KR20170072813A - Dispersant composition for powder - Google Patents

Abstract

[PROBLEMS] In one aspect, a dispersant composition capable of improving the redispersibility of a slurry composition is provided.
(Solution) In an embodiment, a polymer composition comprising a copolymer of a structural unit derived from a (meth) acrylic acid and a structural unit derived from an unsaturated dibasic acid, or a quaternary ammonium salt, Wherein the molar ratio (II) / (I) of the total carboxyl group (I) contained therein and the organic amine or quaternary ammonium and the carboxyl group (II) forming the counter ion therein is 0.33 or more.

Description

DISPERSANT COMPOSITION FOR POWDER [0002]

This disclosure relates to a dispersant composition for powder, a dispersing method, a method for producing a slurry composition, and a slurry composition.

In the production of electronic components such as multilayer ceramic capacitors, a slurry of powder for electronic materials is used. For example, a slurry composition of a dielectric ceramic powder is used as a material for forming a dielectric ceramic layer of a multilayer ceramic capacitor. There has been a demand for a slurry composition that has improved handling properties in conjunction with high performance and miniaturization of electronic devices such as mobile phones and electronic components thereof. For example, in order to miniaturize a multilayer ceramic capacitor, it is required to make a dielectric ceramic layer thinner, and a slurry composition of a dielectric ceramic powder having improved dispersibility and workability is desired.

As a powder dispersant, a polycarboxylic acid-based (co) polymer may be mentioned. Among them, as a dispersant for improving the dispersibility and workability by reducing the viscosity of the slurry composition of the powder, a pigment dispersant comprising a neutralization product of a (co) polymer having an?,? -Unsaturated carboxylic acid as a constitutional unit, (Meth) acrylic acid-unsaturated dibasic acid copolymer having a weight-average molecular weight of from 10,000 to 800,000 (for example, Patent Documents 1 to 3).

In addition, in the ceramics for members for electromagnetic and optics, harmful to the electromagnetic characteristics occurs when metal ions such as Na, K, Mg are mixed. Therefore, a drug which does not contain a metal ion is used as the medicine used for these, For example, ammonium salts have been used as dispersants (for example, Patent Documents 4 to 6).

Japanese Laid-Open Patent Publication No. 7-308563 Japanese Patent Application Laid-Open No. 10-110015 Japanese Patent Application Laid-Open No. 11-217534 Japanese Patent Application Laid-Open No. 2004-123903 Japanese Patent Application Laid-Open No. 2005-288294 Japanese Patent Application Laid-Open No. 2005-290125

However, a slurry composition obtained by dispersing a powder in an aqueous solvent using a conventional dispersant composition is not sufficient in redispersibility after drying. For example, if the slurry composition is allowed to remain attached to the inner wall of a vessel, a pipe or the like, the slurry composition will become firmly adhered to the inner wall with a lapse of time, resulting in a strong water- There is a problem that it is difficult to re-disperse the powder (dried material)

Thus, the disclosure provides, in one aspect, a dispersant composition that can improve the redispersibility of the slurry composition.

The present disclosure relates in one aspect to a composition comprising a polymer composition comprising an organic amine salt or a quaternary ammonium salt of a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid, (II) / (I) of an organic amine or quaternary ammonium and a carboxyl group (II) forming a counter ion among the total carboxyl group (I) contained in the dispersing agent composition is 0.33 or more.

The present disclosure relates to a process for producing a copolymer containing, in another embodiment, a copolymer comprising a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid and an organic amine or a quaternary ammonium (salt) Wherein the molar ratio (II) / (I) of the total carboxyl group (I) and the carboxyl group (II) forming the counter ion from the organic amine or quaternary ammonium among them is 0.33 or more. And a neutralization step of neutralizing with ammonium (salt) to obtain a polymer composition.

The present disclosure relates in another aspect to a dispersing process comprising the step of dispersing a powder in an aqueous solvent using the dispersant composition of the present disclosure.

The present disclosure also relates to a method of making a slurry composition, which further comprises, in another aspect, mixing the dispersant composition, powder, and aqueous solvent associated with the present disclosure and dispersing the powder.

The present disclosure further relates to a slurry composition containing the dispersant composition, powder, and aqueous solvent of the present disclosure in another aspect.

According to the present disclosure, it is possible to provide a powder dispersant composition capable of improving redispersibility of a slurry composition in one or more embodiments.

The present disclosure relates to an organic amine salt or a quaternary ammonium salt of a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid, with an organic amine or quaternary ammonium among the entire carboxyl groups contained in the quaternary ammonium salt, Based on the knowledge that the redispersibility of the slurry composition can be improved by specifying the ratio of carboxyl groups forming ions.

