WO2011148660A1

WO2011148660A1 - Dispersant and dispersion composition

Info

Publication number: WO2011148660A1
Application number: PCT/JP2011/050895
Authority: WO
Inventors: 橋本　賀之; 昭充利根川; 和幸加藤
Original assignee: 第一工業製薬株式会社
Priority date: 2010-05-26
Filing date: 2011-01-19
Publication date: 2011-12-01

Abstract

Provided is a dispersant for non-aqueous dispersion media that can be used for a broad range of substances to be dispersed and which can exhibit excellent dispersion stability with small amounts added. The dispersant for non-aqueous dispersion media comprises a compound represented by Formula (1). R in Formula (1) represents a C1 to C24 alkyl group and/or alkenyl group that comprises an alkyl group and/or alkenyl group with a branched chain. AO in Formula (1) represents a C1 to C4 oxyalkylene group. n represents the mean number of moles of alkylene oxide added and is in the range of 1 to 30. X in Formula (1) is a connecting group comprising carbon atoms, hydrogen atoms and/or oxygen atoms.

Description

Dispersant and dispersion composition

The present invention relates to a dispersant and a dispersion composition using the dispersant.

Isotropic materials and / or anisotropic materials derived from inorganic or organic materials include hybrid materials, surface protective agents, conductive pastes, conductive inks, sensors, precision analysis elements, optical memories, liquid crystal display elements, nanomagnets, heat transfer materials. As a main material in application fields such as media, high-performance catalysts for fuel cells, organic solar cells, nano glass devices, abrasives, drug carriers, environmental catalysts, paints, printing inks, inkjet inks, resists for color filters, inks for writing instruments, etc. in use. In this case, the isotropic material and / or anisotropic material derived from the inorganic or organic material can be processed efficiently by preparing a dispersion as fine particles in an aqueous dispersion medium or non-aqueous dispersion medium. It is used industrially as a substance that improves product characteristics and material properties, contributes to quality stabilization and yield improvement during production.

On the other hand, there is a problem that stable dispersion of the dispersoid becomes difficult by changing the material of the dispersoid, reducing the particle size, and controlling the shape, and the dispersoid is agglomerated in the dispersion medium in a short time. Agglomeration of dispersoids not only causes a decrease in productivity, processing characteristics, handling characteristics, and yield in the production of the dispersion, but also causes deterioration in product characteristics, material properties and quality of the final product. In addition, it is known that undesired phenomena such as transparency, gloss, reduction in coloring power, color separation, and generation of cracks also occur in appearance. A dispersant is used to suppress such aggregation of the dispersoid and achieve dispersion stabilization.

As an organic compound having a carboxyl group as the proposed low molecular weight dispersant, for example, formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid In addition to saturated and unsaturated carboxylic acids having 1 to 20 carbon atoms such as myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid, hydroxycarboxylic acids, alicyclic groups having 6 to 34 carbon atoms, There are aromatic carboxylic acids. Examples of alkenyl succinic anhydrides include octenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, and the like. Examples of organic compounds having a thiol group include mercaptoethanol, mercapto-2-propanol, 1-mercapto-2, 3-propanediol, 3-mercaptopropyltrimethoxysilane, mercaptosuccinic acid, hexanethiol, pentanedithiol, and dodecanethiol. And alkanethiols such as undecanethiol and decanethiol. Examples of the organic compound having a phenol ring include triphenylphosphine, tributylphosphine, trioctylphosphine, and tributylphosphine. Examples of the organic compound having an amino group include propylamine, butylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, and oleylamine. In addition, as a high molecular weight dispersant, a polymer type dispersion having a skeleton such as a carboxyl group, an amino group, a hydroxyl group, an ester bond, an amide bond, an aromatic ring, and a heterocyclic ring, which was mainly developed as a dispersant for pigments and the like. The agent has also been diverted to this application, DISPERBYK series by BYK Chemie (Byk Chemie), Ciba EFKA series, Lubrizol (Lublizol), Solspse by Fuka Additives (EFKA Additives) The Dispalon series manufactured by Enomoto Kasei is available on the market.

In addition, the use of existing surfactants as dispersants has also been proposed. Examples of anionic surfactants include higher fatty acid salts, alkyl sulfonates, alpha olefin sulfonates, alkane sulfonates, and alkylbenzenes. Sulfonates, sulfosuccinates, alkyl sulfates, alkyl ether sulfates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha sulfo fatty acid methyl esters, methyl taurates and so on. Examples of the nonionic surfactant include glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene. Examples include fatty acid esters, fatty acid alkanolamides, and alkyl glucosides. Examples of amphoteric surfactants include alkyl betaines, fatty acid amidopropyl betaines, and alkylamine oxides. Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, and alkyl pyridinium salt. In addition, there are polymer surfactants such as fluorine-based surfactants, cellulose derivatives, polycarboxylates, and polystyrene sulfonates.

Studies have been made to obtain a stable dispersion composition by suppressing the aggregation of the dispersion using the above existing dispersant, but the dispersion medium, diversification of the dispersoid, and the particle size of the dispersoid are very small. The proposed dispersants have not yet fully satisfied the required properties in terms of production, diversification of shapes, higher quality of the final product, improved productivity, and advanced processing characteristics.

For example, when the dispersion medium is water, the interfacial adsorption action based on the hydrophobic interaction of the dispersant, the electroadsorption action due to the ionic group, the π-electron interaction derived from the aromatic ring, and between the particles, Use of electrostatic repulsion between particles by formation of multi-layers, dispersion stabilization by formation of steric barriers, and addition of protective colloids and thickeners as stabilizers are also effective, stabilizing dispersion and suppressing aggregation. A variety of measures that can achieve this can be adopted.

On the other hand, in non-aqueous dispersion media, the effects of hydrophobic interaction, electrical interface adsorption by ionic groups, and electrostatic repulsion are extremely limited. It depends greatly on the acid-base interaction between the specific sites of the particles and the dispersant. In other words, in practice, the selection of the dispersant is individually optimized depending on the surface characteristics of the dispersoid, and the use of the dispersant is extremely limited, and the affinity of the dispersant to the dispersion medium is also combined. In reality, it is necessary to select an optimum dispersant individually according to the dispersion medium to be used.

The various ionic surfactants described above are extremely effective as aqueous dispersants, but many of them cannot be dissolved in a non-aqueous dispersion medium, and their application range is extremely limited.

