Title of Invention	HYDROXYALKYLATED CHITOSAN SOLUTION
Abstract	This invention relates to hydroxyalkylated chitosan solution characterized in that a hydroxyalkylated chitosan and an organic acid or its derivative are contained in an aprotic polar solvent. This invention also relates to a coating process of a substrate, which is characterized by a step of causing the hydroxylalkylated chitosan solution to adhere onto a surface of the substrate, and another step of heating the substrate, which has been obtained in the first-mentioned step, at 100°C or higher for 1 second or longer. This invention can provide a one-pack solution of a chitosan derivative, which is free from crosslinking and stable at room temperature, can form a chitosan coating excellent in waterproofness after heated and dried, and is suited for the coating of a hydrophobic or lipophilic surface. This invention also provides a coating process of a substrate, which makes use of the one-pack solution.

Title of Invention

HYDROXYALKYLATED CHITOSAN SOLUTION

Abstract

This invention relates to hydroxyalkylated chitosan solution characterized in that a hydroxyalkylated chitosan and an organic acid or its derivative are contained in an aprotic polar solvent. This invention also relates to a coating process of a substrate, which is characterized by a step of causing the hydroxylalkylated chitosan solution to adhere onto a surface of the substrate, and another step of heating the substrate, which has been obtained in the first-mentioned step, at 100°C or higher for 1 second or longer. This invention can provide a one-pack solution of a chitosan derivative, which is free from crosslinking and stable at room temperature, can form a chitosan coating excellent in waterproofness after heated and dried, and is suited for the coating of a hydrophobic or lipophilic surface. This invention also provides a coating process of a substrate, which makes use of the one-pack solution.

