JP2020040984A - Aqueous composition and powder composition - Google Patents

Abstract

To provide multifunctional aqueous and powder compositions that have antibacterial, deodorization and mildew-proofing effects and additionally have antivirus and antistatic effects in combination.SOLUTION: The aqueous composition has iron, aluminium, tungsten oxide and sulfonic acid present in an aqueous solvent, which exhibits high antibacterial effect, high deodorization effect and high mildew-proofing effect and additionally exhibits excellent antivirus effect and excellent antistatic effect in combination with the above-mentioned effects. The aqueous composition can be used in a processing agent imparting antibacterial effect, deodorization effect, mildew-proofing effect, antivirus effect and antistatic effect to a fiber product in particular. The aqueous composition can be used in various kinds of applications by virtue of high safety and simple handling and can be used not only for a fiber product but also, for example, various kinds of resin products, films, inks, coating materials, metals and the like and can be also used in spraying construction for furniture, an air-conditioning filter and duct, a building room and a vehicle cabin, interior of a car and the like.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to an aqueous composition and a powder composition having multifunctional properties such as antibacterial, deodorant, antifungal, antiviral, and antistatic.

  The applicant of the present application has grasped the following Patent Documents 1 to 5 as prior art documents relating to a composition having functions such as antibacterial, deodorant, and antifungal.

Japanese Patent No. 5507787 JP 2015-6987 A JP-T-2015-513306 International Publication No. 2009/110233 pamphlet JP 2015-51387 A

[Patent Document 1]
Patent Literature 1 relates to an aqueous composition containing a metal composition, and has the following description.
[Claim 1] A deodorant comprising an aqueous composition containing a metal composition containing iron, aluminum, potassium and titanium, wherein the iron content is 16 to 40 ppm, the aluminum content is 40 to 50 ppm, A deodorant having a potassium content of 0.20 to 0.45 ppm and a titanium content of 0.1 to 27.2 ppm, containing no silver ions, and fixed to an object for use.
[0023] Aluminum, iron and potassium are essential metal components for deodorizing, antibacterial and antifungal effects exhibited by the metal composition proposed by the present inventors.

[Patent Document 2]
Patent Document 2 described above relates to a method for producing a membrane using an aqueous dispersion, and has the following description.
[0012] It is an object of the present invention to provide a method for producing a membrane using an aqueous dispersion liquid which is excellent in dispersibility and hardly precipitates for a long period of time.
[0013] In the method for producing a film according to an embodiment of the present invention, a step of preparing an aqueous dispersion containing at least one kind of fine particles selected from tungsten oxide fine particles and tungsten oxide composite fine particles and a dispersion medium containing water. And applying the aqueous dispersion to a substrate to form a film containing the fine particles, wherein the average primary particle diameter (D50) of the fine particles in the aqueous dispersion is (D50). The range of 1 nm or more and 400 nm or less, the concentration of the fine particles in the aqueous dispersion is 0.1% by mass or more and 40% by mass or less, and the pH of the aqueous dispersion is 1.5 or more and 6.5 or less. It is characterized by being within the range. In the method for producing a film according to the present invention, the tungsten oxide composite material may contain at least one metal element selected from a transition metal element and Al or a compound containing the metal element in an amount of 0.001% by mass as the amount of the metal element. It is contained in the range of not less than 50% by mass and the balance is made of tungsten oxide.

[Patent Document 3]
Patent Document 3 relates to a transparent photocatalytic coating and has the following description.
[0003] Photocatalytic compositions that include a photocatalyst and a cocatalyst can be useful in a variety of photocatalytic applications. In addition, since the cocatalyst can improve the photocatalytic activity of the photocatalyst, the combined use of the photocatalyst and the cocatalyst has higher activity than the photocatalyst alone. In addition, the incorporation of the photocatalyst material / cocatalyst into the photocatalytic coating will help to improve the transparency and photocatalytic activity of the coating material.
[0005] In some embodiments, the photocatalyst can be W-based. In some embodiments, the photocatalyst can be responsive to visible light. In some embodiments, the photocatalyst can be tungsten oxide, doped tungsten oxide powder, or tungsten oxide composite powder.

