JP2006282755A - Aqueous dispersion of organic-inorganic hybrid particles and polishing slurry obtained from same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of organic-inorganic hybrid particles, which is stable in dispersion and whose particle size is uniform, and polishing slurry excellent in polishing performance. <P>SOLUTION: The aqueous dispersion of organic-inorganic hybrid particles comprises a reaction gel of a resin having an anionic group and a metal alcoxide wherein pH is adjusted within the range equal to or greater than 2.0 and less than 8.0. Excellent dispersibility and polishing performance when used as a polishing slurry can be obtained by performing the pH adjustment with an acid compound having an acetic acid group bonded directly to a nitrogen atom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic-inorganic hybrid particle aqueous dispersion having a uniform particle size and stable dispersion, and a polishing slurry excellent in polishing performance obtained therefrom.

  Conventionally, inorganic particles such as ceramics are used alone or in combination with organic polymers for various purposes such as increasing the amount, absorbing ultraviolet light, wear resistance, and imparting optical / electromagnetic properties. Organic polymer particles, on the other hand, are used in toners for electrophotography, matting, colorants, etc. using the flexibility, adhesion, and processability that are properties of polymers. It is difficult to obtain properties such as properties, high elastic modulus, weather resistance, and solvent resistance. Therefore, in order to obtain materials having excellent properties of organic polymers and inorganic materials, compounds of both are used, but in general, the compatibility of inorganic compounds and organic polymers is not sufficient, and various compounds using polyvalent metal alkoxides are used. Although attempts have been made, it is not easy to form an organic-inorganic hybrid material that is a uniform composite material, and it has been difficult to put particles made of such a material into practical use.

  In recent years, in order to achieve high integration and high performance of semiconductors, planarization technology has become an essential technology in the formation of interlayer insulating films, metal plugs, and buried metal wirings in a multilayer wiring forming process. Among these, a chemical mechanical polishing method (chemical mechanical polishing, hereinafter abbreviated as CMP) in which a chemical action between an abrasive and an object to be polished and a mechanical action of abrasive particles is combined is extremely effective. It is. Furthermore, the need for precision polishing is also increasing in the fields of hard disk disks and precision parts such as optical parts, and CMP is extremely important.

  In general, in CMP of a metal film, a CMP slurry made of a mixture of inorganic compound particles such as alumina and silica and an oxidizing agent such as ferric nitrate or hydrogen peroxide is used. When polished, there are problems of surface roughness due to the occurrence of scratches on the metal surface and embedding of abrasive particles in the metal film. In addition, inorganic compound particulate slurry easily aggregates and precipitates, and the generation of scratches due to the aggregated inorganic compound particles having a large particle size is a serious problem. In addition, in a region where the width of the wiring metal film embedded in the groove or opening of the wiring formed in the semiconductor is wide, there is a problem that dishing with a thin central portion is likely to occur.

  In order to improve the disadvantages of the CMP slurry composed of inorganic particles, there have been proposed abrasives and CMP slurries using particles composed of organic polymer compounds or particles containing at least carbon as a main component as abrasive particles (Patent Literature). 1), and specific examples of organic polymer compounds include methacrylic resins such as PMMA, phenol resins having the same hardness, urea resins, melamine resins, polystyrene resins, polyacetal resins, polycarbonate resins, and the like. . However, this method has a problem that the dispersion stability is not always sufficient, and it is necessary to use a dispersion stabilizer in combination, and the hardness of the resin particles is low and the chemical activity is poor, so that the polishing rate is extremely low.

In order to solve such problems, an abrasive comprising an aqueous emulsion containing vinyl compound polymer resin particles obtained by emulsion polymerization and containing a complexing agent that forms ammonia or a water-soluble metal complex has been proposed. (See Patent Document 2 and Patent Document 3). However, in this method, since an emulsifier is used, the dispersion stability is not always good, and the hardness is not always sufficient. Further, the chemical activity on the surface of the resin particles is not great, and the main effect of polishing depends on ammonia added as an essential component and an optional oxidizing agent. Therefore, the above-mentioned dishing improvement has not always been sufficient.
Also, an abrasive containing an aqueous emulsion composed of a complexing agent that reacts with a metal to form a water-soluble metal complex and vinyl compound polymer resin particles obtained by emulsion polymerization without using an emulsifier has been proposed (patent) Reference 4). In this method, since the emulsion polymerization is performed without using an emulsifier, the particle size distribution of the obtained resin particles tends to be wide, and there is a possibility of generation of scratches due to large particle size particles.

An aqueous dispersion containing polymer particles having a cross-linked structure and an average particle size of 0.13 to 0.8 μm, and having a surfactant content of 0.15% by weight or less, and an abrasive comprising the same as a main component Has been proposed (see Patent Document 5). In the present invention, since a crosslinkable monomer and other monomers are copolymerized to form a crosslinked structure, a sufficient hardness cannot be obtained if the crosslinking rate is low, and on the contrary, if the crosslinking rate is increased, the brittleness becomes brittle. In addition to this defect, it was difficult to reduce the particle size of the resulting crosslinked particles.
As a specific method for producing organic-inorganic hybrid particles, for example, seed particles are swollen with a swelling solvent containing a polyvalent metal alkoxide, and then polymerized by an unsaturated double bond in the polyvalent metal alkoxide, and then the polyvalent metal alkoxide is polymerized. A production method in which an alkoxy group of a metal alkoxide is hydrolyzed and condensed is used (see Patent Document 6). However, the particles formed in the manufacturing method have seed particles arranged in the central portion and do not have a uniform internal structure. In addition, the production process such as swelling treatment and subsequent polymerization, and the use of a surfactant and a dispersant is complicated, and it is difficult to control the particle size. For this reason, the particles are not necessarily spherical, and it has been difficult to give the particles sufficient uniformity in terms of shape and physical properties.
Japanese Patent Laid-Open No. 07-086216 Japanese Patent Laid-Open No. 11-176774 JP 11-162910 A JP-A-11-156702 JP 2000-204275 A Japanese Patent Laid-Open No. 07-265686

