JP2012117019A - Coating composition containing chitin nanofiber or chitosan nanofiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new coating composition containing chitin nanofibers or chitosan nanofibers.SOLUTION: There is provided an organic solvent-based coating composition comprising a resin, an organic solvent and one or more kinds of nanofibers selected from chitin nanofibers and chitosan nanofibers.

Description

  The present invention relates to a coating composition containing chitin nanofibers or chitosan nanofibers.

  Various fiber-based reinforcing materials (reinforced fillers) are widely used as additives for coating materials such as paints and adhesives, resin film / sheet materials, and plastic molded products. Glass fibers or carbon fibers occupy the mainstream, but the diameter is on the order of microns. On the other hand, carbon nanotubes with a diameter of nanometer order have recently appeared and are attracting attention as next-generation functional fillers. In addition, application development of naturally-derived cellulose nanofibers is also active. However, an inexpensive method for producing carbon nanotubes has not yet been established, and confirmation of safety is an issue for the future. In the case of cellulose nanofibers, an aqueous dispersion solution is possible, but the dispersion in an organic solvent is not yet studied.

  In general, nanofibers are ultra-fine fibers with a diameter (width) of several tens to several hundreds of nanometers, and they have features such as a significantly larger surface area than conventional fibers, and thus exhibit new and special functions. It is attracting attention and is being used. Polymer materials such as nylon and polyester are mainly used as raw materials for nanofibers. Recently, active research has been conducted on obtaining nanofibers from biological materials and using them for environmental considerations. Has been made.

  Chitin and chitosan are also derived from living organisms, and research into nanofibers is being conducted. For example, the present inventors have made chitin nano-materials from chitin-containing organism-derived materials that are thin, long, homogeneous, crystallized, physical properties, easy to handle, and excellent in accumulated amount, with almost no damage. It has succeeded in developing the manufacturing method for obtaining a fiber (patent document 1).

  In Patent Document 1, by incorporating chitin nanofibers or chitosan nanofibers in the coating composition, a uniform coating film is formed more than the conventional one, and a coating composition having excellent adhesiveness is successfully produced. Has been reported. However, Patent Document 1 reports only a coating composition containing chitin nanofibers or chitosan nanofibers and a water-soluble resin or emulsion, and a method for producing the same, and the coating composition contains water of chitin nanofibers. It is obtained by a method comprising a step of blending a suspension with a water-soluble resin or emulsion.

  In order to expand the application range of chitin nanofibers or chitosan nanofibers as composites, it is very important to study dispersibility in various organic solvents, but no such studies have been made so far. As disclosed in Patent Document 1, chitin nanofibers or chitosan nanofibers were obtained as an aqueous dispersion in the production process, and dispersibility in other organic solvents was unknown.

  Since the chitin nanofiber or chitosan nanofiber surface is hydrophilic, it was expected to have low dispersibility in a hydrophobic organic solvent. In fact, in Patent Document 1, only a water-based acrylic resin emulsion has been obtained for the preparation of a coating material using chitin nanofibers or chitosan nanofibers as reinforcing fibers (fillers).

WO2010 / 073758 pamphlet

  An object of the present invention is to provide a novel coating composition containing chitin nanofibers or chitosan nanofibers.

  As described above, the chitin nanofiber or chitosan nanofiber surface was hydrophilic and expected to have low dispersibility in a hydrophobic organic solvent, so the chitin nanofiber or chitosan nanofiber was used as a reinforcing fiber (filler). Regarding the preparation of the paint, only a water-based acrylic resin emulsion has been obtained, and the combination with other various organic solvent-based paints has not been studied.

  Contrary to this expectation, the present inventors have found that hydrophilic chitin nanofibers or chitosan nanofibers can be well dispersed in an organic solvent regardless of the polarity of the organic solvent.

  That is, the present invention provides an organic solvent-based coating composition containing a resin, an organic solvent, and one or more selected from chitin nanofibers and chitosan nanofibers.

  In the organic solvent-based coating composition of the present invention, preferably, the chitin nanofiber is subjected to at least one deproteinization step and at least one decalcification step by using a chitin-containing material derived from an acidic reagent. It is obtained by a manufacturing method characterized by being subjected to a treatment step and then being subjected to a defibrating step. Alternatively, in the organic solvent-based coating composition of the present invention, preferably, chitosan nanofibers are prepared by using a chitin-containing material derived from at least one deproteinization step, at least one decalcification step, and at least one decalcification step. It is obtained by a production method characterized by being subjected to a deacetylation step and then to a defibrating step. Here, preferably, the chitin-containing organism is a crustacean.

  In the organic solvent-based coating composition of the present invention, the organic solvent is preferably a polar solvent other than water and a nonpolar organic solvent, and preferably the resin is rosin, polylactic acid, polyglutamic acid, polycaprolactone, polyglycolic acid Natural resins such as casein and shellac, polysaccharides such as cellulose, chondroitin sulfate, hyaluronic acid, chitin and chitosan, and nitrocellulose, nylon, rubber resins, phenol resins, melamine resins, acrylic resins, epoxy resins, urethane resins , Polyester resin, polyamide resin, vinyl resin, polyimide resin, ketone resin, silicon-containing polymer, fluorine-containing polymer and the like.

  The organic solvent-based coating composition of the present invention more preferably contains a pigment.

The present invention also provides a step of providing one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers, and one or more organic solvent dispersions selected from the chitin nanofibers and chitosan nanofibers. Blending resin,
The manufacturing method of the organic-solvent type coating composition containing this is provided.