[Patent Document 4]
Patent Document 4 relates to an antibacterial material, an antibacterial film and an antibacterial member using the same, and has the following description.
[0007] It is an object of the present invention to provide an antibacterial material exhibiting practical antibacterial performance regardless of the presence or absence of light irradiation, and an antibacterial film and an antibacterial member using the same.
[0008] The antibacterial material according to the embodiment of the present invention is an antibacterial material including at least one kind of fine particles selected from tungsten oxide fine particles and tungsten oxide composite fine particles, wherein the fine particles are JIS-Z-2801. (2000) Antibacterial processed product-A test piece having the fine particles adhered in the range of 0.02 mg / cm2 or more and 40 mg / cm2 or less, according to the method for testing antibacterial activity, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, and inoculated with at least one bacterium selected from enterohemorrhagic Escherichia coli, and performed an antibacterial evaluation test to evaluate the viable cell count after storage for 24 hours,
R = log (B1 / C1)
(In the formula, B1 is the average value of the number of viable cells after storing the unprocessed test piece for 24 hours, and C1 is the average value of the viable cell number after storing the test piece coated with the fine particles for 24 hours. ()
Is characterized in that the antibacterial activity value R is 0.1 or more.

[Patent Document 5]
Patent Document 5 relates to a photocatalyst and has the following description.
[0008] An object of the present invention is to reduce the contact resistance between a photocatalyst material and a hole-collecting material to facilitate the movement of holes generated by the photocatalytic material to an oxidation site composed of the hole-collecting material. It is to improve the photocatalytic activity.
[0009] The present invention is a photocatalyst containing a photocatalytic material responsive to visible light, a hole collecting material fused with the photocatalytic material, and an electron collecting material. Preferably, the photocatalyst material contains tungsten oxide, and the hole trapping material contains titanium oxide. As the electron trapping material, it is preferable to use at least one of platinum, rhodium, ruthenium, copper, nickel, iron, magnesium, gold, silver and the like. The photocatalyst material and the hole trapping material are closely bonded at an atomic level or bonded in a gradient manner. Or it becomes eutectic. The present invention encompasses the above-described method for producing a photocatalyst material, which comprises a step of fusing the visible light-responsive photocatalyst material, the hole collection material, and the electron collection material at an atomic level by a thermal plasma method.

As described above, Patent Document 1 describes an aqueous composition that declares an antibacterial, deodorant, and antifungal effect.
Many compositions and processing agents having such antibacterial, deodorant, and antifungal effects are on the market, and further development of compositions and processing agents having antiviral and antistatic effects has been made. Is desired.

The present invention has been made with the following objects in view of the above situation.
Provided are a multifunctional aqueous composition and a powder composition which have antibacterial, deodorant, and antifungal effects as well as antiviral and antistatic effects.

In order to achieve the above object, the aqueous composition according to claim 1 has the following configuration.
Iron, aluminum, tungsten oxide, and sulfonic acid are present in the aqueous solvent.

In order to achieve the above object, the powder composition according to claim 2 has the following configuration.
It contains iron, aluminum, tungsten oxide, and sulfonic acid.

In the first aspect of the present invention, iron, aluminum, tungsten oxide, and sulfonic acid are present in an aqueous solvent. Thereby, a high antibacterial effect, a high deodorizing effect, and a high antifungal effect are exhibited. In addition, it exhibits an excellent antiviral effect and an excellent antistatic effect.
In addition, the invention according to claim 1 has a particularly excellent affinity for fibers, and is used as a processing agent for imparting an antibacterial effect, a deodorant effect, an antifungal effect, an antiviral effect, and an antistatic effect to textiles. Can be used.

