JP6305141B2 - Dispersant for non-aqueous dispersion media - Google Patents

Description

  The present invention relates to a reactive dispersant for dispersing solid fine particles in a non-aqueous dispersion medium, a solid particle dispersion using the dispersant, and the like.

  Dispersions in which fine solid particles made of inorganic or organic materials are dispersed in an aqueous dispersion medium or a non-aqueous dispersion medium are used in paints and other various applications, and various dispersants are used to improve the dispersibility. Are used (Patent Documents 1 and 2).

  Such a dispersion has a low dispersion stability due to a change in the material of the dispersoid and a reduction in particle size, and the dispersoid is likely to aggregate in the dispersion medium. Aggregation of the dispersoid is produced in the production of the dispersion. Further, dispersibility is desired because it causes deterioration of product properties, material properties and quality of the final product as well as deterioration of processing properties, processing properties, handling properties and yield.

  In addition, nanometer-sized fine particles (particle diameter of 1 to 100 nm) are likely to aggregate and have a low affinity for the resin, so that it is extremely difficult to uniformly disperse in the resin with an aqueous dispersion medium. A dispersion in which nanoparticles are uniformly dispersed using a dispersant in a dispersion medium is prepared, and a resin is dissolved in this dispersion and mixed, or a solution in which a resin is dissolved in a solvent and the above A method of mixing, dissolving and dispersing the dispersion is used.

  For example, Patent Document 1 discloses a dispersant for inorganic powder having a carboxyl group. Patent Document 2 discloses a dispersant having a carboxyl group for the purpose of surface modification of inorganic nanoparticles. However, these conventional dispersants have a problem that the dispersion stability is not sufficient.

  Further, in order to disperse the fine particles in the non-aqueous medium, a large amount of a dispersant is required. When the particles are dispersed using such a large amount of the dispersant, the resin obtained by curing the resin is The bleed-out of the dispersant is likely to occur, and the bleed-out further causes a decrease in resin physical properties such as water resistance, hardness, and scratch strength.

  In order to solve these problems, a reactive dispersant having a carbon-carbon double bond copolymerizable with a monomer in the molecule has recently been proposed.

  For example, Patent Document 3 discloses a reactive dispersant for a photoresist having a (meth) acryl group at the end of an oxyalkylene chain.

  Patent Document 4 discloses a reactive dispersant for metal oxide fine particles obtained by addition reaction of a carboxyl group-containing (meth) acrylic compound with a vinyl compound polymer having an epoxy group.

  However, these conventional reactive emulsifiers have low dispersibility and dispersion stability depending on the type of the dispersion medium or dispersoid, and the effect of suppressing the deterioration of the physical properties of the resin is still insufficient.

Japanese Patent Laid-Open No. 2000-262883 JP 2005-519143 A JP 2010-134014 A JP 2007-289943 A

  The present invention has been made in view of the problems of the prior art as described above, and the dispersibility and dispersion stability are further improved. In a cured resin obtained by using the resin, a resin caused by bleeding out of the dispersant, etc. An object of the present invention is to provide a reactive dispersant for a non-aqueous dispersion medium, in which a decrease in physical properties is further suppressed.

  The dispersant for a non-aqueous dispersion medium of the present invention (hereinafter simply referred to as “dispersant”) contains a compound represented by the following general formula (1) in order to solve the above problems.

However, in the general formula (1), R ¹ represents a linear or branched alkyl group having 6 to 30 carbon atoms, an alkenyl group or an aryl group, R ² polymerizable carbon - groups having a carbon-carbon double bond 1 represents an average number of repeating units, and is a number in the range of ^{1 to 2} , Y ¹ and Y ² are each a oxyalkylene group having 1 to 4 carbon atoms or a substitution represented by the following general formula (2) And at least one of Y ¹ and Y ² is a substituent represented by the following general formula (2), k and m represent the number of repeating units, and k is a number in the range of 0 to 30. M is a number in the range of 0-30, the sum of k and m (k + m) is a number greater than 0 and less than or equal to 60, and X is at least one carbon atom and at least one hydrogen A linking group having an atom and / or at least one oxygen atom, and n is 0 Is a number of 1, Z is a carboxyl group, a sulfo group, or an group sulfate group or phosphate ester groups, these groups may form a salt.

但し、一般式（２）中、Ａは炭素数１〜３０の炭化水素基である。

However, in General formula (2), A is a C1-C30 hydrocarbon group.

In the dispersant of the present invention, R ² in the general formula (1) is preferably any one of groups represented by the following formulas (3) to (9).

However, R ³ and R ⁴ in formulas (3) to (9) each represent a hydrogen atom or a methyl group.

  Further, X in the general formula (1) is preferably an alkylene group having 1 to 15 carbon atoms or a group represented by the following general formula (10).

  However, B in the general formula (10) 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.

  Z in the general formula (1) is preferably a carboxyl group or a phosphate group.

  The solid particles of the present invention can be obtained by performing the coating and / or impregnation treatment with the dispersant of the present invention.

  The solid particle dispersion composition of the present invention can be obtained by dispersing organic particles or inorganic particles in a non-aqueous dispersion medium using the dispersant of the present invention.

  In the solid particle dispersion composition, any of a solvent, a polymerizable unsaturated monomer, and an oligomer can be used as the non-aqueous dispersion medium.

  The coating composition of the present invention contains the solid particle dispersion composition of the present invention.

  The cured product of the present invention can be obtained by curing the coating composition of the present invention.

  The dispersant of the present invention has a structure represented by the general formula (1), so that the dispersibility and dispersion stability are superior to those of conventional dispersants, and the dispersion stability is excellent with a small amount of addition. It will be a thing. Further, when the dispersant and the monomer are copolymerized when the dispersion composition using this dispersant is cured, in the obtained film or other resin cured product, the resin physical properties can be improved by bleeding out of the dispersant. An adverse effect can be greatly reduced as compared with a conventional reactive dispersant, and a cured resin product having improved hardness, scratch strength, water resistance and the like can be obtained.

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

  As described above, the dispersant of the present invention contains the compound represented by the general formula (1).

  As shown in the general formula (1), this compound has a polymerizable carbon-carbon double bond, and is represented by the substituent represented by the general formula (2) or the substituent represented by the general formula (2) and alkylene. It has a dispersion medium affinity part containing an oxide chain and a dispersoid affinity part indicated by Z, and these dispersion medium affinity part and dispersoid affinity part are connected by a linking group X.

