JP2015000970A - Dispersant for non-aqueous dispersion media - Google Patents

Abstract

【選択図】なし[PROBLEMS] To exhibit excellent dispersion stability with respect to non-aqueous dispersion media with a small amount of addition, and to greatly improve deterioration of resin properties due to bleed-out of a dispersant in a cured resin obtained by using this. Provided is a dispersant for a non-aqueous dispersion medium.
The following general formula (1) (R ¹ is an alkyl group having 6 to 18 carbon atoms, alkenyl group, or aralkyl group, R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is a hydrogen or methyl group, D is a polymerizable unsaturated group, m1 is 1 to 3, m2 is 0 or 1, m3 is 1 to 2, AO is an alkylene oxide having 2 to 4 carbon atoms, and n is an average added mole number of 0 to 1,000. , X is a linking group having at least one carbon atom and at least one hydrogen atom and / or at least one oxygen atom, p is 0 or 1, Z is a carboxyl group, a sulfo group, a sulfate group, A dispersant comprising a compound represented by a phosphate ester group or a salt thereof.

[Selection figure] None

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 tends to occur, and the bleed-out further causes a decrease in resin physical properties such as water resistance, hardness, and scratch resistance.

  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.

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

However, in General Formula (1), R ¹ represents an alkyl group having 6 to 18 carbon atoms, an alkenyl group, or an aralkyl group, and when R ¹ is an aralkyl group, it was selected from groups represented by the following general formula: 1 or 2 groups are represented, and in these formulas, R ³ represents hydrogen or a methyl group; R ² represents an alkyl group having 1 to 4 carbon atoms; D represents the following general formula D-1 or D- 2 represents a polymerizable unsaturated group represented by any one of R ² , wherein R ⁴ represents a hydrogen atom or a methyl group; m 1 represents a number of 1 to 3, and m 2 represents a number of 0 or 1. M3 represents a number of 1 to 2; AO represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n is an average number of moles of alkylene oxide added, and ranges from 0 to 1,000. X represents at least one carbon atom, at least one hydrogen atom, and Or a linking group having at least one oxygen atom, p is a number from 0 or 1; Z represents a carboxyl group, a sulfo group, sulfuric ester group, phosphoric acid ester group, or a salt thereof.

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

  However, Y of Formula (2) is either selected from a C1-C15 alkylene group, 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.

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

  The dispersant for a non-aqueous dispersion medium of the present invention has a polymerizable carbon-carbon double bond, a dispersion medium affinity site containing an alkylene oxide chain, and a dispersion represented by Z as described in the general formula (1). The dispersion medium affinity part and the dispersoid affinity part are connected by a linking group X.

In the general formula (1), the hydrophobic group R ¹ is one or more selected from linear or branched alkyl groups, alkenyl groups and aralkyl groups having 6 to 18 carbon atoms. Is preferably represented by the following formula.

  Specific examples 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, isododecyl group. 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, isonononadecyl group, eicosyl group, isoeicosyl group, heneicosyl group, isoheneicosyl group, docosyl group, isodocosyl group, tricosyl group, isotrico Alkyl group, tetracosyl group, isotetracosyl group, pentacosyl group, isopentacosyl group, hexacosyl group, isohexacosyl group, heptacosyl group, isoheptacosyl group, etc. alkyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Groups, alkenyl groups such as tetradecenyl group and oleyl group, aralkyl groups such as benzyl group, 4-methylbenzyl group, 1-phenylethyl group, 1- (4-tolyl) ethyl group, cumyl group, 4-methylcumyl group It is done.

The polymerizable unsaturated group D in the general formula (1) is represented by any one of the following chemical formulas D-1 and D-2, and R ^{4 in} the formula represents a hydrogen atom or a methyl group. Represents a 1-propenyl group, a 2-methyl-1-propenyl group or a (meth) allyl group. As D, these 1-propenyl group, 2-methyl-1-propenyl group, or (meth) allyl group may be present either alone or as a mixture. It is preferably a group. Further, m3 representing the number of substituents of D is a number of 1 or more, preferably 1 or 2, and the substitution position of D is preferably the ortho position (the 2nd or 6th position). Moreover, it is preferable that m3 exists in the range of 1 <m3 <1.5 as an average value, and each group represented by Chemical formula D-1 and Chemical formula D-2 is a molar ratio of both (D-1). / (D-2) is preferably greater than 2.

