JPH07165518A - Antibacterial inorganic powder - Google Patents

Abstract

PURPOSE:To obtain an antibacterial inorganic powder having a broad antibacterial spectrum and excellent heat-resistance and chemical stability and exhibiting sufficient effect by the contact with a treating object for a short time by treating the surface of inorganic powder with a specific organosilicone phosphonium salt. CONSTITUTION:This antibacterial inorganic powder is produced by treating the surface of inorganic powder with an antibacterial organosilicone phosphonium salt expressed by formula I (R<1> is an alkoxy, a halogen or an acyl; one of R<1> may be OH; R<2> is an alkylene; R<3> to R<5> each is H, an alkyl, an aryl or an aralkyl; X is an anion). The surface-treatment is carried out by immersion, spraying, etc., using a treating liquid controlled to a prescribed concentration. The inorganic powder is especially fine powder selected from oxide, hydroxide, silicate, etc., of Mg, Ca, Ba, Sr, Zn, Si, etc. The surface- treatment may be performed by treating the surface with an organosilicone of formula II and reacting with a triorganophosphine of formula III to convert the silicone compound to a phosphonium salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial inorganic powder consisting of an inorganic powder surface-treated with an organosilicon phosphonium salt.

[0002]

2. Description of the Related Art At present, application development of antibacterial inorganic powder obtained by imparting antibacterial ability to inorganic powder is being developed in various fields such as industry, agriculture and food. For example, those in which silver ions or silver complexes are supported on zeolite, silica gel, calcium phosphate or glass are known as typical ones. On the other hand, inorganic powder carriers such as alkyldimethylbenzylammonium chloride (benzalkonium chloride), quaternary ammonium salt compounds such as di-n-decyldimethylammonium chloride, 2-n-octyl-
It is also known to carry an organic antibacterial agent such as a thiazole compound such as 4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one and an imidazole compound.

[0003]

However, when the above antibacterial inorganic powder carrying silver ions is blended with the resin, a high antibacterial effect is exhibited, but the phenomenon of discoloring the resin brown by light or heat is avoided. I can't. Further, the powder carrying the organic antibacterial agent is excellent in dispersibility in the resin and discoloration resistance, but is poor in heat resistance, and when mixed with the resin because of its relatively high vapor pressure, it may cause sublimation or discoloration. There is a problem that a sufficient antibacterial effect at a low concentration cannot be maintained for a long time due to the runoff or the change with time when the liquid comes into contact.

For example, the above-mentioned inorganic powder carrying a quaternary ammonium salt type antibacterial agent has a comparatively broad antibacterial spectrum, but its heat resistance and durability are insufficient, and it is effective against microorganisms in a short time contact. It has the drawback that it cannot impart a specific antibacterial effect.

As a result of intensive studies on the antibacterial inorganic powder which solves the above-mentioned problems, the present inventors have found that the surface treatment of the inorganic powder with a certain organosilicone phosphonium salt is extremely strong and stable. It was confirmed that the activity was exhibited.

The present invention was developed on the basis of such findings, and its purpose is to possess a broad antibacterial spectrum and excellent heat resistance and chemical stability, and to exert a sufficient antibacterial effect by contact for a short time. It is to provide an antibacterial inorganic powder.

[0007]

The antibacterial inorganic powder according to the present invention for achieving the above object comprises an inorganic powder,
A structural feature is that the surface is treated with an organosilicone phosphonium salt represented by the following general formula (1) having antibacterial properties. However, in the formula (1), R ¹ is selected from the group consisting of an alkoxy group, a halogen atom or an acyl group, one of which may be a hydroxyl group, and R ² has 1 to 6 carbon atoms.
A linear or branched alkylene group, R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, an alkyl group, The aryl group and aralkyl group may be substituted with a hydroxyl group or an alkoxy group, and
Represents an anion.

The inorganic powder used in the present invention is
The organosilicon phosphonium salt is not particularly limited as long as it is a poorly soluble powder that can be surface-treated, but in many cases, Mg, Ca, Ba, Sr, Zn, Cu, Mn,
One or more oxides, hydroxides, silicates, aluminosilicates, phosphates, polyphosphates, borates, sulfates (soluble salts) selected from Ni, Al, Fe, Cr, Ti, Si or Zr. 1), or 2 or more kinds of fine powders selected from carbonates and metal salts are preferably used. Further, these inorganic powders may be natural products or synthetic products.

