JP2007039442A - Antibacterial agent consisting of silver and organic acid anion-containing aluminum sulfate hydroxide particle and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial agent consisting of silver and organic acid anion-containing aluminum sulfate hydroxide particles, excellent in antibacterial property, dispersibility, transparency, white-coloring property and antibacterial power-maintaining characteristics under an environment in contact with tap water, also a method for producing the same and further, an antifungal agent, an antibacterial deodorant, antibacterial paper, an agrochemical and a cosmetic. <P>SOLUTION: This antibacterial agent consists of the particles of silver and the organic acid anion-containing aluminum sulfate hydroxide expressed by formula (1): (Ag<SB>a</SB>B<SB>b-a</SB>)<SB>b</SB>Al<SB>c</SB>A<SB>x</SB>(SO<SB>4</SB>)<SB>y</SB>(OH)<SB>z</SB>pH<SB>2</SB>O. The antifungal agent, antibacterial deodorant, antibacterial paper, agrochemical and cosmetic containing the compound particles are provided. The antibacterial resin composition blended with the antibacterial composition is provided. The antibacterial resin article formed from the resin composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an antibacterial agent comprising silver and organic acid anion-containing aluminum sulfate hydroxide particles. More specifically, the present invention relates to an antibacterial agent comprising silver and organic acid anion-containing aluminum sulfate hydroxide particles having specific particle properties (particle shape, particle size uniformity, average secondary particle size, specific surface area, etc.). The present invention also relates to a method for producing the antibacterial agent.
Furthermore, the present invention also relates to an antibacterial resin composition (including a masterbatch) excellent in filter permeability and dispersibility at the time of kneading extrusion as a performance when the antibacterial agent is kneaded and mixed with a resin. In addition, an antibacterial resin molded article, antibacterial film, and antibacterial fiber that are formed from the resin composition and have excellent dispersibility, transparency, whiteness, and antibacterial properties (including antibacterial activity maintaining properties after contact with tap water) It also relates to antibacterial resin products such as antibacterial paints, antibacterial nonwoven fabrics and antibacterial caulks. It also relates to antifungal agents, antibacterial deodorants, antibacterial paper, agricultural chemicals and cosmetics.

In general, bacteria propagate in hot and humid environments, and may cause serious problems in terms of safety and health and living environment. In order to solve these problems, technologies such as antibacterial resin compositions that prevent damage from bacteria by combining conventional organic antibacterial agents and inorganic antibacterial agents with resins and other objects that are subject to antibacterial properties have been proposed. However, among them, the demand for inorganic antibacterial agents has been increasing recently because inorganic antibacterial agents are relatively safe.
In inorganic antibacterial agents, since silver has a relatively high antibacterial activity and relatively high safety, many antibacterial resin compositions using an antibacterial agent in which silver is supported or ion-exchanged on an inorganic compound have been proposed. ing.

For example, Patent Document 1 discloses a technique of an antibacterial resin composition in which silver is supported on zirconium phosphate. However, in the antibacterial resin composition in which the antibacterial agent is blended with the resin, the whiteness is slightly improved, but the antibacterial property, dispersibility, transparency, and antibacterial activity maintenance property after contact with tap water are all perfect. Rather, there were problems to be solved.
In particular, in this conventional technique, when the antibacterial resin composition is used after being in contact with tap water for a while, the antibacterial activity of the resin composition is completely lost or cannot be used for a long period of time. There is a problem that it becomes impossible to prevent the damage of this, and it was an important issue to solve this problem.
This problem will be further explained with a specific example. Tap water is always used around kitchens, bathrooms, and toilets, and clothes and the like are washed and used many times with tap water. Therefore, an antibacterial resin product used in such a place or under conditions must be able to exhibit antibacterial properties and prevent damage from bacteria even if it is originally in contact with tap water for a long time. However, although the antibacterial resin product according to the conventional technology exhibits a certain degree of antibacterial properties immediately after the resin product is manufactured, the antibacterial activity of the resin product is completely lost or significantly reduced when used in contact with tap water for a while. There was a problem that after the lapse of a long time, damage from bacteria could not be prevented at all.

In patent document 2, the BET method specific surface area represented by the formula of MAl ₃ (SO ₄ ) ₂ (OH) ₆ is 30 m ² / g or less, and the particle shape in which M in the formula is an alkali metal or ammonium group is used. An alkali aluminum sulfate hydroxide having a spindle shape or a spherical shape is disclosed, and in this document, the particle diameter D ₂₅ (large particle side) of 25% of the volume-based cumulative particle diameter measured by the Coulter counter method is 75% value. Examples in which the sharpness Rs = D ₂₅ / D _{75 of the} particle size distribution represented by the formula divided by the particle size D ₇₅ (small particle side) of 1.45 to 1.61 are specifically shown in the examples. Furthermore, its production method and resin blending examples are introduced.
In Paragraph No. 0035 of the above-mentioned patent document, a very general explanation that M of the compound can contain an element having an antibacterial effect, such as Ag, Zn, Cu and the like, and antibacterial particles can be obtained. There is. However, there is no specific description or examples regarding the antibacterial agent, the antibacterial resin product, the antifungal agent, the antibacterial deodorant, the antibacterial paper, the agricultural chemical, and the cosmetic.
Japanese Patent Laid-Open No. 6-212019 JP 2000-7326 A

  Thus, the object of the present invention is to overcome various problems of the inorganic antibacterial agent of the prior art, and when used as an antibacterial object such as a resin, the dispersibility, transparency, white Silver and organic acid anion-containing aluminum composed of silver and organic acid anions contained in alkali aluminum sulfate hydroxide particles in a specific range with excellent antibacterial properties and antibacterial activity maintenance characteristics especially after contact with tap water Providing an antibacterial agent comprising sulfate hydroxide particles, and further specific particle properties (particle shape, particle size uniformity, average secondary particle size, ratio) designed so that the various properties of the antibacterial agent are particularly excellent It is to provide an antibacterial agent comprising silver having a surface area or the like and an aluminum sulfate hydroxide particle containing an organic acid anion, and further to provide a method for producing the antibacterial agent.

Still another object is to provide an antibacterial resin composition (including a masterbatch) having excellent properties of filter passability and dispersibility during resin kneading extrusion when the antibacterial agent is kneaded and mixed using a resin kneading extruder. Providing, and further, antibacterial resin molded article, antibacterial film, antibacterial property, which is molded from the resin composition and has excellent dispersibility, transparency, whiteness, antibacterial property, especially antibacterial activity maintenance property after tap water contact environment It is to provide antibacterial resin products such as fibers, antibacterial nonwoven fabrics, antibacterial paints, and antibacterial caulks.
In view of the problem that in the prior art, antibacterial resin products have been used for a while in a tap water contact environment, the antibacterial activity is completely lost or significantly reduced in a short time. Antibacterial resin composition that can maintain antibacterial properties for a long time even in places where kitchens, bathrooms, toilets, etc., always use tap water, or in products such as clothes that are washed and used several times with tap water It is one of the objects of the present invention to provide an antibacterial agent to be blended in a resin composition and a product therefrom, and a method for producing the antibacterial agent.
Another important issue is a technique that is usually well implemented as a pre-stage for obtaining an antibacterial resin product, that is, when a resin and an antibacterial agent are once produced into a master batch (MB) using a resin kneading extruder. This is to solve the problem that the filter passability (extruder pressure) at the time of kneading extrusion processing is deteriorated and the machine cannot be operated for a long time and the filter must be replaced in a short time. If the machine can be operated for a longer period of time, resources, energy, labor, and time associated with filter replacement can be saved, and the antibacterial resin composition and antibacterial resin product can be provided to society at a low cost. .

  Still another object of the present invention is to provide another product utilizing the characteristics of the antibacterial agent in addition to the antibacterial resin product described above. That is, it is to provide an antifungal agent, an antibacterial deodorant, an antibacterial paper, an agrochemical or a cosmetic.

As a result of diligent researches to achieve the above-mentioned problems, the present inventors dried silver and organic acid anion-containing aluminum sulfate hydroxide particles represented by the following formula (1) and / or the compound particles at 150 ° C. to 600 ° C. The treated or baked compound particles are very antibacterial as antibacterial agent performance, and the resin composition containing 0.001 to 300 parts by weight of the particles with respect to 100 parts by weight of the resin is also very antibacterial. And excellent properties such as filter passability, whiteness, transparency, antibacterial activity maintenance property after contact with tap water, and antibacterial properties formed from the resin composition Antibacterial resin products such as resin molded products, antibacterial films, antibacterial fibers, antibacterial nonwoven fabrics, antibacterial paints, and antibacterial caulking materials are also white, transparent, and maintain antibacterial activity after contact with tap water. It was reached the present invention is excellent in various properties.
Further, the present inventors have found that the particles can be advantageously used as antifungal agents, antibacterial deodorants, agricultural chemicals, and cosmetics in addition to molded articles by using the antibacterial properties, and have reached the present invention.

According to the present invention, an antibacterial agent comprising silver and organic acid anion-containing aluminum sulfate hydroxide particles represented by the following formula (1) is provided.

_{(Ag a B b-a)} b Al c A x (SO 4) y (OH) z · pH 2 O (1)

In the formula (1), a, b, c, x, y, z and p are 0.00001 ≦ a <0.5, 0.7 ≦ b ≦ 1.35, 2.7 <c <3.3, 0.001 ≦ x ≦ 0.5, 1.7 <y <2.5, 4 <z <7 and 0 ≦ p ≦ 5 are satisfied, and B is Na ⁺ , NH ₄ ⁺ , K ⁺ and H ₃ O. Represents at least one kind of monovalent cation selected from the group of ⁺ , and the range of the total value (1b + 3c) of cation valence × mol number is 8 <(1b + 3c) <12, and A is an organic acid anion Represents.

If the antibacterial agent composed of silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles of the present invention is used for the resin, dispersibility, transparency, whiteness, antibacterial property, especially antibacterial force maintenance property after tap water contact environment, kneading extrusion Antibacterial resin composition excellent in all properties of filter passability during processing, and antibacterial resin molded article formed from the resin composition, antibacterial film, antibacterial fiber, antibacterial nonwoven fabric, antibacterial paint, It became possible to provide antibacterial resin products such as antibacterial caulking materials.
In particular, maintaining antibacterial activity characteristics after contact with tap water for a long time has never been possible with the prior art, and this makes it possible to supply tap water such as kitchens, bathrooms, and toilets according to the present invention. An antibacterial agent that can maintain antibacterial properties for a long time even in a place where it is always used, that is, an antibacterial agent that maintains damage from bacteria for a long time even under such conditions, a method for producing the antibacterial agent, an antibacterial resin composition, and an antibacterial property thereof It is a great achievement of the present invention that a new technology related to providing a resin product can be provided.

Another great achievement of the present invention is a technique that is usually performed well as a pre-stage for obtaining an antibacterial resin product, that is, when a resin and an antibacterial agent are once produced into a master batch (MB) using a resin kneading extruder. This also solves the problem that the filter passability (extruder pressure) at the time of resin kneading extrusion processing deteriorates and the machine cannot be operated for a long time and the filter must be replaced in a short time.
This result will be described in more detail. According to the present invention, it is possible to improve the filter passability at the time of resin kneading extrusion, and to operate the machine for a longer period of time. By adding auxiliary materials such as additives and fillers, water, energy, electric power, labor, and time, saving time and providing antibacterial resin compositions and antibacterial resin products to society at a lower cost The industrial value is very large.

  The present invention is described in further detail below.

  According to the present invention, it has also been found that the following properties (i), (ii) and (iii) are independently possessed as the properties of the antibacterial agent particles represented by the formula (1). .

(I) The average secondary particle diameter measured by a laser diffraction scattering method is 0.1 μm to 12 μm, preferably 0.1 to 5 μm.
(Ii) BET method specific surface area 0.1~250m ² / g, preferably 1 to 100 m ² / g
(Iii) Dr = D ₇₅ / D ₂₅ [D ₂₅ represents the particle size of the 25% value (fine particle size side) of the volume-based cumulative particle size distribution curve by the laser diffraction scattering method, and D ₇₅ represents the 75% value (large The particle size distribution defined by (representing the particle size on the particle size side)] has a sharpness of 1.0 to 1.8, preferably 1.01 to 1.5, more preferably 1.01 to 1.3, Most preferably from 1.01 to 1.2

The average secondary particle diameter (i), the BET specific surface area (ii), and the sharpness (Dr) of the particle diameter distribution (iii) are unique characteristics, and these two characteristics are satisfied simultaneously. More preferably, particles that satisfy these three characteristics at the same time are most preferable for achieving the object of the present invention.
Further, the antibacterial agent particles of the present invention are not aggregated particles but are monodispersed and have the following particle shape.
The particles of the antibacterial agent of the present invention have various particle shapes, but are also characterized in that the shapes are uniform and uniform in size, and are monodispersed with little aggregation. . The particle shape of the antibacterial agent can be roughly divided into spherical shape, disc shape (basal stone shape), pair shape (hamburger shape), rice granular shape, rectangular parallelepiped shape, hexagonal plate shape, columnar shape (sake barrel shape), and eight. It is classified into a planar shape. These various particle shapes will be specifically described with reference to FIGS.

1 to 13 are representative SEM photographs of particles obtained according to examples of the present invention. The shape of the particles is observed based on SEM photographs magnified about 10,000 to about 20,000 times. FIG. 14 is a SEM photograph of conventionally known alkali aluminum sulfate hydroxide particles.
Examples of spherical particles are shown in FIGS. 1 to 6, and these spherical particles are spherical with a smooth surface shown in FIG. 1, spherical with small particles on the surface shown in FIG. 2, and rough and even spherical surfaces shown in FIG. 3. 4 having a sphere (scratches and cracks), a sphere having small holes (irregularities) shown in FIG. 4, a sphere having a smooth surface shown in FIG. The surface to be shown can be classified into rough and wrinkled spheres.
An example of a discoidal particle is shown in FIG. 7, which has a dome-like shape that is mostly on the front and back and is similar to a meteorite. The disk-like particles in FIG. 7 have a smooth surface.
An example of a pair of particles is shown in FIG. The feature of this particle is that two of the disk particles with a flat bottom surface and a dome-shaped opposite surface have a pair of shapes with the bottom surface as a symmetry plane, and in the gap around the overlap of the two particles. There is a space. Moreover, the aluminum salt hydroxide which has joined two disks exists in the overlapping center part. The pair of particles look like a hamburger.
An example of rice granular particles is shown in FIG. The rice granular particles have an oval projected shape and a substantially circular shape in the longitudinal cross section. The particles in FIG. 9 have small wrinkles (wrinkles) on the surface.
An example of a rectangular parallelepiped particle is shown in FIG. 10 and is a rectangular parallelepiped close to a regular hexahedron, and the surface is smooth.
An example of the hexagonal plate-like particle is shown in FIG. 11, and this hexagonal plate-like particle is a plate having a hexahedral surface formed by six sides. The six sides do not need to be the same length, and the contact points of the two sides may be rounded.
An example of octahedral particles is shown in FIG. 12, and has an octahedral shape of a tetragonal bipyramidal shape or a decentered octahedral shape.
An example of cylindrical particles is shown in FIG. The cylindrical particles may have a shape in which an intermediate portion swells like a roughly barrel shape (or wine barrel shape), or may have a cylindrical shape with a substantially circular cross section.
The particle | grains of FIG. 13 have many unevenness | corrugations on the surface.
As understood from FIGS. 1 to 13, the particles of the present invention are characterized in that the shape of the particles is uniform in each figure (photograph), the size is uniform, and the dispersibility is good. Yes. The shape of each particle described above is classified and expressed for classification, and there is no problem even if there is a slight deformation or a mixture of other particles in a small proportion. Further, the smoothness on the surface of the particles, the presence of minute irregularities or the presence of small wrinkles (wrinkles) are not particularly limited, and may or may not be present.

Next, the method for specifying the particle shape of the present invention will be described.
One of the measures for specifying the particle shape is Wadell's circularity and sphericity, which has been used in the powder industry.
Wadell's sphericity s is expressed as s = (surface area of a sphere having the same volume as the particle) / (surface area of the particle)
The closer s is to 1, the closer it is to a true sphere.
Wadell's circularity c is defined by c = (peripheral length of the projected area of the particle) / (peripheral length of the projected surface of the particle).

  In the present invention, the shape of the particles may be a spherical shape as shown in FIGS. 1 to 6, and the Wadell sphericity s is 0.95 ≦ s ≦ 1. preferable.