  In the method for producing an organic solvent-based coating composition of the present invention, preferably, the chitin nanofibers are subjected to at least one deproteinization step and at least one decalcification step by subjecting the chitin-containing organism-derived material to acidity. It is obtained by a manufacturing method characterized by being subjected to a step of treating with a reagent and then being subjected to a defibrating step. Alternatively, in the organic solvent-based coating composition of the present invention, preferably, chitosan nanofibers are prepared by using a chitin-containing material derived from at least one deproteinization step, at least one decalcification step, and at least one decalcification step. It is obtained by a production method characterized by being subjected to a deacetylation step and then to a defibrating step. Here, preferably, the chitin-containing organism is a crustacean.

  In the method for producing an organic solvent-based coating composition of the present invention, preferably, the organic solvent is a polar solvent other than water and a nonpolar organic solvent, and preferably the resin is rosin, polylactic acid, polyglutamic acid, polycaprolactone, Natural resins such as polyglycolic acid, casein and shellac, polysaccharides such as cellulose, chondroitin sulfate, hyaluronic acid, chitin and chitosan, and nitrocellulose, nylon, rubber resins, phenolic resins, melamine resins, acrylic resins, epoxy resins , Urethane resin, polyester resin, polyamide resin, vinyl resin, polyimide resin, ketone resin, silicon-containing polymer, fluorine-containing polymer and the like.

  The method for producing an organic solvent-based coating composition of the present invention preferably further includes a step of blending pigments.

  The present invention further includes a coating material, a coating material, an adhesive, an adhesive material, a sealing material, a resin-based injection material, a potting material, a filling, containing one or more selected from chitin nanofibers and chitosan nanofibers dispersed in an organic solvent. An additive composition for adding to a material selected from the group consisting of an agent, putty, plaster material, water glass, textile product, nonwoven fabric, resin film / sheet material, rubber product, cosmetics, soap, and plastic molded article provide.

  According to the present invention, since chitin nanofibers or chitosan nanofibers have been successfully dispersed in various organic solvents, addition to organic solvent-based coating agents has become easy. Among these, hydrophobic organic solvent-substituted chitin or chitosan nanofiber dispersions can be dispersed in general-purpose paint systems such as melamine alkyd resins, thermosetting acrylic resins, epoxy resins, urethane resins, polyester resins, silicone resins, and fluororesins. The filler addition effect is expected to contribute to improvement in coating film performance, particularly strength.

  Established organic solvent dispersion of chitin nanofiber or chitosan nanofiber established by the present invention and functional enhancement with natural environmental compatibility and biodegradability by successful mixing and dispersion in general-purpose coating materials It is epoch-making that the filler became effective effectively as a composite.

  Chitin nanofibers have cationic charge properties, are excellent in metal adsorptivity, pigment adsorptivity, antibacterial properties, solvent resistance, film-forming properties, and are highly reactive. Therefore, the coating composition of the present invention is considered to have a new functionality that has not existed before. Furthermore, the coating composition of the present invention forms a uniform coating film and has excellent adhesion to various objects to be coated.

FIG. 1 shows the result of observation of chitin nanofibers dispersed in isopropyl alcohol, ethyl acetate and methylcyclohexane by a scanning electron microscope.

  In the present specification and claims, the “organic solvent-based coating composition” means “resin”, “organic solvent” and “one or more selected from chitin nanofibers and chitosan nanofibers” defined below. It refers to a coating composition that is essential and may optionally contain pigments and other additives. Among these components, the organic solvent is a non-coating component that volatilizes during film formation, and one or more selected from resins, chitin nanofibers and chitosan nanofibers, pigments and other additives are dried. It is a film-forming component that remains as a coating film afterwards. The “organic solvent-based coating composition” of the present invention is not particularly limited as long as it contains at least one selected from a resin, an organic solvent, and chitin nanofibers and chitosan nanofibers. There is no particular limitation. The “organic solvent-based coating composition” may be used as it is as a coating, or may be used as a coating after being diluted with thinner (also referred to as a diluting solution or a thinning solution).

  In the present specification and claims, “resin” is a main component of a coating film forming component constituting the organic solvent-based coating composition, and refers to a main film-forming component. As the resin, those generally used for paints may be appropriately used depending on the coating film performance required by the organic solvent-based paint composition such as weather resistance, flexibility, and water resistance, and are not particularly limited.

  In the present specification and claims, the “organic solvent” is a volatile non-coating component that constitutes the organic solvent-based coating composition and the thinner for dilution, and since it evaporates itself, Must not. What is necessary is just to use suitably what is generally used for coating materials, and the organic solvent is not particularly limited, and may be one kind of organic solvent or a mixture of two or more kinds of organic solvents. In the present invention, when the organic solvent is a nonpolar organic solvent, the nonpolar organic solvent is present in 99% by weight or more in the volatile liquid component constituting the organic solvent-based coating composition and the dilution thinner. That is, a water content of less than 1% by weight. On the other hand, when the organic solvent is a polar organic solvent other than water, the polar organic solvent is present in 96% by weight or more in the volatile liquid component constituting the organic solvent-based coating composition and the dilution thinner. That is, the water content is less than 4% by weight.