The hydrophobic group R ¹ in the general formula (1) represents a linear or branched alkyl group having 6 to 30 carbon atoms, an alkenyl group, or an aryl group, and these groups may have a substituent. . Specific examples of the alkyl group include hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group. Group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, 2-hexyldecyl group, heptadecyl group, isoheptadecyl group, octadecyl group, Isooctadecyl group, 2-octyldecyl group, 2-hexyldecyl group, nonadecyl group, isononadecyl group, eicosyl group, isoeicosyl group, heneicosyl group, isoheneicosyl group, docosyl group, isodocosyl group, tricosyl group Isotorikoshiru group, tetracosyl group, Isotetorakoshiru group, pentacosyl group, Isopentakoshiru group, hexacosyl group, Isohekisakoshiru group, heptacosyl group, Isoheputakoshiru group and the like.

  Specific examples of the alkenyl group include hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, oleyl group and the like.

  Specific examples of the aryl group include phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butyl. Phenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, Examples include benzylphenyl group, α-naphthyl group, β-naphthyl group and the like.

Next, for the group R ² having a polymerizable carbon-carbon double bond, examples of the polymerizable carbon-carbon double bond include an allyl group, a 2-propenyl group, a methallyl group, a vinyl group, an acrylic group, and a methacryl group. Is mentioned. The group R ² having a polymerizable carbon-carbon double bond is a substituent having one or more of these carbon-carbon double bonds, and is any of the groups represented by the following general formulas (3) to (9). Preferably there is.

However, R ³ and R ⁴ in the general formulas (3) to (9) each represent a hydrogen atom or a methyl group.

In the dispersant of the present invention, the R ² group in the molecule has a polymerizable carbon-carbon double bond, and in the presence of a radical polymerization catalyst or a cationic polymerization catalyst, this R ² group is exposed to ultraviolet rays, electron beams, or heat. It is possible to copolymerize with a polymerizable unsaturated monomer. Thereby, the bleeding out of a dispersing agent can be suppressed and the bad influence on the resin physical property can be reduced. l represents the average number of repeating units and is a number of 1 or more and less than 3, preferably in the range of 1 to 2, more preferably in the range of 1 to 1.5. Depending on the structure of the other part of the formula (1), when l exceeds 2, there is a possibility that the dispersion performance is lowered and a stable dispersion cannot be obtained.

Next, the substituents Y ¹ and Y ² in the general formula (1) are a substituent represented by the general formula (2) or an oxyalkylene group having 1 to 4 carbon atoms, and at least one of Y ¹ and Y ² is It is a substituent shown by the general formula (2).

  However, in General formula (2), A is a C1-C30 hydrocarbon group, and it is preferable that carbon number is 1-20. The hydrocarbon group is preferably an alkylene group or a branched alkylene group.

As the oxyalkylene group having 1 to 4 carbon atoms in the substituents Y ¹ and Y ² , 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. The oxyalkylene group having 1 to 4 carbon atoms may be a homopolymer chain, a random polymer chain or a block polymer chain of two or more alkylene oxides, or a combination thereof.

K and m which show the number of repeating units of the substituents Y ¹ and Y ^{2 in} the formula (1) are numbers in which k is in the range of 0 to 30, m is in the range of 0 to 30, and k And the sum (k + m) of m and m is a number exceeding 0 and not more than 60. Of these, k is preferably 0 to 10, more preferably 0 to 5, and still more preferably 0. Moreover, m is preferably 1 to 20, more preferably 3 to 15, and still more preferably 5 to 10. The sum of k and m (k + m) is preferably 1 to 40, and more preferably 3 to 20.

  The linking group X can then be selected from known structures having at least one carbon atom and further having at least one hydrogen atom and / or at least one oxygen atom, but preferably saturated carbonization. A group formed from any one group selected from a hydrogen group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, and an ester group, or a combination of two or more thereof, and has an alicyclic structure and an aromatic ring structure. It may have a repeating unit. Examples of the combination of two or more groups include groups in which two saturated or unsaturated hydrocarbon groups are linked via an ether group, a carbonyl group, or an ester group.

  X is preferably an alkylene group having 1 to 15 carbon atoms or a group represented by the following general formula (10).

  However, B in the general formula (10) 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.

  When X is an alkylene group, it is more preferably 1 to 8 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 2 carbon atoms.

  When X is a group represented by the general formula (10), B is more preferably an alkylene group or a vinylene group. Further, B preferably has 1 to 8 carbon atoms.

  Next, the dispersoid affinity site Z represents a carboxyl group, a sulfo group, a sulfate ester group, a phosphate ester group, or a salt thereof, and is preferably a carboxyl group or a phosphate ester group. Phosphate esters refer to monoesters, diesters and mixtures thereof.

  Z may be in acid form or form a salt. Examples of the salt to be formed include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts. Specific examples are shown below.

  Examples of the alkali metal salt include sodium salt, potassium salt, lithium salt and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, triisopropanolamine salts, and the like.

  Next, the manufacturing method of the dispersing agent of this invention is demonstrated. Although the dispersing agent of this invention can be manufactured by a well-known method and the example is shown below, it is not limited to these methods.

  For example, after reacting an alcohol derivative or phenol derivative having a linear or branched alkyl group or aryl group having 6 to 30 carbon atoms with an epoxide having a polymerizable carbon-carbon double bond, a lactone is produced by a known method. A method of introducing the dispersoid affinity site Z after ring-opening polymerization of the compound or condensation polymerization of hydroxycarboxylic acid or addition of alkylene oxide is used.

  Examples of the lactone compound include β-propiolactone, δ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, and the like.

  Examples of the hydroxycarboxylic acid include ricinoleic acid, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, lactic acid, glycolic acid, hydroxyisophthalic acid, hydroxypivalic acid, 4-hydroxy Isophthalic acid salicylic acid, 11-oxyhexadecanoic acid, 2-oxide decanoic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, apple Examples include acid, tartaric acid, gluconic acid, 4,4-bis (hydroxyphenyl) butyric acid, glucuronic acid, and 3-hydroxybutanoic acid.