  In the present invention, the shape of the particles is a disc shape (meteorite shape) as shown in FIG. 7 is a spheroid shape having a minor axis as a rotation axis. Specifically, with respect to the projected image of the particle viewed from the direction of the rotation axis, Wadell's circularity c is 0.95 ≦ s ≦ 1, and the ratio of the ellipse (minor axis / major axis) ratio a Is preferably 0.05 ≦ a ≦ 0.5.

  In the present invention, the shape of the particles is a pair (hamburger shape), as shown in FIG. 8, is a particle in which a pair is formed in such a shape that two hemispherical particles overlap each other. The pair of particles have gaps (grooves) at the periphery of the surface where the two hemispherical particles overlap. The ratio t of (minor axis / major axis) of the pair of particles is 0.1 <t <0.5, and the ratio u of (gap width of the seam of the hemisphere) / (minor axis) is 0.05 <u. <0.5 is preferred.

  In the present invention, the shape of the particles is rice-granular, as shown in FIG. 9, is a spheroid shape having a minor axis as a rotation axis, and the ratio a of the ellipse (minor axis / major axis) is 0.1. ≦ a ≦ 0.5, and the Wadell's sphericity s is preferably 0.4 ≦ s <0.75.

  In the present invention, the shape of the particles is a rectangular parallelepiped as long as the shape is similar to a hexahedron or a regular hexahedron as shown in FIG. 10, and the Wadell sphericity s is 0.5 ≦ s ≦ 0.8. It is preferable that

  In the present invention, the shape of the particles is a hexagonal plate shape, which is a flat regular hexagonal column shape as shown in FIG. 11, and the Wadell's circularity c is 0 with respect to the projected image of the particles viewed from the upper surface or the lower surface direction. .95 ≦ c <0.99, and the ratio b of thickness / (diagonal length of regular hexagon) is preferably 0.05 ≦ b ≦ 0.5.

  In the present invention, the shape of the particles is an octahedral shape, which is considered to have a tetrahedral bipyramidal shape or an octahedral shape as shown in FIG. The sphericity s is preferably 0.5 ≦ s ≦ 0.9. However, if the octahedral particles are not carefully examined, they may appear to be hexahedral particles at first glance due to unclearness resulting from insufficient resolution of the SEM photograph.

  In the present invention, the shape of the particles is a columnar shape (sake barrel shape) including a column as shown in FIG. 13, and the radius of the center of the column in the height direction is 1.0-1 of the radius of the upper surface and the lower surface. .2 times the shape, and the Wadell circularity c is 0.95 ≦ c <0.99 with respect to the projected images of the upper surface and the lower surface, and (height) / (the diameter of the upper surface or the lower surface) ) Value d is preferably 1.5 ≦ d ≦ 3.

  According to the present invention, as described above, silver and organic acid anion-containing aluminum salt hydroxide particles are spherical, disc-shaped (meteorite-like), pair-shaped, rectangular parallelepiped, hexagonal plate-shaped, rice grain, depending on the application and purpose. Shape, octahedral shape, cylindrical shape, and the like, and the particle diameter can be controlled.

On the other hand, regarding the particle size, it is possible to provide silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles having an optimum particle size depending on the application and the required filling rate.
These particles are excellent in dispersibility in the resin without aggregation between particles, and the antibacterial agent is blended in the resin so that the antibacterial agent has no or little aggregation in the resin even when blended in the resin. It is considered to be one of the factors that exert antibacterial properties even if the silver content is very small in resin products, and this monodisperse technology alone exhibits unexpectedly high antibacterial activity that could not be achieved with conventional technology. is there.

Regarding the mechanism by which the antibacterial agent of the present invention exhibits such unexpectedly high antibacterial activity, the following second factor is also estimated.
The antibacterial agent particles of the present invention have a high antibacterial effect because the antibacterial agent particles of the present invention incorporate an organic acid as an anion into the internal structure of the molecule. when light strikes the hydroxyl radicals from antibacterial agent particles of the present invention (OH ^-) radicals are easily generated over a long period of time, such as, which can be maintained for a long period of time antimicrobial performance of the antimicrobial agent of the present invention It is estimated that it is also a factor.
Most of the conventional silver inorganic antibacterial agents have a fatal disadvantage that they exhibit antibacterial properties during the period when silver ions can be released from the antibacterial agents, but after that period the antibacterial properties do not appear. However, the present invention fundamentally solves that problem.
Furthermore, according to the present invention, as a third factor of the antibacterial expression improving effect by incorporating an organic acid as an anion into the molecular structure of the antibacterial agent, not only the dispersion effect and the radical generating effect described above, Further, the effect of improving the compatibility with the resin due to the carbon portion of the organic acid of the antibacterial agent particles is added, that is, the present invention succeeds in synergizing these three effects and can exhibit further higher antibacterial performance. It is presumed that

In the present invention, the antibacterial agent represented by the above formula (1) is blended in an amount of 0.001 to 300 parts by weight with respect to 100 parts by weight of the resin, thereby being excellent in filter passability, antibacterial properties, dispersibility, and whiteness during kneading extrusion processing Antibacterial resin composition excellent in antibacterial activity maintaining characteristics after contact with tap water and a resin product formed therefrom, but having high transparency to the resin product. For the purpose of placing importance on added value, it is recommended to add 0.001 to 10 parts by weight, preferably 0.001 to 2 parts by weight. If the blending amount of the antibacterial agent is 0.001 part by weight or less, sufficient antibacterial properties may not be exhibited, and blending 300 parts by weight or more becomes uneconomical depending on the silver content, and transparency is also high. There is a tendency to decrease.
The refractive index of the antibacterial agent of the present invention is about 1.48 to about 1.56, and the refractive index overlaps or is close to that of many resins. Although transparency is not impaired so much, in order to maintain high transparency, it is recommended that the amount of the antibacterial agent is 10 parts by weight or less, preferably 2 parts by weight or less.

  In formula (1) in the present invention, a represents the amount of ion exchange of silver into the antibacterial agent particles, and a higher value of a indicates that silver is ion-exchanged into the antibacterial agent particles and has antibacterial properties. However, if it becomes too high, silver may precipitate or elute from the ion exchanger (solid solution) in the environment to become silver oxide, and the color of the resin molded product containing the antibacterial agent will be dark brown Also, it is not economical, and a is difficult to ion-exchange 0.5 or more. On the other hand, if the value of a is too low, it means that silver has less ion exchange amount to the antibacterial agent particles and does not exhibit antibacterial properties. Therefore, a is constant in order to properly balance the antibacterial properties and color problems. It is desirable to make it a range. In this sense, a in Formula (1) is suitably in the range of 0.00001 to 0.5, preferably 0.00001 to 0.35, and more preferably 0.001 to 0.3.

In the present invention, in the description of “antibacterial agent comprising silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles”, the term “containing” means that when the particles are measured by a powder X-ray diffraction method, other than the formula (1) This means that the amount of the compound composed of silver and organic acid other than the formula (1) is small enough to prevent the compound peak from appearing.
Therefore, the antibacterial agent particles have not only an ion exchanger but also a form in which some silver ions that do not show a peak in powder X-ray diffraction measurement are supported on the particles in a form other than the ion exchanger and / or It is considered that some organic acid anions are adsorbed on the surface of the particles.
In that case, when considering the particles focusing on silver, it is considered that the silver is only composed of a solid solution that is ion-exchanged within the permissible ion-exchange range, and the influence of coloring on the resin product is reduced. The thing which consists only of a perfect silver ion exchanger (solid solution) is preferable.

In formula (1) in the present invention, B may be any of various monovalent cations, but actually means that an ion exchanger can be strongly formed in a wide range where the ionic radius is relatively close to silver ions. In other words, silver does not release from the ion exchanger to become silver oxide when blended with the resin, resulting in a decrease in the whiteness of the resin product (from the white color immediately after molding the resin product to the darkness over time due to the action of light. Na ⁺ , NH ₄ ⁺ , K ^+, and H ₃ O ⁺ are suitable as B in view of the fact that it is difficult to cause a color change from brown to brown, and safety and economy. Further, among these, Na ⁺ , NH ₄ ⁺ and H ₃ O ⁺ are relatively preferable, and among them, NH ₄ ⁺ and H ₃ O ⁺ are more preferable, and NH ₄ ⁺ is most preferable for the purpose. From the viewpoint of anti-tarnish, the amount is preferably as small as possible using the Na ⁺ and / or K ⁺ as B, in particular the amount of using the K ⁺ in less than half of the total moles of B becomes monovalent cations Preferably there is. However, these discoloration can be prevented by adding 0.000001% to 0.1% of a fluorescent brightening agent to the resin. Accordingly, when a large amount of Na ⁺ and K ⁺ is used as B, it is preferable to use an optical brightener to prevent discoloration.

Although it is a part of the antibacterial resin composition of the present invention, in the case of antibacterial agent particles using the relatively preferred embodiment, that is, NH ₄ ^+, Na ⁺ , and H ₃ O ⁺ three kinds of monovalent cations are used. In order to obtain a resin product that does not change color or has relatively little discoloration without using a whitening agent, the amount of Na used is 1/2 of the total molar content of monovalent cations in which the molar content of Na is B. Should be smaller. By doing so, in the present invention, it is possible to obtain a resin product with little or no color change.
When the optical brightener is used, examples thereof include benzohexazole-based 2,5-thiophenediyl (5-tert-butyl-1,3-benzohexazole, 4,4′-bis (benzohexazole- Examples of 2-yl) stilbene, pyrazoline-based, and carmarin-based ones can be given, but those registered in the FDA (Food & Drag Administration) and polyolefin hygiene associations are preferably used.

If b in the formula (1) in the present invention is 0.7 to 1.35, preferably 0.8 to 1.2, most preferably 0.9 to 1.1, the antibacterial agent particles of the present invention are formed. If c is 2.7 to 3.3, preferably 2.8 to 3.2, and most preferably 2.9 to 3.1, the antibacterial agent particles of the present invention are easily formed.
The ionic valence x number of moles of the cation of formula (1) is expressed as (1b + 3c). If the range in the present invention is 8 <(1b + 3c) <12, preferably 9 <(1b + 3c) <11, the antibacterial agent particles of the present invention are easily formed.
In the synthesis of the particles of the formula (1) in the antibacterial agent of the present invention, the particle shape and the particle size are selected and manufactured, the particle size distribution is uniformly adjusted, and the particles are converted into a resin in a monodispersed state as much as possible. In order to make it dispersible, it is necessary to add organic acids during the reaction in the reaction, and the added organic acids can be incorporated into the molecular structure of the antibacterial agent particles.

  Examples of such organic acids include those in which the organic acid anion (A) in formula (1) is at least one selected from the group of anions based on organic carboxylic acids or organic oxycarboxylic acids, but organic acid anions (A) Is preferably at least one selected from the group of anions based on organic carboxylic acids or organic oxycarboxylic acids having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms and 1 to 4 carboxyl groups. Examples include dicarboxylic acids, monocarboxylic acids, tricarboxylic acids, chain carboxylic acids, aromatic carboxylic acids, hydroxy acids, ketone acids, aldehyde acids, phenol acids, amino acids, halogen carboxylic acids, and salts thereof, among which organic acids Anion (A) is oxalate ion, citrate ion, malate ion, tartrate ion, glycerin Ions, and most preferably at least one selected from the group consisting of gallic acid ion, and lactate.

The ratio x of the organic acid anion (A) in the formula (1) is 0.0001 ≦ x ≦ 0.5, preferably 0.0001 ≦ x ≦ 0.4, and more preferably 0.001 ≦ x ≦ 0.2. By doing so, the antibacterial agent particles that achieve the above-mentioned object and have the same particle shape and uniform particle diameter can be obtained. If x exceeds 0.5, this effect is not particularly high and is not economical.
When x is less than 0.0001, it is difficult to obtain the antibacterial agent particles having the above-mentioned shape and uniform particle diameter, and the generation of the hydroxy radicals and the resin with organic acid. The object of the present invention such as improvement of antibacterial properties, which is considered to be due to the effect of improving compatibility, is difficult to achieve.

In the formula (1) of the present invention, if y is 1.7 <y <2.5, preferably 1.8 <y <2.2, the antibacterial particles of the present invention can be easily formed, and z is 4 < If z <7, preferably 5 <z <7, the antibacterial agent particles of the present invention are more easily formed.
P in the formula (1) indicates the amount of crystal water, and usually p is in the range of 0 ≦ p ≦ 5. In order to make p as close to 0 as possible, or to make it 0, an additional drying process or a baking process at 350 ° C. or lower may be performed. The baking treatment is preferably 600 ° C. or lower. If the firing temperature is 500 ° C. or higher, further 550 ° C. or higher, particularly 600 ° C. or higher, there is a possibility that a part of the water-soluble aluminum sulfate represented by the following formula may be formed. May reduce water resistance. However, when the amount added is small, there is no problem with water resistance.
_{(Ag a B b-a)} b AlA x (SO 4) y

If the calcination temperature is 500 ° C. or less, particularly 450 ° C. or less, the water-soluble aluminum sulfate represented by the above formula will not be produced, and even if it is used in a large amount in resin products, the water resistance does not decrease and there is no problem. Absent. Further, when the antibacterial agent particles of the present invention are baked at a temperature of 600 ° C. or higher, the particle shape of the antibacterial agent particles of the present invention as shown in FIGS. From the viewpoint of water resistance and shape maintenance, the firing temperature of the antibacterial agent particles of the present invention is 350 ° C to 600 ° C, preferably 350 ° C to 550 ° C, more preferably 350 ° C to 500 ° C, most preferably 350 ° C to 450 ° C. It is.

It is preferable to carry out the above-described drying treatment or baking treatment in a nitrogen atmosphere from the viewpoint of preventing coloring of the antibacterial agent particles and resin products containing the antibacterial agent particles. The drying process is preferable in terms of preventing coloring even if it is carried out by vacuum drying.
When p is not 0 at the time of resin processing, if there is no problem, for example, if the amount of the antibacterial agent is very small, or if the resin has no particular problem of moisture during resin processing, drying or baking treatment The resin composition can be produced by blending a resin having p of 0 ≦ p ≦ 5, preferably 0 ≦ p ≦ 3.
On the other hand, if it is a problem that p is not 0 or close to 0, it may be used as much as p = 0 or 0 by adding additional drying or baking.
For example, for resins such as polyester resins such as PET and PBT, polyamide resins, polyurethane resins, polycarbonate resins, and polyacetal resins, p (moisture content) subjected to additional drying treatment or baking treatment under the above conditions is 0 or limited. It is recommended to use the antibacterial agent in consideration of approaching zero.

  The particles of the present invention have a sharpness (Dr) of the particle size distribution of the laser diffraction scattering method of 1.0 ≦ Dr ≦ 1.8, preferably 1.0 ≦ Dr ≦ 1.5, more preferably 1.01 ≦. By setting Dr ≦ 1.3, most preferably 1.01 ≦ Dr ≦ 1.2, it is possible to achieve complete dispersion without aggregation in terms of dispersibility in the resin, and that is an element that enhances the antibacterial effect. Although it is conceivable, there is an advantage that clogging of the antibacterial agent to the screen mesh is eliminated or reduced even when a filter (screen mesh) is used, for example, when a masterbatch is produced, for example, during resin extrusion. There is also.

For the purpose of imparting a high antibacterial property to the antibacterial agent-containing antibacterial resin product of the present invention, the smaller the average secondary particles, the better. Is 0.1 to 2 μm, more preferably 0.1 to 1 μm, and most preferably 0.1 μm to 0.5 μm.
However, if the average secondary particle size of the antibacterial agent is less than 0.1 μm, it may be difficult to produce, and if it is 12 μm or more, the antibacterial property of the resin composition or the like may not be so high even if it is added to the resin. . For the purpose of imparting not only antibacterial properties but also high transparency to the resin composition of the present invention, among the antibacterial agents of the present invention, the average secondary particle size is 0.1 to 0.5 μm, preferably 0.1. When using ultrafine particles of ~ 0.4 μm, more preferably 0.1 to 0.3 μm, the characteristics of the antibacterial agent particles of the present invention whose refractive index overlaps or approaches the resin are maximized. In addition, the resin product exhibits the effect of imparting an even higher degree of transparency that could not be achieved with the prior art.

The antibacterial agent used in the present invention has a BET specific surface area of 0.1 to 250 m ² / g.
In order to impart high antibacterial properties to the resin composition, a higher BET method specific surface area is advantageous, but on the other hand, a material with a very high BET method specific surface area may cause a problem that it is difficult to fill the resin. If the BET method specific surface area is too low, sufficient antibacterial properties may not be imparted to the resin composition.
BET specific surface area of the antimicrobial agent in this sense is 0.1~250m ² / g, is preferably 1 to 100 m ² / g and more preferably 10 to 100 m ² / g, most preferably 30 to 100 m ² / g .

