JPS60202162A - Antiseptic and mildewproofing paint composition - Google Patents

Abstract

PURPOSE:To provide a paint compsn. which has low toxicity and potent antiseptic properties and mildewproofness imparted thereto, by incorporating solid zeolite particles retaining a metallic ion having a germicidal activity in paint. CONSTITUTION:Solid zeolite particles having a specific surface area of 150m<2>/g or above and a molar ratio of SiO2/Al2O3 of 14 or below, composed of pref. A type zeolite, X type zeolite, Y type zeolite or mordenite are prepd. and brought into contact with a soln. of a salt contg. a metallic ion (e.g. silver, copper or zinc ion) having a germicidal activity (e.g. a silver nitrate soln. or a copper sulfate soln.) to effect an ion-exchange reaction, thus obtaining solid zeolite particles retaining a metallic ion having a germicidal activity. The solid zeolite particles are blended with paint (e.g. vinyl acetate emulsion paint) to obtain an antiseptic and mildewproofing paint compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition with excellent antiseptic and antifungal properties, which contains zeolite solid particles that retain metal ions having a bactericidal effect.

BACKGROUND ART Environmental pollution due to mold growth on painted surfaces has long been a problem in houses, hospitals, and factories, especially pharmaceutical and food factories. Furthermore, in the case of water-based paints, which have been widely used in recent years because of their high safety and ease of handling, there has been a problem of spoilage due to bacteria or fungi during the manufacturing process and storage.

Therefore, various antiseptic and antifungal agents have been added to paints as a method to prevent the growth of bacteria and mold. That is, since organic metals such as organic mercury agents and their toxicity were pointed out, organic chlorine-based, organic sulfur-based, etc. have been used. However, it cannot be said that its low toxicity, antiseptic, and antifungal properties are necessarily satisfied.

In view of the current situation, the inventors of the present inventors have conducted various studies and have found that a coating composition containing zeolite solid particles that retain metal ions having a bactericidal effect has low toxicity and strong antiseptic and antifungal properties. It is something that has been discovered and perfected non-invention.

In other words, the invention is a preservative containing zeolite-based solid particles in which ion-exchangeable portions of zeolite hold one or more of metal ions having bactericidal properties, such as silver, copper, and iron. It provides a coating composition with antifungal properties.

Zeolites are generally aluminosilicates with a three-dimensionally developed skeletal structure, and are generally AA! 20.
XM based on f, /no・Al2O,・ysio2
- Represented by zH20. M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and 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 crystal water.

Many types of zeolite are known, each having a different composition ratio, pore diameter, specific surface area, etc.

However, the specific surface area of the zeolite solid particles used in the invention is 150 m'/l (based on anhydrous zeolite) or more, and the zeolite component has a specific surface area of 8102/AA! 205
The molar ratio should be 14 or less, preferably 11 or less.

The solution of water-soluble salts of metals having a bactericidal action, such as silver, copper, and zinc, used in the present invention easily undergoes ion exchange with the zeolite, which is not limited to the present invention, and therefore, the solution is prepared by taking advantage of this phenomenon. It is possible to hold the above metal ions alone or in a mixed form in a zeolite stationary phase, but the zeolite particles holding metal ions must have a specific surface area of 150 m2/r or more and a SiO2/A
J20. Two conditions must be met: the molar ratio is 14 or less. It has been found that if this is not the case, the objective of achieving an effective bactericidal action cannot be achieved. This is thought to be due to the fact that the absolute amount of metal ions fixed on the zeolite is insufficient in a state where the effect can be exerted.

In other words, this is thought to be due to the physicochemical properties of the zeolite, such as the amount of exchange groups, exchange rate, and accessibility.

Therefore, SiO, known as molecular sieve
2/AI! Zeolites with a high molar ratio of 203 are completely unsuitable in the invention.

In addition, in zeolite with an 8102/AA'203 molar ratio of 14 or less, it is possible to uniformly retain metal ions that have a bactericidal effect, and for this reason, a sufficient bactericidal effect can only be obtained by using such a zeolite. It turned out that. In addition, zeolite 5102/Al
The acid resistance and alkali resistance of zeolite with a high silica ratio, where the 2O3 molar ratio exceeds 14, increases with the increase in H5io2, but on the other hand, it takes a long time to synthesize this, and from an economic point of view, it is difficult to use a zeolite with such a high silica ratio. is not a good idea. SiO2/AJ2 as described above for paint-free compositions
0. ≦14 natural or synthetic zeolites can be used satisfactorily from the viewpoint of acid resistance and alkali resistance, and are economically advantageous as they are inexpensive. From this point of view, 5in2/AAI20. The molar ratio must be 14 or less.