Full Text	DESCRIPTION HYDROXYALKYLATED CHITOSAN SOLUTION Technical Field [0001] This invention relates to a hydroxyalkylated chitosan solution and its use. Background Art [0002] Chitosan is a naturally-occurring polysaccharide, and industrially, it is produced by deacetylating chitin isolated from crustaceans such as shrimps, lobsters or crabs. Chitosan is equipped with functions such as film-forming properties, antimicrobial activities, water retention properties and flocculating ability, and therefore, have been put in practical use as a functional polymer invarious fields. In recent years, its applications are actively under way especially as a safe functionalizing agent capable of imparting these functions to various substrates. For example, Patent Document 1 discloses a water-based substrate treatment composition containing chitosan or the like and a metal compound. Chitosan is also widely used as antimicrobiality-imparting coating formulations for various films, nonwoven fabrics and fiber products . One of technologies desired for these coating forraulations is concerned with solutions of chitosan or derivatives thereof in solvents other than water. Patent Document 1: JP-A-2003-201576 Disclosure of the Invention Problem to be Solved by the Invention [0003] Chitosan itself dissolves neither in water nor in organic solvents, but in a dilute aqueous acid solution of an organic acid such as citric acid, acetic acid or lactic acid, chitosan forms a salt with the organic acid and dissolves. By coating various substrates with this dilute aqueous acid solution of chitosan and causing its water to evaporate, films can be formed with durability in dry forms . Therefore, such dilute aqueous acid solutions of chitosan can readily impart the unique functions of chitosan to various substrates. [0004] A chitosan solution can be in the form of an aqueous solution, when a substrate surface onto which the chitosan solution is to be applied is hydrophilic . When a substrate surface is hydrophobic or lipophilic, on the other hand, the coating of an aqueous solution of a chitosan derivative results in its repelling so that no uniform coating is available. A solution of a chitosan derivative in a solvent other than water is, therefore, desired for substrates the surfaces of which are hydrophobic or lipophilic. There has, however, been unknown to date any solution of a chitosan derivative, which makes use of a solvent other than water and is suited for coating hydrophobic or lipophilic surfaces. [0005] Chitosan readily dissolves in dilute aqueous acid solutions, but except for such dilute aqueous acid solutions, no solvents are known to able to effectively dissolve chitosan, to say nothing of solvents suited for coating applications. With respect to chitosan derivatives other than those having high degrees of substitution, no solvent is known to be suited either for their dissolution except for the above-mentioned dilute aqueous acid solutions, to say nothing of solvents suited for coating applications. There is, accordingly, an outstanding desire for nonaqueous solvents (organic solvents) capable of preparing solutions of chitosan derivatives, which are suited for coating hydrophobic or lipophilic surfaces. [0006] Further, dry films available from aqueous chitosan solutions, which have been commonly employed, have a problem in that they show solubility to water and are poor in waterproofness, because organic acids remain in the dry films. [0007] Similar to usual polymers , it is also practiced to add various crosslinking agents to aqueous solutions of chitosan so that the resulting coatings are crosslinked (see, for example, JP-B-2781990). This method has already found wide-spread utility in general industrial applications, because it has many advantages such that it can readily achieve crosslinking in a single step by appropriately choosing a crosslinking agent to be used and its use conditions and that it can control the property of the resulting coating ranging from high waterproofness that it practically does not swell in water to such waterproofness that it does not dissolve in water but absorbs water and swells substantially. [0008] However, the crosslinking agents known to date have high reactivity, and therefore, are accompanied by problems in that solutions available after mixing the crosslinking agents are short in pot life and the inherent properties of chitosan are reduced in the resulting coatings although the resulting coatings are provided with improved waterproofness. [0009] Objects of the present invent ion are , therefore, to provide a one-pack solution of a chitosan derivative, which is free from cross linking and stable at room temperature, can form a chitosan coating excellent in waterproof ness after drying under heat, and is suited for the coating of a hydrophobic or lipophilic surface, and a coating process of a substrate, which makes use of the one-pack solution. Means for Solving the Problem [0010] The above-described objects can be achieved by the present invention to be described hereinafter. Described specifically, the present invention provides a hydroxyalkylated chitosan solution comprising an aprotic polar solvent, a hydroxyalkylated chitosan, and an organic acid or a derivative thereof. [0011] In the present invention as described above, the; aprotic polar solvent may preferably be at least one; solvent selected from the group consisting of N,N-dimethy1formamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide; the organic acid may preferably be a polybasic acid; and the polybasic acid may preferably be at least one acid selected from the group consisting of pyromelliticacid, citric acid, trimelliticacid, malic acid, polymaleic acid, phthalic acid, and succinic acid. [0012] In the present invention as described above, the organic acid or the derivative thereof may be used preferably in an amount of from 20 to 300 parts by weight per 100 parts by weight of the hydroxyalkylated chitosan; the hydroxyalkylated chitosan may be contained preferably at a concentration of from 1 to 40 wt%; the hydroxyalkylated chitosan may preferably have a hydroxyalkylation degree of at least 0.2; and the hydroxyalkylated chitosan may preferably be a hydroxyalkylation product of chitosan, the chitosan has a deacetylation degree of at least 30%, and, when the chitosan is dissolved at a concentration of 1 wt% in a 1 wt% aqueous solution of acetic acid, a resulting solution has a viscosity of from 1 mPa.s to 10,000 mPa.s. [0013] The present invention also provides a coating process of a substrate, which comprises a step of causing the above-described hydroxyalkylated chitosan solution to adhere onto a surface of the substrate, and another step of heating the substrate, which has been obtained in the first-mentioned step, at not lower than 100°C for at least 1 second. In the process, the hydroxyalkylated chitosan solution may preferably comprise organic or inorganic particles and the substrate may preferably be a metal article. Advantageous Effects of the Invention [0014] According to the present invention, it is possible to provide a hydroxyalkylated chitosan solution, which can form a chitosan coating of excellent waterproofness on a hydrophobic or lipophilic surface without needing another chemical such as a crosslinking agent, and also a coating process of a substrate, which makes use of the solution. Best Modes for Carrying out the Invention [0015] The present invention will next be described in further detail based on preferred embodiments. As mentioned above, there was not known to date any solution of a chitosan derivative (hydroxyalkylated chitosan), which makes use of an organic solvent suited for coating a hydrophobic or lipophilic surface. The present inventors, therefore, conducted an enthusiastic investigation about conditions for dissolving a hydroxyalkylated chitosan in an organic solvent. As a result, the present inventors found that, when the hydroxyalkylated chitosan and an organic acid or its derivative (which may hereinafter be referred to as "the organic acid", including the derivative) is added to various aprotic polar solvents, the hydroxyalkylated chitosan and the organic acid interact and hydroxyalkylated chitosan solutions are obtained. [0016] Further, the chitosan solution was coated on a surface of a substrate, the solvent was caused to evaporate off by reduced-pressure drying to form a coating, the substrate was heated at 180°C or higher for 30 seconds, and the substrate was then immersed in water. As a result, it was confirmed that even 24 hours later, no changes were visually observed on the coating and the formed coating became a waterproof coating. [0017] The hydroxyalkylated chitosan solution according to the present invention is characterized in that the hydroxyalkylated chitosan and the organic acid are contained in the aprotic polar solvervt. Preferably, the hydroxyalkylated chitosan for use in the present invention may have a structure that an alkylene oxide or oxiranemethanol is added to the amino group of chitosan, like hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosanorglycerylatedchitosan, and may be produced by reacting chitosan with the alkylene oxide or oxiranemethanol. It is, however, to be noted that the hydroxyalkylated chitosan for use in the present the present invention, the glycerylatedchitosan will hereinafter be embraced in the term "hydroxyalkylated chitosan". [0020] From the standpoint of the solubility of such a hydroxyalkylated chitosan in an aprotic polar solvent, the degree of addition of a corresponding alkylene oxide or oxiranemethanol to chitosan [the degree of hydroxyalkylation (nounit) ] may preferably be 0.2 (mole) or greater but 4 (moles) or less per pyranose ring (mole of pyranose) . To obtain such a hydroxyalkylation degree, it is desired to add and react 0.3 (mole) or greater but 10 (moles) or less of the alkylene oxide per pyranose ring (mole pyranose) that makes up chitosan. A hydroxylation degree of 0.2 or less is insufficient from the standpoint of the solubility in the aprotic polar solvent. Even when the hydroxylation degree exceeds 4, on the other hand, the solubility in the aprotic polar solvent does not change so that the setting of the hydroxyalkylation degree beyond 4 is uneconomical. [0021] In the present invention, no particular limitation is imposed on the source of chitosan as a raw material for the hydroxyalkylated chitosan and the production process of the hydroxyalkylated chitosan, and chitosan products which have been industrially manufactured to date are all usable. Further, no particular limitation is imposed either on the deacetylation degree or polymerization degree of chitosan. Preferably, however, the deacetylation degree of chitos an may be 30% orhigher, with 70% to 100% being more preferred and 80% to 100% being still more preferred. [0022] Preferred as chitosan can be such chitosan that as an aqueous solution containing the chitosan at 1 wt% and acetic acid at 1 wt%, the viscosity of the aqueous solution (20°C) ranges from 1 mPa.s to 10,000 mPa.s. A deacetylation degree of lower than 30% is insufficient from the standpoint of the solubility of a hydroxyalkylated chitosan, which is available from a reaction with the corresponding alkylene oxide or oxiranemethanol, in the aprotic polar solvent. If the above-described viscosity is lower than 1 mPa-s, the resulting coating is insufficient in strength. If the above-described viscosity is higher than 10,00 0 mPa.s, on the other hand, a solution of the resulting hydroxyalkylated chitosan has an excessively high viscosity so that the concentration of the hydroxyalkylated chitosan has to be limited at a very low level. Therefore, viscosities outside the above-described range are not preferred. [0023] Chitosan, which is employed as a raw material for the hydroxyalkylated chitosan to be used in the present invention, may more preferably be one having a deacetylation degree of from 80% to 100% and, as an aqueous solution containing 1 wt% of the chitosan and 1 wt% of acetic acid, giving a viscosity of from 3 mPa.s to 100 mPa.s from the standpoints of the solubility of the chitosan and the strength of the resulting coating. [0024] As the organic acid or its derivative for use in the present invention, those known to date can each be used, including organic acids such as salicylic acid, pyromellitic acid, citric acid, trimellitic acid, malicacid, pyrrolidonecarboxylic acid, polymaleic acid, phthalic acid, succinic acid and 1,2,3,4-butanetetracarboxylicacid. Preferred can be polybasic acids, their acid anhydrides, and salts of some or all of their carboxyl groups, notably their ammonium salts and amine salts and alkyl esters, amides, imides, amide-imides and the like of some or all of their carboxyl groups. Preferred as derivatives of these polybasic acids are compounds which regenerate polybasic acids upon heating of coatings to be formed subsequently. More preferably, the polybasic acid can be at least one acid selected from the group consisting of pyromellitic acid, citric acid, trimellitic acid, etc.), carbonates (ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, butylene carbonate, etc.), amides (formamide, N-methylformamide, N-methylacetamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, piperidone, N-methylpiperidone , N-ethylpiperidone, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, methyloxazolidinone, ethyloxazolidinone, etc.), sulfoxides (dimethyl sulfoxide, etc.), andsulfones (tetramethylene sulfone, etc.). Among these, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide are more preferred. With respect to these aprotic polar solvents, a selection is made as desired depending on the application. These aprotic polar solvents may be used either singly or in combination. [0027] As the organic acid and aprotic polar solvent for use in the present invention, general commercial products can be used as they are, or they may be used after purification as needed. Concerning the hydroxyalkylated chitosan, one produced by the above-described process may be used with the reaction solvent, byproducts and/or the like still contained therein, or may be used after purification. [002 8] As the order of addition of the hydroxyalkylated chitosan and organic acid to the aprotic polar solvent upon their dissolution in the solvent to prepare the hydroxyalkylated chitosan solution according to the present invention, either the hydroxyalkylated chitosan or the organic acid may be added first or they may be added at the same time. As their dissolution method, stirring may be conducted with heating as needed although stirring at room temperature is sufficient. [0029] The existence of water contained in individual additives to be used as needed and the existence of water formed when the organic acid is a hydrate or the like affect neither the hydroxyalkylated chitosan solution according to the present invention nor the formation of a coating on a substrate by the solution. No conditions are thus applied to such water. [0030] The concentration of the hydroxyalkylated chitosan in the hydroxyalkylated chitosan solution according to the present invention may range preferably from 1 to 40 wt%, more preferably from 5 to 10 wt% from the viewpoints of coating applicability, transport cost and the like. A concentration lower than 1 wt% makes it difficult to obtain a stable coating, while a concentration higher than 40wt% makes it hard to obtain a homogeneous solution. [0031] The hydroxyalkylated chitosan solution according to the present invention can be used for coating a substrate as it is. For improving the applicability to a substrate, however, it is possible to add an organic substance, such as a cationic surfactant, a nonionic surfactant or a lipophilic or hydrophobic organic solvent, an inorganic filler orthelike. Further, the addition of a preservative, antimold agent or the like is not particularly inhibited. In addition, a crosslinking agent other than an organic acid may also be incorporated in the hydroxyalkylated chitosan solution as needed. [0 032] Examples of the crosslinking agent other than the organic acid include epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and glycerol polyglycidyl ether; isocyanate compounds such as toluylen diisocyanate, xylylenediisocyanate, hexamethylene diisocyanate and phenyl diisocyanate, and blocked isocyanate compounds formed by blocking such isocyanate compounds with blocking agents such as phenols, alcohols, active methylene compounds, mercaptans, acid-amides, imides, amines, imidazoles, ureas, carbamic acids, imines, oximes or sulfites; aldehyde compounds such as glyoxal, glutaraldehyde, and dialdehyde starch; (meth)acrylate compounds such as polyethylene glycol diacrylate, polyethylene glycol dimethacrylate and hexanediol diacrylates; methylol compounds such as methylolmelamine and dimethylol urea; organic acid metal salts such as zirconyl acetate, zirconyl carbonate and titanium lactate; metal alkoxide compounds such as aluminum trimethoxide, aluminum tributoxide, titanium tetraethoxide, titanium tetrabutoxide, zirconium tetrabutoxide, aluminum dipropoxide acethylacetonate, titanium dimethoxide bis ( acetylacetonate) and titanium dibutoxide bis(ethylacetoacetate); carbodiimide compounds; and the like. The use of such a crosslinking agent is not essential. When to be employed, however, the amount of the crosslinking agent may suitably range from 0.1 to 200 wt% based on the hydroxyalkylated chitosan. [0033] The coating process of the present invention for the substrate comprises the step of causing the hydroxyalkylated chitosan solution according to the present invention to adhere onto the surface of the substrate, and the step of heating the substrate, which has been obtained in the first-mentioned step, at not lower than 100°C for at least 1 second. Examples of the substrate to be coated by the hydroxyalkylated chitosan solution according to the present invention include, but are not limited to, glass, ceramics, plastics, metals, fibers, non-woven products, and packaging materials (for example, plastic films, and composite films of aluminum and resins). [0034] According to the coating process of the present invention, various substrates on each of which a coating of a hydroxyalkylated chitosan, said coating containing an organic acid, is applied can each be obtained by applying a hydroxyalkylated chitosan solution onto the substrate by spraying, coating or impregnation to form a coating and then causing the solvent to evaporate from the coating until the content of the solvent in the coating is decreased to 15% or lower, preferably 5% or lower based on the weight of the hydroxyalkylated chitosan in the coating. No particular limitation is imposed on the thickness of each coating to be formed by the above-described process, and the thickness of each coating may generally range from 1 to 500 μm or so. The drying of the substrate with the hydroxyalkylated chitosan solution coated thereon may preferably be conducted under reduced pressure or ambient pressure at a temperature of the boiling point of the solvent or higher. To provide the thus-formed coating with improved waterproofness, the substrate with the coating formed thereon can be heated preferably at 100°C or higher for 1 second or longer, more preferably at 150 to 250°C for 1 second to 10 minutes afterdrying. If the heating temperature is lower than 100°C or the heating time is shorter than 1 second as a heat treatment condition, no coating can be obtained with excellent waterproofness. [0035] The present invention is useful especially when the substrate is an aluminum foil or copper foil to be used for the fabrication of an electrode plate for a nonaqueous electrolyte secondary battery. Described specifically, when an active material for an electrode is added to the above-described solution of the present invention and a layer of the active material is formed on a surface of an