The present invention solves the problems related to the aqueous dispersion containing the organic-inorganic hybrid particles and the polishing slurry obtained therefrom.
That is, an object of the present invention is to provide an aqueous dispersion of organic-inorganic hybrid particles having a stable dispersion and uniform particle diameter, and a polishing slurry having excellent polishing performance.

The above object is achieved by the present invention described below.
That is, the present invention is an aqueous dispersion of organic-inorganic hybrid particles comprising a reaction gel of a resin having an anionic group and a metal alkoxide, wherein the pH is adjusted to a range of 2.0 or more and less than 8.0. An aqueous dispersion of organic-inorganic hybrid particles is provided.
Furthermore, the present invention provides a polishing slurry containing the aqueous dispersion as a main component.
The present invention further relates to a method for producing organic-inorganic hybrid particles comprising a resin having an anionic group and a reaction gel of a polyvalent metal alkoxide, wherein (1) at least a part of which is neutralized with a basic compound A mixing step of producing a mixture in which a polyvalent metal alkoxide is dissolved or suspended in a resin aqueous solution of a resin having a group;
(2) a hydrolysis step in which the polyvalent metal alkoxide in the mixture is hydrolyzed or hydrolyzed and condensed while maintaining the pH of the mixture at 8.0 or higher under a base catalyst;
(3) A method for producing organic-inorganic hybrid particles, comprising a granulating step of lowering the pH in the mixture to 2.0 or more and less than 8.0 and reducing the solubility of the resin to emulsify or granulate the mixture. And the manufacturing method of the aqueous dispersion of the organic-inorganic hybrid particle | grains characterized by adding an acid compound in the said granulation process.

An aqueous dispersion of organic-inorganic hybrid particles containing a resin having an anionic group of the present invention and a reaction gel of a metal alkoxide, the pH of which is adjusted to a range of 2.0 or more and less than 8.0, An organic component and an inorganic component are uniformly mixed to form an aqueous dispersion having a uniform particle size and excellent dispersion stability. Furthermore, it has excellent granulation properties during production and is extremely easy to form. The organic-inorganic hybrid particles obtained from the method for producing an aqueous dispersion of organic-inorganic hybrid particles of the present invention form a domain in which the organic component and the inorganic component have a fine structure, in addition to the hardness that can be used as polishing particles. Combines the characteristics of conventional inorganic particles such as wear resistance, heat resistance, high elastic modulus, weather resistance, and solvent resistance with the characteristics of conventional organic particles such as flexibility, adhesion, workability, and granulation. Yes.
The polishing slurry obtained from the organic-inorganic hybrid particle aqueous dispersion of the present invention has excellent polishing performance, particularly polishing performance for metal, in addition to the dispersion stability of the slurry.

  The aqueous dispersion of organic-inorganic hybrid particles of the present invention comprises a reaction gel of a resin having an anionic group and a metal alkoxide, and the pH of the aqueous dispersion is adjusted to a pH range of 2.0 or more and less than 8.0. Aqueous dispersion. The aqueous dispersion of the organic-inorganic hybrid particles of the present invention performs a hydrolytic condensation reaction of a metal alkoxide in an aqueous solution of a resin in which at least part of an anionic group is neutralized with a base and water dispersibility and solubility are improved. Since it is produced by proceeding, the process proceeds at pH 8.0 or more in the presence of a base in the initial process of production. However, the aqueous dispersion of organic-inorganic hybrid particles formed in this manner is not stable at pH 8.0 or higher and may cause gelation. Therefore, at any stage before the final production of the aqueous dispersion or polishing slurry, by adjusting the pH to be in the pH range of 2.0 or more and less than 8.0, the dispersion stability is extremely high. A good aqueous dispersion and polishing slurry can be produced.

The pH can be adjusted at any stage after hydrolysis of the metal alkoxide in the resin solution and by various methods. By adding an acid compound or, if the base is volatile, by volatilization of the base. The pH may be adjusted to a pH range of 2.0 or more and less than 8.0.
As the acid compound, any organic acid or inorganic acid can be used, but it can be used as an additive in the slurry for polishing, and by using an acid having a metal polishing function, the aqueous dispersion has good dispersion stability. In addition to imparting, it is possible to impart good abrasiveness that can be used as it is as a slurry for polishing.

The acid compound is preferably a compound having an acetic acid group directly connected to a nitrogen atom, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, etc. There is.
More preferable acid compounds include compounds having a hydroxyalkyl group directly connected to a nitrogen atom and an acetic acid group, such as hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethyl. There is glycine.
Furthermore, an aqueous organic / inorganic hybrid particle dispersion excellent in dispersion stability can be obtained by adjusting at least a part of the acetic acid group of the acid compound to an optimum pH with a basic compound.
A compound in which the acid compound has an acetic acid group directly bonded to a nitrogen atom, a compound in which the acid compound has a hydroxyalkyl group and an acetic acid group directly bonded to the nitrogen atom, and at least a part of the acetic acid group of the acid compound is a complex salt with a polyvalent metal By adjusting to an optimum pH with a basic compound that forms, a polishing slurry excellent in metal polishing performance in addition to dispersion stability can be obtained.

