JP5727215B2 - Dispersant and dispersion composition - Google Patents

Description

  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. It is used. At this time, the isotropic material and / or anisotropic material derived from the inorganic or organic material is efficiently processed by preparing a dispersion as fine particles in an aqueous dispersion medium or a non-aqueous dispersion medium. It is used industrially as a substance that improves properties, product characteristics and material properties, and contributes to quality stabilization and yield improvement during production.

  On the other hand, it is difficult to stably disperse the dispersoid by changing the material of the dispersoid, reducing the particle size, and controlling the shape, and there is a problem that the dispersoid aggregates 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 the organic compound 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 manufactured by BYK Chemie, Ciba EFKA series manufactured by EFKA Additives, Solsperse manufactured by Lubrizol, 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. Nonionic surfactants include, for example, 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, polyoxy Examples include ethylene 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.

  In addition, nanometer-sized inorganic fine particles (particle diameter of 1 to 100 nm) or a composite material in which organic fillers and pigments are finely dispersed in a resin is called a polymer nanocomposite. Used in optical material applications. However, nanometer-sized particles tend to aggregate and have a low affinity for the resin, so that it is extremely difficult to uniformly disperse 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. . As an example of such a dispersant, polyoxyethylene alkyl phosphoric acid and polyoxyethylene alkyl carboxylate as mentioned in the above patent are used (Patent Document 1).

  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 2 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.

  Further, Japanese Patent Application No. 2010-120122, which has not been disclosed at the time of filing of the present application, discloses a dispersant for a non-aqueous dispersion medium containing a branched alkyl group and / or alkenyl group. If this dispersant is used, it can be applied to a wide range of dispersoids, and excellent dispersion stability can be exhibited with a small amount of addition. However, development of a dispersant capable of dispersing a larger amount of dispersoids such as inorganic fine particles and fillers is desired.

JP 2004-354568 A JP 2009-74171 A

  The use of polyoxyethylene alkyl phosphoric acid and polyoxyethylene alkyl carboxylate according to the above prior art may not provide desired dispersibility depending on the combination of inorganic fine particles or filler and resin. For example, a dispersion prepared by combining polyoxyethylene alkyl carboxylic acid and phenoxyethyl acrylate (PHE), which is an aromatic general-purpose photo-curing resin material, is remarkably unclear and shows a decrease in dispersibility. For these reasons, a dispersant capable of dispersing inorganic fine particles in various resins is required.

  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. It is another object of the present invention to provide a dispersing agent for dispersion medium suitable for dispersing a large amount of dispersoid. In addition, an object of the present invention is to provide a dispersion composition using the dispersant. Another object of the present invention is to provide organic particles or inorganic particles that are coated with or impregnated with the dispersant.

  In order to achieve the above object, the dispersant of the present invention is a dispersant comprising a compound represented by the following formula (1).

However, R in the above formula (1) represents a styrenated phenyl group represented by the following formula (2), k in the following formula (2) is an average value, and a numerical value in the range of 1 to 5, AO in the above formula (1) represents an oxyalkylene group having 1 to 4 carbon atoms, n is a numerical value in the range of 1 to 30 indicating the average number of added moles of alkylene oxide, and X in the above formula (1) is O atom, S atom, -NR1- (R1 is H or C atoms, H atoms, and groups from any of O atoms) a linking group composed of any of the above formula (1) Y is a linking group composed of any one of C, H, and O atoms.

  Y in the formula (1) is preferably an alkylene group having 1 to 15 carbon atoms or a functional group represented by the following formula (3).

  However, Z in the formula (3) 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.

  The inorganic particles of the present invention are coated with the dispersant described above or impregnated with the dispersant.

  The dispersion composition of the present invention is obtained by dispersing inorganic particles in a non-aqueous dispersion medium using any of the dispersants described above.

  Furthermore, the coating composition of this invention contains said dispersion composition using resin as a non-aqueous dispersion medium.

  In addition, the dispersion composition of the present invention contains a mixture of the above-described dispersion composition using a solvent as a non-aqueous dispersion medium and a resin.

  The member of the present invention is obtained by applying any of the above coating compositions on a substrate and then reacting them.

  According to the present invention, inorganic fine particles or fillers can be dispersed in a dispersion medium that has been difficult with conventional dispersants, and a highly transparent and stable dispersion composition can be provided. Moreover, the dispersing agent which can disperse | distribute a lot of dispersoids stably by addition of a small quantity can be provided. Moreover, the dispersion composition using the dispersing agent and the coating composition containing the dispersion composition can be provided.