aluminum foil or copper foil as a collector, an active material layer having excellent adhesion to the collector can be formed. [0036] It is to be noted that the application of the hydroxylated chitosan solution according to the present invention is not limited to the coating of a substrate by spraying, coating, impregnation or the like. For example, solid particles containing the hydroxyalkylated chitosan can be obtained by drying the hydroxyalkylated chitosan solution in air by a. method such as spray drying. A film with the hydroxyalkylated chitosan contained therein can also be obtained by casting the hydroxyalkylated chitosan solution on a glass plate and then coating it. [0037] As has been described above, the hydroxyalkylated chitosan solution according to the present invention contains only the hydroxyalkylated chitosan, organic acid and aprotic polar solvent as its essential elements, is easy to produce, and is extremely useful as a coating forming composition, which is equipped with functionality and waterproofness, especially for a hydrophobic or lipophilic substrate surface or metal article surface the coating of which with an aqueous solution of chitosan or the like has heretofore been difficult. Examples [0038] The present invention will next be described more specifically based on Examples and Comparative Examples . It is tobe noted that the present invention shall not be limited by these Examples. Chitosan> The compositions of individual glycerylated chitosan solutions employed in the Examples and Comparative Examples are shown in Table 1 . Examples 14-16 are all directed to the same composition, but the composition is repeatedly described because conditions in the coating process of the present invention were different. The expression "viscosity of 1% raw chitosan solution" in the table indicates the viscosity of a 1 wt% acetic acid solution containing 1 wt% of chitosan as a raw material for the corresponding glycerylated chitosan (viscosity measuring method : measured by a Brookfield rotational viscometer under the conditions consisting of a measuring temperature of 20°C and a measuring rotation speed of 30 rpm) . Concerning aprotic polar solvents used in the respective glycerylated chitosan solutions, the following abbreviations are used: NMP (N-methyl-2-pyrrolidone), DMF (N,N-dimethylformamide) , DMSO (dimethylsulfoxide) , DMAC (N,N-dimethylacetamide), and DMI (1,3-dimethyl-2-imidazolidinone). [0039] Example 1 Dispersed in NMP (80 parts by weight) was glycerylated chitosan (deacetylation degree of raw chitosan: 83%; 10 parts by weight) . After salicylic acid (10 parts by weight) was added to the dispersion, the resulting mixture was stirred at room temperature for 4 hours to effect dissolution. After the thus-prepared solution was allowed to stand overnight, it was again stirred at room temperature for 1 hour to effect dissolution so that a glyceryl chitosan solution (100 parts by weight) was prepared. [0040]Examples 2-21 In a similar manner as in Example 1, glycerylated chitosan solutions according to the present invention were each prepared with the viscosity of an aqueous 1 wt% acetic acid solution containing the raw chitosan for the corresponding glycerylated chitosan, the glycerylation degree and weight of the glycerylated chitosan, the kind and weight of the organic acid, the mixing ratio of the glycerylated chitosan to the organic acid and the kind and weight of the aprotic polar solvent being changed as shown in Table 1. The deacetylation degree of the raw chitosan employed was 83%. It is to be noted that, when it was difficult to dissolve the glycerylated chitosan by stirring at room temperature, stirring was conducted with heating to prepare the solution. [0041] Preparation procedures of the various solutions employed as the Comparative Examples will be described hereinafter. Comparative Example 1 Comparative Example 1 is directed to the use of chitosan not subjected to a glycerylation reaction (deacetylation degree: 85%, glycerylation degree: 0, viscosity of anaqueous 1 wt% acetic acid solution containing the chitosan at 1 wt%: 6 mPa.s; hereinafter simply called "the chitosan"). The chitosan (5 parts by weight) was dispersed in NMP (90 parts by weight) . Subsequent to the addition of pyromellitic acid (5 parts by weight) , the thus-obtained mixture was stirred at room temperature for 4 hours, but the chitosan was not dissolved at all. The NMP was then heated to 80°C, at which stirring was conducted for 2 hours. However, the chitosan was not dissolved at all, and therefore, no chitosan NMP solution was obtained. [ 0042]Comparative Example 2 Comparative Example 2 is directed to the preparation of a solution without using any organic acid. Glycerylated chitosan (deacetylation degree of raw chitosan: 83%; lOparts byweight) was dispersed in NMP (90 parts by weight), followed by stirring at room temperature for 4 hours. After the resultant dispersion was allowed to stand overnight, it was again stirred at room temperature for 1 hour to effect dissolution so that a glyceryl chitosan solution (100 parts by weight) was prepared. [ 0043]Comparative Example 3 Dispersed In NMP (90 parts by weight) was glycerylated chitosan (deacetylation degree of raw chitosan: 85%; 5 parts by weight). After pyromellitic acid (5 parts by weight) was added to the dispersion, the resulting mixture was stirred at room temperature for 4 hours to effect dissolution. After the thus-prepared solution was allowed to stand overnight, it was again stirred at room temperature for 1 hour to effect dissolution so that a glyceryl chitosan solution (100 parts by weight) wasprepared. [0046] On coatings obtained by using the individual glycerylated chitosan solutions prepared in accordance with the compositions shown in Table 1 and by following the below-described coating forming method, a waterproofness evaluation test was performed. The evaluation results are shown in Table 2. [0047 ] On surfaces of stainless steel sheets (SUS304, 1 mm thick x 10 cm long x 10 cm wide) which had not been subjected to any pretreatment such as degreasing treatment, the various solutions of Examples 1-21 and Comparative Examples 2 and 3 were coated by a bar coater to give dry coat weights of 2 g/m2, respectively. Under the conditions shown in Table 2, drying was then conducted. The thus-coated stainless steel sheets were provided as specimens to be used in the following evaluation test. [0048] Each specimen was immersed for 24 hours in purified water, and was then dried under heat for 1 hour in a fan dryer controlled at 105°C. After being allowed to cool down to room temperature, its weight was measured, and in accordance with the following formula, the percent residue of its coating was determined. (C - A)/(B - A) x 100 (%) where, A: Weight of a stainless steel sheet before coating a solution, B: Weight of the stainless steel sheet after coating and drying the solution, and C: Weight of the stainless steel after immersing, subsequent to the coating and drying of the solution, the stainless steel for 24 hours in water and then conducting drying again. [0049] The waterproofness of each coating was evaluated in 4 stages based on the value obtained in accordance with the above-described formula. The evaluation method was as follows: A: Percent residue of coating  95% B: 95% > percent residue of coating  80% C: 80% > percent residue of coating  50% D: 50% > percent residue of coating [0052] As is evident from the above results of Table 2, the results of the waterproofness evaluations of the coatings formed using the glycerylated chitosan solutions according to the present invention were good. Comparative Example 1 is directed to the illustrative use of chitosan in place of a glycerylated chitosan. The chitosan was not dissolved in NMP so that no solution was successfully prepared. In Comparative Example 2 , the NMP solution was prepared using the glycerylated chitosan of the high degree of substitution (glycerylation degree: 3.2) without using any organic acid. The coating formed from the solution was not equipped with any waterproofness . In Comparative Example 3, the coating was formed using a vacuum dryer without heated-air drying at high temperatures . Asaresult, the waterproofness of the coating was poor. [0053] To evaluate the pot lives of the above-described glycerylated chitosan solutions, portions of the individual solutions of Examples 1-21 (the solutions of Examples 14-16 were the same) were stored in a room (20to28°C) and in a constant-temperature chamber (50°C), respectively, to observe any changes with time in the solution forms. Even after an elapsed time of 3 months or longer, all of the solutions neither increased in viscosity nor formed a gel, and therefore, were usable for coating substrates. [0054] Example 22 Onto a polyimide film of 50 μm thickness (10 cm x 5 cm), the 5 wt% glycerylated chitosan solution of Example 14 (solution viscosity: 174mPa-s) was coated by a bar coater. Repelling of the NMP solution was not observed at all, and uniform coating was feasible onto the polyimide film the surface of which was hydrophobic. [ 0055]Comparative Example 4 Onto a polyimide film of 50 μm thickness (10 cm x 5 cm), a 5 wt% aqueous solution (solution viscosity: 186mPa.s) of citric acid, said solution containing 5 wt% of chitosan, was coated by a bar coater. The aqueous solution was repelled. It was, therefore, unable to uniformly coat the aqueous solution onto the polyimide film. [0056]Examples 23-25 In Table 3, the compositions of individual hydroxyalkylated chitosan solutions employed as Examples 23-25 are shown. The abbreviations of the aprotic polar solvents used in the individual hydroxyalkylated chitosan solutions are as defined above. The production of the hydroxyalkylated chitosans was conducted in a manner known perse in the art. The raw chitosan for the hydroxyalkylated chitosans was the same as that employed above in Example 6. [0058] On coatings obtained by using the hydroxyalkylated chitosan solutions described in Table 3 and following the same coating forming method as in the case of the glycerylated chitosans, a waterproofness evaluation test was performed in a similar manner as described above. The evaluation results are shown in Table 4. [0060] As is evident from the above results of Table 4, the results of the waterproofness evaluations of the coatings formed using the glycerylated chitosan solutions according to the present invention were good. [ 0061 ] Application Example 1 (Coating formulation, electrode plate) A positive-electrode coating formulation employed in this Example and containing a positive electrode active material was prepared by the procedure to be described hereinafter. As materials for the positive-electrode coating formulation, LiCoO2 powder having particle sizes of from 1 to 100 μm/ acetylene black as a conductive aid and the solution of Example 14 described above in Table 1 were stirred and mixed at a mixing ratio of 90 parts by weight, 5 parts by weight and 50 parts by weight at a rotation speed of 60 rpm for 120 minutes in a planetary mixer to obtain a slurry-form, positive-electrode coating formulation with the positive-electrode active material contained therein. [0062] Using the positive-electrode coating formulation obtained as described above and employing, as a substrate, a collector formed of a 20-μm thick aluminum foil, the positive-electrode coating formulation was applied on one side of the substrate by a "COMMA ROLL COATER". The thus-coated substrate was then dried for 2 minutes in an oven controlled at 110°C, and was further dried for 2 minutes in the oven controlled at 150°C to eliminate the solvent and to have the binder crosslinked, so that a positive electrode plate with an active material layer formed with a dry thickness of 100 μm on the collector was obtained. The positive electrode plate obtained by the above-described procedure was pressed under conditionsof 5, 000 kgf/cm2 to make the coating uniform. Subsequently, aging was conducted for 48 hours in a vacuum oven controlled at 80°C to completely eliminate volatiles (the solvent, the unreacted polybasic acid, etc.). [0063] Parallel lines, which consisted of perpendicularly-intersecting 11 vertical lines and 11 horizontal lines, were drawn by a cutter at intervals of 1 mm on the active material layer to form 100 squares within 1 cm2. A mending tape was applied to the surface of the active material layer, and tape peeling was then conducted. The number of squares which were not peeled off was counted as a measure of adhesiveness. The average of 10 tests was 98.0 squares. Further, the conditions of the active material layer were observed after the electrode plate with the squares formed thereon as described above was immersed at 50°C for 24 hours in a mixed solvent of EC (ethylene carbonate), PC (propylene carbonate) and DME (dimethoxyethane) combined together at a volume ratioof 1:1:2. Neither peeling nor swelling of the active material layer was recognized. [0064]Application Example 2 (Coating formulation, electrode plate) A negative-electrode coating formulation employed in this Example and containing a negative-electrode active material was prepared by the procedure to be described next. Carbon powder obtainedby thermal degradation of coal coke at l,200°C, acetylene black as a conductive aid and the solution of Example 8 described above were stirred and mixed at a mixing ratio of 90 parts by weight, 5 parts by weight and 50 parts by weight at a rotation speed of 60 rpm for 120 minutes in the planetary mixer to obtain a slurry-form coating formulation with the negative-electrode active material contained therein. [0065] The coating formulation containing the negative-electrode active material and obtained as described above was applied onto a copper-foil collector by using the "COMMA ROLL COATER". After the thus-coated collector was processed through a drying step, it was dried for 2 minutes in the oven controlled at 110°C, and was further dried for 2 minutes in the oven controlled at 150°C to eliminate the solvent and to have the binder crosslinked, so that an active material layer was formed with a dry thickness of 100 μm on the collector. A negative electrode plate obtained by the above-described procedure was pressed under conditions of 5,000 kgf/cm2 to make the coating uniform. Subsequently, aging was conducted for 48 hours in a vacuum oven controlled at 80°C to completely eliminate volatiles (the solvent, the unreacted polybasic acid, etc.). [0066] Parallel lines, which consisted of perpendicularly-intersecting 11 vertical lines and 11 horizontal lines, were drawn by a cutter at intervals of 1 mm on the active material layer to form 100 squares within 1 cm2. A mending tape was applied to the surface of the active material layer, and tape peeling was then conducted. The number of squares which were not peeled off was counted as a measure of adhesiveness. The average of 10 tests was 96 squares. Neither peeling nor swelling of the active material layer was recognized. [0067]Application Example 3 (Battery) An electrode unit was first formed by using the positive-electrode plate and negative-electrode plate, which had been obtained above in Application Example 1 and Application Example 2, respectively, and rolling them into a volute form with a separator interposed therebetween. The separator was made of a porous polyolefin (polypropylene, polyethylene or a copolymer thereof) film having a width broader than the positive-electrode plate and a three-dimensional porous (spongy) structure. The electrode unit was then inserted into a bottomed cylindrical, stainless steel can, which would also serve as a negative-electrode terminal, so that a battery of the AA size and 500 mAh rated capacity was assembled. Charged as an electrolyte into the battery was a solution of 1 mole of LiPF6 as a supporting salt in a mixed solvent prepared by combining EC (ethylene carbonate), PC (propylene carbonate) and DME (dimethoxyethane) at a volume ratio of 1:1:2 to give a total volume of 1 liter. [0068] Forthe measurement of battery characteristics, a charge-discharge measuring instrument was used. Twenty (20) batter ies we re charged at the temperature condition of 25°C and the current value of a 0.2 CA charging current, firstly in a charging direction until a battery voltage reached 4.1V. After a break of 10 minutes, the cells were discharged by the same current until 2.75 V was reached. Subsequent to a break of 10 minutes, charging and discharging were then repeated 100 cycles under the same conditions to measure charge-discharge characteristics. When the charge-discharge capacity in the 1st cycle was assumed to be 100, the charge-discharge capacity in the 100th cycle was 96. Industrial Applicability [0069] The hydroxyalkylated chitosan solution according to the present invention is easy to produce, and is extremely useful as a coating composition capable of applying a coating, which is equipped with functionality and waterproofness, to a hydrophobic or lipophilic surface the coating of which with an aqueous solution has heretofore been difficult. It is also useful as a binder upon fabrication of electrode plates for batteries. CLAIMS [1] A hydroxyalkylated chitosan solution comprising an aprotic polar solvent, a hydroxyalkylated chitosan, and an organic acid or a derivative thereof. [2] The solution of claim 1, wherein said aprotic polar solvent is at least one solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide . [3] The solution of claim 1, wherein said organic acid is a polybasic acid. [4] The solution of claim 3, wherein said polybasic acid is at least one acid selected from the group consisting of pyromellitic acid, citric acid, trimellitic acid, malic acid, polymaleic acid, phthalic acid, and succinic acid. [5] The solution of claim 1, wherein said organic acid or said derivative thereof is used in an amount of from 20 to 300 parts by weight per 100 parts by weight of said hydroxyalkylated chitosan. [6] The solution of claim 1, wherein said hydroxyalkylated chitosan is contained at a concentration of from 1 to 40 wt%. [7] The solution of claim 1, wherein said hydroxyalkylated chitosan has a hydroxyalkylation degree of at least 0.2. [8] The solution of claim 1, wherein said hydroxyalkylated chitosan is a hydroxyalkylation product of chitosan, said chitosan has a deacetylation degree of at least 30%, and, when said chitosan is dissolved at a concentration of 1 wt% in a 1 wt% aqueous solution of acetic acid, a resulting solution has a viscosity of from 1 mPa-s to 10,000 mPa.s . [9] A coating process of a substrate, which comprises a step of causing a hydroxyalkylated chitosan solution according to any one of claims 1-8 to adhere ontoa surface of said substrate, andanother step of heating said substrate, which has been obtained in the first-mentioned step, at not lower than 100°C for at least 1 second. [10] The process of claim 9, wherein said hydroxyalkylated chitosan solution comprises organic or inorganic particles and said substrate is a metal article. This invention relates to hydroxyalkylated chitosan solution characterized in that a hydroxyalkylated chitosan and an organic acid or its derivative are contained in an aprotic polar solvent. This invention also relates to a coating process of a substrate, which is characterized by a step of causing the hydroxylalkylated chitosan solution to adhere onto a surface of the substrate, and another step of heating the substrate, which has been obtained in the first-mentioned step, at 100°C or higher for 1 second or longer. This invention can provide a one-pack solution of a chitosan derivative, which is free from crosslinking and stable at room temperature, can form a chitosan coating excellent in waterproofness after heated and dried, and is suited for the coating of a hydrophobic or lipophilic surface. This invention also provides a coating process of a substrate, which makes use of the one-pack solution.