The organic-inorganic hybrid particle in the present invention is a composite particle in which an organic polymer and an inorganic polymer are uniformly distributed in the same particle, and the properties as an inorganic polymer, such as wear resistance and heat resistance, It is a particle that also has characteristics as an organic polymer such as flexibility. The composite particles containing a reaction gel of a resin having an anionic group and a metal alkoxide according to the present invention are an example.
In the present invention, the metal alkoxide reaction gel is a wet gel or a dry gel containing a metal oxide formed by further proceeding with the sol formed by hydrolysis and polymerization of the metal alkoxide. .

The aqueous dispersion of organic-inorganic hybrid particles comprising a reaction gel of a resin having an anionic group and a metal alkoxide according to the present invention has a pH of 2.0 or more and less than 8.0, preferably 2.5 to 7.5 or less. Increases the adhesion between the reaction gel of the resin and the metal alkoxide, and provides excellent dispersion stability. In particular, a reaction gel of a resin having an anionic group and a metal alkoxide is formed at a pH of 8.0 or more in the presence of a base, and then the pH is 2.0 due to the addition of an acid compound or the volatilization of the base if the base is volatile. As described above, the aqueous dispersion adjusted to less than 8.0, preferably pH 2.5 to 7.5, is an organic-inorganic hybrid particle aqueous dispersion that is further excellent in dispersion stability.
The anionic group of the resin used in the production method of the present invention is not particularly limited and includes a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, and a phenolic hydroxyl group. A general resin can be used, which is preferable because it makes it easy to form organic-inorganic hybrid particles by the production method described later.

The resin having an anionic group is not particularly limited, such as a natural resin and a synthetic resin, but a resin suitable for the production method described below is preferably a resin soluble in an organic solvent in the absence of a basic compound. Specifically, acrylic acid resin, maleic acid resin, polyester resin, epoxy resin, phenol resin and the like can be mentioned, and these can be subjected to three-dimensional crosslinking by a known method as necessary after formation of the composite particles. As the acrylic resin, for example, a copolymer of (meth) acrylic acid with at least one monomer selected from the group consisting of styrene, substituted styrene, (meth) acrylic acid ester, and hydroxyalkyl (meth) acrylic acid ester is It is preferable in terms of resin particle formation and crosslinking with polyvalent metal ions.
Specifically, styrene; substituted styrene such as α-methylstyrene; acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid 2-ethylhexyl ester, and other acrylic acid esters; methacrylic acid methyl ester, ethyl methacrylate At least one monomer selected from esters, methacrylic acid esters such as butyl methacrylate and 2-ethylhexyl methacrylate; and hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate; and acrylic acid and methacrylic acid. A (meth) acrylic acid copolymer containing at least one monomer selected from acids is preferred.

The acid value of the resin having an anionic group is not particularly limited. However, when the acid value is less than 10, the resin tends to be insufficient in dispersibility, and an aqueous dispersion of organic-inorganic hybrid particles in the production method described later is formed. Tends to be insufficient. When the acid value exceeds 200, the resin tends to swell or dissolve in water in the production method described later, and it tends to be difficult to obtain a desired aqueous dispersion of organic-inorganic hybrid particles. For this reason, it is preferable that the acid value of resin which has anionic group exists in the range of 10-200. In particular, in the case of a self-water dispersible resin in the range of 50 to 200, since a part of the anionic group of the resin is neutralized with a base, it exhibits good dispersibility or solubility in water. More preferred.
The molecular weight range of the resin is not particularly limited, but a resin having a molecular weight of 1000 or more and 100,000 or less is more preferable. The ratio of the resin to the metal alkoxide is not particularly limited, but is preferably in the range of 0.01: 10 to 10: 1 by mass ratio. When used as a polishing slurry, a smaller resin ratio is more preferable in terms of polishing rate.
When increasing the hardness of organic-inorganic hybrid particles having a high resin ratio, it is not preferable to use a large amount of a monomer having a low glass transition temperature, such as (meth) acrylic acid ester, in the combination of the above monomers. The glass transition temperature of the resin is preferably room temperature or higher, preferably 50 ° C. or higher.

  The resin used in the method for producing an aqueous dispersion of organic-inorganic hybrid particles of the present invention can obtain particles having high strength by organic-inorganic hybridization. However, a crosslinkable monomer and an initiator or a catalyst are previously used as organic-inorganic hybrid particles. Incorporating and cross-linking after particle formation, or preferably taking polyvalent metal ions when forming organic-inorganic hybrid particles to form a so-called ionomer resin in which a part of the anionic group of the resin having an anionic group is cross-linked Thus, it can be made tougher organic-inorganic hybrid particles.

