耳%以上且95莫耳%以下，進一步較佳為60莫耳%以上且90莫耳%以下。 ＜6＞根據＜1＞至＜5＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之重量平均分子量(Mw)較佳為10000～90000，更佳為20000～75000，進一步較佳為30000～65000。 ＜7＞根據＜1＞至＜6＞中任一項記載之粉體用分散劑組合物，其中，有機胺或四級銨為選自單乙醇胺、二乙醇胺、三乙醇胺、以及四甲基銨中之至少1種。 ＜8＞根據＜1＞至＜7＞中任一項記載之粉體用分散劑組合物，其中，來自於(甲基)丙烯酸之構成單元與來自於不飽和二元酸之構成單元的莫耳比較佳為50/50～95/5，更佳為55/45～90/10，進一步較佳為60/40～85/15。 ＜9＞根據＜1＞至＜8＞中任一項記載之粉體用分散劑組合物，其中，不飽和二元酸為選自馬來酸酐、馬來酸及衣康酸中之至少1種。 ＜10＞根據＜1＞至＜9＞中任一項記載之粉體用分散劑組合物，其中，構成共聚物之全部構成單元中來自於(甲基)丙烯酸之構成單元與來自於不飽和二元酸之構成單元的合計量較佳為70質量%以上，更佳為85質量%以上，進一步較佳實質上為100質量%。 ＜11＞根據＜1＞至＜10＞中任一項記載之粉體用分散劑組合物，其中，粉體用分散劑組合物之形態為水溶液，粉體用分散劑組合物之水溶液中聚合物組合物之含量較佳為20～60質量%，更佳為25～50質量%，進一步較佳為30～45質量%。 ＜12＞根據＜1＞至＜11＞中任一項記載之粉體用分散劑組合物，其中，粉體用分散劑組合物之形態為水溶液，粉體用分散劑組合物之水溶液的pH較佳為4.5～11.0，更佳為5.0～10.0，進一步較佳為5.5～9.0。 ＜13＞根據＜1＞至＜12＞中任一項記載之粉體用分散劑組合物，其中，與共聚物中所含之羧基形成抗衡離子的物質不含有金屬(鹽)。 ＜14＞根據＜1＞至＜13＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之中和度相對於共聚物或聚合物組合物中所含之全部羧基100莫耳%，較佳為40莫耳%以上，更佳為50莫耳%以上，進一步較佳為60莫耳%以上。 ＜15＞根據＜1＞至＜14＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之中和度相對於共聚物或聚合物組合物中所含之全部羧基100莫耳%，較佳為100莫耳%以下，更佳為95莫耳%以下，進一步較佳為90莫耳%以下。 ＜16＞根據＜1＞至＜15＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之重量平均分子量(Mw)較佳為10000以上，更佳為20000以上，進一步較佳為30000以上。 ＜17＞根據＜1＞至＜16＞中任一項記載之粉體用分散劑組合物，其中，聚合物組合物之重量平均分子量(Mw)較佳為90000以下，更佳為75000以下，進一步較佳為65000以下。 ＜18＞一種粉體用分散劑組合物之製造方法，其包括如下中和步驟，亦即，將包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物與有機胺或四級銨(鹽)混合，以使該共聚物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上的方式，將該共聚物用有機胺或四級銨(鹽)中和而得到聚合物組合物。 ＜19＞一種分散方法，其包括使用＜1＞至＜17＞中任一項記載之粉體用分散劑組合物使粉體分散於水系溶劑中之步驟。 ＜20＞一種漿料組合物之製造方法，其包括將＜1＞至＜17＞中任一項記載之粉體用分散劑組合物、粉體以及水系溶劑混合且使該粉體分散之步驟。 ＜21＞一種漿料組合物，其含有＜1＞至＜17＞中任一項記載之粉體用分散劑組合物、粉體以及水系溶劑。 ＜22＞根據＜21＞中記載之漿料組合物，其中，漿料組合物中粉體之含量(固體成分)較佳為50質量%以上，更佳為55質量%以上，進一步較佳為60質量%以上，此外，較佳為85質量%以下，更佳為80質量%以下。 ＜23＞根據＜21＞或＜22＞中記載之漿料組合物，其中，粉體用分散劑組合物之含量以固體成分換算，相對於粉體100重量份，較佳為0.3～5.0重量份，更佳為0.4～4.0重量份，進一步較佳為0.5～3.0重量份。 ＜24＞根據＜21＞至＜23＞中任一項記載之漿料組合物，其中，粉體用分散劑組合物之含量以固體成分換算，相對於粉體100重量份，較佳為0.3重量份以上，更佳為0.4重量份以上，進一步較佳為0.5重量份以上。 ＜25＞根據＜21＞至＜24＞中任一項記載之漿料組合物，其中，粉體用分散劑組合物之含量以固體成分換算，相對於粉體100重量份，較佳為5.0重量份以下，更佳為4.0重量份以下，進一步較佳為3.0重量份以下。 [實施例] 以下，利用實施例對本發明進行更詳細的說明，然而此等實施例為示例性的，本發明並不受此等實施例限制。 在後述實施例及比較例中，分散劑中聚合物之鹽的重量平均分子量係利用GPC (凝膠滲透層析)測定。具體條件如下所述。 ＜聚合物組合物之重量平均分子量的測定方法＞ 聚合物組合物之重量平均分子量係利用GPC (凝膠滲透層析)在下述條件下測定。 ［測定條件］ 層析管柱：TSK PWXL＋G4000PWXL＋G2500PWXL (均為Tosoh公司製) 柱溫：40℃ 偵測器：RI或UV (210 nm) 溶離液：0.2 mol/L磷酸緩衝液/乙腈(9/1) 流速：1.0 mL/min 注入量：0.1 mL 標準：聚乙二醇 ［分散劑組合物之製備(實施例1～15、比較例1～9)］ 如後所述，製備出下述表1所示之分散劑組合物(實施例1～15、比較例1～9)。 (實施例1) 向具備攪拌機、溫度計、回流冷卻管、氮氣導入管、滴液漏斗之反應容器中，投入馬來酸酐(三菱化學公司製) 78.5 g及離子交換水80.0 g，加熱至55℃(液溫)後，滴加28質量%氨水溶液(Sigma Aldrich公司製，化學純) 24.3 g，製成馬來酸銨鹽水溶液(中和步驟1)。將構成共聚物(此處為丙烯酸－馬來酸共聚物)之全部單體設為100莫耳%時氨之添加量為8.3莫耳%。 然後，在氮氣氣流下將反應容器內之溶液加熱至100℃後，在維持該溫度的同時，分別自另外的滴液漏斗用3.5小時滴加80質量%丙烯酸水溶液(日本觸媒公司製) 360.5 g及35質量%過氧化氫水溶液(三菱瓦斯化學公司製) 221.5 g，進行聚合反應。結束滴加後，在100℃(液溫)進行10小時熟化，結束聚合反應，得到丙烯酸－馬來酸共聚物。反應結束後，將反應容器內之溶液冷卻至約40℃，在保持約40℃之液溫的同時，滴加單乙醇胺(日本觸媒公司製) 211.2 g而進行中和，得到丙烯酸－馬來酸共聚物之鹽(聚合物組合物)(中和步驟2)。將構成共聚物(此處為丙烯酸－馬來酸共聚物)之全部單體設為100莫耳%時單乙醇胺之添加量為72莫耳%。聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.62。聚合物組合物之中和度為68.6莫耳%。此後，將含有40質量%所得聚合物組合物之水溶液設為分散劑組合物(實施例1)。實施例1之聚合物組合物不含有金屬(鹽)。實施例1之分散劑組合物之水溶液的25℃時的pH為6.0。此處，25℃時的pH係使用pH計(東亞電波工業株式會社，HM－30G)測定的值，為將pH計之電極浸漬至分散劑組合物中2分鐘後的數值。 (實施例2～15、比較例1～9) 除了將單體種類及單體組成比如表1所示地變更，將中和步驟1及中和步驟2中所用之中和劑的種類及其添加量如表1所示地變更以外，利用與實施例1相同的方法，製備出含有40質量%的具有表1所示之重量平均分子量及莫耳比(II)/(I)之聚合物組合物的分散劑組合物(實施例2～15、比較例1～9)。實施例2～15及比較例1～9之聚合物組合物不含有金屬(鹽)。 表1中，AA表示丙烯酸，MA表示馬來酸，MAA表示甲基丙烯酸(三菱人造絲公司製)，IA表示衣康酸(磐田化學工業公司製)，NH3 表示28質量%氨水溶液(Sigma Aldrich公司製)，MEA表示單乙醇胺(日本觸媒公司製)，DEA表示二乙醇胺(日本觸媒公司製)，TEA表示三乙醇胺(日本觸媒公司製)，TMAH表示25質量%四甲基氫氧化銨(昭和電工公司製)。 ［漿料組合物之製備］ 使用實施例1～15及比較例1～9之分散劑組合物，如下所述地製備漿料組合物，對所得漿料組合物之再分散性及分散性進行評價。 ［再分散性之評價］ ＜漿料乾燥物之擦拭試驗＞ 向50 mL樣品瓶中加入12 g平均粒徑200 nm之鈦酸鋇粉體(共立材料公司製BT－HP9DX)、添加量為1.0重量份(相對於鈦酸鋇粉體100重量份，以固體成分換算)之實施例1～15及比較例1～9之各分散劑組合物以及離子交換水，用Yamato科學公司製之超音波清洗器yamato1510進行分散處理(1小時)，製備出60質量%之粉體漿料(漿料組合物)。 將所製備之粉體漿料15 g均勻塗佈在縱10 cm、橫13 cm、深6 cm之不鏽鋼製的方平底盤(バット)上，在室溫下使之乾燥固結24小時，得到漿料乾燥物。其後，用浸入水之廚房紙巾擦拭漿料乾燥物，利用目視觀察自方平底盤上之除去程度。將結果表示於表1中。在表1中，將完全除去之(在方平底盤上利用目視看不到漿料乾燥物)情況表示為A，將未除去之(在方平底盤上利用目視看到漿料乾燥物)情況表示為B。在完全除去之情況下可評價為具有再分散性。 ＜漿料乾燥物之浸漬試驗＞ 使用實施例1～15及比較例1～9之各分散劑組合物，與該漿料乾燥物之擦拭試驗相同地製備出漿料乾燥物。此後，將所製備之粉體漿料15 g均勻塗佈在縱10cm、橫13cm、深6cm之不鏽鋼製的方平底盤上，在室溫下使之乾燥固結24小時，得到漿料乾燥物。然後，在加入1000 mL離子交換水之一次性燒杯中，沉入載放有漿料乾燥物之不鏽鋼製的方平底盤，使之浸漬30分鐘。其後，對向水側溶出之粉體漿料進行取樣，使用雷射散射型粒徑測定裝置(堀場製作所製，LA－920，折射率2.40)測定出平均粒徑。其中對於平均粒徑明顯大於1 mm之樣品，利用目視進行計測。平均粒徑越小，可評價為再分散性越優秀。 作為參考例1，使用比較例1之分散劑組合物，不使之乾燥地製備出60質量%之粉體漿料(漿料組合物)。亦即，向50 mL樣品瓶中加入12 g平均粒徑200 nm之鈦酸鋇粉體(共立材料製，BT－HP9DX)、添加量為1.0重量份(相對於鈦酸鋇粉體100重量份，以固體成分換算)之分散劑以及離子交換水，用Yamato科學公司製之超音波清洗器yamato1510進行分散處理(1小時)，製備出60質量%之粉體漿料(漿料組合物)，測定出該粉體漿料之平均粒徑。將結果表示於表1中。 ［分散性之評價］ 向500 mL一次性燒杯中加入117 g平均粒徑為200 nm之鈦酸鋇粉體(共立材料公司製，BT－HP9DX)、使添加量變為1.0重量份(相對於鈦酸鋇粉體100重量份，以固體成分換算)之實施例1～15及比較例1～9的各分散劑組合物以及離子交換水，用PRIMIX公司製之Homo Disper進行攪拌(2500 rpm×2分鐘)，製備出78質量%之粉體漿料(漿料組合物)。使用東機產業公司製之B型黏度測定裝置TVB－10以轉子之轉速60 rpm測定出所製備之粉體漿料的25℃時的黏度。將結果表示於表1中。黏度越小，可評價為分散性越優異。   [表1]

Figure 105141773-A0304-0001
*1：聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I) 如表1所示，使用實施例1～15之分散劑組合物製備的漿料組合物之乾燥物容易擦拭，而使用比較例1～9之分散劑組合物製備的漿料組合物之乾燥物極難擦拭。使用實施例1～15之分散劑組合物製備的漿料組合物之乾燥物的浸漬溶出物的粒徑小，為與參考例1之60質量%的粉體漿料大致同等的平均粒徑，而使用比較例1～9之分散劑組合物製備的漿料組合物之乾燥物的平均粒徑非常大，可看到粉體凝聚。此外，比較使用實施例1～15之分散劑組合物製備的漿料組合物以及使用比較例1、3～9之分散劑組合物製備的漿料組合物，其結果為，未看到分散效能之特別差異。 [產業上之可利用性] 若使用本發明之分散劑組合物，則可製造提高再分散性之漿料組合物。本發明之漿料組合物可適用於電子零件之製造。The present invention is based on the knowledge that all the carboxyl groups contained in the organic amine salt or quaternary ammonium salt of a copolymer containing a structural unit derived from (meth)acrylic acid and a structural unit derived from an unsaturated dibasic acid Among them, the ratio of carboxyl groups forming counterions with organic amines or quaternary ammonium is specified, thereby improving the redispersibility of the slurry composition. Although the reason why the redispersibility of the slurry composition can be improved is not certain, it can be considered as follows. That is, it can be considered that when the ammonium (NH 4 + ) salt of the copolymer is used as a dispersant, as the slurry composition dries, the ammonium (NH 4 + ) vaporizes and acts as a dispersant. The paste whose surface is hydrophobized and solidified on the powder acts, and the dried slurry residue becomes a hard lumpy and is fixed to the inner wall of a container or the like. On the other hand, it can be considered that when the organic amine salt or quaternary ammonium salt of the copolymer having a carboxyl group that forms a counterion with an organic amine or quaternary ammonium in a specific ratio is used as a dispersant, even the slurry composition Further drying, the organic amine or quaternary ammonium