  In the present specification and claims, “one or more selected from chitin nanofibers and chitosan nanofibers” may be either chitin nanofibers or chitosan nanofibers, or both. Chitin nanofibers are nanofibers having a width (or diameter) of about 2 nm to about 30 nm isolated and extracted from a chitin-containing bio-derived material, and the degree of substitution of the N-acetyl group is 95 to 99%. Here, “the width (or diameter) of the chitin nanofiber is about 2 nm to about 20 nm” means that the entire fiber having a width (or diameter) of about 2 nm to about 20 nm or less when observed with an electron microscope. The state which occupies about 50% or more. The same applies to the width (or diameter) of chitosan nanofibers. Chitosan nanofibers are nanofibers having a width (or diameter) of about 2 nm to about 30 nm, similar to chitin nanofibers, and mainly N-acetyl groups on the surface of the chitin nanofibers are deacetylated. (Chitin nanofibers having a chitosan surface), and the substitution degree of the N-acetyl group of the whole nanofibers is 85 to 95%.

  In the organic solvent-based coating composition of the present invention, the weight ratio of the resin, the organic solvent, one or more selected from chitin nanofibers and chitosan nanofibers, and optionally contained pigments and other additives is Although not particularly limited, preferably, the organic solvent-based coating composition of the present invention has a weight of at least one selected from chitin nanofibers and chitosan nanofibers of 0.05 to 35 wt% with respect to the solid content remaining after film formation. %, More preferably 0.1 to 15% by weight, and particularly preferably 1.0 to 8.0% by weight.

  The resin in the organic solvent-based coating composition of the present invention is not particularly limited. For example, natural resins such as rosin, polylactic acid, polyglutamic acid, polycaprolactone, polyglycolic acid, casein, shellac, cellulose, chondroitin sulfate, hyaluronic acid , Polysaccharides such as chitin and chitosan, and nitrocellulose, nylon, rubber resin, phenol resin, melamine resin, acrylic resin, epoxy resin, urethane resin, polyester resin, polyamide resin, vinyl resin, polyimide resin, ketone resin, Synthetic resins such as silicon-containing polymers and fluorine-containing polymers are preferred.

The organic solvent in the organic solvent-based coating composition of the present invention is not particularly limited. For example, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethyl Butane, n-heptane, n-octane, 2,2,3-trimethylpentane, isooctane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene , Dipentylbenzene, dodecylbenzene, biphenyl, styrene, Clopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, cyclohexene, α-pinene, dipentene, decalin, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene, solvent naphtha, Camphor oil, turpentine oil, pine oil, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tet Lachlorethylene, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1,2,3-trichloropropane, allyl chloride, butyl chloride, sec-butyl chloride, isobutyl chloride, tert-butyl chloride, 1-chloropentane, Chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, 1-chloronaphthalene, methyl bromide, bromoform, ethyl bromide, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, propyl bromide, odor Isopropyl bromide, dibromobenzene, 1-bromonaphthalene, fluorobenzene, benzotrifluoride, hexafluorobenzene, chlorobromoethane, trichlorofluoromethane, 1-bromo-2-chloroethane, 1,1,2-trichloro-1 , 2,2-Trifluoro Ethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, methanol, ethanol, 1-propanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert- Butyl alcohol, n-amyl alcohol, sec-amyl alcohol, 3-pentanol, 2-methyl 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1 -Hexanol, 1-nonano 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, abiethinol, fusel oil, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-methyl -1,3-hexanediol, glycerin, -Ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol, phenol, cresol, xylenol, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether , Butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrol, propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methyl Furan, tetrahydrofuran, tetrahydropyran, dinole, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxy Ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, glycerin ether, crown ether, methylal, acetal, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, Diisobutyl ketone, acetonyl acetone, mesityl oxide, holon, isophorone, cyclohexanone, methylcyclohexanone, acetophenone, camphor, methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate , Isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoacetate Pentyl, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, butyric acid Methyl, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl 2-hydroxy-2-methylpropionate, ethyl isovalerate, isopentyl isovalerate, butyl stearate, pentyl stearate, methyl benzoate, benzoic acid Ethyl, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, ethyl abietic acid, benzyl abietic acid, bis (2-ethylhexyl) adipate, γ-butyrolactone, Diethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, dimethyl phthalate , Diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, dioctyl phthalate, ethylene glycol monoacetate, ethylene diacetate, ethylene glycol ester, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, carbonic acid Dimethyl, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, borate ester, phosphate ester, nitromethane, nitroethane, 1-nitropropane, 2-nitro Propane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-trinitryl, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, Isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, dibutylamine, diisobutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, cyclohexylamine, dicyclo Hexylamine, pyrrole, piperidine, pyridine, picoline, 2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, formamide, N-methylformamide, N, N- Dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, dimethylacrylamide, N, N, N ′, N′-tetramethylurea, 2-pyrrolidone , N-methylpyrrolidone, ε-caprolactam, carbamic acid ester, carbon disulfide, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, furfuryl alcohol , Tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, poly (oxyethylene-oxypropylene) derivative, diacetone alcohol, 2-chloroethanol 1-chloro-2-propanol, 3-chloro-1,2-propanediol, 1,3-dichloro-2-propanol, 2,2,2-trifluoroethanol, 3-hydroxypropionitrile, acetone cyanohydrin, 2-aminoethanol, 2- (dimethylamino) ethanol, 2- (diethylamine) ethanol, diethanolamine, N-butyldiethanolamine, triethanolamine Triisopropanolamine, isopropanolamine, 2,2′-thiodiethanol, furfural, bis (2-chloroethyl) ether, epichlorohydrin, o-nitroanisole, morpholine, N-ethylmorpholine, N-phenylmorpholine, Methyl lactate, ethyl lactate, butyl lactate, pentyl lactate, methyl salicylate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monoethyl ether acetate Tartar, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, methyl acetoacetate, acetate Examples include ethyl acetate, methyl cyanoacetate, ethyl cyanoacetate, o-chloroaniline, hexamethylphosphate triamide. Among these, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2- Dimethylbutane, 2,3-dimethylbutane, n-heptane, n-octane, 2,2,3-trimethylpentane, isooctane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene , Cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylben Emissions, dodecylbenzene, biphenyl, styrene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p- menthane, bicyclohexyl, cyclohexene, alpha-pinene,
Dipentene, decalin, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene, solvent naphtha, camphor oil, turpentine oil, methanol, ethanol, 1-propanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, 3-pentanol, 2-methyl 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2- Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1 Octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol , Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, abietinol, fusel oil, 1,2-ethanediol, 1,2-propanediol 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4 -Diol, 2-methyl-2 4-pentanediol, 2-methyl-1,3-hexanediol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol, phenol, cresol, xylenol , Diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrol, Propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, dineo 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, glycerin ether, methylal, acetal, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone, mesityl oxide, phorone, isophorone, cyclohexanone, methyl cyclohexanone, acetophenone, methyl formate, ethyl formate, propyl formate Butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate Chill, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, propionic acid Ethyl, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl 2-hydroxy-2-methylpropionate, ethyl isovalerate, isopentyl isovalerate, butyl stearate Pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, ethyl abietate, benzyl abiate, bis (2) adipate Ethylhexyl), γ-butyrolactone, diethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, bis sebacate ( 2-ethylhexyl), dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, dioctyl phthalate, ethylene glycol monoacetate, ethylene glycol ester, diethylene glycol monoacetate, monoacetin, diacetin, triacetin , Monobutyrin, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitroethane, 1-nitropropane, 2-nitropro Bread, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-trinitryl, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, allylamine, aniline , Pyrrole, piperidine, pyridine, picoline, quinoline, isoquinoline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N- Methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, dimethylacrylamide, N, N, N ′, N′-teto Methylurea, 2-pyrrolidone, N-methylpyrrolidone, ε-caprolactam, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, ethylene glycol isopropyl ether, Ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, Polypropylene glycol, diacetone alcohol, diethanolamine, triethanolamine, furfural, morpholine, N-ethylmorpholine, N-phenylmorpholine, methyl lactate, ethyl lactate, butyl lactate, pentyl lactate, methyl salicylate, ethylene glycol monomethyl ether acetate Tartar, ethylene glycol monoethyl ether acetate, Polar solvents other than water, such as lenglycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, methyl acetoacetate and ethyl acetoacetate Nonpolar solvents are preferred, n-hexane, n-heptane, n-octane, isooctane, toluene, xylene, styrene, methylcyclohexane, ethylcyclohexane, α-pinene, turpentine oil, methanol, ethanol, n-propyl alcohol, isopropyl alcohol , N-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, tetrahydrofuran, aceto , Methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, dimethyl Acrylamide, N-methylpyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diacetone alcohol, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol mono Chill ether acetate is particularly preferred. As the organic solvent in the organic solvent-based coating composition of the present invention, the above organic solvents may be used alone or in combination of one or more.