  Regarding the alkylene oxide species suitably selected for the dispersant of the present invention, in the general formula (1), AO represents an oxyalkylene group having 1 to 4 carbon atoms, specifically, the alkylene oxide having 2 carbon atoms is ethylene oxide. . The alkylene oxide having 3 carbon atoms is propylene oxide. The alkylene oxide having 4 carbon atoms is tetrahydrofuran or butylene oxide, and is preferably 1,2-butylene oxide or 2,3-butylene oxide. In the dispersant of the present invention, the oxyalkylene chain (-(AO) n-) is a random polymerization of two or more alkylene oxides even if the alkylene oxide is a homopolymer chain for the purpose of adjusting the dispersion medium affinity of the dispersant. It may be a chain, a block polymer chain, or a combination thereof. Although n which shows the average addition mole number of the alkylene oxide of General formula (1) is the range of 0-1,000, it is preferable to exist in the range of 3-20.

  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 is preferably saturated. It is a group formed from any one group selected from a hydrocarbon group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, an ester group, or a combination of two or more thereof, and has an alicyclic structure and an aromatic ring structure. It may have, and 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, and more preferably an alkylene group having 1 to 8 carbon atoms.

X is preferably a group represented by the following general formula (2).

  However, in General 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.

  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. Here, the phosphate ester may be a monoester, a diester, or a mixture 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.

  Hereinafter, a series of steps of the method for producing an emulsifier for emulsion polymerization of the present invention will be described in detail. As a method of obtaining a phenol derivative having a polymerizable group in the aromatic ring, which is an intermediate of the emulsifier for emulsion polymerization of the present invention, (i) a phenol derivative having a substituent in the aromatic ring and an allyl halide are obtained by a known method. The reaction is followed by Claisen rearrangement in the presence of alkali to obtain a phenol derivative having a polymerizable group on the aromatic ring, or (ii) the phenol and allyl halide are reacted by a known method, and then the presence of alkali There is a method of obtaining a phenol derivative having a polymerizable group in an aromatic ring by carrying out Claisen rearrangement and then introducing a substituent into the aromatic ring under known conditions. Using this as an intermediate, a predetermined amount of alkylene oxide is then added, and then the dispersoid affinity site Z is introduced. The synthesis route in the present invention is not particularly limited, and methods other than those described above can also be used.

  Hereinafter, a series of reaction steps will be described by exemplifying a method for obtaining a target compound using styrenated phenol as a starting material.

In the above general formula (1), the polymerizable unsaturated group represented by D is a 1-propenyl group, a 2-methyl-1-propenyl group or a (meth) allyl group as described above. , (Meth) allyl group is introduced by (meth) allylation reaction of styrenated phenol. On the other hand, those having 1-propenyl group or 2-methyl-1-propenyl group are (meth) allylation reaction of styrenated phenol or styrenated alkylphenol (hereinafter sometimes abbreviated as styrenated (alkyl) phenol). Thereafter, it can be introduced by rearrangement to a 1-propenyl group or a 2-methyl-1-propenyl group in the presence of an alkali. Although the following method is illustrated about introduction | transduction of 1-propenyl group of styrenation (alkyl) phenol, this invention is not limited to this synthesis method. That is, an allyl styrenated (alkyl) phenol is obtained by reacting an allyl halide with a styrenated (alkyl) phenol together with a basic substance such as sodium hydroxide or potassium hydroxide and further heating to about 100 ° C. At this stage, by adjusting the amounts of allyl halide and basic substance, monosubstituted or disubstituted allylic groups can be obtained with respect to styrenated (alkyl) phenol. The reaction will be described in more detail with the following general formula. Allyl styrenated phenol is obtained according to the following reaction formulas (i) and (ii).