  When the dispersoid affinity site Z is a carboxylic acid, a method of reacting with a terminal hydroxyl group in the presence of a base using a monohalogenated lower carboxylic acid or a salt thereof, or ring opening with a terminal hydroxyl group using an acid anhydride It can be produced by a reaction method.

  When the dispersoid affinity site Z is a phosphate ester, it can be produced by a method in which a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, oxychlorophosphoric acid or the like is reacted with a terminal hydroxyl group. Depending on the production method, a monoester type compound and a diester type compound are obtained as a mixture, but these may be separated or used as they are as a mixture. Further, the reaction can be performed in the presence of water to increase the content ratio of the monoester compound.

  The dispersant for a non-aqueous dispersion medium of the present invention is within the range limited as described above in order to exhibit the effects of the present invention, and the type of hydrophobic group, lactone, hydroxycarboxylic acid or alkylene oxide, its addition form, and addition By optimizing the molar amount, the structure of the linking group, etc., it is possible to disperse a wider variety of dispersoids than known dispersants, and to disperse and stabilize the dispersoid in a wider variety of dispersion media. Industrial value is great.

  In addition, the dispersing agent of the present invention can be used by reducing the amount of ions contained, in particular, the content of each of alkali metal ions, alkaline earth metal ions, heavy metal ions, and halogen ions by a known purification method. Ions in the dispersant greatly contribute to 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 50 ppm in the dispersant.

  Next, solid particles that are dispersoids that can be used in the present invention will be described. The dispersoid particles dispersed by the dispersant of the present invention are not particularly limited, and may be either inorganic matter-derived particles (inorganic matter particles) or organic matter-derived particles (organic matter particles). In addition, two or more kinds of dispersoid particles can be mixed and used.

  Examples of inorganic-derived particles include iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, and alloys thereof, or mixtures thereof. Is mentioned. As will be described later, in order to stably remove metal particles from the medium, alkanoic acids, fatty acids, hydroxycarboxylic acids, alicyclic, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol derivatives, amines Further, it may be coated with a protective agent such as an amphiphilic polymer, a high molecular surfactant, or 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.

  Examples of organic-derived particles include 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, polyb Naphthalate, polysulfone, polyphenylene sulfide, polyimides or the like.

  The solid particles that become the dispersoid in 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 fibrous.

  Although the magnitude | size of the said solid particle is not specifically limited, Usually, it is a particle diameter (length if it is fibrous) about 1-500 nm. In particular, even a nanometer-sized particle having a particle diameter of about 1 to 100 nm, which is easily aggregated and difficult to disperse in the past, can be dispersed and stabilized by the dispersant of the present invention.

  As the solid particles, those obtained by a known method can be used. The fine particle preparation method includes a breakdown method in which coarse particles are mechanically pulverized and refined, and a build in which several unit particles are generated and particles are formed through the agglomerated cluster state. 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.

  Next, the non-aqueous dispersion medium that can be used in the present invention will be described.

  The non-aqueous dispersion medium that can be used in the present invention is not particularly limited. Examples thereof include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, and amyl. Alcohol, cyclopentanol, hexyl alcohol, cyclohexanol, heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, lauryl alcohol, tridecyl alcohol, octyldodecanol, oleyl Alcohol, furfuryl alcohol, allyl alcohol, ethylene chlorohydrin, benzyl alcohol, α-terpineol, terpineols, 3 Alcohol solvents such as methoxybutanol and diacetone alcohol, aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as n-hexane, cyclohexane and n-heptane, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, Ether solvents such as dibutyl ether, butyl ethyl ether, methyl-t-butyl ether, terpinyl methyl ether, dihydroterpinyl methyl ether, diglyme, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl-n-butyl ketone, Ketone solvents such as methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, acetonyl acetone, isophorone, cyclohexanone, methylcyclohexanone, ethyl formate, Propyl acid, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, amyl acetate, cyclohexyl acetate, ethyl lactate, 3-methoxyacetate Butyl, hexyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isoamyl propionate, methyl acetoacetate, ethyl acetoacetate, γ-butyrolactone, ethylene glycol mono Ethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monome 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 -Glyco such as n-propyl ether, tripropylene glycol mono-n-butyl ether And ether ether solvents and monoalkyl ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl isobutyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether. Examples include alkylene glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, hexylene glycol, polyethylene glycol, and polypropylene glycol. Other examples include halogenated hydrocarbon solvents and amide solvents such as dimethylacetamide. In the solvent exemplified above, the alkyl composition may have a linear structure, a branched structure, or a mixture thereof.

  Further, as the non-aqueous dispersion medium, various resins used for ordinary paints, adhesives, adhesives, and moldings can be used without particular limitation. Specific examples include acrylic resins, polyester resins, alkyd resins, urethane resins, silicone resins, fluorine resins, epoxy resins, polycarbonate resins, polyvinyl chloride resins, and polyvinyl alcohol.

  As the non-aqueous dispersion medium, polymerizable unsaturated monomers and oligomers having at least one carbon-carbon double bond in the molecule can also be used. For example, as monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, polyoxyethylene phenyl ether (meth) acrylate, 2- [2- (Ethoxy) ethoxy] ethyl (meth) acrylate, polyoxyethylene-2-ethylhexyl ether (meth) acrylate, phenylglyceryl ether (meth) acrylate, cyclohexyl ( Data) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate. Examples of the (meth) acrylate having a hydroxyl group include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. Moreover, as a vinyl monomer, N-vinyl pyrrolidone, N-vinyl caprolactone, styrene etc. can be used. In addition, diethyl maleate, dibutyl fumarate, and the like can be used.

  Bifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, other alkylene diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethyl Roruji (meth) Aqua Li rate, polyoxyalkylene bisphenol A di (meth) acrylate.

  Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane alkoxylate tri (meth) acrylate, and tris (acryloxyethyl) isocyanurate. It is done. In addition, examples of the tetrafunctional or higher monomer include pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol poly (meth) acrylate.

  In addition, (meth) acrylate oligomers include urethane (meth) acrylate having a urethane structure in the molecule, epoxy (meth) acrylate formed by ring opening of an epoxy group by reaction of an epoxy compound and (meth) acrylic acid, Examples thereof include polyester (meth) acrylate having a polyester structure in the molecule and polybutadiene (meth) acrylate.