Specifically, for example, calcium oxide, calcium peroxide, calcium hydroxide, magnesium oxide,
Magnesium hydroxide, zinc white, hydrous zinc oxide, cuprous oxide, copper oxide, manganese oxide, hydrous manganese oxide, nickel oxide, alumina, hydrous alumina, iron oxide, hydrous iron oxide, chromium oxide, hydrous chromium oxide, titanium dioxide, Zirconia, silica, zeolite, crystalline aluminosilicate other than zeolite, amorphous aluminosilicate, calcium silicate, magnesium silicate, zinc silicate, aluminum silicate, titanium silicate, zirconium silicate, calcium phosphate, basic calcium phosphate, phosphorus Magnesium phosphate, barium phosphate, zinc phosphate, aluminum phosphate, titanium phosphate, zirconium phosphate, aluminum polyphosphate, calcium phosphite, magnesium phosphite, zinc phosphite, hydrotalcite, hydrocalumite Basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, gypsum, barium sulfate, spinel, Kozeraito, pies office lights, and the like. Further, other powders such as activated carbon and various glass powders may be used. The particle size and shape of the powder may be set or selected according to the purpose of use and is not particularly limited.

The antibacterial inorganic powder according to the present invention is obtained by surface-treating an inorganic powder with an organosilicon phosphonium salt having antibacterial properties represented by the above general formula (1). Specific examples of R ¹ include alkoxy groups such as methoxy, ethoxy and propoxy, halogen atoms such as chlorine and bromine, acyl groups such as acetyl, propionyl and acryloyl, and one may be a hydroxyl group, preferably methoxy. And alkoxy groups such as ethoxy.
R ² contains a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene and ethylethylene, or an oxygen atom or a nitrogen atom. 2 carbon atoms
Although it is a divalent hydrocarbon group having 0 or less, lower alkylene such as methylene, ethylene, propylene or the like is preferable.

Specific examples of R ^{3 to} R ⁵ include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl and octadecyl; aryl groups such as phenyl, tolyl and xylyl; benzyl; Aralkyl group such as phenethyl, hydroxyl group,
Alkoxy group-substituted ones, preferably heptyl, octyl, dodecyl, octadecyl, and other alkyl groups, phenyl, tolyl, and other aryl groups, and more preferably octyl, dodecyl, octadecyl, and other alkyl groups having 6 or more carbon atoms. A phenyl group. Also, R
³ , R ⁴ and R ⁵ may or may not be the same group.

X ⁻ is an anion such as halogen ion of fluorine, chlorine, bromine or iodine, formic acid, acetic acid,
Carboxylic ion such as oxalic acid, sulfate ion, phosphate ion, methyl or dimethyl phosphate, ethyl or diethyl phosphate, antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, perchlorate ion, etc. Among them, halogen ions are preferable.

In the organosilicone phosphonium salt of the above formula (1), when R ^{3 to} R ⁵ are alkyl groups, one of them is different from the same kind, for example, one of the groups is tetradecyl or hexadecyl. The other two are higher alkyl groups such as methyl, ethyl,
When it is a lower alkyl group such as butyl, and when it is of the same kind, and has a carbon number of 6 or more such as hexyl and octyl, the antibacterial activity tends to be higher.

Examples of such organosilicon phosphonium salts include 3- (trimethoxysilyl) -propyltriethylphosphonium chloride, 3- (trimethoxysilyl) -propyltributylphosphonium chloride and 3- (trimethoxysilyl) -propyltrin-.
Octylphosphonium chloride, 3- (trimethoxysilyl) -propyltriphenylphosphonium chloride, 3- (trimethoxysilyl) -propyldimethyloctadecylphosphonium chloride, 3 (trimethoxysilyl) -propyldiethyl n-octadecylphosphonium chloride, 3- ( Trimethoxysilyl) -propyltrin-octylphosphonium bromide, 3- (trimethoxysilyl) -propyltrin-dodecylphosphonium bromide, 3- (trimethoxysilyl) -propyltrin-octylphosphonium iodide, 3-
(Trimethoxysilyl) -propyltrin-dodecylphosphonium iodide, 3- (trimethoxysilyl)-
Examples thereof include propyltributylphosphonium tetrafluoroborate, 3- (trimethoxysilyl) -propyltrin-octylphosphonium perchlorate, and 3- (trimethoxysilyl) -propyltrin-octylhexafluorophosphate.

