JPH03181403A - Antimicrobial liquid and paint - Google Patents

Abstract

PURPOSE:To provide an antimicrobial solution capable of being added to raw solutions for preparing paper, synthetic fibers, etc., by containing a N-long chain acrylamino acid salt of an antimicrobial metal in a dissolution state, and to provide an antimicrobial paint exhibiting the antimicrobial activity for a long period by adding the antimicrobial solution to a paint. CONSTITUTION:An antimicrobial solution containing 0.01-0.3 pt.wt. of a N-long chain acylamino acid salt (acyl is stearoyl, lauroyl, myristoyl or palmitoyl) of an antimicrobial metal (e.g. silver, copper, lead, zinc or tin) in a state dissolved in ammonia water, etc. When the solvent in the antimicrobial solution evaporates, the N-long chain acylamino acid is combined with the antimicrobial metal to form a water-insoluble salt having a high antimicrobial activity. Since the salt has high affinity with organic substances, the salt has good compatibility with the acryl resin in the paint, does not readily flow out from the films of the paints and exhibits a long period antimicrobial activity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel antibacterial liquid having antibacterial effects against various bacteria and molds, and an antibacterial paint containing the same.

[Prior Art] It has been known that silver and copper have a bactericidal effect. For example, silver can be used in the form of an aqueous solution such as silver nitrate (A g").
It is widely used as a disinfectant.

It is also known that silver and its compounds can be adsorbed onto adsorbent materials such as activated carbon, aluminane gel, and zeolite for sterilization purposes.

Examples of the above-mentioned products include those shown in JP-A-62-241939 and JP-A-62-238900, which contain zeolite that retains a metal with bactericidal action in an ionic state. These are polyolefin resin molded articles and paper.

Furthermore, as shown in Japanese Patent Application Laid-Open No. 62-70221, there is an amorphous aluminosilicate having antibacterial and/or bactericidal activity represented by the formula % (where M is silver or the like).

[Problems with the prior art] However, although the above-mentioned silver nitrate exhibits a high antibacterial effect when applied, it does not last long and is easily washed out especially when it comes into contact with water, so it does not have a continuous antibacterial effect. Ta.

In addition, silver and its compounds mentioned above are adsorbed on adsorbent materials such as activated carbon, alumina, silica gel, and zeolite.
Although it has antibacterial and bactericidal effects, it is only adsorbed to zeolite and not chemically bonded, so the bactericidal metal used is not ionized. However, when it comes into contact with liquids, there is a risk of leakage, and there is also a problem with the continuous antibacterial effect. Furthermore, since this antibacterial substance is in the form of fine particles, it has poor dispersibility, and it is particularly difficult to uniformly disperse it in a liquid.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, to have high antibacterial properties, to be in liquid form, and to be suitable for direct application, as well as liquid materials (e.g., paints, antifungal agents, spinning yarns, etc.). The object of the present invention is to provide an easy-to-handle antibacterial liquid that can be easily and uniformly incorporated into liquid detergents (stratification, liquid detergents), and an antibacterial paint containing the same.

[Means for solving the problem] What achieves the above purpose is the use of metal N having antibacterial action.
-An antibacterial liquid containing a long chain acylamino acid salt in a dissolved state.

Moreover, what achieves the above purpose is an antibacterial agent containing an N-long chain acylamino acid ion and a metal ion having an antibacterial effect that forms a water-insoluble salt with the N-long chain acyl amino acid ion. It is preferable that the N-long chain acylamino acid or the acyl group of the N-long chain acylamino acid is a stearoyl group, a lauroyl group, a myristoyl group, or a valmitoyl group. Further, the metal or metal ion is preferably any one selected from the group consisting of silver, copper, lead, zinc, tin, or ions thereof. Furthermore, the solvent of the antibacterial liquid is
Aqueous ammonia is preferred. Moreover, it is preferable that the antibacterial liquid contains alcohol. Furthermore, the N-
The content of the long-chain acylamino acid salt or the combined content of the N-long-chain acylamino acid ion and the metal ion is o, otx with respect to the weight percent (X%) of ammonia in the antibacterial liquid. ~5X parts by weight is preferred. Moreover, it is preferable that the solvent of the antibacterial liquid is morpholine. Furthermore, the total content of the metal N long-chain acylamino acid ion having an antibacterial effect and the metal ion in the antibacterial liquid is 0.01-0.3 with respect to 100 parts by weight of the antibacterial liquid. Parts by weight are preferred. Also achieving the above object is an antibacterial paint containing any of the above antibacterial liquids.

