阅读说明：本技术 用于减少气味的组合物和方法 (Compositions and methods for reducing odor ) 是由 J-E.奧特施泰特 于 2018-12-21 设计创作，主要内容包括：减少气味的方法,其通过以下实现：提供具有3 nm至100 nm的粒度的二氧化硅颗粒的胶态分散体,所述颗粒具有吸附在颗粒表面上的选自铜、银、锌和铁的一种或多种金属的离子,和使所述颗粒中的至少一种与有气味的化合物接触；和/或提供含有选自铜、银、锌和铁的离子的金属离子的硅酸盐水溶液,和使在所述溶液中形成的至少一种带有金属离子的硅酸盐颗粒与有气味的化合物接触。这样的方法中使用的组合物和通过这样的组合物处理的产品。(A method of reducing odor by: providing a colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles, and contacting at least one of said particles with an odoriferous compound; and/or providing an aqueous silicate solution containing metal ions selected from ions of copper, silver, zinc and iron, and contacting at least one silicate particle with metal ions formed in said solution with an odorous compound. Compositions for use in such methods and products treated by such compositions.)

1. A method of reducing odor comprising

(i) Providing a colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles, and contacting at least one of said particles with an odoriferous compound; and/or

(ii) Providing an aqueous silicate solution containing metal ions selected from the group consisting of ions of copper, silver, zinc and iron, and contacting at least one silicate particle bearing metal ions formed in said solution with an odorous compound.

2. The method of claim 1, wherein said odorous compound is present in a vapor phase.

3. The method of claim 2, wherein said particles are contacted with said odorous compound by spraying said dispersion into said gas phase.

4. The method of claim 2 or claim 3, wherein the particles are contacted with the odorous compound by applying the dispersion or solution to a solid surface and contacting the solid surface with the gas phase.

5. The method of claim 1, wherein said odorous compound is present in a liquid phase.

6. The method according to any one of claims 1 to 5, comprising providing a colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles, and contacting at least one of said particles with an odorous compound.

7. The method of claim 6, wherein the ions are at 0.0005-5 ions/nm²The amount of silica particle surface is present on said surface.

8. The method of claim 7, wherein the ions are at 0.01-0.5 ions/nm²The amount of silica particle surface is present on said surface.

9. The method according to any one of claims 6 to 8, wherein the surface of the silica particles contains aluminosilicate sites.

10. The method of any one of claims 6 to 9, wherein the ions are present at a total concentration of 1ppm to 3000ppm by weight of the dispersion.

11. The method of any one of claims 6 to 10, wherein the dispersion has a pH of 8 to 11.

12. The method of any one of claims 6 to 11, wherein the silica particles are present at a concentration of 0.001 to 25% by weight of the dispersion.

13. The method of any one of claims 1 to 12, wherein the one or more metals are selected from the group consisting of iron, copper and zinc.

14. A colloidal dispersion comprising silica particles having a particle size of from 3 nm to 100 nm, said particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles.

Use of (i) a colloidal dispersion containing silica particles having a particle size of from 3 nm to 100 nm, said particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles, and/or (ii) an aqueous silicate solution containing metal ions selected from ions of copper, silver, zinc and iron, for reducing odour in a gas phase, by contacting the dispersion and/or solution with the gas phase.

16. Use according to claim 15, wherein the dispersion and/or solution is contacted with the gas phase by spraying the dispersion into the gas phase.

17. Use according to claim 15 or 16, wherein the dispersion and/or solution is contacted with the gas phase by applying the dispersion onto a solid surface and contacting the solid surface with the gas phase.

18. A liquid composition for producing a surface coating, said composition comprising:

silica particles having a particle size of 3 nm to 100 nm, the particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles; and a liquid carrier for the particles; and/or an aqueous silicate solution containing metal ions selected from the group consisting of copper, silver, zinc and iron ions.

19. A method of treating a solid surface comprising applying a liquid composition according to claim 18 to said surface and allowing said liquid composition in contact with said surface to dry.

20. Non-woven or woven fabrics with

(i) A plurality of silica particles having a particle size of 3 nm to 100 nm, the particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles and/or

(ii) A plurality of silicate particles bearing ions of one or more metals selected from the group consisting of copper, silver, zinc and iron.

21. A nonwoven or woven fabric that has been contacted with:

(i) colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles, and/or

(ii) An aqueous silicate solution containing metal ions selected from the group consisting of copper, silver, zinc and iron ions.

22. The method according to any one of claims 1 to 5, comprising (ii) providing an aqueous silicate solution containing metal ions selected from ions of copper, silver, zinc and iron, and contacting at least one silicate particle bearing metal ions formed in said solution with an odorous compound.

23. The method of claim 22, wherein the ions are present at a total concentration of 1ppm to 5000ppm by weight of the solution.

24. The method of claim 22 or claim 23, wherein the ions are present at a total concentration of 50ppm to 3000ppm by weight of the solution.

25. The method of any one of claims 22 to 24, wherein the ions are present at a total concentration of 100ppm to 2000 ppm by weight of the solution.

26. The method of any one of claims 22 to 25, wherein the solution has a pH of 8 to 13.

27. The method of any one of claims 22 to 26, wherein the solution has a pH of 10 to 12.

28. A process according to any one of claims 22 to 27, wherein the silicate is an alkali metal silicate.

29. The method of claim 28, wherein the alkali silicate comprises SiO at 25:1 to 2:1₂/M₂Alkali metal oxide M with O molar ratio₂O and SiO₂。

30. The method of claim 29, wherein the molar ratio is 6:1 to 2: 1.

31. The method according to any one of claims 22 to 30, wherein the silicate is from 1% to 30% SiO in the solution by weight corresponding to the solution₂Is present in the solution.

32. The method of claim 31, wherein the amount corresponds to 2% to 20% SiO in the solution by weight of the solution₂The concentration of (c).

33. The method of any one of claims 22 to 32, wherein the metal is selected from Fe, Cu and Zn.

34. The method of any one of claims 22 to 33, wherein the solution comprises one or more surfactants.

Technical Field

The present invention relates to metal ion-containing compositions for use in methods of reducing odor. In particular, the present invention relates to colloidal dispersions containing metal ions and their use, in particular in a process for reducing odor. The invention further relates to metal-containing silicate solutions and to their use in a method for reducing odor. The invention also relates to the use of a material comprising silica nanoparticles onto which metal ions have been adsorbed in a method for reducing odour. The invention also relates to a method of reducing odor by contacting such a colloidal dispersion or solution with an odorous compound.

Background and Prior Art

Odors and malodors can cause discomfort in various confined spaces such as toilets, public restrooms, industrial setting buildings, and the like. In some cases, odor masking devices, such as toilet perfumes, are used. It would be advantageous to provide a method effective in reducing the level of odorous compounds or reducing the source of odors.

International patent application No. PCT/SE2010/051007 (WO 2011/037523), incorporated herein by reference, discloses a colloidal dispersion comprising silica support particles to which silver ions have been adsorbed, the silica support particles having a particle size of from 3 nm to 100 nm.

International patent application No. PCT/EP2017/064658 (WO 2017/216285), incorporated herein by reference, discloses a colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm onto which ions of one or more metals selected from the group consisting of metals having atomic numbers 21-31, 39-46, 48-50, 57-82 and 89-93 are adsorbed, and a method of making the dispersion.