In order to surface-treat the inorganic powder with the above-mentioned organosilicone phosphonium salt, a treatment liquid prepared by adjusting the organosilicone phosphonium salt to a desired concentration is used,
A method of treating the inorganic powder with an appropriate means such as a dipping method, a spray method, or a pad method and then drying it can be adopted.
For example, the temperature of the treatment liquid is room temperature to 80 ° C., preferably 40.
It can be obtained by setting the temperature to -60 ° C and immersing the inorganic powder for 15 to 120 minutes, followed by dehydration and drying (110 to 150 ° C).

As another treatment means, the inorganic powder is preliminarily surface-treated with an organosilicone represented by the following general formula (2), and then a triorganophosphine represented by the following general formula (3) is reacted to form phosphonium. You may take the method of converting into a salt.

(R ¹ ) ₃ —Si—R ² · X (2) However, R ₁ and X in the formula (2) are the same as above.

R ³ R ⁴ R ⁵ P (3) However, R ³ R ⁴ and R ⁵ in the formula (3) are the same as above.

Upon surface treatment, if desired, a stabilizer, an antistatic agent, a surfactant, a deodorant, a stain-removing modifier, a pH adjusting agent for promoting the adhesion of the treating agent,
One or more salts such as salts may be added and used in combination.

The amount of the organosilicone phosphonium salt supported on the inorganic powder by the surface treatment is usually 0.01% by weight or more based on the solid content of the inorganic powder, and the upper limit of the supported amount is practically 10% by weight. % Or less is sufficient. However, when the loading amount is less than 0.01% by weight, the antibacterial action cannot be substantially obtained.

[0021]

In the antibacterial inorganic powder according to the present invention, the organosilicon phosphonium salt forms a film on the surface of the inorganic powder, or forms a covalent bond or an anionic group with the hydroxyl group present in the inorganic powder. By coupling, antibacterial properties are imparted, and an excellent antibacterial effect is exhibited against, for example, gram-positive bacteria, gram-negative bacteria, molds, algae, yeasts and the like. Moreover, it has superior heat stability compared to quaternary ammonium salts and other organic compounds,
For example, an organosilicon phosphonium salt having an octyl group has a very high thermal stability at a decomposition temperature of around 350 ° C.
Further, since it is chemically stable, the surface-treated antibacterial inorganic powder has a higher thermal stability and a higher chemical stability. At the same time, antistatic ability is imparted.

The range of application of the antibacterial inorganic powder according to the present invention varies depending on the physical properties of the carrier powder. For example, by blending it with various synthetic resins, rubbers, paints, adhesives, additives such as paper, etc. The antibacterial properties of these base materials can be effectively and effectively improved.

[0023]

EXAMPLES The present invention will now be described in more detail based on examples.

Example 1 (1) Preparation of Organosilicone Phosphonium Salt Solution Acetic acid was added to 200 ml of a mixed solvent (95: 5) of methanol and water to adjust the pH to 4.5. Then, 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride was added with stirring to prepare a 2 wt% concentration solution.

(2) Antibacterial Treatment of Inorganic Powder Hydroxyapatite powder was immersed in the above-mentioned organosilicone phosphonium chloride solution for 30 minutes for surface treatment, and then heat-treated at about 120 ° C. under reduced pressure. After heat treatment, soak in methanol and ultrasonically clean,
After removing unreacted organosilicon, it was dried to obtain an antibacterial inorganic powder. 3- (trimethoxysilyl) -propyltrin-supported on hydroxyapatite
The amount of octylphosphonium chloride is 1.5% by weight
Met.

(3) Antibacterial activity test As a representative of Gram-positive bacteria, Staphylococcus aureus (Staphyrococ
caus aureus) IFO12732, and Escherichia coli IFO3806 as a representative of Gram-negative bacteria were treated with the antibacterial inorganic powder at the organosilicon phosphonium conversion concentration and contact time shown in Tables 1 and 2. Table 1 shows the results of the antibacterial activity test against Staphylococcus aureus, and Table 2 shows the results of the antibacterial activity test against Escherichia coli. The antibacterial activity was evaluated by adding 1 ml to 54 ml of physiological saline.
A solution dilution method was used in which 6 ml of 10 ⁷ bacteria were taken in contact with each other to bring the samples into contact with each other, and then the number of bacteria was measured. Numerical values in the table represent the number of bacteria (cells / ml), and the more significant the decrease in the number of bacteria with respect to the contact time, the stronger the antibacterial activity.