The reason why the redispersibility of the slurry composition can be improved is not clear, but is considered as follows. That is, when the ammonium (NH4 ⁺ ) salt of the copolymer is used as a dispersant, ammonium (NH4 ⁺ ) is vaporized as the slurry composition is dried, and the surface of the dispersant becomes hydrophobic and acts as a glue , And the dried slurry residue is considered to be fixed to the inner wall of the vessel or the like as a hard bulk material. On the other hand, when an organic amine salt or a quaternary ammonium salt of the above copolymer having a carboxyl group forming a counter ion with an organic amine or quaternary ammonium is used as a dispersant, even if the slurry composition is dried, Quaternary ammonium is believed to remain in the dispersant since it is not vaporized (or is not well vaporized). Therefore, it is considered that the dried product of the slurry composition is inhibited from becoming a hard mass, and adhesion of the slurry composition to the inner wall is suppressed, and water is added to the dried product of the slurry composition. However, these are estimates, and the present disclosure is not limited to these mechanisms.

That is, the present disclosure relates to a dispersant composition for powder (hereinafter also referred to as " dispersant composition related to the present disclosure ") in one aspect, which contains a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid (I) contained in the polymer composition and a carboxyl group (II) forming a counter ion with an organic amine or quaternary ammonium among the total carboxyl group (I) contained in the polymer composition, and a polymer composition comprising an organic amine salt of a copolymer or a quaternary ammonium salt. (II) / (I) of 0.33 or more. The dispersant composition according to the present disclosure can improve the redispersibility of the slurry composition. As a result, the dried product of the slurry composition can be dispersed again in the aqueous solvent, thus facilitating cleaning in the vessel, piping, and the like. In addition, a dried product of the slurry composition attached to the inner wall of a vessel, a pipe or the like is dispersed again in an aqueous solvent, and can be reused as a slurry composition.

The term "redispersibility of the slurry composition" in the present disclosure means that the dried product of the slurry composition is dispersed in the aqueous solvent when it is newly brought into contact with the aqueous solvent. The redispersibility of the slurry composition can be measured by the method described in the following Examples.

In the present disclosure, the material constituting the inner wall of a container, a pipe or the like is not particularly limited, but in one or a plurality of embodiments, a metal material can be exemplified, and more specifically, stainless steel can be mentioned.

(Dispersant composition)

In one or more embodiments, the dispersant composition related to the present disclosure may be an organic amine salt or a quaternary ammonium salt of a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid (hereinafter, Quot; polymer composition "). In the present disclosure, the " polymer composition " includes, in one or more embodiments, a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid (hereinafter simply referred to as " Is neutralized by an organic amine or quaternary ammonium (salt). In one or more embodiments, at least a portion of the copolymer may be neutralized with an organic amine or a neutralizing agent other than quaternary ammonium (such as ammonium (salt)). In the present disclosure, the term "organic amine or quaternary ammonium salt" means, in one or more embodiments, at least one kind selected from organic amines, organic amine salts, quaternary ammonium, and quaternary ammonium salts . In the present disclosure, " ammonium (salt) " represents at least one of ammonium and ammonium salts in one or more embodiments.

The dispersant compositions in accordance with the present disclosure may, in one or more embodiments, comprise an aqueous solvent. Examples of the aqueous solvent include water such as ion-exchanged water and ultrapure water, or a mixed solvent of water and a water-soluble organic solvent (such as ethyl alcohol or ethylene glycol). The dispersant composition according to the present disclosure may contain, in one or more embodiments, an optional component such as an additive, in addition to the above-mentioned polymer composition and the aqueous solvent.

In the form of the dispersant composition related to this disclosure, in one or more embodiments, a powdery or aqueous solution can be mentioned. The dispersant composition related to this disclosure may be, in one or more embodiments, the polymer composition itself.

The term "copolymer" in the present disclosure means a resin containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid, and may contain other constituent units in one or more embodiments . In one or more embodiments, the total amount of constituent units derived from (meth) acrylic acid and constituent units derived from unsaturated dibasic acid in the total constituent units constituting the copolymer is preferably 70% by mass or more, more preferably 70% Is 85% by mass or more, and more preferably substantially 100% by mass. Examples of the "other structural units" include? -Olefins, sulfonic acid monomers, styrene, allyl alcohol, and the like.

The "(meth) acrylic acid" in the present disclosure includes at least one member selected from the group consisting of acrylic acid and methacrylic acid in one or more embodiments.

The "unsaturated dibasic acid" in the present disclosure includes, in one or more embodiments, at least one selected from the group consisting of aliphatic unsaturated dibasic acids having 4 to 6 carbon atoms. Specific examples of the unsaturated dibasic acid include at least one member selected from the group consisting of maleic anhydride, maleic acid, and itaconic acid in one or more embodiments.

The "organic amine" in the present disclosure includes primary, secondary or tertiary alkylamines or alkanolamines in one or more embodiments. As the organic amine, in one or more embodiments, monoalkyl (alkyl group having 1 to 3 carbon atoms) amine, dialkyl (alkyl group having 1 to 3 carbon atoms) amine, trialkyl (alkyl group having 1 to 3 carbon atoms) amine, At least one member selected from the group consisting of mono alkanol (alkanol having 1 to 3 carbon atoms) amine, dialkanol (alkanol having 1 to 3 carbon atoms) amine, and trialkanol (alkanol having 1 to 3 carbon atoms) . Specific examples of the organic amine include, in one or more embodiments, at least one kind selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine and tributylamine . As the quaternary ammonium in the present disclosure, in one or more embodiments, tetra-lower alkylammonium can be mentioned, but it is preferable that it does not contain a metal. Specific examples of the quaternary ammonium include tetramethylammonium in one or more embodiments.