The antibacterial resin product in which the antibacterial agent particles of the present invention are blended originally has high acid resistance. However, for the purpose of imparting higher acid resistance to the resin product or for the purpose of preventing discoloration, the present invention The surface of the antibacterial agent particles is coated with at least one acid resistance modifier selected from the group consisting of silicon compounds, phosphorus compounds, boron compounds, aluminum compounds, zirconium compounds, titanium compounds, zinc compounds and tin compounds. The acid resistance can be further improved.
Examples of such acid resistance modifiers include sodium metasilicate, sodium orthosilicate, potassium metasilicate, potassium orthosilicate, water glass, silicic acid, silicone oil; boron compounds such as sodium tetraborate and sodium metaborate. , Potassium tetraborate, potassium metaborate, boric acid; as the aluminum compound, sodium orthoaluminate, sodium metaaluminate, potassium orthoaluminate, potassium metaaluminate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum phosphate; phosphorus compound As potassium phosphate, sodium phosphate, phosphoric acid; zirconium compound as zirconium phosphate, sodium zirconate, potassium zirconate, zirconic acid; titanium compound Titanium chloride, sodium titanate, potassium titanate, titanic acid; zinc compounds such as zinc chloride, zinc nitrate, zinc carbonate, zinc sulfate, zincate; tin compounds such as sodium stannate and potassium stannate A quality agent can be mentioned as an example.

Although the antibacterial agent particles of the present invention are originally monodisperse particles, the dispersibility in the resin is extremely excellent. However, the antibacterial particles of the present invention have the object of further improving dispersibility or preventing discoloration of resin products. For the purpose of suppressing the decrease in mechanical strength when the agent particles are blended in a relatively large amount with the resin, the surface of the antibacterial agent particles of the present invention is made of higher fatty acids, silane coupling agents, aluminate systems. Surface treatment can also be performed with at least one selected from the group of coupling agents, alcohol phosphates, surfactants and the like.
Such surface treating agents include stearic acid, oleic acid, erucic acid, palmitic acid, lauric acid, behenic acid and other higher fatty acids and salts thereof, polyethylene ether sulfate, amide-bonded sulfate, ester-bound sulfate. Surfactants such as salts, ester bond sulfonates, amide bond sulfonates, ether bond sulfonates, ether bond alkyl allyl sulfonates, amide bond alkyl allyl sulfonates, higher alcohols such as stearyl alcohol and oleyl alcohol A sulfate ester salt, a mono- or diester such as orthophosphoric acid and stearyl alcohol or oleyl alcohol, or a mixture thereof, and its acid type or an alkali metal salt or a phosphate ester such as an amine, vinylethoxysilane, vinyl-tolyl ( -Methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane N-beta (aminoethyl) gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyl and methoxysilane Silane coupling agents, isopropyl triisostearoyl titanate, isopropyl tri (aminoethyl) titanate, isopropyl tridecylbenzenesulfonyl titanate, etc. Ring agents, aluminate coupling agents such as acetoalkoxyaluminum aluminum Niu Muzi isopropylate can be exemplified.

The antibacterial agent particles of the present invention can be produced by the following method.
At that time, the content of heavy metals such as lead and cadmium, which is industrially specified in the Ministry of Health and Welfare Notification No. 20 of the Food Sanitation Law, and also means prevention of heat deterioration (improvement of heat resistance deterioration) and coloring prevention of resin products. The content of heavy metals such as iron, manganese, chromium, copper, and nickel is 1% or less, preferably 0.1% or less, more preferably 0.01% by weight or less, and most preferably 0.001% or less. In order to obtain the antibacterial agent particles, first, a high-purity material is selected on the raw material side, and further, in the hydrothermal treatment process where corrosion is particularly likely to occur on the material side of the chemical operation device, the elution of the device material causes iron, manganese, etc. Hastelloy steel excellent in corrosion resistance and stainless steel SUS- in which heavy metal compounds such as chromium, copper, nickel and the like are not mixed into the antibacterial agent particles of the present invention as solid solutions and / or contaminants 16 selecting a steel or the like is preferable.

The antibacterial agent particles of the present invention are basically represented by the following general formula (2) that can be produced by the method described in the specification of International Patent Application PCT / JP2005 / 003831 (filing date: March 1, 2005). This is a method in which the monovalent cation (B) portion of the organic acid anion-containing aluminum sulfate hydroxide particles is ion exchanged with silver.

[B] _b Al _c A _x (SO ₄ ) _y (OH) _z · pH ₂ O Formula (2)

In the formula, the definitions of b, c, x, y, z, p, B, and A mean the same as the formula (1).
In order to synthesize the compound of formula (2), aluminum and sulfuric acid raw materials such as aluminum sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, and calcium sulfate, organic acid raw materials such as oxalic acid, sodium hydroxide, potassium hydroxide And an alkali raw material such as an aqueous ammonia solution by a wet method or a dry method, and B is a sodium-type, potassium-type or ammonium-type silver-free organic acid anion-containing aluminum sulfate hydroxide particle [particle shape is spherical, disc , (Meteorite-like), pair-like (hamburger-like), rice grain, hexagonal plate, hexahedral, and columnar are shown in the following paragraphs 1 to 3]. If acid anion-containing aluminum sulfate hydroxide particles are stirred in contact with a silver solution in a suspension of water or the like, the silver is converted into an organic acid anion. Down-containing aluminum antibacterial agent particles of the present invention as ion-exchanged sulfate hydroxide particles can be produced.

A method for producing silver and organic acid anion-containing aluminum sulfate hydroxide particles having a rectangular parallelepiped shape will be described later.
In any case, silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles can be produced by selecting the shape and particle size, the particle size distribution can be uniformly adjusted, and the particles can be perfectly dispersed in a monodisperse state. In order to make it dispersible in the resin, it is necessary to add the organic acids in the reaction during the reaction, and the added organic acids can be incorporated into the structure of the antibacterial agent particles.
However, some organic acids may be adsorbed on the surface of the antibacterial agent particles.
In any case, organic acids can be contained in the antibacterial agent in order to achieve the object of the present invention.
Even if the organic acid is not added at the time of the reaction and is added after the reaction is completed, the antibacterial agent particles of the present invention having properties such as particle shape, particle diameter uniformity, dispersibility and the like cannot be produced.

Regarding the pulverization treatment of the produced antibacterial agent particles of the present invention, it is not necessary to carry out with a strong mechanical force as in the prior art, and it is also possible to obtain a product that does not aggregate even if it is simply treated with a weak force. It is a feature of the technology.
Hereinafter, examples of the method for producing an antibacterial agent containing aluminum sulfate hydroxide particles containing sodium and potassium, ammonium and hydrogen and organic acid anions will be described.

1, sodium form silver and organic acid anion containing aluminum sulphate aluminum production method the raw material of the sulfate hydroxide particles, such as sodium sulfate sulfate and Al raw material and SO ₄ raw material and Na raw material such as sodium hydroxide, such as oxalic acid The method of manufacturing by the following method using organic acid raw material and soluble silver salts, such as silver nitrate used by ion exchange reaction, as a silver raw material can be illustrated.
For example, Al ₂ (SO ₄ ) ₃ + Na ₂ SO ₄ (or NaNO ₃ ) + H ₂ C ₂ O ₄ is sufficiently dissolved in water, and then sodium hydroxide is added with stirring.
After the addition, the mixture is preferably further stirred for 20 minutes or more in order to disperse well.
It is preferable to perform hydrothermal treatment thereafter.
The hydrothermal treatment temperature is preferably 100 ° C. to 250 ° C., and the treatment time is preferably 1 hour to 30 hours.

The organic acid anion-containing aluminum sulfate hydroxide particles thus obtained are filtered and washed with water as necessary. ,
If it is suspended in a liquid such as water and stirred with a solution of a soluble silver salt such as silver sulfate or silver nitrate, an ion exchange reaction treatment can be carried out, and the silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles of the present invention can be produced. .
The temperature of the ion exchange reaction treatment is preferably 0 ° C. to 100 ° C., and the treatment time is preferably 0.1 to 30 hours under light shielding.

If the treatment temperature at the time of ion exchange is low or the treatment time is too short, the amount of silver ion exchange may be reduced. On the other hand, if the treatment temperature during ion exchange is high or the treatment time is too long, the ion exchange treatment product tends to be colored brown.
Examples of the stirring method in the ion exchange reaction treatment include methods such as vibration and rotation.
The ion exchanged product may be collected by filtration / centrifugation, and if necessary, operations such as washing with water, surface treatment, drying, and pulverization may be further performed as necessary. When the separation by filtration is difficult, a flocculant may be used to improve the separation operation as long as the object of the present invention is not violated. Examples of the flocculant include polymer flocculants such as polyacrylamide. The amount of the polymer flocculant added is preferably 0.2% or less. Addition of 0.2% or more does not improve the furnace operation.

2. Production method of potassium sulfate silver and organic acid anion-containing aluminum sulfate hydroxide particles As raw materials, aluminum sulfate, potassium sulfate and other Al raw materials such as potassium hydroxide, SO ₄ raw material and K raw material, oxalic acid, etc. The method of manufacturing by the following method can be illustrated, using a soluble silver salt such as silver nitrate used in the organic acid raw material and ion exchange reaction as the silver raw material.
For example, Al ₂ (SO ₄ ) ₃ + K ₂ SO ₄ (or KNO ₃ ) + H ₂ C ₂ O ₄ is sufficiently dissolved in water, and then potassium hydroxide is added with stirring. Subsequent operation methods are performed in accordance with 1 above.

3. Method for producing ammonium-type silver and organic acid anion-containing aluminum sulfate hydroxide particles As raw materials, aluminum sulfate, ammonium sulfate and the like, and ammonium nitrate and other Al raw materials and SO ₄ raw materials and NH ₄ raw materials and organic acids such as oxalic acid Examples thereof include a raw material and a soluble silver salt such as silver nitrate used in an ion exchange reaction as a silver raw material, and a method for production by the following method.
For example, Al ₂ (SO ₄ ) ₃ + K ₂ SO ₄ (or KNO ₃ ) + H ₂ C ₂ O ₄ is sufficiently dissolved in water, and then an aqueous ammonia solution is added with stirring. Subsequent operation methods are performed in accordance with 1 above.

4. Method for producing hydrogen-type {(H ₃ O) ⁺ type} cuboidal silver and organic acid anion-containing aluminum sulfate hydroxide particles The cuboidal particles are different from the above-described method for producing spherical and discoidal particles. What mixed and stirred aluminum aqueous solution, aluminum hydroxide suspension, and organic acids, such as a oxalic acid, is 100 to 250 degreeC, Preferably it is 120 to 200 degreeC, 0.5 hour or more, Preferably it is 0.5 to 30 If it is hydrothermally treated for a period of time, preferably 2 to 20 hours, a rectangular parallelepiped, hydrogen type, represented by the chemical formula (H ₃ O) Al ₃ (SO ₄ ) ₂ (OH) ₆ can be obtained.
Examples of the aluminum hydroxide to be used include crystalline gypsite, viaite, boehmite, pseudoboehmite, diaspore, and amorphous aluminum hydroxide, but the amorphous aluminum hydroxide has high particle size uniformity. Is preferable.
Examples of amorphous aluminum hydroxide include dry aluminum hydroxide gel S-100 manufactured by Kyowa Chemical Industry Co., Ltd. and FM.

  In order to improve the micronization and particle size uniformity in this method, rather than immediately subjecting the reaction mixture obtained by mixing and stirring the aluminum sulfate aqueous solution and the aluminum hydroxide suspension to hydrothermal treatment, a certain amount of time has passed after the reaction, for example, When hydrothermally treating the mixture after standing or stirring for 0.5 hour or longer, preferably 5 hours or longer, more preferably 16 hours or longer, aluminum sulfate hydroxide particles having fine particle diameter uniformity are obtained. Subsequent operation methods are performed in accordance with 1 above.

The silver and organic acid anion-containing aluminum sulfate hydroxide particles of the present invention can be identified by powder X-ray diffraction. If silver is ion-exchanged with the particles, the diffraction pattern thereof is the same as that before the ion-exchange, and therefore, the diffraction pattern of the diffracted X-rays may be examined in light of the chemical analysis value. If silver does not ion exchange with the particles and a product coexisting with impurities such as silver oxide is added to the resin, the color of the resin product is dark brown, which is one of the important objects of the present invention. Since it deviates from obtaining a resin product, it is not preferable.
In the present invention, a part of aluminum (Al) which is a trivalent cation of the antibacterial agent represented by the formula (1) is at least one cation selected from the group of Zn ²⁺ and Ti ⁴⁺ , and / or some of monovalent cations B may be contained replaced within a range not damaging the object of the present invention in Ca ^2+.
In that case, the total molar content of Zn ²⁺ and Ti ⁴⁺ is less than or equal to 1/2 of the molar content of aluminum, preferably 1/3 in order not to lower the transparency of the resin product when the antibacterial agent is blended with the resin. Hereinafter, the molar content of Ca ²⁺ is ½ or less, preferably ３ or less of the molar content of the monovalent cation (B), and may be contained in the antibacterial agent particles.

As a method for replacing a part of the trivalent cation aluminum (Al) of the antibacterial agent represented by the formula (1), a salt such as zinc sulfate, titanium sulfate or calcium sulfate containing the metal cation is represented by the formula (2). Used when synthesizing a compound, incorporated into the formula (2), or ion-exchanged with a compound of the formula (2) using a compound containing the metal cation in a solvent and further ion-exchanged with silver by the above-described method. The method of doing can be illustrated. In that case, since Zn ²⁺ and Ti ⁴⁺ are elements having an antibacterial effect, the antibacterial property is exhibited even if the relative content of Ag ¹⁺ is reduced in the formula (1). There is an advantage of reducing the coloring of the molded article, which is preferable in that sense.

In the present invention, (SO ₄ ) _y of the antibacterial agent represented by the formula (1) is a part of (SO ₄ ) _y , and preferably ½ or less of y mol can be replaced with other inorganic acid ions. If the amount is particularly ½ or less, the particle shape and particle size uniformity of the present invention can be maintained without any problems, and the object of the present invention is achieved. _SO ³ 2-as inorganic acid ^{_{ions, PO 4 3-, HPO 3 2-}} , CO 3 2-, NO 3 -, SiO 4 4- and _BO ^{3 3-} like. As a method of replacing a part of (SO ₄ ) _y of the antibacterial agent represented by the formula (1) with another inorganic acid ion, when the salt containing the inorganic acid ion is reacted with the compound represented by the formula (2), aluminum sulfate, In place of sodium sulfate, potassium sulfate or the like, the above-mentioned method is further applied to a product which is incorporated into the formula (2) or ion-exchanged in a solvent using a compound containing the inorganic acid ion in the compound of the formula (2). And a method of ion exchange with silver. In addition to the antibacterial agent particles of formula (1), the particles can be used as an antibacterial agent by additional drying treatment, baking treatment, surface treatment, acid-resistant coating treatment, or added to a resin to provide an antibacterial resin. You can also get a product.

In the present invention, the (OH) _z in the formula (1) becomes antibacterial agent Cl part of (OH) _z ^- in some cases have contained replaced by, the content thereof in the sense of preventing coloration In the antibacterial agent formula (1), it is 0.1 mol or less, preferably 0.01 mol or less, and most preferably 0.001 mol or less.
In the present invention, the antibacterial target resin is not particularly limited, and is processed from a synthetic resin / rubber, natural resin / rubber or the like as a raw material, and is usually molded, fiber, non-woven fabric, paint, caulking material, film, etc. What is necessary is just to be used as a resin product, The one part is illustrated below.

