JP2003206409A - Thermally crosslinkable composition, aqueous solution composition and composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermally crosslinkable composition which is preservable at a normal temperature for one month or more even in a mixed state and after heat treatment under a fixed condition once, forms a coating film having excellent antimicrobial properties and water resistance on the surface of a substrate. <P>SOLUTION: This thermally crosslinkable composition comprises a polymer containing a hydroxy group and/or an amino group and a polybasic acid as essential components (with the proviso that a combination of glycerylated chitosan and 1,2,3,4-butanetetracarboxylic acid is omitted). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat-crosslinkable composition containing a polymer having a hydroxyl group and / or an amino group and a polybasic acid as essential components, and an aqueous solution composition obtained by dissolving the composition in an aqueous medium. And a composite material comprising a base material and a crosslinked product of the above composition.

[0002]

It is well known that chitosan itself has antibacterial properties. Also, compared to chitosan, 3
It is also known that the antibacterial properties of chitosan derivatives having a quaternary and / or quaternary amino group (hereinafter simply referred to as “cationized chitosan”) are further increased.

Therefore, many attempts have been made to impart this cationized chitosan to fibers to make them antimicrobial fibers. The problem here is that cationized chitosan is more water-soluble than chitosan, so that the treated fiber after treating the fiber with the cationized chitosan has insufficient water resistance and satisfactory wash fastness can be obtained. There was nothing. Further, although chitosan is more excellent in water resistance than cationized chitosan, its water resistance is not always practically sufficient.

For this reason, various crosslinking agents have been proposed in order to improve the wash fastness of chitosan or cationized chitosan. However, depending on the type of crosslinking agent and the crosslinking method, chitosan or an intrinsic antibacterial agent may be used. Even if cationized chitosan is used, the cross-linked product often does not exhibit antibacterial properties, and it is difficult to achieve both improvement in water resistance and retention of antibacterial properties.

Further, a conventional crosslinking method is disclosed in JP-A-11-2.
As disclosed in Japanese Patent No. 47067, cross-linking by a two-liquid type of a liquid containing a cationized chitosan and a liquid containing a cross-linking agent is almost the case, and in this case, the operation in fiber treatment requires two steps.

On the other hand, in JP-A No. 12-219605, the crosslinked product exhibits sufficient antibacterial properties, and also in the treatment thereof, a cationized chitosan solution is mixed with a crosslinker solution in advance to form fibers. Although the treatment is carried out in one step, generally, the pot life of the mixed liquid of the cationized chitosan liquid and the cross-linking agent liquid is short, and it is necessary to mix and adjust the two liquids for each treatment. I can't save. In addition, since insoluble substances remain in the processing machinery after the processing operation,
Early and careful cleaning of the processing machinery was required.

Various cross-linking agents have been studied so far in order to solve the above problems, but until now, a cationized chitosan solution and a cross-linking agent were mixed to form one solution, which can be stored at room temperature for one month or more, No effective cross-linking agent has been found that exhibits sufficient water resistance and washing fastness without losing the original antibacterial property once treated under certain conditions.

[0008]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is a view that at room temperature, it does not essentially undergo a crosslinking reaction with chitosan or cationized chitosan, and is stable and strongly crosslinks under certain conditions. We have found a cross-linking agent that has contradictory functions and that does not lose antibacterial properties even after cross-linking, and its cross-linking conditions. One-part type self-crosslinking composition, and an aqueous solution composition comprising the composition.

[0009]

The present invention comprises chitosan or cationized chitosan and polybasic acid as essential components, and removes a part or all of the water content of an aqueous solution composition obtained by dissolving this in an aqueous medium. It was found that an antibacterial and water-resistant molded product can be formed after heating or by heating while removing water.

Furthermore, based on the above findings, hydroxyl groups and /
Alternatively, a polymer having an amino group (hereinafter simply referred to as “OH / N
H ₂ polymer ”) and polybasic acid as essential components,
Regarding an aqueous solution composition obtained by dissolving this in an aqueous medium, extensively studying heating after removing some or all of the water content of the aqueous solution composition or while removing the water content, OH / NH _{It was found that the two} polymers and the cross-linking agent were mixed to form one liquid, which can be stored at room temperature for one month or more, and once obtained, after the treatment under certain conditions, the water-resistant material that was originally intended can be obtained.

Further, the obtained OH / NH ₂ polymer and the polybasic acid heating product not only retain water resistance significantly in practical use, but the OH / NH ₂ polymer is essentially It has been found to retain the functionality it has without losing it. Further, they have found that by applying the heat-crosslinkable composition of the present invention to various base materials, various base materials can be imparted with water resistance and various functions specific to the trunk polymer very easily, and the present invention has been completed. .

Accordingly, the present invention provides a heat-crosslinkable composition characterized by containing an OH / NH ₂ polymer and a polybasic acid as essential components. The above OH / NH ₂ polymer
It is soluble in water having a pH of 1 to 14 or an aqueous medium containing water and an organic solvent at 100 ° C. or lower; OH / NH ₂ polymer is a polysaccharide, polyamino acid, polyvinyl alcohol, polyallylamine, polyvinylamine, polyamidine or polyethylene. Imine or a derivative thereof, or a mixture thereof; the polymer is a carboxylated product, a glycolated product, a tosylated product, a sulfated product, a phosphorus oxide, an etherified product, or an alkylated product of the polymer; The introduction rate is 0.1 to 6 per monomer unit of the polymer; and the polymer has a tertiary and / or quaternary amino group (hereinafter simply referred to as "cation group") or a salt group thereof. preferable.

In the present invention, the polymer is introduced with a cationic group into the trunk polymer by reacting the trunk polymer with a compound represented by the following formula (1) or (2), or the polymer is The above heat-crosslinkable composition, which is a polymer having a cationic group obtained by alkylating the amino group with a compound represented by the following formula (3), when it originally has an amino group, is provided.

[0014]

Further, the compound of the formula (2) is 2,3-
Epoxypropyltrimethylammonium chloride; Polysaccharide is alginic acid, starch, cellulose, chitin, chitosan or pectin; Polyamino acid is polylysine, polyornithine, polyarginine,
Polyhistidine, protamine, gelatin or collagen; the polymer is at least one selected from the group consisting of chitosan, hydroxyalkyl chitosan, polyvinyl alcohol and chitosan having a cationic group; polybasic acid is 3 bases Acid, 4 basic acid or 5 basic acid or a mixture thereof; polybasic acid is ethylenediaminetetraacetic acid, 1,2,3,4
- It is butane tetracarboxylic acid or citric acid, or mixtures thereof; mass ratio of OH / NH ₂ polymer and a polybasic acid, 1: it is 0.01 to 6; and O
Weight average molecular weight of H / NH ₂ polymer (measured by GPC,
Standard Pullulan conversion) (hereinafter simply referred to as "MW")
It is preferably 5,000 to 2,000,000.

In the present invention, the above-mentioned OH / NH ₂ polymer and polybasic acid are contained as essential components, and these are dissolved in an aqueous medium, and after removing a part or all of the water or removing the water. Provided is an aqueous solution composition, which is capable of forming a water resistant film by heating while removing.

Solid content concentration of the above OH / NH ₂ polymer and polybasic acid is 0.1 to 50% by mass;
It is preferable that the OH / NH ₂ polymer further contains a nonionic organic compound and / or a surfactant in a mass ratio of 1 to 50%; and the pH of the aqueous solution is preferably 7 or less.