In the dispersant composition related to the present disclosure, the molar ratio (II) / (I) of the total carboxyl group (I) contained in the polymer composition and the organic amine or quaternary ammonium and the carboxyl group (II) , In one or more embodiments, is at least 0.33, preferably at least 0.4, more preferably at least 0.45, and even more preferably at least 0.5 from the viewpoint of improving the redispersibility of the slurry composition. The molar ratio (II) / (I) is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less, in view of performance as an inherent dispersing agent in one or more embodiments to be. The molar ratio (II) / (I) is preferably 1.0 or less, more preferably 0.95 or less, and still more preferably 0.9 or less, in view of the performance as an inherent dispersant in one or more embodiments. The term " whole carboxyl group " in the present disclosure refers to all carboxyl groups contained in all constituent units constituting the copolymer or polymer composition, and includes a neutralized carboxyl group and a ring-opened carboxyl group. The "molar ratio (II) / (I)" in the present disclosure means the ratio of the carboxyl group forming the counter ion to the organic amine or quaternary ammonium among the total carboxyl groups contained in the copolymer. The calculation method of the "molar ratio (II) / (I)" is, for example, in the case of preparing a salt (polymer composition) of a copolymer of acrylic acid and maleic acid (monomer composition ratio: AA / MA = 83/17) : 72% by mole (based on the total monomer in the copolymer), the number of carboxyl groups derived from acrylic acid and the number of carboxyl groups derived from maleic acid (divalent) relative to all the monomers in the copolymer were 83% (II) / (I) = 72 / (83 + 34) = 0.62. The dispersant composition relating to the present disclosure is obtained by mixing the carboxyl group of the copolymer and the counter ion (Hereinafter, simply referred to as "excess amine") selected from organic amines and quaternary ammoniums which do not form an amide group, and when the dispersant composition related to this disclosure contains an excess amine, The composition contained in the composition The molar ratio (III) / (I) of the organic carboxyl group (I) and the organic amine and quaternary ammonium (III) contained in the dispersant composition is preferably 2.5 or less, more preferably 2.5 or less, from the viewpoint of improving the redispersibility of the slurry composition In the present disclosure, the term "organic amine and quaternary ammonium contained in the dispersant composition" means an organic amine and a quaternary ammonium salt forming a counter ion with the carboxyl group of the copolymer, Ammonium, and organic amines and quaternary ammonium that do not form a counter ion with the carboxyl groups of the copolymer.

In the dispersant composition according to the present disclosure, the degree of neutralization of the polymer composition is, in one or more embodiments, from the viewpoint of improving the dispersion performance of the dispersant, the degree of neutralization of the polymer composition relative to 100 mol% , Preferably from 40 mol% to 100 mol%, more preferably from 50 mol% to 95 mol%, and still more preferably from 60 mol% to 90 mol%. The degree of neutralization of the polymer composition is preferably 40% by mole or more based on 100% by mole of the total carboxyl groups contained in the copolymer or the polymer composition in one or more embodiments from the viewpoint of improving the dispersing performance of the dispersing agent, More preferably 50 mol% or more, still more preferably 60 mol% or more, and from the same viewpoint, 100 mol% or less is preferable, 95 mol% or less is more preferable, and 90 mol% or less is more preferable. In the present disclosure, the term "degree of neutralization" refers to the ratio (mol%) of carboxyl groups neutralized by all the neutralizing agents used in the neutralization process among the entire carboxyl groups (100 mol%) contained in the copolymer or polymer composition. In the present disclosure, " neutralization degree " is expressed by [molar equivalent of carboxyl group neutralized / molar equivalent of entire carboxyl group which can be neutralized] x 100 (mol%). The neutralization degree can be calculated, for example, by preparing a salt (polymer composition) of a copolymer of acrylic acid and maleic acid (monomer composition ratio: AA / MA = 83/17) in an amount of 8.3 mol% Maleic acid (relative to the monomer) and monoethanolamine: 72 mol% (based on the total monomer in the copolymer), the number of carboxyl groups derived from acrylic acid relative to all the monomers in the copolymer was 83 mol% The degree of neutralization of the polymer composition is 100 mol% (8.3 + 72) / (83 + 34) = 68.6 mol%, since the number of carboxyl groups derived from the polyfunctional (meth) acrylate is 17 mol% × 2 = 34 mol%.