Examples of the thermoplastic resin include C _{2 to} C such as polypropylene, ethylene propylene copolymer, high density polyethylene, low density polyethylene, ultrahigh molecular weight polyethylene, linear low density polyethylene, polybutene, and poly-4methylpentene-1. Polymers or copolymers of ₁₂ olefins (α-olefins), copolymers of these olefins and dienes, ethylene vinyl acetate copolymers, ethylene acrylate copolymers, polyolefins such as TPO (thermoplastic polyolefin) resins Resin, polyethylene oxide resin, polystyrene, ABS (acrylonitrile butadiene styrene) resin, AAS (acrylonitrile acryl styrene) resin, AS (acrylonitrile styrene) resin, AES (acrylonitrile EPD styrene) resin Styrenic resins such as MBS (methyl methacrylate butadiene styrene) resin, polyparamethyl styrene resin, ACS (acrylonitrile chlorinated polyethylene styrene) resin, vinyl acetate resin, vinyl propionate resin, phenoxy resin, ionomer resin, polyacetal resin, nylon 6. Polyamide resins such as nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide imide resins, polysulfone resins, polyarylate resins, polyether imide resins, polyether ketone resins, polyphenylene ether resins, polyphenylene sulfide resins , Methacrylic resin, cellulose resin, polycarbonate resin, fluorine resin, polyurethane resin, silicone resin, polyvinyl resin Ether resin, polyvinyl formal resin, polyvinyl butyral resin, polyvinyl alcohol resin, isobutylene-maleic anhydride copolymer resin, further polyvinyl chloride resin, ethylene vinyl chloride copolymer resin, ethylene vinyl acetate copolymer resin, chlorinated vinyl chloride resin, Chlorinated polyethylene, chlorinated polypropylene, coumarone resin, ketone resin, polyvinylidene chloride, polyvinyl dichloride resin, resin having chlorine in molecular structure such as chlorinated polyether, acetate plastic, cellulose acetate, celluloid, liquid crystal polymer, Furthermore, a water absorbing resin etc. can be illustrated as some of them.

Thermosetting resins include epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin, guanamine resin, polyimide resin, urea resin, silicone resin, phenol formaldehyde resin, melamine formaldehyde resin, polyparabenzoic acid resin, polyurethane Examples thereof include resins such as resin, maleic acid resin, urea resin, furan resin, xylene resin, and diallyl phthalate resin.
As rubber, EPDM (ethylene propylene diene copolymer rubber), EPM (ethylene propylene copolymer rubber), butyl rubber, isoprene rubber, SBR (styrene butadiene rubber), NIR (nitrile isoprene rubber), NBR (nitrile butadiene rubber), Urethane rubber, chloroprene rubber, hydrogenated nitrile rubber, polyether rubber, ethylene tetrafluoride / propylene rubber, chlorosulfonated rubber, butadiene rubber, acrylic rubber, chlorinated polyethylene, epichlorohydrin rubber, propylene oxide rubber, ethylene / acrylic rubber Examples thereof include norbornene rubber, polysulfide rubber, fluorine rubber, silicone rubber, natural rubber and the like.
These resins and rubbers may be used alone or in combination of a plurality of types. When a plurality of types are used simultaneously, they may be used after being polymer-alloyed, may be used after blending, or may be used after being laminated. These synthetic resins are not limited by the production method. For example, the polymerization catalyst for polyolefin may be any method such as Ziegler method, Ziegler-Natta method, Friedel-Craft method, metallocene method, and Phillips method.

In the antibacterial resin composition of the present invention, commonly used additives, reinforcing agents, and fillers can be blended within a range that does not impair the object of the present invention. Some of these are exemplified below.
Antioxidant, UV absorber, light stabilizer, heat stabilizer, metal deactivator, plasticizer, antistatic agent, flame retardant, vulcanizing agent, vulcanization accelerator, anti-aging agent, peptizer , Tackifiers, fragrances, lubricants, colorants, nucleating agents, foaming agents, deodorants, polymer alloy compatibilizers, and the like.
The method for obtaining the antibacterial resin composition of the present invention is not particularly limited, and the above-mentioned resins, rubbers and the antibacterial agent particles of the present invention are used, for example, a twin screw extruder, a pressure kneader, an open roll, a Banbury mixer. Etc. using a device such as a pelletizer, a pulverizer, etc., and using a device such as a pelletizer or a pulverizer to make pellets or powders to obtain a resin composition, or a resin was dissolved using a solvent. An example is a method of mixing the antibacterial agent particles of the present invention.

The method for obtaining the molded article of the antibacterial resin composition of the present invention is not particularly limited, and the method for forming the resin composition containing the antibacterial agent obtained by the above-mentioned method into a resin product such as a molded product at the same concentration. Or, once processed into a high concentration as a masterbatch, it is diluted and mixed to a concentration that will eventually be used as a resin product, and then it is injection-molded, extruded, blow-molded, calendered, and compression-molded As an example, a method of making an antibacterial resin product using an apparatus such as a laminate molding machine, and a method of directly injecting and direct injection molding or direct extrusion molding of the antibacterial agent particles after mixing them with the resin it can.
There are no restrictions on the shape, size, thickness, thickness, and usage of the obtained molded product, for example, plate shape, bottle shape, spherical shape, disk shape, sheet shape, wire covering shape, foam, laminated body Anything such as a body may be used, and the molded product can be suitably used in fields requiring antibacterial properties such as kitchens, bathrooms, products around toilets, sanitary products, and air-conditioner outlets.

The method for obtaining the antibacterial film of the present invention is not particularly limited, and an antibacterial resin composition obtained by the above-mentioned method is produced from resins suitable for film production, and is used for the inflation method and the T-die method. A film can be obtained by the calendering method, the casting method, etc., and the film may be further stretched. Further, the film is made into a laminated film of two or more layers by a co-extrusion method, and only the layer requiring antibacterial properties The utilization method which pursued the economical efficiency which uses this antibacterial agent particle of invention as an antibacterial agent can also be illustrated.
There is no restriction | limiting in particular also about the shape of the obtained film, a form, and a usage method, For example, the field | area which requires antibacterial property which also maintained freshness as a film for food packaging, such as vegetable fruit confectionery dried fish, can be illustrated as an example.

There are no particular restrictions on the method for producing the fiber of the present invention, and a resin composition that can be spun as a fiber among the above resin compositions is used, and spinning is performed by a conventionally known melt extrusion method, dry spinning method, wet spinning method, or the like. Further, if necessary, a product such as stretching, twisted yarn, and / or mixing with natural fibers such as cotton, wool, hemp, etc. may be adopted. There is no restriction | limiting in particular also about the utilization method of the obtained fiber, For example, the field | areas which require antimicrobial properties, such as a carpet, clothes, a towel, a napkin, a handkerchief, a glove, a sock, a hat, a muffler, can be illustrated as an example.
As fibers, polypropylene, polyethylene, polyamide (nylon), aramid, acrylic, polyurethane, fluorine, polyclar, polyester, polyvinyl chloride, vinylon, vinylidene, acetate, triacetate And fibers such as rayon, cupra, novoloid, promix, polyacetal, polynosic, and plastic optical fiber.

There is no restriction | limiting in particular in the method of manufacturing the antibacterial nonwoven fabric of this invention, What is necessary is just to employ | adopt a conventionally well-known method.
For example, paper making web method, random web method, parallel web method, cross-laid web method, interlaced web method, tow spread web method, short fiber web method, filament web method, microfiber web method, split film web method, etc. A method may be employed. The antibacterial nonwoven fabric obtained by these methods has antibacterial properties and is light and breathable, and has excellent properties such as shrinkage resistance, so it can be used for sanitary products, clothing interlining and lining, vinyl leather and artificial leather base fabric One example is that it can be used in fields requiring antibacterial properties.

  There are no particular restrictions on the method for industrially producing the antibacterial paint of the present invention, and conventionally known methods can be employed, and pigments, color formers, weathering agents, solvents, cosolvents, diluents, plasticizers, etc. are mixed. In this step, the silver and organic acid anion-containing aluminum sulfate hydroxide particle antibacterial agent of the present invention are mixed, and then kneaded as desired, and the product is obtained through a step of filtration (filtration). In the case of personal use at home, the antibacterial agent particles of the present invention can be mixed with a commercially available paint. For example, when the antibacterial paint of the present invention is used in hospitals, nursing homes, schools, restaurants, etc., damage from bacteria such as Escherichia coli and Staphylococcus aureus can be prevented and the object of the present invention is achieved. Paints include synthetic resin paints (alkyd, aminoalkyd, epoxy, fluorine, urethane, vinyl acetate, acrylic ester, unsaturated polyester, phenol, guanamine, butyral, styrene butadiene, styrene, vinyl chloride, vinylidene chloride, rubber chloride Paint, anticorrosive paint, powder paint, electrical insulating paint), cellulose paint, rubber paint, water-soluble synthetic resin paint (water-soluble alkyd, water-soluble epoxy, water-soluble polybutadiene, water-soluble melamine, water-soluble urea, water-soluble Phenols, water-soluble acrylics, etc.), alcoholic paints, oil-based paints and other paints using resins.

  The method for obtaining the antibacterial caulking material of the present invention is not particularly limited. For example, a basic component organopolysiloxane as a caulking material and a methoxysilane-based adhesion promoter such as γ-aminopropylbis (methylethylketoxyamino) methoxysilane. And then a tetrafunctional or trifunctional silane crosslinking agent, a thickener such as silica aerosil, and other catalysts such as organotin carboxylates that promote the reaction of the polymer with the crosslinking agent if necessary. Furthermore, a method of obtaining the antibacterial agent particles of the present invention together with an antioxidant, an ultraviolet absorber, a plasticizer and the like by a conventionally known method can be exemplified.

As described above, the antibacterial agent represented by the formula (1) of the present invention can be blended with a resin to provide valuable products as various molded products. On the other hand, the antibacterial agent of the present invention can be applied to uses other than resins by utilizing its dispersibility, whiteness, uniformity of particle shape and uniformity of particle diameter.
That is, it can be applied to antifungal agents, antibacterial deodorants (sprays), antibacterial papers, agricultural chemicals and cosmetics by utilizing the antibacterial properties. The antibacterial agent of the present invention is safe for the human body and does not irritate even when it comes into contact with the human body. It can be used as an agent. It can also be sprayed directly on vegetables and fruits as pesticides. Furthermore, even if it mix | blends in cosmetics, it can utilize advantageously.

The antibacterial agent comprising the antibacterial agent particles of the present invention, the antibacterial resin composition in which the antibacterial agent particles are blended, and a method for measuring each physical property such as a molded article formed from the antibacterial resin composition are described below. Show.
Measuring method of particle properties of silver and organic acid anion-containing aluminum sulfate hydroxide particles antibacterial agent;
Recently, the laser diffraction scattering method has become the mainstream for measuring the average secondary particle size and particle size distribution of fine particles. In the present invention, these measurements were performed by the laser diffraction scattering method.

(1) Average secondary particle size: Measured using a particle size distribution measuring apparatus LA-910 (laser diffraction scattering method) manufactured by Horiba.

(2) Sharpness of particle size distribution Dr = D ₇₅ / D ₂₅
The 75% value particle size D ₇₅ (large particle size side) of the laser diffraction scattering method volume-based cumulative particle size distribution curve measured using a Horiba particle size distribution measuring device LA-910 is 25% value particle size D. The sharpness of the particle size distribution represented by the formula divided by ₂₅ (fine particle size side) was defined as Dr = D ₇₅ / D ₂₅ . The smaller the numerical value of Dr, the more sharp the particle size distribution is recognized, which means the particle size uniformity.
However, for spherical particles, the particle size was evaluated in combination with D ₇₅ / D ₂₅ measured by the laser diffraction scattering method and the particle size distribution measurement method by the following SEM photograph.
In that case, the value of D ₇₅ / D ₂₅ by the laser diffraction scattering method and the value of D ₇₅ / D ₂₅ by the SEM photograph almost coincide with each other in a range of about −10 to + 10%. D ₇₅ / D ₂₅ was adopted.
Particle size distribution measurement method by electron micrograph (SEM photograph) (in the case of spherical particles);
Spherical particles of all particles (50 to several hundreds) observed in one SEM photograph are individually measured for the major axis and minor axis to 1/50 mm with calipers, and the average value of major axis and minor axis is obtained. The particle diameter (converted to μm) of each spherical particle was determined, and then the particle diameter corresponding to D ₇₅ % and D ₂₅ % of the cumulative particle diameter was recognized, and Dr = D ₇₅ / D ₂₅ was calculated.

(3) BET method specific surface area: measured with a 12-sample fully automatic surface measuring device Multisorb-12 manufactured by Yuasa Ionics Co., Ltd.

(4) Particle shape: observed with a scanning electron microscope (SEM photograph).
The relationship between the shape (particles) of the particle shape and the antibacterial agent particles of Examples and Comparative Examples is as follows.
Fig. 1, spherical particles with a smooth surface, A1 particles Fig. 2, spherical particles with small particles on the surface, A20 particles Fig. 3, spherical particles with rough surfaces and even wrinkles (scratches and cracks on the sphere), A21 particle diagram 4, spherical particles having holes (irregularities), A22 particles FIG. 5, spherical particles having a smooth surface and a little more straight portions than those in FIG. 1, A30 particles FIG. 6, spherical particles having rough surfaces and wrinkles, A31 particle FIG. 7, disk-like particle particle, B1-1 particle,
FIG. 8, a pair of particles (hamburger particles), C1 particles, FIG. 9, rice granular particles, D1 particles,
FIG. 10, rectangular parallelepiped particle, E1 particle FIG. 11, hexagonal plate particle, F1 particle FIG. 12, octahedral particle, G1 particle FIG. 13, columnar (shu-barrel) particle, H1 particle FIG. 14, surface roughly stretched Aggregate particles in such a state, V1 particles

(5) Ion exchanger formation; The presence or absence of diffraction patterns of silver sulfate and organic acid anion-containing aluminum sulfate hydroxide particles and other diffraction patterns were examined by powder X-ray diffraction.

(6) The content of the organic acid; silver and organic acid anion containing aluminum sulfate hydroxide particles were fired recovered to generate CO ₂ at 1000 ° C., the CO ₂ was measured by JIS R 9101, of the carbon based thereon The content was calculated and the organic acid content was determined from it.
Measuring method of resin products such as antibacterial resin composition, resin molded product, film, fiber, paint, caulking material;

(7) Antibacterial test method In the following tests (a) to (e), E. coli is E. coli. E. coli NBRC 3972 Staphylococcus aureus Aureus NBRC 12732 was used. In Tables 7 to 17, which also show the results of the antibacterial test, cfu is an abbreviation for colony forming unit. cfu / ml represents the number of viable bacteria in 1 ml, and the smaller the value, the higher the antibacterial property.
(A) Molded plate; JIS-Z 2801 (2000 version)
Test piece size: 50mm x 50mm x 2mm
(B) Fiber, non-woven fabric; JIS-L 1902 (2002 edition)
(C) Paint; The paint was coated on a test piece (material is JIS G 3101 SS400) having a size of 50 mm × 50 mm × 2 mm and measured by the method (a).
(D) Film; JIS-Z 2801 (2000 version)
(E) Caulking material: The caulking material was caulked to a thickness of about 1 mm on a test piece (material is JIS G 3101 SS400) having an iron plate size of 50 mm × 50 mm × 2 mm, and measured by the method (a).

(8) Transparency: A haze value H was measured with an AUTOMATIC HAZE METER OPTICAL UNIT TC-HIIIDP of TOKYO DENSYKU CO, LTD on a 2 mm thick plate or a 50 μm film and expressed in% by the following formula.

H = {h ₁ − (h ₂ −h ₁ )} × 100 / h ₁ %
h ₁ = haze value of resin molded product or film to which no antibacterial agent is added h ₂ = haze value of resin molded product or film to which an antibacterial agent is added H It means that

(9) Whiteness: The degree of discoloration of a sample such as a molded product, a film, a fiber, and a non-woven fabric, which had been allowed to stand for 60 days in a room on the north side without direct sunlight, was measured visually.

(10) Antibacterial activity maintenance characteristics after contact with tap water;
The test material described above was immersed in 1000 ml of tap water at 90 ° C. or 70 ° C. for 120 hours, washed thoroughly with tap water, and measured by the methods (a) to (e) in (7) above. . In the case where the specific gravity of the test piece is 1 or less, a wire mesh made of stainless steel SUS-304 was used as a weight to forcibly submerge it in water. The reason for heating tap water to 90 ° C or 70 ° C is to see the antibacterial activity maintenance characteristics after contact with tap water in a short time. It will be an accelerated test.

(11) Filter passability test during kneading extrusion (measurement of extruder pressure)
A filter (screen mesh) was placed in front of the breaker plate in a 30φ biaxial kneading extruder (screw diameter 30 mm) manufactured by Plastic Engineering Laboratory, as viewed from the resin flow direction. One 50 mesh filter was installed on the breaker plate side, one 80 mesh filter in the center, and one 100 mesh filter on the hopper side. In this state, the machine was operated for 2 hours and 24 hours with a screw rotation speed of 170 rpm and a discharge amount of 10 kg / hr, and the pressure was measured with a pressure gauge installed in front of the filter at that time.
The pressure becomes so high that coarse particles that cannot pass through the filter are clogged with a large amount of the filter, which means that the filter passage is bad, and it is necessary to replace the filter so quickly that it is an industrial problem.
In this test, when the pressure is 200 kg / cm ² or more, the machine is in an operating state immediately before breakage, and when the pressure is 150 kg / cm ² or more, if the filter is not replaced, the machine will be overloaded and the machine operation may be hindered. This means that when it is 100 kg / cm ² , it means that it is necessary to prepare for filter replacement, and 100 kg / cm ² or less means that it can be operated without any problems.