International patent application No. PCT/EP2018/069941 (not yet published), incorporated herein by reference, relates to aqueous silicate solutions containing metal ions of atomic number selected from the group consisting of atomic numbers 21-31, 39-50, 57-82 and 89-93, methods of preparing such solutions and their use in, for example, paints and sealants.

Disclosure of Invention

In a first aspect, there is provided a method of reducing odor by contacting a colloidal dispersion as described herein with an odorous compound. The colloidal dispersion is a stable colloidal dispersion comprising silica nanoparticles and metal ions, such as metal ions selected from the group consisting of copper, silver, zinc and iron ions.

In another aspect, a method of reducing odor by contacting a metal-containing silicate solution as described herein with an odorous compound is provided.

In some embodiments, a method for reducing odors in confined spaces such as rooms, buildings, tunnels, pipes, boxes, cabinets and the like is provided.

Some embodiments relate to a method for reducing the level of odorous contaminants in a confined space such as a room, building, or any other confined space where the presence of malodorous airborne substances or compounds may cause discomfort.

In the following description, reference to "colloidal dispersion" according to the invention should also be understood as reference to "metal-containing silicate solution" unless indicated otherwise or apparent from the context. In some embodiments, the colloidal dispersion is a dispersion of silica particles having a particle size of 3 nm to 100 nm to which metal ions are attached as described herein. In some other embodiments, a "colloidal dispersion" is a metal-containing silicate solution as described herein. In some further embodiments, a "colloidal dispersion" comprises both a dispersion of silica particles having a particle size of from 3 nm to 100 nm to which metal ions are attached and a metal-containing silicate solution.

Some embodiments relate to methods of treating air in ducts, living spaces, and other enclosed spaces to achieve odor control, for example, by spraying a composition (or sol) as disclosed herein, such as a sol containing ions of one or more metals selected from copper (Cu), silver (Ag), iron (Fe), and zinc (Zn), into the air of the enclosed space. Furthermore, the sols described herein may be used as coatings or impregnations on the surface of, for example, textiles, walls, or other components used in air filters or in contact with air, such as materials used in air ducts, to reduce the amount of odorous compounds in the air.

Thus, in some aspects, a method for reducing malodor in a confined space is provided comprising contacting a colloidal dispersion (also referred to as a sol) disclosed herein with air in the confined space. The sol may be contacted with the air by any means, such as by spraying directly into the air or by applying the sol to a surface that is in contact with the air in a confined space or a surface that is in contact with the air in a confined space, such as a wall, ceiling, furniture, wash basin (toilet basin), floor, textile, carpet, curtain, air filter, etc.

In some aspects, a method for deodorizing a solid material, such as a textile, a fibrous fabric, or a porous material, is provided comprising contacting the solid material with a sol disclosed herein. For example, malodour or risk of malodour in a solid material may be reduced by applying a sol as defined herein to the material in any way, e.g. by dipping the material into the sol, spraying the sol onto the material, brushing the sol onto the material, etc.

In some embodiments, the methods disclosed herein are performed by using a colloidal dispersion (sol) of silica particles having a particle size of 3 nm to 100 nm, said particles bearing ions of one or more metals selected from Cu, Ag, Zn and Fe at the surface of the particles.

Thus, also provided herein is a colloidal dispersion of silica particles having a particle size of from 3 nm to 100 nm, said particles bearing ions of one or more metals selected from Cu, Ag, Zn and Fe at the surface of the particles, and the use of such a dispersion in a method as mentioned herein, such as a method for reducing odour.

In some embodiments, a method is provided comprising preparing a colloidal dispersion by mixing a silica sol with one or more solutions of one or more salts of Cu, Ag, Zn and Fe to obtain a colloidal dispersion of silica particles bearing metal ions at their surfaces, and using the colloidal dispersion thus obtained in a method of reducing odor.

In some embodiments, a mixture of colloidal dispersions of silica particles (also referred to herein as "silica sols") is used, wherein the metal ions adsorbed on each component sol are different, for example a mixture of one silica sol having one type of metal ion selected from Cu, Ag, Zn and Fe ions adsorbed on the surface of the silica particles and another silica sol having another type of metal ion adsorbed on the surface of the silica particles. The other type of metal ion may also be selected from Cu, Ag, Zn and Fe ions, but in some embodiments it is selected from other metal ions, such as other transition metals.

In yet another embodiment, a mixture of silica sols of different particle sizes obtained by blending silica sols of different particle sizes having the same or different metal ions, for example selected from Cu, Ag, Zn and Fe ions, adsorbed on the surface of the particles is used.

In some embodiments, a stable colloidal dispersion is used that contains silica nanoparticles having at least one metal ion selected from Cu, Ag, Zn and Fe ions adsorbed on the surface, and optionally also another metal ion adsorbed on the surface.

Very advantageously, colloids with a high concentration of polyvalent metals, such as polyvalent transition metals or lanthanides, can be obtained according to the invention.

The particle size and particle size distribution of the colloidal dispersions used herein can be tailored to meet narrow specifications.

Finally, also provided herein is a stable colloidal dispersion comprising silica particles having a particle size of from 3 nm to 100 nm, said particles having ions of one or more metals selected from the group consisting of copper, silver, zinc and iron adsorbed on the surface of the particles.

In some embodiments, the colloidal dispersion is or comprises an aqueous silicate solution containing ions of one or more metals selected from Fe, Cu, Zn, or Ag.

Drawings

Figure 1 shows a textile mill apparatus for use in a method of treating fabric with a formulation according to the invention.

Detailed Description

Silica sol

The particles of the silica sol used to prepare the material of the invention are anionically charged and the sol is an anionic sol.

A suitable source of silica particles of the present invention is commercial silica sols. Such sols are aqueous dispersions of silica particles, and the particles are uniform silica spheres that have no internal surface area or detectable crystallinity. They are typically dispersed in an alkaline medium that reacts with the silica surface to produce a negative charge. Due to the negative charge, the particles repel each other, resulting in a stable product.

In some commercial products, the particle surface is modified with aluminosilicate ions to provide a fixed pH-independent negative charge to the surface, which will make the products more stable to gelation than the sols from which they are prepared. Trivalent aluminum atoms have replaced some of the tetravalent silicon atoms in the particle surface, creating a negative fixed charge that is independent of pH. The surface coverage of Al is much less than that corresponding to Langmuir (Langmuir) monolayers.

The solids content of the sol depends on the particle size and varies from less than 10 wt% silica of the smallest particles of 3 nm to about 50 wt% silica of the larger particles > 20 nm. Surface coverage of particles in aqueous silica solA surface hydroxyl group, a silanol group. The particle size of the silica sol used according to the invention is typically in the range of from 3 nm to 100 nm, preferably from 4 nm to 50 nm, more preferably from 5nm to 25 nm, even more preferably from 5nm to 15 nm, for example from 5nm to 12 nm, or from 5nm to 10 nm. The silica sol preferably has a thickness of typically 20 to 1000 m²Per g, preferably from 30 to 800 m²G, more preferably 100-600 m²G, even more preferably 200-600 m²(iv)/g, and most preferably 200-²Specific surface area per g (e.g. by SEARS titration or BET).