In addition, when the size of the dispersoid particles is a micrometer size, it is possible to design a dispersion system by adopting multi-point adsorption by a plurality of adsorption points and forming a high density and thick protective layer of a three-dimensional barrier, so that a high molecular weight dispersant However, when the size of the dispersoid particles is nanometer size or sub-nanometer size, the dispersion system design with a high molecular weight dispersant is considered due to the difference between the size of the dispersoid particles and the size of the dispersant molecules. Can be difficult or limited. That is, when a high molecular weight dispersant having a remarkably large molecular size relative to the size of the dispersoid particles is used, there are many points between the dispersoid particles and the dispersant and between the dispersant molecule and the dispersant molecule. Adsorption, entanglement, and bridging occur, and aggregation of dispersoid particles is promoted, which has an essential problem in terms of dispersion stabilization.

Furthermore, in order to direct dispersion stabilization, it is a regular method to design a dispersion system using stronger interaction between the dispersoid particles and the dispersant. In addition to ensuring the mechanical and chemical stability of the dispersion composition, taking out the dispersoid particles, and forming a film (high gloss, low temperature and short film-forming properties), in removing the dispersant, Easy separation from the interface is also required as a required performance, which is an important factor in improving the productivity of the final product, processing characteristics, and stabilizing the quality. In this respect as well, existing dispersants do not sufficiently satisfy the required performance.

A nanometer-sized inorganic fine particle (particle size 1 to 100 nm) or a composite material in which organic fillers or pigments are finely dispersed in a resin is called a polymer nanocomposite, but nanometer-size particles easily aggregate and Due to the low affinity, it is very difficult to disperse uniformly in the resin. In order to uniformly disperse nanometer-sized particles in a resin, it is difficult or limited to use an aqueous dispersion medium. Usually, a nanoparticle is uniformly dispersed in a non-aqueous dispersion medium using a dispersant. It is effective to prepare a dispersion, and dissolve and mix the resin in the dispersion, or mix and dissolve and disperse the dispersion in a solution in which the resin is dissolved in a solvent. .

In addition, as a pretreatment for easily redispersing metal particles, metal oxides, pigments and various fillers in a dispersion medium or resin, the dispersoid particles are coated with a surface modifier or a surface protective agent or dispersed. Technology is known to impregnate the surface particles with a surface modifier, etc., but in the prior art, the type of dispersion medium and the amount of dispersoid added are often limited, and the range of use is extremely limited. No dispersant, surface modifier or surface protective agent has been found that can solve this problem. Dispersants that can solve the above problems, that is, without being limited by the type of dispersion medium and the amount of dispersoid added, find a dispersant that is versatile for a wide range of materials, and non-aqueous using the dispersant Using the dispersion or the dispersant as a surface modifier or surface protective agent for a dispersoid, a powdery, granular or pasty substance coated with or impregnated with the dispersant is obtained. If they are used, they are of great industrial utility in terms of solvent substitution, polarity change, mixing with resins and resin solutions.

For example, as this type of prior art, Patent Document 1 discloses metal colloidal particles composed of metal nanoparticles (A) and protective colloids (B) covering the metal nanoparticles (A), Metal colloidal particles in which the protective colloid (B) is composed of an organic compound (B1) having a carboxyl group and a polymer dispersant (B2) are disclosed.

JP 2009-74171 A

Patent Document 1 discloses a dispersant having a carboxyl group. This dispersant is useful when the dispersion medium is water, but dispersibility is poor in a non-aqueous dispersion medium.

The present invention has been made in view of such problems of the prior art, and its purpose is applicable to a wide range of dispersoids, and exhibits excellent dispersion stability with a small amount of addition. An object of the present invention is to provide a dispersant for a non-aqueous dispersion medium that can be used.

Another object of the present invention is to provide a dispersion composition using the dispersant.

Furthermore, an object of the present invention is to provide organic particles or inorganic particles coated with or impregnated with the dispersant.

In order to achieve the above object, the dispersant for a non-aqueous dispersion medium of the present invention comprises a compound represented by the following formula (1).

However, the meaning of the code | symbol of Formula (1) is as follows.
R represents an alkyl group and / or alkenyl group having 1 to 24 carbon atoms containing a branched alkyl group and / or alkenyl group.
AO represents an oxyalkylene group having 1 to 4 carbon atoms, n represents the average number of moles of alkylene oxide added and is in the range of 1 to 30.
X is a linking group consisting of a carbon atom, a hydrogen atom and / or an oxygen atom.
X in the formula (1) is preferably an alkylene group having 1 to 15 carbon atoms.
Further, X in the formula (1) is preferably a substance represented by the following formula (2).

However, the meanings of the symbols in the formula (2) are as follows.
Y is any one selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.
Those which are organic particles and / or inorganic particles which are coated with the dispersant or impregnated with the dispersant are preferred.
What is a dispersion composition formed by dispersing organic particles or inorganic particles in a non-aqueous dispersion medium using the dispersant is preferred.
A member obtained by applying a coating composition containing the dispersion composition using a resin as a non-aqueous dispersion medium on a substrate and then reacting physically or chemically is preferable. A member obtained by physically or chemically reacting after coating a coating composition containing a mixture of the above dispersion composition using a solvent as a non-aqueous dispersion medium with a resin is preferable. .

According to the present invention, it is possible to provide a dispersant for a non-aqueous dispersion medium that can be applied to a wide range of dispersoids and can exhibit excellent dispersion stability with a small amount of addition. Moreover, the dispersion composition which uses the dispersing agent, and the film which consists of the dispersion composition can be provided. Furthermore, organic particles or inorganic particles that are coated with or impregnated with the dispersant can be provided.

The dispersant for non-aqueous dispersion medium of the present invention comprises a compound represented by the following formula (1).

As described in the formula (1), the dispersant for a non-aqueous dispersion medium of the present invention is composed of a dispersion medium affinity part containing an alkylene oxide chain and a dispersoid affinity part consisting of a carboxyl group. The affinity parts are linked by a linking group X.
However, the meaning of the code | symbol of Formula (1) is as follows.
R represents an alkyl group and / or alkenyl group having 1 to 24 carbon atoms containing a branched alkyl group and / or alkenyl group.
AO represents an oxyalkylene group having 1 to 4 carbon atoms, n represents the average number of moles of alkylene oxide added and is in the range of 1 to 30.
X is a linking group consisting of a carbon atom, a hydrogen atom and / or an oxygen atom.

Hereinafter, preferred embodiments of the present invention will be described in detail.