  As described in the formula (1), the dispersant of the present invention has a dispersion medium affinity part comprising a hydrocarbon group containing at least one aromatic ring, and a dispersoid affinity part comprising an oxyalkylene group and a carboxyl group. The dispersion medium affinity part and the dispersoid affinity part are connected by a linking group X. Hereinafter, preferred embodiments of the present invention will be described in detail.

1. Hydrophobic Group (R) In the hydrophobic group (R) that can be used in the dispersant of the present invention, R is a hydrocarbon group containing at least one aromatic ring, specifically, the above-described formula (2) In addition to the styrenated phenyl group represented by formula (I), functional groups containing an octylphenyl group, a nonylphenyl group, a cumylphenyl group, an o-phenyl-phenyl group, a p-phenyl-phenyl group, and the like can be given. Furthermore, functional groups containing polycyclic aromatic hydrocarbons such as naphthalene, anthracene, benzopyrene, chrysene, coronene, corannulene, naphthacene, pyrene, and triphenylene can also be exemplified. In the present application, for example, it is assumed that naphthalene includes two aromatic rings and anthracene includes three aromatic rings. In the dispersant of the present invention, it is considered that the aromatic ring greatly contributes to the improvement of dispersibility. Of these functional groups, the styrenated phenyl group-containing compound represented by the formula (2) can be suitably used to achieve the object of the present invention.

2. Linking group (X)
The linking group (X) is a linking group composed of any one of an O atom, an S atom, and -NR1-, and R1 is a functional group composed of any one of an H atom, a C atom, an H atom, and an O atom. It is. Examples of R1 include saturated linear alkyl groups having 1 to 18 carbon atoms such as n-hexyl and n-octyl groups, saturated branched alkyl groups having 1 to 18 carbon atoms such as 2-ethylhexyl and isodecyl groups, and linole groups. And unsaturated long chain alkyl groups such as linolenic group, oleyl group, coconut alkyl group, beef tallow alkyl group, and cured beef tallow alkyl group.

3. 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, 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.

4). Linking group (Y)
The linking group (Y) can be selected from known structures comprising a carbon atom, a hydrogen atom, and an oxygen atom, but preferably comprises a saturated hydrocarbon group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, and an ester group. It may have an alicyclic structure or an aromatic ring structure, and may have a repeating unit. When the linking group Y contains a nitrogen atom and / or a sulfur atom and / or a phosphorus atom, the linking group Y 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. .

  Y 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, Y in the formula (1) is preferably a substance represented by the above formula (3). However, in Formula (3), Z is either selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.

5. 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 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 ), And the like. 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 that become the dispersoid 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.

6). Dispersion medium The dispersion medium that 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 Nylacetone, isophorone, cyclohexanone, methylcyclohexanone, 2- (1-cyclohexenyl) cyclohexanone methyl isobutyl ketone, cyclohexanone, isophorone and other ketone solvents, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, acetic acid Ethyl acetate, 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.

  Further, 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, tetrahydro Furfuryl alcohol, furfuryl alcohol, allyl alcohol, ethylene chlorohydrin, octyldodecanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neo Amyl alcohol, hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, heptyl alcohol, n-octyl alcohol, 2-ethyl Sil alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, α-terpineol, terpineol C, L-α-terpineol, dihydroterpineol, terpinyloxyethanol, dihydroter Pinyloxyethanol, tersolve MTPH manufactured by Nippon Terpene Chemical Co., Ltd., tersolve DTO-210, tersolve THA-90, tersolve THA-70, cyclohexanol, 3-methoxybutanol, diacetone alcohol, 1,4-butanediol, Octanediol, etc., fine oxocol 140N, fine oxocol 1600, fine oxocol 180, fine oxo, manufactured by Nissan Chemical Industries, Ltd. Alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc. A solvent is 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.

7). 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 dispersant suitably employed in the present invention is not particularly limited as long as the dispersoid can be uniformly dispersed in the non-aqueous dispersion medium, and varies depending on the application, etc. The whole body composition is preferably 100% by weight and is preferably in the range of 0.1 to 20% by weight, and the content of the dispersoid particles is preferably in the range of 1 to 90% by weight. The content of the dispersant is preferably in the range of 1 to 300% by weight with respect to the dispersoid particles. The content of the dispersion medium is preferably in the range of 1 to 99% by weight, with the total dispersion composition being 100% by weight. The average particle size of the dispersoid particles is preferably in the range of 1 to 500 nm, and more preferably in the range of 1 to 100 nm.