The weight average molecular weight (Mw) of the polymer composition is preferably 10000 to 90000, more preferably 10000 to 90000, from the viewpoint of improving the redispersibility of the slurry composition and reducing the viscosity of the slurry composition in one or more embodiments 20000 to 75000, and more preferably 30,000 to 65,000. The weight average molecular weight (Mw) of the polymer composition is preferably 10000 or more, more preferably 20000 or more, from the viewpoint of improving the redispersibility of the slurry composition and reducing the viscosity of the slurry composition in one or more embodiments , And more preferably 30,000 or more, and from the same viewpoint, 90000 or less is preferable, 75000 or less is more preferable, and 65000 or less is more preferable. Here, the weight average molecular weight is a value measured by GPC (gel permeation chromatography), and details of measurement conditions are as shown in the examples.

The molar ratio of the constitutional unit derived from (meth) acrylic acid to the constitutional unit derived from the unsaturated dibasic acid in the polymer composition is preferably in the range of from one aspect or more than one embodiment in view of the improvement of the redispersibility of the slurry composition and the viscosity reduction of the slurry composition Is preferably 50/50 to 95/5, more preferably 55/45 to 90/10, and further preferably 60/40 to 85/15.

When the form of the dispersant composition related to the present disclosure is an aqueous solution, the content of the polymer composition in the aqueous solution of the dispersant composition is, in one or more embodiments, from the viewpoints of improving the redispersibility of the slurry composition and reducing the viscosity of the slurry composition, Is preferably 20 to 60 mass%, more preferably 25 to 50 mass%, and still more preferably 30 to 45 mass%. The content of the polymer composition in the dispersant composition according to the present disclosure can be determined, for example, from the amount of the raw material injected, or can be obtained by measuring the solid content in the dispersant composition related to the present disclosure.

In the case where the form of the dispersant composition related to the present disclosure is an aqueous solution, the pH of the aqueous solution of the dispersant composition is preferably from the viewpoint of improving the redispersibility of the slurry composition and the chemical decomposability of the powder component in one or more embodiments Is 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 according to the present disclosure is used for the dispersion of the powder for electronic materials, the substance forming the counter ion with the carboxyl group contained in the copolymer may be a substance containing a metal (salt) in one or more embodiments . That is, in one or more embodiments, the polymer composition of the present disclosure preferably does not contain a metal (salt). In the present disclosure, "metal (salt)" represents at least one of metal and metal salt in one or more embodiments.

[Method of producing dispersant composition]

The present disclosure relates to a method for producing a dispersant composition relating to the present disclosure (hereinafter also referred to as " a method for producing a dispersant composition related to the present disclosure ") in another aspect, wherein a constitutional unit derived from (meth) acrylic acid and an unsaturated dibasic acid (I) and an organic amine or a quaternary ammonium among them are formed into a counter ion by mixing a copolymer containing the derived constituent unit with an organic amine or quaternary ammonium (salt) And neutralizing the copolymer with an organic amine or a quaternary ammonium salt to obtain a polymer composition such that the molar ratio (II) / (I) of the carboxyl group (II) to the carboxyl group (II) is 0.33 or more will be. According to the method for producing a dispersant composition according to the present disclosure, a dispersant composition capable of improving the redispersibility of the slurry composition can be produced. In the neutralization step, neutralizing agents other than organic amine or quaternary ammonium (salt) (for example, ammonium (salt)) may be used in combination.

The method for producing a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid in the present disclosure is not particularly limited, and for example, a method in which an unsaturated dibasic acid is partially neutralized with a neutralizing agent Followed by polymerization reaction with (meth) acrylic acid. In the polymerization reaction, known polymerization initiators, chain transfer agents and the like can be used. Examples of the polymerization initiator include hydrogen peroxide and the like. Examples of the chain transfer agent include isopropanol and the like. Examples of the neutralizing agent used for partial neutralization include organic amines (salts) and ammonium salts (salts). Specific examples thereof include monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethyl And at least one member selected from the group consisting of amine, tributylamine, tetramethylammonium hydroxide, triethylmethylammonium hydroxide, and aqueous ammonia solution.

[Dispersion method]

The present disclosure can provide, as a further aspect, a dispersion method (hereinafter also referred to as " dispersion method related to the present disclosure ") comprising a step of dispersing a powder in an aqueous solvent using the dispersant composition related to the present disclosure . According to the dispersion method related to the present disclosure, a slurry composition having improved redispersibility of powder can be produced.

Examples of the powder dispersed in the aqueous solvent by the dispersion method related to the present disclosure include powder for electronic materials in one or more embodiments and specific examples thereof include titanates such as carbonates, phosphates, barium titanate, At least one member selected from silicate, zinc oxide, iron oxide, titanium oxide, alumina (aluminum oxide), silica (silicon oxide), magnesium oxide, zirconium oxide, cerium oxide, carbon black and silicon carbide. The powder for electronic material can be used for electronic parts such as an IC package, a wiring board, an insulator, a sensor, an electrode, a magnetic material, a semiconductor, a capacitor, and an optical fiber.

As a water-based solvent used in the dispersion method related to the present disclosure, water or a mixed solution of water and a water-soluble organic solvent such as ethyl alcohol or ethylene glycol may be used in one or more embodiments, to be. Examples of the water include distilled water, ion-exchanged water, ultrapure water and the like.

