WO2011148520A1 - 分散剤および分散体組成物 - Google Patents

分散剤および分散体組成物 Download PDF

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Publication number
WO2011148520A1
WO2011148520A1 PCT/JP2010/063749 JP2010063749W WO2011148520A1 WO 2011148520 A1 WO2011148520 A1 WO 2011148520A1 JP 2010063749 W JP2010063749 W JP 2010063749W WO 2011148520 A1 WO2011148520 A1 WO 2011148520A1
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Prior art keywords
dispersant
group
dispersion
formula
dispersion medium
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PCT/JP2010/063749
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English (en)
French (fr)
Japanese (ja)
Inventor
橋本　賀之
昭充 利根川
和幸 加藤
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第一工業製薬株式会社
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Application filed by 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Priority to PCT/JP2011/050895 priority Critical patent/WO2011148660A1/ja
Priority to KR1020127030911A priority patent/KR101472651B1/ko
Priority to CN201180025934.5A priority patent/CN102906060B/zh
Publication of WO2011148520A1 publication Critical patent/WO2011148520A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C09K23/44—Ether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • aromatic carboxylic acids for example, formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid
  • alkenyl succinic anhydrides include octenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, and the like.
  • organic compounds having a thiol group include mercaptoethanol, mercapto-2-propanol, 1-mercapto-2, 3-propanediol, 3-mercaptopropyltrimethoxysilane, mercaptosuccinic acid, hexanethiol, pentanedithiol, and dodecanethiol.
  • 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.
  • 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.
  • 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 surfactant examples 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.
  • amphoteric surfactants include alkyl betaines, fatty acid amidopropyl betaines, and alkylamine oxides.
  • cationic surfactant examples include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, and alkyl pyridinium salt.
  • polymer surfactants such as fluorine-based surfactants, cellulose derivatives, polycarboxylates, and polystyrene sulfonates.
  • the interfacial adsorption action based on the hydrophobic interaction of the dispersant the electroadsorption action due to the ionic group, the ⁇ -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.
  • 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.
  • the size of the dispersoid particles is a micrometer size
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • an object of the present invention is to provide organic particles or inorganic particles coated with or impregnated with the dispersant.
  • the dispersant for a non-aqueous dispersion medium of the present invention comprises a compound represented by the following formula (1).
  • 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 added moles of alkylene oxide, and is in the range of 1 to 30.
  • X is a linking group comprising 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.
  • X in the formula (1) is preferably a substance represented by the following formula (2).
  • Y 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.
  • a dispersion composition obtained by dispersing organic particles or inorganic particles in a non-aqueous dispersion medium using the above dispersant is preferable.
  • 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.
  • 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.
  • the dispersion composition which uses the dispersing agent, and the film which consists of the dispersion composition can be provided.
  • 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).
  • 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.
  • 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 added moles of alkylene oxide, and is in the range of 1 to 30.
  • X is a linking group comprising a carbon atom, a hydrogen atom and / or an oxygen atom.
  • R is a hydrocarbon group derived from alcohol, R has 1 to 24 carbon atoms, a branched alkyl group and / or 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.
  • known alcohols can be selected.
  • 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.
  • 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.
  • 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.
  • the content of the group is 70% by weight or more, it can be suitably used to achieve the object of the present invention.
  • 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.
  • the hydrophobic group (R) is more preferably a branched alkyl group having 8 to 18 carbon atoms. .
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • X in the formula (1) is preferably a substance represented by the following formula (2).
  • Y 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.
  • dispersant described in the following formula (3) can be more preferably used.
  • R is preferably a branched alkyl group having 8 to 18 carbon atoms
  • n is the average number of moles of ethylene oxide added, preferably in the range of 3 to 20.
  • the dispersoid particles dispersed by the dispersant of the present invention can be selected from inorganic particles and / or organic particles.
  • 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.
  • alkanoic acids and fatty acids alkanoic acids and fatty acids, hydroxycarboxylic acids, alicyclic, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol derivatives
  • protective agents such as amines, an amphiphilic polymer, a high molecular surfactant, and a low molecular surfactant.
  • 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.
  • the dispersoid particles to be dispersed in the present invention those obtained by a known method can be used.