Full Text

DESCRIPTION
HYDROXYALKYLATED CHITOSAN SOLUTION
Technical Field
[0001] This invention relates to a hydroxyalkylated
chitosan solution and its use.
Background Art
[0002] Chitosan is a naturally-occurring
polysaccharide, and industrially, it is produced by
deacetylating chitin isolated from crustaceans such
as shrimps, lobsters or crabs. Chitosan is equipped
with functions such as film-forming properties,
antimicrobial activities, water retention
properties and flocculating ability, and therefore,
have been put in practical use as a functional polymer
invarious fields. In recent years, its applications
are actively under way especially as a safe
functionalizing agent capable of imparting these
functions to various substrates. For example,
Patent Document 1 discloses a water-based substrate
treatment composition containing chitosan or the like
and a metal compound. Chitosan is also widely used
as antimicrobiality-imparting coating formulations
for various films, nonwoven fabrics and fiber products .

One of technologies desired for these coating
forraulations is concerned with solutions of chitosan
or derivatives thereof in solvents other than water.
Patent Document 1: JP-A-2003-201576
Disclosure of the Invention
Problem to be Solved by the Invention
[0003] Chitosan itself dissolves neither in water nor
in organic solvents, but in a dilute aqueous acid
solution of an organic acid such as citric acid, acetic
acid or lactic acid, chitosan forms a salt with the
organic acid and dissolves. By coating various
substrates with this dilute aqueous acid solution
of chitosan and causing its water to evaporate, films
can be formed with durability in dry forms . Therefore,
such dilute aqueous acid solutions of chitosan can
readily impart the unique functions of chitosan to
various substrates.
[0004] A chitosan solution can be in the form of an
aqueous solution, when a substrate surface onto which
the chitosan solution is to be applied is hydrophilic .
When a substrate surface is hydrophobic or lipophilic,
on the other hand, the coating of an aqueous solution
of a chitosan derivative results in its repelling
so that no uniform coating is available. A solution
of a chitosan derivative in a solvent other than water

is, therefore, desired for substrates the surfaces
of which are hydrophobic or lipophilic. There has,
however, been unknown to date any solution of a
chitosan derivative, which makes use of a solvent
other than water and is suited for coating hydrophobic
or lipophilic surfaces.
[0005] Chitosan readily dissolves in dilute aqueous
acid solutions, but except for such dilute aqueous
acid solutions, no solvents are known to able to
effectively dissolve chitosan, to say nothing of
solvents suited for coating applications. With
respect to chitosan derivatives other than those
having high degrees of substitution, no solvent is
known to be suited either for their dissolution except
for the above-mentioned dilute aqueous acid solutions,
to say nothing of solvents suited for coating
applications. There is, accordingly, an
outstanding desire for nonaqueous solvents (organic
solvents) capable of preparing solutions of chitosan
derivatives, which are suited for coating hydrophobic
or lipophilic surfaces.
[0006] Further, dry films available from aqueous
chitosan solutions, which have been commonly employed,
have a problem in that they show solubility to water
and are poor in waterproofness, because organic acids
remain in the dry films.