The invention according to claim 2 contains iron, aluminum, tungsten oxide, and sulfonic acid. Thereby, a high antibacterial effect, a high deodorizing effect, and a high antifungal effect are exhibited. In addition, it exhibits an excellent antiviral effect and an excellent antistatic effect.
In addition, the invention according to claim 2 provides an antibacterial effect, a deodorant effect, a fungicidal effect, an antiviral effect, and an antistatic effect, especially for fibers, resin products, films, inks, paints, etc. having low water permeability. Can be used as a processing agent for imparting

  Next, an embodiment for carrying out the present invention will be described.

〔Overview〕
In the aqueous composition of the present embodiment, iron, aluminum, tungsten oxide, and sulfonic acid are present in an aqueous solvent.
The powder composition of the present embodiment contains iron, aluminum, tungsten oxide, and sulfonic acid. This powder composition can be obtained by removing water from the aqueous composition.
In the composition of the present embodiment, a viscous liquid / solid / powder can be added by adding aluminum carbonate or the like.

The aqueous composition and the powder composition can be used as a surface treating agent for, for example, textiles and leather.
The aqueous composition is immersed and infiltrated into a fiber product, leather, or the like, applied to the surface, and dried to remove moisture. As a result, an antibacterial effect, a deodorant effect, a fungicidal effect, an antiviral effect, and an antistatic effect can be imparted to textiles, leather, and the like, which are objects to be treated.
The above-mentioned powder composition is applied to or printed on the surface of fibers, resin products, films, etc. having low water permeability, and kneaded into fiber raw materials, resin raw materials, inks, paints, etc. to be treated. An antibacterial effect, a deodorant effect, a fungicide effect, an antiviral effect, and an antistatic effect can be imparted to textiles, leather, resin products, films, inks, paints, and the like.

〔iron〕
The iron can be present as iron ions in the aqueous composition by dissolving an iron salt in the aqueous solvent. Specific examples of the iron salt include iron (II) chloride, iron (III) chloride, iron (II) sulfate, iron (III) sulfate, iron nitrate (II), and iron (III) nitrate. .

  The iron can exist as iron ions (II) and iron ions (III) in the aqueous composition. Besides these, they may be present as iron ions (IV).

  The iron present as iron ions in the aqueous composition is mainly replaced by the various iron sulfonic acid salts described above by the addition of sulfonic acid.

  The iron is an element involved in the Fenton reaction and the oxidation reaction. When the aqueous composition and the powder composition of the present embodiment are used as a surface processing agent, for example, on the surface of a processing target such as a textile product or leather, it acts together with moisture or oxygen existing in the air to form the processing target. It oxidatively destroys biomolecules and organic compounds adhering to the surface, and exhibits antibacterial, deodorant, antifungal and antiviral effects.

The content of iron in the aqueous composition is preferably 0.00003% by mass to 0.0867% by mass, and most preferably 0.0026% by mass.
The content of iron in the powder composition is preferably from 0.09% by mass to 0.16% by mass, and most preferably 0.1001% by mass.

〔aluminum〕
The aluminum can be present as aluminum ions in the aqueous composition by dissolving the aluminum salt in the aqueous solvent. Specific examples of the aluminum salt include aluminum sulfate and aluminum carbonate.

  The aluminum exists as an aluminum ion (III) in the aqueous composition.

  The aluminum, when the aqueous composition and the powder composition of the present embodiment are used as a surface treatment agent or a kneading agent, for example, on the surface of an object to be processed such as textiles or leather, the moisture existing in the air or Acts together with oxygen to neutralize and adsorb ammonia-based substances adhering to the surface of the workpiece, and to decompose acid-based substances such as acetic acid and isovaleric acid. Complement effect, antiviral effect.

