JPH02268104A - Antimicrobial composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having improved processability in production of antimicrobial product and antimicrobial property with small specific gravity as a whole and large surface area of metal having antimicrobial action by adhering the metal onto the surface of fine particle of water insoluble inorganic oxide. CONSTITUTION:Fine particles of water-insoluble inorganic oxide preferably having <=1mum averaged particle diameter, e.g. zeolite, diatom earth, mica, kaolin, alumina, talc, silica gel simple substance or mixture of same substances are used as carriers. Metal having antimicrobial properties, preferably silver and/or copper is adhered on the surface of said carrier having small specific gravity in an amount of >=1wt.% to said carrier, and respectively >=0.5wt.% in a case of using the both of silver and copper as the metal to reduce specific gravity. Said substance is added to fiber product, etc., in production of same product to suppress or inhibit deviated dispersing by sedimentation in producing antimicrobial product and to make easy to handle, and simultaneously make ionization easy by enlarging the surface area of said metal to afford antimicrobial composition having exceedingly improved antimicrobial properties in lower cost than conventional product.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an antibacterial composition, which is added during the production of textile products, films, plastic molded products, paints, etc., and provides antibacterial properties to these products. used for.

(Prior Art) Conventional antibacterial compositions added to produce the above-mentioned antibacterial products include organic and inorganic compositions. The main components are trichlorocarbanide, polyhexamethylene biguanide hydrochloride, octadecyldimethyl-3-trimethoxysilylbropylammonium chloride, etc. Examples of the use of inorganic compositions include Acrylic cotton or thread was made to contain copper sulfide or copper during the dyeing process, or silver powder or copper powder was added.

(Problems to be Solved by the Invention and Objectives of the Invention) Among the antibacterial compositions that have been used conventionally, organic compositions are volatile and therefore do not escape during the manufacturing process of antibacterial products. Because of its easy-to-use properties, the antibacterial properties of the product are unstable, and when exposed to high temperatures during the manufacturing process of antibacterial products, it reacts with the polymer that is to become the matrix, significantly inhibiting the original properties of the polymer. The problem is that there are many things to do.

On the other hand, inorganic compositions containing antibacterial metal compounds as a main component are blended during the production of fibers, films, etc., and are in a dispersed state in the final product. The mechanism of action is that metals with antibacterial properties are ionized and transferred to the surface of the product, thereby exhibiting antibacterial properties.

The method of incorporating copper sulfide or copper into acrylic cotton or yarn during the dyeing process has problems in that it is expensive because it requires a long number of steps and a long reaction time.

Furthermore, when silver powder, copper powder, etc. are used, due to their high specific gravity, they tend to settle before producing antibacterial products, which is not only inconvenient to handle, but also requires a large amount of compounding. There were issues from the front.

Therefore, an object of the present invention is to provide an antibacterial composition which has a relatively small proportion of metals having an antibacterial effect, has a low specific gravity, and has sufficient antibacterial properties.

(Means and effects for solving the problem and achieving the object) According to the present invention, the above problem is solved by the fact that a metal having an antibacterial effect is attached to the surface of water-insoluble inorganic oxide fine particles. The antibacterial composition basically solves the problem and achieves the above objectives.

That is, in the present invention, by using a water-insoluble inorganic oxide with a small specific gravity as a carrier, the overall specific gravity is reduced, thereby facilitating handling during the production of antibacterial products. By using insoluble inorganic oxides as fine particles, the surface area of the antibacterial metal to be adhered to is increased, facilitating ionization and improving antibacterial properties.

Zeolite (
There is no problem with using aluminosilicate), diatomaceous earth, mica, alumina, kaolin (clay), talc, silica gel alone, or a mixture of these, but if it is a mixture, take the ionicity of the particles into consideration and Care must be taken to prevent agglomeration. The average particle size of these water-insoluble inorganic oxides is preferably 1 μm or less. In some cases, the average particle size of water-insoluble inorganic oxide fine particles does not necessarily have the above-mentioned limit, but when the final product is made into a thin product such as fiber, film, or paint, water-insoluble inorganic oxide fine particles If the average particle size is 19 μm or more, the maximum particle size will also be large, causing noticeable unevenness on the surface of the final product, resulting in a deterioration in appearance and quality. In particular, when blending the antibacterial composition of the present invention to produce antibacterial synthetic fibers, it is recommended to use water-insoluble inorganic oxide fine particles with an average particle size of 0.5μ or less. is preferred, IL, maximum particle size 10 μm
This is because if the water-insoluble inorganic oxide particles above exist, there is a risk of clogging the spinning nozzle.The smaller the average particle diameter of the water-insoluble inorganic oxide fine particles as a carrier, the more likely they are to clog the spinning nozzle. It should be noted that the surface area of the attached antibacterial metal increases and the antibacterial properties are improved.