The present invention also comprises a method for producing a crosslinked product, which comprises heating the composition to 80 ° C. or higher, and carrying out the crosslinking on a substrate to integrate the substrate and the crosslinked product. A composite material characterized by the above. The base material is a metal such as aluminum or iron, glass, natural resin, synthetic resin,
It is preferably ceramics, paper, fibers, woven cloth, non-woven cloth or leather.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Next, preferred embodiments will be given.
The present invention will be described in more detail. The present invention is OH / NH
₂The polymer and polybasic acid are essential components, and both are heated.
React and crosslink. Therefore, before heating, both
It is preferable that they are uniformly mixed in terms of reaction efficiency.
Therefore, OH / NH used in the present invention ₂Poly
As a mer, the OH / NH₂Polymer pH 1-14
100 parts of water or an aqueous medium containing an organic solvent
It is desirable that it be soluble at or below ° C.

Examples of the above-mentioned polymers include polysaccharides, polyamino acids, polyvinyl alcohol, polyallylamine, polyvinylamine, polyamidine or polyethyleneimine or their derivatives, or a mixture thereof.

Examples of the above-mentioned polymer derivatives which are soluble in water having a pH of 1 to 14 or a medium containing water and an organic solvent include carboxylated products, glycolized products of the polymers,
Examples thereof include tosylated products, sulfated products, phosphorus oxides, etherified products, alkylated products and salts thereof.

Among the polysaccharides, polyamino acids, polyvinyl alcohol, polyallylamine, polyvinylamine, polyamidine or polyethyleneimine or their derivatives, the polysaccharide has the advantage of being a natural product or derived from a natural product. In particular, among the polysaccharides, alginic acid, starch, cellulose, chitin, chitosan and pectin are preferable because they are easily available in large quantities.

Among them, chitin, chitosan, cellulose or derivatives thereof are particularly preferable, and chitosan, chitosan derivatives, cationized chitosan or salts thereof (hereinafter sometimes simply referred to as “chitosans”) are most preferable. Is. For example, chitosan itself has various unique functions such as antibacterial property, and the chitosan has good crosslinkability with the polybasic acid used in the present invention. There are many advantages such as interaction with the substrate for carrying out the invention, such as fiber, metal and glass, for example, good adhesion. However, the present invention is not limited to these, and OH
There is no special limitation on the / NH ₂ polymer, and it is also a feature of the present invention that it can be widely used.

Polyvinyl alcohol preferably used as the OH / NH ₂ polymer in the present invention (hereinafter simply referred to as "P
"VA") is a widely used polymer, and any polymer produced by a conventionally known method can be used, but the production method, the degree of polymerization, the degree of saponification, etc. are not limited. It may also be a copolymer with another monomer.

As the polyallylamine, polyvinylamine, polyethyleneimine, or polyamidine used in the present invention, any of those produced by a conventionally known method can be used, and the production method and the degree of polymerization are not limited. It may also be a copolymer with another monomer.

The polyamino acid may be a natural product or a synthetic product. Examples thereof include polylysine, polyornithine, polyarginine, polyhistidine, protamine, gelatin, collagen and the like.

The polysaccharide used in the present invention may be a natural product or a synthetic product. Naturally occurring polysaccharides include seaweed-derived alginic acid, potato starch, cotton cellulose,
Examples thereof include chitosan derived from crustaceans. For example, an example of chitosan used in the present invention is obtained by deacetylating chitin existing in the crustaceans of crabs and shrimps, which is a well-known material per se, and various types of Various degrees of acetylation and various MW are easily available from the market and can be easily produced. In the present invention, any of these known chitosans can be used.

When a polymer having an amino group in the molecule, such as polyvinylamine, polyamidine, chitosan, or a cellulose derivative, is used, an acid is added to the polymer to cause a salt-forming reaction with the amino group to increase the antibacterial property,
It is also well known to increase water solubility. Also in the present invention, salts of these polymers can be used.

The acid used for the salt formation may be any acid as long as it has a certain degree of solubility in an aqueous medium, for example, hydrochloric acid, formic acid, acetic acid, propionic acid, butyric acid,
Taurine, pyrrolidonecarboxylic acid, citric acid, malic acid, lactic acid, hydroxymalonic acid, malonic acid, succinic acid,
Adipic acid, benzoic acid, salicylic acid, aminobenzoic acid,
Examples thereof include organic acids such as phthalic acid and vitamin C.
Particularly preferred are naturally occurring organic acids such as lactic acid, malic acid and citric acid.

The amount of such an acid used cannot be unconditionally specified because it varies depending on the deacetylation degree of chitosan, the basicity of polyvinylamine and polyamidine, and the equivalent of acid, but in short, the produced polyvinylamine, A salt with an acid such as polyamidine, chitosan, and a cellulose derivative is an amount that can maintain water solubility. Generally, the amount of the acid used is about 0 per one amino group in polyvinylamine, polyamidine, chitosan, and a cellulose derivative. ．
It is in the range of 8 to 2 mol.

Methods and conditions for synthesizing carboxylates, glycolates, tosylates, sulfates, phosphorus oxides, etherified products, alkylated products of polysaccharides, polyamino acids, PVA, polyallylamine, polyvinylamine, polyamidine or polyethyleneimine are also conventionally known. Either method can be applied. In this case, the introduction rate of the substituent is preferably 0.1 to 6 per monomer unit constituting the polymer. If it is less than 0.1, the characteristics of the introduced group may not be clearly exhibited, and if it is more than 6, crosslinking of the polymer may be insufficient.

The polymer having a cationic group can be easily obtained by reacting the trunk polymer with a compound represented by the following formula (1) or the following formula (2). In the case of a polymer having an amino group originally, the amino group can be alkylated with a compound represented by the following formula (3) to give a polymer having a cation group. The reaction method and conditions in this case may be any conventionally known methods and conditions.

[0033]

Examples of the compound represented by the formula (1) include 2-chloroethyldiethylamine or its hydrochloride, 3-chloro-2-hydroxypropyldiethylamine and 2,3-epoxypropyldimethylamine. Examples of the compound represented by (2) include 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-epoxypropyltrimethylammonium chloride. In particular, epoxy compounds such as 2,3-epoxypropyldimethylamine and 2,3-epoxypropyltrimethylammonium chloride are advantageous in that they do not form a salt during the reaction. The latter has stronger antibacterial activity than the former, and the latter is selected particularly when the composition of the present invention aims at antibacterial.

The reaction of the compound represented by the formula (1) or (2) with the above-mentioned polymer may be carried out by a conventionally known method. For example, in the case of chitosan, it is composed of 60 to 100 mol% of deacetylated chitin. 2,3-Epoxypropyltrimethylammonium chloride was added to chitosan at an appropriate ratio in hydrous isopropyl alcohol, and the mixture was added at 50 ° C. for 6 hours.
The desired cationized chitosan is obtained by the addition reaction for a time. At this time, a catalyst such as sodium hydroxide may be used to improve the introduction rate of the cationic group. Here, the starting material chitosan is not particularly limited in its deacetylation degree and MW, and can be freely selected depending on the purpose of use.

Furthermore, these cationized chitosans are
It does not necessarily have to be isolated as a pure substance and may contain some by-products and unreacted substances generated by the above reaction, and may be in the form of powder or aqueous solution. Among the polymers having a cation group, cationized chitosan or cationized cellulose derivative is advantageous in terms of safety and crosslinkability.