Stabilization of commercial silica sols is typically achieved by adjusting the pH of the sol to 8.0 to 10.0, typically by the addition of a base, typically sodium hydroxide solution. The sol also contains small amounts of other electrolytes such as sodium chloride and sodium sulfate.

The stability of high concentration silica sols is very sensitive to the presence of electrolytes. By using ion exchange resins, the electrolyte concentration can be minimized. The composite sol of the present invention can be prepared by using a commercial silica sol or a modified commercial silica sol, for example, by treating the sol with a sodium aluminate solution to generate aluminosilicate sites on the surface of the particles, thereby obtaining a silica sol stable in a pH range of 3 to 12, more particularly 4 to 11, by methods well known to those of ordinary skill in the art.

Thus, in some embodiments, at least some of the silica particles of the composite sols of the present invention have aluminosilicate sites on the surface of the particles.

A suitable method for introducing aluminosilicate sites on the surface of colloidal silica is to use a weak acid cation resin to remove sodium ions from the silica sol-sodium aluminate system, thus causing reaction of aluminate ions with the silica surface. In such systems, the pH typically does not drop below pH 5 even with an excess of weak acid cation exchange resin.

Will be directed to give the required number of aluminosilicate sites/nm²The calculated amount of sodium aluminate solution on the particle surface is simply added to the slurry of colloidal silica and resin.

Literature referenceThe generation of aluminosilicate sites on Silica surfaces is well described (e.g. in Iler, the chemistry of Silica, 1979, pages 407 to 409). Such a description also indicates that it is difficult to introduce far more than about 2 aluminosilicate sites/nm, for example²A silica surface.

When the aluminized silica particles are used in the composite sol of the present invention, the concentration of aluminosilicate sites on the surface of the silica particles is about 0.2 sites/nm²To about 2.0 sites/nm²In the range of, for example, 0.30 sites/nm²To 1.50 sites/nm²Or 0.3 sites/nm²To 1.25 sites/nm²Or 0.4 sites/nm²To 1.0 site/nm²E.g. 0.4 sites/nm²To 0.8 sites/nm²。

Stability of

The term stable as used in the present invention means that the product should be stable to gelling, which means that the relative viscosity should not increase more than 100% (e.g. 5 to 10 mPas) over a period of about two months. The term also refers to stability to precipitation; i.e. without significant precipitation of solid content, characterized in that, if stored under normal (e.g. ambient or optionally light-tight) conditions, no more than 20% of the solid matter precipitates and settles to a sludge at the bottom over a period of two months.

Metal ion

The metal used according to the invention is preferably selected from Cu, Ag, Fe and Zn, more preferably from Cu and Ag. In some embodiments, the metal used is Cu. In some other embodiments, the metal used is Ag. In some embodiments, the metal is a metal that can exist in more than one oxidation state, such as Cu or Fe. In some embodiments, the metal is selected from Cu, Fe, and Zn, for example, selected from Cu and Zn.

If further metal ions are present in the colloidal dispersion of the invention, the metal may for example be selected from Sc, Ti, V, Cr, Mn, Co, Ni and Ga.

The nanocomposites used according to the invention are prepared by contacting a non-metallic support material in the form of, for example, colloidal silica with a solution comprising metal ions as described herein. The reactants and products used in the various formulations and methods are in the field of colloid and colloid chemistry, and appropriate care must be taken to account for the concentration of the reactants and products, to maintain a high charge on the colloidal particles, to use high quality water, preferably deionized water, to observe the appropriate rate of component addition and order of addition, to operate within a conserved but realistic temperature range, and to provide sufficient stirring and agitation to maintain stability to gelling or aggregation of the reactants and products. The selection and optimization conditions of the foregoing types are considered to be within the ability of those of ordinary skill in the art in light of the present specification and the specific examples.

The colloidal silica sol used to prepare the composite sol of the present invention typically has 0.1 wt.% or less of SiO₂To the concentration of undiluted sol which may contain 50% by weight or more of SiO₂。

As used above, most soluble salts of the mentioned metals can be used for preparing the material of the present invention.

In order to achieve strong adsorption (attachment) of metal ions on the surface of the nano-sized carrier particles, the charge of the latter should be high, but of opposite sign to that of the metal ions.

The charge on the colloidal silica particles or silica particles in an aqueous environment increases exponentially with pH and is about 10 and very low (typically 10) at pH^-4) Almost 0.5 negative charge units/nm at electrolyte concentration²The surface of the particles. Colloidal silica has a local stability maximum at the point of zero charge, which occurs at about pH 2.0. The stability of the silica sol first decreases with pH and reaches a minimum around pH 6, after which the sol enters a region of high stability between pH 8 and pH 11.

Especially the stability of solutions of transition metals in water to gelation and flocculation is quite sensitive to pH. If the pH is raised to a few units above the natural pH of the solution, gelation and/or flocculation will occur. In experiments conducted by the present inventors, only a few drops, e.g. 3 to 5 drops of 1M NaOH (sample size is typically 50 g and drop weight from plastic pipette is typically 0.025 g) need to be added before flocs can be seen in the solution for most transition metal solutions. The exact value of the pH at which floc formation becomes visible to the naked eye depends on the type and concentration of the metal in the solution.

Although the silica sol is stable over a wide pH range, it is preferred to prepare the formulation of the invention over a pH range of 8 to 12, more particularly 9 to 11, with the silica sol being the most stable.

The concentration of the metal solution used according to the invention is preferably about 0.1 mM (10)^-4mol/L) to about 200 mM, such as about 0.2 mM to about 100 mM, such as about 0.5 mM to about 50 mM, or about 1 mM to about 20 mM, or about 2 mM to about 10mM, although both higher and lower concentrations are contemplated to be possible. The concentration of the metal in the composite sol will decrease slightly due to the dilution effect of the metal solution mixed with the silica sol. Thus, a composite sol can be prepared according to the present invention that contains from about 0.01 mM or less of metal cation to about 100 mM or more of metal cation, for example from about 0.05 mM to about 50 mM, or from about 0.1 mM to about 40 mM, or from about 0.5 mM to about 30 mM, or from about 1 mM to about 10mM of cation of one or more metals of the present invention.

In some embodiments, the silica sol used contains aluminosilicate modified silica particles. The adsorption of metal cations on the aluminosilicate-modified silica sol can be carried out over a wide pH range, such as a pH of about 3 to a pH of about 12, such as a pH of about 4 to a pH of about 11.5, or a pH of about 5 to a pH of about 11, such as a pH of about 6 to a pH of about 10.5. However, it is preferred to perform the adsorption in the pH range where the silica sol is most stable, i.e. in the alkaline range, e.g. in the pH range of about 8 to about 11, e.g. about 8 to 10.5.

The pH can be controlled in different steps of the process for preparing the composite sol of the present invention. In most of the examples described below, the silica sol is added to a metal salt solution and then the pH is adjusted to 10 to 11 by adding a 1M NaOH-solution to the metal containing silica sol. Alternatively, the base may be added to the silica sol prior to adding the sol to the metal salt solution or prior to adding the metal salt solution to the sol.