The metal of the polyvalent metal alkoxide used in the production method of the present invention is a divalent or higher polyvalent metal, silicon, titanium, zirconium, cerium, calcium, barium, manganese, zinc, nickel, tin, copper, iron, cobalt , Boron, aluminum, tungsten, bismuth, molybdenum, niobium, yttrium, strontium, gallium, germanium, and the like, but are not limited thereto, and at least one kind can be included.
As the alkoxide combined with the metal, at least one alkoxy group (OR) is bonded to the metal, and R of the alkoxy group (OR) is an alkyl group, an alkylene group, an allyl group, a vinyl group, or a vinylbenzyl group. , A (meth) acrylate group or the like may be selected arbitrarily, but an alkyl group having 1 to 4 carbon atoms is common and easy to use. In addition, other functional groups may be directly bonded to the metal. For example, a hydroxyl group, an alkyl group, an alkylene group, an allyl group, a vinyl group, a vinylbenzyl group, a (meth) acrylate group, a carboxyl group, an acetylacetone group, an acetoacetate group. There are ligands such as acetate groups. When all the functional groups bonded to the metal are alkoxy groups, it is possible to form an inorganic polymer chain consisting only of siloxane bonds by hydrolytic polycondensation of the metal alkoxide, and to exhibit higher properties as an inorganic compound. This is preferable. Specific examples of the compound include, but are not limited to, the following.

In the present invention, the base is used to improve the solubility and dispersibility of the resin having an anionic group and to proceed with the hydrolysis and condensation of the metal alkoxide. At least a part of the anionic group in the resin having an anionic group is neutralized to form a counter ion with the base, thereby increasing the hydrophilicity of the resin. The basic compound used is a monovalent base, and examples thereof include alkali metals such as lithium, potassium and sodium, ammonia, and organic bases such as organic amine, alcohol amine, morpholine and pyridine. These act as hydrolysis catalysts for metal alkoxides, but as catalysts, alcohol amines such as monoethanolamine, diethanolamine, triethanolamine, etc. that have the effect of suppressing rapid hydrolysis of metal alkoxides. It is preferable to use it because the resin and the metal oxide are more uniformly mixed during emulsification. Among them, the volatile base useful in the present invention includes the above-mentioned ammonia or organic amines. When these organic-inorganic hybrid particles of the present invention are used, for example, as a polishing agent, particularly in semiconductors, the alkali metal ion component is reduced as much as possible, and the use of alcohol amine or the like leads to semiconductor characteristics due to residual metal ions. It is preferable because the adverse effect of can be eliminated.

The amount of the monovalent base used should be an amount corresponding to 10% or more, preferably 50 mol% or more of the anionic group of the resin, and an amount corresponding to 100 mol% or more if necessary depending on the purpose of use. Even when a base is added, an aqueous dispersion of organic-inorganic hybrid particles that are stable in a fine particle size with an increased free base amount can be obtained.
On the other hand, when the amount of the monovalent base added is reduced, the particle diameter of the organic-inorganic hybrid particles can be increased. Thus, by adjusting the amount of monovalent base, an aqueous dispersion of organic-inorganic hybrid particles having a uniform particle size and an arbitrary particle size can be obtained.

  The aqueous dispersion of the organic-inorganic hybrid particles may sometimes cause gelation, particularly in the presence of alkali. Therefore, the pH of the aqueous dispersion needs to be adjusted to 2.0 or more and less than 8.0. When a volatile base is used in the hydrolysis step of the metal alkoxide, the pH can be adjusted by volatilizing the base, but by adding an acid compound into the aqueous medium. You can also. Examples of acid compounds that can be used include general hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid, phosphonic acid, sulfonic acid, oxalic acid having a hydroxyalkyl group and a carboxyl group in the same molecule, glycolic acid, Although there are diglycolic acid and the like, it is preferable to use an acid compound having a metal polishing effect because polishing properties and dispersion stability as a polishing slurry can be simultaneously provided. As an acid compound having a metal polishing effect, a compound having an acetic acid group directly bonded to a nitrogen atom, specifically, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2 -Hydroxypropanetetraacetic acid and the like.

  More preferable acid compounds are compounds having a hydroxyalkyl group and an acetic acid group directly connected to a nitrogen atom, and compounds having a hydroxyalkyl group and an acetic acid group directly connected to a nitrogen atom. Specifically, hydroxyethyliminodiacetic acid, hydroxy A compound selected from ethylethylenediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, and dihydroxyethylglycine is preferred.

  Although it is necessary to adjust the pH of the aqueous dispersion of the present invention to 2.0 or more and less than 8.0, the dispersion of the organic-inorganic hybrid particles is particularly adjusted by adjusting the pH to a range of 2.5 to 7.5. The stability can be kept better, which is preferable. A polishing slurry obtained from an aqueous dispersion containing an acetic acid group directly connected to the nitrogen atom or a compound having a hydroxyalkyl group and an acetic acid group is excellent in polishing performance, particularly metal polishing performance, in addition to the stability of the slurry. This is presumably because the chelate structure was imparted to the surface of the organic-inorganic hybrid particles and the chelate performance was expressed.

  In addition, the acid compound does not need to be completely free of acid groups, and some of the acid groups are alkali metals such as Na and Li, ammonia, organic amines, alcohol amines, and other basic groups such as pyridine, morpholine, etc. It may be neutralized with a compound. However, alkali metals are generally not preferred for applications such as electronic parts.

  Moreover, when a basic compound itself forms a complex salt with a polyvalent metal, it exhibits a polishing effect excellent in metal polishing. Examples of basic compounds that form complex salts with polyvalent metals include the above-mentioned ammonia and alcohol amines, triazole compounds such as benzotriazole, tolyltriazole, and 1-hydroxybenzotriazole, benzimidazole compounds, o-phenanthroline, 2, 2 Examples include, but are not limited to, '-bipyridyl, 3-methyl-1-phenyl-5-pyrazolone. By using a basic compound that forms a complex salt with these polyvalent metals and an acid compound such as hydroxyalkyliminocarboxylic acid, an excellent metal polishing performance is exhibited due to its synergistic effect.