Therefore, the antibacterial liquid of the present invention will be explained using Examples.

The antibacterial liquid of the present invention is an antibacterial liquid containing a dissolved N-long chain acylamino acid salt of a metal having an antibacterial effect.

This antibacterial liquid can be used in various liquids, such as liquid paints, stock solutions for producing paper, etc., stock solutions for producing synthetic fibers (
For example, it can be easily added to regenerated cellulose spinning stock solutions such as cuprammonium cellulose and cellulose acetate), and since this antibacterial liquid is a liquid, it can be uniformly dispersed in the liquid to which it is added. Can be added to the condition.

As the solvent in the antibacterial liquid evaporates, N
- A long chain acylamino acid and a metal having antibacterial activity combine to form a water-insoluble salt, and the formed N-long chain acylamino acid salt has a high antibacterial effect. And especially,
This N-long chain acylamino acid antibacterial metal salt has a long chain acyl group and thus has high affinity with organic substances.

For this reason, for example, organic substances contained in paint (
For example, it has good compatibility with acrylic synthetic resins, alkyd synthetic resins, epoxy synthetic resins, vinyl ester synthetic resins, polyurethane synthetic resins, silicone synthetic resins, fluorine synthetic resins), and forms a paint film. Furthermore, even if a liquid such as water comes into contact with the paint film surface, the N-long chain acylamino acid antibacterial metal salt is insoluble in water, so the antibacterial metal is easily removed. It exhibits long-term antibacterial action without leakage.

Therefore, the antibacterial II substance of the present invention will be specifically explained.

The antibacterial liquid of the present invention contains a dissolved N-long chain acylamino acid salt of a metal having an antibacterial effect as described above. Specifically, in an antibacterial liquid, an N-long chain acylamino acid ion and a metal ion having an antibacterial effect that forms a water-insoluble salt with the N-long chain acylamino acid ion are present in an antibacterial liquid without forming a salt. , it is thought to exist in an ionic state.

The N-long chain acylamino acid or ion thereof contained in the antibacterial liquid of the present invention is an amino acid having a long chain acyl group (fatty acid residue) at the N position or an ion thereof.

The long-chain acyl group is preferably one that has high compatibility and affinity with the synthetic resin as described above, and for that purpose higher fatty acid residues are preferable, such as decanoyl group, lauroyl group, myristoyl group, valmitoyl group, stearoyl group. and oleoyl groups are preferred. Further, the acyl group is not limited to a single type, and a plurality of types of the above-mentioned acyl groups may be used.

The amino acid may be monoaminomonocarboxylic acid, monoaminodicarboxylic acid, or diaminomonocarboxylic acid. When the N-acylamino acid antibacterial metal salt formed using the antibacterial liquid of the present invention is to have high antibacterial properties, it is preferable to use monoamino dicarboxylic acid; Since it has two carboxyl groups, metals having antibacterial activity are likely to bind thereto, and the antibacterial effect as a whole can be made strong. However, for general uses of antibacterial liquids, salts in which one metal having antibacterial activity is bound to an amino acid have sufficient antibacterial activity.

Specific examples of amino acids include monoaminomonocarboxylic acids such as glycine, alanine, valine, leucine, phenylalanine, thyronone, threonine, tryptophan, and methionine, and monoaminodicarboxylic acids such as aspartic acid and glutamic acid. Diaminomonocarboxylic acids include lysine, arginine, and histidine.

In addition, the antibacterial metals or ions thereof contained in the antibacterial liquid of the present invention include silver, copper, lead,
Zinc, tin or ions thereof can be preferably used. Further, the metal is not limited to one type, and multiple types of metal may be used. Of the above metals, silver or copper is more preferred from the standpoint of antibacterial activity and safety, and silver is particularly preferred from the standpoint of antimicrobial activity.

