JPH0468068A - Antibacterial and mildewproofing wax composition and its manufacture - Google Patents

Abstract

PURPOSE:To obtain the title composition which has high safety for living body and maintains antibacterial and mildewproofing properties over a long period of time by incorporating solid particles of bactericidal zeolite carrying metallic ions having a specified bactericidal activity. CONSTITUTION:Any one of a water-base wax, an oil-base wax, an emulsifiable wax, a fruit wax, and a resin wax is mixed with solid particles of bactericidal zeolite which comprise solid zeolite particles having a specific surface of at least 150m<2>/g and a molar ratio of SiO2 to Al2O3 of at most 14 and carrying bactericidal silver ions and, if desired metallic ions selected from copper ions and zinc ions in an amount of at most about 90% of the ion exchange capacity of the zeolite particles and which are substantially free from impurities such as a bactericidal substituted metal hydroxide on the surface thereof at the weight ratio of the solid particles to the wax of (0.01 to 30):(99.99 to 70). The obtained composition exhibits characteristics inherent in wax, has excellent bactericidal and mildewproofing properties, and maintains the effect over a long period of time.

Description

Detailed Description of the Invention "Industrial Field of Application" The present invention is directed to the use of silver ions having a bactericidal effect and, if desired, metal ions selected from the group of bactericidal metal ions consisting of copper ions and zinc ions. The object of the present invention is to provide an antibacterial and antifungal wax composition containing germicidal zeolite solid particles supporting the same, and a method for producing the same.

[Prior art] Vegetable, mineral or animal wax (natural wax; synthetic wax), natural resin such as pine resin, synthetic resin such as polyethylene, polyvinyl acetate, polyvinyl chloride, polystyrene resin, acrylic resin. As a base material, solvents such as mineral spirit, mineral turpentine, solvent naphtha, and terpene oil, emulsifiers and water solvents such as 5pan, Tween-based activators, triethanolamine soap, and phorpholine soap are added. Various wax products are currently manufactured by adding surfactants, dyes, fragrances, plasticizers, antistatic agents, etc., depending on the case. These wax products can be used as polishes for floor polishes (floor polish or floor wax), automotive polishes (car wax), furniture and furnishing polishes, chemical creams, and citrus fruits. It is used as a polishing agent, so-called fruit wax, as a film-forming agent for the epidermis.

In recent years, protecting the living environment from pollution and keeping it clean has become an urgent social issue. In view of this situation, the demand for antibacterial and antifungal properties of various wax products is gradually increasing. However, a satisfactory technical method for imparting desirable antibacterial and antifungal functions to wax products using inorganic antibacterial agents that are highly safe for living organisms, that is, have low toxicity, has not yet emerged. In the current situation.

[Problems to be Solved by the Invention] The present invention proposes a novel antibacterial and antifungal wax composition. The present invention provides a means for adding and mixing the specified bactericidal zeolite solid particles to various waxes to make them antibacterial and antifungal and maintain their effects over a long period of time without reducing the physical properties of the latter. provide.

[Means for Solving the Problems] As a result of intensive research by the present inventors on making wax products antibacterial and antifungal using organic and inorganic antibacterial agents,
The latter is safer than the former antibacterial agent, has good dispersibility in wax products, has less evaporation loss, and products containing the latter have excellent antibacterial activity against bacteria and fungi. - It was discovered that the antifungal effect lasts for a long time.

Among the latter inorganic antibacterial agents, there are so-called bactericidal zeolite solid particles in which a specified amount of ion-exchangeable metals in zeolite are replaced with bactericidal metal ions of silver, copper, and zinc. Products that do not contain impure components that are side reaction products of metals are structurally stable, and when mixed uniformly with various waxes to prepare wax compositions, their antibacterial and antifungal properties The present inventors have completed the invention after confirming that the effects are extremely excellent and that the above effects are exhibited over a long period of time.

The details of the invention are described below.

The present invention provides zeolite solid particles with a specific surface area of 150 rf/g or more and a S 10 /A R203 molar ratio of 14 or less, in which about 90% or less of the ion exchange capacity has bactericidal silver ions and, if desired, bactericidal silver ions. and metal ions selected from the group consisting of copper ions and zinc ions, and substantially no impurity components such as hydroxides of sterilizing substitutional metals are present on the surface of the sterilizing solid particles. This is an antibacterial and antifungal wax composition containing bactericidal zeolite solid particles.

The present invention also provides a method for producing a novel antibacterial and antifungal wax composition containing the above-mentioned bactericidal zeolite solid particles, which is constructed as follows. About 90% or less of the ion exchange capacity of the zeolite solid particles with a specific surface area of 150 rrl'/g or more and a SiO2/AΩ203 molar ratio of 14 or less contains bactericidal silver ions and, if desired, copper ions and zinc. Germicidal zeolite solid particles supported by metal ions selected from the group consisting of ions, and substantially free of impurity components such as hydroxides of sterilizing substituted metals on the surface of the sterilizing solid particles. 0.01 to 30 parts by weight of the zeolite solid particles to aqueous wax, oil wax,
Emulsifying wax, fruit wax, or resin wax, an antibacterial and antifungal water-based wax, oil-based wax, emulsification characterized by adding and mixing with any of the above waxes in a proportion of 99.99 to 70 parts by weight. It consists of a process for producing sex wax, fruit wax, or resin wax.

The bactericidal zeolite solid particles (zeolite solid particles supporting bactericidal metal ions) used in the preparation of the antibacterial/antifungal wax composition of the present invention are natural or synthetic zeolites (crystalline ) in which some or most of the ion-exchangeable metals are bactericidal metal ions selected from the group consisting of silver ions (essential metal ions) and, if desired, copper ions and zinc ions. This term refers to a zeolite in which the above-mentioned sterilizing metal is stably supported by ionic bonds on the zeolite matrix through ion exchange with ions.

In preparing the bactericidal zeolite solid particles used in the present invention, suitable bactericidal metal ions include the three types of metal ions, silver, copper, and zinc, as described above, and among these, silver ion is an essential metal ion. Used as an ion. The reason for using silver as an essential metal in the composition of the bactericidal zeolite solid particles and using copper or zinc in combination is not only to improve the bactericidal and antifungal effect, but also to improve the bactericidal zeolite particles containing silver by coexisting such divalent metals. This is to improve the heat resistance and weather (light) resistance of the material.

The zeolite used as the material of the present invention will be explained. Zeolite is generally a crystalline aluminosilicate with a three-dimensionally developed shunt structure, and its formula is based on Ag2O3, xM20・Ag2
It is expressed as O3・ysi02ZH20. The above M represents an ion-exchangeable metal ion, which is usually 1 to 2
It is a valence metal ion and also includes NH4+. Further, n corresponds to this valence. On the other hand, X and y represent the coefficients of metal oxide and silica, respectively, and 2 represents the number of crystallized water. There are many types of zeolites with different physical properties such as chemical composition, crystal structure, pore size, and specific surface area. However, the specific surface area of the zeolite solid particles used in the present invention (
SSA) is 150 rrr/g (based on anhydrous zeolite)
Above, SiO2/A of the zeolite constituents
The II 203 molar ratio should be 14 or less, preferably 11 or less.

Salt aqueous solutions containing silver, copper, or zinc metal ions that have bactericidal properties easily undergo ion exchange with the zeolite specified in the present invention, so the above-mentioned salts may be used alone or in combination with bactericidal metal ions. Perform ion exchange to support the required amount of sterilizing metal on the zeolite matrix,
Germicidal zeolite solid particles carrying only silver, copper or zinc, or composites of sterilizing metals, e.g. Ag-C
u.