Example 2 3- (trimethoxysilyl) -propyltri-n-hexylphosphonium chloride was used in place of 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride, and otherwise the same as in Example 1. An antibacterial inorganic powder was obtained depending on the conditions. 3- (Trimethoxysilyl) -propyltrin supported on hydroxyapatite
The amount of hexylphosphonium chloride was 1.4% by weight. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

Example 3 An antibacterial inorganic powder was obtained under the same conditions as in Example 1 except that titanium dioxide powder was used in place of hydroxyapatite. The reaction-supported 3- (trimethoxysilyl) -propyltri-n-octylphosphonium chloride on titanium dioxide was 4.0 μmol / g (titanium dioxide).
Met. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
It was also published in.

Example 4 Ca-A type zeolite powder was used in place of hydroxyapatite and 3- (trimethoxysilyl) -propyltrin.
3- (trimethoxysilyl) -propyldimethyl n-octadecylphosphonium chloride was used in place of the -octylphosphonium chloride, otherwise Example 1
An antibacterial inorganic powder was obtained under the same conditions as above. 3- (Trimethoxysilyl) supported on Ca-A type zeolite
The amount of -propyldimethyl n-octadecylphosphonium chloride was 1.4% by weight. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

Example 5 A zirconium phosphate powder was used in place of hydroxyapatite, and an antibacterial inorganic powder was obtained under the same conditions as in Example 1 except for the above. The amount of 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride supported on zirconium phosphate was 1.4% by weight. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

Example 6 Alumina powder was used in place of hydroxyapatite, and other conditions were the same as in Example 1 to obtain an antibacterial inorganic powder. The amount of 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride supported on alumina was 1.6% by weight. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

Example 7 Silica powder was used instead of hydroxyapatite,
Others were the same as in Example 1 to obtain an antibacterial inorganic powder. The amount of 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride supported on silica was 1.5% by weight. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

Example 8 An antibacterial inorganic powder was obtained under the same conditions as in Example 1 except that light calcium carbonate powder was used instead of hydroxyapatite. The amount of 3- (trimethoxysilyl) -propyltrin-octylphosphonium chloride supported on light calcium carbonate was 1.4% important. An antibacterial activity test was conducted on this antibacterial inorganic powder in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[0034]

[Table 1]

[0035]

[Table 2]

From the results shown in Tables 1 and 2, it is clearly recognized that the antibacterial inorganic powder of the present invention exerts an excellent antibacterial effect by contact for a short time. The antibacterial inorganic powder was heat-treated at 250 ° C. for 20 minutes and then similarly subjected to an antibacterial activity test. As a result, the antibacterial effect was not substantially changed, and sufficient thermal stability was confirmed.

[0037]

As described above, according to the present invention, various inorganic powders are surface-treated with an organosilicon phosphonium salt having antibacterial properties, so that they have a broad antibacterial spectrum and a sufficient antibacterial effect can be obtained by contact for a short time. It is possible to provide a durable and thermally and chemically stable antibacterial inorganic powder that exhibits effects. Therefore, it can be expected to be useful as a blended powder for a wide range of applications requiring antibacterial properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiko Inaba 9-15-1, Kameido, Koto-ku, Tokyo Nippon Chemical Industry Co., Ltd. Research & Development Division (72) Inventor Seiji Shimura 9-15, Kameido, Koto-ku, Tokyo 1 R & D Headquarters of Nippon Kagaku Kogyo Co., Ltd.

Claims (2)

[Claims] 1. An antibacterial inorganic powder characterized by being surface-treated with an organosilicon phosphonium salt represented by the following general formula (1) having antibacterial properties. However, in the formula (1), R ¹ is selected from the group consisting of an alkoxy group, a halogen atom or an acyl group, one of which may be a hydroxyl group, and R ² has 1 to 6 carbon atoms.
A linear or branched alkylene group, R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, an alkyl group, The aryl group and aralkyl group may be substituted with a hydroxyl group or an alkoxy group, and
Represents an anion. 2. The inorganic powder is Mg, Ca, Ba or S.
r, Zn, Cu, Mn, Ni, Al, Fe, Cr, T
One or more oxides, hydroxides, silicates, aluminosilicates, phosphates, polyphosphates, borates, sulfates (excluding soluble salts), carbonates or metals selected from i, Si or Zr. The antibacterial inorganic powder according to claim 1, which is one or more fine powders selected from acid salts.