  The dispersion media exemplified above are examples of the dispersion medium that can be used in the present invention, and the dispersion medium is not limited to these. In addition, a dispersion medium can be used individually by 1 type, or can mix and use 2 or more types. In addition, the present invention aims to provide a dispersant that can obtain a fine particle dispersion in a non-aqueous environment, regardless of whether the dispersion medium is intentional or accidental. It does not exclude cases where water is mixed or mixed in either the middle or final product design stage.

  Since the dispersant of the present invention has a polymerizable carbon-carbon double bond in the molecule, when a polymerizable unsaturated monomer and oligomer are selected as the non-aqueous dispersion medium, a radical polymerization catalyst or a cationic polymerization catalyst is used. In the presence of a non-reactive dispersant, the dispersant of the present invention is copolymerized with a polymerizable unsaturated monomer and fixed as a resin component by energy rays such as ultraviolet rays and electron beams, or heat. The adverse effect on the physical properties of the resin due to the bleeding out of the dispersant, which has been a problem at the time, can be reduced.

  When the dispersion composition of the present invention is cured by energy ray irradiation or heating as described above, it is desirable to use a polymerization initiator in combination. The polymerization initiator species includes a radical polymerization catalyst or a cationic polymerization catalyst, and can be classified into photo (energy ray) polymerization or thermal polymerization depending on the means of polymerization initiation. The dispersant of the present invention can be applied to any of them.

  As the polymerization initiator, a known polymerization initiator can be appropriately selected and used. For example, as a radical photopolymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, acetophenone, benzophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2-methyl [4- (methylthio) phenyl] morpholino-1-propanone, benzoin methyl ether, benzoin ethyl ether, 2-chlorothioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide And bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide. These may be used alone or in combination of two or more. Examples of radical thermal polymerization initiators include ammonium persulfate, benzoyl peroxide, and azobisisobutyronitrile. Examples of cationic photopolymerization initiators include onium salts such as triphenylsulfonium hexachlorophosphate and aryldiazonium salts. Examples of cationic thermal polymerization initiators include Lewis acids such as boron trifluoride ether complex salts.

  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. , Preferably in the range of 0.5 to 70% by mass. Moreover, the suitable use density | concentration of the dispersing agent of this invention exists in the range of 1-5,000 mass% with respect to a dispersoid particle, and the range of 1-1,000 mass% is more suitable.

  The dispersion composition of the present invention can be prepared using a known stirring means, homogenizing means, or 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, bead mills such as continuous disk type bead mills, continuous annular type bead mills, sand mills, jet mills, etc. Is 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. Although the specific method for using a dispersing agent as a protective agent of a solid particle is not specifically limited, For example, the method of manufacturing microparticles | fine-particles in presence of a dispersing agent is mentioned.

  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 known protective agents in terms of these functions, and is known by optimally selecting the composition of the hydrophobic group, the addition form of the alkylene oxide and its added molar amount, the type of the hydrophobic group, the linking group, and the like. This has the advantage that the desired dispersoid can be dispersed and stabilized in a wider range of dispersion medium than the protective agent of the above.

  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 mass”, and “%” indicates “mass%”. However, the present invention is not limited to the following examples, and can be appropriately changed or modified without departing from the technical scope of the present invention.

<Synthesis of dispersant>
[Production Example 1 (Synthesis of Dispersant 1)]
In a reactor equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 318 g (1.0 mol) of styrenated phenol (mono / di / tri = 15/55/30, mass ratio), hydroxylated as a catalyst 5 g of potassium was charged and dehydrated under reduced pressure at 105 ° C. for 30 minutes. 137 g (1.2 mol) of allyl glycidyl ether was gradually added dropwise and reacted at 100 ° C. for 5 hours. Next, 1141.4 g (10 mol) of ε-caprolactone and 1.0 g of tetrabutyl titanate were added, and the reaction was continued at 180 ° C. in a nitrogen atmosphere until the remaining ε-caprolactone was 1% or less.

Next, after adding 1000 g of toluene and stirring the mixture uniformly, 151 g (1.3 mol) of sodium monochloroacetate and 52 g (1.3 mol) of sodium hydroxide were gradually added while maintaining the temperature of the reaction system at 60 ° C. or lower. After the addition, the mixture was reacted at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension was washed with distilled water, and the solvent was distilled off under reduced pressure to disperse the dispersant 1 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, l: 1.2, Y ² _{: -C (= O) - (} CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 2 (Synthesis of Dispersant 2)]
Dispersion was performed in the same manner as in Production Example 1, except that 283 g (1.0 mol) of benzylated phenol (mono / di / tri = 15/60/25 mass ratio) was used instead of styrenated phenol. Agent 2 (R ¹ : benzylated phenyl group, R ² : allyl group, k: 0, l: 1.2, Y ² : —C (═O) — (CH ₂ ) ₅ —O—, m: 10, X: CH ₂ , n: 1, Z: COOH).

[Production Example 3 (Synthesis of Dispersant 3)]
The same operation as in Production Example 1 was performed except that 212 g (1.0 mol) of cumylphenol was used instead of styrenated phenol, and dispersant 3 (R ¹ : cumylphenyl group, R ² : allyl group, k: 0 _{^{, l: 1.2, Y 2:}} -C (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 4 (Synthesis of Dispersant 4)]
The same operation as in Production Example 1 was performed except that 220 g (1.0 mol) of nonylphenol was used instead of styrenated phenol, and dispersant 4 (R ¹ : nonylphenyl group, R ² : allyl group, k: 0, _{^{l: 1.2, Y 2: -C}} (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 5 (Synthesis of Dispersant 5)]
The same operation as in Production Example 1 was performed except that 186 g (1.0 mol) of lauryl alcohol was used instead of styrenated phenol, and dispersant 5 (R ¹ : lauryl group, R ² : allyl group, k: 0, _{^{l: 1.2, Y 2: -C}} (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 6 (Synthesis of Dispersant 6)]
Except that the amount of allyl glycidyl ether used was 171 g (1.5 mol), the same operation as in Production Example 1 was performed, and dispersant 6 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, _{^{l: 1.5, Y 2: -C}} (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 7 (Synthesis of Dispersant 7)]
The same operation as in Production Example 1 was performed except that 228 g (1.2 mol) of 1-propenylphenyl glycidyl ether was used instead of allyl glycidyl ether, and dispersant 7 (R ¹ : styrenated phenyl group, R ² : propenyl). Phenyl group, k: 0, l: 1.2, Y ² : —C (═O) — (CH ₂ ) ₅ —O—, m: 10, X: CH ₂ , n: 1, Z: COOH). Obtained.