It is possible to prepare so-called composite zeolite sterilizing particles such as Ag-Zn. However, the zeolite particles carrying bactericidal metal ions have a specific surface area of 150rrl'/g or more and a SiO/A
Two conditions must be met: the N203 molar ratio is 14 or less. It has been found that if this is not the case, a wax composition which is the object of achieving an effective bactericidal action cannot be obtained. This is thought to be mainly due to the lack of an absolute amount of bactericidal metal ions fixed in the zeolite in a state where they can exert their effects. In other words, this is thought to be due to the physicochemical properties of zeolite, such as its exchange capacity, exchange rate, and accessibility.

Therefore, S i , known as molecular sieve
Zeolites with an O/A 1203 molar ratio greater than the above-mentioned specific value are unsuitable as materials for the present invention. On the other hand, in zeolites with a SiO2/Aρ203 molar ratio of 14 or less, it is easily possible to uniformly and stably retain one or more metal ions having a bactericidal effect, and for this purpose, such zeolites can be used. It was found that sufficient antibacterial, sterilizing, and antifungal effects could be obtained for the first time. In addition, S i O/A11)20
The acid resistance and alkali resistance of zeolites with a high silica ratio exceeding 14 (3 molar ratio exceeding 14) increase as the SiO2 content increases, but on the other hand, the synthesis thereof takes a long time, and the ion exchange capacity of such zeolites is small. In addition, since it takes a long time for the pore diffusion of sterilizing metal ions within the matrix,
From this point of view, it is not advisable to use zeolite with a high silica ratio in the present invention. The aforementioned S i O/
A natural or synthetic zeolite with a molar ratio of A N 203 ≦14 is suitable as a material for preparing the bactericidal zeolite solid particles used in the present invention, which is stable in terms of physical properties and can be antibacterial and used in the wax field. There is no problem when adding it to the water, and it is economically advantageous because it is inexpensive. Based on the above-mentioned reasons, the specific surface area of the zeolite used in the present invention is limited to 150 ryf/g or more, and the SiO/Aρ203 molar ratio is limited to 14 or less.

As the zeolite material used in the present invention with a specific surface area of 150 rrI''/g or more and a SiO/Aβ203 molar ratio of 14 or less, any natural or synthetic zeolite can be used.For example, as a natural zeolite is analcin (AnaleiIllc; SiO/Al
2O3 = 3, 6-5, 6), chabasite (Ch
abazitc; S i O/AN 203=3.2
~6.0 and 6.4~7.6), clinoptilolite (
CIinoptllolfte;SiO/Aρ20
s = 8.5-10.5), erionite (Eri
onite; S i 02 /A, Q 203=5.
8-7.4), Faujasite
; S i 02 /Al2O3=4.2-4.6),
Mordenite (SiO/Al2O
3-8.34~10.0), Phylampsite (Ph
iljpsite; S i O2/A (1203=2
．． 6 to 6.4), etc. These typical natural zeolites are suitable as materials for the present invention.

On the other hand, a typical example of synthetic zeolide is A-type zeolite (
SiO2/Ag203=1.4-2.4), X-type zeolite (S i O2/Ag203=2-3), Y-type zeolite (SiO2/Ag203=3-6), mordenite (S t 02 / Ag2O3-9 -10), and these synthetic zeolites are also suitable as the zeolite mill used in the present invention. Among these exemplified zeolites, particularly preferred are synthetic A-type zeolite, X-type zeolite, Y-type zeolite, and synthetic or natural mordenite. When preparing the bactericidal zeolite used in the present invention, the above-mentioned preferred zeolites can be used alone or in the form of a mixture as a raw material.

In addition, the zeolite limited as described above has a large exchange capacity and has the advantage of being able to hold a large amount of individual silver, copper or zinc ions having bactericidal properties as well as the above-mentioned complex metal ions. It is characterized by a rapid ion exchange reaction between sterilizing metal ions and sterilizing metal ions. Furthermore, by using such zeolite, it is possible to adjust the amount of silver, silver-copper, or silver-zinc supported on the zeolite solid particles depending on the purpose of use of the bactericidal zeolite solid particles used in the present invention in the wax field. This has the advantage that it can be easily carried out by adjusting the ion exchange conditions.

Although the particle size and shape of the zeolite material, which are limited as described above, are not particularly limited in this application,
In consideration of the ion exchange reaction for preparing the bactericidal zeolite, which will be described later, a powder to particulate zeolite material is preferable.

Next, a method for preparing the bactericidal zeolite solid particles used in this application will be explained. In the present invention, 150rrl
'/g or more specific surface area and 14 or less SiO/Al2
Using a zeolite with an O3 molar ratio, up to about 90% of its ion exchange capacity is a metal selected from the group consisting of bactericidal silver ions and optionally copper and zinc ions. It is important to prepare bactericidal zeolite solid particles which are supported by ions and which are substantially free of impurity components such as bactericidal substituted metal hydroxides on the surface of the bactericidal zeolite solid particles. .

Sterilizing solid theolite? +'j, When preparing silver zeolite, silver-copper zeolide, silver-copper-zinc, etc. using an ion exchange reaction, in addition to the usual ion exchange reaction, hydration of sterilizing metal ions in the zeolite solid phase is necessary. In order to prevent side reactions such as decomposition from occurring and the surface of the sterilizing zeolite solid particles being contaminated by precipitation of side reaction products such as oxides, hydroxides and basic salts of sterilizing metals, It is important to coordinate the reaction conditions.

For example, when ion exchange is performed under conditions that increase the ion exchange rate of silver when preparing bactericidal silver zeolite solid particles, side reactions occur in addition to the ion exchange reactions that normally produce silver zeolite, resulting in silver oxide, silver A phenomenon is observed in which side reaction products such as hydroxides and silver base salts coat the surface of the produced white silver zeolite particles, and the above-mentioned impurity components precipitate inside the solid phase of the silver zeolite. For this,
Silver zeolite particles, which should be white in nature, are contaminated by side reaction products and change color due to the formation of silver clusters, becoming gray, yellow, orange, and sometimes red.

Such a phenomenon is caused by the presence of antibacterial zeolite solid particles, such as Na
During the preparation of AgZ (Z=Affi zeolite/?) body, it is clearly observed that the exchange rate of silver is around 57%.

Furthermore, in order to increase the silver exchange rate to 90% or more, it is necessary to increase the concentration of silver-containing salts present in the aqueous solution phase during ion exchange. As the salt concentration of the aqueous solution phase increases, the degree of contamination of the antibacterial silver zeolite solid particles by side reaction products accompanying ion exchange tends to increase rapidly. Antibacterial silver zeolite solid particles are originally white as described above, but when the above phenomenon occurs, they change color and change their physical properties as described above. When the antibacterial zeolite solid particles are contaminated by the precipitation of impure components, the antibacterial to bactericidal ability of the antibacterial silver zeolite against bacteria and fungi decreases in proportion to the amount of contamination. Antimicrobial zeolite solid particles containing other germicidal metals in addition to silver content, such as NaCu
Z.

When preparing NaCuY (Y=Y-type zeolite matrix), etc., if the ion exchange conditions are not appropriate, a phenomenon similar to that of silver zeolite described above can be observed, and impurity components may precipitate on the surface of the antibacterial zeolite due to side reactions. Can be seen.