In order to use the aqueous dispersion of the present invention as a metal polishing slurry, known etchants include, in addition to the above compounds, water-soluble chelate compounds, aminoacetic acids such as glycine, amidosulfuric acid, or mixed acids thereof. Etching agents containing oxidizing agents such as hydrogen peroxide, nitric acid, hypochlorous acid, and ozone water.
As a chemical reagent that forms a protective film by reacting with a metal material, in addition to the basic compound that forms a complex salt with the polyvalent metal, amino acids including thiourea, salicylaldoxime, cuperone, ethylenediamine, and sulfur, particularly Cysteine, p-aminobenzaldehyde, haloacetic acid, thiols such as phosphonic acids such as dodecyl mercaptan and octane phosphonic acid, monosaccharides such as glucose and fructose, and derivatives of these substances or mixtures thereof, N-benzoyl-N- Phenylhydroxylamine or a BPA derivative thereof can be used.
Further, aqueous solutions of nitric acid, ammonia, ammonium salts such as ammonium persulfate, ammonium nitrate, ammonium chloride, and chromic acid can also be used.
In addition, preservatives, surfactants, and the like can be used in combination with the metal polishing slurry.

An aqueous dispersion of organic-inorganic hybrid particles comprising a reaction gel of a resin having an anionic group and a metal alkoxide according to the present invention, the aqueous dispersion of organic-inorganic hybrid particles having a pH adjusted to 2.0 or more and less than 8.0 Specifically as a manufacturing method of a body, it can manufacture with the manufacturing method which has the following processes.
(1) A polyvalent metal alkoxide or a hydrolysis-condensation product of a polyvalent metal alkoxide is dissolved or suspended in an aqueous solution having an anionic group neutralized with a basic compound and having an anionic group at pH 8.0 or higher. A mixing step for producing a turbid mixture;
(2) a hydrolysis step of hydrolyzing or hydrolyzing and condensing the polyhydric metal alkoxide or the polyhydric metal alkoxide hydrolysis condensation product in the mixture while maintaining the pH of the mixture at 8.0 or higher; ,
(3) pH adjustment is performed so that the pH of the mixture is 2.0 or more and less than 8.0, preferably pH 2.5 or more and 7.5 or less, and the solubility of the resin in the mixture is lowered to emulsify the mixture. Alternatively, a granulation step of suspending and precipitating a hydrolysis condensation product of a resin and a polyvalent alkoxide,
(4) A method for producing an aqueous dispersion of organic-inorganic hybrid particles, comprising a step of hydrolyzing and polycondensing the mixture, to which an acid compound having a hydroxyl group is added as necessary, and gelling within the particles.

  That is, in the method for producing an aqueous dispersion of the present invention, an acid compound is added to a resin solution containing a polyvalent metal alkoxide or a hydrolysis condensation product of a polyvalent metal alkoxide to reduce the solubility of the resin. And a polyhydric metal alkoxide or a polyhydric metal alkoxide hydrolyzed condensation product are emulsified or granulated and simultaneously silanol groups on the particle surface are blocked. More preferably, the polyhydric metal alkoxide or polyvalent metal alkoxide in the mixture particles is further subjected to hydrolysis and polycondensation to perform gelation in the particles to produce an aqueous dispersion of organic-inorganic hybrid particles.

Hereinafter, a detailed description will be given for each step of the production method effective for the present invention.
(1) Mixing step for preparing a mixture in which a polyvalent metal alkoxide is dissolved or suspended in an aqueous resin solution of a resin having an anionic group In the mixing step, a resin having an anionic group and a polyvalent metal alkoxide or a polyvalent metal alkoxide A hydrolysis condensation product of a valent metal alkoxide and a basic compound are added to produce an aqueous resin solution containing a polyvalent metal alkoxide or a hydrolysis condensation product of a polyvalent metal alkoxide.
If the polyvalent metal alkoxide is brought into contact with water before it is incorporated into the resin, hydrolysis proceeds excessively and agglomerates are likely to be formed. Therefore, in order to produce uniform organic-inorganic hybrid particles, the alcohol-based solvent described above is used. Such a hydrolysis inhibitor may be used. By using alcohol together, hydrolysis of the polyhydric metal alkoxide, which is a dealcoholization reaction, is suppressed. On the other hand, the solubility of the polyvalent metal alkoxide in the aqueous resin solution is increased, and the resin and the polyvalent metal alkoxide are uniformly distributed. It is preferable because it is easy to mix. Examples of hydrolysis inhibitors include alcohol amines that also act as bases and alcohols that also act as solvents for dissolving resins, as well as chelating agents such as acetylacetone, acetoacetate, alkyl acetoacetate, acetoin, and diethylene glycol. -Polyols such as polyethylene glycol can be suitably used.

  In the mixing step, a water-miscible organic solvent for dissolving the resin having an anionic group can be used in combination. Examples of water-miscible organic solvents include ketone solvents such as acetone, dimethyl ketone, and methyl ethyl ketone, alcohol solvents such as methanol, ethanol, and isopropyl alcohol, ester solvents such as ethyl acetate, ethylene glycol monomethyl ether, and ethylene glycol dimethyl ether. Any solvent can be used as long as it dissolves the resin and is water-miscible either alone or in combination with other organic solvents, such as glycol ether solvents such as amides.