Therefore, preferred specific examples of the N-long chain anluamino acid salts dissolved in the antibacterial liquid of the present invention include silver N-stearoylglutamate, silver N-lauroylglutamate, silver N-myristoylglutamate, and N-stearoylasparagine. silver acid, silver N-lauroyl aspartate, silver N-myristoyl aspartate, silver N-stearoylglutamate, N-lauroylglutamate ft
, copper N-myristoylglutamate, silver N-stearoyl aspartate, silver N-lauroyl aspartate,
Copper N-myristoyl aspartate, silver N-stearoylvaline, silver N-lauroylvaline, silver N-myristoylvaline, copper copper N-stearoylvaline, copper copper N-lauroylvaline, copper copper N-myristoylvaline, silver N-stearoylphenylalanine, N -Lauroylphenylalanine silver, N-myristoylphenylalanine silver, N-stearoylphenylalanine silver, N-lauroylphenylalanine M, N-myristoylphenylalanine copper, N
-stearoyl arginine silver, N-lauroyl arginine silver, N-myristoyl arginine silver, N-stearoyl arginine copper, N-lauroyl arginine silver, N-myristoyl arginine silver, etc.

The above-mentioned N-long chain acylamino acid antibacterial metal salt is poorly soluble in water and various organic solvents. Therefore, as a result of intensive studies by the present inventors, some solvents contain N-
It was found that long-chain acyl amino acids were dissolved without being denatured and were in a stable state.

As the aqueous solvent used in the antibacterial liquid of the present invention, aqueous ammonia is suitable, and in particular, the concentration is o, t-to weight %, and the pH is 10 to 12, particularly 10 to 11.
Aqueous ammonia was suitable. The content (dissolved weight) of the N-acylamino acid antibacterial metal salt in this ammonia water or the combined content of the N-long chain acylamino acid ion and the metal ion is the weight percent of ammonia in the antibacterial liquid ( X%>, preferably 0.01X to 5X parts by weight.

If the amount of the antibacterial liquid of the present invention is 1 part or more by weight of 0.01 , has little effect on the formulation of other ingredients. Further, if it is 5 parts by weight or less, the N-acylamino acid antibacterial metal salt can be reliably dissolved in the antibacterial liquid in a stable state. In addition, in order to reduce the ammonia odor of antibacterial liquids using ammonia water, we add liquids that have an aromatic odor and are compatible with water, such as alcohol, or conversely, add highly concentrated ammonia water to alcohol. Preferably, a solvent antimicrobial liquid stock solution is added. As the alcohol, methyl alcohol, ethyl alcohol, etc. can be suitably used. When the a degree of ammonia in the alcohol-containing solvent is 1% by weight or less, the ammonia odor is considerably reduced, and in particular, when it is 0.1% by weight or less, it is preferable because it does not give a feeling of disgust to the handler during use.

Furthermore, the organic solvent used in the antibacterial liquid is preferably morpholine. The content of the N-long chain acylamino acid antibacterial metal salt in morpholine or the combined content of the N-long chain acylamino acid ion and the metal ion is 0 with respect to 100 parts by weight of morpholine.
．． The amount is preferably 01 to 0.3 parts by weight. 0.01
% or more, in order to exhibit antibacterial properties, it is not necessary to add this antibacterial liquid in a large amount to the liquid, and it does not affect the blending of other components in the liquid. I have little to give. Further, if the amount is 0.3 ffiffi part or less, the N-acylamino acid antibacterial metal salt can be reliably dissolved in a stable state in the antibacterial liquid.

Also, antibacterial properties using morpholine solvent? A liquid having an aromatic odor and being compatible with morpholine, such as alcohol, is added to the skin, or conversely, a high concentration of morpholine solvent is anti-mold to alcohol.

Body fluids may also be added. As the alcohol, methyl alcohol, ethyl alcohol, etc. can be suitably used.

The antibacterial liquid of the present invention can be formed as follows.

First, a water-soluble salt of a metal having antibacterial properties, such as silver nitrate, copper nitrate, silver sulfate, copper chloride, copper sulfate, etc., is added to an aqueous solution of an alkali metal salt such as sodium or potassium of an N-long chain acylamino acid. By mixing the aqueous solution, N-
A powdered N-long chain acylamino acid antibacterial metal salt is obtained by preparing a long chain acylamino acid antibacterial metal salt and drying (for example, heat drying, freeze drying). Then,
The antibacterial liquid of the present invention can be easily prepared by adding a predetermined amount of N-long chain acylamino acid antibacterial metal salt to a solvent such as aqueous ammonia or morpholine at the above concentration and stirring.