will not vaporize (or difficult to vaporize), so it will remain in the dispersant. From this, it can be considered that the dry matter of the slurry composition can be prevented from becoming hard lumps, and it can be prevented from being fixed to the inner wall of the container, etc., when water is added to the dry matter of the slurry composition, it will be dispersed again In the water. However, these are all speculations, and the present invention is not limited to these mechanisms. That is, one aspect of the present invention relates to a dispersant composition for powders (hereinafter also referred to as "the dispersant composition of the present invention"), the dispersant composition for powders contains a polymer composition, The polymer composition contains an organic amine salt or a quaternary ammonium salt comprising a copolymer of structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid, and the polymer composition contains The molar ratio (II)/(I) of all the carboxyl groups (I) to the carboxyl group (II) which forms a counter ion with an organic amine or quaternary ammonium is 0.33 or more. According to the dispersant composition of the present invention, the redispersibility of the slurry composition can be improved. Thereby, the dried substance of the slurry composition can be dispersed again in the water-based solvent, and therefore, the cleaning in the container, piping, etc. becomes easy. In addition, the dried substance of the slurry composition adhering to the inner wall of a container, a pipe, etc., is re-dispersed in an aqueous solvent, and it can be reused as a slurry composition. The "re-dispersibility of the slurry composition" in the present invention means that the dried product of the slurry composition will be dispersed in the aqueous solvent when it comes into contact with the aqueous solvent again. The re-dispersibility of the slurry composition can be measured by the method described in the following Examples. In the present invention, the material constituting the inner wall of the container, piping, etc. is not particularly limited. However, in one or more embodiments, a metal material may be used, and specifically, stainless steel may be used. (Dispersant composition) In one or more embodiments, the dispersant composition of the present invention contains an organic copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid. Amine salt or quaternary ammonium salt (hereinafter also referred to as "polymer composition"). In the present invention, the "polymer composition" in one or more embodiments is a copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid (hereinafter also referred to simply as "Copolymer") is a substance obtained by neutralizing at least a part of an organic amine or a quaternary ammonium (salt). In one or more embodiments, at least a part of the copolymer may also be neutralized with an organic amine or a neutralizing agent (ammonium (salt), etc.) other than quaternary ammonium. In one or more embodiments of the present invention, "organic amine or quaternary ammonium (salt)" means at least one selected from the group consisting of organic amine, organic amine salt, quaternary ammonium, and quaternary ammonium salt. In one or more embodiments of the present invention, "ammonium (salt)" means at least one of ammonium and ammonium salt. In one or more embodiments of the dispersant composition of the present invention, an aqueous solvent may be included. Examples of the water-based solvent include water such as ion-exchanged water and ultrapure water, or a mixed solvent of water and a water-soluble organic solvent (ethanol, ethylene glycol, etc.). In addition, in one or more embodiments of the dispersant composition of the present invention, in addition to the above-mentioned polymer composition and water-based solvent, optional components such as additives may also be included. As the form of the dispersant composition of the present invention, in one or more embodiments, a powder form or an aqueous solution can be mentioned. In one or more embodiments of the present invention, the dispersant composition may also be the polymer composition itself. The so-called "copolymer" in the present invention is a copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid. In one or more embodiments, other structural units may be included. . In one or more embodiments, the total amount of structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid among all structural units constituting the copolymer is preferably 70% by mass or more, and more It is preferably 85% by mass or more, and more preferably substantially 100% by mass. Examples of "other structural units" include α-olefins, sulfonic acid monomers, styrene, and allyl alcohol. As the "(meth)acrylic acid" of the present invention, in one or more embodiments, at least one selected from acrylic acid and methacrylic acid can be cited. The "unsaturated dibasic acid" in the present invention may include at least one selected from aliphatic unsaturated dibasic acids having 4 to 6 carbon atoms in one or more embodiments. As a specific unsaturated dibasic acid, in one or more embodiments, at least one selected from maleic anhydride, maleic acid, and itaconic acid can be cited. As the "organic amine" of the present invention, in one or more embodiments, a primary, secondary or tertiary alkylamine or alkanolamine can be mentioned. As organic amines, in one or more embodiments, amines selected from monoalkyl (alkyl groups with 1 to 3 carbon atoms), dialkyl (alkyl groups with 1 to 3 carbon atoms) amines, Trialkyl (the alkyl group has 1 to 3 carbon atoms) amines, monoalkanols (alkanols have 1 to 3 carbon atoms) amines, dialkanols (alkanols have 1 to 3 carbon atoms) amines, and three At least one of alkanol (alkanol having 1 to 3 carbon atoms) amine. As specific organic amines, in one or more embodiments, at least one selected from monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine, and tributylamine can be cited . As the "quaternary ammonium" of the present invention, in one or more embodiments, tetra-lower alkyl ammonium can be cited, but it is preferred that the quaternary ammonium does not contain metal. As a specific quaternary ammonium, in one or more embodiments, tetramethylammonium can be cited. In the dispersant composition of the present invention, the molar ratio (II)/(I) of all the carboxyl groups (I) contained in the polymer composition and the carboxyl groups (II) that form counterions with organic amines or quaternary ammonium ), in one or more embodiments, it is 0.33 