If the pressure after 24 hours from the start of operation of the machine is up to 150 Kg / cm ² , the filter needs to be changed about once a day, which is barely meaningful industrially.
In addition, this measurement was measured at an antibacterial agent blending concentration of 95% by weight of resin and 5% by weight of antibacterial agent, and the antibacterial agent on the left side of the vertical double line shown in Table-7 to Table-9. This is separately carried out under blending conditions different from the blending amount concentration. The other conditions for kneading extrusion were the same as those on the left side of the vertical double line.

  Hereinafter, the method for producing antibacterial agent particles of the present invention will be specifically described based on examples.

In the formulas of the following examples, when the numerical value of b in formula (1) is 1, 1 is omitted.
Production of silver and organic acid anion-containing aluminum sulfate hydroxide particles antibacterial agent;

<Examples> I-1 to I-47 and <Comparative Examples> I-1 to I-9
(Manufacture of A, B, C, D, E, F, G, H particles)
Production of spherical particles (A particles) ; Examples I-1 to 31
Example I-1
Use the _{[Ag 0.1 (NH 4) 0.9} ] Al 3 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 · 0.5H 2 O of the following raw material A1 particles were obtained by the following synthesis method.
Raw material used Ammonium sulfate 264.28 g = 2 mol
Succinic acid (H ₂ C ₂ O ₄ .2H ₂ O) 38 g = 0.3 mol
1.04 mol / L aluminum sulfate × 1923 ml = 2.0 mol
9.0 mol / L aqueous ammonia solution × 894.5 ml = 8.05 mol Synthesis method 264.28 g of ammonium sulfate (NH ₄ ) ₂ SO ₄ was dissolved in 4.0 L of ion-exchanged water.
38 g of oxalic acid (H ₂ C ₂ O ₄ .2H ₂ O) was dissolved in 1.0 L of ion exchange water.

The oxalic acid aqueous solution and the aluminum sulfate Al ₂ (SO ₄ ) ₃ aqueous solution were added to the ammonium sulfate (NH ₄ ) ₂ SO ₄ aqueous solution under stirring to prepare a mixed acidic aqueous solution.
The mixed acidic aqueous solution is heated to 50 ° C. or lower with good stirring (to dissolve the precipitated crystal), and then 894.5 ml of the above aqueous ammonia solution is added to the mixed acidic aqueous solution over 25 minutes to form an ammonium type. A slurry of precipitates of aluminum sulfate hydroxide particles containing organic acid anions was prepared.
The slurry was further hydrothermally treated at 100 ° C. for 1 hour.
The treated precipitate was filtered, washed with water, dried and pulverized to obtain a powder sample.
100 g of the sample was taken and suspended in 600 ml of a 0.025 mol / L silver sulfate aqueous solution and stirred, and ion exchange treatment between ammonium ions and silver ions was performed at 30 ° C. for 8 hours under light shielding.
The sample after ion exchange was filtered, washed, dried (105 ° C. × 6 hours), and pulverized.
A1 particles were obtained by these treatment processes. The results are shown in Table-1.

Example I-2
_{[Ag 0.1 (NH 4) 0.9} ] Al 3 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 prepared in)
The A1 particles obtained in Example I-1 were dried at 150 ° C. for 2 hours to obtain A2 particles.

Example I-3
Synthesis of [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.0001 (SO ₄ ) _1.9999 (OH) _{6 In} Example I-1, the amount of oxalic acid used was 0. .0005 mol (0.063 g) is different from Example I-1 except that the other processing steps are carried out according to Example I-1 and further dried at 150 ° C. for 2 hours to obtain A3 particles. It was.

Example I-4
Production of [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.01 (SO ₄ ) _1.999 (OH) _{6 In} Example I-1, the amount of oxalic acid used was 0. .05 mol (6.3 g) was different from Example I-1 except that the other treatment steps were carried out according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain A4 particles. It was.

Example I-5
[Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.4 (SO ₄ ) _1.7 (OH) Production of _5.8 Amount of oxalic acid used in Example I-1 Was changed to 1.5 mol (189.1 g) only from Example I-1, and the other processing steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain A5 particles. Got.

Example I-6
[Ag _0.1 (NH ₄ ) _0.9 ] Al _2.7 (C ₂ O ₄ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{5.1 In} Example I-1, aluminum sulfate The amount of A was changed to 1731 ml (1.8 mol), only different from Example I-1, and the other processing steps were carried out in accordance with Example I-1, and further dried at 150 ° C. for 2 hours to obtain A6. Particles were obtained.

Example I-7 Preparation of [Ag _0.1 (NH ₄ ) _0.9 ] Al _3.3 (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _6.9 Example I- In Example 1, the amount of aluminum sulfate used was changed to 2115 ml (2.2 mol), only different from Example I-1, and the other treatment steps were carried out in accordance with Example I-1, and at 150 ° C. A7 particles were obtained by drying for 2 hours.

Example I-8
_{[Ag 0.1 (NH 4) 0.9} ] Al 3 (C 2 O 4) 0.1 (SO 4) 2.4 (OH) preparation of ₅₎
Example I-1 differs from Example I-1 only in that the amount of ammonium sulfate (NH ₄ ) ₂ SO ₄ used was changed to 2.3 mol (303.9 g). This was carried out according to I-1, and further dried at 150 ° C. for 2 hours to obtain A8 particles.

Example I-9
[Ag _0.1 (NH ₄ ) _1.10 ] _1.2 Preparation of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6.02 In} Example I-1, ammonia was used. Example I-1 was that the stirring time after addition of the aqueous solution was changed to 2 hours, the amount of the added aqueous ammonia solution was changed to 1093 ml (9.84 mol), and the hydrothermal treatment time was changed to 30 minutes. The other processing steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain A9 particles.

Example I-10
Production of [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-1, hydrothermal treatment at 100 ° C. Only the difference from Example I-1 was that the time was changed to 45 minutes, and the other treatment steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain A10 particles.

Example I-11
[Ag _0.1 (NH ₄ ) _0.76 ] _0.86 Preparation of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{5.68 In} Example I-1, ammonia was used. The only difference from Example I-1 was that the time for adding the aqueous solution was changed to 40 minutes and that the amount of the added aqueous ammonia solution was changed to 755 ml (6.8 mol). −1, and further dried at 150 ° C. for 2 hours to obtain A11 particles.

Example I-12
Synthesis of [Ag _0.3 (NH ₄ ) _0.7 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-1, a silver sulfate aqueous solution for ion exchange Only the difference from Example I-1 was that the amount of was changed to 1800 ml, and the other treatment steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain A12 particles.

Example I-13
Production of [Ag _0.001 (NH ₄ ) _0.999 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-1, a silver sulfate aqueous solution for ion exchange Was changed to silver nitrate aqueous solution, the concentration was changed to 0.001 mol / L, the liquid volume was changed to 300 ml, and the processing temperature was changed to 15 ° C., except for Example I-1. This was carried out according to I-1, and further dried at 150 ° C. for 2 hours to obtain A13 particles.

Example I-14
[Ag _0.00001 (NH ₄ ) _0.99999 ] _{Production of} Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-13, the silver nitrate aqueous solution for ion exchange was prepared. Only the difference from Example I-13 was that the concentration was changed to 0.00001 mol / L, and the other processing steps were performed in accordance with Example I-1, and further dried at 150 ° C. for 2 hours to obtain A14 particles. .

Example I-15
Obtained in _{[Ag 0.1 (NH 4) 0.9} ] Al 3 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 · 0.5H 2 O prepared in Example I-1 of 50 g of the sample was suspended in an 80 ° C. aqueous solution containing 1.5 g of sodium stearate, stirred for 30 minutes for surface treatment, dehydrated, washed with water, dried (105 ° C. × 6 hours), and pulverized to obtain A15 particles.

Example I-16
_{[Ag 0.1 (NH 4) 0.9} ] samples obtained in _{Al 3 (C 2 O 4)} 0.1 (SO 4) 1.9 (OH) 6 · 2H 2 O prepared in Example I-1 of Was subjected to a moisture absorption treatment for 25 hours in a NaCl atmosphere at 30 ° C. and a relative humidity of 75% to obtain A16 particles.

Example I-17 Baked product of Example 1 at 400 ° C. for 1 hour The sample obtained in Example I-1 was fired in a nitrogen atmosphere at 400 ° C. for 1 hour to obtain A17 particles.
According to the powder X-ray diffraction method, they were all [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ . The shape was spherical.
A0.001 g of A17 particles was placed in 100 ml of ion-exchanged water and stirred at 20 ° C. for 30 minutes. After dehydration, washing and drying at 120 ° C. for 16 hours, there was no weight loss and the weight was 10.00 g.

Example I-18 Baked product of Example 1 at 500 ° C. for 1 hour The sample obtained in Example I-1 was baked in a nitrogen atmosphere at 500 ° C. for 1 hour to obtain A18 particles.
According to the powder X-ray diffraction method, they were all [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ . The shape was spherical.
After 10.00 g of A18 particles were placed in 100 ml of ion-exchanged water and stirred at 20 ° C. for 30 minutes, it was dehydrated, washed with water and dried at 120 ° C. for 16 hours.

Example I-19
[Ag _0.001 K _0.999 ] Production of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ A19 particles were obtained by the following method using the following raw materials. .
Raw material used Potassium sulfate 2mol 348g
Succinic acid (H ₂ C ₂ O ₄ .2H ₂ O) 0.3 mol 38 g
1.04 mol / L aluminum sulfate aqueous solution 2.0 mol 1923 ml
7.5 mol / L KOH aqueous solution 8.4 mol 1120 ml
Synthesis Method 348 g of potassium sulfate (K ₂ SO ₄ ) was dissolved in 4.0 L of ion exchange water.
38 g of oxalic acid (H ₂ C ₂ O ₄ .2H ₂ O) was dissolved in 1.0 L of ion exchange water.
The oxalic acid aqueous solution and the aluminum sulfate Al ₂ (SO ₄ ) ₃ aqueous solution were added to the potassium sulfate (K ₂ SO ₄ ) aqueous solution under stirring to prepare a mixed acidic aqueous solution.
The mixed acidic aqueous solution is stirred well, and 1120 ml of the above potassium hydroxide aqueous solution is added to the mixed acidic aqueous solution over 25 minutes to form a potassium-type organic acid anion-containing aluminum sulfate hydroxide particle precipitate slurry. It was. .
The slurry was further stirred for 1 hour, and then hydrothermally treated at 140 ° C. for 2 hours by an autoclave.
The treated precipitate was filtered, washed with water and dried to obtain a powder sample.
A 100 g sample was taken and suspended in 300 ml of a 0.001 mol / L silver nitrate aqueous solution and stirred, and an ion exchange treatment between potassium and silver was performed at 25 ° C. for 1 hour in the dark.
The sample after ion exchange was filtered, washed, dried (105 ° C. × 6 hours), and pulverized.
After passing through these treatment steps, it was further dried at 200 ° C. for 2 hours to obtain A19 particles.

Example I-20
[Ag _0.001 K _1.179 ] _{1.18 Preparation of} Al ₃ (SO ₄ ) _2.26 (NO ₃ ) _0.04 (C ₂ O ₄ ) _0.07 (OH) _5.48 Example I- 19 except that the potassium sulfate used was changed to potassium nitrate KNO ₃ and that was different from Example I-19, and other treatment processes were performed according to Example I-19 to obtain A20 particles.

Example I-21
[Ag _0.001 K _1.179 ] _{1.18 Preparation of} Al ₃ (SO ₄ ) _2.26 (NO ₃ ) _0.04 (C ₂ O ₄ ) _0.07 (OH) _5.48 Example I- 19 is different from Example I-19 in which KNO ₃ is changed to KNO ₃ instead of K ₂ SO ₄ and the hydrothermal treatment condition is changed to 160 ° × 2 hours, and other processing steps are different from those in Example I-19. According to the same manner, A21 particles were obtained.

Example I-22
[Ag _0.001 K _0.999 ] Production of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-19, the hydrothermal treatment temperature was changed from 140 ° C to 170 ° C. Only the difference from Example I-19 was that the temperature was changed to ° C., and the other treatment steps were performed according to Example I-19 to obtain A22 particles.

Example I-23 Preparation of [Ag _0.1 Na _0.9 ] Al ₃ (C ₆ H ₅ O ₇ ) _0.067 (SO ₄ ) _1.9 (OH) ₆ A23 particles were obtained by this method.
Raw material used Sodium sulfate 2 mol 284.06 g
Citric acid _{(C 6 H 8 O 7 ·} H 2 O) 0.3 mol 63g
1.04 mol / L aluminum sulfate aqueous solution 2.0 mol 1923 ml
3.36 mol / L NaOH aqueous solution 8.2 mol 2440.5 ml
Synthesis Method 284.06 g of sodium sulfate (Na ₂ SO ₄ ) was dissolved in 4.0 L of ion exchange water.
63 g of citric acid was dissolved in 1.0 L of ion exchange water.
The citric acid aqueous solution and the aluminum sulfate Al ₂ (SO ₄ ) ₃ aqueous solution were added to the sodium sulfate (Na ₂ SO ₄ ) aqueous solution under stirring to make a mixed acidic aqueous solution.
The sodium hydroxide aqueous solution 2440.5 ml was added to the mixed acidic aqueous solution under stirring over 25 minutes to form a sodium-type silver and organic acid anion-containing aluminum sulfate hydroxide particle precipitate slurry.
The slurry was further stirred for 10 hours, and then hydrothermally treated at 170 ° C. for 2 hours by an autoclave. The precipitate after the hydrothermal treatment was filtered, washed, dried and pulverized to obtain a powder sample.
Other treatment steps were performed according to Example I-1, and dried at 150 ° C. for 2 hours to obtain A23 particles.

Example I-24
[Ag _0.1 Na _0.9 ] Al ₃ (C ₆ H ₅ O ₇ ) _0.067 (SO ₄ ) _{Preparation of 1.9} (OH) _{6 In} Example I-23, the addition time of sodium hydroxide was 40 minutes and the stirring time after addition of sodium hydroxide was changed to 1 hour, except that it was different from Example I-23. The other treatment steps were carried out in accordance with Example I-23, and further at 150 ° C. It dried for 2 hours and obtained A24 particle | grains.

Example I-25
Production of [Ag _0.1 Na _0.9 ] Al ₃ (C ₄ H ₄ O ₆ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ Using the following raw materials, A25 particles were prepared by the following method. Obtained.
Raw material used Sodium sulfate 2 mol 284.06 g
Tartaric acid (C ₄ H ₆ O ₆ ) 0.3 mol 45 g
1.04 mol / L aluminum sulfate aqueous solution 2.0 mol 1923 ml
3.36 mol / L NaOH aqueous solution 8.2 mol 2440.5 ml
Synthesis Method 284.06 g of sodium sulfate (Na ₂ SO ₄ ) was dissolved in 4.0 L of ion exchange water.
45 g of tartaric acid (C ₄ H ₆ O ₆ ) was dissolved in 1.0 L of ion exchange water.
The oxalic acid aqueous solution and the aluminum sulfate Al ₂ (SO ₄ ) ₃ aqueous solution were added to the potassium sulfate (K ₂ SO ₄ ) aqueous solution under stirring to prepare a mixed acidic aqueous solution.
The mixed acidic aqueous solution is stirred well, and the above sodium hydroxide aqueous solution 244.05 ml is added to the mixed acidic aqueous solution over 25 minutes to add sodium-type silver and organic acid anion-containing aluminum sulfate hydroxide particle precipitate slurry. made.
The slurry was further stirred for 5 hours, and then hydrothermally treated at 170 ° C. for 2 hours by an autoclave.
The suspension after hydrothermal treatment was filtered, washed with water, dried and pulverized.
The other treatment steps were performed according to Example I-1, and dried at 150 ° C. for 2 hours to produce A25 particles.

Example I-26
[Ag _0.1 Na _0.9 ] Al ₃ (C ₄ H ₄ O ₆ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-24, the amount of sodium hydroxide was 8 The difference was that the molar amount (2381 ml) was changed, and the addition time was changed to 40 minutes, which was different from Example I-25. The other processing steps were performed according to Example I-25, and A26 particles were obtained.