  A preferred method for producing chitin nanofibers and chitosan nanofibers used in the organic solvent-based coating composition of the present invention is described in WO2010 / 073758. Specifically, chitin nanofibers and chitosan nanofibers used in the present invention are preferably produced by the following production method.

The chitin nanofiber used in the organic solvent-based coating composition of the present invention is preferably
A bio-derived material derived from chitin
Subjected to at least one deproteinization step and at least one decalcification step;
Subject to a step of treating with an acidic reagent,
It is obtained by a manufacturing method characterized by being subjected to a defibrating process.

On the other hand, the chitosan nanofiber used in the organic solvent-based coating composition of the present invention is preferably
A bio-derived material derived from chitin
Subject to at least one deproteinization step and at least one decalcification step, and at least one deacetylation step;
It is obtained by a manufacturing method characterized by being subjected to a defibrating process.

  The above chitin or chitosan nanofiber can be obtained from a biotin-derived material. Examples of chitin-containing organisms include, but are not limited to, crustaceans, insects, and krill. Examples of the material derived from chitin-containing organisms that are raw materials for chitin or chitosan nanofibers include insect hulls, krill shells, crustacean shells, hulls, and the like. As materials derived from chitin-containing organisms, organisms with a high chitin content, for example, shells and hulls of crustaceans such as shrimps and crabs are preferred. Shrimp, crab shells, shells, etc. occupy most of the parts discarded after consumption. In addition, since shrimp and crabs are consumed in large quantities, shrimp and crab skins can be obtained in large quantities, which is convenient.

  The chitin or chitosan nanofibers obtained by the above-described production method described in the pamphlet of WO2010 / 073758 are thin and homogeneous, are long, molecules are elongated, and have high strength. An extended chain crystal is a fibrous crystal that is regularly arranged in a state in which a rigid polymer is fully stretched to form a bundle, and since it has few defects, it can exhibit strong physical properties. . In particular, crustacean chitin such as shrimp and crab is highly crystalline alpha chitin, so chitin or chitosan nanofibers obtained from crustacean shell such as shrimp and crab have the above excellent characteristics. It is remarkable.

  Hereinafter, although the manufacturing method described in the pamphlet of WO2010 / 073758 will be described in detail, the chitin or chitosan nanofiber used in the present invention is not limited to that obtained by the manufacturing method.

Manufacturing method of chitin nanofiber First, a biotin-derived material derived from chitin,
It is subjected to at least one deproteinization step and at least one decalcification step.