[Production Example 8 (Synthesis of Dispersant 8)]
The same operation as in Production Example 1 was performed except that 170 g (1.2 mol) of glycidyl methacrylate was used instead of allyl glycidyl ether, and dispersant 8 (R ¹ : styrenated phenyl group, R ² : methacryl group, k: _{^{0, l: 1.2, Y 2}} : -C (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 9 (Synthesis of Dispersant 9)]
The same operation as in Production Example 1 was conducted except that 860.9 g (10 mol) of γ-butyrolactone was used instead of ε-caprolactone, and dispersant 9 (R ¹ : styrenated phenyl group, R ² : allyl group, k _{^{: 0, l: 1.2, Y}} 2: -C (= O) - (CH 2) 3 -O-, m: 5, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 10 (Synthesis of Dispersant 10)]
Except that 1001.2 g (10 mol) of δ-valerolactone was used instead of ε-caprolactone, the same operation as in Production Example 1 was performed, and dispersant 10 (R ¹ : styrenated phenyl group, R ² : allyl group, _{^{k: 0, l: 1.2,}} Y 2: -C (= O) - (CH 2) 4 -O-, m: 20, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 11 (Synthesis of Dispersant 11)]
In a reactor equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 318 g (1.0 mol) of styrenated phenol (mono / di / tri = 15/55/30, mass ratio), hydroxylated as a catalyst 5 g of potassium was charged and dehydrated under reduced pressure at 105 ° C. for 30 minutes. 137 g (1.2 mol) of allyl glycidyl ether was gradually added dropwise and reacted at 100 ° C. for 5 hours. Next, a test tube was attached to the reactor, 1802.9 g (6 mol) of 12-hydroxystearic acid and 1.0 g of tetrabutyl titanate were added, and the remaining acid value at 180 ° C. in a nitrogen atmosphere was 2 mgKOH / g or less. Reacted.

Next, after removing the test tube and adding 1000 g of toluene and stirring the mixture uniformly, 151 g (1.3 mol) of sodium monochloroacetate and 52 g (1.3 mol) of sodium hydroxide while maintaining the temperature of the reaction system at 60 ° C. or lower. ) Was gradually added, followed by reaction at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension was washed with distilled water, and the solvent was distilled off under reduced pressure to disperse the dispersant 11 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, l: 1.2, Y ² _{: -C (= O) - (} CH 2) 10 -CH (C 6 H 13) O-, m: 10, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 12 (Synthesis of Dispersant 12)]
Except that the amount of ε-caprolactone used was 57.7 g (5 mol), the same operation as in Production Example 1 was performed, and dispersant 12 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, _{^{l: 1.2, Y 2: -C}} (= O) - (CH 2) 5 -O-, m: 20, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 13 (Synthesis of Dispersant 13)]
In a reactor equipped with a stirrer, a thermometer and a nitrogen introduction tube, 318 g (1.0 mol) of styrenated phenol (mono / di / tri = 15/55/30 mass ratio), 141.4 g of ε-caprolactone (10 Mol), 0.5 g of tetrabutyl titanate was charged, and the reaction was continued in a nitrogen atmosphere at 180 ° C. until the remaining ε-caprolactone was 1% or less. Next, 5 g of potassium hydroxide was charged as a catalyst and dehydrated under reduced pressure at 105 ° C. for 30 minutes. 137 g (1.2 mol) of allyl glycidyl ether was gradually added dropwise and reacted at 100 ° C. for 5 hours.

Next, after adding 1000 g of toluene and stirring the mixture uniformly, 151 g (1.3 mol) of sodium monochloroacetate and 52 g (1.3 mol) of sodium hydroxide were gradually added while maintaining the temperature of the reaction system at 60 ° C. or lower. After the addition, the mixture was reacted at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure to disperse the dispersant 13 (R ¹ : styrenated phenyl group, R ² : allyl group, Y ¹ : —C (═O) — ( _{CH 2) 5 -O-, k:} 10, l: 1.2, m: 0, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 14 (Synthesis of Dispersant 14)]
Except that the amount of ε-caprolactone used was 57.7 g (5 mol), the same operation as in Production Example 13 was performed, and dispersant 14 (R ¹ : styrenated phenyl group, R ² : allyl group, Y ¹ :- _{C (= O) - (CH} 2) 5 -O-, k: 5, l: 1.2, m: 0, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 15 (Synthesis of Dispersant 15)]
Stirring phenol (mono / di / tri = 15/55/30 mass ratio) 318 g (1.0 mol), ε-caprolactone 57.7 g (5) Mol), 0.5 g of tetrabutyl titanate was charged, and the reaction was continued in a nitrogen atmosphere at 180 ° C. until the remaining ε-caprolactone was 1% or less. Next, 5 g of potassium hydroxide was charged as a catalyst and dehydrated under reduced pressure at 105 ° C. for 30 minutes. 137 g (1.2 mol) of allyl glycidyl ether was gradually added dropwise and reacted at 100 ° C. for 5 hours. Further, 57.7 g (5 mol) of ε-caprolactone and 0.5 g of tetrabutyl titanate were charged, and then reacted at 180 ° C. in a nitrogen atmosphere until the remaining ε-caprolactone was 1% or less.

Next, after adding 1000 g of toluene and stirring the mixture uniformly, 151 g (1.3 mol) of sodium monochloroacetate and 52 g (1.3 mol) of sodium hydroxide were gradually added while maintaining the temperature of the reaction system at 60 ° C. or lower. After the addition, the mixture was reacted at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure, whereby dispersant 15 (R ¹ : styrenated phenyl group, R ² : allyl group, Y ¹ : —C (═O) — ( ^{_{CH 2) 5 -O-, k:}} 5, l: 1.2, Y 2: -C (= O) - (CH 2) 5 -O-, m: 5, X: CH 2, n: 1, Z: COOH) was obtained.