Example I-27
_{[Ag 0.1 (NH 4) 0.9} ] Al 2.94 Zn 0.01 Ti 0.01 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 · 0.5H 2 Production of O 2.5 g of zinc sulfate and titanium sulfate {Ti ₂ (SO ₄ ) ₃ } in the mixed acidic solution of Example I-1 (however, the amount of the aluminum sulfate aqueous solution used in the mixed acidic solution was reduced to 1885 ml) The addition of a sulfuric acid solution containing 2.5 g, and the silver ion exchange treatment temperature was changed to 80 ° C. and the treatment time was changed to 16 hours, except that Example I-1 was the same as in Example I-1. A27 particles were obtained.

Example I-28
_{[Ag 0.1 (NH 4) 0.9} ] Al 2.25 Zn 0.5 Ti 0.25 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 · 0.5H 2 Production of O 2 The mixed acidic solution of Example I-1 (however, the amount of the aluminum sulfate aqueous solution used in the mixed acidic solution was reduced to 1442 ml) contains 125 g of zinc sulfate and 63 g of titanium sulfate {Ti 2 (SO ₄ ) ₃ }. The addition of a sulfuric acid solution and the change of the silver ion exchange treatment temperature to 80 ° C. and the treatment time to 30 hours were different from Example I-1, and the others were carried out in accordance with Example I-1, and the A28 particles were changed. Obtained.

Example I-29
[Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.15 (PO ₄ ) _0.5 (OH) ₆ Production of Ammonium Phosphate 74.5 g 371 g of A-1 particles just before ion exchange with silver (after hydrothermal treatment) were added to an aqueous solution in which 500 ml of water was dissolved, and stirred at 100 ° C. for 1 hour to incorporate PO ₄ ³⁻ into the particles. The subsequent treatment process was carried out in accordance with Example I-1, and further dried at 150 ° C. for 2 hours to obtain silver and organic acid anion-containing aluminum sulfate phosphate hydroxide A29 particles.
Note in this example, sodium carbonate instead of sodium phosphate, sodium nitrate, sodium silicate, only that was used to replace the sodium borate was tested differently but ^{_{CO 3 2-, NO 3 -,}} SiO 4 2- Silver and organic acid anion-containing aluminum inorganic acid salt hydroxide particles having particle properties similar to those of A-29 particles containing inorganic acid ions of BO ₃ ^3- were obtained.

Example I-30
Preparation of [Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) _1.9 (C ₄ H ₄ O ₅ ) _0.1 (OH) _{6 In} Example I-25, the organic acid used was tartaric acid. The change to DL-apple succinic acid was only different from Example I-25, and other treatment steps were performed according to Example I-25 to obtain A30 particles.
Various characteristics are shown in Table 1. The particle shape at this time was spherical as shown in FIG.

Example I-31
[Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) _1.9 Production of [C ₆ H ₂ (OH) ₃ COO] _0.067 (OH) ₆ Organic acid used in Example I-23 Was changed from citric acid to gallic acid [C ₆ H ₄ (OH) ₃ COOH], only different from Example I-23, and other treatment steps were performed according to Example I-23 to obtain A31 particles. It was. Various characteristics are shown in Table 1.
The particle shape at this time was spherical as shown in FIG.

Comparative Example I-1
Production of [Ag _0.1 (NH ₄ ) _0.9 ] Al ₃ (SO ₄ ) ₂ (OH) _{6 In} Example I-1, the fact that no succinic acid was used was different from Example I-1. The other treatment steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain V1 particles.

Comparative Example I-2
Production of NH ₄ Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-1, the fact that ion exchange was not carried out with a silver solution and Example I-1 Other than that, the other processing steps were carried out according to Example I-1 and further dried at 150 ° C. for 2 hours to obtain V2 particles.

Comparative Example I-3
Production of KAl ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-19, the difference from Example I-19 was that ion exchange was not performed with a silver solution. The other treatment steps were performed according to Example I-19 to obtain V3 particles.

Production of discoid particles (meteorite particles; B particles); (Examples I-32 to 34)
Example I-3-1
Production of [Ag _0.1 Na _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ B1 particles were obtained by the following method using the following raw materials. .
Raw material used Sodium sulfate 2 mol 284.06 g
Succinic acid (H ₂ C ₂ O ₄ .2H ₂ O) 0.3 mol 38 g
1.04 mol / L aluminum sulfate aqueous solution 2.0 mol 1923 ml
3.36 mol / L NaOH aqueous solution 8.2 mol 2440.5 ml
Synthesis Method 284.06 g of sodium sulfate (Na ₂ SO ₄ ) was dissolved in 4.0 L of ion exchange water.
38 g of oxalic acid was dissolved in 1.0 L of ion exchange water.
The oxalic acid aqueous solution and the aluminum sulfate Al ₂ (SO ₄ ) ₃ aqueous solution were added to the sodium sulfate (Na ₂ SO ₄ ) aqueous solution under stirring to form a mixed acidic aqueous solution.

The mixed acidic aqueous solution is thoroughly stirred, and 2440.5 ml of the sodium hydroxide aqueous solution is added to the mixed acidic aqueous solution over 20 minutes to add sodium-type silver and organic acid anion-containing aluminum sulfate hydroxide particle precipitate slurry. made.
The slurry was further stirred for 5 hours, and then hydrothermally treated at 170 ° C. for 2 hours by an autoclave. The treated precipitate was filtered, washed with water and dried. Then, 100 g of the sample was taken, suspended in 600 ml of a 0.025 mol / L silver sulfate aqueous solution, stirred, and subjected to sodium-silver ion exchange treatment at 25 ° C. for 5 hours. 0.02 g of a polyacrylamide polymer flocculant (Sumitomo Chemical's Sumifloc FN-20) was added to the sample after the replacement, and the mixture was stirred for 10 minutes, filtered, washed with water, dried (105 ° C. × 6 hours), and pulverized. After these treatment steps, the particles were further dried at 200 ° C. for 2 hours to obtain B1-1 particles.

Example I-3-2
A mixture of 2.6 g of zinc sulfate heptahydrate (Wako Pure Chemical Industries grade 1) and 2.2 g of ammonium sulfate (Wako Pure Chemical Industries grade 1) in 1,000 ml of ion-exchanged water at 80 ° C. was prepared. . 95 g of B1-1 particles were added to the mixed solution and stirred for 6 hours, followed by dehydration, washing with water and drying to produce B1-2 particles treated with zinc and ammonium. The Zn content of the particles was 0.1%, the NH ₄ content was 0.4%, and the BET specific surface area was 60 m ² / g, but the other particle properties were the same as the B1-1 particles. It was.
Next, A20 particles, C1 particles, D1 particles, E1 particles, F1 particles, G1 particles, and H1 particles were treated in the same manner as above to obtain a treated product.
The Zn content of the treated product was 0.1%, and the NH ₄ content was 0.4%, which were almost the same.
Although the BET specific surface area of the treated product increased by about 6 times before the treatment, the average secondary particle size, the shape of the uniform particle size, and other particle shapes were almost the same as the particle properties before the treatment. Met.
The whiteness of the resin composition when the treated product was added to the resin was further improved when the product before the treatment was added.

Example I-33
[Ag _0.1 Na _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-32, 0.5 mol of sodium sulfate was used. Example I-32 that the reaction mother liquor containing / L sodium sulfate was changed to 4.0 L, the addition time of sodium hydroxide was changed to 40 minutes, and the stirring time after addition was changed to 1 hour. Differently, other processing steps were performed according to Example I-32 to obtain B2 particles.

Example I-34 [Ag _0.001 Na _0.999 ] Preparation of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-32, an aqueous silver sulfate solution was prepared. The concentration was changed to 0.00025 mol / L, only different from Example I-32. The other processing steps were performed in accordance with Example I-32 to obtain B3 particles.

Comparative Example I-4- (1)
Production of NaAl ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ Example I-32 differs from Example I-32 in that no ion exchange treatment with silver ions is performed. The other treatment steps were performed according to Example I-32 to obtain W1 particles.

Comparative Example I-4- (2)
Production of [Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) ₂ (OH) ₆ Example I-32 was different from Example I-32 except that succinic acid was not used. The treatment process was performed according to Example I-32 to obtain W2 particles.

Production of paired (hamburger-like) particles (C particles); Examples I-35 to 37
In Example _{I-35 [Ag 0.1 Na 0.9} ] Al 3 (C 2 O 4) 0.1 (SO 4) 1.9 (OH) 6 prepared in Example I-32 of the autoclave treatment temperature Was changed to 180 ° C. and a treatment time of 10 hours, only different from Example I-32. The other treatment steps were carried out according to Example I-32 to obtain C1 particles.

Example I-36
[Ag _0.1 Na _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) Production of _1.9 (OH) _{6 In} Example I-32, the autoclave treatment temperature was 180 ° C. The time was changed to 10 hours, the sodium sulfate used was 4.0 L of reaction mother liquor containing 0.5 mol / L sodium sulfate, and the addition time of sodium hydroxide was changed to 40 minutes. Other than the process of Example I-32, the other processing steps were performed according to Example I-32 to obtain C2 particles.

Example I-37
[Ag _0.001 Na _0.999 ] Preparation of Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-32, the concentration of the silver sulfate solution was 0.00025 The change to mol / L, and the change to autoclave treatment temperature of 180 ° C. and treatment time of 10 hours are only different from Example I-32. C3 particles were obtained.

Comparative Example I-5- (1) NaAl ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆
Example I-35 is different from Example I-35 in that the ion exchange treatment with silver ions is not performed, and the other processing steps are performed in accordance with Example I-35 to obtain X1 particles.

Comparative Example I-5- (2)
[Ag _0.1 Na _0.9 ] Preparation of Al ₃ (SO ₄ ) ₂ (OH) _{6 In} Example I-35, oxalic acid was not used except that it was different from Example I-35. The treatment process was performed according to Example I-35 to obtain X2 particles.

Production of Rice Granular Particles (D Particles); Examples I-38-40
Example I-38
[Ag _0.1 Na _0.9 ] Al ₃ (C ₂ H ₄ O ₆ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-23, tartaric acid was used instead of citric acid. The modification was only different from Example I-23, and the other treatment steps were performed according to Example I-23, and further dried at 150 ° C. for 2 hours to obtain D1 particles.

Example I-39
[Ag _0.1 Na _0.9 ] Al ₃ (C ₂ H ₄ O ₆ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-23, tartaric acid was used instead of citric acid. The change was made, and the addition time of the NaOH aqueous solution was changed to 35 minutes, only that it was different from Example I-23. The other treatment steps were performed in accordance with Example I-23, and further dried at 150 ° C. for 2 hours. D2 particles were obtained.

Example I-40
Preparation of [Ag _0.001 Na _0.999 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-23, tartaric acid was used instead of citric acid. In addition, although the silver ion concentration was changed to 0.00025 mol / L, it was different from Example I-23, and the other processing steps were performed according to Example I-23, and further at 150 ° C. for 2 hours. D3 particles were obtained by drying.

Comparative Example I-6- (1)
NaAl ₃ (C ₂ H ₄ O ₆ ) _0.1 (SO ₄ ) _1.9 (OH) ₆
Example I-38 is different from Example I-38 in that the exchange with silver ions is not performed, and other processing steps are performed in accordance with Example I-38 to obtain Y1 particles. It was.

Comparative Example I-6- (2)
Production of [Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) ₂ (OH) _{6 In} Example I-38, tartaric acid was not used, only that it was different from Example I-38. The synthesis process was performed according to Example I-38, and further dried at 200 ° C. for 2 hours to obtain Y2 particles.

Production of rectangular parallelepiped particles (E particles); Examples I-41 to 44
Example I-41
[Ag _0.1 (H ₃ O) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆ Production of E1 The following raw materials were used and E1 was prepared by the following method. Particles were obtained.
Raw materials used 1.04 mol / L aluminum sulfate 2.0 mol 1923 ml
Aluminum hydroxide Al (OH) ₃ 2.0 mol 156.02 g
(Aluminum hydroxide; dry aluminum hydroxide gel S-100 manufactured by Kyowa Chemical Industry Co., Ltd .: amorphous)
Succinic acid (H ₂ C ₂ O ₄ .2H ₂ O) 0.25 mol 31.52 g
Synthetic method While stirring in the aqueous solution of aluminum sulfate, the oxalic acid is added, and further, the aluminum hydroxide Al (OH) ₃ is added with stirring to form a hydrogen-type organic acid anion-containing aluminum sulfate hydroxide particle precipitate slurry. made.
Ion exchange water was added to the slurry to dilute the slurry to 7.0 L, and the mixture was further stirred at room temperature for 15 hours, followed by hydrothermal treatment at 170 ° C. for 5 hours by an autoclave.
The treated solution was filtered, washed with water, dried and pulverized to obtain a sample.
Other treatment steps were performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain E1 particles.

Example I-42
[Ag _0.1 (H ₃ O) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-41, stirring before autoclaving Unlike Example I-41, the time was changed to 30 minutes, and the autoclave treatment temperature was 150 ° C. and the treatment time was changed to 2 hours. The other treatment steps were performed according to Example I-41, and E2 Particles were obtained.

Example I-43
[Ag _0.001 (H ₃ O) _0.999 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) ₆
In Example I-41, the silver ion concentration for exchange was changed to 0.00025 mol / L, except that Example I-41 was different, and the other processing steps were performed according to Example I-41. E3 particles were obtained.

Example I-44
[Ag _0.1 (H ₃ O) _0.9 ] Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) Preparation of _1.9 (OH) _{6 In} Example I-41, stirring before autoclaving The change in time to 2 hours was only different from Example I-41, and the other processing steps were performed according to Example I-41 to obtain E4 particles.

Comparative Example I-7- (1)
Production of (H ₃ O) Al ₃ (C ₂ O ₄ ) _0.1 (SO ₄ ) _1.9 (OH) _{6 In} Example I-41, the silver ion exchange treatment is not performed. Other than 41, the other treatment process was performed according to Example I-41 to obtain Z1 particles.

Comparative Example I-7- (2)
Production of [Ag _0.1 (H ₃ O) _0.9 ] Al ₃ (SO ₄ ) ₂ (OH) ₆ Example I-41 was different from Example I-41 in that no succinic acid was used. The other treatment steps were performed according to Example I-41 to obtain Z2 particles.

Comparative Example I-9
The R1 particles of Comparative Example I-9 are silver-supported zirconium phosphates having an average secondary particle diameter of 1.0 μm, Dr = 4.5, a BET specific surface area of 4 m ² / g, and a silver content of 3%. The particle properties of the particles are shown in Table-5.

Production of hexagonal plate-like particles (F particles); Example I-45
Example I-45
Preparation of [Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) _1.9 (C ₂ O ₄ ) _0.1 (OH) ₆ 2 mol of aluminum sulfate and 2 mol of sodium sulfate were dissolved in 6000 ml of pure water. And 31.52 g (0.25 mol) of succinic acid was placed therein. 1800 ml of an aqueous solution containing 8.8 mol (352 g) of sodium hydroxide was added to the mixed solution under stirring, and further stirred at room temperature for 30 minutes, then hydrothermally treated at 180 ° C. for 20 hours, and then cooled to room temperature. The solution was washed with filtered water and dried at 95 ° C. for 15 hours to obtain organic acid anion-containing aluminum sulfate hydroxide particles.
The subsequent treatment process was performed according to Example I-1, and further dried at 150 ° C. for 2 hours to obtain F1 particles.
Various characteristics are shown in Table 6.
The particle shape at this time was a hexagonal plate shape shown in FIG.

Production of octahedral particles (G particles); Example I-46
Example I-46
[Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) _1.9 Preparation of [CH ₃ CH (OH) COO] _0.067 (OH) _{6 In} Example I-23, the organic acid used was citrated. The only difference from Example I-23 was that the acid was changed to L-lactic acid [CH ₃ CH (OH) COOH], and the other treatment steps were performed according to Example I-23 to obtain G1 particles. Various characteristics are shown in Table 6.
The particle shape at this time was octahedral as shown in FIG.

Production of cylindrical particles (barrel-like particles; H particles); Example I-47
Example I-47
[Ag _0.1 Na _0.9 ] Al ₃ (SO ₄ ) _1.9 Preparation of [HOCH ₂ CH (OH) COO] _0.067 (OH) _{6 In} Example I-23, the organic acid used was citrated. Only the difference from the acid to DL-glyceric acid [HOCH ₂ CH (OH) COOH] was different from Example I-23, and the other treatment steps were performed according to Example I-23 to obtain H1 particles. Various characteristics are shown in Table 6.
The particle shape at this time was a columnar shape (sake barrel-like particle) shown in FIG.