In particular, the introduction rate of the cation groups of the cationized chitosan or cationized cellulose derivative used is preferably in the range of 0.1 to 6 per sugar unit. If the introduction rate is 0.1 or less, the antibacterial property becomes weak, and 6
In order to introduce the above, more severe reaction conditions are required, but this does not lead to a corresponding improvement in antibacterial properties.

In the case of chitosans, the MW of the polymer is preferably 5,000 or more, more preferably 30,000 to 1,000,000. When the MW is less than 5,000, the strength of the film formed from the composition of the present invention is insufficient, while when it exceeds 1 million, the viscosity of the aqueous solution composition of the present invention becomes too high, and the aqueous solution composition There is no choice but to keep the concentration of chitosans in the product extremely low.

As the polybasic acid used as a crosslinking agent for the various polymers as described above, a tribasic acid, a tetrabasic acid or a pentabasic acid is preferable. Crosslinking may be insufficient with a dibasic acid, and cost may be disadvantageous with a dibasic acid or more.
Examples of polybasic acids include the following.

<Dibasic acid> Oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, methylglutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, itaconic acid, muconic acid, citraconic acid, glutaconic acid, acetylenedicarboxylic acid, tartaric acid, malic acid, spiculisporic acid, glutamic acid, glutathione, aspartic acid, cystine, Acetylcystine, diglycolic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, thiodiglycolic acid, thionyldiglycolic acid, sulfonyldiglycolic acid, polyethylene oxide diglycolic acid (PEG acid), pyridinedicarboxylic acid, pyrazinedicarboxylic acid, epoxy Succinic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, naphthalenedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanedicarboxylic acid, diphenyls Honjikarubon acid, diphenylmethane dicarboxylic acid, sulfuric acid

<3 basic acid> Citric acid, isocitric acid, aconitic acid, propanetricarboxylic acid, butanetricarboxylic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, carboxyethylthiosuccinic acid, trimellitic acid, trimesic acid, cyclohexanetricarboxylic acid Acid, naphthalene tricarboxylic acid

<4 basic acid> ethylenediaminetetraacetic acid, ethylenediamine N, N'-succinic acid, 1,2,
3,4-butanetetracarboxylic acid, pentenetetracarboxylic acid, hexenetetracarboxylic acid, glutamic acid diacetic acid, maleated methylcyclohexenetetracarboxylic acid, furantetracarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, phthalocyaninetetracarboxylic acid, Monocyclic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid and cyclopentanetetracarboxylic acid, bicyclo [2,2,1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo [ Two
2,2] octane-2,3,5,6-tetracarboxylic acids and other polycyclic tetracarboxylic acids having a bicyclo ring, norbornane ring or tetracyclo ring structure

<5-basic acid> diethylenetriaminepentaacetic acid <others> phthalocyanine polycarboxylic acid, phytic acid, hexametaphosphoric acid, polyphosphoric acid, polyacrylic acid,
Polymethacrylic acid, polymaleic acid and their copolymers, styrene-maleic acid copolymer, isobutylene
Maleic acid copolymer, vinyl ether / maleic acid copolymer, alginic acid, pectic acid, carboxymethyl cellulose, polyglutamic acid, polymalic acid, polyaspartic acid, acrylic acid / maleic acid / vinyl alcohol copolymer, tartrate monosuccinic acid, Tartrate dimonosuccinic acid

Among these, ethylenediaminetetraacetic acid, 1,2,3,4-butanetetracarboxylic acid (BTC), citric acid alone or in a mixture thereof is advantageous in view of crosslinkability.

Furthermore, BTC is particularly excellent in terms of cross-linking property, antibacterial property and deodorant property. This BTC itself is also a known substance, and it can be obtained from the market and used in the present invention. It is known that BTC is used as a cross-linking agent for a water-soluble polymer having a hydroxyl group by using an oxo salt of phosphorus as an essential component and using it in combination with it (JP-A-7-102110). In the present invention, BT
It is known that C, for example, as a water-proofing agent for cationized chitosan, does not require the oxo salt of phosphorus and exerts a sufficient function by itself, and that both forms a highly water-resistant antibacterial film. Has not been done. Of course, in the present invention, it is also possible to use an oxo salt of phosphorus in combination.

In the composition of the present invention, the mass ratio of OH / NH ₂ polymer to polybasic acid is preferably 1: 0.01-6. Mass ratio of OH / NH ₂ polymer and polybasic acid is 0.0
If it is 1 or less, crosslinking of the polymer is insufficient, and if it is 6 or more, cost performance is insufficient. The MW of the OH / NH ₂ polymer is preferably 5,000 to 2,000,000. MW is 5,000
When it is 0 or less, the crosslinked product tends to be brittle, and when the aqueous solution composition of the present invention is coated, the MW is 20.
If it exceeds 0,000, it will be difficult to obtain a uniform coating film.

In the present invention, it is convenient to use an OH / NH ₂ polymer and a polybasic acid as essential components and dissolve them in an aqueous medium to use as an aqueous solution composition. The water resistant film can be formed after removing a part or all of the water content or by heating while removing the water content. In this case, heating to 80 ° C. or higher, and more preferably 120 ° C. to 200 ° C. is desirable for completion of crosslinking.

When dissolving the above essential components in an aqueous medium, heating may be carried out if necessary. The aqueous medium used is preferably distilled water, but may be ordinary tap water depending on the use of the aqueous solution composition of the present invention, and if necessary, a hydrophilic organic solvent such as alcohol or ketone and water. May be a mixed solvent of The pH of the aqueous solution is preferably 7 or less. If it is more than this, crosslinking may not be successful.

In the above aqueous solution composition, the solid content concentration of the OH / NH ₂ polymer as an essential component and the polybasic acid is preferably 0.1 to 50% by mass. When the MW of the polymer used is large and the solution viscosity is high, the solid content concentration may need to be 0.1% by mass,
If it is less than this, a stable film cannot be obtained. Further, when the solid content concentration exceeds 50% by mass, it is difficult to obtain a uniform solution.

In particular, the ratio of chitosan to polybasic acid used is 1: 0.01 to 6 by mass, preferably 1: 0.2 to 3.0 parts by mass of polybasic acid based on chitosan. . When the amount of the polybasic acid used is less than 0.01 part by mass, the water resistance of the formed film is insufficient, and the effect of suppressing the generation of odor generated during baking due to chitosan is insufficient. . On the other hand, when the amount of the polybasic acid used exceeds 6 parts by mass, the hydrophilicity and flexibility of the formed film deteriorates, and the water resistance of the film does not improve depending on the amount used, and therefore it is uneconomical. Is.

A nonionic organic compound and / or a surfactant may be used in combination for the purpose of increasing the use characteristics of the aqueous solution composition of the present invention. For example, it is also effective to improve the suitability in treating fibers and the texture of treated products. The standard of the additional amount is about 1 to 50% by mass ratio of the nonionic organic compound and / or the surfactant to the OH / NH ₂ polymer.

Examples of the nonionic organic compound include glycerin, pentaerythritol, trimethylolpropane, glucose, fructose, mannitol, lactose, trehalose, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyethylene oxide and polypropylene oxide. Random, block copolymers, polyoxyethylene alkyl ethers, and the like, but are not limited thereto.