[Production Example 16 (Synthesis of Dispersant 16)]
In an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, a raw material introduction pipe, and a pressure reducing exhaust pipe, styrenated phenol (mono / di / tri = 15/55/30) (Mass ratio) 318 g (1.0 mol), 5 g of potassium hydroxide as a catalyst were charged, the atmosphere in the autoclave was replaced with nitrogen, the temperature was raised to 100 ° C. under reduced pressure, and then 220 g of ethylene oxide (5.0 g) The reaction was carried out under the conditions of a pressure of 0.15 MPa and a temperature of 120 ° C.

The obtained reaction product was transferred to a reactor equipped with a stirrer, a thermometer, and a nitrogen introducing tube, and 57.7 g (5 mol) of ε-caprolactone and 0.5 g of tetrabutyl titanate were charged, and then at 180 ° C. in a nitrogen atmosphere. The reaction was continued until the remaining ε-caprolactone was 1% or less. Next, after adding 1000 g of toluene and stirring the mixture uniformly, 151 g (1.3 mol) of sodium monochloroacetate and 52 g (1.3 mol) of sodium hydroxide were gradually added while maintaining the temperature of the reaction system at 60 ° C. or lower. After the addition, the mixture was reacted at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure, whereby dispersant 16 (R ¹ : styrenated phenyl group, R ² : allyl group, Y ¹ : — (CH ₂ ) ₂ —O. _{^{-, k: 5, l:}} 1.2, Y 2: -C (= O) - (CH 2) 5 -O-, m: 5, X: CH 2, n: 1, Z: COOH) to give the It was.

[Production Example 17 (Synthesis of Dispersant 17)]
Stirring phenol (mono / di / tri = 15/55/30 mass ratio) 318 g (1.0 mol), ε-caprolactone 57.7 g (5) Mol), 0.5 g of tetrabutyl titanate was charged, and the reaction was continued in a nitrogen atmosphere at 180 ° C. until the remaining ε-caprolactone was 1% or less. Next, 5 g of potassium hydroxide was charged as a catalyst and dehydrated under reduced pressure at 105 ° C. for 30 minutes. 137 g (1.2 mol) of allyl glycidyl ether was gradually added dropwise and reacted at 100 ° C. for 5 hours.

  The obtained reaction product was transferred to an autoclave equipped with a temperature controller equipped with a stirrer, thermometer, nitrogen inlet tube, raw material inlet tube, and pressure reducing exhaust pipe, and the atmosphere in the autoclave was replaced with nitrogen, and the pressure was reduced. After raising the temperature to 100 ° C. under the conditions, the reaction was conducted under the conditions of a pressure of 0.15 MPa and a temperature of 120 ° C. while sequentially introducing 220 g (5.0 mol) of ethylene oxide.

The obtained reaction product was transferred to a reactor equipped with a stirrer and a thermometer, 1000 g of toluene was added and stirred uniformly, and then 151 g (1.3 mol) of sodium monochloroacetate was maintained while maintaining the temperature of the reaction system at 60 ° C. or lower. After gradually adding 52 g (1.3 mol) of sodium hydroxide, the mixture was reacted at 80 ° C. for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. This white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure to disperse the dispersant 17 (R ¹ : styrenated phenyl group, R ² : allyl group, Y ¹ : —C (═O) — ( _{^{CH 2) 5 -O-, k:}} 5, l: 1.2, Y 2 :-( CH 2) 2 -O-, m: 5, X: CH 2, n: 1, Z: COOH) to give the It was.

[Production Example 18 (Synthesis of Dispersant 18)]
Dispersant 18 (R ¹ : styrenated phenyl group, R ² ) was prepared by reacting 156 g (1 mol) of suberic acid anhydride with 120 mol of ε-caprolactone adduct obtained in the same manner as in Production Example 1 at 120 ° C. for 2 hours. allyl _{^{group, k: 0, l: 1.2}} , Y 2: -C (= O) - (CH 2) 5 -O-, m: 10, X: -C (= O) - (CH 2) _6- , n: 1, Z: COOH).

[Production Example 19 (Synthesis of Dispersant 19)]
Dispersant 19 (R ¹ : styrenated phenyl group, R ² ) was prepared by reacting 100 g (1 mol) of succinic anhydride at 120 ° C. for 2 hours with ε-caprolactone 10 mol adduct obtained in the same manner as in Production Example 1. allyl _{^{group, k: 0, l: 1.2}} , Y 2: -C (= O) - (CH 2) 5 -O-, m: 10, X: -C (= O) - (CH 2) _2- , n: 1, Z: COOH).

[Production Example 20 (Synthesis of Dispersant 20)]
Dispersant 20 (R ¹ : styrenated phenyl group, R ² ) was obtained by reacting 198 g (1 mol) of maleic anhydride with 120 mol of maleic anhydride obtained in the same manner as in Production Example 1 at 120 ° C. for 2 hours. An allyl group, k: 0, l: 1.2, Y ² : ethylene oxide, m: 10, X: —C (═O) —CH═CH—, n: 1, Z: COOH) was obtained.

[Production Example 21 (Synthesis of Dispersant 21)]
Dispersant 21 (R ¹ : styrenated phenyl group, R) was prepared by reacting 47 g (0.33 mol) of phosphoric anhydride at 80 ° C. for 5 hours with ε-caprolactone 10 mol adduct obtained in the same manner as in Production Example 1. ² : allyl group, k: 0, l: 1.2, Y ² : —C (═O) — (CH ₂ ) ₅ —O—, m: 10, n: 0, Z: phosphoric acid monoester PO ₃ H ₂ / phosphoric acid diester PO ₂ H) was obtained.

[Production Example 22 (Synthesis of Dispersant 22)]
An ethylene oxide 10 mol adduct obtained in the same manner as in Production Example 1 was placed in a reactor, and 117 g (1.0 mol) of chlorosulfonic acid was added dropwise over about 1 hour. The liquid temperature was maintained at 10-15 ° C. After completion of the dropwise addition of chlorosulfonic acid, nitrogen gas is passed through the reaction solution to remove by-produced hydrogen chloride gas, and dispersant 22 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, l _{^{: 1.2, Y 2: -C (}} = O) - (CH 2) 5 -O-, m: 10, n: 0, Z: to give a sulfone group).

[Comparative Production Example 1 (Synthesis of Dispersant of Comparative Example 1)]
The same operation as in Production Example 1 was performed except that 60 g (1.0 mol) of 1-propanol was used instead of styrenated phenol, and the dispersant of Comparative Example 1 (R ¹ : 1-propyl group, R ² : allyl) _{^{group, k: 0, l: 1.2}} , Y 2: -C (= O) - (CH 2) 5 -O-, m: 10, X: CH 2, n: 1, Z: COOH) to give the It was.