The bactericidal zeolite solid particles used in the present invention by being added to and mixed with waxes exhibit antibacterial and bactericidal properties that are desirable for waxes, and are free from impurities as mentioned above so as not to adversely affect their physical properties. It is desirable to use a material that contains as little precipitates as possible. For this purpose, in the present invention, as stated above, 150 ri"/g
: Specific surface area of 1- and SiO/Aρ203 of 14 or less
using a zeolite having a molar ratio of up to about 90% of its ion exchange capacity supported by bactericidal silver ions and, if desired, metal ions selected from the group consisting of copper ions and zinc ions; and the bactericidal zeolite solid particles (e.g. NaAgZnZ; NaA
gZnY; NaAgCuX; NaAgCuY, however, the above Na may be other non-antibacterial metals (monovalent to divalent metals, NH
(including 4+), the - portion or all may be substituted. Y and X represent the matrix of Y-type zeolite and It is desired to prepare a wax composition having antibacterial and antifungal properties by adding it to a variety of substances.

The replacement of the zeolite solid particles with the ion-exchangeable metal by the sterilizing metal should, as already mentioned, be less than the ion-exchange capacity of the zeolite, especially less than about 90% of it.

By taking such measures, precipitation of impurity components can be suppressed. Bacterial zeolite solid particles whose ion exchange capacity exceeds the saturation value and are physically adsorbed have a significantly high degree of surface contamination, and the bactericidal effect and durability thereof are insufficient. For example, a marine paint containing 20 to 30% by weight of zeolite saturated with copper, zinc, silver, etc. is known (France Patent No. 1061158). However, although this paint is suitable for exterminating shellfish and algae, it was found that its bactericidal properties were not satisfactory.

In other words, as is clear from the above explanation, the zeolite saturated with the metals mentioned above is contaminated with impurity components that are deposited on the surface of the antibacterial zeolite due to many side reactions, and as a result, its bactericidal performance is impaired. It was found that there is a tendency for the antibacterial properties to decrease compared to the original antibacterial zeolite.

Next, the case where the ceolite grains (non-antibacterial) defined in the present invention are converted into bactericidal zeolite particles will be explained by giving an example.

Normally sterilizing silver theorai!・When preparing solid particles,
A solution of a water-soluble salt such as silver nitrate is used for ion exchange, but in this case, the salt concentration should not be excessively high, and the pH of the water 78 liquid phase should be 7 or less, preferably 3.5 to 6.8. It is desirable to make adjustments accordingly.

For example, when converting ion-exchangeable metals such as sodium ions in A-type zeolite, When the silver ion concentration is high, for example, 1-2M AgNO3, silver ions replace sodium ions in the zeolite solid phase, and at the same time, silver oxides, hydroxides, and bases are formed in the zeolite solid phase due to side reactions. There is a tendency for salts to precipitate. Due to this phenomenon, the porosity and specific surface area of the bactericidal zeolite decrease in proportion to the amount of precipitation compared to the original zeolite. Furthermore, even if the specific surface area does not decrease significantly, the bactericidal and antibacterial activity tends to decrease due to the precipitation of impurity components as described above on the silver zeolite solid phase. In order to prevent the precipitation of such silver compounds into the silver zeolite phase, the concentration of the silver solution should be maintained in a more dilute state, for example, below 0.3M AgNO3, and at the same time, the pH of the aqueous solution phase during ion exchange should be adjusted as described above. It is desirable to adjust it to 7 or less, preferably in the range of 3.5 to 6.8. The safest concentration of AgNO3 is 0.1M or less. It has been found that when using an AgNO3 solution with such a concentration, the specific surface area of the germicidal zeolite solid particles obtained is almost the same as that of the original material zeolite, and that its antibacterial and bactericidal properties are also exhibited in a favorable manner. .

Next, during the preparation of germicidal steel zeolite solid particles, side reactions similar to those seen in the preparation of silver zeolite solid particles by ion exchange are induced, resulting in the problem of contamination of copper zeolite particles. For example, when converting an ion-exchangeable metal such as sodium ion in A-type zeolite, X-type zeolite, Y-type zeolite, or mordenite with copper ion to convert it into copper zeolite, I M Cu S
When using O4 solution, Cu2+ is N in the zeolite solid phase.
However, at the same time, a basic precipitate such as Cu3 (SO4) (OH)4 is precipitated in the solid phase due to a side reaction, so the porosity of the produced copper zeolite decreases. The specific surface area also tends to decrease. When such precipitates are observed, the inherent antibacterial activity of the antibacterial steel zeolite particles decreases in proportion to the amount of precipitates. In order to prevent the precipitation of impurity components such as ``2 series'', the water-soluble copper salt solution used should be kept in a diluted state, for example, 0.1M or less,
It is more preferable to carry out the ion exchange reaction by maintaining the pH at 0.05M or less and by keeping the pH of the aqueous solution phase slightly acidic (p11≦5). By employing such a method, the specific surface area of the germicidal steel ceolite particles obtained is approximately equal to that of the raw zeolite, and active particles having a favorable germicidal effect can be obtained.

When preparing bactericidal zinc zeolite by exchanging ion-exchangeable metals such as sodium ions in A-type zeolite, X-type zeolite, Y-type zeolite or mordenite with zinc ions, when the salts used are around 1 to 3M There is almost no tendency for side reaction products to precipitate as seen in the above-mentioned ion exchange of silver and copper. Generally, the bactericidal zinc zeolite particles used in the present invention are easily prepared with the desired quality by carrying out ion exchange in a slightly acidic region using zinc salts at a concentration near the above-mentioned concentration.

The above-mentioned sterilizing zeolite solid particles can be prepared by using a sterilizing metal-containing solution having the above-mentioned concentration and liquid properties, and carrying out ion exchange between the sterilizing metal-containing solution and the zeolite material in a batch method. Furthermore, in order to increase the sterilizing metal content in the zeolite material, the number of batch treatments may be increased. On the other hand, if the zeolite material is sterilized by ion exchange using the Carlam method using a salt solution containing sterilizing metal ions having the concentration described above, the ion exchange tower is filled with the zeolite material having an appropriate particle size. However, if this is treated at a predetermined flow rate with a pH-adjusted saline solution containing sterilizing metal ions, sterilizing zeolite solid particles can be easily prepared.

As mentioned above, the bactericidal zeolite solid particles in which silver-zinc, silver-copper, etc. are supported on a zeolite matrix specified by ion bonding, used in the present invention, have an ion exchange capacity of about 90% of the ion exchange capacity of the zeolite used. % or less is retained by the sterilizing metal, and the surfaces of the sterilizing solid particles are substantially free of the impurity components described above. The sterilizing particles are made by the ion exchange method as described above.
Silver zeolite, silver zeolite, and zinc zeolite can be prepared individually, and if necessary, predetermined amounts of these germicidal zeolites can be mixed to prepare the desired germicidal zeolite solid particles. Alternatively, if the zeolite specified in this application is ion-exchanged with a bactericidal salt aqueous solution consisting of silver and zinc or a bactericidal salt aqueous solution consisting of silver and copper, homogeneous bactericidal zeolite solid particles containing a composite bactericidal metal can be obtained. Easily prepared.

Preferred zeolite materials used as starting materials in preparing the bactericidal zeolite solid particles used in the present invention are A-type zeolite, Y-type zeolite, and Y-type zeolite as described in Table 1.
type zeolite, type X zeolite and mordenite. The calculated value of the sterilizing metal content (anhydrous basis) when the ion-exchangeable sodium in these Na-type zeolites is saturated with the sterilizing metals used in this application, silver, copper (II), or zinc, is as shown in the table. It is. In addition, the value of the ion exchange capacity of each zeolite is also shown as 0. However, based on the reasons stated above, the total content of sterilizing metals in the sterilizing zeolite solid particles used in the present invention is
It is necessary to maintain the ion exchange capacity of the zeolite at about 90% or less. For example, the total content of sterilizing metals such as silver and zinc contained in the particles of NaAgZnZ and NaAgZnY should be adjusted so that they are supported at about 90% or less of the ion exchange capacity of the above-mentioned A-type zeolite and Y-type zeolite, respectively. is necessary. In addition, the ion-exchangeable metal (Na) in the bactericidal zeolite solid particles is other than other mono- to divalent non-antibacterial metals [alkali metals, alkaline earth metals ('N
(including H4+), and others] may be used. Next, when the sterilizing zeolite solid particles used in the present invention are comprised of a mixture of the preferred zeolites mentioned above, the sterilizing metal content contained therein is about 90% of the total white exchange capacity of the mixed zeolite. % or less.