  • 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.
  • 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.
  • a method for preparing metal nanoparticles among the dispersoid particles will be exemplified.
  • 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.
  • 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.
  • 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.
  • 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 iso
  • 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.
  • 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.
  • (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the dispersion composition of the present invention can be prepared using known stirring means, homogenizing means, and dispersing means.
  • 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.
  • the dispersion treatment can be performed in an ultrasonic wave generation bath.
  • 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.
  • a coating composition containing the dispersion composition of the present invention using a resin as a non-aqueous dispersion medium or a 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.
  • 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 solvent isopropanol or diethylene glycol monobutyl ether acetate
  • 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.
  • MgO magnesium oxide
  • zirconia balls having a diameter of 10 mm.
  • 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.
  • the starting alcohol of the branched C11-14 alkyl group is EXXAL13 manufactured by Exxon Mobil.
  • 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 further 5 parts of zirconium oxide (ZrO 2 ) as a dispersoid is added to the product name Ultra Apex Mill UAM-005 (Using zirconia beads with a diameter of 50 ⁇ m and a peripheral speed of 10 m / second) for 2 hours.
  • Ultra Apex Mill UAM-005 Using zirconia beads with a diameter of 50 ⁇ m and a peripheral speed of 10 m / second
  • 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.
  • 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.
  • 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 ⁇ m 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.
  • ⁇ Although the coating film has a slight turbidity, 12-point alphabet characters can be identified.
  • the coating film is turbid and 12-point alphabet characters cannot be identified.
  • 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.
  • 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.
  • evaluation was performed based on the same as above. The results are shown in Table 4.
  • 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.
  • 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.
  • Example 4 Preparation of Zirconium Oxide Acrylate Monomer Dispersion (1) >> Hydrophobic groups (R) and oxyalkylene groups having the compositions shown in Table 5 below were prepared by dissolving 100 parts of zirconium oxide powder (trade name PCS manufactured by Nippon Electric Works Co., Ltd., having a primary particle diameter of 30 nm) in 400 parts of methyl ethyl ketone.
  • zirconium oxide powder trade name PCS manufactured by Nippon Electric Works Co., Ltd., having a primary particle diameter of 30 nm
  • the dispersant of the present invention comprising (— (AO) n—) and a compound represented by the formula (1) containing a linking group (X) (numbers shown at the left end of Table 5 are (1) -1 to (1) ) -6)
  • 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 Mill manufactured by Kotobuki Kogyo Co., Ltd., to which 10 parts of a dispersant of the comparative example comprising the compounds shown ((1) -Comparative Example 1, (1) -Comparative Example 1 'shown in Table 5) was added.
  • UAM-005 (using zirconia beads with a diameter of 50 ⁇ m, peripheral speed 10 m / sec) 4 hours pulverizing treatment was performed to prepare a zirconium oxide dispersion.
  • 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)
  • the solvent methyl ethyl ketone was removed under reduced pressure using a rotary evaporator to obtain an acrylate monomer dispersion (1) of zirconium oxide.
  • ⁇ When the dispersion is placed in a glass container having a depth of 5 cm, 12-point alphabet characters are visible. The dispersion is transparent.
  • 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.
  • ⁇ 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 ⁇ m, 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.
  • X The cured film is cloudy and 12-point alphabet characters cannot be identified.
  • the starting alcohol for the branched C11-14 alkyl group is EXXAL13 manufactured by Exxon Mobil.
  • the dispersion of the present invention has excellent dispersibility (transparency of appearance) and a high refractive index
  • 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.
  • the dispersions of the comparative examples were agglomerated, so viscosity and refraction The rate could not be measured and there was turbidity.
  • the photopolymerization cured film of the dispersion of the comparative example was turbid, and the refractive index and pencil hardness could not be measured.
  • EO represents ethylene oxide
  • PO represents propylene oxide
  • 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.
  • 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.

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JP5213148B1 (ja) * 2011-11-25 2013-06-19 第一工業製薬株式会社 光半導体封止材用樹脂組成物
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US20210238413A1 (en) 2018-05-11 2021-08-05 Samyang Corporation Solid dispersion, preparation method therefor, chain-extended polyurethane using same, and epoxy resin composition comprising same
JP7275798B2 (ja) * 2019-04-18 2023-05-18 東洋インキＳｃホールディングス株式会社 組成物、被覆セルロース繊維、およびその製造方法
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