1. About hydrophobic group (R)
Regarding the hydrophobic group (R) that can be used in the dispersant of the present invention, R is a hydrocarbon group derived from alcohol, and R is a C1-C24 group, and is a branched alkyl group and / or alkenyl group. When R is an alkyl group and / or an alkenyl group, the raw material alcohol that can be used may have a single carbon number or a mixture of alcohols having different carbon numbers. The raw material alcohol may be synthetically or naturally derived, and the chemical structure may be a single composition or a mixture of a plurality of isomers. As the raw material alcohol that can be used, known alcohols can be selected. Specific examples include butanol, isobutanol, pentanol and / or its isomer, hexanol and / or its isomer, heptanol and / or its isomer derived from synthesis. , Octanol and / or its isomer, 3,5,5-trimethyl-1-hexanol, isononanol, isodecanol, isoform produced by the oxo process via higher olefins derived from propylene or butene, or mixtures thereof Undecanol, isododecanol, isotridecanol, Neodol 23, 25, 45 manufactured by Shell Chemicals, SAFOL23 manufactured by Sasol, EXXAL7, EXXAL8N, EXXAL9, EXXAL10, EXXAL11 and EXXXA manufactured by Exxon Mobil 13 illustrates another example of a higher alcohol which can be suitably used. Furthermore, natural octyl alcohol, decyl alcohol, lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), stearyl alcohol (1-octadecanol), oleyl alcohol (Cis-9-octadecene-1-ol) and the like are also examples of higher alcohols that can be used. A single composition of Guerbet Alcohol having a 2-alkyl-1-alkanol type chemical structure, or a mixture thereof is also an example of a higher alcohol that can be suitably used. 2-ethyl-1-hexanol 2-propyl-1-hexanol, 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-heptanol, 2-ethyl-1-octanol, 2-hexyl-1-decanol, 2 In addition to heptyl-1-undecanol, 2-octyl-1-dodecanol, 2-decyl-1-tetradecanol, there are isostearyl alcohols derived from branched alcohols. Moreover, it is also possible to mix | blend and use 2 or more types of said various alcohol. However, in the dispersant of the present invention, as described above, the hydrophobic group (R) that is suitably selected is an alcohol-derived hydrocarbon group having 3 to 24 carbon atoms, and a branched alkyl group and / or alkenyl group. When the content of the group is 70% by weight or more, it can be suitably used to achieve the object of the present invention.

When the hydrophobic group (R) is hydrogen or a hydrocarbon group having 1 to 2 carbon atoms, or when the carbon number exceeds 25, the hydrophobic group (R) has a carbon number in the range of 3 to 24. Even in some cases, when the content of the linear alkyl group and / or alkenyl group exceeds 30% by weight, the dispersoid cannot be stably dispersed in the non-aqueous dispersion medium or can be used. The selection range of the medium may be limited, or substitution or mixing with a different type of dispersion medium may occur in the dispersion preparation process. As a result, the stability of the dispersion is significantly reduced, resulting in immediate sedimentation, and the stability over time is significantly reduced, resulting in problems such as a decrease in added value, productivity, processing characteristics, and quality deterioration of the final product. . In order to avoid these problems and make the action of the dispersant of the present invention particularly effective, the hydrophobic group (R) is more preferably a branched alkyl group having 8 to 18 carbon atoms. .

2. Oxyalkylene group (AO) n
For the alkylene oxide species suitably selected for the dispersant of the present invention, in formula (1), AO represents an oxyalkylene group having 1 to 4 carbon atoms, specifically, the alkylene oxide having 2 carbon atoms is ethylene oxide. The alkylene oxide having 3 carbon atoms is propylene oxide. The alkylene oxide having 4 carbon atoms is tetrahydrofuran or butylene oxide, and is preferably 1,2-butylene oxide or 2,3-butylene oxide. In the dispersant of the present invention, the oxyalkylene chain (-(AO) n-) is a random polymerization of two or more alkylene oxides even if the alkylene oxide is a homopolymer chain for the purpose of adjusting the dispersion medium affinity of the dispersant. It may be a chain, a block polymer chain, or a combination thereof. N which shows the average added mole number of the alkylene oxide of Formula (1) is in the range of 1 to 30, but is preferably in the range of 3 to 20.

3. Linking group (X)
The linking group (X) can be selected from a known structure consisting of a carbon atom, a hydrogen atom, and an oxygen atom, preferably a saturated hydrocarbon group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, or an ester group. It may have an alicyclic structure or an aromatic ring structure, and may have a repeating unit. When the linking group X contains a nitrogen atom and / or a sulfur atom and / or a phosphorus atom, the linking group X is not suitable as a structural factor of the dispersant of the present invention because it has an action of weakening the affinity effect of the carboxyl group on the dispersoid. .

Further, X in the formula (1) is preferably an alkylene group having 1 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

Further, X in the formula (1) is preferably a substance represented by the following formula (2).

However, the meanings of the symbols in the formula (2) are as follows.
Y is any one selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.

4). More preferable dispersant In the present invention, the dispersant described in the following formula (3) can be more preferably used.

However, in formula (3), R is preferably a branched alkyl group having 8 to 18 carbon atoms, and n is the average number of moles of ethylene oxide added, preferably in the range of 3 to 20. By limiting the composition of the dispersant to this range, the applicability to expansion of the selection range of non-aqueous dispersion media that can be used for dispersion preparation, mixing of different types of dispersion media, and substitution is improved. In this way, by limiting the composition range of the dispersant, it works more favorably with respect to the stability of the dispersion over time. Can be achieved.

5. Dispersant Production Method The dispersant of the present invention can be produced by a known method. For example, using a general nonionic surfactant compound obtained by adding an alkylene oxide to an alcohol, amine, or thiol by a known method as a raw material, a monohalogenated lower carboxylic acid or a salt thereof is used. Although it can manufacture by the method of making it react with a hydroxyl group, or the method of ring-opening reaction with the hydroxyl group of the alkylene oxide terminal using an acid anhydride, it is not limited to these methods.