[Slurry composition]

The present disclosure also provides, as yet another embodiment, a dispersant composition comprising a slurry composition (hereinafter also referred to as " slurry composition "), an aqueous solvent, a powder, and a dispersant composition, Lt; RTI ID = 0.0 > slurry < / RTI > The slurry composition according to the present disclosure can improve redispersibility. As the powder and the aqueous solvent used in the slurry composition according to the present disclosure, the same dispersing method as that described in the present disclosure can be used.

The content (solid content) of the powder in the slurry composition according to the present disclosure is not particularly limited, but is preferably 50% by mass or more from the viewpoint of improvement of drying efficiency and productivity in one or a plurality of embodiments, More preferably 55% by mass or more, furthermore 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.

The content of the dispersant composition in the slurry composition according to the present disclosure is preferably 0.3 to 5.0 parts by weight, based on 100 parts by weight of the powder, in terms of solid content, in view of viscosity reduction of the slurry composition in one or more embodiments. More preferably 0.4 to 4.0 parts by weight, still more preferably 0.5 to 3.0 parts by weight. The content of the dispersant composition in the one or more embodiments is preferably 0.3 parts by weight or more, more preferably 0.4 parts by weight or more, and more preferably 0.4 parts by weight or less, based on 100 parts by weight of the powder in terms of solid content from the viewpoint of viscosity reduction of the slurry composition. More preferably 0.5 part by weight or more, and from the same viewpoint, it is preferably 5.0 parts by weight or less, more preferably 4.0 parts by weight or less, still more preferably 3.0 parts by weight or less.

[Method of producing slurry composition]

The present disclosure further provides a method for producing a slurry composition (hereinafter, also referred to as a " method for producing a slurry composition relating to the present disclosure "), a powder, a dispersant composition related to the present disclosure, and an aqueous solvent, And a step of dispersing the powder. According to the present disclosure, a slurry composition having improved redispersibility can be produced. As the powder and the aqueous solvent used in the method for producing the slurry composition according to the present disclosure, the same dispersing method as that described in the present disclosure can be used. In the method of preparing the slurry composition according to the present disclosure, the powder and the dispersant composition may be mixed so as to be the content of the slurry composition related to the present disclosure described above.

The present disclosure also relates to one or more of the following embodiments.

≪ 1 > A polymer composition comprising an organic amine salt or a quaternary ammonium salt of a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid,

Wherein the molar ratio (II) / (I) of the total carboxyl group (I) contained in the polymer composition and the organic amine or the quaternary ammonium and the carboxyl group (II) forming the counter ion therein is 0.33 or more.

<2> The powder dispersant composition 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 molar ratio (II) / (I) is preferably 2.5 or less, more preferably 2.0 or less, further preferably 1.5 or less, or preferably 1.0 or less, more preferably 0.95 or less, Is not more than 0.9. &Lt; 1 &gt;

<4> The powder dispersant composition according to any one of <1> to <3>, wherein the powder is a powder for an electronic material.

<5> The degree of neutralization of the polymer composition is preferably from 40 mol% to 100 mol%, more preferably from 50 mol% to 95 mol%, based on 100 mol% of the total carboxyl groups contained in the copolymer or polymer composition , More preferably not less than 60 mol% and not more than 90 mol%, based on the total amount of the dispersant.

<6> The polymer composition according to any one of <1> to <5>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 10,000 to 900,000, more preferably 20,000 to 75,000, and still more preferably 30000 to 65,000. Powder dispersant composition.

<7> The powder according to any one of <1> to <6>, wherein the organic amine or quaternary ammonium is at least one selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and tetramethylammonium / RTI &gt;

<8> The molar ratio of the (meth) acrylic acid-derived structural unit to the unsaturated dibasic acid-derived structural unit is preferably 50/50 to 95/5, more preferably 55/45 to 90/10, The powder dispersant composition according to any one of &lt; 1 &gt; to &lt; 7 &gt;

<9> The powder dispersant composition according to any one of <1> to <8>, wherein the unsaturated dibasic acid is at least one selected from maleic anhydride, maleic acid and itaconic acid.

<10> The total amount of constituent units derived from (meth) acrylic acid and constituent units derived from unsaturated dibasic acid in the entire constituent units constituting the copolymer is preferably 70% by mass or more, more preferably 85% by mass or more, And more preferably substantially 100% by mass, based on the total mass of the powder dispersant composition.

The content of the polymer composition in the aqueous solution of the powder dispersant composition is preferably 20 to 60 mass%, more preferably 25 to 50 mass%, further preferably 30 By mass to 45% by mass, based on the total mass of the dispersion.

<12> The powder dispersant composition according to <1>, wherein the form of the powder dispersant composition is an aqueous solution and the pH of the aqueous solution of the powder dispersant composition is preferably 4.5 to 11.0, more preferably 5.0 to 10.0, and still more preferably 5.5 to 9.0. &Lt; 11 &gt;.