As the surface active agent, a cationic surface active agent, a nonionic surface active agent or an amphoteric surface active agent can be used. For example, choline chloride, polyoxyethylene dodecylamine, polyoxyethylene octadecylamine, dimethyldodecyl betaine, alkyldiaminoethylglycine, lanolin fatty acid aminoethyldimethylammonium ethylsulfate, oxyethylene alkyl ether, alkyl glycoside, alkyl polyglycoside,
Sucrose fatty acid ester, glycerin alkyl ether,
Examples thereof include, but are not limited to, glycerin alkyl ester and the like. Further, two or more kinds of the above nonionic organic compounds or surfactants may be used in combination.

OH / NH ₂ polymer used in the present invention,
In particular, 1 to 50% by mass of the nonionic organic compound and / or the surfactant relative to the chitosan, more specifically 1 to 20% by mass of the nonionic organic compound, and the surfactant 1 to
It is preferable from the viewpoint of the balance between the water resistance and the economic effect of the film formed of 20% by mass.

The aqueous solution composition of the present invention comprises, in addition to the above-mentioned components, lower monocarboxylic acids, dihydrazides such as adipic acid dihydrazide, etc. as a polymer dissolution aid, and preservatives, as long as the object of the present invention is not impaired. Alternatively, antifungal agents, organic solvents, fine particle fillers, oil agents and the like may be added.

The aqueous solution composition of the present invention obtained as described above has a viscosity of 5 to 5 despite containing a crosslinking component.
It is stable without thickening or gelling even when left at 30 ° C for 1 month or longer. Therefore, it can be used as a one-pack type treating agent. Then, the aqueous solution composition is applied to the surface of an article and dried by heating to form an antibacterial film having excellent water resistance. During the heat-drying, the film to be formed passes through the ultimate temperature of 80 ° C. or higher, preferably 120 ° C. to 200 ° C., whereby a water-resistant antibacterial film firmly adhered to the article surface is produced.

The aqueous solution composition of the present invention is useful in many applications. For example, by spray-drying the aqueous solution composition and then heating it, antibacterial water-resistant particulates such as cationized chitosan can be obtained. This granular material is useful as an antibacterial agent. Further, the aqueous solution composition of the present invention is a surface-modified metal such as aluminum or iron, various fiber products made of natural or synthetic fibers, paper, synthetic paper, wood, glass, ceramics, ceramics, natural or synthetic resin products and the like. It is useful as a quality agent, and provides various products with excellent antibacterial and deodorant properties, texture improvement, and dyeability.

[0058]

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative / reference examples. In the text, "part" or "%" is based on mass. The present invention is not limited to these examples.

Example A <Examples of chitosan and chitosan derivatives other than cationized chitosan and other OH / NH ₂ polymers> The composition of the aqueous solution composition used as Example A is shown in Tables A-1 to 1 below. 3 and the method of making them is described below. Incidentally, "A component" chitosan or a chitosan derivative and other OH / NH ₂ polymers in Table A-1, "B component" a polybasic acid, "C component" and a nonionic compound, "component D Represents a surfactant. In addition, Examples A-2, 7 to 9 and Example A-1
Although 0 and 11 have the same composition, they are duplicated for convenience of the description of the subsequent examples.

Example A-1 10 parts of chitosan (deacetylation degree 84 mol%, MW 30,000) was dispersed in 75 parts of pure water to prepare 1,2,3,4-butanetetracarboxylic acid (BT).
C) After adding 15 parts, the mixture was stirred at room temperature for 4 hours to dissolve,
100 parts of an aqueous solution composition was prepared.

<Examples A-2 to A-9> An aqueous solution composition was prepared in the same manner as in Example A-1, except that the MW and compounding ratio of chitosan and the amount of BTC used in Example A-1 were changed. Prepared.

<Examples A-10 and A-11> Pure water 9
Chitosan (deacetylation degree 87 mol%, MW10
5) Disperse 5 parts, add 5 parts citric acid, and then add 4 parts at room temperature.
Stir for hours to dissolve and prepare 100 parts of an aqueous solution composition.

Example A-12 5 parts of chitosan (deacetylation degree: 87 mol%, MW 100,000) was dispersed in 85 parts of pure water, 10 parts of citric acid was added, and the mixture was stirred at room temperature for 4 hours. Dissolved and prepared 100 parts aqueous solution composition.

Example A-13 5 parts of chitosan (deacetylation degree: 92 mol%, MW 100,000) were dispersed in 80 parts of pure water, 7.5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours. Dissolved. Subsequently, 1 part of glycerin was added and stirred, and finally water was added to adjust the total amount to 100 parts to obtain an aqueous solution composition.

Example A-14 5 parts of chitosan (deacetylation degree: 95 mol%, MW 100,000) was dispersed in 80 parts of pure water, 7.5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours. Dissolved. Subsequently, 1 part of 75% choline chloride aqueous solution was added and stirred, and finally water was added to adjust the total amount to 100 parts to obtain an aqueous solution composition.

Example A-15 5 parts of chitosan (deacetylation degree: 87 mol%, MW 100,000) was dispersed in 80 parts of pure water, 7.5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours. Dissolved. Subsequently, 1 part of glycerin and 0.5 part of sucrose stearate (manufactured by Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-1670) were added and stirred, and finally water was added to make 100 parts in total. Was adjusted so that an aqueous solution composition was obtained.

Example A-16 3 parts of tosylated chitin (substitution degree 0.1, MW 250,000) was dispersed in 94 parts of pure water, and B was added.
After adding 3 parts of TC, the mixture was stirred at room temperature for 4 hours to dissolve, and
An aqueous solution composition of 00 parts was prepared.

<Example A-17> 5 parts of carboxymethyl chitosan (substitution degree 1.4, MW 130,000) was dispersed in 90 parts of pure water, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution. , 100 parts of an aqueous solution composition was prepared.

<Example A-18> 5 parts of succinyl chitosan (substitution degree 0.3, MW 110,000) was dispersed in 90 parts of pure water, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours to dissolve it. 100 parts of an aqueous solution composition was prepared.

<Example A-19> 5 parts of hydroxyethyl chitosan (substitution degree 1.1, MW 150,000) was dispersed in 90 parts of pure water, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours to dissolve. , 100 parts of an aqueous solution composition was prepared.

<Example A-20> 5 parts of hydroxypropyl chitosan (degree of substitution 0.9, MW 130,000) was dispersed in 90 parts of pure water, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution. , 100 parts of an aqueous solution composition was prepared.

<Example A-21> Dihydroxypropyl chitosan (substitution degree 1.2, MW 100,000) 5 was added to 90 parts of pure water.
Parts were dispersed, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours to dissolve, to prepare 100 parts of an aqueous solution composition.

<Example A-22> 89.7 parts of pure water was mixed with dihydroxypropyl chitosan (substitution degree 2.2, MW 13).
10 parts) were dispersed, 0.3 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours and dissolved to prepare 100 parts of an aqueous solution composition.

<Example A-23> 1 part of dihydroxypropyl chitosan (degree of substitution 3.7, MW 160,000) was added to 75 parts of pure water.
After 0 part was dispersed and 15 parts of BTC were added, the mixture was stirred at room temperature for 4 hours and dissolved to prepare 100 parts of an aqueous solution composition.