The content of aluminum in the aqueous composition is preferably 0.002% by mass to 6.66% by mass, and most preferably 0.2% by mass.
The content of aluminum in the powder composition is preferably from 6.925% by mass to 12.01% by mass, and most preferably 7.6947% by mass.

(Tungsten oxide)
The tungsten oxide is present in the aqueous composition by dispersing the powder in an aqueous solvent. In the powder composition, a powder is mixed and present.

By functioning as a photocatalyst, the tungsten oxide shifts the equilibrium in a direction in which the partner substance is easily oxidized in the above-described oxidation reaction by iron. Thereby, the antibacterial effect, the deodorant effect, the antifungal effect, and the antiviral effect are increased.

The content of tungsten oxide in the aqueous composition is preferably 0.000001% by mass to 0.0026% by mass, and most preferably 0.0001% by mass.
The content of tungsten oxide in the powder composition is preferably 0.00274% by mass to 0.006% by mass, and most preferably 0.003% by mass.

〔Sulfonic acid〕
The sulfonic acid can be present as a sulfonic acid ion in the aqueous composition.

  The sulfonic acid ions in the aqueous composition mainly exist as various sulfonic acid salts described below.

  As the sulfonic acid, aromatic monovalent sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid and p-phenolsulfonic acid can be used.

  The reason that sulfonic acid was used favorably is that although there are products that mainly use metal salts, there is no previous case that combines metal salts and sulfonic acid as main materials, and this objective was sufficiently achieved in terms of function. This is because multiple functions can be improved. Among these, p-toluenesulfonic acid can be most preferably used. The reasons are that the properties are well known and the safety is high, that the objective is sufficiently achieved in terms of function, that the cost is not high, and the like.

The content of the sulfonic acid in the aqueous composition is preferably 0.00011% by mass to 0.3667% by mass, and most preferably 0.011% by mass.
The content of the sulfonic acid in the powder composition is preferably from 0.3813% by mass to 0.6011% by mass, and most preferably 0.4236% by mass.

  In the composition of the present embodiment, the ratio of iron to aluminum is preferably 1.3% iron and 98.7% aluminum. The ratio of sulfonic acid to metal (iron + aluminum) is preferably 94.2% metal (iron + aluminum): 5.2% sulfonic acid. The proportion of tungsten oxide to iron is preferably 96% iron: 4% tungsten oxide.

(Production method)
As described above, the aqueous composition of the present embodiment can be obtained by charging an iron salt, an aluminum salt, a tungsten oxide powder, and a sulfonic acid into an aqueous solvent and stirring the mixture as appropriate. At this time, the iron salt, the aluminum salt, and the sulfonic acid are dissolved in the aqueous solvent, and the tungsten oxide powder is dispersed in the aqueous solvent.

  The powder composition of the present embodiment can be obtained by removing water from the aqueous composition. Also, a viscous liquid / solid / powder can be prepared by adding aluminum carbonate or the like.

[Example of usage]
The aqueous composition and the powder composition can be used as a surface treating agent for, for example, textiles and leather.
The aqueous composition is immersed and infiltrated or applied to the surface of a fiber product, leather, or the like, and dried to remove moisture. As a result, an antibacterial effect, a deodorant effect, a fungicidal effect, an antiviral effect, and an antistatic effect can be imparted to textiles, leather, and the like, which are objects to be treated.
The above-mentioned powder composition is applied to or printed on the surface of fibers, resin products, films, etc. having low water permeability, and kneaded into fiber raw materials, resin raw materials, inks, paints, etc. to be treated. An antibacterial effect, a deodorant effect, a fungicide effect, an antiviral effect, and an antistatic effect can be imparted to textiles, leather, resin products, films, inks, paints, and the like.

  Next, examples will be described. Note that the present invention is not intended to limit the present invention to the following examples.