or more. From the viewpoint of improving the redispersibility of the slurry composition, it is preferably 0.4 or more, more preferably 0.45 or more, and still more preferably 0.5 or more. In addition, for the molar ratio (II)/(I), in one or more embodiments, from the standpoint of the original performance as a dispersant, it is preferably 2.5 or less, more preferably 2.0 or less, and furthermore Preferably, it is 1.5 or less. Regarding the molar ratio (II)/(I), in one or more embodiments, from the viewpoint of the original performance as a dispersant, it is preferably 1.0 or less, more preferably 0.95 or less, and still more preferably Below 0.9. The term "all carboxyl groups" in the present invention refers to all carboxyl groups contained in all the constituent units constituting the copolymer or polymer composition, and also includes neutralized carboxyl groups and groups that become carboxyl groups after ring opening. The so-called "mole ratio (II)/(I)" in the present invention refers to the ratio of carboxyl groups that form counterions with organic amines or quaternary ammonium among all carboxyl groups contained in the copolymer. For the calculation method of "mole ratio (II)/(I)", for example, in the production of a salt (polymer composition) of a copolymer of acrylic acid and maleic acid (monomer composition ratio: AA/MA=83/17) When using monoethanolamine: 72 mol% (relative to all monomers in the copolymer) for neutralization, the number of carboxyl groups derived from acrylic acid is 83 relative to all monomers in the copolymer. Mole%, the number of carboxyl groups derived from maleic acid (dibasic acid) is 17 mol%×2=34 mol%, so the mol ratio (II)/(I)=72/(83+34)=0.62. The dispersant composition of the present invention may also contain at least one selected from the group consisting of organic amines and quaternary ammonium (hereinafter also referred to as "excess amine") that does not form a counter ion with the carboxyl group of the copolymer. When the dispersant composition of the present invention contains excess amine, the molar ratio of all carboxyl groups (I) contained in the polymer composition and the organic amine and quaternary ammonium (III) contained in the dispersant composition The ratio (III)/(I) is preferably 2.5 or less from the viewpoint of improving the redispersibility of the slurry composition, more preferably 2.0 or less, and still more preferably 1.5 or less. In the present invention, the "organic amine and quaternary ammonium contained in the dispersant composition" include organic amines and quaternary ammonium that form a counterion with the carboxyl group of the copolymer, and organic amines that do not form a counterion with the carboxyl group of the copolymer. Quaternary ammonium. In the dispersant composition of the present invention, for the degree of neutralization of the polymer composition, in one or more embodiments, from the viewpoint of improving the dispersing performance of the dispersant, it is compared with the degree of neutralization in the copolymer or polymer composition. All carboxyl groups contained are 100 mol%, preferably 40 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 95 mol% or less, and still more preferably 60 mol% or more and 90 mol% Mole% or less. Regarding the degree of neutralization of the polymer composition, in one or more embodiments, from the viewpoint of improving the dispersing performance of the dispersant, 100 mole% relative to all carboxyl groups contained in the copolymer or polymer composition , Preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, and from the same point of view, preferably 100 mol% or less, more preferably 95 mol% Mole% or less, more preferably 90 mole% or less. In the present invention, the "degree of neutralization" refers to the carboxyl groups neutralized by all the neutralizing agents used in the neutralization step among all the carboxyl groups (100 mol%) contained in the copolymer or polymer composition The ratio (mol%). In the present invention, the "degree of neutralization" is represented by [mole equivalent of neutralized carboxyl groups/mole equivalent of all neutralizable carboxyl groups]×100 (mole%). For the calculation method of the degree of neutralization, for example, when producing a salt (polymer composition) of a copolymer of acrylic acid and maleic acid (monomer composition ratio: AA/MA=83/17), ammonium salt: 8.3 Mo Ear% (relative to all monomers in the copolymer) and monoethanolamine: 72 mol% (relative to all monomers in the copolymer) in the case of neutralization, due to relative to all monomers in the copolymer In other words, the number of carboxyl groups derived from acrylic acid is 83 mol%, and the number of carboxyl groups derived from maleic acid (dibasic acid) is 17 mol%×2=34 mol%, so the degree of neutralization of the polymer composition = 100 mol%×(8.3+72)/(83+34)=68.6 mol%. Regarding the weight average molecular weight (Mw) of the polymer composition, in one or more embodiments, from the viewpoint of improving the redispersibility of the slurry composition and reducing the viscosity of the slurry composition, it is preferably 10,000 to 90000, more preferably 20,000-75,000, still more preferably 30,000-65,000. Regarding the weight average molecular weight (Mw) of the polymer composition, in one or more embodiments, from the viewpoint of improving the redispersibility of the slurry composition and reducing the viscosity of the slurry composition, it is preferably 10,000 or more , More preferably 20,000 or more, still more preferably 30,000 or more, and from the same viewpoint, it is preferably 90,000 or less, more preferably 75,000 or less, and still more preferably 65,000 or less. Here, the weight average molecular weight is a value measured by GPC (gel permeation chromatography), and the details of the measurement conditions are as shown in the examples. Regarding the molar ratio of the structural unit derived from (meth)acrylic acid to the structural unit derived from unsaturated dibasic acid in the polymer composition, in one or more embodiments, the self-improving slurry composition From the viewpoint of redispersibility and reduction of the viscosity of the slurry composition, it is preferably 50/50 to 95/5, more preferably 55/45 to 90/10, and still more preferably 60/40 to 85/15. When the form of the dispersant composition of the present invention is an aqueous solution, for the content of the polymer composition in the aqueous solution of the dispersant composition, in one or more embodiments, the re-dispersibility of the slurry