The amount of silver occupied in the bactericidal zeolite solid particles used in the preparation of antibacterial and antifungal wax compositions is usually sufficient at 30% by weight or less, and the more preferable range is from 0.1 to 30% by weight. It is 25% by weight. -Blade steel (II)
The content of zinc in the bactericidal zeolite particles is usually 20% by weight or less, more preferably 0.1 to 1% by weight.
It is 7% by weight.

The content of the sterilizing metal in the sterilizing zeolite solid particles containing a composite sterilizing metal such as Ag-Zn or Ag-Cu is 0.1 to 0.1 when added to a normal wax composition.
It is sufficient if it is within the range of 25% by weight.

Next, the shape and particle size of the sterilizing zeolite solid particles used in the present invention are not particularly limited in the present invention, but powder to particulate ones are preferable. In order to uniformly disperse the wax, depending on the shape of the wax, fine powder, for example, fine powder of 15 μm or less, more preferably 3 μm or less, may be used.
Antibacterial and antifungal wax compositions are sometimes prepared using micron-sized fine powder. Furthermore, the particles are added to waxes in a hydrous state (containing crystallization water) or in an anhydrous state, depending on the properties of the wax product. Furthermore, an organic or inorganic dispersant may be used in combination in order to increase the degree of dispersion of the bactericidal solid particles into the wax and make it more homogeneous.

The antibacterial and antifungal wax composition of the present application will be explained.

The antibacterial and antifungal wax composition of the present invention has 150 m
”/g or more specific surface area and 14 or less SiO/A, 02
Approximately 90% or less of the ion exchange capacity of the zeolite solid particles having a molar ratio of 0.03 is supported by bactericidal silver ions and, if desired, metal ions selected from the group consisting of copper ions and zinc ions. The present composition contains sterilizing zeolite solid particles which have a sterilizing effect and are substantially free of impurity components such as hydroxides of sterilizing substituted metals on the surface of the sterilizing solid particles. is completely new. The antibacterial and antifungal wax composition of the present invention includes all antibacterial and antifungal waxes such as aqueous waxes, oil waxes, emulsifying waxes, fruit waxes, and resin waxes. For example, bactericidal zeolite is used in emulsifying solid wax (white paste), resin wax (liquid), liquid wax (oil-based liquid, emulsifying liquid, aqueous liquid), solid wax (oil-based solid), etc. seen in the examples below. All wax compositions obtained by incorporating particles are included in the present invention. If the ratio of the bactericidal zeolite solid particles to the total weight of the antibacterial and antifungal wax composition is 0.01 to 30% by weight, sufficient antibacterial and antifungal effects will be exhibited. Addition of bactericidal zeolite solid particles below this lower limit to waxes is unsatisfactory in terms of bactericidal effect, and particularly unsatisfactory in terms of antifungal effect. On the other hand, even if the amount exceeds the upper limit, for example, 40% by weight or more, the bactericidal and antifungal effects are almost unchanged, and the physical properties of the wax composition are affected, degrading its original performance. There is a tendency. The range of the content of the bactericidal solid particles in the antibacterial/antifungal wax composition is 0.01 to 30% by weight as described in I-1, but the more preferable range is 0.05 to 20% by weight. The amount is %. In the present application, as described above, the identified bactericidal solid particles have good dispersibility in waxes, and it is possible to easily prepare a homogeneous antibacterial and antifungal wax composition. When the wax is in liquid form (oil-based liquid, emulsifying liquid, aqueous liquid), it is effective to add a dispersant to make the dispersion of the sterilizing solid particles more homogeneous.

Furthermore, the present invention provides that the zeolite with a specific surface area of 150 rr+'/g'- and a SiO/Al2O3 molar ratio of 14 or less is made of a group consisting of bactericidal silver ions and, if desired, copper ions and zinc ions. Germicidal zeolite solid particles supported by selected metal ions and substantially free of impurity components such as hydroxides of sterilizing substituted metals on the surface of the zeolite solid particles are It is characterized by adding and mixing with any of the above waxes at a ratio of 0.01 to 30 parts by weight of particles to 99.99 to 70 parts by weight of aqueous wax, oil wax, emulsifying wax, fruit wax, or resin fuchs. The present invention provides a method for producing antibacterial and antifungal water-based wax, oil-based wax, emulsifying wax, fruit wax, or resin wax.

Wax products are manufactured using waxes (vegetable wax, mineral wax, animal wax), natural and synthetic resins, solvents such as petroleum or water, surfactants, emulsifiers, etc. as base materials. However, the bactericidal zeolite solid particles used in the present invention have excellent dispersibility in wax products, and are characterized by exhibiting sufficient antibacterial and antifungal effects over a long period of time. For example, if the required amount of the bactericidal zeolite solid particles of the present application is added and mixed with a floor brightener, an automobile brightener, a furniture/furnishing brightener, a fruit brightener, etc., the agent described in -1- can be used. In addition to its original purpose, it can also add antibacterial and antifungal effects. In addition, an appropriate amount of sterilizing zeolite solid particles can be added to oil-based polishes in which wax is dissolved in an organic solvent, aqueous waxes made by emulsifying wax in water, and resin waxes based on emulsions (synthetic resin emulsion-based polishes). For example, antibacterial and antifungal functions can be imparted to these materials.

Rinley's water-based wax "MR" is mainly composed of natural wax, synthetic wax, synthetic resin, surfactant, water, etc., and in addition, for example, 1 to 5% of the bactericidal zeolite solid particles specified in this application are added. It has been confirmed that by incorporating it to form an aqueous wax composition, it is possible to impart antibacterial and antifungal abilities in addition to the original functions. Next, Linley's oil-based wax "BA" is carnauba wax, synthetic wax,
The main ingredients are mineral high melting point wax, mineral turpentine organic solvent, oil-soluble dyes and fragrances.
．． It was found that excellent antibacterial and antifungal effects were exhibited when 2 to 5% bactericidal zeolite solid particles were added and mixed. Linley's emulsifying wax "WA" (white wood wax) is composed of carnauba wax, synthetic wax, high melting point mineral wax, anti-slip agent, synthetic resin, organic solvent, surfactant and water. On the other hand, it was confirmed that preferable antibacterial and antifungal effects can be achieved by adding and mixing 5% or less of bactericidal theolite solid particles and sufficiently dispersing them. Furthermore, Linley PALMO5T
AR (resin wax) is mainly composed of a metal crosslinked synthetic resin emulsion, a high melting point wax emulsion, a leveling agent, a surfactant, a plasticizer, an antistatic agent, and water, and has a viscosity of 4.0±2. Oe, p, (23°C), to which fine powder of bactericidal zeolite solid particles 1
It was found that by uniformly dispersing ~5%, excellent antibacterial and antifungal effects were exhibited, similar to the previous example.

Furthermore, Linle hanging floor wax (E6LO7) is composed of silicone oil, fatty acid salt surfactant, silicate abrasive, aliphatic organic solvent, fragrance and water. The viscosity is 770C,p (25°C), and 0.2
It was confirmed that the content of Koki at ~5% showed excellent antibacterial and antifungal effects.