The aqueous compositions of the examples were prepared as follows.
Preparation of Test Solution Iron salt and aluminum salt were dissolved in pure water, and 0.0026% by mass of iron ions and 0.2% by mass of aluminum ions were present. In the above solution, p-toluenesulfonic acid was dissolved to be present at 0.011% by mass. Further, 0.0001% by mass of tungsten oxide powder was dispersed to obtain a stock solution. The stock solution was diluted 50- to 100-fold with pure water to obtain a test solution of Example.

  (1) Antibacterial test, (2) Deodorant test, (3) Antifungal test, (4) Antiviral property Each of the tests and (5) the charging test was performed, and the effect was confirmed.

(1) Antibacterial test 1 Test method: Quantitative test (bacterial liquid absorption method) based on JIS L 1902: 2008.
However, the washing method is based on the test method of JIS L 0217 103.
The viable cell count is measured by the pour plating method, the evaluation method, and the common logarithm of the viable cell count of a standard cotton cloth. Ma is immediately after the inoculation, and Mb 18 hours later.
-For the cloth sample of the example, the common logarithm of the viable cell count is measured. The measurement was performed for the case where washing was performed 0 times and for the case where washing was performed 10 times. Mo is immediately after the inoculation and Mc 18 hours later.
-The bactericidal activity value and the bacteriostatic activity value were calculated and evaluated as follows.
Bactericidal activity value = Ma-Mc
Bacteriostatic activity value = (Mb-Ma)-(Mc-Mo)

"Results" The results when Staphylococcus aureus, Klebsiella pneumoniae, MRSA, Pseudomonas aeruginosa, Escherichia coli, and Moraxella were used as test strains are shown in Tables 1 to 6, respectively. Each showed good antibacterial performance.

(2) Deodorant test ① Test method:
(Single company) Textile Evaluation Technology Council SEK Mark Textile Product Certification Standard, Mutually applicable 21. Deodorant test (detection tube method, gas chromatograph method)
However, the washing treatment method is based on JIS L 0217 103, repeated 10 times, and hanging and drying.
The laundry detergent used was a JAFET standard combination detergent.
◆ Evaluation method The initial gas concentration was as follows, and the component concentration after 2 hours was measured, and the reduction rate was evaluated.
Ammonia: 100ppm
Acetic acid: 30 ppm
Isovaleric acid: about 38 ppm
Nonenal: about 14 ppm
Trimethylamine: 28 ppm
Pyridine: 12 ppm
Formaldehyde: 15ppm
Indole: about 33 ppm

◆ Results The results are shown in Table 7 below. Each showed good deodorant performance.

(3) Antifungal test ① Test method:
0.2 mL of a spore suspension adjusted to about 10 ⁵ mL with a 1/20 Sabouraud dextrose medium was inoculated to sterilized material (0.2 g) of about 18 mm square, and cultured at 25 ° C. for 42 hours. After the culture, the ATP concentration of the spores on the sample was measured by a luminescence measurement method.
The washing method is based on the test method of JIS L 0217 103 (the detergent is a JAFET standard combination detergent).
◆ Evaluation method ・ ATP amount of standard cotton cloth is measured. Aa immediately after the inoculation and Fb after 42 hours.
-ATP amount is measured for the cloth sample of the example. The measurement was performed for the case where washing was performed 0 times and for the case where washing was performed 10 times. Immediately after the inoculation is designated as Fo and 42 hours later as Mc.
-The growth value and the antifungal activity value were calculated and evaluated as follows.
Growth value = Fb-Fa
Bacteriostatic activity value = (Fb-Fa)-(Fc-Fo)

◆ Results The results obtained when the black mold and Trichophyton were used as test strains are shown in Tables 8 to 9 below. Each showed good antifungal performance.