The molar ratio of 5102/Al2O5 used in the invention is 14
As the zeolite material described below, either natural or synthetic zeolite can be used. For example, 7 is a natural zeolite called Anal-cime:
S i O2/kl 20 g ~5.6~5.6
), Chabazite: SiO2
/AJ,O,=j2~6.0 and 6.4~7.6)
, clinoptilolite (Olino-ptilolite)
e: 13102/A1203=Ij, 5-10.
5), Erionite (SiO
2/A1205=5.8~7.4), Faujasite: 5to2/A72o5=4
．． 2-4.6), -E-/l/l/Bunite orden
ite:, 8102/Al2O.

= 8.34~10.0), phillipsite (Ph1
111pe ite: SiO2/Al2Os
= 2.6 to 4 +, 4), etc. These typical natural zeolites are suitable for the present invention. On the other hand, a typical synthetic zeolide is 8-type zeolite)
(EliO□/A1205=1.4-2.4), X-type zeolite (S102/k120.:=2-5),
Y-type zeolide (Sin2/AA!203=3~6
), mordenite (S10□/IJ20°=9~10)
These synthetic zeolites are suitable as uninvented zeolite materials. Particularly preferred are synthetic A-type zeolides, X-type zeolides, Y-type zeolides and synthetic or natural mordenites.

The zeolite is preferably in the form of fine particles, particularly preferably in the form of powder particles with a particle size of 5 microns or less, preferably 2 microns or less.

In the present invention, metal ions must be retained in the zeolite solid particles by an ion exchange reaction. If it is simply adsorbed or attached without ion exchange, the bactericidal effect and its sustainability will be insufficient.

Taking as an example the case of converting various zeolites defined in the invention into the non-invention A2-zeolite, a solution of a water-soluble silver salt such as silver nitrate is normally used when converting Af-zeolite; Care must be taken not to increase the concentration too much.

For example, A-type or FiX-type zeolide (sodium-
type) to A2-zeolite using an ion exchange reaction, if the silver ion concentration is high (for example, 1 to 2
When MArN03 is used) silver ions replace sodium ions in the solid phase by ion exchange, and at the same time, silver oxides etc. are precipitated in the zeolite solid phase. For this,
The disadvantage is that the porosity of zeolite is reduced and the specific surface area is significantly reduced. Furthermore, even if the specific surface area does not decrease significantly, the bactericidal activity decreases due to the presence of silver oxide itself. In order to prevent such excess silver from being deposited on the zeolite phase, the concentration of the silver solution should be diluted, for example, 0.3 MAjNO,
It is necessary to maintain the following. Extremely safe Atto
The concentration of No. 5 is 0.1M or less. Such a concentration of Atto
When a solution is used, the specific surface area of the Af-zeolite obtained is almost the same as that of the converted material zeolite,
It was found that the bactericidal effect can be demonstrated under optimal conditions.

Next, when converting the zeolites defined in the non-invention into Ou-zeolite, the same phenomenon as in the case of A2-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, when converting 8-type or Due to the precipitation of basic precipitates such as Cu3(SO2)(OH)4 in the phase, the porosity of the zeolite is reduced and the specific surface area is significantly reduced. In order to prevent such excessive copper precipitation into the zeolite phase, it is preferable to maintain the concentration of the aqueous preparation used in a more dilute state, for example, at 0.05 M or less. It has been found that the specific surface area of the Ou-zeolite obtained when using a 0uSO4 solution of such a concentration is almost the same as that of the zeolite used as the conversion material, and that it has the advantage of exhibiting its bactericidal effect in an optimal state.

It has been mentioned that during conversion to Af-zeolite and Cu-zeolite, solid matter may precipitate on the zeolite solid phase depending on the concentration of salts used for ion exchange.
When converting to n-zeolite, the salts used are 2
This phenomenon is not observed in the vicinity of ~3M. Zn-zeolite, which is usually used in the invention, can be easily obtained by using salts having concentrations around the above range.

Above mentioned Af-zeolite, Cm-zeolite and Zn
- When carrying out the ion exchange reaction in a batch process for conversion to zeolite, the zeolite material may be immersed in a salt solution having the above-mentioned concentration. In order to increase the metal content in the zeolite material, the number of batch treatments may be increased. - When treating a zeolite material by a column method using a salt solution having the above-mentioned concentration, the desired metal-zeolide can be easily obtained by filling an adsorption tower with the zeolite material and passing the salt solution through it. is obtained.