composition is improved From the viewpoint of reducing the viscosity of the slurry composition, it is preferably 20-60% by mass, more preferably 25-50% by mass, and still more preferably 30-45% by mass. The content of the polymer composition in the dispersant composition of the present invention can be determined by, for example, the amount of raw materials charged, or it can also be determined by measuring the solid content in the dispersant composition of the present invention. When the form of the dispersant composition of the present invention is an aqueous solution, the pH of the aqueous solution of the dispersant composition is self-improving the redispersibility of the slurry composition and the difference in the powder composition in one or more embodiments. From the viewpoint of resistance to chemical decomposition, it is preferably 4.5 to 11.0, more preferably 5.0 to 10.0, and still more preferably 5.5 to 9.0. When the dispersant composition of the present invention is used for the dispersion of powders for electronic materials, it is preferable that the substance that forms a counter ion with the carboxyl group contained in the copolymer is not used in one or more embodiments. Contains metals (salts). That is, in one or more embodiments of the polymer composition of the present invention, it is preferable that no metal (salt) is contained. In one or more embodiments of the present invention, "metal (salt)" means at least one of a metal and a metal salt. [Method for manufacturing dispersant composition] The present invention, in another aspect, relates to a method for manufacturing the dispersant composition of the present invention (hereinafter also referred to as "the manufacturing method for the dispersant composition of the present invention") , Including the following neutralization step, that is, the copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid is mixed with organic amine or quaternary ammonium (salt) to make The molar ratio (II)/(I) of all the carboxyl groups (I) contained in the copolymer and the carboxyl groups (II) that form counterions with organic amines or quaternary ammonium is 0.33 or more, and the copolymer The polymer composition is obtained by neutralization with organic amine or quaternary ammonium (salt). According to the method for producing a dispersant composition of the present invention, a dispersant composition capable of improving the redispersibility of the slurry composition can be produced. In this neutralization step, an organic amine or a neutralizer (for example, ammonium (salt)) other than quaternary ammonium (salt) may be used in combination. The method for producing a copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid of the present invention is not particularly limited, but for example, it can be used to neutralize unsaturated dibasic acid After the agent is partially neutralized, it is obtained by polymerization reaction with (meth)acrylic acid. In the polymerization reaction, a known polymerization initiator, chain transfer agent, etc. can be used. As a polymerization initiator, hydrogen peroxide etc. are mentioned. As a chain transfer agent, isopropanol etc. are mentioned. As the neutralizing agent used in the partial neutralization, organic amines (salts) or ammonium (salts) can be used. Specifically, it can be selected from monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylene. At least one of triamine, triethylamine, tributylamine, tetramethylammonium hydroxide, triethylmethylammonium hydroxide, and aqueous ammonia solution. [Dispersion method] As another aspect of the present invention, a dispersion method (hereinafter also referred to as the "dispersion method of the present invention") including the step of dispersing powder in an aqueous solvent using the dispersant composition of the present invention can be provided. According to the dispersion method of the present invention, a slurry composition with improved powder redispersibility can be produced. As a powder dispersed in an aqueous solvent by the dispersion method of the present invention, in one or more embodiments, powders for electronic materials can be cited, specifically, selected from carbonates, phosphates, and titanium At least one of titanate, silicate, zinc oxide, iron oxide, titanium oxide, aluminum oxide (alumina), silicon dioxide (silica), magnesium oxide, zirconium oxide, cerium oxide, carbon black, and silicon carbide 1 kind. The powder for electronic materials can be used in electronic parts such as IC packages, wiring boards, insulators, sensors, electrodes, magnetic bodies, semiconductors, capacitors, and optical fibers, for example. As the water-based solvent used in the dispersion method of the present invention, in one or more embodiments, water, or a mixed solution of water and a water-soluble organic solvent such as ethanol and ethylene glycol, is preferably water. As water, distilled water, ion-exchange water, ultrapure water, etc. are mentioned, for example. [Slurry composition] As another aspect of the present invention, it is possible to provide a slurry composition (hereinafter also referred to as "the slurry composition of the present invention"), the slurry composition containing a combination of an aqueous solvent, a powder, and a dispersant The dispersant composition is the dispersant composition of the present invention. According to the slurry composition of the present invention, the redispersibility can be improved. As the powder and water-based solvent used in the slurry composition of the present invention, the same ones as the above-mentioned dispersion method of the present invention can be used. The content (solid content) of the powder in the slurry composition of the present invention is not specifically defined. However, in one or more embodiments, from the viewpoint of improving drying efficiency and productivity, it is preferably 50% by mass or more, more preferably It is 55% by mass or more, more preferably 60% by mass or more. On the other hand, the content (solid content) of the powder is preferably 85% by mass or less, more preferably 80% by mass or less from the viewpoint of fluidity in one or more embodiments. Regarding the content of the dispersant composition in the slurry composition of the present invention, in one or more embodiments, from the viewpoint of reducing the viscosity of the slurry composition, in terms of solid content, relative to 100 parts by weight of the powder, It is preferably 0.3 to 5.0 parts by weight, more preferably 0.4 to 4.0 parts by weight, and still more preferably 