  If necessary, inorganic or organic insoluble particles may be added to the mixture. In the addition of these particles, it is necessary to disperse in the mixture after the addition, or to add a self-water-dispersible resin in the mixture, a resin compatible with the solvent, or a material dispersed in the solvent to the mixture. Can do. By using inorganic or organic particles prepared separately in this way, these particles can be used as a core and the surface can be coated with the hybrid of the present invention to facilitate particle formation or reduce manufacturing costs. Can do.

(2) Hydrolysis condensation step In the hydrolysis condensation step, polyvalent metal alkoxide hydrolysis and condensation using a base catalyst in order to make the pH of the resin solution containing an anionic group 8.0 or higher. Or subjecting the hydrolysis condensation product of the polyvalent metal alkoxide to further hydrolysis condensation. A known base catalyst is used, but a part of the emulsifying base for making an aqueous dispersion of a resin having an anionic group may be used as the base catalyst. Specific examples include ammonia, organic amines such as alkylamine / alcoholamine, pyridine, piperazine and other basic compounds.

  In the hydrolysis-condensation step, the time and temperature conditions can be appropriately set according to the blending of the mixture, but in order to perform sufficient hydrolysis and condensation before the emulsification granulation step, it is at room temperature or more and 3 to 48 hours. preferable. The polyhydric metal alkoxide may be hydrolyzed and condensed at the same time as the next step (emulsification), but the hydrolysis and condensation step should proceed sufficiently in the mixture before the emulsification (particle formation) step. Thus, particles in which the inorganic material and the organic polymer are more uniformly mixed can be formed. Also, the storage stability of the aqueous dispersion is improved.

  As a result of the hydrolysis-condensation step, the metal oxide sol is formed as a hydrolysis product or condensation product from the polyvalent metal alkoxide. Formation of a product gel is not preferable because it easily becomes an obstacle to the subsequent emulsification process.

(3) Emulsification step or granulation step of mixture In the emulsification granulation step, a uniform mixture of resin and metal oxide sol which is a hydrolysis condensate of polyvalent metal alkoxide formed in the hydrolysis condensation step is used. Emulsify or granulate in water.
The method of emulsifying or granulating the mixture can be performed by lowering the solubility of the resin in the mixture. Specific methods include volatilizing a part of water as a solvent and reducing the solubility of the resin by lowering the temperature. However, in the production method of the present invention, the resin is prepared by lowering the pH of the mixture. A method of reducing solubility is used. This method is preferable because the solubility of the resin can be easily controlled.

  The acid is added little by little to the mixture with stirring to lower the pH to such an extent that the resin does not harden, that is, 2.0 or more and less than 8.0, and a volatile basic compound is used as the basic compound in advance. In addition, a method of volatilizing the basic compound can be used. In this case, there is an advantage that alcohol generated by hydrolysis and polycondensation of the metal alkoxide is also distilled off. When the solubility of the resin is lowered, an emulsion is formed in which the hydrophobic group of the resin gradually faces inward and the hydrophilic group faces outward, and the mixture containing the resin becomes emulsified.

(4) Intraparticle gelation step If necessary, the polyvalent metal alkoxide or polyvalent metal alkoxide contained in the droplets of the mixture formed and emulsified or granulated as described above is hydrolyzed. Further condensation of the condensation product proceeds to promote intraparticle gelation. In this step, by heating and distilling off the alcohol produced by hydrolysis condensation, intra-particle gelation proceeds further, and organic-inorganic hybrid particles in which the metal oxide gel and the resin are uniformly mixed are formed.

  In the production method of the present invention, in a suitable stage of the process including at least a resin having an anionic group and a metal alkoxide, aging is performed at a temperature of room temperature or higher, preferably 30 ° C. or higher and 100 ° C. or lower. This is useful in preparing a dispersion of emulsified particles made of gel.

  An aqueous dispersion containing abrasive particles made of organic-inorganic hybrid particles obtained according to the above-described production method is used as an aqueous abrasive slurry as it is, and an organic solvent having a boiling point lower than that of water as much as possible after emulsification is used. It is desirable to prepare by introducing a step of removing, whereby the dissolution and swelling of the abrasive particles are eliminated, and an excellent polishing ability and a stable aqueous dispersion can be obtained.

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “part” represents “part by mass”.
Example 1
Ammonia aqueous solution of acrylic resin (acrylic acid / styrene / 2-ethylhexyl acrylate = 55/20/25; acid value 160; molecular weight 27,000) (resin content 20 mass%, 28% ammonia water 4.5% ) While stirring a mixed solution of 0.5 parts, 0.2 parts of 4% aqueous ammonia and 88.6 parts of water, 10 parts of Si (O—C ₂ H ₅ ) ₄ was added and stirred at 80 ° C. for 3 hours. Thus, a dispersion having a pH of 8.5 was obtained.

A part of the obtained dispersion liquid was distilled off ethanol, ammonia, a part of water and residual Si (O—C ₂ H ₅ ) ₄ generated from Si (O—C ₂ H ₅ ) ₄ using a rotary evaporator to obtain a pH of 6 .9, an aqueous dispersion having a solid content of 5% was obtained. Coarse particles were removed by centrifugation to obtain an organic-inorganic hybrid particle fat particle aqueous dispersion. The obtained organic-inorganic hybrid particles had a volume average particle size of 20 nm, good particle size uniformity, no sediment, and stable dispersion.
3 parts of nitrilotriacetic acid diammonium salt and 3 parts of 30% hydrogen peroxide solution were added to 100 parts of the obtained aqueous dispersion of organic-inorganic hybrid particles to obtain a polishing slurry having a pH of 3.5.
Using the obtained polishing slurry, using a desktop small lapping machine FACT200S (manufactured by Nano Factor Co., Ltd.), a load of 100 g / cm ² , a rotation speed of 80 rotations 30 minutes, a slurry supply amount 20 ml, a polishing pad surfin-ssw-1 ( Copper was polished with Fujimi Incorporated. The surface of the obtained copper had a metallic luster and the average roughness Ra value was 15 nm. The polishing rate was 2000 mm / min in thickness.