6). Dispersoid particles The dispersoid particles dispersed by the dispersant of the present invention can be selected from inorganic particles and / or organic particles. For example, the inorganic substance-derived particles include iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, and alloys thereof, or a mixture thereof. Can be used. At that time, in order to stably take out the aforementioned metal particles from the medium, alkanoic acids and fatty acids, hydroxycarboxylic acids, alicyclic, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol derivatives, You may coat | cover with protective agents, such as amines, an amphiphilic polymer, a high molecular surfactant, and a low molecular surfactant. Others, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, Aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black , Graphite, rock wool, glass wool, glass fiber, carbon fiber, carbon nanofiber, carbon nanotube (single wall nanotube, double wall nanotube, multiwall nanochu B) etc. In addition, as organic particles, azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazolone, perylene, phthalocyanine, anthrapyridine, dioxazine, etc. Organic pigment, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, acetate fiber, cellulose, hemicellulose, lignin, chitin , Chitosan, starch, polyacetal, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone polybutylene terephthalate, polyethylene naphthalate, poly Chi naphthalate, polysulfone, polyphenylene sulfide, polyimides or the like. The dispersoid particles dispersed by the dispersant of the present invention may be crystalline or amorphous. Further, the dispersoid particles dispersed by the dispersant of the present invention may be isotropic particles, anisotropic particles, or may be fibrous.

As the dispersoid particles to be dispersed in the present invention, those obtained by a known method can be used. As a method for preparing fine particles, a top-down method in which coarse particles are mechanically pulverized and refined, and a bottom in which particles are formed through a cluster state in which several unit particles are generated and aggregated. Although there are two types of up systems, any one prepared by any method can be suitably used. Further, they may be either a wet method or a dry method. The bottom-up method includes a physical method and a chemical method, and any method may be used. The dispersant of the present invention may be used in a top-down process in which coarse particles are mechanically pulverized and refined to form a number of unit particles that pass through the agglomerated cluster state. May be used in a bottom-up process in which particles are formed, or after preparing fine particles in advance by the above-described method, a surface modifier or surface protection is used to stably remove the dispersoid particles from the medium. It is also possible to use particles taken out after being coated or impregnated with a known protective agent called an agent. As the protective agent, the above-mentioned known dispersants can be substituted.

In order to more specifically explain the bottom-up method, a method for preparing metal nanoparticles among the dispersoid particles will be exemplified. Among the bottom-up methods, a representative example of a physical method is an in-gas evaporation method in which bulk metal is evaporated in an inert gas and cooled and condensed by collision with the gas to generate nanoparticles. Chemical methods include a liquid phase reduction method in which metal ions are reduced in the liquid phase in the presence of a protective agent, and the generated zero-valent metal is stabilized at the nanosize, and a metal complex thermal decomposition method. is there. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, a method combining a chemical reduction method and a light irradiation method, or the like can be used.

Further, as described above, the dispersoid particles that can be suitably used in the present invention may be those obtained by any of the top-down method and the bottom-up method, and they are aqueous, non-aqueous, and in the gas phase. It may be prepared in any environment.

7). Dispersion medium The dispersion medium which can be used in the present invention includes toluene, xylene, aromatic hydrocarbon solvents, hydrocarbon solvents such as n-hexane, cyclohexane and n-heptane, and halogenated carbonization such as methylene chloride, chloroform and dichloroethane. Ether solvents such as hydrogen solvents, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, dibutyl ether, butyl ethyl ether, methyl-t-butyl ether, terpinyl methyl ether, dihydroterpinyl methyl ether, diglyme 1,3-dioxolane Solvent, acetone, acetophenone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, aceto Ketone solvents such as nilacetone, isophorone, cyclohexanone, methylcyclohexanone, 2- (1-cyclohexenyl) cyclohexanone methyl isobutyl ketone, cyclohexanone, isophorone, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, acetic acid Ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, (iso) amyl acetate, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, Ester solvents such as butyl lopionate, isoamyl propionate, γ-butyrolactone, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono n-butyl ether , Triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene glycol mono n-propyl ether, triethylene glycol mono n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono n-propyl ether, tripropylene glycol mono n-butyl ether, etc. And glycol ether solvents of these monoethers, and dialkyl ether solvents such as acetate solvents of diethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl isobutyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether. Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, heptanol, n-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol, tetrahydrofurfuryl Alcohol, furfuryl alcohol, allyl alcohol, ethylene chlorohydrin, octyldodecanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neoamyl alcohol Hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, heptyl alcohol, n-octyl alcohol, 2-ethylhexyl Lucol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, α-terpineol, terpineol C, L-α-terpineol, dihydroterpineol, terpinyloxyethanol, dihydroterpi Nyloxyethanol, Tersolve MTPH, Tersolve DTO-210, Tersolve THA-90, Tersolve THA-70 manufactured by Nippon Terpene Chemical Co., Ltd., cyclohexanol, 3-methoxybutanol, diacetone alcohol, 1,4-butanediol, octane Diol, etc., Fine Oxocol 140N, Fine Oxocol 1600, Fine Oxocol 180, Fine Oxocol manufactured by Nissan Chemical Industries, Ltd. Alcohol solvents such as 80N, fine oxocol 2000, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, hexylene glycol, polyethylene glycol, and polypropylene glycol Can be mentioned. Other examples include amide solvents such as dimethylacetamide and dimethylformamide. In addition, (meth) acrylic acid having a reactive group as a dispersion medium, (meth) acrylic acid esters, vinyl monomers such as vinyl acetate, vinyl ether derivatives, and ethylenically unsaturated monomers such as polyallyl derivatives Can also be used. In addition, various resins, oligomers, and monomers used for ordinary paints, adhesives, and moldings can be used without any particular limitation. Specific examples include acrylic resins, polyester resins, alkyd resins, urethane resins, silicone resins, fluororesins, epoxy resins, polycarbonate resins, polyvinyl chloride resins, and polypinyl alcohols. In addition, the said dispersion medium can be used suitably individually or in mixture of 2 or more types. The dispersant of the present invention is intended to provide a fine particle dispersion in a non-aqueous environment, whether intentionally or accidentally with respect to the dispersion medium, during the production process of the fine particle dispersion, Or, for the purpose of use or in the final product design, mixing or mixing of water is not denied.

8). Others The dispersant of the present invention can be produced by a known method, and the composition is optimally selected by specifically limiting the type of the hydrophobic group, the alkylene oxide type and its addition form, the added molar amount, the linking group, etc. within the above range. By doing so, a wider variety of dispersoids can be dispersed than in known dispersants, and the industrial utility value is great in that the dispersoids can be dispersed and stabilized in a wider variety of dispersion media.

In addition, the dispersant of the present invention can be used by reducing the content of ionic species, particularly alkali metal ions, alkaline earth metal ions, heavy metal ions, and halogen ions contained by a known purification method. The ionic species in the dispersant is greatly affected by the dispersion stability, touch resistance, oxidation resistance, electrical properties (conductive properties, insulation properties), aging stability, heat resistance, low humidity, and weather resistance of the dispersion. However, it is desirable that the content of the ions is less than 10 ppm in the dispersant.