<Example A-24> Dihydroxypropyl chitosan (substitution degree 2.2, MW 40) was added to 97.8 parts of pure water.
2 parts), 0.2 parts of EDTA (ethylenediaminetetraacetic acid) was added, and the mixture was stirred at room temperature for 4 hours to dissolve, to prepare 100 parts of an aqueous solution composition.

<Example A-25> 50 parts of a 20% aqueous polyvinylamine solution was dispersed in 40 parts of pure water, stirred at room temperature for 30 minutes, added with 10 parts of BTC, and further stirred at room temperature for 1 hour to dissolve, and 100 Some aqueous solution compositions were prepared.

<Example A-26> 25 parts of a 20% polyallylamine aqueous solution were dispersed in 70 parts of pure water, stirred at room temperature for 30 minutes, added with 5 parts of BTC, and further stirred at room temperature for 1 hour to dissolve them. Some aqueous solution compositions were prepared.

<Example A-27> 25 parts of a 20% polyamidine aqueous solution was dispersed in 70 parts of pure water, stirred at room temperature for 30 minutes, added with 5 parts of BTC, further stirred at room temperature for 1 hour to dissolve, and 100 parts were added. An aqueous solution composition of was prepared.

<Example A-28> 20 parts of polyethyleneimine (MW 10,000 manufactured by Wako Pure Chemical Industries, Ltd.) was dispersed in 76 parts of pure water, and the mixture was stirred at room temperature for 2 hours to dissolve it, and 4 parts of BTC was added. Then, the mixture was further stirred at room temperature for 1 hour and dissolved to prepare 100 parts of an aqueous solution composition.

<Example A-29> 30% polyethyleneimine P-70 solution (manufactured by Wako Pure Chemical Industries, Ltd., MW 70,000)
After 68 parts of pure water was added to 30 parts of the mixture and stirred, 2 parts of BTC was added and further stirred at room temperature for 1 hour to dissolve, to prepare 100 parts of an aqueous solution composition.

Example A-30 25 parts of pure water was added to 60 parts of an aqueous solution of polylysine (manufactured by Chisso Corp., 50% aqueous solution, MW 50 thousand), and after stirring, 15 parts of BTC was added.
Further, the mixture was stirred at room temperature for 1 hour and dissolved to prepare 100 parts of an aqueous solution composition.

<Example A-31> 20 parts of protamine sulfate (manufactured by Tokyo Chemical Industry Co., Ltd., MW 60,000) was dispersed in 70 parts of pure water, dissolved by stirring at room temperature for 2 hours, and 10 parts of BTC was added. In addition, the mixture was further stirred at room temperature for 1 hour and dissolved to prepare 100 parts of an aqueous solution composition.

<Example A-32> 90 parts of pure water were mixed with hydroxyethyl cellulose (Tokyo Chemical Industry Co., Ltd., MW13).
5 parts), 5 parts of BTC were added, and 5 parts of BTC was added, followed by stirring at room temperature for 4 hours to dissolve, to prepare 100 parts of an aqueous solution composition.

<Example A-33> 94 parts of pure water was mixed with hydroxypropyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd., MW3).
Disperse 3 parts of (0000), add 3 parts of BTC, and then add 4 parts at room temperature.
Stir for hours to dissolve and prepare 100 parts of an aqueous solution composition.

<Example A-34> After adding 5 parts of polyvinyl alcohol to 85 parts of normal temperature water with stirring, the mixture was heated to 95 ° C and dissolved by stirring for 2 hours while maintaining the temperature. After cooling to room temperature, 5 parts of BTC was added and then stirred at room temperature for 1 hour to dissolve. Finally, water was added to adjust the total amount to 100 parts, and the mixture was stirred for 30 minutes to prepare an aqueous solution composition.

<Example A-35> 5 parts of soluble starch was dispersed in 90 parts of pure water, and 5 parts of BTC was added thereto, followed by 4 at room temperature.
Stir for hours to dissolve and prepare 100 parts of an aqueous solution composition.

<Example A-36> 2 parts of pectin was dispersed in 96 parts of pure water, 2 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution to prepare 100 parts of an aqueous solution composition.

<Example A-37> 5 parts of water-soluble galactomannan was dispersed in 90 parts of pure water, and 5 parts of BTC was added.
Stir for 4 hours at room temperature to dissolve and prepare 100 parts of an aqueous solution composition.

Example A-38 1 part of pullulan was dispersed in 98 parts of pure water, 1 part of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution to prepare 100 parts of an aqueous solution composition.

<Example A-39> 1 part of guar gum was dispersed in 98 parts of pure water, 1 part of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution to prepare 100 parts of an aqueous solution composition.

<Example A-40> 1 part of propylene glycol alginate was dispersed in 98 parts of pure water, 1 part of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution to prepare 100 parts of an aqueous solution composition. did.

<Example A-41> 3 parts of polyhydroxyethyl methacrylate were dispersed in 94 parts of pure water, 3 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours for dissolution to prepare 100 parts of an aqueous solution composition. Prepared.

The compositions of the aqueous solution compositions used as comparative and reference examples are shown in Table A-1-4, and the preparation methods thereof are described below. <Comparative Example A-1> Comparative Example A-1 is an aqueous solution composition using lactic acid as an acid component. Disperse 5 parts of chitosan (deacetylation degree 87 mol%, MW 100,000) in 80 parts of pure water, add 5 parts of lactic acid, dissolve by stirring at room temperature for 4 hours, and add pure water to make the total amount. An aqueous solution composition was obtained by adjusting the amount to 100 parts.

<Reference Example A-2> Reference Example A-2 is an aqueous solution composition using adipic acid as an acid component.
Part is chitosan (deacetylation degree 87 mol%, MW10
5 parts), 5 parts of adipic acid were added, and then dissolved by stirring for 4 hours at room temperature, and pure water was added to adjust the total amount to 100 parts to obtain an aqueous solution composition. It was

<Reference Example A-3> By the same method as in Example A-1, 100 parts of an aqueous solution composition was obtained.

<Reference Example A-4> 40 parts of pure water was mixed with 30 parts of polyethyleneimine (Wako Pure Chemical Industries, Ltd., MW 0.18 million).
Parts were dispersed and dissolved by stirring at room temperature for 2 hours, then 6 parts of BTC was added and further stirred at room temperature for 1 hour to dissolve, and pure water was added to adjust the total amount to 100 parts to prepare an aqueous solution. A composition was obtained.

<Reference Example A-5> 5 parts of succinyl chitosan (degree of substitution 0.3, MW 110,000) was dispersed in 50 parts of pure water,
After adding 5 parts of BTC, it was dissolved by stirring at room temperature for 4 hours. After dissolution, 35 parts of a 10% aqueous sodium hydroxide solution was added, and pure water was added to adjust the total amount to 100 parts to obtain an aqueous solution composition.

<Reference Example A-6> 70 parts of pure water was mixed with 10 parts of dihydroxypropyl chitosan (substitution degree 2.2, MW 130,000).
Parts were dispersed, 5 parts of BTC was added, and the mixture was stirred at room temperature for 4 hours to dissolve. After the dissolution, 10 parts of a 40% sodium hydroxide aqueous solution was added, and pure water was added to adjust the total amount to 100 parts to obtain an aqueous solution composition.