In addition, at this time, depending on the reaction conditions such as the charged ratio of styrenated phenol and allyl halide, the amount of catalyst, the reaction temperature and the like, the reactions of the following reaction formulas (iii) and (iv) proceed, and the diallyl form is a secondary To be born.

  Thus, according to the above reaction formulas (i) to (iv), a reaction composition containing a diallyl body and the like in addition to the target (mono) allyl body can be obtained. By heating these reaction compositions in the presence of an alkali hydroxide, the allyl group is rearranged to a 1-propenyl group, and the main target propenyl styrenated phenol is obtained. A composition containing a certain amount of styrenated phenol can be obtained.

  Hereinafter, the following steps and subsequent steps will be described by taking allyl styrenated phenol obtained by the above reaction formula (ii) as an example. A predetermined amount of alkylene oxide is added to the obtained allylstyrenated phenol by a known method, and then the dispersoid affinity site Z is introduced.

  When the dispersoid affinity site Z is a carboxylic acid, a method in which a monohalogenated lower carboxylic acid or a salt thereof is used and reacted with a hydroxyl group at the alkylene oxide terminal in the presence of a base, or an alkylene oxide terminal using an acid anhydride is used. It can manufacture by the method by a ring-opening reaction with the hydroxyl group.

  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, phosphoric acid oxychloride is reacted with a hydroxyl group at the end of alkylene oxide. 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 includes a hydrophobic group type, an alkylene oxide species and its addition form, an added molar amount, and a linking group within the range limited as described above in order to exhibit the effects of the present invention. By optimizing the structure and the like, it is possible to disperse a wider variety of dispersoids than known dispersants, and the industrial utility value in that the dispersoids can be dispersed and stabilized in a wider variety of dispersion media. large.

  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. At that time, as will be described later, in order to stably take out the metal particles from the medium, alkanoic acids, fatty acids, hydroxycarboxylic acids, alicyclic, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol derivatives , Amines, amphiphilic polymers, polymeric surfactants, low molecular surfactants and other protective agents. Others, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, Aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black , Graphite, rock wool, glass wool, glass fiber, carbon fiber, carbon nanofiber, carbon nanotube (single wall nanotube, double wall nanotube, multiwall nanochu B) etc.

  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. As a method for preparing fine particles, a top-down method in which coarse particles are mechanically pulverized and refined, and a bottom in which particles are formed through a cluster state in which several unit particles are generated and aggregated. Although there are two types of up systems, any one prepared by any method can be suitably used. Further, they may be either a wet method or a dry method.

  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 reactive 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.

  The coating composition of the present invention contains a dispersion using a resin monomer or oligomer as a non-aqueous dispersion medium or a dispersion composition of the present invention using a solvent as a non-aqueous dispersion medium and a resin. Is. Although the base material which apply | coats these coating compositions is not specifically limited, For example, glass, a resin film, a glass composite, ceramics, a metal, a steel plate etc. can be used suitably.

  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%”. In Tables 1 to 4, EO represents ethylene oxide, and PO represents propylene oxide. 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 (Invention Product 1)]
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 230 g (1.0 mol) of styrenated phenol (mixture of monostyrenated phenol: distyrenated phenol: tristyrenated phenol = 72: 27: 1), NaOH 40 g (1.0 mol) and 210 g of acetone were charged, and the internal temperature was raised to 40 ° C. while stirring. Next, 91 g (1.2 mol) of allyl chloride was added dropwise over 1 hour. After completion of dropping, the reaction was further continued at 40 ° C. for 2 hours. The reaction product was filtered to remove NaCl as a by-product, and then acetone was removed under reduced pressure to obtain 314 g of allylstyrenated phenyl ether. This allyl phenyl ether was charged into an autoclave, and stirred at 200 ° C. for 5 hours. At this stage, a rearrangement reaction occurred to give 2-allyl styrenated phenol. 290 g of this 2-allyl styrenated phenol was transferred to an autoclave, and 440 g (10 mol) of ethylene oxide was added under the conditions of a pressure of 1.5 kg / cm ³ and a temperature of 130 ° C. using potassium hydroxide as a catalyst. Got. During this reaction, the allyl group quantitatively changed to a 1-propenyl group. Next, 743 g (1 mol) of this intermediate A and 151 g (1.3 mol) of sodium monochloroacetate were placed in a reactor in a toluene solvent and stirred uniformly. Thereafter, 52 g (1.3 mol) of sodium hydroxide was added under the condition that the temperature of the reaction system was 60 ° C., and then the temperature of the reaction system was raised to 80 ° C. and reacted for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. Subsequently, this white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain a compound represented by the following general formula (1) (Product 1 of the present invention).