In addition, the method is not limited to the above method, and a salt of a metal having antibacterial properties, such as silver nitrate, is added to an aqueous solution of an alkali metal salt such as sodium or potassium of an N long-chain acylamino acid in a solvent such as aqueous ammonia or morpholine at the above concentration. It may also be formed by mixing aqueous solutions of water-soluble salts such as copper nitrate, silver sulfate, copper chloride, copper sulfate, and the like.

This antibacterial liquid is applied directly or mixed with a liquid such as paint, and as the solvent in the antibacterial liquid evaporates, the N-long chain acylamino acid and the metal with antibacterial action are combined. The N-long chain acylamino acid antibacterial metal salt is combined to form a water-insoluble salt.
It has a high antibacterial effect. Then, the N-long chain acylamino acid antibacterial metal salt formed has at least one
Since it is a salt in which two antibacterial metals are combined, it has extremely high antibacterial activity.Furthermore, since the basic skeleton is made of amino acids, it has extremely low toxicity and can be safely used for a variety of purposes.

This antibacterial liquid can be used in various liquids, such as liquid paints, stock solutions for producing paper, etc., stock solutions for producing synthetic fibers (
For example, it can be easily added to regenerated cellulose spinning materials such as cuprammonium cellulose and cellulose acetate. The N-acyl amino acids and antibacterial metals in the antibacterial liquid added to the stock solution for manufacturing paper, etc., and the stock solution for manufacturing synthetic fibers combine during the manufacturing process of paper and synthetic fibers, and the insoluble N-acyl Forms amino acid antibacterial metal salts. The formed antibacterial metal salt has a high affinity with paper and synthetic fiber materials due to its acyl group, so the physical properties of paper and synthetic fiber materials are less likely to deteriorate, and the antibacterial metal salt also flows out easily. Never. Antibacterial fibers containing antibacterial metal salts produced by adding this antibacterial liquid can be used for various purposes.
For example, woven fabrics may include clothing (eg, socks), sheets, filter materials, and non-woven fabrics may include filter materials, packaging materials, and the like. As the synthetic fiber, polyacrylonitrile, regenerated cellulose (eg, cellulose acetate, cellulose cuprammonium), etc. can be suitably used.

In addition, the stock solution for paper production to which the antibacterial liquid is added may be either a stock solution for Western paper production or a stock solution for Japanese paper production.
By using these stock solutions, various types of antibacterial paper with antibacterial properties can be manufactured, such as hybrid paper, tissue paper (e.g., tissue paper, dust paper, toilet paper, napkin or towel paper, sanitary paper), packaging paper, etc. Paper, coated paper (for example, art paper, coated paper), uncoated paper, printing paper, drawing paper, etc. Paperboard includes corrugated paper, white paperboard, corrugated paperboard, colored paperboard, chipboard, corrugated paper, etc. It is possible to produce paper with antibacterial properties such as banknote base paper and mount paper.

Moreover, the antibacterial liquid can also be included in a coating agent for imparting antibacterial properties to the surface of paper, for example. Then, by applying this coating agent to the paper surface and drying it, the solvent in the antibacterial liquid evaporates and the above-mentioned N-acylamino acid antibacterial metal salt is formed, resulting in a highly antibacterial coating on the paper surface. can be given gender.

Examples of the coating agent include aqueous adhesive cellulose-based substances such as carboxymethyl cellulose, methyl cellulose, oxypropyl cellulose, oxyethyl cellulose, and PvA.
(polyvinyl alcohol), PvP (polyvinylpyrrolidone), vinylpyrrolidone-vinyl acetate copolymer, etc. can be used, and this aqueous liquid contains an antibacterial liquid using aqueous ammonia, which is the aqueous solvent mentioned above, as a solvent. It can be used suitably. Antimicrobial liquid concentration in the coating agent, in particular N-acyl amino acid antimicrobial metal salt (dissolved state)
A sufficient antibacterial effect can be imparted to the paper if the concentration is about o,oot to 1% by weight, and particularly preferably about 0.01 to 0.5% by weight. .