  Deproteinization removes the protein that forms the matrix surrounding the chitin nanofibers. Examples of the deproteinization treatment include an alkali treatment method and a proteolytic enzyme method such as protease, and the alkali treatment method is preferred. In deproteinization by alkali treatment, an aqueous solution of an alkali such as potassium hydroxide, sodium hydroxide, or lithium hydroxide is preferably used, and the concentration depends on the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc. Depending on the case, it is usually selected from about 2 to about 10% (w / v), preferably about 3 to about 7% (w / v), for example about 5% (w / v). The temperature of deproteinization by the alkali treatment can be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but is usually about 80 ° C. or higher, preferably about 90 ° C. or higher, Preferably, it is carried out while refluxing an alkaline aqueous solution. The treatment time can also be appropriately selected depending on the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but it is usually several hours to about 3 days, preferably several hours to about 2 days. Good.

  The deashing removes the ash that surrounds the chitin nanofibers, mainly calcium carbonate. The decalcification treatment includes an acid treatment method and an ethylenediamine tetraacetic acid treatment method, and an acid treatment method is preferred. In deashing by acid treatment, an aqueous solution of hydrochloric acid is preferably used, and the concentration thereof can be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc. It is 4 to about 12% (w / v), preferably about 5 to about 10% (w / v). The temperature of deproteinization by acid treatment can be appropriately selected according to the amount of chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but is usually about 10 to about 50 ° C., preferably about 20 to about It may be 30 ° C., for example room temperature. The decalcification time by the acid treatment can be appropriately selected according to the amount of the material derived from the chitin-containing organism, the kind of the chitin-containing organism, the site, etc., but usually several hours to several days, preferably about 1 to about 3 days. For example, you may carry out for 2 days.

Then, it attaches | subjects to the process processed with an acidic reagent.
Dispersibility of chitin nanofibers can be improved by treating the decalcified chitin-containing material with an acidic reagent. The treatment method with an acidic reagent is not particularly limited as long as it is a method for allowing the acidic reagent to penetrate into the material. The treatment with an acidic reagent can be typically performed by immersing the decalcified chitin-containing material in an aqueous acid solution. In this step, not only the improvement of dispersibility but also the variation in the width (or diameter) of the chitin nanofibers can be suppressed. The acid that can be used in this step may be any acid and is not particularly limited, but a weak acid is preferred. Examples of the weak acid include, but are not limited to, acetic acid, malic acid, formic acid, chloroacetic acid, fluoroacetic acid, propionic acid, butyric acid, lactic acid, citric acid, malonic acid, and ascorbic acid. The preferred weak acid used in this step is acetic acid. In this step, the pH of the aqueous weak acid solution is usually adjusted to about 2 to about 5, preferably about 2.5 to about 4.5, such as about 3 to about 4. The temperature of this step can be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but is usually about 10 to about 50 ° C., preferably about 20 to about 30 ° C., For example, it may be room temperature. The treatment time of this step can also be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but is usually 1 hour to about 1 day, preferably about 3 to about 12 hours. For example, it may be overnight. This acid treatment step may be performed at any stage before the defibration step, but preferably after the deproteinization and decalcification, the purification of chitin nanofibers proceeds to some extent. It may be performed immediately before the defibrating step.

  Then, it is subjected to a defibrating process. The outer skin (mostly chitin nanofibers) obtained in the above process is defibrated to obtain the target chitin nanofiber. Since chitin nanofibers are hydrogen-bonded and strongly agglomerate when dried, it is preferable to perform each step of the method for producing chitin nanofibers without always drying the material. For the defibrating treatment, an apparatus such as a stone mill grinder, a high-pressure homogenizer, and a freeze grinding apparatus can be used, and the grinder treatment is preferably performed using a stone mill grinder. If a device capable of applying a stronger load, such as a stone mill, is used, it is possible to quickly disentangle even shell-derived alpha chitin such as crabs and shrimps. Thereafter, the obtained chitin nanofibers may be dispersed in an aqueous medium such as water.

Method for Producing Chitosan Nanofiber The chitin-containing organism-derived material is subjected to at least one deproteinization step, at least one decalcification step, and at least one deacetylation step, and then to a defibration step. The deproteinization step, the deashing step, and the defibration step are the same as described above with respect to the production of chitin nanofibers. In addition, it is also possible to perform a deproteinization process and a deacetylation process simultaneously. Furthermore, it is also possible to produce chitosan nanofibers by subjecting a commercially available chitin powder that has already undergone a deproteinization step and a deashing step to a deacetylation step. Although several methods are known as the deacetylation method, an alkali treatment method is preferable. In the deacetylation by alkali treatment, an aqueous solution of an alkali such as potassium hydroxide, sodium hydroxide or lithium hydroxide is preferably used, and its concentration is usually about 20 to about 50% (w / v), preferably about 30 to about 40% (w / v), for example about 40% (w / v). The temperature of deacetylation by alkali treatment can be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but is usually about 80 ° C. or higher, preferably about 90 ° C. or higher, More preferably, it is carried out while refluxing an alkaline aqueous solution. The treatment time can also be appropriately selected according to the amount of the chitin-containing organism-derived material, the type of chitin-containing organism, the site, etc., but it is usually 30 minutes to about 3 days, preferably 30 minutes to overnight. . In addition, since chitosan nanofibers are hydrogen-bonded and strongly aggregated when dried, it is preferable to perform each step of the method for producing chitosan nanofibers without always drying the material.

  In the above method for producing chitin or chitosan nanofiber, a decoloring step may be performed if necessary or desired. The decolorization step may be performed at any stage of the above method, but is preferably performed after the deproteinization and decalcification treatments are completed. Decolorization may be carried out by any method, but it is preferable to use a chlorine bleaching agent, an oxygen bleaching agent, or a reducing bleaching agent. For example, about 1 to about 2% of hypochlorous acid in a buffer solution such as an acetate buffer solution. It may be carried out with sodium chlorate at about 70 to about 90 ° C. for several hours.