<13> The powder dispersant composition according to any one of <1> to <12>, wherein the substance forming the counter ion with a carboxyl group contained in the copolymer contains no metal (salt).

The neutralization degree of the polymer composition is preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 60 mol% or more, based on 100 mol% of the total carboxyl groups contained in the copolymer or polymer composition The powder dispersant composition according to any one of &lt; 1 &gt; to &lt; 13 &gt;.

The degree of neutralization of the polymer composition is preferably 100 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, relative to 100 mol% of the total carboxyl groups contained in the copolymer or polymer composition The powder dispersant composition according to any one of &lt; 1 &gt; to &lt; 14 &gt;.

<15> The powder dispersant composition according to any one of <1> to <15>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 10000 or more, more preferably 20000 or more, and still more preferably 30000 or more.

<17> The powder dispersant composition according to any one of <1> to <16>, wherein the weight average molecular weight (Mw) of the polymer composition is preferably 90000 or less, more preferably 75000 or less, still more preferably 65000 or less.

(18) A method of mixing a copolymer containing a (meth) acrylic acid-derived structural unit and an unsaturated dibasic acid-derived structural unit with an organic amine or a quaternary ammonium salt, (II) / (I) of the organic amine or quaternary ammonium and the carboxyl group (II) forming the counter ion is 0.33 or more, and the copolymer is neutralized with an organic amine or a quaternary ammonium salt To obtain a polymer composition. &Lt; Desc / Clms Page number 19 &gt;

<19> A dispersion method comprising a step of dispersing a powder in an aqueous solvent using the powder dispersant composition according to any one of <1> to <17>.

<20> A method for producing a slurry composition, which comprises a step of mixing the powder dispersant composition, powder, and aqueous solvent described in any one of <1> to <17> and dispersing the powder.

<21> A slurry composition comprising the powder dispersant composition, powder, and aqueous solvent according to any one of <1> to <17>.

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, still more preferably 60% by mass or more, and preferably 85% Or less, more preferably 80 mass% or less, based on the total mass of the slurry composition.

The content of the powder dispersant composition is preferably 0.3 to 5.0 parts by weight, more preferably 0.4 to 4.0 parts by weight, still more preferably 0.5 to 3.0 parts by weight, in terms of solid content, relative to 100 parts by weight of the powder , &Lt; 21 &gt; or &lt; 22 &gt;.

The content of the powder dispersant composition in terms of solid content is preferably at least 0.3 part by weight, more preferably at least 0.4 part by weight, and most preferably at least 0.5 part by weight, based on 100 parts by weight of the powder, The slurry composition according to any one of <21> to <23>.

The content of the powder dispersant composition is preferably 5.0 parts by weight or less, more preferably 4.0 parts by weight or less, more preferably 3.0 parts by weight or less, based on 100 parts by weight of the powder in terms of solid content, The slurry composition according to any one of the preceding claims.

Example

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but these are only illustrative and not intended to limit the present disclosure to these Examples.

In the following Examples and Comparative Examples, the weight average molecular weight of the salt of the polymer in the dispersing agent was measured by GPC (gel permeation chromatography). Specific conditions are as follows.

&Lt; Method of measuring weight average molecular weight of polymer composition &gt;

The weight average molecular weight of the polymer composition was measured by GPC (Gel Permeation Chromatography) under the following conditions.

[Measuring conditions]

Column: TSK PWXL + G4000PWXL + G2500PWXL (all Toso Co., Ltd.)

Column temperature: 40 DEG C

Detector: RI or UV (210 nm)

Eluent: 0.2 mol / l phosphate buffer / acetonitrile (9/1)

Flow rate: 1.0 ml / min

Injection amount: 0.1 ml

Standard: Polyethylene glycol

[Preparation of dispersant composition (Examples 1 to 15, Comparative Examples 1 to 9)]

The dispersant compositions shown in Table 1 below (Examples 1 to 15 and Comparative Examples 1 to 9) were prepared as described below.

(Example 1)

78.5 g of maleic anhydride (manufactured by Mitsubishi Chemical Corporation) and 80.0 g of ion-exchanged water were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, heated at 55 캜 (liquid temperature) 24.3 g of a 28% by mass ammonia aqueous solution (manufactured by Sigma-Aldrich Chemical Co., Ltd., reagent grade) was added dropwise to obtain an aqueous solution of maleic acid ammonium salt (neutralization step 1). When the total monomer constituting the copolymer (here, acrylic acid-maleic acid copolymer) was taken as 100 mol%, the addition amount of ammonia was 8.3 mol%.