  The dispersant of the present invention can be produced by a known method. For example, a general nonionic surfactant compound in which alkylene oxide is added to alcohol, amine, or thiol is used as a raw material, and a monohalogenated lower carboxylic acid or a salt thereof is used to react with a hydroxyl group at the end of alkylene oxide in the presence of a base. Although it can manufacture by the method or the method by a ring-opening reaction with the hydroxyl group of the alkylene oxide terminal using an acid anhydride, it does not limit to these methods.

  In addition, 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 adopted 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.

  Examples of the present invention and comparative examples will be described below. 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 Styrenated Phenol (k = 3) Ethylene Oxide 8 Mole Adduct)
In an autoclave, 415 g (1 mol) of styrenated phenol (k = 3) and 1 g (0.018 mol) of potassium hydroxide were charged and mixed uniformly. Thereafter, 352 g (8 mol) of ethylene oxide was added dropwise to the reaction system under the condition that the temperature of the reaction system was 130 ° C. After completion of the dropwise addition of ethylene oxide, the pressure was maintained at 0.1 MPa at this temperature and aged for 1 hour to obtain a styrenated phenol 8EO adduct.

Production Example 2 ((Synthesis of Styrenated Phenol (k = 3) Ethylene Oxide 14 Mole Adduct)
A styrenated phenol 14EO adduct was obtained in the same manner as in Production Example 1 except that the amount of ethylene oxide added in Production Example 1 was changed to 616 g (14 mol).

Production Example 3 (Synthesis of Dispersant 1)
In a toluene solvent, 767 g (1 mol) of the styrenated phenol (k = 3) ethylene oxide 8 mol adduct obtained in Production Example 1 and 152 g (1.3 mol) of sodium monochloroacetate are placed in a reactor so as to be uniform. Stir. Thereafter, 52 g 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 aged for 3 hours. After aging, the mixture was cooled to 50 ° C., and 117 g (1.2 mol) of 98% sulfuric acid was added dropwise at 50 ° C. 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 thereby disperse the dispersant 1 described in Example 1 (R: styrenated phenyl group (k = 3), AO: ethylene oxide, n : 8, X: O, Y: CH ₂ ).

Production Example 4 (Synthesis of dispersant of Example 2)
In Production Example 3, the same procedure as in Production Example 1 except that 1020 g (1 mol) of styrenated phenol (k = 3) ethylene oxide 14 mol adduct was used instead of the 8 mol adduct of styrenated phenol (k = 3). The dispersant described in Example 2 (R: styrenated phenyl (k = 3), AO: ethylene oxide, n: 14, X: O, Y: CH ₂ ) was obtained.

Production Example 5 (Synthesis of dispersant of Example 3)
The dispersant described in Example 3 (R: styrene) was prepared by reacting 654 g (1 mol) of styrenated phenol (k = 2) ethylene oxide 8 mol adduct and 100 g (1 mol) of succinic anhydride at 120 ° C. for 2 hours. A phenyl group (k = 2), AO: ethylene oxide, n: 8, X: O, Y: COCH ₂ CH ₂ ) was obtained.

Production Example 6 (Synthesis of dispersant of Example 4)
In Production Example 3, the same procedure as in Production Example 1 except that 654 g (1 mol) of styrenated phenol (k = 2) ethylene oxide 8 mol adduct was used instead of 8 mol adduct of styrenated phenol (k = 3). The dispersion 4 described in Example 4 (R: styrenated phenyl group (k = 2), AO: ethylene oxide, n: 8, X: O, Y: CH ₂ ) was obtained.

Production Example 7 (Synthesis of dispersant of Comparative Example 1)
Production Example 3 Production Example 3 except that 640 g (1 mol) of isotridecyl alcohol ethylene oxide 10-mole adduct was used as the raw material EO adduct instead of styrenated phenol (k = 3) ethylene oxide 8-mole adduct. 3 was performed to obtain a dispersant (R: isodecyl group, AO: ethylene oxide, n: 10, X: O, Y: CH ₂ ) described in Comparative Example 3.
Commercially available materials were used for all the materials shown above and the other materials used in the examples and comparative examples.

<Preparation of Zirconium Oxide Acrylate Monomer Dispersion>
In 100 parts of a commercially available zirconium oxide dispersion (trade name SZR-M manufactured by Sakai Chemical Co., Ltd., a dispersion containing methanol having a primary particle diameter of 3 nm and 30% by weight), 1.5 parts of a dispersant shown in Table 1 below. And phenoxyethyl acrylate (trade name New Frontier PHE manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) or phenylthioethyl acrylate (product of DAELIN Chemical Co. Ltd, trade name: Electromer HRI-01) or o-phenylphenoxyethyl acrylate 28.5 And 12 parts of 3-methoxy-3-methylbutanol were added and mixed, and then methanol was removed under reduced pressure using a rotary evaporator to obtain an acrylate monomer dispersion of zirconium oxide. For o-phenylphenoxyethyl acrylate, dispersions were made using commercially available materials.