[Production Example 2 (Product 2 of the present invention)]
A compound represented by the following general formula (1) (Product 2 of the present invention) was obtained according to Production Example 1 except that the amount of ethylene oxide was increased from 440 g (10 mol) to 1320 g (30 mol).

[Production Example 3 (Invention product 3)]
Except for using a monostyrenated phenol instead of a mixture of distyrenated phenol and monostyrenated phenol and increasing the amount of allyl chloride from 91 g (1.2 mol) to 152 g (2.0 mol), Accordingly, a compound represented by the following general formula (1) (Product 3 of the present invention) was obtained.

[Production Example 4 (Invention Product 4)]
A compound represented by the following general formula (1) according to Production Example 1 except that the amount of allyl chloride was reduced from 91 g (1.2 mol) to 76 g (1.0 mol) (Product 4 of the present invention) Got.

[Production Example 5 (Product 5 of the present invention)]
The amount of allyl chloride was reduced from 91 g (1.2 mol) to 84 g (1.1 mol), and cumylphenol was used instead of the mixture of distyrenated phenol and monostyrenated phenol. Thus, a compound represented by the following general formula (1) (Product 5 of the present invention) was obtained.

[Production Example 6 (Product 6 of the present invention)]
A compound represented by the following general formula (1) according to Production Example 1 except that 290 g (5 mol) of propylene oxide and then 220 g (5 mol) of ethylene oxide were reacted instead of ethylene oxide (product of the present invention) 6) was obtained.

[Production Example 7 (Invention Product 7)]
By reacting 743 g (1 mol) of Intermediate A with 100 g (1 mol) of succinic anhydride at 120 ° C. for 2 hours, a compound represented by the following general formula (1) (Product 7 of the present invention) was obtained.

[Production Example 8 (Invention Product 8)]
The compound (present invention product 8) represented by the following general formula (1) was obtained by allowing 743 g (1 mol) of Intermediate A to react with 156 g (1 mol) of suberic acid anhydride at 120 ° C. for 2 hours.

[Production Example 9 (Product 9 of the present invention)]
By reacting 743 g (1 mole) of intermediate A with 198 g (1 mole) of maleic anhydride at 120 ° C. for 2 hours, a compound represented by the following general formula (1) (Product 9 of the present invention) was obtained.

[Production Example 10 (Invention Product 10)]
The compound represented by the following general formula (1) (Product 10 of the present invention) was obtained by reacting 743 g (1 mol) of Intermediate A with 47 g (0.33 mol) of phosphoric anhydride at 80 ° C. for 5 hours. When this composition was confirmed by NMR, the ratio of monoester / diester was 56/44.

[Production Example 11 (Invention Product 11)]
A compound represented by the following general formula (1) (Product 11 of the present invention) was obtained according to Production Example 1 except that noniphenol was used instead of the mixture of distyrenated phenol and monostyrenated phenol.