The content of the dispersoid particles suitably used in the present invention in the dispersion medium is not particularly limited as long as it can be uniformly dispersed in the non-aqueous dispersion medium, and varies depending on the application. The content is preferably in the range of 0.5 to 70% by mass. The average particle diameter of the dispersoid particles is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 100 nm. Further, the preferred use condition of the dispersant of the present invention is preferably in the range of 1 to 300% by weight with respect to the dispersoid particles.

Also, the dispersion composition of the present invention can be prepared using known stirring means, homogenizing means, and dispersing means. Examples of dispersers that can be used include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibration ball mills, paint shakers, continuous disk type bead mills, bead mills such as continuous annular type bead mills, sand mills, and jets. Mill etc. are mentioned. Further, the dispersion treatment can be performed in an ultrasonic wave generation bath.

Further, the dispersant of the present invention not only exhibits an excellent dispersion stabilization effect compared to known techniques for the dispersion stabilization of dispersoid particles in a non-aqueous dispersion medium, but also disperses the dispersoid particles as a medium. It can be used as a protective agent for taking out from inside stably. Functions of the protective agent for stably taking out the dispersoid particles from the medium include suppression of aggregation of the generated particles, suppression of adsorption to the container wall surface and prevention of contamination, provision of easy redispersibility, oxidation of metal particles, prevention of particle surface Examples include surface modification, prevention of functional surface deterioration, solvent replacement and shock mitigation during polarity change, powder flowability improvement, and powder solidification prevention. The dispersant of the present invention is superior to the known protective agents in terms of the above functions, and is more suitable than the known protective agents by optimally selecting the addition form of alkylene oxide and the addition molar amount thereof, the type of hydrophobic group, the linking group, and the like. A desired dispersoid can be dispersed and stabilized in a wide range of dispersion media.

Coating composition containing the dispersion composition of the present invention using a resin as a non-aqueous dispersion medium or coating composition containing a mixture of the dispersion composition of the present invention and a resin using a solvent as a non-aqueous dispersion medium As a base material on which the coating is applied, for example, glass, resin film, glass composite, ceramics, metal / steel plate and the like can be used.

Hereinafter, examples and comparative examples of the present invention will be described. In the following, “part” indicating the blending amount indicates “part by weight” and “%” indicates “% by weight”. Needless to say, the present invention is not limited to the following examples, and appropriate changes and modifications can be made without departing from the technical scope of the present invention.

<Synthesis of dispersant>
[Production Example 1 (Synthesis of Dispersant 1)]
In a toluene solvent, 598 g (1 mol) of an isodecyl alcohol ethylene oxide 10 mol adduct and 151 g (1.3 mol) of sodium monochloroacetate were placed in a reactor and stirred uniformly. Thereafter, 52 g (1.3 mol) of sodium hydroxide was added under the condition that the temperature of the reaction system was 60 ° C., and then the temperature of the reaction system was raised to 80 ° C. and reacted for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. Subsequently, this white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain Dispersant 1 (R: isodecyl group, AO: ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 2 (Synthesis of Dispersant 2)]
The same procedure as in Production Example 1 was carried out except that 598 g (1 mol) of 2-propyl-1-heptyl alcohol ethylene oxide 10 mol adduct was used instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, Dispersant 2 (R: 2-propyl-1-heptyl group, AO: ethylene oxide, n: 10, X: CH ₂ ) was obtained.

[Production Example 3 (Synthesis of Dispersant 3)]
The same procedure as in Production Example 1 was conducted, except that 640 g (1 mol) of isotridecyl alcohol ethylene oxide 10 mol adduct was used instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, and dispersant 3 ( R: isotridecyl group, AO: ethylene oxide, n: 10, X: CH ₂ ) was obtained.

[Production Example 4 (Synthesis of Dispersant 4)]
In place of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, 1080 g (1 mol) of isotridecyl alcohol ethylene oxide 20 mol adduct was used, and the same operation as in Production Example 1 was carried out. R: isotridecyl group, AO: ethylene oxide, n: 20, X: CH ₂ ) was obtained.

[Production Example 5 (Synthesis of Dispersant 5)]
Instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, 710 g (1 mol) of ethylene oxide 5 mol / propylene oxide 5 mol random adduct of branched C11-14 alcohol (product name: EXXAL13, manufactured by Exxon Mobil) ) Was used in the same manner as in Production Example 1 to obtain Dispersant 5 (R: branched C11-14 alkyl group, AO: ethylene oxide and propylene oxide, n: 10, X: CH ₂ ).

[Production Example 6 (Synthesis of Dispersant 6)]
Instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, 668 g (1 mol) of propylene oxide 2 mol / ethylene oxide 8 mol block adduct of branched C11-14 alcohol (product name: EXXAL13, manufactured by ExxonMobil) ) Was used in the same manner as in Production Example 1 to obtain a dispersant 6 (R: branched C11-14 alkyl group, AO: propylene oxide and ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 7 (Synthesis of Dispersant 7)]
Instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10-mole adduct, 954 g (1 mol) of isobutyl alcohol ethylene oxide 20-mole adduct was used, and the same operation as in Production Example 1 was carried out, and dispersant 7 (R: An isobutyl group, AO: ethylene oxide, n: 20, X: CH ₂ ) was obtained.

[Production Example 8 (Synthesis of Dispersant 8)]
Instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, 306 g (1 mol) of isobutyl alcohol propylene oxide 4 mol adduct was used, and the same operation as in Production Example 1 was carried out, and dispersant 8 (R : Isobutyl group, AO: propylene oxide, n: 4, X: CH ₂ ).

[Production Example 9 (Synthesis of Dispersant 9)]
Dispersant 9 (R: isobutyl group, AO: ethylene oxide, n: 20, X) by reacting 954 g (1 mol) of isobutyl alcohol ethylene oxide 20 mol adduct and 156 g (1 mol) of suberic acid anhydride at 120 ° C. for 2 hours. : CO (CH ₂ ) ₆ ) was obtained.

[Production Example 10 (Dispersant Synthesis of Dispersant 10)]
By reacting 510 g (1 mol) of 2-propyl-1-heptyl alcohol ethylene oxide 8 mol adduct and 100 g (1 mol) of succinic anhydride at 120 ° C. for 2 hours, dispersant 10 (R: 2-propyl-1- A heptyl group, AO: ethylene oxide, n: 8, X: COCH ₂ CH ₂ ) was obtained.