<Characteristic evaluation of dispersion>
a. Appearance transparency Whether the acrylate monomer dispersion of zirconium oxide is placed in a transparent glass container, and a paper with an alphabet printed with 12 points is placed under the glass container, and whether the alphabet can be distinguished through the dispersion Thus, the transparency of the dispersion was evaluated. The evaluation criteria are as follows.
○: When the dispersion is placed in a glass container having a depth of 1 cm, 12-point alphabet characters are clearly visible. The dispersion is transparent.
X: When the dispersion is put in a glass container having a depth of 1 cm, 12-point alphabet characters cannot be clearly seen. The dispersion is turbid. The results are shown in Table 1.

b. Evaluation of Viscosity of Dispersion Viscosity of an acrylate monomer dispersion of zirconium oxide having good dispersibility was measured at 25 ° C. using an E-type viscometer (trade name RE-80R manufactured by Toki Sangyo Co., Ltd.). . The results are also shown in Table 1.

c. Evaluation of refractive index of the dispersion The refractive index of the acrylate monomer dispersion of zirconium oxide having good dispersibility was measured at 25 ° C. using an Abbe refractometer (trade name NAR-IT manufactured by Atago Co., Ltd.). Went. The results are also shown in Table 1.

  As can be seen from Table 1, Examples 1 to 6 using a dispersant having an aromatic ring in the hydrophobic group and a terminal group of carboxylic acid are very excellent for a dispersoid containing an aromatic acrylate monomer. As can be seen from FIG. On the other hand, in the case of Comparative Examples 1 to 3 and 6 in which the hydrophobic group does not contain an aromatic ring, dispersibility was poor at the same dispersant addition amount as in Examples 1 to 6. Furthermore, even in the case where the hydrophobic group contains an aromatic ring, in the case of Comparative Example 4 in which the terminal group is a carboxylic acid sodium salt, or in Comparative Example 5 in which the terminal group is an alcohol, the dispersibility in the solvent is greatly inferior. As a result. From this, it can be seen that in the present invention, the carboxylic acid of the terminal group together with the aromatic ring has an important role in dispersibility.

Some dispersions shown in Examples 1 to 6 have a viscosity as low as 1400 to 4000 mPa · sec, depending on the combination of the dispersant and the acrylate monomer species, regardless of the conditions not including the diluent solvent. When the viscosity of the dispersion is low, coating on the substrate becomes easy, and thus it can be said that the industrial value is high.
In addition, the refractive indexes of the dispersions shown in Examples 1 to 6 are 1.6 to 1.645, which are improved compared to the original acrylate monomer species, respectively, and the dispersant of the present invention and zirconium oxide are used. By using the used dispersion composition, a dispersion composition excellent in transparency and high refractive index and a coating material can be provided.

  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 a nano-sized inorganic substance or organic substance, which is a main component in the above-mentioned product and its production process, in a non-aqueous dispersion medium. It is effective for obtaining 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 (7)

A dispersant comprising a compound represented by the following formula (1).

( However, R in formula (1) represents a styrenated phenyl group represented by the following formula (2) ,

K in the formula (2) is an average value and is a numerical value in the range of 1 to 5,
AO in formula (1) represents an oxyalkylene group having 1 to 4 carbon atoms, n is a numerical value in the range of 1 to 30 indicating the average number of added moles of alkylene oxide,
X in the formula (1) is a linking group composed of any one of an O atom, an S atom, and —NR 1 — (R 1 is a group composed of an H atom or a C atom, an H atom, or an O atom). ,
Y in Formula (1) is a linking group composed of any one of C, H, and O atoms. ) The dispersant according to claim 1, wherein Y in the formula (1) is an alkylene group having 1 to 15 carbon atoms or a functional group represented by the following formula (3).

However, Z in the formula (3) 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. Or they are coated with dispersing agents or inorganic particles obtained by impregnating the dispersant according to claim 1 or 2. Claim 1 or 2 dispersion composition obtained by dispersing inorganic particles using a dispersing agent in a non-aqueous dispersing medium according to. The coating composition containing the dispersion composition of Claim 4 using resin as a non-aqueous dispersion medium. The coating composition containing the mixture of the dispersion composition and resin of Claim 4 using a solvent as a non-aqueous dispersion medium. The member obtained by making the coating composition of Claim 5 or 6 apply | coat on a base material, and making it react.