[Production Example 12 (Invention Product 12)]
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 253 g (1.0 mol) of styrenated methylphenol (monostyrenated methylphenol: distyrenated methylphenol: tristyrenated methylphenol = 70: 20: 10) Then, NaOH 40 g (1.0 mol) and acetone 210 g were charged, and the internal temperature was raised to 40 ° C. while stirring. Next, 91 g (1.2 mol) of allyl chloride was added dropwise over 1 hour. After completion of dropping, the reaction was further continued at 40 ° C. for 2 hours. The reaction product was filtered to remove NaCl as a by-product, and then acetone was removed under reduced pressure to obtain 302 g of 2-allylstyrenated methylphenyl ether. This 2-allyl styrenated methyl phenyl ether was charged into an autoclave and stirred at 200 ° C. for 5 hours. At this stage, a rearrangement reaction occurred to give 2-allylstyrenated methylphenol. 302 g of this 2-allyl styrenated methylphenol was transferred to an autoclave, and 440 g (10 mol) of ethylene oxide was added under the conditions of a pressure of 1.5 kg / cm ³ and a temperature of 130 ° C. using potassium hydroxide as a catalyst. During this reaction, the allyl group quantitatively changed to a 1-propenyl group. Next, the ethylene oxide adduct and 151 g (1.3 mol) of sodium monochloroacetate were placed in a toluene solvent and stirred to be uniform. Thereafter, 52 g (1.3 mol) of sodium hydroxide was added under the condition that the temperature of the reaction system was 60 ° C., and then the temperature of the reaction system was raised to 80 ° C. and reacted for 3 hours. After the reaction, 120 g (1.2 mol) of 98% sulfuric acid was added dropwise to obtain a white suspension. Subsequently, this white suspension was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain a compound represented by the following general formula (1) (Product 12 of the present invention).

[Production Example 13 (Invention Product 13)]
A compound represented by the following general formula (1) (Product 13 of the present invention) was obtained according to Production Example 1 except that the temperature during the addition reaction of ethylene oxide was changed from 130 ° C to 115 ° C. During this reaction, the allyl group changed to a 1-propenyl group with a conversion rate of 80%.

[Production Example 14 (Product 14 of the present invention)]
A compound represented by the following general formula (1) (Product 14 of the present invention) was obtained according to Production Example 1 except that ethylene oxide was not added.

[Production Example 15 (Invention Product 15)]
After reacting 743 g (1 mol) of Intermediate A with 97 g (1 mol) of sulfamic acid at 110 ° C. for 2 hours, purification was performed to obtain a compound represented by the following general formula (1) (Product 15 of the present invention). .

  The comparative products are as follows.

(Comparative product 1)

(Comparative product 2)

(Comparative product 3)

(Comparative product 4) Polyoxyethylene (10) Isodecyl ether acetate Na (20% aqueous solution)
(Comparative product 5) Octylamine (Comparative product 6) Butanoic acid (Comparative product 7) 2-Ethylhexanoic acid (Comparative product 8) Decanoic acid (Comparative product 9) Benzoic acid (Comparative product 10) Polyethylene glycol (600) Acetic acid (Comparative product 11) Polyoxyethylene (6) Isotridecyl ether phosphate ester (Comparative product 12) Dodecylbenzenesulfonic acid (Comparative product 13) Dodecylbenzenesulfonic acid Ca salt (Comparative product 14) Polyvinylpyrrolidone (Daiichi Kogyo) Product name, Pitzkor K-30, manufactured by Pharmaceutical Co., Ltd.
(Comparative product 15) Polyvinyl alcohol part saponified product (manufactured by Kuraray Co., Ltd., trade name Kuraray Poval PVA403)
(Comparative product 16) Styrene maleic acid copolymer (manufactured by ATOFINA, trade name SMA1000)
(Comparative product 17) Polymer pigment dispersant (manufactured by BYK Chemie, trade name DISPERBYK-163)
(Comparative Product 18) Polymeric pigment dispersant (manufactured by BYK Chemie, trade name DISPERBYK-2001)
(Comparative product 19) Polymeric pigment dispersant (Ajinomoto Fine Techno Co., Ltd., trade name Ajisper PB-822)