Next, Linley's fruit wax - FWA is composed of natural wax, natural resin, morpholine fatty acid salt, water and food additive flavoring. By adding 0.01 to 4% of NaAgZnY) and uniformly dispersing it, it has new antibacterial and antifungal functions)-J
- It turned out that it is possible to Fruit wax compositions with such antibacterial and antifungal properties have almost no toxicity and are highly safe, so they are suitable as coating agents for the epidermis of fruits and fruit vegetables.

[Effects of the Invention] The antibacterial and antifungal wax composition containing the bactericidal theolite solid particles of the present invention not only exhibits the inherent properties of wax, but also has excellent sterilization properties against general bacteria. As seen in the examples related to the mold resistance test, it has the characteristic of exhibiting an extremely favorable mold-proofing effect. Furthermore, the use of the composition of the present invention has the advantage that the above-mentioned antibacterial and antifungal effects are maintained for a long period of time.

[Example] Next, reference examples and examples will be described as specific examples of the present invention. The present invention is not limited to this embodiment unless it exceeds the gist thereof.

In order to evaluate the sterilization to antibacterial effect and antifungal effect of the specimens of the examples, an antibacterial power evaluation test using a drop method (dropping method) and a mold resistance test were conducted.

(1) Mold resistance evaluation test The mold resistance test of the specimen was conducted according to JI822911.

(i) Bacterial strain used Aspcrgillus nigcr If-'0-4
407; Pan1c order 1fum funiculosu
m I['0-6345; Chaetomium g
lobO3umIPO-6347; Glioclad
ium virens IFO-6355; Aureo
basidium pulluland IFO-63
53゜(11) Preparation of spore suspension After culturing the above bacterial strain on a potato dextrose agar slant medium until sufficient spores are formed, the spores are sterilized at 0.05%.
The spores were suspended in a dioctyl sodium sulfosuccinate solution to obtain a single spore suspension.

A mixed spore suspension was prepared by mixing equal amounts of each single spore suspension.

(iii) Test operations (a) The JIS method was followed. The sample was placed in a Petri dish, and the mixed spore suspension was sprinkled onto it until the surface was wet.

(b) After culturing the Petri dish at a temperature of 29° C. and a humidity of 85% or higher for 30 days, the state of growth of mycelia formed on the surface of the sample was observed with the naked eye.

The following medium was used for the above culture.

Medium composition: KH2PO4 (0.7g), K2HPO4
<0.7g> , M g S 0 ・7H20(0,
7g), NH4N03 (1,0g), NaC(1(
0,005g), F e S O4'7 N20 (0
,002g), ZnSO4' 7H20 (0,001g
), Mn5o4-7H20 (0,002g), agar (1
5g) and pure water (1000ml) (iv) Evaluation of test results Evaluation of test results was performed in the following five stages.

However, the percentage below indicates the percentage relative to the surface area.

1 Slight bacterial growth (10% or less) 2 Slight bacterial growth (10-30%) 3 Intermediate bacterial growth (3
0-60%) (i) Bacterial strain used: Eschcriehia coli IFO-1273
4; Pscudomonasacruginosa
II'o-12689゜(if) Preparation of bacterial suspension Test bacterial cells cultured on ordinary agar medium at 37°C for 18 hours were grown in phosphate buffer (1/15M, pH=7.2) for 74 hours to yield 108 cells. /ml suspension was prepared and diluted as appropriate for use in the test.

(iii) Test procedure using the drop method 1 ml of the bacterial solution was dropped onto each surface (one side) of a specimen (50 x 50 mm) washed with alcohol cotton and stored at 25°C.

In the measurement, the number of bacteria was determined for the bacterial solution on the subject by a pour plate culture method using a medium for bacterial count measurement.

For the above culture, Mucler l1i for bacteria is used.
nton2 (BBL) medium was used.

Reference Example 1 This example relates to a preparation example of bactericidal theolite solid particles carrying silver as a bactericidal metal.

Sodium type A zeolite (N a Z ; 1.0
3Na 0-Ail O1,94SiO.xH2O;
Dav (average t+'7.end-diameter) = 1.5 um; S
1.0 kg of dry powder of SA (specific surface area) = 671 ryi''/g) was washed with water so that the PTL of the single-liquid solution at the end of washing was 8.7.Next, water was added to the washed NaZ. Prepare a zeolite slurry by adding about 1.5Ω, keep it under stirring, add 0.05N HN
The O3 solution was gradually added dropwise, and the ptl of the slurry liquid was maintained at around 4. 0.05M for the above slurry liquid
The pH of the aqueous phase was finally adjusted to 4.1 after about 4.4 mL of AgNO3 solution was slowly added dropwise under stirring, and then continuous stirring was carried out for 3 h 40 min to dissolve the solution in NaZ. An ion exchange reaction between Na+ and Ag+ was carried out at room temperature. After the reaction is complete, the zeolite solid phase is filtered,
The solid phase was then washed with water until no Ag+ was detected in the furnace liquor, and the washed product was subsequently dried at 100-110°C. The dried product was crushed to finally prepare NaAgZ fine powder.

In this reference example, 0.92 kg of dry NaAgZ powder was used.
was obtained, with Dav=1.6 μm (light transmission method) and Ag=2.98% (based on anhydrous NaAgZ powder). Also S S A = 669 rr? /g. The NaAgZ fine powder obtained in this reference example completely shows the structure of type A zeolite according to X-ray diffraction and electron microscopy tests, and the presence of impurity components such as silver oxide and basic salts in it. No particles were observed, indicating that the material was composed of high quality bactericidal zeolite particles.

Reference Example 2 This example relates to a preparation example of sterilizing zeolite solid particles carrying a composite of silver and zinc as sterilizing metals.

Sodium type Y theolite (N a Y ; 1.1
2Na O-Ag 0 ・4.36SiO-xH2O
;Dav=0.49μn+;SSA=932
rrr/g) 0') Wash 1.0 kg of dry powder with water to remove free alkali contained in NaY,
The pH of each family member was set to 8.8 at the end of washing.

Next, water was added to the water-washed NaY to prepare a zeolite slurry, and the slurry was kept under stirring and a dilute nitric acid solution was gradually added dropwise to maintain the pH of the slurry at 4 or less. After diluting the slurry lfk with water, a mixed sterilizing salt solution of 0.019M AgN was added.
About 8 g of O31,,35M Zn(NOs)2 was added, and then the pl+ of the aqueous phase was finally adjusted to 3.9 (total volume of the aqueous phase was about 9 g). The above mixture was stirred for 4 hours to dissolve some of the Na+ in NaY and Ag.
+ and Zn2+ ion exchange reactions were carried out at room temperature. After the reaction is complete, the zeolite solid phase is filtered and then Ag
The solid phase was washed with water until Zn2+ and Zn2+ were no longer observed in the solution, and the washed product was subsequently dried at 100-110°C. The dried product was crushed to finally prepare NaAgZnY fine powder.

In this reference example, dry NaAgZnY powder 0.8
3 kg was obtained, Dav = 0.51 μm (light transmission method), and the content of sterilizing metal was Ag = 2.12%.
.

Zn = 8.69% (based on anhydrous NaAgZnY). Further, S S A =934rrr/g. The NaAgZnY fine powder obtained in this reference example completely shows a Y-type theolite structure according to X-ray diffraction and electron microscopy tests, and contains impurity silver and zinc oxides,
The presence of hydroxides, basic salts, etc. was not observed, and it was confirmed that the product was composed of Q@ bactericidal zeolite particles.