0.5 to 3.0 parts by weight. Regarding the content of the dispersant composition, in one or more embodiments, from the viewpoint of reducing the viscosity of the slurry composition, in terms of solid content, it is preferably 0.3 parts by weight or more relative to 100 parts by weight of the powder , More preferably 0.4 parts by weight or more, still more preferably 0.5 parts by weight or more, and from the same viewpoint, preferably 5.0 parts by weight or less, more preferably 4.0 parts by weight or less, and still more preferably 3.0 parts by weight or less . [Method for manufacturing slurry composition] As another aspect of the present invention, a method for manufacturing a slurry composition (hereinafter also referred to as "the manufacturing method of the slurry composition of the present invention") can be provided. The production method includes a step of mixing the powder, the dispersant composition of the present invention, and an aqueous solvent, and dispersing the powder. According to the present invention, a slurry composition with improved redispersibility can be produced. As the powder and water-based solvent used in the manufacturing method of the slurry composition of the present invention, the same ones as in the dispersion method of the present invention can be used. In the method for producing the slurry composition of the present invention, a method of mixing the powder and the dispersant composition so as to achieve the content of the slurry composition of the present invention can be mentioned. The present invention also relates to one or more of the following embodiments. <1> A dispersant composition for powder comprising a polymer composition containing a copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid Organic amine salt or quaternary ammonium salt, the molar ratio (II)/( of all the carboxyl groups (I) contained in the polymer composition to the carboxyl group (II) that forms a counterion with the organic amine or quaternary ammonium I) is 0.33 or more. <2> The dispersant composition for powders according to <1>, wherein the molar ratio (II)/(I) is preferably 0.4 or more, more preferably 0.45 or more, and still more preferably 0.5 or more. <3> The dispersant composition for powders according to <1> or <2>, wherein the molar ratio (II)/(I) is preferably 2.5 or less, more preferably 2.0 or less, and still more preferably 1.5 or less, or preferably 1.0 or less, more preferably 0.95 or less, and still more preferably 0.9 or less. <4> The dispersant composition for powder according to any one of <1> to <3>, wherein the powder is a powder for electronic materials. <5> The powder dispersant composition according to any one of <1> to <4>, wherein the degree of neutralization of the polymer composition is relative to all carboxyl groups contained in the copolymer or polymer composition 100 mol%, preferably 40 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 95 mol% or less, still more preferably 60 mol% or more and 90 mol% or less . <6> The dispersant composition for powders according to any one of <1> to <5>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 10,000 to 90,000, more preferably 20,000 to 75,000, more preferably 30,000-65,000. <7> The dispersant composition for powders according to any one of <1> to <6>, wherein the organic amine or quaternary ammonium is selected from monoethanolamine, diethanolamine, triethanolamine, and tetramethylammonium At least one of them. <8> The dispersant composition for powders according to any one of <1> to <7>, wherein the constituent unit derived from (meth)acrylic acid and the constituent unit derived from unsaturated dibasic acid are moly The ear ratio is preferably 50/50 to 95/5, more preferably 55/45 to 90/10, and still more preferably 60/40 to 85/15. <9> The dispersant composition for powders according to any one of <1> to <8>, wherein the unsaturated dibasic acid is at least 1 selected from maleic anhydride, maleic acid, and itaconic acid Kind. <10> The dispersant composition for powders according to any one of <1> to <9>, wherein all the structural units constituting the copolymer are derived from (meth)acrylic acid and are derived from unsaturated The total amount of the constituent units of the dibasic acid is preferably 70% by mass or more, more preferably 85% by mass or more, and still more preferably substantially 100% by mass. <11> The dispersant composition for powders according to any one of <1> to <10>, wherein the dispersant composition for powders is in the form of an aqueous solution, and the dispersant composition for powders polymerizes in the aqueous solution The content of the composition is preferably 20-60% by mass, more preferably 25-50% by mass, and still more preferably 30-45% by mass. <12> The dispersant composition for powders according to any one of <1> to <11>, wherein the form of the dispersant composition for powders is an aqueous solution, and the pH of the aqueous solution of the dispersant composition for powders It is preferably from 4.5 to 11.0, more preferably from 5.0 to 10.0, and even more preferably from 5.5 to 9.0. <13> The dispersant composition for powder according to any one of <1> to <12>, wherein the substance that forms a counter ion with the carboxyl group contained in the copolymer does not contain a metal (salt). <14> The dispersant composition for powders according to any one of <1> to <13>, wherein the degree of neutralization of the polymer composition is relative to all carboxyl groups contained in the copolymer or polymer composition 100 mol%, preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 60 mol% or more. <15> The powder dispersant composition according to any one of <1> to <14>, wherein the degree of neutralization of the polymer composition is relative to all the carboxyl groups contained in the copolymer or polymer composition 100 mol%, preferably 100 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less. <16> The dispersant composition for powders according to any one of <1> to <15>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 10,000 or more, more preferably 20,000 or more, More preferably, it is 30,000 or more. <17> The dispersant composition for powders according to any one of <1> to <16>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 90,000 or less, more preferably 75,000 or less, More preferably, it is 65,000 or less. <18> A method for producing a dispersant composition for powders, which includes a neutralization step, that is, copolymerization of a structural unit derived from (meth)acrylic acid and a