[0007] Similar to usual polymers , it is also practiced
to add various crosslinking agents to aqueous
solutions of chitosan so that the resulting coatings
are crosslinked (see, for example, JP-B-2781990).
This method has already found wide-spread utility
in general industrial applications, because it has
many advantages such that it can readily achieve
crosslinking in a single step by appropriately
choosing a crosslinking agent to be used and its use
conditions and that it can control the property of
the resulting coating ranging from high
waterproofness that it practically does not swell
in water to such waterproofness that it does not
dissolve in water but absorbs water and swells
substantially.
[0008] However, the crosslinking agents known to date
have high reactivity, and therefore, are accompanied
by problems in that solutions available after mixing
the crosslinking agents are short in pot life and
the inherent properties of chitosan are reduced in
the resulting coatings although the resulting
coatings are provided with improved waterproofness.
[0009] Objects of the present invent ion are , therefore,
to provide a one-pack solution of a chitosan
derivative, which is free from cross linking and stable
at room temperature, can form a chitosan coating

excellent in waterproof ness after drying under heat,
and is suited for the coating of a hydrophobic or
lipophilic surface, and a coating process of a
substrate, which makes use of the one-pack solution.
Means for Solving the Problem
[0010] The above-described objects can be achieved by
the present invention to be described hereinafter.
Described specifically, the present invention
provides a hydroxyalkylated chitosan solution
comprising an aprotic polar solvent, a
hydroxyalkylated chitosan, and an organic acid or
a derivative thereof.
[0011] In the present invention as described above,
the; aprotic polar solvent may preferably be at least
one; solvent selected from the group consisting of
N,N-dimethy1formamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, and dimethyl
sulfoxide; the organic acid may preferably be a
polybasic acid; and the polybasic acid may preferably
be at least one acid selected from the group consisting
of pyromelliticacid, citric acid, trimelliticacid,
malic acid, polymaleic acid, phthalic acid, and
succinic acid.
[0012] In the present invention as described above,

the organic acid or the derivative thereof may be
used preferably in an amount of from 20 to 300 parts
by weight per 100 parts by weight of the
hydroxyalkylated chitosan; the hydroxyalkylated
chitosan may be contained preferably at a
concentration of from 1 to 40 wt%; the
hydroxyalkylated chitosan may preferably have a
hydroxyalkylation degree of at least 0.2; and the
hydroxyalkylated chitosan may preferably be a
hydroxyalkylation product of chitosan, the chitosan
has a deacetylation degree of at least 30%, and, when
the chitosan is dissolved at a concentration of 1
wt% in a 1 wt% aqueous solution of acetic acid, a
resulting solution has a viscosity of from 1 mPa.s
to 10,000 mPa.s.
[0013] The present invention also provides a coating
process of a substrate, which comprises a step of
causing the above-described hydroxyalkylated
chitosan solution to adhere onto a surface of the
substrate, and another step of heating the substrate,
which has been obtained in the first-mentioned step,
at not lower than 100°C for at least 1 second. In
the process, the hydroxyalkylated chitosan solution
may preferably comprise organic or inorganic
particles and the substrate may preferably be a metal
article.

Advantageous Effects of the Invention
[0014] According to the present invention, it is
possible to provide a hydroxyalkylated chitosan
solution, which can form a chitosan coating of
excellent waterproofness on a hydrophobic or
lipophilic surface without needing another chemical
such as a crosslinking agent, and also a coating
process of a substrate, which makes use of the
solution.
Best Modes for Carrying out the Invention
[0015] The present invention will next be described
in further detail based on preferred embodiments.
As mentioned above, there was not known to date
any solution of a chitosan derivative
(hydroxyalkylated chitosan), which makes use of an
organic solvent suited for coating a hydrophobic or
lipophilic surface. The present inventors,
therefore, conducted an enthusiastic investigation
about conditions for dissolving a hydroxyalkylated
chitosan in an organic solvent. As a result, the
present inventors found that, when the
hydroxyalkylated chitosan and an organic acid or its
derivative (which may hereinafter be referred to as
"the organic acid", including the derivative) is added

to various aprotic polar solvents, the
hydroxyalkylated chitosan and the organic acid
interact and hydroxyalkylated chitosan solutions are
obtained.
[0016] Further, the chitosan solution was coated on
a surface of a substrate, the solvent was caused to
evaporate off by reduced-pressure drying to form a
coating, the substrate was heated at 180°C or higher
for 30 seconds, and the substrate was then immersed
in water. As a result, it was confirmed that even
24 hours later, no changes were visually observed
on the coating and the formed coating became a
waterproof coating.
[0017] The hydroxyalkylated chitosan solution
according to the present invention is characterized
in that the hydroxyalkylated chitosan and the organic
acid are contained in the aprotic polar solvervt.
Preferably, the hydroxyalkylated chitosan for
use in the present invention may have a structure
that an alkylene oxide or oxiranemethanol is added
to the amino group of chitosan, like hydroxyethyl
chitosan, hydroxypropyl chitosan, hydroxybutyl
chitosanorglycerylatedchitosan, and may be produced
by reacting chitosan with the alkylene oxide or
oxiranemethanol. It is, however, to be noted that
the hydroxyalkylated chitosan for use in the present

the present invention, the glycerylatedchitosan will
hereinafter be embraced in the term "hydroxyalkylated
chitosan".
[0020] From the standpoint of the solubility of such
a hydroxyalkylated chitosan in an aprotic polar
solvent, the degree of addition of a corresponding
alkylene oxide or oxiranemethanol to chitosan [the
degree of hydroxyalkylation (nounit) ] may preferably
be 0.2 (mole) or greater but 4 (moles) or less per
pyranose ring (mole of pyranose) . To obtain such
a hydroxyalkylation degree, it is desired to add and
react 0.3 (mole) or greater but 10 (moles) or less
of the alkylene oxide per pyranose ring (mole
pyranose) that makes up chitosan. A hydroxylation
degree of 0.2 or less is insufficient from the
standpoint of the solubility in the aprotic polar
solvent. Even when the hydroxylation degree exceeds
4, on the other hand, the solubility in the aprotic
polar solvent does not change so that the setting
of the hydroxyalkylation degree beyond 4 is
uneconomical.
[0021] In the present invention, no particular
limitation is imposed on the source of chitosan as
a raw material for the hydroxyalkylated chitosan and
the production process of the hydroxyalkylated
chitosan, and chitosan products which have been

industrially manufactured to date are all usable.
Further, no particular limitation is imposed either
on the deacetylation degree or polymerization degree
of chitosan. Preferably, however, the
deacetylation degree of chitos an may be 30% orhigher,
with 70% to 100% being more preferred and 80% to 100%
being still more preferred.
[0022] Preferred as chitosan can be such chitosan that
as an aqueous solution containing the chitosan at
1 wt% and acetic acid at 1 wt%, the viscosity of the
aqueous solution (20°C) ranges from 1 mPa.s to 10,000
mPa.s. A deacetylation degree of lower than 30% is
insufficient from the standpoint of the solubility
of a hydroxyalkylated chitosan, which is available
from a reaction with the corresponding alkylene oxide
or oxiranemethanol, in the aprotic polar solvent.
If the above-described viscosity is lower than 1 mPa-s,
the resulting coating is insufficient in strength.
If the above-described viscosity is higher than 10,00 0
mPa.s, on the other hand, a solution of the resulting
hydroxyalkylated chitosan has an excessively high
viscosity so that the concentration of the
hydroxyalkylated chitosan has to be limited at a very
low level. Therefore, viscosities outside the
above-described range are not preferred.
[0023] Chitosan, which is employed as a raw material

for the hydroxyalkylated chitosan to be used in the
present invention, may more preferably be one having
a deacetylation degree of from 80% to 100% and, as
an aqueous solution containing 1 wt% of the chitosan
and 1 wt% of acetic acid, giving a viscosity of from
3 mPa.s to 100 mPa.s from the standpoints of the
solubility of the chitosan and the strength of the
resulting coating.
[0024] As the organic acid or its derivative for use
in the present invention, those known to date can
each be used, including organic acids such as
salicylic acid, pyromellitic acid, citric acid,
trimellitic acid, malicacid, pyrrolidonecarboxylic
acid, polymaleic acid, phthalic acid, succinic acid
and 1,2,3,4-butanetetracarboxylicacid. Preferred
can be polybasic acids, their acid anhydrides, and
salts of some or all of their carboxyl groups, notably
their ammonium salts and amine salts and alkyl esters,
amides, imides, amide-imides and the like of some
or all of their carboxyl groups. Preferred as
derivatives of these polybasic acids are compounds
which regenerate polybasic acids upon heating of
coatings to be formed subsequently.
More preferably, the polybasic acid can be at
least one acid selected from the group consisting
of pyromellitic acid, citric acid, trimellitic acid,