Example 1 This example relates to a preparation example of a wax composition (emulsifiable solid wax; white paste form) of the present invention having antibacterial and antifungal properties and a mold resistance test of the prepared product.

When preparing the present wax composition, sterilizing zeolite solid particles [NaAgZnY powder prepared in Reference Example-2: Ag = 2.12%; Zn = 11.69%
(Anhydrous NaAgZnY standard): DaV=0.5
A fine powder of Yffi zeolite containing silver and zinc was used.

In this example, solid wax (LW-BL) is used.

LW-2 and LW-3) were prepared by the following method. Natural wax (carnauba wax, montan wax) as a material,
Synthetic wax (ADEKA WAX; Asahi Denka), emulsifier (sorbitan fatty acid ester, polyoxyethylene nonylphenol ether), petroleum solvent (mineral spirit), and bactericidal theolite solid particles (N a A g Z n
Pour a predetermined amount of Y) into a measuring container. The mixture was then heated to one degree above the melting point of the wax and stirred to ensure homogeneity. Next, a predetermined amount of hot water (95°C±5°C) was added while stirring and mixing were continued. After emulsification was completed, a predetermined amount of anti-slip agent (colloidal silica) was added. Cooling was started, and the contents were filled into a predetermined container in a fluidized state to prepare the emulsifiable solid wax of the present invention. Emulsifiable solid wax (LW-BL, LW-
2 and LW-3) were used as test pieces in the shape of 50 x 50 squares (approximately 3 mm thick), and a mold resistance test was conducted using these test pieces.

The composition of the materials in Example-1 is as shown in the table below: Carnauba wax Montan wax Adeca wax Sorbitan fatty acid ester Polyoxyethylene noniphenyl ether Mineral spirit 35 Sterilizing zeolite solid particles * Colloidal silica
There were 5.

10 parts by weight* NaAgZnY (anhydrous basis) was added to the entire material mixture described in 1- above in the following content.

Test piece: LW-BL (for blank test; emulsifiable solid wax without the addition of bactericidal theolite solid particles); LW-2 (Na
AgZnY, emulsifiable solid wax containing 1%); LW-
3 (NaAgZnY, 3% Nail emulsifiable solid wax) Table 2 Mold resistance test (Example 1) Test object Type and amount of antibacterial agent Evaluation value symbol
(JIS method) LW-BL No additives 4 LW-2NaAgZnY, 1% I LW-3NaAgZnY, 3% 0 The mold resistance test results are shown in Table 2. Sample LW- containing 1% bactericidal zeolite solid particles NaAgZnY
The evaluation values of sample LW-3 containing 2 and 3% are 1 and 0, respectively. On the other hand, the evaluation value of the blank test sample LW-BL, which does not contain the bactericidal theolite solid particles mentioned above, was 4.
Therefore, no antifungal ability was observed. From these test results, it is clear that the antibacterial and antifungal solid wax (emulsifiable solid wax) composition of the present invention has an excellent antifungal function.

Example 2 This example shows the Fuchs composition of the present invention (resin wax; Permostar Pro; liquid; suspension) which has antibacterial and antifungal properties.
Examples of preparation and mold resistance testing of the preparations.

When preparing the present wax composition, fine powder of type A theolite containing silver and zinc [NaAgZnZ; Ag = 3.12%;
=5.34% (anhydrous NaAgZ nZ standard); D
av=3.2μm; SSA=617rrr/
g) was used.

In this example, specimens LP-BL, LP-2 and LP-3 impregnated with resin wax (Palmostar Pro) were prepared by the following method. A small amount of water is placed in a container in advance, and while stirring, a predetermined amount of plasticizer (tributoxyethyl phosphate, diethylene glycol monoethyl ether) is added. Next, a pre-emulsion-polymerized acrylic synthetic resin emulsion (Prifle B536;
(Rohm & Haas) was added to L and the contents were stirred. Furthermore, for the contents described in 1., pre-emulsified polyethylene emulsion (HITIC E-4B;
Toho Chemical) was flowed in and stirred. A predetermined amount of the bactericidal theolite solid particles described above was added to the resulting mixture, and stirring was continued for 20 minutes to finally prepare the resin wax of the present invention. -4- The resin wax (suspension) prepared as described above was impregnated and coated on a 50 x 50 mm sheet of paper, and a mold resistance test was conducted using this.

The composition of element H in Example-2 was as follows.

Water 47 parts by weight Tributoxyethyl phosphate 2 Diethylene glycol monoethyl ether 4 Brimal B-33640 Hytic E-487 * The content of NaAgZnZ in the entire material mixture was adjusted to 1% and 3%.

LP-BL: Blank test sample with no antibacterial agent added, L
Prepared by impregnating it in the resin wax composition described below.

LP-2: A test piece obtained by impregnating the above resin wax composition containing 1% of NaAgZnZ as anhydride.

LP-3: NaAgZnZ as anhydride, 3% H content
A test piece obtained by impregnating the above resin wax composition.

Table 3 Mold resistance test (Example test) Resin impregnated into test piece
Note 9 “7” Composition” (JIS method) Type and amount of antibacterial agent added LP-BL No antibacterial agent added LP-2NaAgZnZ, 1% LP-3NaAgZnZ, 3% Resin wax composition obtained in this example 50850m
Test piece LP-BL obtained by impregnating paper with m (for blank test; no antibacterial agent added)
Table 3 shows the test results of the mold resistance of the test piece LP-3 obtained by impregnating the specimen with a resin wax composition containing 3% of NaAgZnZ and NaAgZnZ. The evaluation values of the specimens impregnated with resin wax compositions containing 1% and 3% of sterilizing zeolite solid particles NaAgZnZ were all 0.
On the other hand, the evaluation value of the sample LP-BL for the blank test was 1, indicating the occurrence of mold. From these test results, it is clear that the antibacterial and antifungal resin wax composition of the present invention exhibits a preferable antifungal effect when it contains 1% of bactericidal zeolite solid particles.

Example 3 This example shows a wax composition of the present invention having antibacterial and antifungal properties [liquid wax (oil-based liquid); blue! This paper relates to an example of the preparation of [V-turbid liquid] and the evaluation of the mold resistance test of the prepared product.

In this Example-3, the same fine powder of germicidal zeolite solid particles NaAgZnZ as used in Example-2 was used.

In this example, test pieces LB-BL, LB-2, and LB-3 impregnated with liquid wax (oil-based liquid) were prepared by the following method. Predetermined amounts of natural wax (carnauba wax, paraffin wax, wax wax), synthetic wax (Adeka Wax; Asahi Denka), polyethylene wax, and sterilizing zeolite solid particles were put into a melting container, and the mixture was heated to melt and mix. Petroleum based solvent (Mineral Split), anti-slip agent (Colloidal Silica) and dye were then added and mixed. The mixture was cooled to prepare a liquid wax (oil-based liquid) of the present invention.

- The liquid wax prepared as described above has a size of 50 x 50 mm.
A test piece was prepared by impregnating and coating paper, and the mold resistance test was conducted using this test piece.

The composition of the materials in Example-3 was as follows.

Carnauba wax 3 small parts Paraffin wax 3 Nuca wax
2 Polyethylene wax 2 Mineral spirits!・88 Colloidal Silica 2 Dye Small amount sterilizing theolite solid R ** The S content of NaAgZnZ in all the above material mixtures was adjusted to 1% and 3%.

LB BL: A blank test specimen with no antibacterial agent added, prepared by impregnating it with the lfk-like wax composition described in -1-.

LB-2: A test piece obtained by impregnating NaAgZnZ as an anhydride with 1% of the liquid wax composition described in 6.