[Comparative Production Example 2 (Synthesis of Dispersant of Comparative Example 2)]
The same operation as in Production Example 1 was carried out except that the ε-caprolactone addition operation was not performed, and the dispersant of Comparative Example 2 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, l: 1.2) , M: 0, X: CH ₂ , n: 1, Z: COOH).

[Comparative Production Example 3 (Synthesis of Dispersant of Comparative Example 3)]
In Production Example 1, the composition obtained at the end of addition of ε-caprolactone was used as the dispersant of Comparative Example 3 (R ¹ : styrenated phenyl group, R ² : allyl group, k: 0, l: 1.2, Y ² : _{-C (= O) - (CH} 2) 5 -O-, m: 10, X: CH 2, n: 0, Z: was H).

[Dispersion test 1]
Solvents shown in Tables 1 and 2 as dispersion media containing 1.5 parts (in terms of solid content) of the dispersant of the present invention shown in Table 1 below and 1.5 parts in terms of solid dispersant (in terms of solid content) shown in Table 2 It melt | dissolved in 68.5 parts, and also refined | miniaturized for 12 hours with the paint shaker to what added 30 ml of magnesium oxide (MgO) as a dispersoid, and 100 ml of zirconia beads of diameter 0.5mm. 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.
A: All dispersoids are dispersed in the liquid, and no sediment is observed at the bottom of the container. ○: Most of the dispersoids are dispersed in the liquid, but a very small amount of sediment is observed at the bottom of the container. ×: Most dispersoids settle to the bottom

  From the results shown in Table 1 and Table 2, it can be seen that the dispersion using the dispersant of the present invention is more excellent in dispersibility than the comparative example.

[Dispersion test 2]
A predetermined amount of the dispersant of the present invention and the dispersant of the comparative example shown in Table 3 below are dissolved in a predetermined amount of the dispersion medium shown in Table 3 as a dispersion medium, respectively, and further zirconium oxide (ZrO ₂ as a dispersoid). ) 5 parts was added to the mixture with a bead mill (manufactured by Kotobuki Kogyo Co., Ltd., trade name Ultra Apex Mill UAM-005, zirconia beads having a diameter of 50 μm, peripheral speed 10 m / sec) for 2 hours. The resulting treatment liquid is transferred to a transparent container, the dispersibility of the treatment liquid in the container immediately after the miniaturization treatment, and the treatment liquid in the container after 24 hours (dispersant is 0.25 part of dispersoid. The dispersion stability of 5 parts of the treatment liquid) was evaluated based on the same criteria as above by observing the treatment liquid visually. In addition, a dynamic light scattering method using a particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac UPAMODEL 9230) for a part of the treatment liquid (treatment liquid having a dispersant of 0.25 part and a dispersoid of 5 parts). The 50% volume particle size (D50) measured by the above was used as the particle size of zirconium oxide immediately after the refinement treatment. The blending amount of the dispersion medium with respect to the dispersant is 94.5 parts, 94.75 parts of the dispersion medium with respect to 0.5 part, 0.25 part, 0.15 part, and 0.05 part of the dispersant, respectively. 94.85 parts and 94.95 parts. In Table 3, the amount of dispersant used (zirconium oxide) was 10% 0.5% dispersant, 5% 0.25 parts dispersant, 3% 0.15 parts dispersant, 1% dispersed. This corresponds to 0.05 parts of the agent. Table 3 shows the visual evaluation of the dispersibility and dispersion stability and the particle diameter measurement results of zirconium oxide.

  Further, the dispersant or comparative dispersant of the present invention having the composition shown in Table 3 below, zirconium oxide, and the zirconium oxide dispersion comprising a dispersion medium (dispersant 0.25 part, zirconium oxide 5.00 parts, A dispersion obtained by mixing 70 parts of a dispersion medium (94.75 parts) with 70 parts of a methyl ethyl ketone solution in which 25 parts of an acrylic resin (product name: Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd.) is dissolved. The refinement process was carried out for 2 hours using a trade name, Ultra Apex Mill UAM-005, using zirconia beads having a diameter of 50 μm, and a peripheral speed of 10 m / sec. 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 based on the above criteria by visually observing the treatment liquid. The results are shown in Table 3.

Moreover, after apply | coating the said dispersion liquid (after 2 hours refinement | miniaturization process) on the 10-mm-thick clean 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.
◎: Alphabetic characters of 12 points can be clearly distinguished. ○: Slight turbidity is generated in the coating film, but alphabetic characters of 12 points can be determined. X: The coating film is turbid. Unable to distinguish 12 point alphabetic characters

  As shown in Table 3, the dispersibility and dispersion stability of those using the dispersant of the present invention were superior to those of the comparative examples. Further, as shown in the same 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. The effect of the dispersant of the present invention is clear. 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.

[Dispersion test 3]
1. Preparation of Zirconium Oxide Acrylate Monomer Dispersion (1) Zirconium oxide powder (manufactured by Nippon Electric Works Co., Ltd., trade name PCS, primary particle diameter 30 nm) mixed with 100 parts of methyl ethyl ketone is shown in Table 4 below. What added the dispersion | distribution agent of this invention shown or 10 parts of comparative dispersing agents is a bead mill (the Kotobuki Industries Co., Ltd. brand name ultra apex mill UAM-005, the use of the zirconia bead of diameter 50 micrometers, peripheral speed 10m / sec). A refinement treatment for 4 hours was performed to prepare a zirconium oxide dispersion. To 100 parts of the resulting zirconium oxide dispersion, 10 parts of phenoxyethyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd., trade name New Frontier PHE) and pentaerythritol triacrylate (Daiichi Kogyo Seiyaku Co., Ltd., trade name) After adding and mixing 10 parts of New Frontier PET-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.