The rate at which the metal salt solution can be mixed with the silica sol without destabilizing the sol depends on the conditions used in the preparation. The rate of addition may be rapid, so long as an increment of added salt is rapidly dispersed throughout the sol, and vice versa. However, the robustness of the colloidal system according to the invention is quite surprising. In many small scale preparations, it is practical to inject silica sols into magnetically agitated metal salt solutions in very short periods of time, e.g., less than 10 to 15 seconds, without destabilizing the sol. However, in most small-scale laboratory preparations, for example those of sols containing about 1000ppm of metal, longer addition times, typically 2 to 3 minutes, are used in order to be within safe limits with regard to good stability to gelling or aggregation. A similar time scale would be suitable for larger scale preparations provided that sufficient stirring or agitation is used.

In this specification, any ppm value is calculated on a weight basis. Thus, for example, in a metal ion solution containing n ppm of metal, there is n mg of metal per kg of solution. Also, in the silica sol containing n ppm of metal, n mg of metal is present per kg of the metal-containing silica sol.

For the purposes of the present invention, and unless otherwise indicated or apparent from the context, "metal" means a metal selected from the group consisting of copper, silver, iron and zinc, preferably copper and silver.

Sols of a given concentration of a selected metal can be prepared in different ways. In one method, an amount of a metal solution is added to a silica sol having a particular silica particle size and concentration value. In another method, the same amount of metal solution is added to a sol having the same silica particle size but a higher, e.g., four times higher, silica concentration. The total concentration of the selected metals was the same in both sols, but the metal concentration on the particle surface of the former sol was higher than the metal concentration on the particle surface of the latter sol (four times higher). Thus, a material of the present invention having a given total concentration of metal and a given particle size can be obtained by combining a high concentration of particles, i.e. a high concentration of silica, with a low concentration of metal on the surface of the particles, or by combining a high surface concentration of metal with a low silica concentration.

SiO of the composite sol of the invention₂The concentration is typically from about 0.001 wt%, for example about 0.005 wt%, or about 0.01 wt%, or about 0.05 wt%, or about 0.1 wt%, or about 0.5 wt%, or about 1 wt%, or about 2 wt%, to about 25 wt%, or about 20 wt%, or about 15 wt%, or about 10 wt%, or about 8 wt%, or about 5 wt% SiO₂The remainder (up to 100% in total) typically comprises the selected metal ion or ions and water. For example, in some embodiments, the SiO of the composite sol of the present invention₂The concentration ranges from about 0.005 wt% to about 15 wt%, for example from about 0.1 wt% to about 10 wt%, or from about 0.5 wt% to about 5 wt%.

Distribution of metal on particle surface

Knowing the concentration of the metal in the sol, the atomic weight of the metal in question, the specific surface area of the silica particles and the weight percent concentration of silica, the per nm can be calculated according to equation (1)²SiO₂Surface concentration C of metal atoms (ions) on the particle surface_s：

C_s＝60M₁/(M_metAK)＝(60/AK)(M₁/M_met) (1)

Wherein

M₁Is the concentration of the metal in the sol, in ppm,

M_metis the atomic weight of the metal, in g,

a is the specific surface area of the sol particles in m²In units of/g, and

k is the concentration of silica in weight percent

The metal ion concentration at the surface of the final particles comprising the material of the present invention is about 0.0005, or about 0.004, or about 0.005, or about 0.006, or about 0.008, or about 0.01, or about 0.02, or about 0.00050.03, or about 0.04, or about 0.05, or about 0.08, or about 0.1 metal ions/nm²To about 5, or to about 4, or to about 3, or to about 2 metal ions/nm²E.g. to about 1 metal ion/nm²Within the range. In some embodiments, the colloidal silica sols of the present invention have a metal ion concentration on the particle surface of about 0.01 metal ions/nm²To about 2 metal ions/nm²E.g., about 0.01 to about 1 metal ion/nm²Or from about 0.05 to about 1 metal ion/nm²More preferably from about 0.1 to about 0.8 metal ions/nm²Within the range.

In the case of silica particles having aluminosilicate sites on the surface, it is believed that typically one metal ion adsorbs on one Al-Si site, but not all Al-Si sites may have adsorbed transition metal species adsorbed on them. The number ratio between metal ions and Al-Si sites may vary from 0.01 to about 1.0, but is preferably between 0.05 and 0.8, for example between 0.1 and 0.6.

According to the present invention, "adsorption" refers to the attachment of metal ions to a surface, whether by electrostatic or ionic bonding or any other type of bonding such as partial covalent bonding. The adsorption of metal ions on the surface of the silica particles can be monitored by measuring the Zeta potential of the colloidal sol.

The loading of the metal ions relative to the silica particles can be expressed as the number of metal cations per unit of surface area of the silica particles. This is the "specific metal loading" or surface concentration c of the metal cation_s。

The support of the metal ion on the silica particles in the composite sol can also be represented by the number n of metal ions in each silica particle_m. However, for very low metal loadings, it may be more meaningful to express the relationship between the number of metal ions in the silica sol and the number of particles as the inverse of the number of metal ions per silica particle, i.e. the inverse of the number of metal ions per silica particle

。

And c_sThe relationship between is given by equation (2):

(2)

wherein

n_mIs the number of metal ions per silica particle in the composite sol,

A_pis the surface area of one silica particle in the composite sol, and

c_sis the surface concentration of metal ions on the surface of the silica particles.

Equation (2) showsWith the surface area A of the particles_pAnd the surface concentration c of metal ions on the surface of the silica particles_sIn inverse proportion.

For c_s0.0005 ions/nm²Table 1 shows

I.e. how the number of silica particles per ion varies as a function of the silica particle size.

TABLE 1 number of silica particles per metal ion as a function of particle size in composite sols, c_s0.0005 ions/nm²

Particle size (nm)	Number of particles/ion
		5	25
7	13
		12	4.4
22	1.3

As can be seen from Table 1, at c_s0.0005 ions/nm²And a particle size of 5nm, 4 of the 100 silica particles in the composite sol of the invention carry one metal cation, i.e. 25 particles are present for each metal ion in the composite sol.

In other words, the number ratio of metal ions to silica particles in the composite sol of the invention can vary from a high value, at which more than one metal ion is present per silica nanoparticle, for example more than 10 metal ions per silica nanoparticle, to a low value, at which more than one silica nanoparticle is present per metal ion, for example more than 10 silica nanoparticles per metal ion.

In some embodiments, the metal ion is present at least 0.0005 ions/nm²At least 0.001 ions/nm²At least 0.005 ions/nm²At least 0.01 metal ions/nm²At least 0.02 metal ions/nm²At least 0.05 metal ions/nm²At least 0.08 metal ions/nm²Or at least 0.1 metal ions/nm²(ii) a And at most 5 metal ions/nm²At most 2 metal ions/nm²At most 1 metal ion/nm²At most 0.8 metal ions/nm²At most 0.6 metal ions/nm²At most 0.4 metal ions/nm²At most 0.2 metal ions/nm²Or at most 0.15 metal ions/nm²Is present at the surface of the nanoparticles.