Next, 360.5 g of an 80 mass% acrylic acid aqueous solution (manufactured by Nippon Catalysts Co., Ltd.) and a 35 mass% aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Company) of 221.5 g were added dropwise to the respective dropping funnels over 3.5 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was aged at 100 ° C (liquid temperature) for 10 hours to complete the polymerization reaction to obtain an acrylic acid-maleic acid copolymer. After completion of the reaction, the solution in the reaction vessel was cooled to about 40 캜, and 211.2 g of monoethanolamine (manufactured by Nippon Catalysts) was added dropwise while maintaining the liquid temperature at about 40 캜 to neutralize the acrylic acid-maleic acid copolymer salt Polymer composition) (neutralization step 2). The addition amount of the monoethanolamine was 72 mol% when 100 mol% of the total monomer constituting the copolymer (here, acrylic acid-maleic acid copolymer) was taken as 100 mol%. The molar ratio (II) / (I) of the total carboxyl group (I) contained in the polymer composition and the carboxyl group (II) in which the organic amine or quaternary ammonium and the counter ion were formed was 0.62. The neutralization degree of the polymer composition was 68.6 mol%. Then, 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 contains no metal (salt). The pH of the aqueous solution of the dispersant composition of Example 1 at 25 캜 was 6.0. Here, the pH at 25 占 폚 is a value measured using a pH meter (HM-30G, TOA Radio Co., Ltd.), and is a value after two minutes after immersing the electrode of the pH meter in the dispersant composition.

(Examples 2 to 15 and Comparative Examples 1 to 9)

Except that the types of monomers and monomer composition ratios were changed as shown in Table 1, the types of neutralizing agents used in neutralization step 1 and neutralization step 2, and the addition amounts thereof were changed as shown in Table 1, (Examples 2 to 15 and Comparative Examples 1 to 9) containing 40 mass% of a polymer composition having a weight average molecular weight and a molar ratio (II) / (I) shown in Table 1 were prepared. The polymer compositions of Examples 2 to 15 and Comparative Examples 1 to 9 do not contain a metal (salt).

In Table 1, AA is acrylic acid, MA is maleic acid, MAA is methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.), IA is itaconic acid (manufactured by Iwata Chemical), NH ₃ is 28 mass% , DEA for diethanolamine (manufactured by Nippon Catalysts), TEA for triethanolamine (manufactured by Nippon Catalysts Co., Ltd.), TMAH for 25% by mass of tetramethylammonium hydroxide (produced by Nippon Kagaku K.K.), MEA for monoethanolamine Respectively.

[Preparation of slurry composition]

Using the dispersant compositions of Examples 1 to 15 and Comparative Examples 1 to 9, the slurry composition was prepared as follows, and the redispersibility and dispersibility of the obtained slurry composition were evaluated.

[Evaluation of Redistribution]

&Lt; Wipe test of slurry &

12 g of barium titanate powder (BT-HP9DX, manufactured by Kyoritsu Material Co.) having an average particle diameter of 200 nm, 12 g of each of the dispersant compositions of Examples 1 to 15 and Comparative Examples 1 to 9 in an addition amount of 1.0 weight (Slurry composition) of 60% by mass was added to the dispersion liquid (1 hour) with an ultrasonic cleaner yamato 1510 manufactured by Yamato Scientific Co., Ltd., .

15 g of the prepared powdery slurry was uniformly applied to a stainless steel bat having a length of 10 cm, a width of 13 cm and a depth of 6 cm and dried and cured at room temperature for 24 hours to obtain a slurry dried product. Thereafter, the slurry dried material was wiped off with a paper towel impregnated with water, and the degree of removal from the bat was visually observed. The results are shown in Table 1. In Table 1, A indicates a case where the slurry dried completely on the bat was not visually observed, and B indicates the case where the slurry dried on the bat was visually confirmed. If it is completely removed, it can be evaluated as redistribution.

&Lt; Immersion Test of Slurry &gt;

Using the respective dispersant compositions of Examples 1 to 15 and Comparative Examples 1 to 9, the slurry dried material was prepared in the same manner as in the wiping test of the slurry dried material. Then, 15 g of the prepared powdery slurry was uniformly applied to a stainless steel bat of 10 cm in length, 13 cm in width and 6 cm in depth and dried and cured at room temperature for 24 hours to obtain a slurry dried product. Next, a stainless steel bath in which the slurry dried product was placed was immersed in a disto-beaker containing 1000 ml of ion-exchanged water and immersed for 30 minutes. Thereafter, the powder slurry eluted to the water side was sampled, and the average particle diameter was measured using a laser scattering particle size analyzer (Horiba, LA-920, refractive index 2.40). Measurement was carried out with naked eyes for samples whose average particle diameter was clearly larger than 1 mm. The smaller the average particle diameter, the better the redispersibility.

As a reference example 1, 60% by mass of a powder slurry (slurry composition) was prepared without using the dispersant composition of Comparative Example 1, without drying. That is, 12 g of barium titanate powder (BT-HP9DX, manufactured by Kyoritsu Material Co., Ltd.) having an average particle diameter of 200 nm and 12 g of a dispersant in an amount of 1.0 part by weight (in terms of solid content relative to 100 parts by weight of barium titanate powder) Ion exchanged water was added and dispersed (1 hour) with an ultrasonic cleaner yamato 1510 manufactured by Yamato Scientific Co., Ltd. to prepare a 60% by mass powder slurry (slurry composition), and the average particle size of the powder slurry was measured. The results are shown in Table 1.