Comparative Example A-7 Comparative Example A-7 is an aqueous solution composition using polyethylene glycol diglycidyl ether (abbreviated as PEGDGE) as a crosslinking agent. 5 parts of chitosan (deacetylation degree: 87 mol%, MW 100,000) was dispersed in 70 parts of pure water, 5 parts of lactic acid was added, and the mixture was stirred at room temperature for 2 hours to be dissolved. Then, PEGDGE1
Parts and 10 parts of a 10% sodium hydroxide aqueous solution were added, and pure water was further added to adjust the total amount to 100 parts to obtain an aqueous solution composition.

[0100]

[0101]

[0102]

[0103]

Using the aqueous solution compositions prepared by the compositions shown in Tables A-1-1 to A-4, the water resistance evaluation test and the pot life evaluation test of the film obtained by the following film forming method were conducted. The evaluation results are shown in Tables A-2-1 to A-4.

<Pretreatment method> Using an alkaline degreasing agent Fine Cleaner 4377K (manufactured by Nippon Parkerizing Co., Ltd.) on the surface of an aluminum material (JIS 1050) having a thickness of 100 to 110 μm, it was adjusted to 2% with tap water. Alkaline degreasing was performed by spraying at 60 ° C. for 10 seconds using the prepared aqueous solution. Then, a clean aluminum surface was obtained by washing with tap water and drying.

<Film Forming Method> Examples A-1 to A-41 and Comparative / Reference Examples A-1 to A-41 were formed on the surface of the aluminum plate (10 cm × 10 cm) using a bar coater.
The aqueous solution composition of -7 was applied so as to give a dry film amount of 1 g / m ² , and then treated under the conditions shown in Tables A-2-1 to A-4. This was used as a test material used in the following evaluation tests.

1) Water resistance evaluation test The test material was immersed in pure water for 24 hours and then heated to 100 ° C.
It was heat-dried for 30 minutes in the blast dryer adjusted to. After allowing to cool to room temperature, mass measurement was carried out, the coating film residual rate was obtained from the formula shown below, and water resistance was evaluated in four stages. The evaluation method is as follows. (C−A) / (B−A) × 100 (%) A: Mass of aluminum plate before hydrophilic surface treatment. B: Mass of the aluminum plate after hydrophilic surface treatment. C: Mass of aluminum plate immersed in water for 24 hours after hydrophilic surface treatment.

<Water resistance evaluation criteria> A: The coating film residual rate is 95% or more. Good: The coating film residual rate is 80% or more and less than 95%. Δ: The coating film residual rate is 50% or more and less than 80%. X: The coating film residual rate is less than 50%.

2) Pot life evaluation test The aqueous solution compositions of Examples A-1 to A-41 and Comparative and Reference Examples A-1 to A-7 used for film formation were left at 30 ° C. to increase the viscosity or The time until gelation was measured.
The pot life of the aqueous solution composition was evaluated according to the following evaluation criteria.

<Pot Life Evaluation Criteria> A: No thickening or gelation occurs even after 90 days or more. ◯: Thickened or gelled in 30 days to less than 90 days. Δ: Thickened or gelled in 7 days or more and less than 30 days. X: Thickened or gelled in less than 7 days.

[0111]

[0112]

[0113]

[0114]

As is clear from the results of Tables A-2-1 to A-4 above, in the present invention, good results are obtained in the water resistance of the film formed from the aqueous solution composition and the pot life of the aqueous solution composition. Was obtained. Examples A-1 to A-4 are
An aqueous solution composition was prepared by changing the MW of chitosan, and the evaluation results in Table A-2-1 were good. Example A
-5 and A-6 are examples in which the use ratio of BTC was increased, but the evaluation results were good. Examples A-7 to A-
In No. 9, the test was conducted by changing the heating and drying conditions of the coating, but all the results were acceptable. In Examples A-10 to A-12, the type of polybasic acid was changed to citric acid, and the evaluation results were good. Examples A-13 to A-15, to which the nonionic organic compound and the surfactant were added, all showed high water resistance of the film. Examples A-16 to A-21 were tested using various chitosan derivatives, and the evaluation results were all good.

In Example A-22, the mass ratio of dihydroxypropyl chitosan (A) and BTC (B) was B / A = 0.
The water resistance of the film was slightly deteriorated. In Example A-23, the degree of substitution of dihydroxypropyl chitosan was 3.7, and it was found that the water resistance of the film can be imparted even to a very hydrophilic chitosan derivative. In Example A-24, the type of polybasic acid was changed to EDTA, and the result was acceptable. Examples A-25 to A-41 are examples of OH / NH ₂ polymers other than chitosan and a chitosan derivative, and the evaluation results were all good.

In Comparative Example A-1 and Reference Example A-2, the acid components were changed to lactic acid and adipic acid to prepare aqueous solution compositions, and the water resistance of the film was poor. Reference Example A-3 was tested by changing the heating and drying conditions to 70 ° C., but sufficient water resistance of the film was not obtained. Reference example A
In Nos. -5 and A-6, the pH of the aqueous solution composition was adjusted to 7 or higher, and the coating film flowed off in all cases. In Comparative Example A-7, an aqueous solution composition was prepared by changing the cross-linking agent from BTC to PEGDGE, and although the water resistance of the film was good, the aqueous solution composition used in the test was allowed to stand until the next day. However, the whole solution was thickened and the pot life was poor.

Example B <Production Examples, Examples and Comparative Examples Concerning Cationized Chitosan><Production Example 1> Chitosan (Deacetylation degree: 85 mol%, M
W50,000) 30 parts 75% hydrous isopropyl alcohol 6
This was dispersed in 00 parts, 49 parts of 2,3-epoxypropyltrimethylammonium chloride was added, and the mixture was reacted at 65 ° C. for 24 hours with stirring. The introduction rate (substitution degree) of the quaternary ammonium salt group in the obtained cationized chitosan was 1.1. The degree of substitution was calculated from the colloid equivalent values of chitosan and cationized chitosan.

<Production Example 2> Chitosan (Deacetylation degree: 8
30 parts of 2 mol%, MW 90,000 was dispersed in 600 parts of 75% hydrous isopropyl alcohol, 10 parts of 2,3-epoxypropyltrimethylammonium chloride was added, and the mixture was reacted at 65 ° C. for 7 hours with stirring. The introduction rate (substitution degree) of the quaternary ammonium salt group in the obtained cationized chitosan was 0.2.

<Production Example 3> Chitosan (Deacetylation degree: 8
30 parts of 9 mol% and MW of 50,000) were dispersed in 600 parts of 65% hydrous isopropyl alcohol, 80 parts of 2,3-epoxypropyltrimethylammonium chloride was added, and the mixture was reacted at 65 ° C. for 38 hours with stirring. The introduction rate (degree of substitution) of the quaternary ammonium salt group in the obtained cationized chitosan was 1.9.

<Production Example 4> Chitosan (Deacetylation degree 9
30 parts of 5 mol%, MW 40,000) were dispersed in 600 parts of 65% hydrous isopropyl alcohol, 150 parts of 2,3-epoxypropyltrimethylammonium chloride was added, and the mixture was reacted at 65 ° C. for 72 hours with stirring. The introduction rate (substitution degree) of the quaternary ammonium salt group in the obtained cationized chitosan was 3.2.

The compositions of the aqueous solution compositions used as Example B are shown in Tables B-1-1 and B-2 below, and the methods for preparing them are described below. In Table B-1, "A component" represents cationized chitosan, "B component" represents polybasic acid, and "C component" represents other components.