In some embodiments, the metal ion is present at 0.0005 to 0.8 metal ions/nm²0.001 to 0.8 metal ions/nm²Or 0.005 to 0.8 metal ions/nm²For example 0.0005 to 0.5 metal ions/nm²0.001 to 0.5 metal ions/nm²0.0005 to 0.2 metal ions/nm²0.001 to 0.2 metal ions/nm²Or 0.005 to 0.2 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.8 metal ions/nm²E.g. 0.02 to 0.8 metal ions/nm²0.04 to 0.8 metal ions/nm²0.06 to 0.8 metal ions/nm²Or 0.08 to 0.8 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.5 metal ions/nm²E.g. 0.02 to 0.5 metal ions/nm²0.04 to 0.5 metal ions/nm²0.06 to 0.5 metal ions/nm²Or 0.08 to 0.5 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.2 metal ions/nm²E.g. 0.02 to 0.2 metal ions/nm²0.04 to 0.2 metal ions/nm²0.06 to 0.2 metal ions/nm²Or 0.08 to 0.2 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.15 metal ions/nm²E.g. 0.02 to 0.15 metal ions/nm²0.04 to 0.15 metal ions/nm²0.06 to 0.15 metal ions/nm²Or 0.08 to 0.15 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.12 metal ions/nm²E.g. 0.02 to 0.12 metal ions/nm²0.04 to 0.12 metal ions/nm²0.06 to 0.12 metal ions/nm²Or 0.08 to 0.12 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the metal ion is present at 0.01 to 0.1 metal ions/nm²E.g. 0.02 to 0.1 metal ions/nm²0.04 to 0.1 metal ions/nm²0.06 to 0.1 metal ions/nm²Or 0.08 to 0.1 metal ions/nm²A surface concentration in the range is present at the surface of the nanoparticle.

In some embodiments, the colloidal dispersion contains 100ppm to 1000ppm by weight of metal ions, 1% to 20% by weight of SiO₂The silica particles have a size of 3 nm to 50 nm.

In some embodiments, the colloidal dispersion contains 100ppm to 500ppm by weight of metal ions, 2% to 10% by weight of SiO₂And wherein the silica particles have a size of 3 nm to 20 nm.

In some embodiments, the colloidal dispersion contains 200ppm to 500ppm by weight of metal ions, 2% to 8% by weight of SiO₂And wherein the silica particles have a size of 3 nm to 10 nm.

In some embodiments, the colloidal dispersion contains 200ppm to 400ppm by weight of metal ions, 3% to 7% by weight of SiO₂And wherein the silica particles have a size of 3 nm to 7 nm; for example, a colloidal dispersion as defined herein may contain about 300ppm by weight of metal ions, about 5% by weight of SiO₂The silica particles are about 5nm in size. In some of these embodiments, the metal is selected from copper (Cu)²⁺) Silver (Ag)⁺) And zinc (Zn)²⁺). In some other of these embodiments, the metal is selected from copper (Cu)²⁺) Silver (Ag)⁺) And iron (Fe)²⁺And Fe³⁺In particular Fe³⁺). In some embodiments, the metal is copper (Cu)²⁺). In some other embodiments, the metal is silver (Ag)⁺). In other embodiments, the metal is zinc (Zn)²⁺). In other embodiments, the metal is iron (Fe)²⁺Or Fe³⁺In particular Fe³⁺)。

In some embodiments, the molar ratio of metal ions to silica particles (i.e., the number of ions per particle) is from 1 to 20, or from 1 to less than 10, e.g., from 1 to 9, from 1 to 8, from 1 to 7, from 1 to 6, from 1 to 5, from 1 to 4, or from 1 to 3. In some of these embodiments, the molar ratio is at least 9, or at least 8, or at least 7, or at least 6, or at least 5, or at least 4, or at least 3, or at least 2.

In still other of these embodiments, more than one metal is present in the colloidal dispersion, e.g., the metal is a mixture of silver and copper.

The carrier liquid of the colloidal dispersion is typically deionized water. However, other liquids, such as organic solvents, may also be included, if appropriate.

Metal-containing silicate solution

The silicate solution used according to the invention is a "non-true solution" or a "colloidal solution". Depending on, for example, the silicate concentration, at least a portion of the silicate does not dissolve at the molecular level, but oligomers of different sizes may form.

The silicate used according to the invention may be, for example, an alkali metal silicate or a quaternary ammonium silicate. In some embodiments, the silicate of the present invention is an alkali metal silicate. In some other embodiments, the silicate is a quaternary ammonium silicate.

In some embodiments, the silicate is a silicate containing R₄N⁺Quaternary ammonium silicates of the type ammonium ion in which each R is independently selected from aliphatic or aromatic groups, for example C1-C6 alkyl or phenyl, optionally bearing other functional groups such as hydroxyl functional groups. For example, in some embodiments, the quaternary ammonium silicate is a tetraalkylammonium silicate salt, wherein the alkyl group can contain, for example, 1 to 6 carbon atoms, or 1 to 3 carbon atoms, e.g., the alkyl group can be a methyl groupAnd (4) a base. Quaternary ammonium silicates useful according to the present invention can be prepared as described in U.S. patent No. 9,695,111, the teachings of which are incorporated herein by reference.

Commercially available silicate solutions are also suitable sources of the soluble silicates of the present invention. For example, in some embodiments, the silicate solution is a commercially available alkali silicate solution, such as that sold by PQ Corporation (www.pqcorp.com)).

In alkali silicate solutions, the key variable is the alkali metal, usually lithium (Li), sodium (Na) or potassium (K); SiO in silicate₂Ratio to alkali metal oxide; and the concentration of silicate in the solution.

SiO₂Ratio to alkali metal oxide (SiO)₂/M₂O) may be expressed as a weight ratio or a molar ratio. In the case of sodium silicate, these two ratios are almost the same. Thus, the weight ratio of sodium silicate is converted to a molar ratio by a multiplication factor of 1.03; for potassium silicate, the weight ratio is multiplied by a factor of 1.57 to obtain the molar ratio. For lithium silicate, the factor is 0.50.

For sodium silicate, SiO₂/Na₂The O weight ratio is in the range of about 1.6 to about 4.

SiO of potassium silicate₂/K₂The O weight ratio varies between about 1.5 to about 2.5, which corresponds to a molar ratio of 2.3 to 3.8.

SiO of lithium silicate₂/Li₂The O weight ratio varies from about 6.0 to about 20.0, which corresponds to a molar ratio of about 3.0 to about 10.0.

During the development of concentrated silica sols stabilized with NaOH, SiO's at about 4:1 to 25:1 were found₂/Na₂In the O ratio range, the concentrated compositions are generally unstable and eventually gel. When a 3.25 ratio sodium silicate solution is added to the concentrated silica sol, for example to add SiO₂/Na₂When the O ratio was decreased from 100:1 to 5:1, a gel was immediately formed. However, it was found that by aging or heating the gel, a stable solution was formed again. Thus, SiO₂/Na₂O in a weight ratio of 4.2:1 to 6:1 and 10-30% SiO₂The silicate solution may be prepared from the original 5-25 nm particlesThe silica sol of (4).

If changed to 3.25 (SiO)₂/K₂O) molar ratio of potassium silicate to the alkali-stable concentrated silica sol, no gelling occurs. Thus, a silica concentration of 15-30% by weight and SiO may be used₂/K₂A stable mixture of colloidal silica and potassium silicate was prepared with an O molar ratio of 11:1 to 24: 1.