LB-3: 2J (piece) obtained by impregnating the liquid wax composition described above containing 3% of NaAgZnZ as anhydride.

Table 4 Mold resistance test (Example 3) Test piece Liquid impregnated into test piece Evaluation I symbol '7 y 9 Z composition' (JIS method) Type and content of antibacterial agent LB-BL No antibacterial agent added 3LB-2
NaAgZnZ, 1% 0LB-3NaAgZnY
, 3% The mold resistance test results for 0 samples are shown in Table 4.

Germicidal zeolite solid particles (NaAgZnZ; Example-
The evaluation values of the test pieces LB-2 and LB-3 obtained by coating the same product (same as that used in 2) three times with liquid wax compositions impregnated with 1% and 3% were both 0. and
It was found to have excellent antifungal properties. On the other hand, in the blank test specimen LBBL, which did not contain the above-mentioned bactericidal zeolite solid particles A#, no antifungal ability was observed at all. These tests confirmed that the antibacterial and antifungal LFK wax (oil-based liquid wax) composition of the present invention exhibits excellent antifungal effects when 1% of bactericidal theolite solid particles are present. It was done.

Example 4 This example relates to a preparation example of a wax composition of the present invention having antibacterial and antifungal properties [liquid wax (emulsifiable liquid wax); white] and a mold resistance test of the prepared product.

In preparing the present composition, a fine powder of type A zeolite made by pounding silver and zinc and a fine powder of type A zeolite made by pounding silver and copper are used as the bactericidal zeolite solid particles. It was done. The aforementioned NaAgZnZ fine powder is the same as that used in Example 2. Also, the above Na
As AgCuZ powder, Ag = 3.26%, Cu = 5
．． 61% (based on anhydrous NaAgCuZ), Dav=2.9
μm and 5SA=624 rrIll/g were used.

In this example, test pieces LLW-BL, LLW-2, and LLW-3 impregnated with liquid wax (γL-forming liquid) were prepared by the following method. Natural wax (carbanal wax,
paraffin wax), synthetic wax (Adeka wax; Asahi Denka)
Predetermined amounts of emulsifier (sorbitan fatty acid ester, polyoxyethylene nonylphenol ether) and bactericidal zeolite solid particles (NaAgZnZ or NaAgCuZ) were put into an emulsification container and heated and dissolved.

A petroleum solvent was poured into the mixture, and then a predetermined amount of hot water (95° C.±5° C.) was poured into the mixture while stirring. Subsequently, a predetermined amount of anti-slip agent (colloidal lurica) was added. The mixture was homogenized and then rapidly cooled to prepare a liquid wax (emulsifiable liquid wax) composition of the present invention. The wax composition prepared as described above is 50X5
A test piece was prepared by impregnating and coating a paper with 0% oxidation, and a mold resistance test was conducted using this.

The composition of the materials in Example-4 was as follows.

Carnauba wax 4 parts by weight Paraffin wax 5 Adeka wax
2 Sorbitan fatty acid ester 1 Polyoxyethylene nonylphenyl ether 6 parts by weight Sterilizing Ceolite) Solid particles *Mineral spirit 25 Water
52 colloidal silica
5* NaAg in all material mixtures listed in 1-
The gold content of ZnZ was adjusted to 1% and 3%. Also, when using NaAgCuZ, the amount of N in the total material mixture was adjusted to 1% and 3%.
The aAgCuZ content was adjusted to 3%.

LLW-BL: Specimen for blank test without addition of antibacterial agent (test piece obtained by impregnating with the liquid wax composition of 1).

LLW-2: A test piece obtained by impregnating the above liquid wax composition containing 1% of NaAgZnZ as anhydride.

LLW-3: A test piece obtained by impregnating NaAgZnZ as an anhydride with the above liquid wax composition containing 3% white.

LLW-4: A test piece obtained by impregnating the above liquid wax composition containing 3% of NaAgCuZ as anhydride.

Table 5 Mold resistance test (Example 4) Test piece Liquid impregnated into test piece Record of evaluation values
No. '7y '77-, Composition "" (JIS method) Type and content of antibacterial agent LLW-BL No antibacterial agent added 4LLW-
2NaAgZnZ, 1% 0LLW-3NaAgZn
Z, 3% 0LLW-4NaAgCuZ, 3% 0
The results of the mold resistance test of the specimens are shown in Table 5.

N having the aforementioned composition as bactericidal zeolite solid particles
Test samples LLW-2 and LL obtained by impregnation coating with liquid wax compositions containing 1% and 3% of aAgZnZ
The evaluation values of W-3 are all 0. Also, NaAgCu
The evaluation value of sample LLW-4 obtained by impregnation coating with a liquid wax composition containing 3% Z was also 0. On the other hand, sample LLW-B for blank test obtained by impregnating and coating bactericidal zeolide solid particles with a liquid wax composition without SG.
The evaluation value of L was 4, which was found to show almost no mold resistance. From the above tests, it is clear that the wax composition [liquid wax (emulsifiable liquid wax)] of the present invention exhibits an excellent antifungal effect.

Example 5 This example relates to a preparation example of a wax composition of the present invention having -G antibacterial and antifungal properties [liquid wax (aqueous liquid wax); for floors; Rinley E6LO7] and a mold resistance test of the prepared product. It is.

When preparing the present antibacterial wax composition (Rinley E6L07), the same bactericidal zeolite solid particles (NaAgZnY; Ag=2.12 as used in Example-1) were used.
%; Zn=8.69% (based on anhydrous NaAgZnY)
;Dav=0.511m;5SA=934r
d/g'J was used.

In this example, test pieces W-1, W-
2 and W-3 were prepared. Natural wax (carnauba wax, paraffin wax), synthetic wax (Adeka wax; Asahi Denka),
Predetermined amounts of an emulsifier (sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether) and sterilizing zeolite solid particles NaAgZnY were put into an emulsification container and heated. A predetermined amount of hot water was added while keeping the mixture under stirring. After completing the above operation, the contents were rapidly cooled. After cooling, a predetermined amount of alkali-soluble resin (Duretsu; Sumitomo Bakelite) made into an aqueous T solution was poured into the mixture and stirred to prepare the liquid wax composition of the present invention. The wax composition prepared as described above was impregnated onto a 50 x 50 mm piece of paper to prepare a test piece, which was used to conduct a mold resistance test.

The composition of the materials in Example-5 was as follows.

Carnauba wax 4 Small parts Paraffin wax 4 Adeka wax 2 Sorbitan fatty acid ester 1 Polyoxyethylene sorbitan fatty acid ester 2 Polyoxyethylene nonylphenol ether 0.5 Sterilizing theolite solid particles *Water
85.5 Durets 1 Water The contents of NaAgZnY in the above-mentioned all-soak mixtures were adjusted to 0.5% and 1%.

W-1 = Specimen for blank test without addition of antibacterial agent (test c obtained by impregnating with the above liquid wax composition) W-2: NaAgZnY as anhydride, 0.5%i
Test piece W-3 obtained by impregnating the above liquid wax composition for 3-h: Test piece obtained by impregnating the above liquid wax composition containing 1% NaAgZnY as anhydride. Table-6 Mold resistance test (Example-5), (1 test piece Liquid state made into a test piece Symbol of evaluation value 7''''Composition'' (JIS method) W-1 No antibacterial agent added 4 W-2NaAgZnY, 0.5% 0 The table below shows the test results of mold resistance of test pieces obtained using the liquid wax (aqueous liquid wax) composition prepared by the above method.
6. NaAgZnY with the aforementioned composition 0
．． Specimens W2 and W-3 obtained by impregnating and coating test paper (50 x 50 mm) with liquid wax compositions obtained by dispersing 5% and 1% both exhibited excellent antifungal effects,
As shown, the evaluation value is 0, while the blank test W-1
The evaluation value of the specimen was 4, and its antifungal ability was hardly recognized. The antibacterial and antifungal liquid wax (aqueous liquid) composition of the present invention (Rinley E6LO7)
; for floors) clearly has excellent mold resistance.