Example B-1 3 parts of cationized chitosan of Production Example 1 was dispersed in 96.7 parts of pure water, and 1,
2,3,4-butanetetracarboxylic acid (BTC) 0.3
Parts were added and dissolved by stirring at room temperature for 2 hours to prepare 100 parts of an aqueous solution composition.

<Examples B-2 to B-19> Table B-1-1
The cationized chitosan produced by the method of Production Examples 1 to 4 using the chitosan having the MW described in (Example B-14 to
The cationized chitosan of 16 was produced in the same manner as in Production Example 1) and the same method as in Example B-1 was used.
An aqueous solution composition having the compounding ratio described in 1-1 was prepared. The compositions of Examples B-3 and 17 to 19 are the same, but they are duplicated for the sake of convenience in the description of the subsequent Examples.

<Example B-20> The cationized chitosan of Production Example 1 (cationization degree: 1.1 MW) was added to 99.3 parts of pure water.
(80,000) 0.5 part was dispersed, 0.1 part of BTC was further added, and the mixture was stirred at room temperature for 2 hours to be dissolved. Subsequently, 0.1 part of polyethylene glycol (PEG) (# 400) was added and stirred to prepare 100 parts of an aqueous solution composition.

<Example B-21> An aqueous solution composition was prepared in the same manner as in Example B-2 except that ethylenediaminetetraacetic acid (EDTA) was used instead of BTC.

<Example B-22> An aqueous solution composition was prepared in the same manner as in Example B-2 except that citric acid was used instead of BTC.

<Example B-23> An aqueous solution composition was prepared in the same manner as in Example B-2 except that succinic acid was used instead of BTC.

Example B-24 10 parts of chitosan (deacetylation degree 84 mol%, MW 80,000) were dispersed in 80% hydrous isopropyl alcohol, and 30 parts of 2-chloroethyldiethylamine hydrochloride was added thereto. After stirring at room temperature for 5 hours, 70 parts of a 10% sodium hydroxide aqueous solution was added, and the mixture was heated under reflux for 3 hours to obtain diethylaminoethylchitosan.
The introduction rate (degree of substitution) of the tertiary amino group in the obtained diethylaminoethyl chitosan was 1.3, and an aqueous solution composition was prepared in the same manner as in Example B-2.

Comparative Example B-1 This comparative example is an aqueous solution composition using acetic acid as an acid. Cationized chitosan of Production Example 1 (substitution degree 1.1, MW 80,000) 1 was added to 98 parts of pure water.
100 parts of an aqueous solution composition was prepared by dispersing 1 part of the solution, adding 1 part of acetic acid, stirring and dissolving at room temperature for 2 hours.

Comparative Example B-2 This comparative example is an aqueous solution composition containing no crosslinking agent. The cationized chitosan of Production Example 3 (substitution degree 1.9, MW10) was added to 99 parts of pure water.
1 part) was dispersed and stirred at room temperature for 2 hours to be dissolved to prepare 100 parts of an aqueous solution composition.

Reference Examples B-3 and B-4 This example is an aqueous solution composition in which the compounding ratio of BTC as a cross-linking agent to cationized chitosan was increased, and the aqueous solution composition was prepared in the same manner as in Example B-1. A solution composition was prepared.

Comparative Example B-5 This comparative example is an aqueous solution composition using PEGDGE as a crosslinking agent. Pure water 8
0 parts of cationized chitosan of Production Example 1 (substitution degree 1.1,
1 part of MW 80,000 was dispersed and dissolved by stirring at room temperature for 2 hours. Subsequently, 1 part of PEGDGE and 10 parts of a 10% sodium hydroxide aqueous solution were added, and pure water was further added to adjust the total amount to 100 parts.

Reference Example B-6 This example is an aqueous solution composition using the chitosan (deacetylation degree 85 mol%, MW 80,000) used in Production Example 1 in which the cationization reaction was not carried out. Was prepared in the same manner as in Example B-1.

[0135]

[0136]

<Examples B-25 to B-48, Comparative / Reference Examples B-7 to B-12> Using the aqueous solution compositions of Examples and Comparative / Reference Examples, the following cloth processing method and Table B were used. -2
Cationized chitosan (comparative example B-12 is chitosan) was adhered to a cotton cloth under the processing conditions described in 1. to obtain a processed cloth.
Using each of the obtained processed cloths, a washing durability test (JIS L 0217 103, using JAFET standard detergent) by a home washing machine was performed 10 times, and then an antibacterial property test was conducted by the unified test method. The evaluation results are shown in Table B-3-1 and Table B-3-1.

<Cloth processing method> Cotton cloth (20 cm x 20 c
m) to the aqueous solution composition shown in Table B-1-1-2 at 25 ° C.
After soaking for 3 minutes in the above condition, the product was squeezed at the squeezing ratio shown in Table B-2, and then pre-dried and heat-treated under the conditions shown in Table B-2. In Comparative Example B-11, preheating was not performed.

[0139]

<Antibacterial Test> A bacteriostatic evaluation method (unified test method) defined by SEK (Textile Products New Function Evaluation Council) was adopted, and a test was conducted using Staphylococcus aureus. The test method was as follows: A broth suspension of the above-mentioned test bacteria in the logarithmic growth phase was added to a sterilized sample cloth, and the number of viable bacteria after culturing at 37 ° C for 18 hours in a closed container was measured. The number was calculated and evaluated according to the following criteria. Test condition: logB-logA> 1.5 (test established when 1.5 or more). Antibacterial activity value: logB-logC (passes 2.2 or more). Bactericidal activity value: logA-logC (passes 0.0 or more). However, A: the number of bacteria recovered immediately after inoculation of unprocessed cloth (or standard cloth). B: Number of bacteria collected after culturing untreated cloth (or standard cloth) for 18 hours. C: Number of bacteria recovered after culturing the bacteriostatically treated cloth for 18 hours. ○: Pass ×: Fail

[0141]

[0142]

As is clear from the results of Table B-3-1 and Table B-2, in the present invention, by fixing the cationized chitosan to the cotton cloth by BTC, good antibacterial results were obtained even after the washing durability test. . Examples B-25 to B-29 (using the aqueous solution compositions of Examples B-1 to B-5, respectively) had the same mass ratio of cationized chitosan (A) and BTC (B), It was prepared by changing the composition concentration, and the evaluation result was good.

Examples B-30 to B-34 (using the aqueous solution compositions of Examples B-6 to B-10, respectively) were prepared by changing the mass ratio of cationized chitosan (A) and BTC (B). As prepared, the evaluation result was good. Example B-
35-B-37 (using the aqueous solution compositions of Examples B-11-B-13, respectively) were cationized chitosan (A).
It was prepared by changing the substitution degree of, and the evaluation result was good. Examples B-38 to B-40 (respectively Example B-
14 to B-16 using an aqueous solution composition),
The test was conducted by changing the MW of the cationized chitosan (A) and the concentration of the aqueous solution composition. Examples B-41 to B-43 (using the aqueous solution compositions of Examples B-17 to B-19, respectively) were tested under different heat treatment conditions. In all cases the results were acceptable.

Further, as in Example B-44 (using the aqueous solution composition of Example B-20), a nonionic compound for imparting a soft texture to fibers such as polyethylene glycol (PEG) is added. Also, good antibacterial performance was obtained.