2. Production of Zirconium Oxide Acrylate Monomer Dispersion (2) 100 parts of commercially available zirconium oxide dispersion (manufactured by Sakai Chemical Co., Ltd., trade name SZR-M, primary particle diameter 3 nm, dispersion containing 30% by mass of methanol) 3 parts of the dispersant or comparative dispersant of the present invention having the composition shown in Table 4 below, 15 parts of phenoxyethyl acrylate (trade name New Frontier PHE, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), pentaerythritol tris After adding and mixing 15 parts of acrylate (Daiichi Kogyo Seiyaku Co., Ltd., trade name New Frontier PET-3), the solvent methanol was removed under reduced pressure using a rotary evaporator, and an acrylate monomer dispersion of zirconium oxide was obtained. (2) was obtained.

3. Preparation of Zirconium Oxide Acrylate Monomer Dispersion (3) 100 parts of a commercially available zirconium oxide dispersion (manufactured by Sakai Chemical Co., Ltd., trade name SZR-M, primary particle diameter 3 nm, dispersion containing 30% by mass of methanol) In addition, 3 parts of the dispersant or comparative dispersant of the present invention having the composition shown in Table 4 below and 28.5 parts of o-phenylphenoxyethyl acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD OPP-1) Then, the solvent methanol was removed under reduced pressure using a rotary evaporator to obtain an acrylate monomer dispersion (3) of zirconium oxide.

<Characteristic evaluation of acrylate monomer dispersion>
Regarding the dispersibility of the acrylate monomer dispersions (1), (2) and (3) obtained as described above, the transparency, viscosity and refractive index were evaluated or measured by the following methods. The results are shown in Table 4.

a. Transparency Place the acrylate monomer dispersion of zirconium oxide in a transparent glass container, place a paper with the alphabet printed at 12 points under the glass container, and put the alphabet over the dispersion for the transparency of the dispersion. From the point of whether it can be discriminated, it was evaluated according to the following criteria.
A: When the dispersion is put in a glass container having a depth of 5 cm, 12-point alphabet characters can be seen (the dispersion is transparent).
○: When the dispersion is put into a glass container having a depth of 1 cm, 12-point alphabet characters are clearly visible (the dispersion has a slight turbidity).
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 cloudy).

b. Viscosity 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.).

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.).

<Creation and characteristic evaluation of photopolymerized cured film>
Furthermore, production and evaluation of the photopolymerized cured films of the acrylate monomer dispersions (1), (2) and (3) of the zirconium oxide were performed as follows.

That is, 1 part of a photopolymerization initiator (trade name IRGACURE 184, manufactured by BASF Corporation) is added to and mixed with 100 parts of the zirconium oxide acrylate monomer dispersion (1), (2) or (3), and the zirconium oxide paste is mixed. Got. The zirconium oxide paste was applied on a polyethylene terephthalate film with an applicator (manufactured by Kodaira Seisakusho, YA type) 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. The transparency, refractive index, pencil hardness and water resistance of the obtained coating film were evaluated or measured as follows. The results are shown in Table 4.

a. Transparency Whether or not the alphabet of the photopolymerized cured film obtained on the polyethylene terephthalate film can be distinguished through the cured film by placing a paper with the alphabet printed at 12 points under the polyethylene terephthalate film. From this point, the following criteria were evaluated.
◎: Alphabetic characters of 12 points can be clearly distinguished. ○: Slight turbidity is generated in the cured film, but alphabetic characters of 12 points can be distinguished. X: The cured film is turbid. Unable to distinguish 12 point alphabetic characters

b. Refractive index The refractive index of the photopolymerized cured film was measured at 25 ° C. using a prism coupler (manufactured by Seki Technotron, MODEL 2010 / M).

c. Pencil Hardness The pencil hardness of the photopolymerized cured film was confirmed by conducting a scratch test with a pencil having a predetermined hardness in accordance with JIS K5400.

d. The water-resistant photopolymerized cured film was immersed in a constant temperature water bath at 60 ° C. for 3 days, and the transparency of the photopolymerized cured film was evaluated according to the same criteria as a.

  As shown in Table 4, the dispersion of the present invention has excellent dispersibility (transparency in 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. With good pencil hardness and high water resistance.

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 an isotropic material and / or an 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 (10)

The dispersing agent for non-aqueous dispersion media containing the compound shown by following General formula (1).

However, in the general formula (1), R ¹ represents a linear or branched alkyl group having 6 to 30 carbon atoms, an alkenyl group or an aryl group, R ² polymerizable carbon - groups having a carbon-carbon double bond , L represents the average number of repeating units and is a number in the range of 1-2,
Y ¹ and Y ² are each an oxyalkylene group having 1 to 4 carbon atoms or a substituent represented by the following general formula (2), and at least one of Y ¹ and Y ² is represented by the following general formula (2). K and m represent the number of repeating units, k is a number in the range of 0 to 30, m is a number in the range of 0 to 30, and the sum of k and m (k + m) Is a number greater than 0 and less than or equal to 60,
X is a linking group having at least one carbon atom and at least one hydrogen atom and / or at least one oxygen atom, n is a number of 0 or 1;
Z represents any group of a carboxyl group, a sulfo group, a sulfate ester group, or a phosphate ester group, and these groups may form a salt.

However, in General formula (2), A is a C1-C30 hydrocarbon group. The dispersant for a non-aqueous dispersion medium according to claim 1, wherein R ^{2 in the} general formula (1) is any one of groups represented by the following general formulas (3) to (9).

However, R ³ and R ⁴ in the general formulas (3) to (9) each represent a hydrogen atom or a methyl group. The dispersant for a non-aqueous dispersion medium according to claim 1 or 2, wherein X in the general formula (1) is an alkylene group having 1 to 15 carbon atoms or a group represented by the following general formula (10). .

However, B in the general formula (10) 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 dispersant for a non-aqueous dispersion medium according to any one of claims 1 to 3, wherein Z in the general formula (1) is a carboxyl group or a phosphate group.   Solid particles coated and / or impregnated with the dispersant for non-aqueous dispersion medium according to any one of claims 1 to 4.   A solid particle dispersion composition obtained by dispersing organic particles or inorganic particles in a non-aqueous dispersion medium using the dispersant for non-aqueous dispersion media according to claim 1.   The solid particle dispersion composition according to claim 6, wherein the non-aqueous dispersion medium is a solvent.   The solid particle dispersion composition according to claim 7, wherein the non-aqueous dispersion medium is a polymerizable unsaturated monomer or oligomer.   A coating composition comprising the solid particle dispersion composition according to claim 7 or 8. A cured product obtained by curing the coating composition according to claim 9.