In the antibacterial composition of the present invention, various metals having an antibacterial effect can be considered, such as silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, and mercury. From the viewpoint of hygiene, it is preferable to use silver, copper, or both.These silver or copper metals may be in the form of ions such as oxides or chlorides, but it is preferable that they are insoluble in water. Preferably, the amount deposited is 1 wt relative to the water-insoluble inorganic oxide fine particles serving as the carrier.
It is X or more. In this case, the lower limit value takes into account antibacterial performance and usage. That is, if the amount of antibacterial metal deposited in the antibacterial composition is less than 1 wt. There is a need to relatively increase the amount of antibacterial composition blended into the spinning solution, but if 6x or more of the antibacterial composition is added to the spinning dope, yarn breakage will increase during spinning and productivity will decrease. It is. In addition, when both silver and copper are used, the amount of these deposited is 0.5wt1 or more, respectively, based on the water-insoluble inorganic oxide fine particles. The reason for setting the lower limit value in this case is the same as above.

In order to produce the antibacterial composition according to the present invention by attaching silver, copper, or both to water-insoluble inorganic oxide fine particles as a carrier, a well-known vacuum evaporation method or a reduction precipitation method can be used. .

Among these, in the vacuum evaporation method, water-insoluble inorganic oxide fine particles are set in the chamber of a evaporation device, the evaporation source (silver, copper, or a piece of silver-copper alloy) is placed on a tungsten basket, and the water-insoluble inorganic oxide particles are placed in the chamber. and reduce the pressure in the chamber to about 2 x 10-' Torr), and then heat the tungsten basket while vibrating the water-insoluble inorganic oxide fine particles to evaporate the vapor deposition source metal. It can be implemented by

On the other hand, the reduction precipitation method involves dispersing water-insoluble inorganic oxide fine particles in pure water, mixing this dispersion with a plating solution, and then adding a plating reducing solution to this mixed solution while stirring. It can be implemented.

Of these two methods, the vacuum evaporation method is limited in the direction of irradiation of the evaporated metal, so vibrations are applied to the water-insoluble inorganic oxide particles in order to uniformly adhere the antibacterial metal to the water-insoluble inorganic oxide particles. In this case, the coarse particles tend to be on top and the fine particles on the bottom. Therefore, if the water-insoluble inorganic oxide fine particles are not uniform in particle size, the amount of antibacterial metal deposited may be affected. However, according to the reduction precipitation method, the antibacterial metal is deposited on the dispersed water-insoluble inorganic oxide fine particles, so it is possible to adhere uniformly, and the amount of adhesion can be easily controlled. , the latter method is preferable to the former.

(Examples, etc.) Next, production examples and usage examples of the antibacterial composition according to the present invention (
The present invention will be explained in more detail with reference to (Manufacturing of antibacterial fibers and evaluation of antibacterial properties).

Note that X and parts referred to below are based on weight unless otherwise specified.

艮1” Lyu (1) The following three types of liquids were prepared.

A) Zeolite dispersion 65 g of zeolite powder (average particle size 0.5 μm) was dispersed in 300 mj of pure water.

B) Silver plating solution: 20 g of silver nitrate was dissolved in pure water to make 800 mJ, and then ammonium hydroxide was added to adjust the pH to 11.

C) Reducing solution for silver plating 100 g of potassium sodium tartrate (tetrahydrate) was dissolved in pure water to give a concentration of 700 mj, and the temperature of the solution was maintained at 30°C.

(2) Operation The above zeolite dispersion (A) is coated with silver plating solution (B).
was added and mixed, and while stirring at a liquid temperature of 30°C, the above-mentioned reducing solution for silver plating was added and stirring was continued to completely reduce the silver ions, and then stirring was continued for an additional hour.

After that, stirring was stopped, filtered by suction using No. 5C filter paper, thoroughly washed with pure water, and dried in an air dryer at 80°C.
The desired antibacterial composition was obtained by drying for 2 hours.

When the state of silver adhesion in this antibacterial composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the zeolite powder.

According to chemical analysis, the silver coverage was 16.3X.