[Usage example 1]
68.5 parts of the solvent shown in Table 1 as a dispersion medium are 1.5 parts (in terms of solid content) of the dispersant of the present invention shown in Table 1 below and 1.5 parts of the dispersant in the comparative example (in terms of solid content). In addition, 30 parts of magnesium oxide (MgO) as a dispersoid and 100 ml of zirconia beads having a diameter of 0.5 mm were added, and a refinement process was carried out for 12 hours using a paint shaker. 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 Table 1.
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, 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 shown in Table 2 below or a predetermined amount of the dispersant of the comparative example was dissolved in methyl ethyl ketone as a dispersion medium, and 5 parts of zirconium oxide (ZrO ₂ ) as a dispersoid was further added. The product was refined for 2 hours with a bead mill (trade name Ultra Apex Mill UAM-005, using zirconia beads with a diameter of 50 μm, peripheral speed 10 m / sec, manufactured by Kotobuki Kogyo Co., Ltd.). As a result, the obtained treatment liquid is transferred to a transparent container, and the dispersibility of the treatment liquid in the container immediately after the miniaturization treatment and the treatment liquid in the container after 24 hours (dispersing agent is dispersed at 0.25 parts). The dispersion stability of the processing solution having a quality of 5 parts) was evaluated based on the same criteria as above by observing the processing solution visually. In addition, for a part of the processing liquid (processing liquid having a dispersant of 0.25 part and a dispersoid of 5 parts), a particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac UPA MODEL 9230) is used, The particle diameter of zirconium oxide was measured. In addition, the compounding quantity of the methyl ethyl ketone with respect to a dispersing agent is 94.5 parts, 94.75 parts, 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 2 shows the visual evaluation of the dispersibility and dispersion stability and the particle diameter measurement results of zirconium oxide.

  Further, the dispersant of the present invention having the composition shown in Table 2 below or the dispersant of the comparative example, and the above-mentioned zirconium oxide dispersion comprising zirconium oxide and methyl ethyl ketone (dispersant 0.25 part, zirconium oxide 5.00 parts) A dispersion obtained by mixing 70 parts of methyl ethyl ketone (94.75 parts) with 70 parts of methyl ethyl ketone solution in which 25 parts of acrylic resin (trade 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 by visually observing the treatment liquid according to the above criteria.

Moreover, after apply | coating the said dispersion liquid (after 2 hours refinement | miniaturization process) on a 10-mm-thick clean glass plate, it dried for 1 hour with a 120 degreeC dryer, 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.
◎: 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 2, it can be seen that those using the dispersant of the present invention are excellent in dispersibility and dispersion stability. Further, as shown in the table, the particle size of the dispersoid in the dispersion using the dispersant of the present invention is much smaller than the particle size of the dispersoid in the dispersion of the comparative example. The effect of the inventive dispersant is obvious. 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]
<Preparation of Zirconium Oxide Acrylate Monomer Dispersion>
A mixture of 100 parts of zirconium oxide powder (Nippon Denko Co., Ltd., trade name PCS, having a primary particle diameter of 30 nm) and 400 parts of methyl ethyl ketone is mixed with the dispersant or comparative example of the present invention shown in Table 3 below. After adding 10 parts of dispersant, refinement treatment was carried out for 4 hours in a bead mill (manufactured by Kotobuki Industries Co., Ltd., trade name Ultra Apex Mill UAM-005, using zirconia beads with a diameter of 50 μm, peripheral speed 10 m / sec). Thus, a zirconium oxide dispersion was produced. 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. The obtained dispersion was evaluated for appearance transparency, viscosity, and refractive index. The evaluation results are shown in Table 3.

<Dispersion evaluation>
a. Transparency of appearance Place the acrylate monomer dispersion of zirconium oxide in a transparent glass container, place a paper with alphabet printed at 12 points under the glass container, and check the transparency of the dispersion over the dispersion. The following criteria were used to evaluate whether the alphabet could be distinguished.
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.).

<Production of photopolymerized cured film of zirconium oxide>
One part of a photopolymerization initiator (trade name: IRGACURE 184, manufactured by BASF) was added to and mixed with 100 parts of the acrylate monomer dispersion of zirconium oxide to obtain a zirconium oxide paste. 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 obtained dispersion was evaluated for transparency, refractive index, pencil hardness, and water resistance. The evaluation results are shown in Table 3.