etc.), carbonates (ethylene carbonate, ethyl methyl
carbonate, diethyl carbonate, dimethyl carbonate,
propylene carbonate, butylene carbonate, etc.),
amides (formamide, N-methylformamide,
N-methylacetamide, N-ethylformamide,
N,N-dimethylformamide, N,N-diethylformamide,
acetamide, N-methylacetamide, N-ethylacetamide,
N,N-dimethylacetamide, N,N-diethylacetamide,
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
piperidone, N-methylpiperidone , N-ethylpiperidone,
hexamethylphosphoric triamide,
1,3-dimethyl-2-imidazolidinone,
methyloxazolidinone, ethyloxazolidinone, etc.),
sulfoxides (dimethyl sulfoxide, etc.), andsulfones
(tetramethylene sulfone, etc.). Among these,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl
sulfoxide are more preferred. With respect to these
aprotic polar solvents, a selection is made as desired
depending on the application. These aprotic polar
solvents may be used either singly or in combination.
[0027] As the organic acid and aprotic polar solvent
for use in the present invention, general commercial
products can be used as they are, or they may be used
after purification as needed. Concerning the

hydroxyalkylated chitosan, one produced by the
above-described process may be used with the reaction
solvent, byproducts and/or the like still contained
therein, or may be used after purification.
[002 8] As the order of addition of the hydroxyalkylated
chitosan and organic acid to the aprotic polar solvent
upon their dissolution in the solvent to prepare the
hydroxyalkylated chitosan solution according to the
present invention, either the hydroxyalkylated
chitosan or the organic acid may be added first or
they may be added at the same time. As their
dissolution method, stirring may be conducted with
heating as needed although stirring at room
temperature is sufficient.
[0029] The existence of water contained in individual
additives to be used as needed and the existence of
water formed when the organic acid is a hydrate or
the like affect neither the hydroxyalkylated chitosan
solution according to the present invention nor the
formation of a coating on a substrate by the solution.
No conditions are thus applied to such water.
[0030] The concentration of the hydroxyalkylated
chitosan in the hydroxyalkylated chitosan solution
according to the present invention may range
preferably from 1 to 40 wt%, more preferably from
5 to 10 wt% from the viewpoints of coating

applicability, transport cost and the like. A
concentration lower than 1 wt% makes it difficult
to obtain a stable coating, while a concentration
higher than 40wt% makes it hard to obtain a homogeneous
solution.
[0031] The hydroxyalkylated chitosan solution
according to the present invention can be used for
coating a substrate as it is. For improving the
applicability to a substrate, however, it is possible
to add an organic substance, such as a cationic
surfactant, a nonionic surfactant or a lipophilic
or hydrophobic organic solvent, an inorganic filler
orthelike. Further, the addition of a preservative,
antimold agent or the like is not particularly
inhibited. In addition, a crosslinking agent other
than an organic acid may also be incorporated in the
hydroxyalkylated chitosan solution as needed.
[0 032] Examples of the crosslinking agent other than
the organic acid include epoxy compounds such as
ethylene glycol diglycidyl ether, polyethylene
glycol diglycidyl ether and glycerol polyglycidyl
ether; isocyanate compounds such as toluylen
diisocyanate, xylylenediisocyanate, hexamethylene
diisocyanate and phenyl diisocyanate, and blocked
isocyanate compounds formed by blocking such
isocyanate compounds with blocking agents such as

phenols, alcohols, active methylene compounds,
mercaptans, acid-amides, imides, amines, imidazoles,
ureas, carbamic acids, imines, oximes or sulfites;
aldehyde compounds such as glyoxal, glutaraldehyde,
and dialdehyde starch; (meth)acrylate compounds such
as polyethylene glycol diacrylate, polyethylene
glycol dimethacrylate and hexanediol diacrylates;
methylol compounds such as methylolmelamine and
dimethylol urea; organic acid metal salts such as
zirconyl acetate, zirconyl carbonate and titanium
lactate; metal alkoxide compounds such as aluminum
trimethoxide, aluminum tributoxide, titanium
tetraethoxide, titanium tetrabutoxide, zirconium
tetrabutoxide, aluminum dipropoxide
acethylacetonate, titanium dimethoxide
bis ( acetylacetonate) and titanium dibutoxide
bis(ethylacetoacetate); carbodiimide compounds;
and the like. The use of such a crosslinking agent
is not essential. When to be employed, however, the
amount of the crosslinking agent may suitably range
from 0.1 to 200 wt% based on the hydroxyalkylated
chitosan.
[0033] The coating process of the present invention
for the substrate comprises the step of causing the
hydroxyalkylated chitosan solution according to the
present invention to adhere onto the surface of the

substrate, and the step of heating the substrate,
which has been obtained in the first-mentioned step,
at not lower than 100°C for at least 1 second. Examples
of the substrate to be coated by the hydroxyalkylated
chitosan solution according to the present invention
include, but are not limited to, glass, ceramics,
plastics, metals, fibers, non-woven products, and
packaging materials (for example, plastic films, and
composite films of aluminum and resins).
[0034] According to the coating process of the present
invention, various substrates on each of which a
coating of a hydroxyalkylated chitosan, said coating
containing an organic acid, is applied can each be
obtained by applying a hydroxyalkylated chitosan
solution onto the substrate by spraying, coating or
impregnation to form a coating and then causing the
solvent to evaporate from the coating until the
content of the solvent in the coating is decreased
to 15% or lower, preferably 5% or lower based on the
weight of the hydroxyalkylated chitosan in the coating.
No particular limitation is imposed on the thickness
of each coating to be formed by the above-described
process, and the thickness of each coating may
generally range from 1 to 500 μm or so. The drying
of the substrate with the hydroxyalkylated chitosan
solution coated thereon may preferably be conducted

under reduced pressure or ambient pressure at a
temperature of the boiling point of the solvent or
higher. To provide the thus-formed coating with
improved waterproofness, the substrate with the
coating formed thereon can be heated preferably at
100°C or higher for 1 second or longer, more preferably
at 150 to 250°C for 1 second to 10 minutes afterdrying.
If the heating temperature is lower than 100°C or
the heating time is shorter than 1 second as a heat
treatment condition, no coating can be obtained with
excellent waterproofness.
[0035] The present invention is useful especially when
the substrate is an aluminum foil or copper foil to
be used for the fabrication of an electrode plate
for a nonaqueous electrolyte secondary battery.
Described specifically, when an active material for
an electrode is added to the above-described solution
of the present invention and a layer of the active
material is formed on a surface of an aluminum foil
or copper foil as a collector, an active material
layer having excellent adhesion to the collector can
be formed.
[0036] It is to be noted that the application of the
hydroxylated chitosan solution according to the
present invention is not limited to the coating of
a substrate by spraying, coating, impregnation or

the like. For example, solid particles containing
the hydroxyalkylated chitosan can be obtained by
drying the hydroxyalkylated chitosan solution in air
by a. method such as spray drying. A film with the
hydroxyalkylated chitosan contained therein can also
be obtained by casting the hydroxyalkylated chitosan
solution on a glass plate and then coating it.
[0037] As has been described above, the
hydroxyalkylated chitosan solution according to the
present invention contains only the hydroxyalkylated
chitosan, organic acid and aprotic polar solvent as
its essential elements, is easy to produce, and is
extremely useful as a coating forming composition,
which is equipped with functionality and
waterproofness, especially for a hydrophobic or
lipophilic substrate surface or metal article surface
the coating of which with an aqueous solution of
chitosan or the like has heretofore been difficult.
Examples
[0038] The present invention will next be described
more specifically based on Examples and Comparative
Examples . It is tobe noted that the present invention
shall not be limited by these Examples.
Chitosan>

The compositions of individual glycerylated
chitosan solutions employed in the Examples and
Comparative Examples are shown in Table 1 . Examples
14-16 are all directed to the same composition, but
the composition is repeatedly described because
conditions in the coating process of the present
invention were different. The expression
"viscosity of 1% raw chitosan solution" in the table
indicates the viscosity of a 1 wt% acetic acid solution
containing 1 wt% of chitosan as a raw material for
the corresponding glycerylated chitosan (viscosity
measuring method : measured by a Brookfield rotational
viscometer under the conditions consisting of a
measuring temperature of 20°C and a measuring rotation
speed of 30 rpm) . Concerning aprotic polar solvents
used in the respective glycerylated chitosan
solutions, the following abbreviations are used: NMP
(N-methyl-2-pyrrolidone), DMF
(N,N-dimethylformamide) , DMSO (dimethylsulfoxide) ,
DMAC (N,N-dimethylacetamide), and DMI
(1,3-dimethyl-2-imidazolidinone).
[0039] Example 1
Dispersed in NMP (80 parts by weight) was
glycerylated chitosan (deacetylation degree of raw
chitosan: 83%; 10 parts by weight) . After salicylic
acid (10 parts by weight) was added to the dispersion,

the resulting mixture was stirred at room temperature
for 4 hours to effect dissolution. After the
thus-prepared solution was allowed to stand overnight,
it was again stirred at room temperature for 1 hour
to effect dissolution so that a glyceryl chitosan
solution (100 parts by weight) was prepared.
[0040]Examples 2-21
In a similar manner as in Example 1, glycerylated
chitosan solutions according to the present invention were
each prepared with the viscosity of an aqueous 1 wt% acetic
acid solution containing the raw chitosan for the
corresponding glycerylated chitosan, the glycerylation
degree and weight of the glycerylated chitosan, the kind
and weight of the organic acid, the mixing ratio of the
glycerylated chitosan to the organic acid and the kind and
weight of the aprotic polar solvent being changed as shown
in Table 1. The deacetylation degree of the raw chitosan
employed was 83%. It is to be noted that, when it was difficult
to dissolve the glycerylated chitosan by stirring at room
temperature, stirring was conducted with heating to prepare
the solution.
[0041] Preparation procedures of the various solutions
employed as the Comparative Examples will be described
hereinafter.
Comparative Example 1
Comparative Example 1 is directed to the use of chitosan