Number 11112 - Alumina, kaolin, water-insoluble inorganic oxide dispersion
Talc, silica gel and diatomaceous earth powder at 241% each.
Five types of antibacterial compositions were obtained in exactly the same manner as in Production Example 1, except that 3 g was taken and used as each dispersion, and stirring was continued for 2 hours after complete reduction of silver ions.

According to EP) 4A observation, silver was uniformly deposited on the surface of the water-insoluble inorganic oxide powder in all antibacterial compositions, and according to chemical analysis, the amount of silver deposited was 5.5% in each case.
It was 0%.

11 Takumi J (1) The following copper plating solution and reducing solution for copper plating were prepared.

B') Copper plating solution Copper sulfate (pentahydrate) 34.6g, potassium sodium tartrate (tetrahydrate) 173g, and sodium hydroxide 5
0g was dissolved in pure water to make 500μ1.

C') Copper plating reducing solution: 150 mj of 37% formaldehyde solution, kept at a liquid temperature of 30°C.

(2) Operation Add the above copper plating solution (B') to the alumina dispersion (A) prepared in Production Example 1 and mix. While stirring at a liquid temperature of 30°C, the above copper plating reducing solution (C' ) and continued stirring to completely reduce the copper ions, and then continued stirring for an additional hour.

After that, stirring was stopped, filtered by suction using No. 5C filter paper, thoroughly washed with pure water, and dried in an air dryer at 80°C.
The desired antibacterial composition was obtained by drying for 2 hours.

When the state of copper adhesion in this antibacterial composition was observed by EPMA, it was found that copper was uniformly adhered to the surface of the alumina powder.

According to chemical analysis, the amount of copper deposited was 11.9%.

1 m2 1 child 16 zeolite, kaolin, talc, silica gel, and diatomaceous earth powder each as a water-insoluble inorganic oxide dispersion
Five types of antibacterial compositions were obtained in exactly the same manner as in Production Example 5, except that 6.1 g was taken and used as each dispersion, and stirring was continued for 2 hours after complete reduction of copper ions. Ta.

According to EPMA @Survey, copper is uniformly attached to the surface of the water-insoluble inorganic oxide powder in all antibacterial compositions, and chemical analysis shows that the amount of copper attached is 5.5% in each case.
It was 0%.

i.A.A.A.A.
20 parts by weight of an antibacterial composition to which 5% of g.
Hereinafter abbreviated as MA) / Sodium methallylsulfonate =
2 parts by weight of an acrylic polymer (A) with a composition of 90.0/9.0/1.0 and a molecular weight of 50,000 and 78 parts by weight of dimethylformamide (hereinafter abbreviated as DMF) were mixed for about 1 hour using a homomixer. After dispersing the antibacterial agent predispersion for about 5 minutes using a sand grinder, 20 parts by weight of the acrylic polymer (A) and DMF were continuously added.
The above-mentioned antibacterial composition is added to the spinning stock solution consisting of 80 parts by weight in an amount of 1.0.0.7.
They were added and mixed using a pipeline mixer to a concentration of 0.2% by weight, and wet-spun according to a conventional method to obtain a 3-denier antibacterial acrylic fiber.

The antibacterial evaluation of this fiber is shown in Table 1 below.

According to this table, it can be seen that good antibacterial properties are brought about by adding 0.7% or more of the above antibacterial composition. The antibacterial properties were evaluated by spinning antibacterial acrylic fibers into No. 30 single yarn using a conventional method, and then circularly knitting them. This was carried out using the "shake flask method" method according to the processed product certification standard (the same applies to the following usage examples).

In Tables 1.2.3 and 4 below, the column to the right of the number of washes indicates the bacterial reduction rate of the test object.

Ag
Antibacterial acrylic fibers were obtained using the same composition and method as in Use Example 1 using an antibacterial composition to which 5% of the antibacterial composition was adhered.

The antibacterial evaluation of this fiber is shown in Table 1 below.

According to this table, it can be seen that good antibacterial properties are brought about by adding 0.8% or more of the above antibacterial composition.

"Rikaku Takumi" Cu
Use example 1 using an antibacterial composition with 9% adhesion of
Antibacterial acrylic fibers were obtained using the same composition and method.

The antibacterial evaluation of this fiber is shown in Table 2 below, which shows that good antibacterial properties can be obtained by adding 0.5% or more of the above antibacterial composition.

1. Kaolin fine particles with an average particle size of 0.5 μI are used as a carrier, and Cu
Antibacterial acrylic fibers were obtained using the same composition and method as in Use Example 1 using an antibacterial composition to which 5% of the antibacterial composition was adhered.

The antibacterial evaluation of this fiber is shown in Table 2 below.