In addition, as coating agents, non-aqueous ones include silicone resin coating agents (e.g., dimethylsiloxane coating agents, methylhydrodiene polysiloxane coating agents, methyltrichlorosiloxane coating agents, silane coupling agents), Further, a fluororesin coating agent or the like can be used, and as the non-aqueous liquid, an antibacterial liquid using morpholine, which is the above-mentioned non-aqueous solvent, as a solvent can be suitably used. The concentration of the antibacterial liquid in the coating agent, especially the concentration of the N-acylamino acid antibacterial metal salt (dissolved state), is 0.001 to
If it has a content of about 0.5% by weight, a sufficient antibacterial effect can be imparted to the paper, and particularly preferably 0.01 to 0.5% by weight.
It is about 0.5% by weight.

Next, the antibacterial paint containing the antibacterial liquid of the present invention will be explained.

Paints used include fatty acid paints, epoxy resin paints, solvent-free epoxy resin paints, vinyl ester paints, polyurethane resin paints, solvent-free polyurethane resin paints, silicone resin paints, and fluorine resin paints. There are paints, etc.

An antibacterial paint can be created by adding an antibacterial liquid using aqueous ammonia, which is the aqueous solvent described above, as a solvent to the water-based paint among the above-mentioned paints. Further, an antibacterial paint can be created by adding an antibacterial liquid containing morpholine, which is a non-aqueous solvent, as a solvent to the water-based paint of the above-mentioned paint. The concentration of the antibacterial liquid in the paint, especially the concentration of the N-acylamino acid antibacterial metal salt (dissolved state), is 0.001-1.
If it has about 0% by weight, a sufficient antibacterial effect can be imparted to the coated surface, and particularly preferably 0% by weight.
．． It is about 0.01 to 0.5% by weight. The antibacterial paint of the present invention can be used in a wide range of areas, including the interior and exterior walls and floors of houses (for example, kitchens and bathrooms).

Next, the antibacterial liquid of the present invention and Examples using the antibacterial liquid of the present invention will be described.

(Example 1) As an alkali metal salt of N-long chain acylamino acid, N-
Using disodium stearoyl-L-glutamate (manufactured by Ajinomoto Co., Inc., trade name Amisoft 15-21), an aqueous solution was prepared by dissolving 279 parts of disodium N-stearoyl-L-glutamate in 1000 avQ of water.

Using silver as a metal having antibacterial properties, a silver nitrate aqueous solution was prepared by dissolving 16 g of silver nitrate in 10ooIIIQ of water. Then, by mixing the above aqueous silver nitrate solution with the above aqueous solution of disodium N-stearoyl-L-glutamate, a precipitate is formed, and this precipitate is heated and dried to obtain approximately 37 g
I got 9.

and N-stearoyl-r-po1 obtained as above.
By adding ShishiS SOKEKURA 1OY 10Z7 SOEMA 1 and LOOxQ and stirring at 25°C for about 10 minutes, a light brown transparent antibacterial liquid (pH about 11, N-stearoyl-L-glutamic acid) is produced. A silver concentration of 1%) was obtained. Note that the added silver N-stearoyl-L-glutamate is dissolved, and when visually recognized, the insoluble silver N-stearoyl-L-glutamate is dissolved.
-Silver glutamate could not be confirmed.

(Example 2) Using the antibacterial liquid prepared in Example 1 above as a stock solution, the antibacterial liquid was diluted 10 times with water (pH approximately IQ, N-
Silver stearoyl-L-glutamate (concentration: approximately 0.1%) was prepared.

(Example 3) An antibacterial liquid prepared by using the antibacterial liquid prepared in Example 1 as a stock solution and diluting it 100 times with methyl alcohol (silver N-stearoyl-glutamate concentration approximately 0.0
1%) was created. The antibacterial liquid in this example was
There was almost no ammonia smell left.

(Example 4) By adding 5 g of silver N-stearoyl L-glutamate prepared in Example I to 5% ammonia water 1001 (2) and stirring at 25°C for about 10 minutes, a light brown transparent antibacterial product was obtained. A liquid (pH approximately 11.3, silver N-stearoyl-L-glutamate concentration 5%) was obtained.The added silver N-stearoyl-L-glutamate was dissolved, and visually confirmed that the insoluble N- Silver stearoyl-L glutamate could not be confirmed.