<Evaluation of coating film after photopolymerization>
a. Transparency of appearance Place the paper with the alphabet printed at 12 points under the polyethylene terephthalate film, and the transparency of the photopolymerized cured film obtained on the polyethylene terephthalate film can be distinguished through the cured film In terms of whether or not it was evaluated according to the following criteria.
◎: 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 measured by 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 determined as a. Evaluation was made based on the same criteria as the appearance transparency.

  As shown in Table 3, the dispersion of the present invention has excellent dispersibility (transparency of appearance) and high refractive index, and the photopolymerized cured film of the dispersion of the present invention has excellent transparency and high refractive index. It can be seen that it has good pencil hardness and high water resistance.

[Dispersion test 4]
<Preparation of Zirconium Oxide Acrylate Monomer Dispersion>
100 parts of a commercially available zirconium oxide dispersion (manufactured by Sakai Chemical Co., Ltd., trade name SZR-M, dispersion containing a primary particle diameter of 3 nm and 30% by weight of methanol) is dispersed in the present invention shown in Table 4 below. 3 parts of a dispersant or comparative example, 15 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 15 parts of New Frontier PET-3), the solvent methanol was removed under reduced pressure using a rotary evaporator to obtain an acrylate monomer dispersion (2) of zirconium oxide. The obtained dispersion was evaluated for appearance transparency, viscosity, and refractive index. The obtained dispersion was evaluated for appearance transparency, viscosity, and refractive index. The evaluation method is the same as in Test Example 3 above. The evaluation results are shown in Table 4.

  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. It can be seen that it has good pencil hardness and high water resistance.

[Dispersion test 5]
<Preparation of Zirconium Oxide Acrylate Monomer Dispersion>
The dispersion of the present invention shown in Table 5 below is added to 100 parts of a commercially available zirconium oxide dispersion (manufactured by Sakai Chemical Co., Ltd., trade name SZR-M, dispersion containing a primary particle size of 3 nm and 30% by weight of methanol). 3 parts of the dispersant or the dispersant of Comparative Example and 28.5 parts of o-phenylphenoxyethyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd., trade name KAYARAD OPP-1) were added and mixed, and then the solvent methanol was added. Removal under reduced pressure using a rotary evaporator gave an acrylate monomer dispersion (2) of zirconium oxide. The obtained dispersion was evaluated for appearance transparency, viscosity, and refractive index. The evaluation method is the same as in Test Example 3 above. The evaluation results are shown in Table 5.

  As shown in Table 5, the dispersion of the present invention has excellent dispersibility (transparency of appearance) and a high refractive index, and the photopolymerized cured film of the dispersion of the present invention has excellent transparency and a high refractive index. It can be seen that it has good pencil hardness 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 which consists of a compound shown by following General formula (1).

However, in General Formula (1), R ¹ represents an alkyl group having 6 to 18 carbon atoms, an alkenyl group, or an aralkyl group, and when R ¹ is an aralkyl group, it was selected from groups represented by the following general formula: Represents one or two groups, in which R ³ represents hydrogen or a methyl group;
R ² represents an alkyl group having 1 to 4 carbon atoms;
D represents a polymerizable unsaturated group represented by any of the following general formulas D-1 or D-2, and in these formulas, R ⁴ represents a hydrogen atom or a methyl group;
m1 represents a number of 1 to 3, m2 represents a number of 0 or 1, m3 represents a number of 1 to 2;
AO represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n represents the average number of added moles of alkylene oxide, and represents a number in the range of 0 to 1,000;
X is a linking group having at least one carbon atom and at least one hydrogen atom and / or at least one oxygen atom, and p represents a number of 0 or 1;
Z represents a carboxyl group, a sulfo group, a sulfate ester group, a phosphate ester group, or a salt thereof.

  The dispersant for non-aqueous dispersion medium according to claim 1, wherein X in the general formula (1) is an alkylene group having 1 to 15 carbon atoms. The dispersant for non-aqueous dispersion medium according to claim 1, wherein X in the general formula (1) is a group represented by the following formula (2).

However, Y of Formula (2) is either selected from a C1-C15 alkylene group, 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 6, 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.