Similarly, a silica concentration of 15-30 wt.% and SiO may be used₂/Li₂A stable mixture of colloidal silica and lithium silicate was prepared with a molar ratio of O from 4:1 to 25: 1.

Alkali metal silicate solutions typically contain both silicate ions and colloidal polymeric (including oligomeric) silicate species, which are driven by monomeric SO₄ ^4-Polymerization of the units to form siloxane (Si-O-Si) bonds. Polymeric materials, which may be linear or cyclic, do not have uniform dimensions. The degree of polymerization generally follows SiO₂/Me₂The O ratio increases and the silicate concentration increases.

Generally, the term "silicate solution" as used herein refers to a liquid phase containing polymeric (including oligomeric) silicate species, although it should be recognized that some silicates may also be present as dissolved non-polymeric species.

Thus, in some embodiments, the formulations according to the present invention comprise from about 2% to about 30% by weight of SiO, based on the total weight of the formulation₂Containing SiO in a concentration of about 6:1 to about 2:1₂/Na₂Sodium silicate in O mole ratio.

In some embodiments, the formulations according to the present invention comprise from about 2% to about 30% by weight of SiO, based on the total weight of the formulation₂Containing SiO in a concentration of about 2:1 to about 25:1₂/K₂Potassium silicate in molar ratio of O.

In some embodiments, the formulations according to the present invention comprise from about 2% to about 30% by weight of SiO, based on the total weight of the formulation₂Containing SiO in a concentration of about 2:1 to about 25:1₂/Li₂Lithium silicate in molar ratio of O.

In some further embodiments, the formulation according to the invention contains more than one type of silicate, for example more than one type of quaternary ammonium silicate, or more than one type of alkali metal silicate, or mixtures thereof. For example, in some embodiments, the formulation contains lithium silicate and at least one other type of silicate selected from sodium silicate and potassium silicate. In some embodiments, the formulation contains sodium silicate and at least one other type of silicate selected from lithium silicate and potassium silicate. In some embodiments, the formulation contains potassium silicate and at least one other type of silicate selected from lithium silicate and sodium silicate.

In some embodiments, the formulation contains lithium silicate and sodium silicate. In some other embodiments, the formulation contains lithium silicate and potassium silicate. In some other embodiments, the formulation contains sodium silicate and potassium silicate.

The formulation contains one or more metals selected from the group consisting of Fe (iron), Cu (copper), Zn (zinc) and Ag (silver). Typically, the metal is present in the formulation in an amount of from 1ppm to 5000ppm (all ppm values being by weight), for example from 10ppm to 5000ppm, based on the total amount of the formulation. In some embodiments, the metal is present in an amount from 10ppm to 4000ppm, e.g., from 10ppm to 3500 ppm, from 10ppm to 3000ppm, from 10ppm to 2500 ppm, from 10ppm to 2000 ppm, from 10ppm to 1500 ppm, from 10ppm to 1000ppm, from 10ppm to 800 ppm, or from 10ppm to 700 ppm, or from 10ppm to 500 ppm.

The "metal" in the formulations of the invention as referred to herein above is Fe, Cu, Zn or Ag, i.e. it does not include alkali metals, such as those inherently present in alkali metal silicates.

In some embodiments, the metal is present in the formulation in an amount of 100ppm to 5000ppm, 100ppm to 4000ppm, e.g., 100ppm to 3500 ppm, 100ppm to 3000ppm, 100ppm to 2500 ppm, 100ppm to 2000 ppm, 100ppm to 1500 ppm, 100ppm to 1000ppm, 100ppm to 800 ppm, or 100ppm to 500 ppm.

In some other embodiments, the metal is present in the formulation in an amount of 200ppm to 5000ppm, 200ppm to 4000ppm, e.g., 200ppm to 3500 ppm, 200ppm to 3000ppm, 200ppm to 2500 ppm, 200ppm to 2000 ppm, 200ppm to 1500 ppm, 200ppm to 1000ppm, 200ppm to 800 ppm.

In some other embodiments, the metal is present in the formulation in an amount of 300ppm to 5000ppm, 300ppm to 4000ppm, e.g., 300ppm to 3500 ppm, 300ppm to 3000ppm, 300ppm to 2500 ppm, 300ppm to 2000 ppm, 300ppm to 1500 ppm, 300ppm to 1000ppm, 300ppm to 800 ppm.

In some other embodiments, the metal is present in the formulation in an amount from 400ppm to 5000ppm, 400ppm to 4000ppm, e.g., 400ppm to 3500 ppm, 400ppm to 3000ppm, 400ppm to 2500 ppm, 400ppm to 2000 ppm, 400ppm to 1500 ppm, 400ppm to 1000ppm, 400ppm to 800 ppm.

In some other embodiments, the metal is present in the formulation in an amount of 500ppm to 5000ppm, 500ppm to 4000ppm, e.g., 500ppm to 3500 ppm, 500ppm to 3000ppm, 500ppm to 2500 ppm, 500ppm to 2000 ppm, 500ppm to 1500 ppm, 500ppm to 1000ppm, or 500ppm to 800 ppm.

In some of these embodiments, the formulations according to the invention contain SiO having a ratio of about 6:1 to about 2:1, such as about 5:1 to about 2:1, such as about 4.5:1 to about 2.5:1₂/Na₂Sodium silicate in an amount corresponding to about 1% to about 30%, or about 2% to about 25%, or about 3% to about 20%, or about 4% to about 15% by weight of SiO based on the total weight of the formulation₂And (4) concentration.

In some embodiments, formulations according to the invention contain SiO having a ratio of about 25:1 to about 2:1, e.g., about 10:1 to about 2:1, or about 5:1 to about 2:1₂/K₂O in a molar ratio corresponding to about 1% to about 30%, or about 2% to about 25%, or about 3% to about 20%, or about 4% to about 15% by weight of SiO based on the total weight of the formulation₂And (4) concentration.

In some embodiments, the formulations according to the invention contain SiO between about 25:1 and about 2:1, such as between about 10:1 and about 2:1, or between about 5:1 and about 2:1₂/Li₂Lithium silicate in a molar ratio of O corresponding to about 1% to about 30% by weight based on the total weight of the formulationWeight%, or from about 2 to about 25 weight%, or from about 3 to about 20 weight%, or from about 4 to about 15 weight% of SiO₂And (4) concentration.

For example, in some embodiments, the formulation is a solution containing ions of one or more metals as defined above and one or more alkali metal silicates, each alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) of from 25:1 to 2:1, such as from 6:1 to 2:1, such as from 5:1 to 2:1, or from 4.5:1 to 2:1, such as from 4.5:1 to 2.5:1, or from 4.5:1 to 3:1, or from 4:1 to 3:1₂:Me₂O), the one or more metals are present in a concentration of from 10ppm to 5000ppm, such as from 100ppm to 5000ppm, from 200ppm to 4000ppm, or from 200ppm to 3500 ppm, such as from 200ppm to 3000ppm, or from 200ppm to 2500 ppm, or from 200ppm to 2000 ppm, such as from 200ppm to 1500 ppm, based on the weight of the formulation, and the one or more alkali metal silicates are present in a concentration corresponding to from about 1% to about 30%, such as from about 2% to about 25%, or from about 3% to about 20%, or from about 4% to about 15%, based on the weight of the formulation, of SiO₂The total amount of concentration present.