<Example 5> 0.19 of the N-stearoyl L-glutamate silver prepared in Example 1 was added to morpholine 100zf2,
By stirring at 25°C for about 10 minutes, a pale yellow transparent antibacterial liquid (silver N-stearoyl-L-glutamate concentration 0.1%) was obtained.

Note that the added silver N-stearoyl-L-glutamate was dissolved, and no insoluble silver N-stearoyl-L-glutamate could be visually confirmed.

(Example 6) Using the antibacterial liquid prepared in Example 5 above as a stock solution, the antibacterial liquid (N-
Silver stearoyl-L-glutamate concentration approximately 0.05%)
It was created.

(Example 7) Disodium N-stearoyl-L-glutamate (manufactured by Ajinomoto Co., Inc., trade name Amisoft H3-21) was added to 1 part water.
An aqueous solution was prepared by dissolving 839 in 000*(i).

Using copper as a metal having antibacterial properties, a copper nitrate aqueous solution was prepared by dissolving 39 g of copper nitrate in 10003112 of water. Then, by mixing the above aqueous copper nitrate solution with the above aqueous solution of disodium N-stearoyl-L-glutamate, a precipitate is formed, and this precipitate is heated and dried to produce approximately 93
I got g.

Then, 0.2 g of silver N-stearoyl-glutamate obtained as above was added to 2% ammonia water 100 + 272 g.
by adding to the solution and stirring at 25°C for about 10 minutes.
A blue transparent antibacterial liquid (T)H (approximately 12% N-stearoyl-L to copper glutamate concentration 0.2%) was obtained. Note that the added silver N-stearoyl-L-glutamate was dissolved, and no insoluble silver N-stearoyl-L-glutamate could be visually confirmed.

(Example 8) An antibacterial liquid (pH approximately 12, N-
Copper stearoyl-L-glutamate concentration approximately 0.02%)
It was created.

(Example 9) The antibacterial liquid prepared in Example 7 above was used as li&, and the antibacterial liquid was diluted 100 times with methyl alcohol (N-stearoyl-L-copper glutamate concentration: about 0.0.
002%) was created. Note that the antibacterial liquid of this example had almost no residual ammonia odor.

(Example 10) N-stearoyl-L-glutamic acid created in Example 7! ] O-1qG MoJl/Ho II 71
nntx0 and stirred at 25°C for about 10 minutes, a blue transparent antibacterial liquid (silver N-stearoyl-glutamate concentration 0.1%) was obtained.

Note that the added silver N-stearoyl-L-glutamate was dissolved, and no insoluble steel N-stearoyl-L-glutamate could be visually confirmed.

(Example 11) N-stearoyl-L- produced in Example 1 above
1 g of silver glutamate and N prepared in Example 7 above
-10% silver stearoyl-L-glutamate 0.29
Add 100m and 721m of ammonia water, and at 25°C approx.
A bluish-brown clear antibacterial liquid (pH approximately 12) was obtained by stirring for 0 minutes. In addition, the added N-
Silver stearoyl-L-glutamate and silver N-stearoyl-L-glutamate were dissolved, and insoluble silver N-stearoyl-L-glutamate and silver N-stearoyl-L-glutamate were not visually confirmed.

(Example 12) Using the antibacterial liquid prepared in Example U above as a stock solution, the antibacterial liquid was diluted 10 times with water (pH approximately 11, N-
Silver stearoyl-L-glutamate mrlo, x%, N
-Copper stearoyl-L-glutamate concentration approximately 0.02%
)It was created.

(Example 13) An antibacterial liquid (silver N-stearoyl-L-glutamate 1 degree 0.0
1%, copper N-stearoyl-L glutamate concentration approximately 0.
002%) was created.

Note that the antibacterial liquid of this example had almost no residual ammonia odor.

(Example 14) N-stearoyl-L- produced in Example 1 above
By adding 0.19 g of silver glutamate and 0.1 g of silver N-stearoyl-L-glutamate prepared in Example 7 above to Morpholine 100j112 and stirring at room temperature for about 10 minutes, a bluish-brown transparent antibacterial substance was obtained. sex l
Insect body (silver N-stearoyl-L-glutamate concentration 0.
1%, N-stearoyl-L-glutamine [copper concentration 0.
1%). Note that the added silver N-stearoyl-L-glutamate and silver N-stearoyl-L-glutamate were dissolved, and insoluble silver N-stearoyl-L-glutamate could not be confirmed visually.