structural unit derived from unsaturated dibasic acid The compound is mixed with organic amine or quaternary ammonium (salt) so that the molar ratio (II) of all the carboxyl groups (I) contained in the copolymer and the carboxyl group (II) that forms a counterion with the organic amine or quaternary ammonium (salt) When )/(I) is 0.33 or more, the copolymer is neutralized with an organic amine or quaternary ammonium (salt) to obtain a polymer composition. <19> A dispersion method comprising the step of dispersing powder in an aqueous solvent using the powder dispersant composition described in any one of <1> to <17>. <20> A method for producing a slurry composition, comprising the steps of mixing the dispersant composition for powder as described in any one of <1> to <17>, a powder, and an aqueous solvent, and dispersing the powder . <21> A slurry composition containing the dispersant composition for powder as described in any one of <1> to <17>, a powder, and an aqueous solvent. <22> The slurry composition according to <21>, wherein the content (solid content) of the powder in the slurry composition is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more, more preferably 85% by mass or less, more preferably 80% by mass or less. <23> According to the slurry composition described in <21> or <22>, the content of the dispersant composition for powder is calculated as solid content, and is preferably 0.3 to 5.0 parts by weight relative to 100 parts by weight of the powder Parts, more preferably 0.4 to 4.0 parts by weight, still more preferably 0.5 to 3.0 parts by weight. <24> The slurry composition according to any one of <21> to <23>, wherein the content of the dispersant composition for powder is calculated as solid content, and is preferably 0.3 relative to 100 parts by weight of the powder Part by weight or more, more preferably 0.4 part by weight or more, still more preferably 0.5 part by weight or more. <25> The slurry composition according to any one of <21> to <24>, wherein the content of the dispersant composition for powder is calculated as solid content, and is preferably 5.0 with respect to 100 parts by weight of the powder Parts by weight or less, more preferably 4.0 parts by weight or less, and still more preferably 3.0 parts by weight or less. [Examples] Hereinafter, the present invention will be described in more detail by using examples. However, these examples are exemplary, and the present invention is not limited by these examples. In the following Examples and Comparative Examples, the weight average molecular weight of the salt of the polymer in the dispersant is measured by GPC (Gel Permeation Chromatography). The specific conditions are as follows. <Method for measuring the weight average molecular weight of the polymer composition> The weight average molecular weight of the polymer composition is measured by GPC (gel permeation chromatography) under the following conditions. [Measurement conditions] Chromatography column: TSK PWXL＋G4000PWXL＋G2500PWXL (all manufactured by Tosoh) Column temperature: 40℃ Detector: RI or UV (210 nm) Eluent: 0.2 mol/L phosphate buffer/acetonitrile (9/1 ) Flow rate: 1.0 mL/min Injection volume: 0.1 mL Standard: polyethylene glycol [Preparation of dispersant composition (Examples 1-15, Comparative Examples 1-9)] As described later, the following Table 1 was prepared The dispersant composition shown (Examples 1-15, Comparative Examples 1-9). (Example 1) Into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a nitrogen introduction tube, and a dropping funnel, 78.5 g of maleic anhydride (manufactured by Mitsubishi Chemical Corporation) and 80.0 g of ion-exchange water were put in, and heated to 55°C After (liquid temperature), 24.3 g of a 28% by mass ammonia aqueous solution (manufactured by Sigma Aldrich, chemically pure) was added dropwise to prepare an ammonium maleate aqueous solution (neutralization step 1). When all the monomers constituting the copolymer (herein, the acrylic acid-maleic acid copolymer) are set to 100 mol%, the amount of ammonia added is 8.3 mol%. Then, after heating the solution in the reaction vessel to 100°C under a nitrogen stream, while maintaining the temperature, an 80% by mass acrylic acid aqueous solution (manufactured by Nippon Shokubai Co., Ltd.) was added dropwise over 3.5 hours from another dropping funnel. 360.5 g and 221.5 g of a 35 mass% hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and polymerized. After the dripping was completed, maturation was performed at 100°C (liquid temperature) for 10 hours, the polymerization reaction was terminated, and an acrylic acid-maleic acid copolymer was obtained. After the reaction, the solution in the reaction vessel was cooled to about 40°C, and 211.2 g of monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) was added dropwise while maintaining a liquid temperature of about 40°C for neutralization, and acrylic acid-maleic acid was obtained. Salt of acid copolymer (polymer composition) (neutralization step 2). When all the monomers constituting the copolymer (herein, the acrylic acid-maleic acid copolymer) are set to 100 mol%, the addition amount of monoethanolamine is 72 mol%. The molar ratio (II)/(I) of all the carboxyl groups (I) contained in the polymer composition to the carboxyl groups (II) that form a counterion with the organic amine or quaternary ammonium is 0.62. The degree of neutralization of the polymer composition was 68.6 mol%. Thereafter, an aqueous solution containing 40% by mass of the obtained polymer composition was used as a dispersant composition (Example 1). The polymer composition of Example 1 does not contain metal (salt). The pH of the aqueous solution of the dispersant composition of Example 1 at 25°C was 6.0. Here, the pH at 25° C. is a value measured with a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is a value after immersing the electrode of the pH meter in the dispersant composition for 2 minutes. (Examples 2-15, Comparative Examples 1-9) In addition to changing the monomer types and monomer composition ratios as shown in Table 1, the types and types of neutralizing agents used in neutralization step 1 and neutralization step 2 were changed. Except that the addition amount was changed as shown in Table 1, the same method as in Example 1 was used to prepare a polymer containing 40% by mass and having the weight average molecular weight and molar ratio (II)/(I) shown in Table 1. The dispersant composition of the composition (Examples 2-15, Comparative Examples 1-9). The polymer compositions of Examples 2 to 15 