  Furthermore, a pulverization step may be performed in order to efficiently perform the deproteinization step, the deashing step, the decolorization step, the defibration step, and the treatment with the acidic reagent. The pulverization step may be performed at any stage of the above method, but is preferably performed immediately before the defibration step. The pulverization step may be performed by any method, but a method such as a homogenizer treatment or a mixer treatment is preferable, and may be performed by, for example, a household food processor.

  The steps such as the deproteinization step, the deashing step, the decolorization step, and the pulverization step may be repeated, repeated a plurality of times, or alternately. In addition, the order of the steps is not limited.

  The organic solvent-based coating composition of the present invention may contain a pigment such as a colored pigment, an extender pigment, or an antirust or design functional pigment. Examples of pigments to be added include zinc white, lead white, lithopone, titanium dioxide, precipitated barium sulfate, calcium carbonate, slaked lime, talc, barite powder, molybdenum white, resurge, molybdenum red, silver vermilion, red lead, iron oxide red , Titanium yellow, yellow lead, zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide), cobalt oxide, iron black, carbon black, titanium black, mica-like oxidation Inorganic pigments such as iron, titanium dioxide-coated mica, lead suboxide, zinc sulfide, aluminum powder, soluble azo pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lake, isoindolinone, quinacridone, dioxazine violet, perinone -Organic pigments such as perylene.

  The organic solvent-based coating composition of the present invention may contain one or more selected from resins, organic solvents, chitin nanofibers and chitosan nanofibers, and optionally other additives in addition to the pigment. Other additives include plasticizers, dispersants, anti-settling agents, emulsifiers, thickeners, antifoaming agents, antibacterial agents, fungicides, antiseptics, anti-skinning agents, anti-sagging agents, and leveling agents. , Matting agents, desiccants, adsorbents and the like.

The present invention further provides a method for producing the organic solvent-based coating composition of the present invention comprising the following steps:
Providing one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers, and blending a resin with one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers .

  First, one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers are provided. The method for providing such a dispersion is not particularly limited. According to the production method described in the pamphlet of WO2010 / 073758, chitin nanofibers and chitosan nanofibers are usually suspended in an aqueous medium such as water or an aqueous solution containing an acid. Obtained as an aqueous suspension. Place the aqueous suspension of chitin nanofibers and chitosan nanofibers in, for example, a centrifuge tube, centrifuge, remove the supernatant by decantation, add ethanol in the same amount as the removed amount, and centrifuge I do. Finally, the same operation is repeated until the water concentration becomes 0.1% or less. Next, using the chitin or chitosan nanofiber dispersion in this ethanol dispersion state, the same operation as described above was repeated using an organic solvent until the ethanol concentration became 0.1% or less. A uniformly dispersed dispersion is obtained without aggregation of the fibers and chitosan nanofibers.

  Next, the resin is blended with one or more organic solvent dispersions selected from the chitin nanofibers and chitosan nanofibers obtained. When blending, the pigment and other additives may be blended together as desired, or the components may be blended separately, and the order of blending the components is not particularly limited.

  The blending can be performed by a known method such as mixing, mixing, stirring, sonication, dispersion, supercritical processing, or the like. The resin to be blended, the pigment, and the other additives may be any materials that can be mixed with or compatible with one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers. Also good. Conditions such as the blend ratio, blend temperature, and time of each component can be appropriately selected by those skilled in the art.

  In the method for producing an organic solvent-based coating composition of the present invention, preferred production methods, preferred origins, and preferred organic solvents, resins, and pigments of chitin nanofibers and chitosan nanofibers are as described above.

  The present invention further includes a coating material, a coating material, an adhesive, an adhesive material, a sealing material, a resin-based injection material, a potting material, a filling, containing one or more selected from chitin nanofibers and chitosan nanofibers dispersed in an organic solvent. An additive composition for adding to a material selected from the group consisting of an agent, putty, plaster material, water glass, textile product, nonwoven fabric, resin film / sheet material, rubber product, cosmetics, soap, and plastic molded product provide.

  Since chitin nanofibers and chitosan nanofibers have high crystallinity, they have excellent physical properties not found in other nanofibers. And as mentioned above, crustaceans, especially shells and shells of shrimp and crabs, are discarded in large quantities. Obtaining useful chitin or chitosan nanofibers from these is an environmentally friendly technology and also cost-effective. It is advantageous. Furthermore, as described above, chitin or chitosan nanofibers have excellent physical properties, so that such excellent physical properties can be imparted to resins and materials as described above.

  EXAMPLES Hereinafter, the present invention will be described in more detail and specifically with reference to examples, but the examples should not be construed as limiting the present invention. Unless otherwise specified,% in the examples is weight / volume%.

1. Outline We investigated the effect of chitin nanofibers on the mixability and coating performance of chitin nanofibers and paints. Specifically, as described in detail below, chitin nanofibers dispersed in an acetic acid aqueous solution were used, and the dispersion medium was replaced with ethanol from the aqueous system. Next, chitin nanofibers were obtained in which the dispersion medium was gradually replaced from ethanol to methylcyclohexane, and finally almost completely replaced with methylcyclohexane (hereinafter also referred to simply as MCH). The MCH-substituted chitin nanofibers were mixed with various types of paints to evaluate mechanical properties. It was found that the mechanical properties of the paint were improved as a result of mixing with the baking type melamine alkyd resin paint.