(Example 15) The antibacterial liquid 10112 prepared in Example 2 was used as a commercially available water-based paint (acrylic synthetic resin paint, manufactured by Kanpe Home Paint Co., Ltd., trade name: water-based glossy paint (white), product code: 627-001). The antibacterial paint of the present invention (silver N-stearyl-L-glutamate concentration: 0.01%) was prepared by adding the antibacterial paint to 90 g and mixing well.

(Example 16) The antibacterial liquid 1Oj112 prepared in Example 12 was mixed with a commercially available water-based paint (acrylic synthetic resin paint, De-Nope Karanai 01 ratio, h4+ system audience paint).
white), product code 627-001), add to 90g,
By mixing thoroughly, the antibacterial paint of the present invention (concentrated silver N-stearoyl-L-glutamate [o, ot%, N-
Copper stearoyl-L-glutamate concentration approximately 0.002%
)It was created.

(Example 17) The antibacterial liquid 2off12 prepared in Example 6 was mixed with a commercially available oil-based paint (alkyd-based synthetic resin paint, manufactured by Kanpe Home Paint Co., Ltd., trade name: oil-based one-coat for iron parts (white),
Product Food 123-001) 809+= was added and mixed thoroughly to create the antibacterial paint of the present invention (silver N-stearoyl-glutamate concentration 0.01%).

(Example tg) The antibacterial liquid 20xQ prepared in Example 6 was mixed with a commercially available urethane varnish (manufactured by Kanpe Home Paint Co., Ltd., product name: Flexible Yaari Rouryoku, Bath Varnish (Transparent), Product Code: 33
By adding 0-001) 809 and mixing well, the antibacterial paint of the present invention is prepared.
Ma bolt -/ +1・ -T -No +1.
)9 Ko・no JI light b eye, Ith
dt0.01%).

(Example 19) The antibacterial liquid 20xQ prepared in Example 14 above was applied to a commercially available oil-based paint (alkyd-based synthetic resin paint, manufactured by Kanpe Home Paint Co., Ltd., product name: Oil-based Shiny Relowka, bath varnish (transparent), product code 330-001) so9
By adding the antibacterial paint of the present invention (silver N-stearoyl-L-glutamate concentration 0.0
1%, copper N-stearoyl-glutamate concentration approximately 0
．． 002%) was created.

(Comparative example) 10 g of silver nitrate aqueous solution (A degree 0.1%) was added to a commercially available water-based paint (acrylic synthetic resin paint, manufactured by Kanpe Home Paint Co., Ltd., product name: water-based glossy paint (white), product code: 62
7-001) was added to 9o9 and mixed well to create a paint containing silver nitrate (silver nitrate aqueous solution 0.01%).

[Experiment l] The antibacterial activity of the antibacterial liquid of the present invention was tested.

The following strains were used as test strains.

Escherichia coli IFO3301 (
Escherichia coli) Pseudomonas aeruginos
a IID P-1 (Pseudomonas aeruginosa) Staphylococ
cus aureus IFO12732 (Staphylococcus aureus) Vivrio parahaemolyticu
s Engineering FO12711 (Vibrio parahaemolyticus) Then, the above bacteria were grown in an enrichment medium (AATCC Broth for Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus; AATCC Broth with 3% salt added for Vibrio parahaemolyticus).
Culture for 24 hours at °C to prepare a bacterial solution for inoculation.
ar, for Vibrio parahaemolyticus, 3% salt ^^TCCA
An experimental medium was prepared by adding an inoculating bacterial solution at a ratio of 111Q to 150mQ (using gar), dispensed into sterilized petri dishes, and solidified to produce 4 plates of each experimental medium. .