[Production Example 11 (Synthesis of Dispersant 11)]
Dispersant 11 (R: isodecyl group, AO: ethylene oxide, n: 10, X by reacting 598 g (1 mol) of isodecyl alcohol ethylene oxide adduct and 98 g (1 mol) of maleic anhydride at 120 ° C. for 2 hours. : COCH = CH) was obtained.

[Production Example 12 (Dispersant Synthesis of Dispersant 12)]
By dispersing 640 g (1 mol) of isotridecyl alcohol ethylene oxide adduct and 98 g (1 mol) of maleic anhydride at 120 ° C. for 2 hours, dispersant 12 (R: isotridecyl group, AO: ethylene oxide, n: 10, X: COCH = CH) was obtained.

[Production Example 13 (Synthesis of Dispersant 13)]
Instead of 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct, 637 g (1 mol) of ethylene oxide 10 mol adduct of a mixture of isotridecyl alcohol (80 wt%) / lauryl alcohol (20 wt%) was used. The same operation as in Production Example 1 was performed to obtain a dispersant 13 (R: isotridecyl group and lauryl group, AO: ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 14 (Dispersant Synthesis of Dispersant 14)]
Dispersant 14 (R: isobutyl group, AO: ethylene oxide, n: 20, by reacting 954 g (1 mol) of isobutyl alcohol ethylene oxide 20 mol adduct and 192 g (1 mol) of trimellitic anhydride at 120 ° C. for 2 hours. X: COC ₆ H ₃ ).

[Example 1]
The dispersion of the present invention comprising a compound represented by the formula (1) containing a hydrophobic group (R), an oxyalkylene group (-(AO) n-) and a linking group (X) having the composition shown in Table 1 below. Formula (1) containing 1.5 parts of the agent (in terms of solid content) or a hydrophobic group (R) having the composition shown in Table 2 below, an oxyalkylene group (— (AO) n—), and a linking group (X) ) Is dissolved in 68.5 parts of a solvent (isopropanol or diethylene glycol monobutyl ether acetate) as a dispersion medium, and further dispersed as a dispersoid. A refinement process was carried out for 24 hours with a ball mill to 30 parts of magnesium oxide (MgO) and 100 milliliters of zirconia balls having a diameter of 10 mm. As a result, the obtained treatment liquid was transferred to a transparent container, and the dispersibility of the treatment liquid in the container was evaluated by visually observing the treatment liquid based on the following criteria. The results are shown in Tables 1 and 2.
(Double-circle): All the dispersoids disperse | distribute in a liquid, and a sediment is not seen in the bottom part of a container.
○: Most of the dispersoid is dispersed in the liquid, but a slight amount of sediment is observed at the bottom of the container.
X: Dispersoids are observed in the liquid, or the liquid is cloudy.

As shown in Table 1, it can be seen that those using the dispersant of the present invention are excellent in dispersibility.

[Example 2]
The dispersion of the present invention comprising a compound represented by the formula (1) containing a hydrophobic group (R), an oxyalkylene group (-(AO) n-) and a linking group (R) having the composition shown in Table 3 below. A predetermined amount of the agent (numbers shown at the left end of Table 3, 1, 2, 3, 4, 7, 10, 12, 13) or a hydrophobic group (R) having the composition shown in Table 3 below, and an oxyalkylene group Comparative dispersants (Comparative Examples 1, 2, 3, 5, 11 shown in Table 3) comprising (-(AO) n-) and a compound represented by formula (1) containing a linking group (R) Is dissolved in a predetermined amount of methyl ethyl ketone as a dispersion medium, and 5 parts of zirconium oxide (ZrO2) as a dispersoid is further added to the product name Ultra Apex Mill UAM-005 (by Kotobuki Kogyo Co., Ltd.). Using a zirconia bead with a diameter of 50 μm, refinement for 2 hours at a peripheral speed of 10 m / sec) Subjecting was. As a result, the obtained treatment liquid is transferred to a transparent container, and the dispersibility of the treatment liquid in the container immediately after the miniaturization treatment and the treatment liquid in the container after 24 hours (dispersing agent is dispersed at 0.25 parts). The dispersion stability of the processing solution having a quality of 5 parts) was evaluated based on the same criteria as above by observing the processing solution visually. Further, with respect to a part of the treatment liquid (treatment liquid having a dispersant of 0.25 part and a dispersoid of 5 parts), the particle diameter of zirconium oxide immediately after the refinement treatment was measured using Microtrac UPA MODEL 9230. In addition, the compounding quantity of the methyl ethyl ketone with respect to a dispersing agent is 94.5 parts, 94.75 parts, 94.75 parts of methyl ethyl ketone with respect to 0.5 parts, 0.25 parts, 0.15 parts, and 0.05 parts of dispersing agents, respectively. 85 parts and 94.95 parts. Table 3 shows the visual evaluation of the dispersibility and dispersion stability and the particle diameter measurement results of zirconium oxide.

Moreover, the dispersion of the comparative example which consists of the dispersing agent of this invention which consists of a compound shown by the formula (1) which has a composition shown in the following Table 3, or the compound shown by the formula (1) which has a composition shown in the following Table 3 70 parts of a dispersion in which the ratio of the agent, methyl ethyl ketone as the dispersion medium, and zirconium oxide as the dispersoid is 0.25 parts to 94.75 parts to 5 parts, is made of acrylic resin (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). A dispersion obtained by mixing 70 parts of methyl ethyl ketone solution in which 25 parts of ACRYPET VH) was dissolved was used as a trade name Ultra Apex Mill UAM-005 (50 μm diameter zirconia beads manufactured by Kotobuki Kogyo Co., Ltd.). Second) for 2 hours. As a result, the obtained treatment liquid was transferred to a transparent container, and the dispersibility of the treatment liquid in the container was evaluated by visually observing the treatment liquid according to the above criteria. The results are shown in Table 3.

Moreover, after apply | coating the said dispersion liquid (after 2 hours refinement | miniaturization process) on a clean 10 mm thick glass plate, it dried at 120 degreeC with the dryer for 1 hour, and obtained the coating film. Next, a paper on which the alphabet printed at 12 points is placed under the glass plate, and the transparency of the coating film obtained on the glass plate, whether the alphabet can be distinguished over the coating film, Evaluation was made according to the following criteria. The results are shown in Table 3.
A: 12-point alphabet characters can be clearly distinguished.
○: Although the coating film is slightly turbid, 12-point alphabet characters can be distinguished.
X: The coating film is turbid, and 12-point alphabet characters cannot be identified.