2. Method (1) Preparation of aqueous solution of chitin nanofibers in acetic acid aqueous solution As described in the pamphlet of International Publication WO2010 / 073758, an aqueous suspension of chitin nanofibers was obtained. Specifically, dried crab shell (Canada, purchased from Kawai Fertilizer, 100 g) was added to a 5% KOH aqueous solution and refluxed for 6 hours to remove protein in the crab shell. The treated crab shell was filtered and washed well with water until neutral. The crab shell was stirred with 7% aqueous HCl at room temperature for 2 days to remove ash in the crab shell. The crab shell was filtered again and washed well with water until neutral. The treated crab shell was added to a 0.3 M sodium acetate buffer solution of 1.7% NaClO ₂ and stirred at 80 ° C. for 6 hours to remove the pigment contained in the crab shell. The crab shell was filtered again and washed well with water until neutral. The crab shell was dispersed in water, and the dispersion was crushed with a home mixer, then acetic acid was added to adjust the pH to 3, and the mixture was stirred overnight. The acetic acid-treated crab shell was subjected to a stone mill type grinder (Supermass colloider (MKCA 6-2)) to defibrate chitin nanofibers. The resulting aqueous acetic acid dispersion of chitin nanofibers had an acetic acid concentration of about 1% and a chitin nanofiber concentration of about 1%.

(2) Solvent replacement of chitin nanofibers About 200 ml of chitin nanofibers dispersed in an acetic acid aqueous solution was placed in a 250 ml capacity centrifuge tube and centrifuged under conditions of 3500 rpm × 20 minutes. The supernatant was removed by decantation, the same amount of ethanol as that removed was added, and the mixture was centrifuged under the same conditions. Finally, the same operation was repeated until the water concentration became 0.1% or less.
Next, using the chitin nanofiber dispersion in the ethanol dispersion state, the same operation as described above was repeated until the ethanol concentration became 0.1% or less to obtain methylcyclohexane-substituted chitin nanofibers.

(3) Mixing into paints Ratio of paint: methylcyclohexane-substituted chitin nanofibers = 8: 2 (weight ratio) to baked melamine alkyd resin-based paint (manufactured by Nippon Paint Co., Ltd., Olga Eco (White) and (Clear)) And mixed well with a disper.

(4) Painting Paint: Mixture of untreated baked melamine alkyd resin-based paint and MCH-substituted chitin nanofibers with dedicated thinner (Orga Select 520 Thinner, Nippon Paint Co., Ltd.) And air spray coating so that the film thickness becomes about 30 μm, and then dried at 110 ° C. for 10 minutes. A polished steel plate (89 mm × 110 mm × 1.3 mm) was used as the plate.

(5) Film thickness measurement It measured by the method according to the manufacturer's instruction | indication with the film thickness measuring device (LZ-330C by Kett).

(6) Measurement of coating film strength The coating film strength was measured for the following two items.
(I) Cupping resistance, which is a mechanical property of the coating film, was evaluated by a method based on JIS K5600-5-2 (coating general test method).
(Ii) Scratch hardness (pencil method), which is a mechanical property of the coating film, was evaluated by a method based on JIS K5600-5-4 (coating general test method).

3. Results The results of solvent substitution of chitin nanofibers are shown in Table 1.

  As shown in Table 1, as a result of substituting the dispersion medium from water to ethanol, ethanol dispersion chitin nanofibers having a water content reduced to about 0.06% can be obtained by performing centrifugation 13 times. It was. Next, starting from ethanol-dispersed chitin nanofibers, MCH (methylcyclohexane) dispersion in which the ethanol content was reduced to about 0.07% by centrifugation five times as a result of replacing the dispersion medium from ethanol to methylcyclohexane Chitin nanofibers could be obtained.

Table 2 shows the results of evaluating the mechanical properties of the paint mixed with MCH-substituted chitin nanofibers and the untreated paint.

As shown in Table 2, the mixing properties of the MCH (methylcyclohexane) -substituted chitin nanofibers and the coating material were good, and no foreign matter or aggregates were produced, resulting in a uniform coating solution.
As for pencil hardness, mixing with MCH-substituted chitin nanofibers improves both clear and white compared to untreated baked melamine alkyd resin-based paint alone. In the cupping resistance test, MCH (methylcyclohexane) substitution By mixing chitin nanofibers, the steel ball indentation depth became deeper and the coating film was more deformable and followable than the untreated baked melamine alkyd resin-based paint alone.

1. Outline The dispersibility of chitin nanofibers in various organic solvents was investigated. Specifically, by the same method as in Example 1, chitin nanofibers dispersed in an acetic acid aqueous solution were used, and the dispersion medium was replaced with isopropanol, ethyl acetate, or methylcyclohexane from an aqueous system via ethanol. The isopropanol, ethyl acetate or methylcyclohexane-substituted chitin nanofibers were subjected to SEM observation. As a result of SEM observation, it was found that chitin nanofibers were well dispersed in any of isopropanol, ethyl acetate, and methylcyclohexane.

2. Method (1) Preparation of aqueous solution of chitin nanofibers in acetic acid aqueous solution By the same method as in Example 1, an aqueous acetic acid dispersion of chitin nanofibers having an acetic acid concentration of about 1% and a chitin nanofiber concentration of about 1% was obtained.