not subjected to a glycerylation reaction (deacetylation
degree: 85%, glycerylation degree: 0, viscosity of anaqueous
1 wt% acetic acid solution containing the chitosan at 1 wt%:
6 mPa.s; hereinafter simply called "the chitosan"). The
chitosan (5 parts by weight) was dispersed in NMP (90 parts
by weight) . Subsequent to the addition of pyromellitic acid
(5 parts by weight) , the thus-obtained mixture was stirred
at room temperature for 4 hours, but the chitosan was not
dissolved at all. The NMP was then heated to 80°C, at which
stirring was conducted for 2 hours. However, the chitosan
was not dissolved at all, and therefore, no chitosan NMP
solution was obtained.
[ 0042]Comparative Example 2
Comparative Example 2 is directed to the preparation
of a solution without using any organic acid. Glycerylated
chitosan (deacetylation degree of raw chitosan: 83%; lOparts
byweight) was dispersed in NMP (90 parts by weight), followed
by stirring at room temperature for 4 hours. After the
resultant dispersion was allowed to stand overnight, it
was again stirred at room temperature for 1 hour to
effect dissolution so that a glyceryl chitosan
solution (100 parts by weight) was prepared.
[ 0043]Comparative Example 3
Dispersed In NMP (90 parts by weight) was
glycerylated chitosan (deacetylation degree of raw
chitosan: 85%; 5 parts by weight). After

pyromellitic acid (5 parts by weight) was added to
the dispersion, the resulting mixture was stirred
at room temperature for 4 hours to effect dissolution.
After the thus-prepared solution was allowed to stand
overnight, it was again stirred at room temperature
for 1 hour to effect dissolution so that a glyceryl
chitosan solution (100 parts by weight) wasprepared.

[0046] On coatings obtained by using the individual
glycerylated chitosan solutions prepared in
accordance with the compositions shown in Table 1
and by following the below-described coating forming
method, a waterproofness evaluation test was
performed. The evaluation results are shown in Table
2.
[0047 ]
On surfaces of stainless steel sheets (SUS304, 1 mm
thick x 10 cm long x 10 cm wide) which had not been subjected
to any pretreatment such as degreasing treatment, the various
solutions of Examples 1-21 and Comparative Examples 2 and
3 were coated by a bar coater to give dry coat weights of
2 g/m2, respectively. Under the conditions shown in Table
2, drying was then conducted. The thus-coated stainless
steel sheets were provided as specimens to be used in the
following evaluation test.
[0048]
Each specimen was immersed for 24 hours in purified
water, and was then dried under heat for 1 hour in a fan
dryer controlled at 105°C. After being allowed to cool down
to room temperature, its weight was measured, and in
accordance with the following formula, the percent residue
of its coating was determined.
(C - A)/(B - A) x 100 (%)
where,

A: Weight of a stainless steel sheet before coating
a solution,
B: Weight of the stainless steel sheet after coating
and drying the solution, and
C: Weight of the stainless steel after immersing,
subsequent to the coating and drying of the solution,
the stainless steel for 24 hours in water and then
conducting drying again.
[0049]
The waterproofness of each coating was evaluated in
4 stages based on the value obtained in accordance with the
above-described formula. The evaluation method was as
follows:
A: Percent residue of coating  95%
B: 95% > percent residue of coating  80%
C: 80% > percent residue of coating  50%
D: 50% > percent residue of coating

[0052] As is evident from the above results of Table
2, the results of the waterproofness evaluations of
the coatings formed using the glycerylated chitosan
solutions according to the present invention were
good. Comparative Example 1 is directed to the
illustrative use of chitosan in place of a
glycerylated chitosan. The chitosan was not
dissolved in NMP so that no solution was successfully
prepared. In Comparative Example 2 , the NMP solution
was prepared using the glycerylated chitosan of the
high degree of substitution (glycerylation degree:
3.2) without using any organic acid. The coating
formed from the solution was not equipped with any
waterproofness . In Comparative Example 3, the
coating was formed using a vacuum dryer without
heated-air drying at high temperatures . Asaresult,
the waterproofness of the coating was poor.
[0053] To evaluate the pot lives of the above-described
glycerylated chitosan solutions, portions of the
individual solutions of Examples 1-21 (the solutions
of Examples 14-16 were the same) were stored in a
room (20to28°C) and in a constant-temperature chamber
(50°C), respectively, to observe any changes with
time in the solution forms. Even after an elapsed
time of 3 months or longer, all of the solutions neither
increased in viscosity nor formed a gel, and therefore,

were usable for coating substrates.
[0054] Example 22
Onto a polyimide film of 50 μm thickness (10 cm x 5
cm), the 5 wt% glycerylated chitosan solution of Example
14 (solution viscosity: 174mPa-s) was coated by a bar coater.
Repelling of the NMP solution was not observed at all, and
uniform coating was feasible onto the polyimide film the
surface of which was hydrophobic.
[ 0055]Comparative Example 4
Onto a polyimide film of 50 μm thickness (10 cm x 5
cm), a 5 wt% aqueous solution (solution viscosity: 186mPa.s)
of citric acid, said solution containing 5 wt% of chitosan,
was coated by a bar coater. The aqueous solution was repelled.
It was, therefore, unable to uniformly coat the aqueous
solution onto the polyimide film.
[0056]Examples 23-25
In Table 3, the compositions of individual
hydroxyalkylated chitosan solutions employed as Examples
23-25 are shown. The abbreviations of the aprotic polar
solvents used in the individual hydroxyalkylated chitosan
solutions are as defined above. The production of the
hydroxyalkylated chitosans was conducted in a manner known
perse in the art. The raw chitosan for the hydroxyalkylated
chitosans was the same as that employed above in Example
6.

[0058] On coatings obtained by using the
hydroxyalkylated chitosan solutions described in
Table 3 and following the same coating forming method
as in the case of the glycerylated chitosans, a
waterproofness evaluation test was performed in a
similar manner as described above. The evaluation
results are shown in Table 4.

[0060] As is evident from the above results of Table
4, the results of the waterproofness evaluations of
the coatings formed using the glycerylated chitosan
solutions according to the present invention were
good.
[ 0061 ]
Application Example 1 (Coating formulation,
electrode plate)
A positive-electrode coating formulation
employed in this Example and containing a positive
electrode active material was prepared by the
procedure to be described hereinafter. As materials
for the positive-electrode coating formulation,
LiCoO2 powder having particle sizes of from 1 to 100
μm/ acetylene black as a conductive aid and the
solution of Example 14 described above in Table 1
were stirred and mixed at a mixing ratio of 90 parts
by weight, 5 parts by weight and 50 parts by weight
at a rotation speed of 60 rpm for 120 minutes in a
planetary mixer to obtain a slurry-form,
positive-electrode coating formulation with the
positive-electrode active material contained
therein.
[0062] Using the positive-electrode coating
formulation obtained as described above and employing,
as a substrate, a collector formed of a 20-μm thick

aluminum foil, the positive-electrode coating
formulation was applied on one side of the substrate
by a "COMMA ROLL COATER". The thus-coated substrate
was then dried for 2 minutes in an oven controlled
at 110°C, and was further dried for 2 minutes in the
oven controlled at 150°C to eliminate the solvent
and to have the binder crosslinked, so that a positive
electrode plate with an active material layer formed
with a dry thickness of 100 μm on the collector was
obtained. The positive electrode plate obtained by
the above-described procedure was pressed under
conditionsof 5, 000 kgf/cm2 to make the coating uniform.
Subsequently, aging was conducted for 48 hours in
a vacuum oven controlled at 80°C to completely
eliminate volatiles (the solvent, the unreacted
polybasic acid, etc.).
[0063] Parallel lines, which consisted of
perpendicularly-intersecting 11 vertical lines and
11 horizontal lines, were drawn by a cutter at
intervals of 1 mm on the active material layer to
form 100 squares within 1 cm2. A mending tape was
applied to the surface of the active material layer,
and tape peeling was then conducted. The number of
squares which were not peeled off was counted as a
measure of adhesiveness. The average of 10 tests
was 98.0 squares. Further, the conditions of the

active material layer were observed after the
electrode plate with the squares formed thereon as
described above was immersed at 50°C for 24 hours
in a mixed solvent of EC (ethylene carbonate), PC
(propylene carbonate) and DME (dimethoxyethane)
combined together at a volume ratioof 1:1:2. Neither
peeling nor swelling of the active material layer
was recognized.
[0064]Application Example 2 (Coating formulation,
electrode plate)
A negative-electrode coating formulation
employed in this Example and containing a
negative-electrode active material was prepared by
the procedure to be described next. Carbon powder
obtainedby thermal degradation of coal coke at l,200°C,
acetylene black as a conductive aid and the solution
of Example 8 described above were stirred and mixed
at a mixing ratio of 90 parts by weight, 5 parts by
weight and 50 parts by weight at a rotation speed
of 60 rpm for 120 minutes in the planetary mixer to
obtain a slurry-form coating formulation with the
negative-electrode active material contained
therein.
[0065] The coating formulation containing the
negative-electrode active material and obtained as
described above was applied onto a copper-foil

collector by using the "COMMA ROLL COATER". After
the thus-coated collector was processed through a
drying step, it was dried for 2 minutes in the oven
controlled at 110°C, and was further dried for 2
minutes in the oven controlled at 150°C to eliminate
the solvent and to have the binder crosslinked, so
that an active material layer was formed with a dry
thickness of 100 μm on the collector. A negative
electrode plate obtained by the above-described
procedure was pressed under conditions of 5,000
kgf/cm2 to make the coating uniform. Subsequently,
aging was conducted for 48 hours in a vacuum oven
controlled at 80°C to completely eliminate volatiles
(the solvent, the unreacted polybasic acid, etc.).
[0066] Parallel lines, which consisted of
perpendicularly-intersecting 11 vertical lines and
11 horizontal lines, were drawn by a cutter at
intervals of 1 mm on the active material layer to
form 100 squares within 1 cm2. A mending tape was
applied to the surface of the active material layer,
and tape peeling was then conducted. The number of
squares which were not peeled off was counted as a
measure of adhesiveness. The average of 10 tests
was 96 squares. Neither peeling nor swelling of the
active material layer was recognized.
[0067]Application Example 3 (Battery)