(Comparative Example 1)
Copper was polished in the same manner with the slurry composition excluding nitrilotriacetic acid diammonium salt of Example 1. The obtained copper surface had no metallic luster and was hardly polished.

(Example 2)
Ammonia aqueous solution of acrylic resin (acrylic acid / styrene / 2-ethylhexyl acrylate = 55/20/25; acid value 160; molecular weight 27,000) (resin content 20 mass%, 28% ammonia water 4.5% ) While stirring a mixed solution of 0.5 parts, 0.2 parts of 4% aqueous ammonia and 88.6 parts of water, 10 parts of Si (O—C ₂ H ₅ ) ₄ was added and stirred at 80 ° C. for 3 hours. Thus, a dispersion having a pH of 8.5 was obtained.

Ethylenediaminetetraacetic acid (0.1 part) was added to the obtained dispersion and stirred at 80 ° C. for 1 hour, and then a part of ethanol, ammonia and water produced from Si (O—C ₂ H ₅ ) ₄ using a rotary evaporator. And residual Si (O—C ₂ H ₅ ) ₄ was distilled off to obtain an aqueous dispersion having a pH of 2.8 and a solid content of 5%. Coarse particles were removed by centrifugation to obtain an organic-inorganic hybrid particle fat particle aqueous dispersion. The obtained organic-inorganic hybrid particles had a volume average particle size of 30 nm, good uniformity in particle size, no sediment, and stable dispersion.
3 parts of nitrilotriacetic acid diammonium salt and 3 parts of 30% hydrogen peroxide solution were added to 100 parts of the obtained aqueous dispersion of organic-inorganic hybrid particles to obtain a polishing slurry having a pH of 3.5.
Using the obtained polishing slurry, using a desktop small lapping machine FACT200S (manufactured by Nano Factor Co., Ltd.), a load of 100 g / cm ² , a rotation speed of 80 rotations 30 minutes, a slurry supply amount 20 ml, a polishing pad surfin-ssw-1 ( Copper was polished with Fujimi Incorporated. The obtained copper surface had a metallic luster and the average roughness Ra value was 20 nm. The polishing rate was 1800 mm / min in thickness.

(Comparative Example 2)
Copper was polished in the same manner as in Example 2 except for the composition of ethylenediaminetetraacetic acid and nitrilotriacetic acid diammonium. The obtained copper surface had no metallic luster and was hardly polished.

(Example 3)
Ammonia aqueous solution of acrylic resin (acrylic acid / styrene / 2-ethylhexyl acrylate = 55/20/25; acid value 160; molecular weight 27,000) (resin content 20 mass%, 28% ammonia water 4.5% ) While stirring a mixed solution of 0.5 parts, 0.2 parts of 4% aqueous ammonia and 88.6 parts of water, 10 parts of Si (O—C ₂ H ₅ ) ₄ was added and stirred at 80 ° C. for 3 hours. Thus, a dispersion having a pH of 8.5 was obtained.

0.2 parts of hydroxyethyliminodiacetic acid was added to the obtained dispersion and stirred at 80 ° C. for 1 hour, and then ethanol, ammonia and water generated from Si (O—C ₂ H ₅ ) ₄ using a rotary evaporator. Part and residual Si (O—C ₂ H ₅ ) ₄ were distilled off to obtain an aqueous dispersion having a pH of 2.8 and a solid content of 5%. Coarse particles were removed by centrifugation to obtain an organic-inorganic hybrid particle fat particle aqueous dispersion. The obtained organic-inorganic hybrid particles had a volume average particle size of 25 nm, good particle size uniformity, no sediment, and stable dispersion.
3 parts of nitrilotriacetic acid diammonium salt and 3 parts of 30% hydrogen peroxide solution were added to 100 parts of the obtained aqueous dispersion of organic-inorganic hybrid particles to obtain a polishing slurry having a pH of 3.5.
Using the obtained polishing slurry, using a desktop small lapping machine FACT200S (manufactured by Nano Factor Co., Ltd.), a load of 100 g / cm ² , a rotation speed of 80 rotations 30 minutes, a slurry supply amount 20 ml, a polishing pad surfin-ssw-1 ( Copper was polished with Fujimi Incorporated. The surface of the obtained copper had a metallic luster and the average roughness Ra value was 15 nm. The polishing rate was 2000 mm / min in thickness.

(Comparative Example 3)
Copper was polished in the same manner with the same composition as Example 3 except for hydroxyethyliminodiacetic acid and nitrilotriacetic acid diammonium. The obtained copper surface had no metallic luster and was hardly polished.