(4) Antiviral test ① Test method:
According to ISO18184 Textiles-Determination of anticipational activity of textile products.
However, the washing method is based on JIS L 0217 103 (the detergent uses a JAFET standard combination detergent).
Measuring method of virus infectious titer: Plaque assay
◆ Evaluation method The infection titer was measured immediately after inoculation of the standard cotton cloth. Similarly, the infectious titer was measured 2 hours after inoculation of a standard cotton cloth, and was defined as Vb. In the same manner, in the examples, the infectious titer was measured 2 hours after the inoculation, and the measured value was Vc. In the example, the measurement was performed for 0 washes and 10 washes.
The antiviral activity value was calculated by the following equation.
Antiviral activity value = Vb−Vc

◆ Results ◇ Influenza virus Influenza A virus (H3N2): ATCC VR-1679
The results are shown in Table 10 below. Good results were shown.

◇ネコカリシウイルス Ｆｅｌｉｎｅ ｃａｌｉｃｉｖｉｒｕｓ：ＡＴＣＣ ＶＲ−７８２
結果を下記の表１１に示す。良好な結果を示した。

◇ Feline calicivirus: ATCC VR-782
The results are shown in Table 11 below. Good results were shown.

(5) Charging test 性 Test method:
According to JIS L 1094, the measurement of the half-life and the measurement of the triboelectric voltage were performed. Polyester fabric was used as a test cloth.
In each case, the environment of the test room is room temperature 20 ° C. and humidity 40%.
<Evaluation method> Half-life After charging with an applied voltage of 10 kV, the time (second) until the charged voltage attenuated to 1/2 was measured.
(4) Friction charging voltage A friction cloth (cotton / hair) was rubbed while rotating the drum to which the test piece was attached, and the charging voltage (V) was measured 60 seconds after the start of friction.

◆ Results ◇ Half-life In the examples, measurement was not possible due to the small charged voltage. The unprocessed product as a comparative example took 120 seconds or more.
◇ Friction band voltage The results are shown in Table 12 below. It showed very good performance.

[Operation and effect of the embodiment]
In the present embodiment, the following operation and effect can be obtained.
In this embodiment, iron, aluminum, tungsten oxide, and sulfonic acid are present in an aqueous solvent. Thereby, a high antibacterial effect, a high deodorizing effect, and a high antifungal effect are exhibited. In addition, it exhibits an excellent antiviral effect and an excellent antistatic effect.

  In the aqueous composition, it is particularly excellent in affinity with the fiber, and can be used as a processing agent for imparting an antibacterial effect, a deodorant effect, an antifungal effect, an antiviral effect, and an antistatic effect to textiles. .

  In powder compositions, antibacterial effect, deodorant effect, antifungal effect, antiviral effect, antistatic effect, especially for materials with low permeability of aqueous compositions such as fibers, resin products, films, inks, and paints Can be used as a processing agent for imparting

(Modification)
The aqueous composition and the powder composition of the present invention can be adjusted in content, blended with other agents, or added with appropriate additives, depending on the place of use and conditions of use. . As these other additives and additives, for example, by blending with other deodorants, antibacterial or antifungal agents, antistatic agents, antiviral agents, etc., the effect can be additively or synergistically enhanced. it can.

[Summary]
The aqueous composition and the powder composition of the present invention have high safety and are easy to handle, so that they can be used for various purposes. It can be used not only for textile products, but also for various types of resin products, films, inks, paints, metals, etc., and spray construction for furniture, air conditioning filters, ducts, building interiors, vehicle interiors, vehicle interiors, etc. Can also be used.

Specifically, the aqueous composition can be mainly used as a processing agent for fibers (yarns, fabrics, and products), and can be sprayed on indoor walls, ceilings, floors, and other sprayable places (for example, in a car, It can be used in trains, aircraft, etc.
The powder composition can be used for kneading into an object which cannot be used for water, for example, resin or the like, mixing with ink or paint, or applying to a film or metal.

Claims (2)

An aqueous composition, wherein iron, aluminum, tungsten oxide, and sulfonic acid are present in an aqueous solvent. A powder composition comprising iron, aluminum, tungsten oxide, and sulfonic acid.