In addition, each of the particles A1 to A31, B1 to B3, C1 to C3, D1 to D3, E1 to E4, F1, G1 and H1 of Example I is a high-purity raw material (impurity content Pb, Cd, As, All of Ba is 0.1 ppm or less, Fe is 10 ppm or less, and Mn, Cu, Cr, and Ni are refined to 1 ppm or less), and the equipment is made of the above-mentioned corrosion-resistant material. Used and synthesized.
Therefore, unlike natural alunite, the impurity content was 0.1 ppm or less for Pb, Cd, As, and Ba, 10 ppm or less for Fe, 1 ppm or less for Mn, Cu, Cr, and Ni, and 100 ppm or less for Cl.
The impurity content was measured by an atomic absorption method, an ICP-AES method (Inductively Coupled Plasma-Atomic Emission Spectroscopy), or a fluorescent X-ray method.
Next, the antibacterial resin composition and the method for producing the antibacterial resin product when the antibacterial agent of the present invention is blended with a resin will be specifically described based on examples. The compounding amount of the compounding agent is based on 100 parts by weight of the resin.
As the optical brightener, 2,5-thiophenediyl (5-tert-butyl-1,3-benzohexazole) was added in an amount shown in each table.

Polypropylene molded products;
Examples II-1 to 32 and Comparative Examples II-1 to II-4
Example II-1 is 100 parts by weight of transparent injection molding grade polypropylene, 0.06 parts by weight of A1 particles described in Table 1, and the optical brightener is 2,5-thiophenediyl (5-tert-butyl-1,3 -Benzohexazole) The addition amount shown in Table-1} was previously mixed, and kneaded at 230 ° C. using a twin-screw kneading extruder to obtain a mixed pellet, which was injection-molded to 2 mm at 230 ° C. Test pieces for each test are prepared and antibacterial properties (immediately after molding and antibacterial activity maintaining properties after contact with tap water), transparency, and whiteness are determined according to the measurement methods (7) to (10) of the resin products. It was measured. The results are shown on the left side of the vertical double line in Table-7.
The test of filter passability test (extruder pressure) during kneading extrusion was performed by the above method (11).
The results are shown on the right side of the vertical double line in Table-7.
In the tests of Examples II-2 to 32, the used antibacterial agent particles and the blending amounts used in Example II-1 were partially changed as shown in Table 7, but other than that, the same as in Example II-1 A test piece was prepared and each test was conducted.
The results are shown in Table-7.

Comparative Example II-1 is a silver-containing aluminum sulfate hydroxide particle containing no organic acid, and V1, W2, X2, Y2, Z2 particles having a large Dr width (particle size distribution width) or silver-supporting phosphorus. Whereas the R1 particles are zirconium acid, the test of Comparative Example II-2 is where no antibacterial agent is added, whereas Comparative Example II-3 is the aluminum sulfate hydroxide particles V2 that do not contain silver, but Comparative Example II. -4 is also aluminum sulfate hydroxide particles V3 particles that do not contain silver, but unlike Example II-1, only some antibacterial agents differ as shown in Table 1 for the antibacterial compounding amount. For other conditions, test pieces were prepared and the same measurements were performed as in Example II-1.
The results are shown in Table-7.

In the examples, it was confirmed that the antibacterial property immediately after molding, the antibacterial activity maintaining property after contact with tap water, transparency, color, and excellent filter passability during kneading extrusion processing, while in the comparative example Had problems with at least one of these characteristics.
Further, in this experiment, the antibacterial property and the transparency become higher as the average secondary particle size of the silver and organic acid anion-containing aluminum sulfate hydroxide particle antibacterial agent is finer, and the higher the BET method specific surface area is, the higher the antibacterial property is. It was observed that the antibacterial property is high, the Dr width (particle size distribution width) is small, the particle size is uniform and the organic acid is included in a certain range, and the antibacterial property tends to be high.
On the other hand, looking at the comparative example, V1, W2, X2, Y2, which are silver-containing aluminum sulfate hydroxide particles containing no organic acid in Comparative Example II-1 and have a large Dr width (particle size distribution width). When Z2 particles are used, the characteristic that the organic acid is not contained appears, the antibacterial property is insufficient, and the filter passability at the time of kneading and extruding deteriorates immediately after operation until the machine is difficult to operate, Transparency was also slightly reduced.

In Comparative Example II-1, it was recognized that the compound containing zirconium phosphate-based R1 particles was inferior in antibacterial activity maintaining characteristics after tap water contact environment and transparency as compared with Examples.
In Comparative Example II-2, there was no problem in transparency and color because no antibacterial agent was blended, but it was needless to say that no antibacterial effect was observed and the object of the present invention was not achieved.
In Comparative Example II-4, although 300 parts by weight of the organic acid anion-containing aluminum sulfate hydroxide particles were blended, it was not an organic acid anion-containing aluminum sulfate hydroxide particle containing silver, so no antibacterial effect was observed. I couldn't.
In other words, even if aluminum sulfate hydroxide particles are used as a summary of the comparative examples, as is understood from Comparative Examples II-3 and II-4, even aluminum sulfate hydroxide particles do not contain silver. It was found that the molded article could not be given antibacterial properties.

Polystyrene, acrylic resin transparent resin molded article Examples II-33, 34 and Comparative Examples II-5, 6, 7
In Examples II-33 and 34, the antibacterial target resin in Example II-1 was changed from polypropylene to a transparent resin such as polystyrene and acrylic resin, and the blending amounts of antibacterial agent and fluorescent whitening agent are shown in Table-8. Thus, only the temperature at the time of kneading and molding was changed to 210 ° C., and the others were performed according to Example II-1. In addition, the addition amount of a compounding agent is as showing in Table-8.
In Comparative Example II-5, no antibacterial agent was added in Example II-33, Comparative Example II-6 was changed to V2 particles, and Comparative Example II-7 was changed to Y1 particles. Other than that was performed according to Example II-33. The results of antibacterial properties, transparency and color are shown in Table-8.
As shown in the following Table-8, the molded articles of the examples are not impaired in transparency, are colorless (white), and have antibacterial properties (immediately after molding and after contact with tap water). It was confirmed to be excellent.
On the other hand, in the comparative example, even the aluminum sulfate hydroxide particles did not contain silver, and therefore no antibacterial property was exhibited.

Polycarbonate, polyethylene terephthalate, nylon 6,6, polyacetal resin molded product Examples II-35 and 36 and Comparative Examples II-8 and 9
In Examples II-35 and 36, the resin to be antibacterial in Example II-1 is required to have transparency such as polypropylene, polycarbonate, polyethylene terephthalate, nylon 6,6, polyacetal resin, etc. The blending amount of antibacterial agent and antibacterial agent and blending amount of fluorescent brightening agent is changed as shown in Table 9, and the kneading and molding temperatures are the common processing temperatures of each resin. (PC, PET, nylon 6 · 6 for 290 ° C., polyacetal for 190 ° C.), others were tested according to Example II-1.
However, in Examples II-35 and 36, the antibacterial agent is a dry-treated A ₂ , B ₁ , C ₁ , D ₁ , E ₁ , F ₁ , G ₁ , H ₁ particle or a baked A17 or A18 particle. 0.1 part by weight was used, Comparative Example 8 was free of antibacterial agent, and Comparative Example 9 was 0.1 part by weight of a V2 particle fired 400 ° C or 500 ° C. The results of antibacterial properties, transparency, color, and extruder pressure are shown in Table-9.
Of course, silver streaks did not occur in the molded products obtained in Examples II-35 and 36.

As shown in Table-9 below, in the examples, the transparency of the molded product is hardly impaired, the color is also colorless (white), and the antibacterial property (the antibacterial activity maintaining property immediately after molding and after the tap water contact environment) Also confirmed to be excellent.
On the other hand, the antibacterial property was not expressed at all in the comparative example.

Film Example II-37 and Comparative Example II-10
A mixture of 90% by weight of LDPE resin and antibacterial agents A2, B1, C1, D1, E1, F1, G1, and H1 particles, each 10% by weight in total 100% by weight using a pressure kneader for 15 minutes at 120 ° C. It was hot-cut with an extrusion granulator to obtain master batch pellets having a diameter of about 3 mm at 120 ° C.

The master batch pellets and the LDPE resin before making the master batch were mixed so as to have the composition shown in Table-10 to obtain a film having a thickness of 50 μm by the T-die method and the inflation method.
In Comparative Example II-10, a film was obtained in the same manner using only the LDPE resin before making the master batch.
The film was measured for antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water), transparency and whiteness by the above methods. The results are shown in Table-10. In Comparative Example II-10, a film was also prepared for the additive-free antibacterial agent, and the same measurement as in Example II-37 was performed. The results are shown in Table-10.
As shown in the following Table-10, the transparency of the film of the example is not impaired, the color is also colorless (white), and excellent in antibacterial properties (immediately after forming and antibacterial activity maintaining property after water contact environment). It was confirmed that
On the other hand, the antibacterial property was not expressed at all in the comparative example.

Example II-38
For 100 parts by weight of each of polypropylene, LDPE, HDPE, ionomer resin, nylon 6/66 copolymer resin, PET resin and AS resin, a mixed pellet of 0.1 part by weight of A2 particles is obtained using a biaxial kneading extruder. It was.
A film having a thickness of 50 μm was obtained from each of the pellets by T-die method.
The film was measured for antibacterial properties (immediately after molding and antibacterial activity maintaining characteristics in a tap water contact environment), transparency, and whiteness by the above methods. The results are shown in Table-10.
For each film obtained in the examples, the transparency is not impaired, the color is also colorless (white), and the antibacterial property (immediately after molding and after contact with tap water) is excellent. confirmed.
On the other hand, the antibacterial property was not expressed at all in the comparative example.

PVC molded product Example II-39 and Comparative Example II-11
In Example II-39, 100 parts by weight of polyvinyl chloride resin, 0.1 part by weight of the antibacterial agent particles shown in Table-11, 1.2 parts by weight of octyltin mercapto, 0.8 part by weight of glycerin ricinoleate, montanic acid ester 0 A composition of 4 parts by weight was kneaded at 180 ° C. for 3 minutes using an open roll to obtain a molded plate having a thickness of 2 mm at 180 ° C. using a compression molding machine.
The molded plate was measured for antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water) by the above method. The results are shown in Table-11.
In Comparative Example II-11, the same measurement was performed using a molded plate having no antibacterial agent and a 2 mm-thick molded plate. The results are shown in Table-11.
As shown in the following Table-11, it was confirmed that the molded plates of the examples were excellent in antibacterial properties (immediately after molding and antibacterial activity maintaining characteristics after contact with tap water) and transparency. On the other hand, the antibacterial property was not expressed at all in the comparative example.

Thermosetting resin molded product Example II-40 and Comparative Examples II-12 and 13
In Example II-40, 100 parts by weight of unsaturated polyester resin, 1 part by weight of antibacterial agent particles shown in Table-12, 3 parts by weight of curing agent (HY951 manufactured by Ciba Special Chemical Co., Ltd.), 1 part by weight of stearic acid, antioxidant ( Irganox 1010 manufactured by Ciba Special Chemical Co., Ltd. 0.5 parts by weight, 0.001 part by weight of optical brightener, average secondary particle diameter of 30 μm, BET method specific surface area of 1 m ² / g for artificial surrogate stone use 150 wt. Of aluminum hydroxide The part was kneaded with a kneader and cured at 90 ° C. for 15 minutes to obtain a plate having a thickness of 2 mm.

The molded plate was measured for antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water) by the above method. The results are shown in Table-12.
In Comparative Examples II-12 and 13, as in Example II-40, the antibacterial agent-free additive and the R1 particles were individually formed into 2 mm-thick molded plates and subjected to the same measurement. The results are shown in Table-12.
It was confirmed that the molded plate of the example was excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water). On the other hand, in Comparative Example II-12, no antibacterial property was expressed.
In Comparative Example II-13, although antibacterial properties were observed immediately after molding, it was found that there was no antibacterial activity maintaining property in a tap water contact environment.

Example II-41
Example II-41 is the same as Example II-40 except that the antibacterial agent-use particles were changed to E2 particles, the blending amount was changed to 300 parts by weight, and stearic acid was changed to 3 parts by weight. A molded plate was prepared in the same manner as in Example II-40, and the same measurement was performed. The results are shown in Table-12.
It was confirmed that the molded plate was excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water).

Example II-42
In Example II-40, the antibacterial target resin was changed from unsaturated polyester resin to phenol resin, melamine resin, and epoxy resin, the antibacterial agent was changed to E4 particles, and the others were made in accordance with Example II-40. The same measurement was performed. The results are shown in Table-12. It was confirmed that the obtained molded plate was excellent in antibacterial property (antibacterial activity maintaining property immediately after molding and after contact with tap water).

The following can be understood by summarizing Examples II-40 to 42 and Comparative Examples II-12 and 13.
The thermosetting resin antibacterial product of the present invention can be suitably used without losing the antibacterial property (antibacterial activity maintaining property after contact with tap water) for a long time even in artificial marble applications used in hand-washing, bathing water, etc. Is shown.
On the other hand, in Comparative Example II-13 containing the silver-supported zirconium of the prior art, although antibacterial properties immediately after molding are recognized, the antibacterial activity maintaining property is completely in the tap water contact environment and there is no meaning in such use. Show.

Rubber molded product Example II-43 and Comparative Example II-14
EPDM (ethylene / propylene ratio = 50/50) 100 parts by weight, antibacterial agent particles 0.5 parts by weight shown in Table-13, dicumyl peroxide 3 parts by weight, poly (2,2,4-trimethyl-1,2 0.5 parts by weight of dihydroquinoline), 1 part by weight of a silane coupling agent (A-172 manufactured by Nihon Unica), 0.5 part by weight of stearic acid, 1 part by weight of sulfur, 0.001 part by weight of optical brightener, rutile A composition comprising 5 parts by weight of type titanium oxide was kneaded at 50 ° C. using an open roll, and vulcanized at 160 ° C. for 30 minutes after 1 day to obtain a molded plate having a thickness of 2 mm.

The molded plate was measured for antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water) by the above method. The results are shown in Table-13.
In Comparative Example II-14, the same measurement was performed using a molded plate having a thickness of 2 mm separately for those without the addition of the antibacterial agent. The results are shown in Table-13.
It was confirmed that the molded plates of the examples were excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water). On the other hand, in Comparative Example II-14, no antibacterial property was expressed.

Example II-44
As in Example II-43, except that the antibacterial agent-use particles were changed to A14 particles in Example II-43, the blending amount was changed to 200 parts by weight, and stearic acid was changed to 2 parts by weight. A molded plate was prepared and the same measurement was performed. The results are shown in Table-13.
It was confirmed that the molded plate was excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water).

Fiber Example II-45, Comparative Example 15
100 parts by weight of polypropylene for fibers and 2 parts by weight of antibacterial agent A2 particles are kneaded in advance using a twin-screw kneading extruder and spun to 100 denier by a melting method using an extruder equipped with a 300 mesh screen. Fiber was obtained. The antibacterial property (antibacterial activity maintaining property immediately after molding and after contact with tap water) of the fiber was measured by the above method. The results are shown in Table-14.
In Comparative Example II-15, the same measurement was performed using a 100-denyl fiber with no antibacterial agent added. The results are shown in Table-14.
It was confirmed that the fibers of the examples are excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after spinning and after contact with tap water).
This means that, for example, textile products such as gloves and socks do not lose or hardly lose antibacterial properties even after washing several tens or hundreds of times.
In the above-described extrusion melting method, in the examples, the screen was not clogged with coarse particles, and the spinning operation was not hindered.

Non-woven fabric Example II-46, Comparative Example II-16
Each polypropylene fiber obtained in Example II-45 and Comparative Example II-15 was subjected to the antibacterial property test by making a nonwoven fabric with a density of 0.06 g / cm ³ by the paper making web method and the random web method. In the examples, excellent antibacterial effects (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water) were obtained.
On the other hand, the antibacterial property was not expressed at all in the comparative example. The results are shown in Table-15.