Then, a polypropylene sheet having a circular hole with a diameter of 2 cm in the center was placed on top of a sterile petri dish filled with the above-mentioned experimental flat plate culture medium so that the above-mentioned circular hole was located approximately in the center of the dish, and each bacterial About 0.5XQ of the antibacterial liquid of Example 2 was sprayed onto the petri dish in which the bacteria had been cultured, and about 0.5 m of the antibacterial liquid of Examples 3.5 and 6 was applied to the other petri dishes in the same manner. After spraying and culturing at 37° C. for 24 hours, the growth state of the bacteria was confirmed.

As a result, in the petri dishes coated with the liquid in which the antibacterial liquids of Examples 2.3.5 and 6 were dissolved, approximately 2 to
A 2.5-inch area where bacteria did not grow was observed, and active bacteria growth was observed in areas other than the above-mentioned center.

(Experiment 2) The paints of Example 15, Example 16, Example 17, Example 18, Example 19, and Comparative Example were applied to test pieces of wood and dried. When all of the test pieces of wood were exposed to direct sunlight outdoors, the painted surfaces almost uniformly turned black and gray. Then, when water was poured on the discolored coated surface of the test piece of wood and the changes in the texture of the coated surface were observed, Example 15,
Example 16, Example 17, Example 18 and Example 19
In the test pieces of wood coated with the paint, there was almost no change in color, confirming that the metal with antibacterial properties did not easily flow out. On the other hand, in the test piece of wood coated with the paint of the comparative example, the black-gray color gradually became lighter as water was poured over it, and it was confirmed that the silver was gradually flowing out.

[Effects of the Invention] Since the antibacterial liquid of the present invention contains a dissolved N-long chain acylamino acid salt of a metal having an antibacterial effect, it can be used with various liquids, such as liquid paints. , can easily be used as a stock solution for manufacturing paper, etc., or a stock solution for manufacturing synthetic fibers, etc.
When the solvent in the antibacterial liquid evaporates, the N-long chain acylamino acid and the metal with antibacterial activity combine to form a water-insoluble salt. The resulting N-long chain acylamino acid salt has high antibacterial activity. In particular, this N-long chain acylamino acid antibacterial metal salt has a high affinity with organic substances because it has an N-long chain acyl group. For this reason, for example, it has good compatibility with organic substances contained in paints,
The N-long chain acylamino acid antibacterial metal salt does not easily flow out of the formed paint film, and even if a liquid such as water comes into contact with the paint film surface, the N-long chain acylamino acid antibacterial metal salt is insoluble in water. Characterized by long-term antibacterial action, with no release of antibacterial metals.

Claims (10)

[Claims] (1) An antibacterial liquid characterized by containing a dissolved N-long chain acylamino acid salt of a metal having an antibacterial effect. (2) An antibacterial liquid characterized by containing an N-long chain acylamino acid ion and a metal ion having an antibacterial effect that forms a water-insoluble salt with the N-long chain acylamino acid ion. (3) The antibacterial liquid according to claim 1 or 2, wherein the acyl group of the N-long chain acylamino acid is any one of a stearoyl group, a lauroyl group, a myristoyl group, and a valmitoyl group. (4) The antibacterial liquid according to any one of claims 1 to 3, wherein the metal or metal ion is any one selected from the group consisting of silver, copper, lead, zinc, tin, or ions thereof. . (5) The antibacterial liquid according to any one of claims 1 to 4, wherein the solvent of the antibacterial liquid is aqueous ammonia. (6) The antibacterial liquid according to any one of claims 1 to 5, wherein the antibacterial liquid contains alcohol. (7) N- of the metal having antibacterial action in the antibacterial liquid
The content of the long-chain acylamino acid salt or the combined content of the N-long-chain acylamino acid ion and the metal ion is 0.01X with respect to the weight percent (X%) of ammonia in the antibacterial liquid. 7. An antimicrobial liquid according to any one of claims 1 to 6, wherein the antibacterial liquid is ~5X parts by weight. (8) The antibacterial liquid according to any one of claims 1 to 4, wherein the solvent of the antibacterial liquid is morpholine. (9) N- of the metal having antibacterial action in the antibacterial liquid
The content of the long-chain acylamino acid salt or the combined content of the N-long-chain acylamino acid ion and the metal ion is from 0.01 to 100 parts by weight of the antibacterial liquid.
Antibacterial liquid according to claim 8, which is 0.3 parts by weight. (10) An antibacterial paint containing the antibacterial liquid according to any one of claims 1 to 9.