and Comparative Examples 1 to 9 do not contain metals (salts). In Table 1, AA means acrylic acid, MA means maleic acid, MAA means methacrylic acid (manufactured by Mitsubishi Rayon Corporation), IA means itaconic acid (manufactured by Iwata Chemical Co., Ltd.), and NH 3 means 28% by mass ammonia solution (Sigma Aldrich Corporation), MEA means monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.), DEA stands for diethanolamine (manufactured by Nippon Shokubai Co., Ltd.), TEA stands for triethanolamine (manufactured by Nippon Shokubai Co., Ltd.), and TMAH represents 25% by mass of tetramethylhydrogen Ammonium oxide (manufactured by Showa Denko Corporation). [Preparation of slurry composition] Using the dispersant compositions of Examples 1-15 and Comparative Examples 1-9, slurry compositions were prepared as follows, and the redispersibility and dispersibility of the obtained slurry compositions were measured Evaluation. [Evaluation of redispersibility] <Wipe test of dried slurry> Add 12 g of barium titanate powder (BT-HP9DX manufactured by Kyoritsu Materials Co., Ltd.) with an average particle size of 200 nm to a 50 mL sample bottle, and the addition amount is 1.0 Parts by weight (relative to 100 parts by weight of barium titanate powder, calculated as solid content) of the dispersant compositions of Examples 1-15 and Comparative Examples 1-9 and ion-exchanged water, using ultrasonic waves manufactured by Yamato Science Co., Ltd. The washer yamato 1510 was subjected to dispersion treatment (1 hour) to prepare a 60% by mass powder slurry (slurry composition). Coat 15 g of the prepared powder slurry uniformly on a stainless steel box with a length of 10 cm, a width of 13 cm, and a depth of 6 cm, and dry and solidify it at room temperature for 24 hours to obtain Dry slurry. After that, wipe the dried slurry with a kitchen paper towel soaked in water, and visually observe the degree of removal from the flat bottom plate. The results are shown in Table 1. In Table 1, the completely removed (the dry matter of the slurry can not be seen visually on the square flat tray) is denoted as A, and the situation that is not removed (the dry matter of the slurry can be visually seen on the square flat bottom plate) is denoted as A Denoted as B. In the case of complete removal, it can be evaluated as having redispersibility. <Immersion test of dried slurry> Using the dispersant compositions of Examples 1 to 15 and Comparative Examples 1 to 9, the dried slurry was prepared in the same manner as the wiping test of the dried slurry. After that, 15 g of the prepared powder slurry was uniformly coated on a stainless steel square plate with a length of 10 cm, a width of 13 cm, and a depth of 6 cm, and dried and solidified at room temperature for 24 hours to obtain a dried slurry . Then, in a disposable beaker containing 1000 mL of ion-exchanged water, sink into a stainless steel box containing the dried slurry, and immerse it for 30 minutes. After that, the powder slurry eluted to the water side was sampled, and the average particle size was measured using a laser scattering type particle size measuring device (manufactured by Horiba, LA-920, refractive index 2.40). Among them, for samples with an average particle size significantly greater than 1 mm, the measurement is performed visually. The smaller the average particle size, the better the redispersibility can be evaluated. As Reference Example 1, the dispersant composition of Comparative Example 1 was used, and a 60% by mass powder slurry (slurry composition) was prepared without drying it. That is, 12 g of barium titanate powder (manufactured by Kyoritsu Materials, BT-HP9DX) with an average particle diameter of 200 nm was added to a 50 mL sample bottle, and the addition amount was 1.0 parts by weight (relative to 100 parts by weight of barium titanate powder). , In terms of solid content) dispersant and ion-exchanged water were dispersed (1 hour) with the ultrasonic cleaner Yamato 1510 manufactured by Yamato Science Co., to prepare a 60% by mass powder slurry (slurry composition), The average particle size of the powder slurry was measured. The results are shown in Table 1. [Evaluation of Dispersibility] Add 117 g of barium titanate powder (manufactured by Kyoritsu Materials Co., Ltd., BT-HP9DX) with an average particle diameter of 200 nm to a 500 mL disposable beaker, and make the addition amount 1.0 part by weight (relative to titanium 100 parts by weight of barium acid powder, in terms of solid content) The dispersant compositions of Examples 1-15 and Comparative Examples 1-9 and ion-exchanged water were stirred with Homo Disper manufactured by PRIMIX (2500 rpm×2) Minutes) to prepare a 78% by mass powder slurry (slurry composition). The viscosity of the prepared powder slurry at 25°C was measured using a B-type viscosity measuring device TVB-10 manufactured by Toki Sangyo Co., Ltd. at a rotor speed of 60 rpm. The results are shown in Table 1. The smaller the viscosity, the better the dispersibility can be evaluated. [Table 1]
Figure 105141773-A0304-0001
 *1: The molar ratio (II)/(I) of all the carboxyl groups (I) contained in the polymer composition and the carboxyl groups (II) that form counterions with organic amines or quaternary ammonium is shown in Table 1. The dry matter of the slurry composition prepared using the dispersant composition of Examples 1-15 is easy to wipe, while the dry matter of the slurry composition prepared using the dispersant composition of Comparative Examples 1-9 is extremely difficult to wipe. The particle size of the impregnated eluate of the dried product of the slurry composition prepared using the dispersant composition of Examples 1 to 15 is small, which is approximately the same average particle size as the 60% by mass powder slurry of Reference Example 1. On the other hand, the average particle size of the dried product of the slurry composition prepared using the dispersant composition of Comparative Examples 1 to 9 was very large, and powder aggregation was observed. In addition, comparing the slurry compositions prepared using the dispersant compositions of Examples 1-15 and the slurry compositions prepared using the dispersant compositions of Comparative Examples 1, 3-9, the result is that no dispersion efficiency is seen The special difference. [Industrial Applicability] If the dispersant composition of the present invention is used, a slurry composition with improved redispersibility can be produced. The slurry composition of the present invention can be applied to the manufacture of electronic parts.