The amount of metal in the metal-zeolide (based on anhydrous zeolite) is 30% by weight or less for silver;
The preferred range is 0.001-5% by weight. -1 Regarding the copper and zinc used in the invention, the amount of copper or zinc in the metal zeolide (based on Maisui zeolite) is 35% by weight or less, and the preferable range is 0°01 to 15% by weight.
It is in weight%. It is also possible to use silver, copper and zinc ions in combination, in which case the total amount of metal ions is 55% of the metal-zeolide (based on anhydrous zeolite).
It may be less than or equal to 10% by weight, and the preferable range depends on the composition ratio of the metal ions, but is approximately 15% by weight.

Further, even if metal ions other than silver, copper, and zinc, such as sodium, potassium, calcium, or other metal ions, coexist, the bactericidal effect is not hindered, so the residual or coexistence of these ions is not a problem.

There are no restrictions on the coating film forming elements and coating auxiliary elements in the invention, but typical examples include acrylic resin-based and vinyl acetate-based emulsion paints, acrylic resin-based and alkyd resin-based solvents. Examples include mold paint.

In order to make a coating composition containing zeolite solid particles holding metal ions having a bactericidal effect, it is possible to make a coating composition containing zeolite solid particles holding metal ions having a bactericidal effect by adding them into a coating film forming element together with coating film auxiliary elements and stirring to uniformly disperse them. good.

In the present invention, the amount of zeolite solid particles added (9% by weight relative to the coating composition) and the amount of metal having a bactericidal effect (9% by weight relative to the metal zeolite) are both related to the bactericidal effect. In order to exhibit sufficient antiseptic and mold resistance, the value of AXB (%) should be 0.025 or more for silver-zeolide, 1 or more for copper-zeolide, and 1.0 for zinc-zeolide. It is desirable to adjust the value to 5 or more.

The bonding strength between zeolite and antibacterial metal ions such as silver, copper, and zinc as defined in the non-invention is extremely large, and the coating composition containing such metal zeolite has strong antiseptic and antifungal properties and lasts for a long time. The characteristic advantage of non-inventiveness is worth mentioning.

Furthermore, the zeolite particles that hold metal ions that have a bactericidal effect are aluminosilicate containing copper, zinc, sodium, potassium, etc., and it is also noteworthy that their toxicity is low. This is a characteristic advantage.

It was confirmed that the thus obtained coating composition had excellent antiseptic and mold-proofing properties during the manufacturing process, during storage, and after painting.

Next, non-invention examples will be described, but non-invention is not limited to non-invention examples.

In addition, in the present examples and comparative examples, unless otherwise specified, ``chi'' is % by weight.

Reference Example 1 Table 1 shows unconverted natural and synthetic zeolite particles used in the examples of the present invention. Each zeolite was obtained by crushing and classifying crude raw materials to obtain the desired particle size. In Table 1, the 8-type zeolide is abbreviated as 21, the x-type zeolide as 22, the Y-type zeolide as z3, and natural mordenite t-24. The particle diameter, water content, and specific surface area of these zeolites were as shown in Table 1.

Next, 250 pieces each of fine powder dried products of various zeolites listed in Table 1.
f was sampled, and 500% M silver nitrate aqueous solution was added to each sample, and the resulting mixture was kept under stirring at room temperature for 3 hours to perform ion exchange.

The silver-zeolite obtained by such an ion exchange method was filtered and washed with water to remove excess silver ions. Next, the water-washed silver-zeolide was dried at 100 to 105 mm and then ground to obtain a fine powder of silver-zeolide. The silver content and specific surface area of the obtained dried silver-zeolide product were as shown in Table 2.

Among silver-zeolite conversion products, silver-A type zeolide t-
25. Silver-X type zeolite 26. Silver-Y type zeolite)
t z71 silver-natural mordenite is abbreviated as z8.

Reference Example 2 Fine powder dried product table 2 of synthesized zeolites of A-type zeolite) (Z,) and Y-type zeolite) (Z,) shown in Table 1
50f were collected, and 1 part of a 20 M sulfuric acid aqueous solution was added to each. The resulting mixture was kept under stirring at 40 t- for 5 hours. The copper-zeolide obtained by this ion exchange method was separated by centrifugation. Next, the same process as above was repeated.

In the unprepared method, such batch processing was carried out five times. The finally obtained converted product was filtered under suction and then washed with water until free of formic acid ions. Next, the water-washed copper-zeolide was dried with a 100-105 millimeter and pulverized to obtain a finely powdered copper-zeolide conversion product.