Paint Example II-47, Comparative Example II-17
In a facility having a cooling facility, 3 parts by weight of triethylene glycol dimethacrylate, 10 parts by weight of dialkyl phthalate, 0.003 part by weight of hydroquinone with respect to 60 parts by weight of methyl methacrylate and 40 parts by weight of 2-ethylhexyl acrylate Parts, 0.5 parts by weight of paraffin wax having a melting point of 46 ° C., 0.5 parts by weight of paraffin wax having a melting point of 54 ° C., 0.7 parts by weight of N, N-di8hydroxypropyl 9-P toluidine 25 parts by weight of a copolymer of methacrylate and n-butyl methacrylate (Tg = 66 ° C., Mw = 40,000) was gradually added and stirred at 60 ° C. for 2 hours and cooled to 30 ° C.

From this, 1 part by weight of the A2 particles of Example I-2, 7 parts by weight of the colorant Mitsubishi Rayon Toner P-400, 300 parts by weight of the aggregate Mitsubishi Rayon KM17, 2 parts by weight of the polymerization initiator diacyl peroxide The paint was left to stand at 20 ° C. for 1 hour to form a paint film, and an antibacterial test was carried out by the method (c) of (7). The results are shown in Table-16.
In Comparative Example II-17, an antibacterial agent-free additive was applied in the same manner as in Example II-47, and the same measurement was performed. The results are shown in Table-16.
The paints of the examples were confirmed to be excellent in antibacterial properties ((antibacterial activity maintaining characteristics immediately after molding and after contact with tap water)), whereas the comparative examples exhibited no antibacterial properties.

Caulking Material Example II-48 and Comparative Example II-18
1 part by weight of γ-aminopropylbis (methylethylketoxyamino) methoxysilane is mixed with 100 parts by weight of polydimethylsiloxane having a silanol-terminated 25 ° C. viscosity of 50,000 centipoise for 10 minutes, and then 5 parts by weight of methyltris (methylethylketoxyamino) silane was added to the mixture and mixed under vacuum for 15 minutes, 5 parts by weight of fumed silica having a BET specific surface area of 200 m ² / g, 0.1 part by weight of dibutyltin laurate, antibacterial agent A2 1 part by weight of particles was added and mixed under vacuum for 10 minutes.
The mixed composition was dropped on a polyethylene sheet to a thickness of 2 mm to obtain a test piece for antibacterial test. This was applied by the antibacterial test method (7) (e) and an antibacterial test was conducted. The results are shown in Table-17. In the comparative example, the same measurement was performed using a caulking material with no antibacterial agent added. The results are shown in Table-17.
It was confirmed that the caulking materials of the examples were excellent in antibacterial properties (antibacterial activity maintaining characteristics immediately after molding and after contact with tap water). On the other hand, the antibacterial property was not expressed at all in the comparative example.

It should be noted that each of the molded products, films, etc. of Examples II-1 to II-48, which were once baked at 900 ° C., was dissolved in sulfuric acid and nitric acid to form a solution, and then included in the molded products, films, etc. of each Example. Heavy metals were measured by atomic absorption method, ICP-AE method (Inductively Coupled Plasma-Atomic Emission Spectroscopy), or fluorescent X-ray method, but each resin molded product, film, fiber, etc. of Examples II-1 to II-48 Pb, Cd, As, and Ba contained in all were 0.1 ppm or less, Fe was 5 ppm or less, and Mn, Cu, Cr, and Ni were each 1 ppm or less.
Accordingly, it has been found that the antibacterial resin composition of the present invention and the product formed therefrom are not only high in safety but also excellent in heat deterioration resistance.

Antifungal Example II-49, Comparative Examples II-19 and II-20
The anti-fungal agent particles of the present invention and the comparative example were reduced in the minimum inhibitory concentration in the standard method of the Japanese Society of Chemotherapy (2003 revised version), which was different only in that the medium was changed from the sensitive MHB medium to Nissui Pharmaceutical's potato dextrose agar medium. The antifungal performance of each particle was measured and expressed as ppm as the minimum inhibitory concentration.
It shows that anti-mold performance is so high that this figure is small.
The measurement results are shown in Table-18 below.
Free mold: * 1: Caldosporium Caldosporides NBRC 6348 (black mold),
* 2: Colletotricum coccodes NBRC 5256 (eggplant black spot root rot pathogen),
* 3: Ustilaginodia virens NBRC 9175 (rice koji pathogen) was used.

It was found that the antifungal agent of the present invention exhibits a far superior antifungal performance than the antifungal agent of the comparative example.

Cosmetic Example II-50, Comparative Example II-21
A water-in-oil cream emulsified cosmetic using the ingredients shown in Table 19 below and the comparative examples was prepared. In the table, 1 to 5 are oily materials, 6 and 7 are a mixture of a surfactant and 10 antibacterial agent, and A is a mixture of the substance 8 purified water in the table and a mixture of 9 humectants. After each mixture A and B was heated to 70 ° C., the mixture B was poured into the mixture A with stirring, emulsified, and then cooled.
The antibacterial test was performed after 30 days of emulsification. This was carried out according to (c) of (7) above using E. coli NBRC 3972. Further, 1 g of the creams of Examples and Comparative Examples were applied to the armpits of people who had a bad odor on the side, and 10 people smelled whether or not there was a bad odor after 8 hours.
The measurement results are shown in Table 19 below.

As a result of the experiment, it was found that the examples were excellent in antibacterial properties and highly effective in suppressing malodor.
Further, in the present invention, there was no rough feeling as a feel when the cosmetic was applied to the face, but the disc-like particles (A1 particles) were very smooth.
On the other hand, in the comparative example, the only difference was that the antibacterial agent of the example was replaced with R1 particles, or no antibacterial agent was added at all, but there was no antibacterial property and no odor prevention effect. found.

Antibacterial deodorant spray Example II-51, Comparative Examples II-21 and II-22
Place 2.3 parts by weight of dipropylene glycol in a container heated to 70 ° C., and further add 2.5 parts by weight of lauric acid, 1 part by weight of myristic acid, and further 3.2 parts by weight of triethanolamine. In addition, a solution was made.
Next, this solution was gradually poured into 90 parts by weight of ion-exchanged water heated to 70 ° C. to emulsify it to prepare a foam base solution, which was cooled to 25 ° C.
1 part by weight of the antibacterial agent particles of the present invention was added to the foam base solution and stirred and mixed to prepare an antibacterial deodorant foam aerosol composition.
180 g of this composition and 20 g of propellant (LPG 0.34 MPa) were filled in a tin can spray-type container to prepare an antibacterial deodorant foam aerosol spray.
On the other hand, sweat was collected so that a 15 cm × 15 cm cotton handkerchief would be 0.5 g and 5 g heavier after a person with a bad odor on the side regularly exercised. 1 g each of the antibacterial deodorant foam aerosol spray was sprayed on the front and back of the handkerchief and allowed to stand in a thermostatic bath at 30 ° C. for 10 days. The measurement results are shown in Table-20 below.

  It has been found that the antibacterial agent of the present invention exhibits a malodor prevention performance far superior to that of the comparative example.

Antibacterial paper Example II-52, Comparative Examples II-23 and II-24
82% bleached chemi pulp, 1% antibacterial agent of the present invention, 5% starch (dry paper strength enhancer), 5% urea-formaldehyde resin (wet paper strength enhancer), 2% titanium dioxide (inorganic filler) Then, 5% of an ink (adhesive binder) containing a polyamide-based resin as a main component was mixed, and paper having a thickness of 0.1 mm was made using a paper machine. This paper was cut into 5 cm × 5 cm, and the same test as (a) of the antibacterial test method (7) was performed. The measurement results are shown in Table-21 below.

  It was found that the antibacterial agent of the present invention exhibits far superior antibacterial performance than that of the comparative example.

Agricultural chemical (anti-fungal agent)
Example II-53, Comparative Examples II-25 and II-26
In Examples, 10 parts by weight of the particles of the present invention, 30 parts by weight of silane coupling agent surface modified light calcium carbonate (inorganic fine powder), 5 parts by weight of polyoxyethylene alkyl allyl ether (surfactant), ethylene glycol (surfactant) Agent) 10 parts by weight, xanthan gum (emulsification stabilizer) 0.2 parts by weight and water 44.8 parts by weight are mixed uniformly with a homomixer, and then uniformly wet-ground with a ball mill to obtain an aqueous suspended agricultural chemical composition. Yeah. This was diluted 1/100 with water and placed in a commercially available plastic spray device.
The comparative example was different from the examples in that the particles of the examples were replaced with the following particles or Bordeaux soot powder, and the other experimental methods were the same as in the examples.

On the other hand, eggplant and rice grown to about 20 cm each were prepared.
Eggplants are sprayed on leaves, stems and roots with 1 g of Colletotricum coccodes NBRC 5256 (Nasca black rot fungus) suspension prepared to 1 × 10 ⁶ cells / ml, and diluted 1/100 the day after that 1 g of the aqueous suspension pesticide composition thus obtained was sprayed in the same manner, and the degree of occurrence of eggplant sunspot rot was observed 30 days later. However, the eggplant test was carried out by placing the soil in a pot with a diameter of 33 cm and a depth of 30 cm so that the soil had a height of 27 cm.
The rice is sprayed on leaves, stems, and roots at 1 g of a suspension of Ustilaginoidia virens NBRC 9175 (rice koji pathogen) prepared to 1 × 10 ⁶ cells / ml. Further, 1 g of the aqueous suspension pesticide composition was sprayed in the same manner, and the degree of occurrence of rice koji was observed 30 days later. However, the rice test was carried out under the condition that the soil was barely cut from the surface by placing the soil in a pot with a diameter of 33 cm and a depth of 30 cm so that the soil had a height of 27 cm, but there was sufficient water in the soil. The measurement results are shown in Table-22 below.

  It has been found that the agrochemical composition of the present invention exhibits far superior agrochemical performance than the comparative agrochemical composition.

It is a SEM photograph of the spherical particle (particle name: A1) in Example I-1. It is a SEM photograph of the spherical particle (particle name: A20) in Example I-20. It is a SEM photograph of the spherical particle (particle name: A21) in Example I-21. It is a SEM photograph of the spherical particle (particle name: A22) in Example I-22. It is a SEM photograph of the spherical particle (particle name: A30) in Example I-30. It is a SEM photograph of the spherical particle (particle name: A31) in Example I-31. It is a SEM photograph of the disk shaped particle | grains (particle name: B1-1) in Example I-32. It is a SEM photograph of a pair of particles (particle name: C1) in Example I-35. It is a SEM photograph of the rice granular particle (particle name: D1) in Example I-38. It is a SEM photograph of the rectangular parallelepiped particle (particle name: E1) in Example I-41. It is a SEM photograph of the hexagonal plate-like particle (particle name: F1) in Example I-45. It is a SEM photograph of the octahedral particle | grains (particle name: G1) in Example I-46. It is a SEM photograph of the cylindrical particle (particle name: H1) in Example I-47. It is a SEM photograph of the aggregated particle (particle name: V1) in Comparative Example I-1.

Claims (29)

An antibacterial agent comprising silver and organic acid anion-containing aluminum sulfate hydroxide particles represented by the following formula (1).

_{(Ag a B b-a)} b Al c A x (SO 4) y (OH) z · pH 2 O (1)

In the formula (1), a, b, c, x, y, z and p are 0.00001 ≦ a <0.5, 0.7 ≦ b ≦ 1.35, 2.7 <c <3.3, 0.001 ≦ x ≦ 0.5, 1.7 <y <2.5, 4 <z <7, 0 ≦ p ≦ 5, B is a group of Na ⁺ , NH ₄ ⁺ , K ⁺ and H ₃ O ⁺ 1 represents at least one monovalent cation selected from the formula (1b + 3c) <12 in the range of cation valence × mol number (1b + 3c), and A represents an organic acid anion. The antibacterial agent according to claim 1, wherein the organic acid anion A according to claim 1 is at least one selected from the group of anions based on organic carboxylic acids or organic oxycarboxylic acids. The organic acid anion A according to claim 1 is at least one selected from the group consisting of anions based on organic carboxylic acids or organic oxycarboxylic acids having 1 to 15 carbon atoms. Agent. The antibacterial agent according to claim 1, wherein B in the formula (1) is at least one monovalent cation selected from the group of Na ⁺ , H ₃ O ⁺ , and NH ₄ ⁺ . Consists in the formula (1) 1/2 or less of the aluminum c moles as calculated in the total number of moles of the c moles of Al ^{Zn 2+} and / or ^{Ti 4+} at medium Al _c was replaced by ^{Zn 2+} and / or ^{Ti 4+} The antibacterial agent according to claim 1. Equation (1) in the _{(SO 4) SO} ⁴ part of ² of ^{_{y, PO 4 3-, CO 3}} 2-, NO 3 -, at least selected from _SiO ^{4 4-and} _BO ^{3 3-} group The antibacterial agent according to claim 1, wherein the antibacterial agent is replaced with one other inorganic acid ion. The antibacterial agent according to claim 1, wherein the particles have the following particle properties (i) and (ii).
(I) An average secondary particle diameter measured by a laser diffraction scattering method is 0.1 μm to 12 μm,
(Ii) BET method specific surface area of 0.1 to 250 m ² / g. The _{particles, (iii) Dr = D 75} / D 25 (D 25 represents a particle size of 25% value of the volume-based cumulative particle size distribution curve by a laser diffraction scattering _{method, D 75} particle size of 75% of values The antibacterial agent according to claim 1, wherein the sharpness of the particle size distribution defined by (1) is in the range of 1.0≤Dr≤1.8. The particles observed in SEM photographs are spherical, disc-shaped (meteorite-like), pair-like (hamburger-like), rice-grained, rectangular parallelepiped, hexagonal plate-like, cylindrical (sake barrel-like), octahedral The antibacterial agent according to claim 1, which is either one. The antibacterial agent according to claim 1, wherein the particles have an average secondary particle diameter of 0.1 to 5 µm measured by a laser diffraction scattering method. The antibacterial agent according to claim 1, wherein the particles have a BET specific surface area of 1 to 100 m ² / g. In the formula (1), a, b, c, x, y, z and p are 0.001 ≦ a <0.3, 0.9 ≦ b ≦ 1.2, 2.7 <c <3.3, 0.001 ≦ x ≦ 0.2,1.7 satisfied <y <2.3,5 <z <7,0 ≦ p <3, B is ^{_{Na +, NH 4 +, H}} 3 O + group 2. The antibacterial agent according to claim 1, wherein the antibacterial agent represents at least one kind of monovalent cation selected from 1 and a range of valence of cation × number of moles (1b + 3c) satisfies 9 <(1b + 3c) <11. 2. In formula (1), A represents an organic acid anion which is at least one selected from the group consisting of oxalate ion, citrate ion, malate ion, tartrate ion, glycerate ion, gallate ion and lactate ion. Antibacterial agent. The surface of the antibacterial agent according to claim 1 is selected from the group consisting of higher fatty acids, silane coupling agents, titanate coupling agents, aluminate coupling agents, alcohol phosphate esters, surfactants and the like. The antibacterial agent according to claim 1, wherein the antibacterial agent is surface-treated with at least one kind. An organic acid anion-containing aluminum sulfate by adding an alkali aqueous solution composed of a monovalent cation and an organic acid to a mixed aqueous solution of aluminum sulfate and a monovalent cation sulfate and / or nitrate, followed by a heating reaction. 2. The silver according to claim 1, wherein after the salt hydroxide particles are formed, the obtained particles and an aqueous solution containing silver are contact-stirred to ion-exchange a part of the cations of the particles with silver. A method for producing an organic acid anion-containing aluminum sulfate hydroxide particle antibacterial agent. The antibacterial agent of Claim 1 is mix | blended 0.001-300 weight part with respect to 100 weight part of resin, The resin composition which has antimicrobial property. An antibacterial resin composition characterized in that the antibacterial agent according to claim 1 is blended in an amount of 0.001 to 2 parts by weight with respect to 100 parts by weight of the resin and is excellent in transparency. An antibacterial resin molded product formed from the resin composition according to claim 16. An antibacterial film formed from the resin composition according to claim 16. An antibacterial fiber formed from the resin composition according to claim 16. An antibacterial nonwoven fabric formed from the resin composition according to claim 16. The antibacterial coating material formed from the resin composition of Claim 16. The antibacterial caulking material formed from the resin composition of Claim 16. The antibacterial resin product according to any one of claims 16 to 23, wherein the whiteness is improved by adding 0.000001 to 0.1 part by weight of a fluorescent whitening agent to 100 parts by weight of the resin. An antifungal agent comprising the antibacterial agent according to claim 1. A cosmetic comprising the antibacterial agent according to claim 1. An antibacterial paper containing the antibacterial agent according to claim 1. An antibacterial deodorant spray comprising the antibacterial agent according to claim 1. An agrochemical comprising the antibacterial agent according to claim 1.