Example B-30 (using the aqueous solution composition of Example B-6) was cationized chitosan (A) and BTC.
The mass ratio of (B) was prepared at B / A = 1.0,
Antibacterial performance was slightly reduced. In Example B-35 (using the aqueous solution composition of Example B-11), the cationization degree of the cationized chitosan (A) was 0.2,
As a result, the antibacterial property was slightly lowered. From these results, the mass ratio of cationized chitosan (A) and BTC (B) is B / A = 0.01 to 0.9, and the cationization degree of cationized chitosan (A) is It is understood that the range of 0.3 to 3 is more preferable.

In Example B-41 (using the aqueous solution composition of Example B-17), when the heat treatment temperature was 120 ° C, the antibacterial performance was considerably low, and it was more preferable that the heat treatment temperature was 120 ° C or higher. It can be said to be preferable.

Examples B-45 to B-47 (using the aqueous solution compositions of Examples B-21 to B-23, respectively) were prepared by converting polybasic acid from BTC to ethylenediaminetetraacetic acid (EDT).
A) and an aqueous solution composition prepared by changing to citric acid and succinic acid. The antibacterial properties before washing were similar to those of BTC, but after the washing, the antibacterial properties were somewhat decreased, but it is practical. It was something.

Example B-48 (using the aqueous solution composition of Example B-24) was prepared by using an aqueous solution composition containing a tertiary amino group-containing chitosan. Although it was lower than that of ammonium group-containing chitosan), the antibacterial activity was hardly decreased by washing and the washing fastness was sufficient. In addition, neither aqueous solution composition used in Example B produced thickening or gelation even after 30 days.

Comparative Example B-7 (using the aqueous solution composition of Comparative Example B-1) was an aqueous solution composition prepared by changing the cross-linking agent from BTC to acetic acid, and had antibacterial properties before washing similar to that of BTC. However, the antibacterial property was lost after washing.

Comparative Example B-8 (using the aqueous solution composition of Comparative Example B-2) was an aqueous solution composition prepared without using a crosslinking agent, and no antibacterial property was observed. Reference Example B-9
And 10 (using the aqueous solution compositions of Reference Examples B-3 and 4, respectively) are the BTCs for cationized chitosan.
An aqueous solution composition was prepared by increasing the compounding ratio of
No antibacterial property was observed when the blending ratio of BTC was increased.

Comparative Example B-11 (using the aqueous solution composition of Comparative Example B-5) was an aqueous solution composition prepared by changing the cross-linking agent from BTC to PEGDGE, and had good antibacterial properties. However, when the aqueous solution composition used in the test was allowed to stand until the next day, the entire solution was thickened. Further, the aqueous solution composition that had been allowed to stand until the next day was processed into a cloth again, and an antibacterial property test was conducted after a washing durability test, but no antibacterial property was observed.

Reference Example B-12 (using the aqueous solution composition of Reference Example B-6) was prepared by preparing an aqueous solution composition containing only chitosan and BTC without cationization. I couldn't do it.

[0154]

As described above, according to the present invention, even in a mixed state, it can be stored at room temperature for 1 month or more, and once heat-treated under a certain condition, a film excellent in antibacterial properties and water resistance is formed on the substrate surface. The heat-crosslinkable composition formed in the above can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tetsuro Otsuki             1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan Par             Within Colorizing Co., Ltd. (72) Inventor Ryoji Morita             1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan Par             Within Colorizing Co., Ltd. (72) Inventor Shinya Tsuchida             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Masayuki Kobayashi             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Takanori Yamanan             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. F-term (reference) 4J002 AB001 AB011 AB041 AB051                       AD001 AD011 AD031 BE021                       BQ001 EC057 ED037 ED067                       EF066 EF076 EF106 EF116                       EH037 EH047 EL027 EN036                       EN097 FD317

Claims (22)

[Claims] 1. A polymer having a hydroxyl group and / or an amino group and a polybasic acid as essential components (excluding a combination of glycerylated chitosan and 1,2,3,4-butanetetracarboxylic acid). A heat-crosslinkable composition characterized by the above. 2. The heat-crosslinkable composition according to claim 1, wherein the polymer is soluble in water having a pH of 1 to 14 or an aqueous medium containing water and an organic solvent at 100 ° C. or lower. 3. The polymer is a polysaccharide, a polyamino acid,
The heat-crosslinkable composition according to claim 1, which is polyvinyl alcohol, polyallylamine, polyvinylamine, polyamidine or polyethyleneimine or a derivative thereof, or a mixture thereof. 4. The heat-crosslinkable composition according to claim 1, wherein the polymer is a carboxylate, glycolide, tosylate, sulfate, phosphorus oxide, ether or alkyl of the polymer. 5. The heat-crosslinkable composition according to claim 1, wherein the polymer has a substituent introduction rate of 0.1 to 6 per monomer unit of the polymer. 6. The polymer is tertiary and / or quaternary.
The heat-crosslinkable composition according to claim 1, which has a primary amino group or a salt group thereof. 7. The polymer comprises introducing a tertiary or quaternized amino group into the trunk polymer by reacting the trunk polymer with a compound represented by the following formula (1) or formula (2), or When the polymer originally has amino groups, it is a polymer having tertiary and / or quaternary amino groups obtained by alkylating those amino groups with a compound represented by the following formula (3). Sex composition. 8. The compound represented by formula (2) is 2,3
-The heat-crosslinkable composition according to claim 7, which is epoxypropyltrimethylammonium chloride. 9. The heat-crosslinkable composition according to claim 3, wherein the polysaccharide is alginic acid, starch, cellulose, chitin, chitosan or pectin. 10. The heat-crosslinkable composition according to claim 3, wherein the polyamino acid is polylysine, polyornithine, polyarginine, polyhistidine, protamine, gelatin or collagen. 11. The heat-crosslinkable composition according to claim 1, wherein the polymer is at least one selected from the group consisting of chitosan, hydroxyalkyl chitosan, polyvinyl alcohol, and chitosan having a tertiary and / or quaternary amino group. Composition. 12. The heat-crosslinkable composition according to claim 1, wherein the polybasic acid is a tribasic acid, a tetrabasic acid, a pentabasic acid or a mixture thereof. 13. The heat-crosslinkable composition according to claim 1, wherein the polybasic acid is ethylenediaminetetraacetic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid or a mixture thereof. 14. The mass ratio of the polymer to the polybasic acid is
The heat-crosslinkable composition according to claim 1, which is 1: 0.01 to 6. 15. The weight average molecular weight of the polymer is
The heat-crosslinkable composition according to claim 1, which has an amount of 5,000 to 2,000,000. 16. The composition according to claim 1 is dissolved in an aqueous medium, and after removing a part or all of water,
Alternatively, an aqueous solution composition which is capable of forming a water resistant film by heating while removing water. 17. The aqueous solution composition according to claim 16, wherein a solid content concentration of the polymer and the polybasic acid is 0.1 to 50% by mass. 18. A mass ratio of 1 to 50 with respect to the polymer.
The aqueous solution composition according to claim 16, which further comprises% nonionic organic compound and / or surfactant. 19. The aqueous solution composition according to claim 16, which has a pH of 7 or less. 20. A method for producing a crosslinked product, which comprises heating the composition according to claim 1 to 80 ° C. or higher. 21. A composite material, wherein the cross-linking according to claim 20 is performed on a base material, and the base material and the cross-linked product are integrated. 22. The base material is a metal such as aluminum or iron, glass, natural resin, synthetic resin, ceramics, paper,
The composite material according to claim 21, which is a fiber, a woven fabric, a non-woven fabric, or leather.