In some embodiments, the formulation is a solution containing metal ions, such as transition metal ions, as defined above, and an alkali metal silicate selected from lithium silicate, sodium silicate and potassium silicate, wherein the silica is in contact with an alkali metal oxide (SiO)₂:Me₂O) is from 25:1 to 2:1, such as from 6:1 to 2:1, such as from 5:1 to 2:1, or from 4.5:1 to 2:1, such as from 4.5:1 to 2.5:1, or from 4.5:1 to 3:1, or from 4:1 to 3:1, wherein the metal is present in a concentration of from 10ppm to 5000ppm, such as from 100ppm to 5000ppm, from 200ppm to 4000ppm, or from 200ppm to 3500 ppm, such as from 200ppm to 3000ppm, or from 200ppm to 2500 ppm, or from 200ppm to 2000 ppm, such as from 200ppm to 1500 ppm, based on the weight of the formulation, and the alkali metal silicate is present in a concentration corresponding to from about 1% to about 30%, such as from about 2% to about 25%, or from about 3% to about 20%, or from about 4% to about 15%, based on the weight of the formulation, of SiO₂The total amount of concentration present.

In some embodiments, the formulation is a solution containing a metal ion and an alkali metal silicate, the metal ion being 2 based on the weight of the formulation0ppm to 5000ppm, such as 50ppm to 5000ppm, 100ppm to 4000ppm, or 200ppm to 3500 ppm, such as 300ppm to 3000ppm, or 400ppm to 2500 ppm, or 500ppm to 2000 ppm, such as 600 ppm to 1500 ppm, the alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO 1 to 3: 1) of 15:1 to 2:1, such as 6:1 to 2:1, such as 5:1 to 2:1, or 4.5:1 to 2:1, such as 4.5:1 to 2.5:1, or 4.5:1 to 3:1, or 4:1 to 3:1₂:Me₂O) at a concentration corresponding to about 1% to about 30%, for example about 2% to about 25%, or about 3% to about 20%, or about 4% to about 15%, SiO by weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 5000ppm, or 200ppm to 3500 ppm, such as 200ppm to 3000pmm, or 200ppm to 2500 ppm, or 200ppm to 2000 ppm, such as 200ppm to 1500 ppm, based on the weight of the formulation, and an alkali metal silicate having a molar ratio of silicon dioxide to alkali metal oxide (SiO 1 to 2: 1) of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 5000ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 4000ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions and an alkali metal silicate, the metal ions being based100ppm to 3500 ppm by weight of the formulation, the alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 2% to about 20% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 3000ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 2500 ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 2000 ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 100ppm to 1500 ppm based on the weight of the formulation and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions and alkali metal silicate, the metal ions being from 100ppm to 1000ppm based on the weight of the formulation, andthe alkali metal silicate has a molar ratio of silica to alkali metal oxide (SiO) of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some embodiments, the formulation is a solution containing metal ions in the range of 300ppm to 5000ppm, such as 300ppm to 4000ppm, or 400ppm to 3000pmm, or 500ppm to 2500 ppm, based on the weight of the formulation, and an alkali metal silicate having a silica to alkali metal oxide molar ratio (SiO) in the range of 5:1 to 2:1₂:Me₂O) in a concentration corresponding to about 1% to about 30% SiO, based on the weight of the formulation₂And (4) concentration.

In some of these embodiments, the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) is 4.5:1 to 2: 1.

In still other of these embodiments, the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) is 5:1 to 2.5: 1.

In still other of these embodiments, the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) is 4.5:1 to 2.5: 1.

In still other of these embodiments, the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) is 5:1 to 3: 1.

In still other of these embodiments, the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) is 4.5:1 to 3: 1.

In some embodiments, the formulation is 100ppm to 5000ppm of a metal ion based on the weight of the formulation; and the molar ratio of silica to alkali metal oxide (SiO)₂:Me₂O) a mixture of alkali metal silicate solutions of 5:1 to 2:1, the alkali metal silicate being present in an amount corresponding to about 1 wt.% to about 30 wt.%, or about 2 wt.% to about 25 wt.%, or about 3 wt.% to about 20 wt.%, or about 4 wt.% to about 15 wt.%, or about 5 wt.% to about 10 wt.% of SiO, based on the total weight of the formulation₂And (4) concentration.

In some embodiments, the formulation contains one or more surfactants selected from the group consisting of nonionic surfactants, amphoteric (or zwitterionic) surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorinated surfactants, and polymeric surfactants. In some embodiments, the surfactant is a nonionic surfactant. For example, in some embodiments, the formulation contains from 0.01% to 5%, such as from 0.02% to 2%, or from 0.05% to 1%, such as from 0.1% to 0.5%, of a surfactant or mixture of surfactants, based on the weight of the formulation.

The formulations according to the invention are prepared by mixing a silicate solution with a solution comprising metal ions, such as transition metal ions or ions of any of the metals as mentioned above. Care must be taken with respect to reactant and product concentrations, for example, using quality water, preferably deionized water, observing the appropriate component addition rates and order of addition, operating within a conserved but realistic temperature range and providing adequate stirring and agitation.

The concentration of silica used in the various formulations of the present invention is from one (1) weight percent SiO₂Or lower to commercially available undiluted solutions of alkali metal silicates which may contain 25% by weight or more, for example 5% to 20% by weight of SiO₂。

In some embodiments, the formulation is a lithium silicate solution comprising a metal ion and lithium silicate, the metal ion having a concentration of at least 10ppm, more preferably at least 100ppm, or at least 200ppm, and at most 5000ppm, such as at most 4500 ppm, at most 4000ppm, at most 3500 ppm, at most 3000ppm, such as at most 2500 ppm, at most 2000 ppm, at most 1800 ppm, at most 1500 ppm, at most 1000ppm, at most 800 ppm, at most 700 ppm, or at most 500ppm based on the total weight of the solution, the lithium silicate having an SiO of about 6:1 to about 2:1, such as about 5:1 to about 3:1, about 4:5 to about 3:1, or about 4:1 to about 3:1, such as about 3.5:1 to about 3:1₂:Li₂O molar ratio, the concentration of which is at least 2%, or at least 3%, based on the total weight of the solution, for example toAt least 4%, or at least 5% and at most 25%, or at most 20%, or at most 18%, or at most 16%, or at most 10%, or at most 8%.

In some embodiments, the formulation is a sodium silicate solution containing metal ions at a concentration of at least 10ppm, more preferably at least 100ppm, or at least 200ppm, and at most 5000ppm, such as at most 4500 ppm, at most 4000ppm, at most 3500 ppm, at most 3000ppm, such as at most 2500 ppm, at most 2000 ppm, at most 1800 ppm, at most 1500 ppm, at most 1000ppm, at most 800 ppm, at most 700 ppm, or at most 500ppm, and sodium silicate having an SiO of about 6:1 to about 2:1, such as about 5:1 to about 3:1, about 4:5 to about 3:1, or about 4:1 to about 3:1, such as about 3.5:1 to about 3:1, based on the total weight of the solution₂:Na₂An O molar ratio at a concentration of at least 2%, or at least 3%, such as at least 4%, or at least 5% and at most 25%, or at most 20%, or at most 18%, or at most 16%, or at most 10%, or at most 8%, based on the total weight of the solution.