Table 2 shows the copper content and specific surface area of the copper-zeolite conversion product obtained by the above method. Among the copper-zeolide conversion products, copper-A type zeolide was used as z9. Copper-Y type zeolite is abbreviated as z+o+.

Reference Example 250f of dry powders of A-type zeolite (Z,) and X-type zeolide (z2) shown in Table 1 were collected, and
The mixture obtained by adding 1 part of M zinc chloride solution was kept at around 60 mm with stirring for 3 hours and 20 minutes. The zinc-zeolide obtained by such ion exchange was separated by centrifugation. Next, the same process as above was repeated. In this preparation method, the batch process was carried out four times. The finally obtained converted product was washed with water to remove excess zinc ions.

Next, the zinc conversion product was dried at around 100 υ, and then ground to obtain a fine powder of zinc-Hitogaki theoride.

Next, the water-washed zinc-zeolide was dried at 100 to 105 mm and then ground to obtain a fine powder of zinc-zeolide.

Table 2 shows the zinc content and specific surface area of the two types of zinc-zeolite conversion products obtained by the above method.

Among the zinc-zeolide conversion products, zinc-A type zeolide is z, 1. Zinc-X type zeolite, 2. It is abbreviated as

Example 1 and Comparative Example 1 70% emulsion containing 43% acrylic resin, 10% titanium dioxide, 10% hydroxyl ethyl cellulose
%, 25% Demol EP 8% (manufactured by Kao Soap ■) 100f of acrylic resin emulsion paint consisting of 2% water was weighed into a tin-plated can, and various zeolites shown in Table 2 at the specified concentration were added to it and stirred. Mixed. Comparative Examples 1-21 and 1-2 are those to which type A zeolite (Z) shown in Table 1 was added and those to which no zeolite was added.

Next, Bacillus 5ubj; 1lis diluted to about I x 10'4 as paint spoilage bacteria
Pseudomonasa elno sa and -
1 d of mixed suspension of Escherichia coli
inoculated into the paint. After the can was sealed and cultured for 28 υ for 7 days, the bactericidal effect was evaluated from the number of viable bacteria in the paint. The results are shown in Table 3.

Table 3 The uninvented coating composition had a strong bactericidal effect and exhibited excellent antiseptic properties during the manufacturing process and storage. Incidentally, the coating properties of a coating composition containing the above-mentioned zeolite and a composition containing no zeolite were compared, but no difference was observed.

Example 2 and Comparative Example 2 Various zeolites shown in Table 2 at predetermined concentrations were added to the acrylic resin emulsion paint shown in Example 1 and mixed with stirring. Comparative Example 2-1 is a sample to which type A zeolite (Z) shown in Table 1 is added, and Comparative Example 2-2 is a sample to which zeolite is not added.

A test piece was prepared by applying the above coating composition twice to a woodblock measuring 50 mm in diameter x 2 mm so as to form a uniform coating, and drying at room temperature for 48 hours. The test piece was immersed in water for 18 hours, taken out, left to stand at room temperature for 2 hours, and then dried for 2 hours at 8°C to 85°C.

(The above drying was all done by hanging the test piece.) Next, the cough test piece was washed with 111 parts of water, 4 parts of glucose, and 10 parts of peptone.
Flat plate 01 consisting of the composition of f1 agar IDf @ospori
um cladoepori, oides, aurso
ba-Bidium Pu1lu'1ans and Gl
Mixed spore suspension of iocladium virens 1
ml evenly spread over the surface of the medium and the test piece,
The petrie dish was covered with a lid and cultured for 14 days at 28 days. The results are shown in Table 4. +10 if bacteria has grown.

The case where the bacteria grew on about % or less of the test piece is indicated as +, and the case where the bacteria grew on about % or more is indicated as -.

The uninvented coating composition had a strong bactericidal effect and was shown to have excellent antifungal properties.

Claims (1)

[Scope of Claims] (2) A preservative and anti-mold coating composition comprising zeolite solid particles retaining metal ions having a bactericidal effect. (2) A zeolite solid particle containing 150 m2/f The coating composition according to claim 1, which has a specific surface area of 14 or less and a SiO2/A7203 molar ratio of 14 or less. (3) The zeolite solid particles are A-type zeolide, X-
2. The coating composition according to claim 1, which comprises Y-type zeolide, Y-type zeolide, or mordenite. (4) The coating composition according to claim 1, wherein the metal ion having a bactericidal effect is one or more metal ions selected from the group consisting of silver, copper, and zinc.