An electrode unit was first formed by using
the positive-electrode plate and negative-electrode
plate, which had been obtained above in Application
Example 1 and Application Example 2, respectively,
and rolling them into a volute form with a separator
interposed therebetween. The separator was made of
a porous polyolefin (polypropylene, polyethylene or
a copolymer thereof) film having a width broader than
the positive-electrode plate and a three-dimensional
porous (spongy) structure. The electrode unit was
then inserted into a bottomed cylindrical, stainless
steel can, which would also serve as a
negative-electrode terminal, so that a battery of
the AA size and 500 mAh rated capacity was assembled.
Charged as an electrolyte into the battery was a
solution of 1 mole of LiPF6 as a supporting salt in
a mixed solvent prepared by combining EC (ethylene
carbonate), PC (propylene carbonate) and DME
(dimethoxyethane) at a volume ratio of 1:1:2 to give
a total volume of 1 liter.
[0068] Forthe measurement of battery characteristics,
a charge-discharge measuring instrument was used.
Twenty (20) batter ies we re charged at the temperature
condition of 25°C and the current value of a 0.2 CA
charging current, firstly in a charging direction
until a battery voltage reached 4.1V. After a break

of 10 minutes, the cells were discharged by the same
current until 2.75 V was reached. Subsequent to a
break of 10 minutes, charging and discharging were
then repeated 100 cycles under the same conditions
to measure charge-discharge characteristics. When
the charge-discharge capacity in the 1st cycle was
assumed to be 100, the charge-discharge capacity in
the 100th cycle was 96.
Industrial Applicability
[0069] The hydroxyalkylated chitosan solution
according to the present invention is easy to produce,
and is extremely useful as a coating composition
capable of applying a coating, which is equipped with
functionality and waterproofness, to a hydrophobic
or lipophilic surface the coating of which with an
aqueous solution has heretofore been difficult. It
is also useful as a binder upon fabrication of
electrode plates for batteries.

CLAIMS
[1] A hydroxyalkylated chitosan solution
comprising an aprotic polar solvent, a
hydroxyalkylated chitosan, and an organic acid or
a derivative thereof.
[2] The solution of claim 1, wherein said aprotic
polar solvent is at least one solvent selected from
the group consisting of N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, and dimethyl
sulfoxide .
[3] The solution of claim 1, wherein said organic
acid is a polybasic acid.
[4] The solution of claim 3, wherein said polybasic
acid is at least one acid selected from the group
consisting of pyromellitic acid, citric acid,
trimellitic acid, malic acid, polymaleic acid,
phthalic acid, and succinic acid.
[5] The solution of claim 1, wherein said organic
acid or said derivative thereof is used in an amount
of from 20 to 300 parts by weight per 100 parts by
weight of said hydroxyalkylated chitosan.
[6] The solution of claim 1, wherein said
hydroxyalkylated chitosan is contained at a
concentration of from 1 to 40 wt%.

[7] The solution of claim 1, wherein said
hydroxyalkylated chitosan has a hydroxyalkylation
degree of at least 0.2.
[8] The solution of claim 1, wherein said
hydroxyalkylated chitosan is a hydroxyalkylation
product of chitosan, said chitosan has a
deacetylation degree of at least 30%, and, when said
chitosan is dissolved at a concentration of 1 wt%
in a 1 wt% aqueous solution of acetic acid, a resulting
solution has a viscosity of from 1 mPa-s to 10,000
mPa.s .
[9] A coating process of a substrate, which
comprises a step of causing a hydroxyalkylated
chitosan solution according to any one of claims 1-8
to adhere ontoa surface of said substrate, andanother
step of heating said substrate, which has been
obtained in the first-mentioned step, at not lower
than 100°C for at least 1 second.
[10] The process of claim 9, wherein said
hydroxyalkylated chitosan solution comprises
organic or inorganic particles and said substrate
is a metal article.

This invention relates to hydroxyalkylated chitosan solution
characterized in that a hydroxyalkylated chitosan and an organic
acid or its derivative are contained in an aprotic polar solvent.
This invention also relates to a coating process of a substrate,
which is characterized by a step of causing the hydroxylalkylated
chitosan solution to adhere onto a surface of the substrate,
and another step of heating the substrate, which has been
obtained in the first-mentioned step, at 100°C or higher
for 1 second or longer. This invention can provide a
one-pack solution of a chitosan derivative, which is free
from crosslinking and stable at room temperature, can form
a chitosan coating excellent in waterproofness after heated
and dried, and is suited for the coating of a hydrophobic
or lipophilic surface. This invention also provides a
coating process of a substrate, which makes use of the
one-pack solution.

Documents:

02888-kolnp-2008-abstract.pdf

02888-kolnp-2008-claims.pdf

02888-kolnp-2008-correspondence others.pdf

02888-kolnp-2008-description complete.pdf

02888-kolnp-2008-form 1.pdf

02888-kolnp-2008-form 2.pdf

02888-kolnp-2008-form 3.pdf

02888-kolnp-2008-form 5.pdf

02888-kolnp-2008-international publication.pdf

02888-kolnp-2008-others pct form.pdf

02888-kolnp-2008-pct request form.pdf

2888-KOLNP-2008-(05-01-2012)-ABSTRACT.pdf

2888-KOLNP-2008-(05-01-2012)-CLAIMS.pdf

2888-KOLNP-2008-(05-01-2012)-CORRESPONDENCE.pdf

2888-KOLNP-2008-(05-01-2012)-DESCRIPTION (COMPLETE).pdf

2888-KOLNP-2008-(05-01-2012)-FORM-1.pdf

2888-KOLNP-2008-(05-01-2012)-FORM-2.pdf

2888-KOLNP-2008-(10-07-2012)-CORRESPONDENCE.pdf

2888-KOLNP-2008-ABSTRACT.pdf

2888-KOLNP-2008-AMANDED CLAIMS.pdf

2888-KOLNP-2008-CORRESPONDENCE 1.2.pdf

2888-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

2888-KOLNP-2008-CORRESPONDENCE-1.3.pdf

2888-KOLNP-2008-DESCRIPTION (COMPLETE).pdf

2888-KOLNP-2008-EXAMINATION REPORT REPLY RECIEVED.pdf

2888-KOLNP-2008-EXAMINATION REPORT.pdf

2888-KOLNP-2008-FORM 1.pdf

2888-KOLNP-2008-FORM 18-1.2.pdf

2888-kolnp-2008-form 18.pdf

2888-KOLNP-2008-FORM 2.pdf

2888-KOLNP-2008-FORM 26.pdf

2888-KOLNP-2008-FORM 3-1.1.pdf

2888-KOLNP-2008-FORM 3.pdf

2888-KOLNP-2008-FORM 5.pdf

2888-KOLNP-2008-GRANTED-ABSTRACT.pdf

2888-KOLNP-2008-GRANTED-CLAIMS.pdf

2888-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

2888-KOLNP-2008-GRANTED-FORM 1.pdf

2888-KOLNP-2008-GRANTED-FORM 2.pdf

2888-KOLNP-2008-GRANTED-SPECIFICATION.pdf

2888-KOLNP-2008-INTERNATIONAL EXM REPORT.pdf

2888-KOLNP-2008-INTERNATIONAL SEARCH REPORT.pdf

2888-KOLNP-2008-OTHERS-1.1.pdf

2888-KOLNP-2008-OTHERS.pdf

2888-KOLNP-2008-PA.pdf

2888-KOLNP-2008-PETITION UNDER RULE 137.pdf

2888-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf

2888-KOLNP-2008-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

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Patent Number

253641

Indian Patent Application Number

2888/KOLNP/2008

PG Journal Number

32/2012

Publication Date

10-Aug-2012

Grant Date

08-Aug-2012

Date of Filing

16-Jul-2008

Name of Patentee

DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD.

Applicant Address

7-6-, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO

Inventors:

#	Inventor's Name	Inventor's Address
1	SANNAN, TAKANORI	C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD 7-6-, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383
2	TSUCHIDA, SHINYA	C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD 7-6-, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383
3	KOBAYASHI, NOBUYUKI	C/O DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD 7-6-, NIHONBASHI BAKURO-CHO 1-CHOME, CHUO-KU, TOKYO 103-8383

PCT International Classification Number

C08L 5/08,B05D 7/14

PCT International Application Number

PCT/JP2006/325237

PCT International Filing date

2006-12-19

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2006-016554	2006-01-25	Japan
2	2006-213775	2006-08-04	Japan