As shown in Table 3, it can be seen that those using the dispersant of the present invention are excellent in dispersibility and dispersion stability. Further, as shown in the table, the particle size of the dispersoid in the dispersion using the dispersant of the present invention is much smaller than the particle size of the dispersoid in the dispersion of the comparative example. This is evidence that the dispersion of the invention is excellent in dispersibility. Furthermore, as shown in the table, the transparency of the coating film made of the dispersion of the present invention is excellent, and the excellent dispersibility of the dispersion of the present invention has been demonstrated.

Note that the dispersion stability of the comparative dispersant was not measured. Moreover, the particle diameter of the zirconium oxide of Comparative Example 3, Comparative Example 5, and Comparative Example 11 was not measured.

Example 3
The dispersion of the present invention comprising a compound represented by the formula (1) containing a hydrophobic group (R), an oxyalkylene group (— (AO) n—), and a linking group (R) having the composition shown in Table 4 below. 1 part of an agent (numbers 1, 2, 3, 4, and 12 shown at the left end of Table 4) or a hydrophobic group (R) having the composition shown in Table 4 below and an oxyalkylene group (-(AO) n- And 1 part of a dispersant of Comparative Examples (Comparative Examples 1, 2, 3, and 14 shown in Table 4) comprising a compound represented by the formula (1) containing a linking group (R) as diethylene glycol as a dispersion medium Dissolved in 70 parts of monobutyl ether acetate, plus 1 part of multi-wall carbon nanotubes (trade name VGCF-X, manufactured by Showa Denko KK) as a dispersoid, paint shaker (rocking mill manufactured by Seiwa Giken, product) Name RM-5, diameter 0.5mm (Using luconia beads) for 12 hours. As a result, the obtained treatment liquid is transferred to a transparent container, and the treatment liquid is dispersed with respect to the dispersibility of the treatment liquid in the container immediately after the miniaturization treatment and the dispersion stability of the treatment liquid in the container after 24 hours. By visual observation, evaluation was performed based on the same as above. The results are shown in Table 4.

Moreover, the dispersion of the comparative example which consists of the dispersing agent of this invention which consists of a compound shown by the formula (1) which has a composition shown in the following Table 4, or the compound shown by the formula (1) which has a composition shown in the following Table 4 Dispersion 10 in which the ratio of the agent, diethylene glycol monobutyl ether acetate as a dispersion medium, and multi-wall carbon nanotubes (trade name VGCF-X, manufactured by Showa Denko KK) as a dispersoid is 1 part to 70 parts to 1 part 30 parts of diethylene glycol monobutyl ether acetate was added to the part, and refinement treatment was carried out for 1 hour using the paint shaker. The dispersion stability of the treatment liquid after dilution with diethylene glycol monobutyl ether acetate was defined as dilution stability, and this dilution stability was evaluated on the same basis as the dispersibility. The results are shown in Table 4.

Moreover, the dispersion of the comparative example which consists of the dispersing agent of this invention which consists of a compound shown by the formula (1) which has a composition shown in the following Table 4, or the compound shown by the formula (1) which has a composition shown in the following Table 4 The above-mentioned paint shaker was used for 12 hours of refinement for the ratio of the agent, diethylene glycol monobutyl ether acetate as the dispersion medium, and multi-wall carbon nanotubes as the dispersoid to 1 part to 70 parts to 1 part. A dispersion obtained by mixing 70 parts of the dispersion obtained above with 70 parts of a methyl ethyl ketone solution in which 25 parts of acrylic resin (trade name Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.) was dissolved was prepared on a clean glass plate having a thickness of 10 mm. Then, it was dried at 120 ° C. for 1 hour with a dryer to obtain a coating film. Next, a paper on which the alphabet printed at 12 points is placed under the glass plate, and the transparency of the coating film obtained on the glass plate, whether the alphabet can be distinguished over the coating film, Evaluation was based on the same criteria. The results are shown in Table 4.

As shown in Table 4, it can be seen that those using the dispersant of the present invention are excellent in dispersibility, dispersion stability and dilution stability. Moreover, as shown in the table, the transparency of the coating film comprising the dispersion of the present invention is excellent, and the excellent dispersibility of the dispersion of the present invention has been demonstrated. In addition, the transparency of the coating film was not measured about the dispersing agent of the comparative example.

Example 4
<< Preparation of Zirconium Oxide Acrylate Monomer Dispersion (1) >>
Hydrophobic groups (R) having the composition shown in Table 5 below and oxyalkylene mixed with 100 parts of zirconium oxide powder (trade name PCS manufactured by NIPPON DENKO CO., LTD., Having a primary particle diameter of 30 nm) and 400 parts of methyl ethyl ketone. The dispersant of the present invention comprising a compound represented by the formula (1) containing a group (— (AO) n—) and a linking group (X) (numbers shown at the left end of Table 5 are (1) -1 to ( 1) -6)) Formula (1) containing 10 parts or a hydrophobic group (R) having the composition shown in Table 5 below, an oxyalkylene group (— (AO) n—), and a linking group (X) A product name Ultra Apex manufactured by Kotobuki Kogyo Co., Ltd., to which 10 parts of a dispersant of the comparative example ((1) -Comparative Example 1, (1) -Comparative Example 1 ′ shown in Table 5) was added. Mill UAM-005 (using zirconia beads with a diameter of 50 μm, peripheral speed 10 m / s In was performed for 4 hours pulverizing treatment, to prepare a zirconium oxide dispersion. To 100 parts of the resulting zirconium oxide dispersion, 10 parts of phenoxyethyl acrylate (trade name New Frontier PHE manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and pentaerythritol triacrylate (trade name New Frontier PET-made by Daiichi Kogyo Seiyaku Co., Ltd.) 3) After adding and mixing 10 parts, the solvent methyl ethyl ketone was removed under reduced pressure using a rotary evaporator to obtain an acrylate monomer dispersion (1) of zirconium oxide.

<< Preparation of Zirconium Oxide Acrylate Monomer Dispersion (2) >>
100 parts of a commercially available zirconium oxide dispersion (trade name SZR-M manufactured by Sakai Chemical Co., Ltd., dispersion containing a primary particle size of 3 nm and 30% by weight of methanol) has the formula (1 3 parts of the dispersant of the present invention comprising the compound represented by the formula (the number shown at the left end of Table 5 is the number (2) -1 to (2) -13) or having the composition shown in Table 5 below (1 ) 3 parts of a dispersant of a comparative example ((2) -Comparative Example 2, (2) -Comparative Example 2 'shown in Table 5) and phenoxyethyl acrylate (commercial product of Daiichi Kogyo Seiyaku Co., Ltd.) 15 parts of New Frontier PHE) and 15 parts of pentaerythritol triacrylate (trade name New Frontier PET-3 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added and mixed, and then the solvent methanol was used using a rotary evaporator. Reduced pressure to remove to obtain acrylate monomer dispersion of zirconium oxide (2).