Example 6 This example relates to a preparation example of a wax composition [solid wax (oil-based solid)] of the present invention that exhibits antibacterial and antifungal properties, and an evaluation test of the antibacterial activity of the prepared product using the drop method.

When preparing this composition, NaAgZnZ fine powder [Ag -3,28%;
Zn = 5.12% (anhydrous NaAgZnZ standard);
Dav=2.6μm; S5A=620rr'I
ll/g) was used.

In this example, solid wax compositions (WSBL, WS
-1, WS-2 and WS-3) were prepared by the following method. Natural wax (carnauba wax, paraffin wax, wax wax), synthetic wax (Adeka wax (Asahi Denka), polyethylene wax), and bactericidal theolite solid powder NaAgZn
A predetermined amount of Z was put into a dissolution vessel and then mixed under heat.

Further, a predetermined amount of a stone-based solvent is added to the mixture,
Subsequently anti-slip agents (colloidal silica) and dyes were added. After uniformly mixing, the contents were cooled to finally prepare the oil-based solid wax composition of the present invention.

The monthly formulation of Example-6 was as follows.

Carnauba. 7 parts by weight paraffin wax 10 parts by weight
6 polyethylene wax
4. Germicidal Zeolite Solid Particles-* Mineral Spirit 70. Colloidal Silica 2.* The content of NaAgZnZ in the entire material mixture described in 1- was adjusted to 1, 2, and 3%.

Specimen: 50X50n+n+ (thickness approx. 2mm) WS-
BL: Blank test specimen, with no antibacterial agent in the oil-based solid wax composition WS-1: NaAgZnZ,
Oil-based solid wax composition WS-2 containing 1% NaAgZnZ as anhydride, 2% vs.
h-oil-based solid wax composition WS-3: NaAg
An oil-based solid wax composition containing 3% ZnZ as an anhydride.The oil-based solid wax composition prepared by the method described above was applied to a test piece of 50 x 50 mm (about 2 mm thick) (W
SBL, WS-1, WS-2 and WS-3),
Using these test pieces, the above-mentioned drop method (spray method)
An evaluation test for antibacterial activity was conducted, and the results shown in Table 7 were obtained.

Table 7 Antibacterial activity test by drop method (Example 6) Symbol Type and Escherichia Pseu
domonas added fit coil aeru
ginosa (for blank test) WS-I NaAgZnZ, 1% 00WS-
2NaAgZn2.2% 00 (Footnote) Starting bacterial count at the start of the test: Eschcriehia colt 9.6XIO”
cells/ml; Pscudomonas acr
uginosa 1.7x 106eel Is/ml
.

Shape of object: 50X 50mm (thickness approx. 2mm)
*The number of viable bacteria per ml after 6 hours has elapsed is indicated.The specimens made of the oil-based solid wax composition of the present invention containing 1 to 3% of the bactericidal zeolite solid particles NaAgZnZ were as shown in Table 7. In, Escherichia col.
t (E. coli) and Pseudomonasaerugi
It exhibits excellent antibacterial activity against bacteria such as Pseudomonas aeruginosa (Pseudomonas aeruginosa), and all of the bacteria were completely killed 6 hours after the start of the antibacterial test. On the other hand, in the sample WS-BL for the blank test, no antibacterial or bactericidal effect against the bacteria was observed. There is no doubt that the antibacterial and antifungal wax composition of the present invention exhibits superior bactericidal activity against bacteria as compared to such antibacterial activity tests.

Embodiments of the invention are as follows.

About 90% or less of the ion exchange capacity of the zeolite solid particles with a specific surface area of 1,150rrf'/g or more and a SiO/Al2O3 molar ratio of 14 or less, or bactericidal silver ions and, if desired, copper ions. and metal ions selected from the group consisting of zinc ions,
An antibacterial and antifungal wax composition containing bactericidal zeolite solid particles in which impurity components such as bactericidal substituted metal hydroxides are substantially absent on the surface of the bactericidal solid particles.

2. Item 1-1-2, characterized in that the solid particles of theolide are composed of A-type theolide, X-type zeolite, Y-type zeolite, mordenite, or a mixed zeolite of at least two of the above-mentioned zeolites. The antibacterial and antifungal wax composition described above.

3. The antibacterial and antifungal wax composition described in item 1 above, which is comprised of an aqueous wax.

4. The antibacterial and antifungal wax composition according to item 1 above, which is comprised of an oil-based wax.

5. The antibacterial and antifungal wax composition as described in item 1 above, which comprises an emulsifying wax.

6. The antibacterial and antifungal wax composition according to item 1 above, which is comprised of a resin wax.

7. The antibacterial agent described in item 1 above, which is made of fruit wax.
Mildew-resistant wax composition.

8. The antibacterial and antifungal property according to any one of items 1 to 7, characterized in that the ratio of the bactericidal zeolite solid particles to the total weight of the wax composition is 0.01 to 30% by weight]-2 wax composition.

9. About 90% or less of the H ion exchange capacity of the zeolite solid particles with a specific surface area of more than 150 rr+'/g and a SiO/Al2O3 molar ratio of less than 14 contains bactericidal silver ions and, if desired, copper. ions and metal ions selected from the group consisting of zinc ions,
Furthermore, the sterilizing solid particles of sterilizing theolite, which are substantially free of impurity components such as hydroxides of sterilizing substituted metals on the surface of the sterilizing solid particles, are mixed with 0.01 to 30 parts by weight of the sterilizing solid particles of the aqueous wax. , oil wax, emulsifying wax,
Fruit wax or resin wax 99.99-7
An antibacterial and antifungal aqueous wax, characterized in that it is added to or mixed with any of the waxes described above in a proportion of 0 parts by weight;
A method for producing oil-based waxes, emulsifying waxes, fruit waxes, or resinous waxes.

(4 other people) hand Continued Supplementary Positive book

Claims (1)

[Claims] 1. Specific surface area of 150 m^2/g or more and S of 14 or less
Approximately 90% or less of the ion exchange capacity of the zeolite solid particles with a molar ratio of iO_2/Al_2O_3 is supported by bactericidal silver ions and, if desired, metal ions selected from the group consisting of copper ions and zinc ions. An antibacterial and antifungal wax composition containing bactericidal zeolite solid particles which are sterilized and substantially free of impurity components such as bactericidal substituted metal hydroxides on the surface of the bactericidal solid particles. 2. Specific surface area of 150 m^2/g or more and S of 14 or less
Approximately 90% or less of the ion exchange capacity of the zeolite solid particles with a molar ratio of iO_2/Al_2O_3 is supported by bactericidal silver ions and, if desired, metal ions selected from the group consisting of copper ions and zinc ions. The sterilizing zeolite solid particles are made of sterilizing zeolite solid particles that are sterilizing and substantially free of impurity components such as hydroxides of sterilizing substituted metals on the surface of the sterilizing zeolite solid particles.
30 parts by weight to 99.9 parts water-based wax, oil-based wax, emulsifying wax, fruit wax, or resin wax
A method for producing an antibacterial and antifungal aqueous wax, oil wax, emulsifying wax, fruit wax, or resin wax, which comprises adding and mixing 9 to 70 parts by weight of any of the above waxes.