According to this table, it can be seen that good antibacterial properties are brought about by adding 0.8% or more of the above antibacterial composition.

1 Anal Takumi j Antibacterial properties were obtained using the same composition and method as in Use Example 1 using an antibacterial composition in which zeolite and alumina fine particles with an average particle size of 0.5 μm were used as carriers, and 5% Ag and 5% Cu were attached. Acrylic fibers were obtained.

The antibacterial evaluation of this fiber is shown in Table 3 below.

According to this table, it can be seen that adding 0.5% or more of the above-mentioned antibacterial composition brings about good antibacterial properties.

吏口燵 1 Using the same composition and method as in Use Example 1, using an antibacterial composition in which kaolin and diatomaceous earth microparticles with an average particle size of 0.5μ are used as a carrier, and 5% of Ag and 5% of Cu are attached respectively. Antibacterial acrylic fibers were obtained.

The antibacterial evaluation of this fiber is shown in Table 3 below.

According to this table, it can be seen that good antibacterial properties are brought about by adding 0.6% or more of the above antibacterial composition.

Using an antibacterial composition containing talc and silica gel microparticles with an average particle size of 0.5 μ as a carrier, and adhering 5X Ag and 5% Cu, antibacterial treatment was carried out using the same composition and method as in Use Example 1. A synthetic acrylic fiber was obtained.

The antibacterial evaluation of this fiber is shown in Table 4 below. According to this table, it can be seen that good antibacterial properties tend to be achieved by adding 0.5% or more of the above antibacterial composition.

11 Takumi J Using silica gel fine particles with an average particle size of 0.5μ as a carrier, A
20 parts by weight of antibacterial composition to which 5% of g was attached, AN/M
A/Sodium methallylsulfonate = 90.0/9.0/
Acrylic polymer (A) 2 with a composition of 1.0 and a molecular weight of 50,000
78 parts by weight of DMF were dispersed for about 1 hour using a homomixer.Then, the above antibacterial composition preliminary dispersion was dispersed for about 5 minutes using a sand grinder, and then the acrylic composition was dispersed continuously for about 5 minutes using a sand grinder. Polymer (A) 23 parts by weight,
The above-mentioned antibacterial agent is added to the spinning stock solution consisting of 77 parts by weight of DMF at 0.3% by weight based on the above-mentioned acrylic polymer (A).
They were added and mixed using a pipeline mixer and wet-spun according to a conventional method to obtain a 3-denier antibacterial acrylic fiber. The antibacterial evaluation of this fiber is shown in Table 5 below.

According to this table, it can be seen that the antibacterial fibers described above have good antibacterial properties against various bacteria.

(Effects of the Invention) From the above, the present invention provides the following effects.

(1) Since silver and copper are attached to the surface of water-insoluble inorganic oxide fine particles, their surface area is higher than that of conventional particles of silver powder or copper powder only, even if they have the same particle size and weight. becomes exponentially larger.

(2) Therefore, even if the amount of silver and copper used is much lower than that of conventional products, the antibacterial effect is significantly improved, and therefore, the antibacterial composition of the present invention can be supplied at a relatively lower price than conventional products. can do.

(3) Since the carrier of the antibacterial composition of the present invention is a water-insoluble inorganic oxide, the overall specific gravity is about 1/2 to 1/3 compared to silver or copper. When producing antibacterial products, it is possible to suppress or prevent partial fractionation due to sedimentation.

Claims (6)

[Claims] (1) An antibacterial composition characterized in that a metal having an antibacterial effect is attached to the surface of water-insoluble inorganic oxide fine particles. (2) The antibacterial composition according to claim (1), wherein the metal having an antibacterial effect is at least one of silver and copper. (3) The antibacterial composition according to claim (1) or (2), wherein the water-insoluble inorganic oxide fine particles have an average particle size of 1 μm or less. (4) The antibacterial agent according to any one of claims (1) to (3), wherein the amount of the metal having an antibacterial effect attached is 1 wt% or more based on the water-insoluble inorganic oxide fine particles. sexual composition. (5) The metals having antibacterial effects are both silver and copper,
Claim (1) characterized in that the adhesion amount thereof is 0.5 wt% or more based on the water-insoluble inorganic oxide fine particles.
The antibacterial composition according to any one of 1) to (4). (6) Any one of claims (1) to (5), wherein the water-insoluble inorganic oxide fine particles are zeolite, diatomaceous earth, mica, kaolin, alumina, talc, silica gel alone, or a mixture thereof. The antibacterial composition described in .