<Characteristic evaluation of dispersion>
a. Transparency of appearance Place the acrylate monomer dispersion of zirconium oxide in a transparent glass container, place a paper with alphabet printed at 12 points under the glass container, and check the transparency of the dispersion over the dispersion. The following criteria were used to evaluate whether the alphabet could be distinguished. The results are shown in Table 5.
A: When the dispersion is put into a glass container having a depth of 5 cm, 12-point alphabet characters can be seen. The dispersion is transparent.
○: When the dispersion is placed in a glass container having a depth of 1 cm, 12-point alphabet characters are clearly visible. There is a slight turbidity in the dispersion.
X: When the dispersion is put into a glass container having a depth of 1 cm, 12-point alphabet characters cannot be clearly seen. The dispersion is turbid.

B. Viscosity Measurement The viscosity of the acrylate monomer dispersion of zirconium oxide was measured at 25 ° C. using an E-type viscometer (trade name RE-80R manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 5.

C. Refractive index The refractive index of the zirconium oxide acrylate monomer dispersion was measured at 25 ° C. using an Abbe refractometer (trade name NAR-1T manufactured by Atago Co., Ltd.). The results are shown in Table 5.

<< Preparation of photopolymerized cured film of zirconium oxide >>
One part of a photopolymerization initiator (IGACURE184) was added to and mixed with 100 parts of the acrylate monomer dispersion (1) or (2) of zirconium oxide to obtain a zirconium oxide paste. The zirconium oxide paste was applied on a polyethylene terephthalate film with an applicator (YA type manufactured by Kodaira Seisakusho Co., Ltd.) with a film thickness of about 50 μm, and then with a high pressure mercury lamp at a strength of 80 W / cm, about 200 mJ / cm ^2. A photopolymerized cured film of an acrylate monomer dispersion of zirconium oxide was obtained by irradiating with ultraviolet rays having the energy of 1.

<Characteristic evaluation of photopolymerized cured film>
a. Transparency of appearance Place the paper with the alphabet printed at 12 points under the polyethylene terephthalate film, and the transparency of the photopolymerized cured film obtained on the polyethylene terephthalate film can be distinguished through the cured film In terms of whether or not it was evaluated according to the following criteria. The results are shown in Table 5.
A: 12-point alphabet characters can be clearly distinguished.
○: A slight turbidity occurs in the cured film, but 12-point alphabet characters can be identified.
X: The cured film has turbidity, and 12-point alphabet characters cannot be identified.

B. Refractive index The refractive index of the photopolymerized cured film was measured at 25 ° C. using a prism coupler (MODEL 2010 / M) manufactured by Seki Technotron. The results are shown in Table 5.

C. Pencil hardness About the pencil hardness of the photopolymerization cured film, the photopolymerization cured film was scratched with a pencil having a predetermined hardness in accordance with JISK5400. The results are shown in Table 5.

As shown in Table 5, the dispersion of the present invention has excellent dispersibility (transparency of appearance) and a high refractive index, and the photopolymerized cured film of the dispersion of the present invention has excellent transparency and a high refractive index. It can be seen that it has good pencil hardness.

However, the dispersions of the comparative examples ((1) —Comparative Example 1, (1) —Comparative Example 1 ′, (2) —Comparative Example 2, (2) —Comparative Example 2 ′) were agglomerated, so viscosity and refraction The rate could not be measured and there was turbidity. Moreover, the photopolymerization cured film of the dispersion of the comparative example was turbid, and the refractive index and pencil hardness could not be measured.

In Tables 1 to 5, EO represents ethylene oxide and PO represents propylene oxide.

Note that the refractive index of the dispersion composed of the dispersant of the comparative example could not be measured. Further, the refractive index and pencil hardness of the photopolymerized cured film of the dispersion composed of the dispersant of Comparative Example could not be measured.

The dispersion composition of the present invention includes a hybrid material, a surface protective agent, a conductive paste, a conductive ink, a sensor, a precision analysis element, an optical memory, a liquid crystal display element, a nanomagnet, a heat transfer medium, a high-performance catalyst for a fuel cell, Organic solar cells, nano glass devices, abrasives, drug carriers, environmental catalysts, paints, printing inks, inkjet inks, color filter resists, writing instrument inks, optical thin films, adhesives, antireflection films, hard coat films, etc. Can be used in The dispersant of the present invention stabilizes dispersion of the isotropic material and / or anisotropic material derived from the nano-sized inorganic or organic material, which is the main component in the product and its production process, in a non-aqueous dispersion medium. Therefore, it is effective to obtain desired product characteristics, processing characteristics, quality stabilization, and productivity improvement by suppressing dispersoid aggregation in the dispersion medium and achieving long-term dispersion stabilization.

Claims

The dispersing agent for non-aqueous dispersion media which consists of a compound shown by following formula (1).

However, R of Formula (1) shows the alkyl group and / or alkenyl group which are C1-C24 containing the alkyl group and / or alkenyl group which have a branched chain,
AO in formula (1) represents an oxyalkylene group having 1 to 4 carbon atoms, n represents the average number of moles of alkylene oxide added, and ranges from 1 to 30;
X in the formula (1) is a linking group composed of a carbon atom, a hydrogen atom and / or an oxygen atom.
The dispersant for a non-aqueous dispersion medium according to claim 1, wherein X in the formula (1) is an alkylene group having 1 to 15 carbon atoms.
The dispersant for a non-aqueous dispersion medium according to claim 1, wherein X in the formula (1) is a substance represented by the following formula (2).

However, Y in Formula (2) is any selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.
Organic particles and / or inorganic particles which are coated with the dispersant for non-aqueous dispersion medium according to claim 1, 2 or 3 or impregnated with the dispersant.
A dispersion composition obtained by dispersing organic particles or inorganic particles in a non-aqueous dispersion medium using the dispersant for a non-aqueous dispersion medium according to claim 1, 2 or 3.
A coating composition containing the dispersion composition according to claim 5, wherein a resin is used as the non-aqueous dispersion medium.
A coating composition containing a mixture of the dispersion composition and the resin according to claim 5, wherein a solvent is used as the non-aqueous dispersion medium.
A member obtained by applying a coating composition according to claim 6 or 7 on a substrate and then reacting physically or chemically.