[Evaluation of dispersibility]

117 g of barium titanate powder (BT-HP9DX, manufactured by Kyoritsu Material Co., Ltd.) having an average particle diameter of 200 nm and 117 g of each of the dispersant compositions of Examples 1 to 15 and Comparative Examples 1 to 9 in an addition amount of 1.0 part by weight (In terms of solid content relative to 100 parts by weight of barium titanate powder), and ion-exchanged water were added, and the mixture was stirred (2500 rpm for 2 minutes) with a homodisperser manufactured by Freimix to obtain 78% To prepare a slurry (slurry composition). The viscosity of the prepared powder slurry at 25 캜 was measured using a B-type viscosity measuring apparatus TVB-10 manufactured by Toray Industries, Inc., at a rotating speed of the rotor of 60 rpm. The results are shown in Table 1. The smaller the viscosity, the better the dispersibility.

As shown in Table 1, the dried product of the slurry composition prepared using the dispersant compositions of Examples 1 to 15 was easy to polish, whereas the dried product of the slurry composition prepared using the dispersant compositions of Comparative Examples 1 to 9 was polished Was very difficult. The immersion eluates of the dried slurry compositions prepared using the dispersant compositions of Examples 1 to 15 had fine particle sizes and were almost the same average particle size as the 60% by mass powder slurry of Reference Example 1, The dried product of the slurry composition prepared using the dispersant composition of No. 9 had an extremely large average particle diameter, and the agglomeration of the powder was confirmed. Further, the slurry compositions prepared using the dispersant compositions of Examples 1 to 15 and the slurry compositions prepared using the dispersant compositions of Comparative Examples 1 and 3 to 9 were compared, and as a result, there was no particular difference in dispersion performance.

By using the dispersant composition of the present disclosure, a slurry composition having improved redispersibility can be produced. The slurry composition of the present disclosure can be suitably used for the production of electronic parts.

Claims (18)

A polymer composition comprising an organic amine salt or a quaternary ammonium salt of a copolymer containing a constituent unit derived from a (meth) acrylic acid and a constituent unit derived from an unsaturated dibasic acid,
(I) having a molar ratio (II) / (I) of an organic amine or a quaternary ammonium and a carboxyl group (II) forming a counter ion in the above polymer composition is 0.33 or more Dispersant composition. The method according to claim 1,
Wherein the molar ratio (II) / (I) is 0.4 or more. The method according to claim 1,
Wherein the molar ratio (II) / (I) is 1.0 or less. The method according to claim 1,
The powder is a powder for an electronic material. The method according to claim 1,
The neutralization degree of the polymer composition is from 40 mol% to 100 mol% with respect to 100 mol% of the total carboxyl groups contained in the copolymer or the polymer composition. The method according to claim 1,
Wherein the polymer composition has a weight average molecular weight (Mw) of 10000 or more and 90000 or less. The method according to claim 1,
Wherein the organic amine is at least one member selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine,
Wherein the quaternary ammonium is tetramethylammonium. The method according to claim 1,
Wherein the molar ratio of the (meth) acrylic acid-derived structural unit to the unsaturated dibasic acid-based structural unit is 50/50 to 95/5. The method according to claim 1,
Wherein the unsaturated dibasic acid is at least one selected from maleic anhydride, maleic acid and itaconic acid. The method according to claim 1,
Wherein the total amount of constituent units derived from (meth) acrylic acid and constituent units derived from unsaturated dibasic acid in the total constituent units constituting the copolymer is 70 mass% or more. The method according to claim 1,
When the form of the powder dispersant composition is an aqueous solution,
Wherein the content of the polymer composition in the aqueous solution of the powder dispersant composition is 20 to 60 mass%. The method according to claim 1,
A substance for forming a counter ion with a carboxyl group contained in the copolymer does not contain a metal (salt). (Meth) acrylic acid-derived structural unit and an unsaturated dibasic acid-based structural unit and an organic amine or a quaternary ammonium salt (salt) are mixed, and the total carboxyl group (I) contained in the copolymer and The copolymer is neutralized with an organic amine or quaternary ammonium (salt) so that the molar ratio (II) / (I) of the organic amine or quaternary ammonium and the carboxyl group (II) By weight based on the total weight of the powder. A dispersion method comprising a step of dispersing a powder in an aqueous solvent using the powder dispersant composition according to any one of claims 1 to 12. A method for producing a slurry composition, comprising the step of mixing the powder dispersant composition, powder, and aqueous solvent according to any one of claims 1 to 12 and dispersing the powder. A slurry composition containing the powder dispersant composition, powder, and aqueous solvent according to any one of claims 1 to 12. 17. The method of claim 16,
(Solid content) of the powder in the slurry composition is 50 mass% or more and 85 mass% or less. 17. The method of claim 16,
Wherein the content of the powder dispersant composition is 0.3 to 5.0 parts by weight based on 100 parts by weight of the powder in terms of solid content.