(2) Solvent replacement of chitin nanofibers About 200 ml of chitin nanofibers dispersed in an acetic acid aqueous solution was placed in a 250 ml capacity centrifuge tube and centrifuged under conditions of 3500 rpm × 20 minutes. The supernatant was removed by decantation, the same amount of ethanol as that removed was added, and the mixture was centrifuged under the same conditions. Finally, the same operation was repeated until the water concentration became 0.1% or less.
Next, using the chitin nanofiber dispersion in this ethanol dispersion state, the same operation is repeated until the ethanol concentration becomes 0.1% or less to obtain isopropanol, ethyl acetate or methylcyclohexane-substituted chitin nanofibers. It was.

(3) SEM observation Isopropanol, ethyl acetate or methylcyclohexane-substituted chitin nanofibers were observed with a field emission scanning electron microscope (JEOL Ltd., JSM-6701F). A lower secondary electron detector (LEI) was used as a detector.

3. Results The results of SEM observation are shown in FIG. As is clear from FIG. 1, in any of isopropanol, ethyl acetate, and methylcyclohexane, chitin nanofibers are well dispersed, and each fiber is observed in a relatively independent state without aggregation. It was.

  According to the present invention, hydrophilic chitin or chitosan nanofibers were dispersible without being well aggregated regardless of the polarity of the organic solvent. This made it possible to add chitin or chitosan nanofibers to organic solvent-based paints. Among them, hydrophobic organic solvent-substituted chitin or chitosan nanofibers can be dispersed in general-purpose paint systems such as melamine alkyd resin, thermosetting acrylic resin, epoxy resin, urethane resin, polyester resin, silicone resin, and fluororesin. The filler addition effect can contribute to the improvement of the coating film performance, particularly the mechanical strength of the coating film, and can enhance the mechanical properties of various paints.

Claims (17)

  An organic solvent-based coating composition comprising a resin, an organic solvent, and one or more selected from chitin nanofibers and chitosan nanofibers. Chitin nanofiber is a chitin-containing material
Subjected to at least one deproteinization step and at least one decalcification step;
Subject to a step of treating with an acidic reagent,
2. The organic solvent-based coating composition according to claim 1, which is obtained by a production method which is subjected to a defibrating process. Chitosan nanofiber is a chitin-containing material
Subject to at least one deproteinization step and at least one decalcification step, and at least one deacetylation step;
2. The organic solvent-based coating composition according to claim 1, which is obtained by a production method which is subjected to a defibrating process.   The organic solvent-based coating composition according to claim 2 or 3, wherein the chitin-containing organism is a crustacean.   The organic solvent-based coating composition according to any one of claims 1 to 4, wherein the organic solvent is selected from polar organic solvents other than water and nonpolar organic solvents.   The organic solvent-based coating composition according to any one of claims 1 to 5, wherein the resin is selected from the group consisting of natural resins, polysaccharides, and synthetic resins.   The natural resin is selected from rosin, polylactic acid, polyglutamic acid, polycaprolactone, polyglycolic acid, casein, and shellac, the polysaccharide is selected from cellulose, chondroitin sulfate, hyaluronic acid, chitin, and chitosan, and the synthetic resin is , Nitrocellulose, nylon, rubber resin, phenol resin, melamine resin, acrylic resin, epoxy resin, urethane resin, polyester resin, polyamide resin, vinyl resin, polyimide resin, ketone resin, silicon-containing polymer, and fluorine-containing polymer The organic solvent-based coating composition according to claim 6, which is selected from:   Furthermore, the organic-solvent type coating composition in any one of Claims 1-7 containing a pigment. Providing one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers, and blending a resin with one or more organic solvent dispersions selected from chitin nanofibers and chitosan nanofibers ,
The manufacturing method of the organic-solvent type coating composition containing this. Chitin nanofiber is a chitin-containing material
Subjected to at least one deproteinization step and at least one decalcification step;
Subject to a step of treating with an acidic reagent,
The method for producing an organic solvent-based coating composition according to claim 9, which is obtained by a production method characterized by being subjected to a defibrating step. Chitosan nanofiber is a chitin-containing material
Subject to at least one deproteinization step and at least one decalcification step, and at least one deacetylation step;
The method for producing an organic solvent-based coating composition according to claim 9, which is obtained by a production method characterized by being subjected to a defibrating step.   The method for producing an organic solvent-based coating composition according to claim 10 or 11, wherein the chitin-containing organism is a crustacean.   The method for producing an organic solvent-based coating composition according to any one of claims 9 to 12, wherein the organic solvent is selected from polar organic solvents other than water and nonpolar organic solvents.   The method for producing an organic solvent-based coating composition according to any one of claims 9 to 13, wherein the resin is selected from the group consisting of natural resins, polysaccharides, and synthetic resins.   The natural resin is selected from rosin, polylactic acid, polyglutamic acid, polycaprolactone, polyglycolic acid, casein, and shellac, the polysaccharide is selected from cellulose, chondroitin sulfate, hyaluronic acid, chitin, and chitosan, and the synthetic resin is , Nitrocellulose, nylon, rubber resin, phenol resin, melamine resin, acrylic resin, epoxy resin, urethane resin, polyester resin, polyamide resin, vinyl resin, polyimide resin, ketone resin, silicon-containing polymer, and fluorine-containing polymer The manufacturing method of the organic-solvent type coating composition of Claim 14 selected from these.   Furthermore, the manufacturing method of the organic-solvent type coating composition in any one of Claims 9-15 including the process of blending a pigment.   Paints, coating materials, adhesives, adhesives, sealing materials, resin-based injection materials, potting materials, fillers, putty, plaster containing at least one selected from chitin nanofibers and chitosan nanofibers dispersed in organic solvents An additive composition for addition to a material selected from the group consisting of materials, water glass, textile products, nonwoven fabrics, resin film / sheet materials, rubber products, cosmetics, soaps, and plastic molded products.