Example 4
Ammonia aqueous solution of acrylic resin (acrylic acid / styrene / 2-ethylhexyl acrylate = 55/20/25; acid value 160; molecular weight 27,000) (resin content 20 mass%, 28% ammonia water 4.5% ) While stirring a mixed solution of 0.5 parts, 0.2 parts of 4% aqueous ammonia and 88.6 parts of water, 10 parts of Si (O—C ₂ H ₅ ) ₄ was added and stirred at 80 ° C. for 3 hours. Thus, a dispersion having a pH of 8.5 was obtained.
To the obtained dispersion, 2 parts of dihydroxyethylglycine and 0.5 part of 1-hydroxybenzotriazole were added, stirred at 80 ° C. for 1 hour, and then generated from Si (O—C ₂ H ₅ ) ₄ using a rotary evaporator. A part of ethanol, ammonia, water and residual Si (O—C ₂ H ₅ ) ₄ were distilled off to obtain an aqueous dispersion having a pH of 6.8 and a solid content of 5%. Coarse particles were removed by centrifugation to obtain an organic-inorganic hybrid particle fat particle aqueous dispersion. The obtained organic-inorganic hybrid particles had a volume average particle size of 20 nm, good particle size uniformity, no sediment, and stable dispersion.

3 parts of 30% aqueous hydrogen peroxide was added to 100 parts of the obtained aqueous dispersion of organic-inorganic hybrid particles to obtain a polishing slurry having a pH of 6.5.
Using the obtained polishing slurry, using a desktop small lapping machine FACT200S (manufactured by Nano Factor Co., Ltd.), a load of 100 g / cm ² , a rotation speed of 80 rotations 30 minutes, a slurry supply amount 20 ml, a polishing pad surfin-ssw-1 ( Copper was polished with Fujimi Incorporated. The surface of the obtained copper had a metallic luster and the average roughness Ra value was 10 nm. The polishing rate was 1800 mm / min in thickness.

(Comparative Example 4)
Copper was polished in the same manner as in the composition of Example 4 except for dihydroxyethylglycine and 1-hydroxybenzotriazole. The obtained copper surface had no metallic luster and was hardly polished.

The organic-inorganic hybrid particle aqueous dispersion and hybrid particles obtained from the method for producing an aqueous dispersion of organic-inorganic hybrid particles of the present invention include an abrasive, an anti-wear coating material or a molded product / adhesive, which uses its mechanical strength, Various industrial uses as particles alone or paints, such as various optical films and optical communication materials that utilize optical properties, electronic materials such as semiconductor encapsulants that utilize their electrical properties and heat resistance, and other composite materials Is possible.

Claims (14)

An aqueous dispersion of organic-inorganic hybrid particles comprising a reaction gel of a resin having an anionic group and a metal alkoxide, wherein the pH is adjusted to a range of 2.0 or more and less than 8.0, and the organic-inorganic hybrid is characterized in that An aqueous dispersion of particles. The organic-inorganic hybrid particle according to claim 1, wherein the organic-inorganic hybrid particle is formed by hydrolysis of the metal alkoxide in a resin solution in which the reaction gel in the particle has the anionic group having a pH of 8.0 or more. An aqueous dispersion of inorganic hybrid particles. The aqueous dispersion of organic-inorganic hybrid particles according to claim 2, wherein the pH range is adjusted by adding an acid compound. The aqueous dispersion of organic-inorganic hybrid particles according to claim 3, wherein the acid compound is added in the process of forming a resin solution containing a hydrolysis product of a metal alkoxide into particles. The aqueous dispersion of organic-inorganic hybrid particles according to claim 3 or 4, wherein the acid compound is a compound having an acetic acid group directly bonded to a nitrogen atom. The aqueous dispersion of organic-inorganic hybrid particles according to claim 5, wherein the acid compound is a compound having a hydroxyalkyl group and an acetic acid group directly bonded to a nitrogen atom. The compound having a hydroxyalkyl group and an acetic acid group directly bonded to a nitrogen atom is at least from the group consisting of hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, and dihydroxyethylglycine. The aqueous dispersion of organic-inorganic hybrid particles according to claim 6, which is at least one compound selected. The aqueous dispersion of organic-inorganic hybrid particles according to claim 3, wherein at least a part of the acetic acid group of the acid compound is neutralized with a basic compound. The aqueous dispersion of organic-inorganic hybrid particles according to claim 8, wherein the basic compound is a basic compound that forms a complex salt with a polyvalent metal. A polishing slurry comprising the aqueous dispersion of organic-inorganic hybrid particles according to claim 3 as a main component. A method for producing organic-inorganic hybrid particles comprising a resin having an anionic group and a reaction gel of a polyvalent metal alkoxide, wherein (1) a resin having an anionic group at least partially neutralized with a basic compound A mixing step for producing a mixture in which a polyvalent metal alkoxide is dissolved or suspended in an aqueous resin solution;
(2) a hydrolysis step in which the polyvalent metal alkoxide in the mixture is hydrolyzed or hydrolyzed and condensed while maintaining the pH of the mixture at 8.0 or higher under a base catalyst;
(3) A particle forming step of lowering the pH in the mixture to 2.0 or more and less than 8.0, lowering the solubility of the resin, and emulsifying or granulating the mixture, and the particle forming step Then, the manufacturing method of the aqueous dispersion of the organic-inorganic hybrid particle | grains characterized by adding an acid compound. The method for producing an aqueous dispersion of organic-inorganic hybrid particles according to claim 11, wherein the acid compound is an acid compound having an acetic acid group directly bonded to a nitrogen atom. The method for producing an aqueous dispersion of organic-inorganic hybrid particles according to claim 12, wherein the acid compound having an acetic acid group directly bonded to a nitrogen atom is a compound having a hydroxyalkyl group and an acetic acid group directly bonded to a nitrogen atom. The method for producing an aqueous dispersion of organic-inorganic hybrid particles according to claim 12 or 13, wherein at least a part of the acetic acid group of the acid compound is neutralized with a basic compound.