Claims (15)

一種粉體用分散劑組合物，其含有聚合物組合物，該聚合物組合物含有包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物的有機胺鹽或四級銨鹽，該聚合物組合物中所含之全部羧基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上，該不飽和二元酸為選自馬來酸酐、馬來酸及衣康酸中之至少1種，該有機胺為選自單乙醇胺、二乙醇胺以及三乙醇胺中之至少1種，該四級銨為四甲基銨，該粉體用分散劑組合物之形態為水溶液，該粉體用分散劑組合物之水溶液中，該聚合物組合物之含量為20~60質量%。 A dispersant composition for powder comprising a polymer composition containing an organic amine containing a copolymer of structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid Salt or quaternary ammonium salt, the molar ratio (II)/(I) of all the carboxyl groups (I) contained in the polymer composition and the carboxyl group (II) that forms a counterion with the organic amine or quaternary ammonium is 0.33 or more, the unsaturated dibasic acid is at least one selected from maleic anhydride, maleic acid and itaconic acid, and the organic amine is at least one selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine, the The quaternary ammonium is tetramethylammonium, the dispersant composition for powders is in the form of an aqueous solution, and the content of the polymer composition in the aqueous solution of the dispersant composition for powders is 20-60% by mass. 如請求項1之粉體用分散劑組合物，其中，該莫耳比(II)/(I)為0.4以上。 The dispersant composition for powder of claim 1, wherein the molar ratio (II)/(I) is 0.4 or more. 如請求項1之粉體用分散劑組合物，其中，該莫耳比(II)/(I)為1.0以下。 The dispersant composition for powders of claim 1, wherein the molar ratio (II)/(I) is 1.0 or less. 如請求項1之粉體用分散劑組合物，其中，粉體為電子材料用粉體。 The dispersant composition for powder according to claim 1, wherein the powder is a powder for electronic materials. 如請求項1之粉體用分散劑組合物，其中，該聚合物組合物之中和度相對於該共聚物或該聚合物組合物中所含之全部羧基100莫耳%為40莫耳%以上且100莫耳%以下。 The dispersant composition for powder of claim 1, wherein the degree of neutralization of the polymer composition is 40 mol% relative to 100 mol% of all carboxyl groups contained in the copolymer or the polymer composition Above and below 100 mol%. 如請求項1之粉體用分散劑組合物，其中，該聚合物組合物之重量平均分子量，亦即Mw為10000以上且90000以下。 The powder dispersant composition of claim 1, wherein the weight average molecular weight of the polymer composition, that is, Mw, is 10,000 or more and 90,000 or less. 如請求項1之粉體用分散劑組合物，其中，該來自於(甲基)丙烯酸之構成單元與該來自於不飽和二元酸之構成單元的莫耳比為50/50~95/5。 The dispersant composition for powder of claim 1, wherein the molar ratio of the structural unit derived from (meth)acrylic acid to the structural unit derived from unsaturated dibasic acid is 50/50 to 95/5 . 如請求項1之粉體用分散劑組合物，其中，構成該共聚物之全部構成單元中來自於(甲基)丙烯酸之構成單元與來自於不飽和二元酸之構成單元的合計量為70質量%以上。 The dispersant composition for powders of claim 1, wherein the total amount of structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid among all structural units constituting the copolymer is 70 Above mass%. 如請求項1至8中任一項之粉體用分散劑組合物，其中，與該共聚物中所含之羧基形成抗衡離子的物質不包含金屬(鹽)。 The dispersant composition for powder according to any one of claims 1 to 8, wherein the substance that forms a counter ion with the carboxyl group contained in the copolymer does not contain a metal (salt). 一種粉體用分散劑組合物的製造方法，其包括如下中和步驟，亦即，將包含來自於(甲基)丙烯酸之構成單元及來自於不飽和二元酸之構成單元的共聚物與有機胺或四級銨(鹽)混合，以使該共聚物中所含之全部羧 基(I)與其中與有機胺或四級銨形成抗衡離子之羧基(II)的莫耳比(II)/(I)為0.33以上的方式，將該共聚物用有機胺或四級銨(鹽)中和而得到聚合物組合物，該不飽和二元酸為選自馬來酸酐、馬來酸及衣康酸中之至少1種，該有機胺為選自單乙醇胺、二乙醇胺以及三乙醇胺中之至少1種，該四級銨為四甲基銨，該粉體用分散劑組合物之形態為水溶液，該粉體用分散劑組合物之水溶液中，該聚合物組合物之含量為20~60質量%。 A method for producing a dispersant composition for powders, which includes the following neutralization step, that is, a copolymer containing structural units derived from (meth)acrylic acid and structural units derived from unsaturated dibasic acid and organic Amine or quaternary ammonium (salt) is mixed so that all the carboxylic acids contained in the copolymer The molar ratio (II)/(I) between the group (I) and the carboxyl group (II) which forms a counterion with an organic amine or quaternary ammonium is 0.33 or more, and the copolymer uses an organic amine or quaternary ammonium ( Salt) neutralized to obtain a polymer composition, the unsaturated dibasic acid is at least one selected from maleic anhydride, maleic acid and itaconic acid, and the organic amine is selected from monoethanolamine, diethanolamine and triethanolamine. At least one of ethanolamine, the quaternary ammonium is tetramethylammonium, the dispersant composition for powders is in the form of an aqueous solution, and the content of the polymer composition in the aqueous solution of the dispersant composition for powders is 20-60% by mass. 一種分散方法，其包括使用如請求項1至9中任一項之粉體用分散劑組合物使粉體分散於水系溶劑中之步驟。 A dispersion method comprising the step of dispersing powder in an aqueous solvent using the powder dispersant composition according to any one of claims 1 to 9. 一種漿料組合物之製造方法，其包括將如請求項1至9中任一項之粉體用分散劑組合物、粉體以及水系溶劑混合且使該粉體分散之步驟。 A method for producing a slurry composition, which includes the steps of mixing the dispersant composition for powder as claimed in any one of claims 1 to 9, a powder, and an aqueous solvent, and dispersing the powder. 一種漿料組合物，其包括如請求項1至9中任一項之粉體用分散劑組合物、粉體以及水系溶劑。 A slurry composition comprising the dispersant composition for powder as claimed in any one of claims 1 to 9, powder and an aqueous solvent. 如請求項13之漿料組合物，其中，漿料組合物中粉體之含量，亦即固體成分之含量為50質量%以上且85質量%以下。 The slurry composition of claim 13, wherein the content of the powder in the slurry composition, that is, the content of the solid content is 50% by mass or more and 85% by mass or less. 如請求項13之漿料組合物，其中，粉體用分散劑組合物之含量以固體成分換算相對於粉體100重量份為0.3~5.0重量份。 The slurry composition of claim 13, wherein the content of the dispersant composition for powder is 0.3 to 5.0 parts by weight in terms of solid content relative to 100 parts by weight of the powder.
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