In some embodiments, the formulation is a lithium silicate solution comprising a metal ion at a concentration of at least 10ppm, more preferably at least 100ppm, or at least 200ppm, and at most 5000ppm, such as at most 4500 ppm, at most 4000ppm, at most 3500 ppm, at most 3000ppm, such as at most 2500 ppm, at most 2000 ppm, at most 1800 ppm, at most 1500 ppm, at most 1000ppm, at most 800 ppm, at most 700 ppm, or at most 500ppm, and potassium silicate having an SiO of about 6:1 to about 2:1, such as about 5:1 to about 3:1, about 4:5 to about 3:1, or about 4:1 to about 3:1, such as about 3.5:1 to about 3:1, based on the total weight of the solution₂:K₂An O molar ratio at a concentration of at least 2%, or at least 3%, such as at least 4%, or at least 5% and at most 25%, or at most 20%, or at most 18%, or at most 16%, or at most 10%, or at most 8%, based on the total weight of the solution.

The metal ion is a cation of any one or more of the metals mentioned herein. In some embodiments, the metal ion is selected from Zn, Fe, Cu, and Ag; for example selected from Zn, Fe and Cu; or selected from Zn and Cu; or a cation of any one or more metals selected from Fe and Cu. In some embodiments, the metal is Zn. In some embodiments, the metal is Fe. In some embodiments, the metal is Cu. In some embodiments, the metal is Ag.

In the solution defined herein, the silicate and metal ions selected from Zn, Fe, Cu and Ag form metal silicate species which are not considered particles but may be small metal-containing oligomeric and/or polymeric species typically less than 3 nm in size, for example about 2 nm or less. These materials may be referred to herein as "silicate particles with metal ions".

Method for producing metal-containing silicate solutions

Also provided herein is a process for preparing an aqueous alkali metal silicate solution containing ions of a metal having an atomic number selected from the group consisting of atomic numbers 21-31, 39-50, 57-82, and 89-93, said process comprising mixing an aqueous silicate solution with an aqueous solution of a water-soluble salt of said metal. A surprising feature of the process described herein is that the process does not involve the use of complexing or chelating agents. Thus, in the process of the present invention, the metal as defined above need not be reacted with a complexing or chelating agent prior to mixing with the aqueous silicate solution. Thus, preferably, the formulation is prepared with an aqueous solution of a water-soluble salt of the metal, which aqueous solution is free of complexing agents for the metal ions; the process of the present invention does not include reacting the metal cation with a complexing agent.

Use of colloidal dispersions

The colloidal dispersions provided herein are useful for removing gaseous compounds and/or odorous compounds. The term "gaseous compound" or "gas" or the like refers to any molecule or compound that can exist as a gas or vapor. The term "odorous compound" or "odor" or the like refers to any molecule or compound detectable by the olfactory system, e.g. at a certain gas phase concentration, the so-called odor threshold, which is perceivable by the human olfactory sense. The odorous compounds may be present as gaseous compounds, but also in other media, such as liquids, from which they may evaporate. The term "remove" refers to the effect of reducing the concentration of gaseous and/or odorous compounds, for example, in a confined space or in the vicinity of an object from which the gaseous and/or odorous compounds may otherwise be released.

The method of reducing odor as provided herein generally comprises contacting a particle as defined herein or a colloidal dispersion as defined herein with an odorous compound. The odorous compound may be selected from compounds such as thiols, ammonia, amines, sulfides, disulfides, trisulfides, thiols, ketones, diketones, carboxylic acids, aldehydes, terpenes.

Unless otherwise indicated or apparent from the context, the term "particle" or "nanoparticle" refers to a silica particle as defined herein that has adsorbed one or more metal ions.

The term "colloidal dispersion" as used herein refers to a stable colloidal dispersion of silica particles as defined herein having adsorbed one or more metal ions, unless otherwise indicated or apparent from the context.

Also provided herein is a substrate treated with the colloidal dispersion as provided herein. In one embodiment, the substrate comprises a nonwoven, woven, or paper fabric; for example, the substrate may be part of a filtration device, such as an air filter, or part of furniture, wallpaper, curtains, packaging, and the like.

Thus, in some embodiments, a nonwoven or woven fabric is provided with

(i) A plurality of silica particles having a particle size of 3 nm to 100 nm, the particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles and/or

(ii) A plurality of silicate particles bearing ions of one or more metals selected from the group consisting of copper, silver, zinc and iron.

Thus, some embodiments include contacting the nonwoven or woven fabric with:

(i) colloidal dispersion of silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles, and/or

(ii) An aqueous silicate solution containing metal ions selected from the group consisting of copper, silver, zinc and iron ions.

Some additional embodiments include nonwoven or woven fabrics that have been treated as described herein.

Thus, in some embodiments, the compositions of the present invention are used to treat textiles to provide them with resistance to malodours from sources such as sweat, smoke, etc. or to provide them with deodorising properties. For example, the step of impregnating any textile may be applied in a textile mill setting, as generally shown in fig. 1. In such an arrangement, the fabric is fed into a bath containing an aqueous dispersion of metal ion-bearing silica particles as described herein, for example containing the particles of the invention at a concentration of from 0.001 wt% to 10 wt%, or from 0.01 wt% to 1 wt%, for example 0.1 wt%; or into an aqueous silicate solution as disclosed herein.

The fabric is contacted with the bath for a time sufficient to allow sufficient wetting by the liquid composition. The subsequent steps are those usually applied for the wet treatment of textiles, such as mechanical dehumidification, followed by vacuum dehumidification, straightening of the fabric and drying of the fabric.

In some other embodiments, the compositions of the present invention may be incorporated into laundry detergents, such as liquid laundry detergents, or into fabric conditioners, such as liquid fabric softeners. For example, the compositions (dispersions, solutions) of the present invention may be included in such products in an amount of from 5% to 50% by volume, such as from 5% to 25% by volume, or from 5% to 20% by volume, or from 10% to 25% by volume, based on the volume of the final product. In addition to the compositions of the present invention, the detergent or conditioner may contain any conventional ingredients used in such products.

In some other embodiments, the compositions of the present invention may also be included in products for cleaning and removing malodours, for example in washing machines. For example, the compositions (dispersions, solutions) of the invention may be included in such products in an amount of from 5% to 50% by volume, such as from 5% to 25% by volume, or from 5% to 20% by volume, or from 10% to 25% by volume.

In some other embodiments, the compositions of the present invention are included in liquid products for removing malodors emanating from liquid phases such as may be found in sewers, plume, and the like. For example, the compositions (dispersions, solutions) of the invention may be included in such products in an amount of from 5% to 50% by volume, such as from 5% to 25% by volume, or from 5% to 20% by volume, or from 10% to 25% by volume.

Advantageously, treatment of textiles with the formulations of the present invention may provide a number of other properties to the textile in addition to anti-odour properties, for example one or more properties selected from:

improved wicking, i.e. the fabric feels drier, as moisture wicks from the body to the fabric surface where it evaporates,

-improved dry soil repellency and/or dry soil repellency,

increased friction between fibres, higher tensile strength and improved abrasion resistance,

-an improved fabric structure and seam release,

-dry hand, and

matting the fabric.

The textile treated according to the invention may be of any type, for example, it may be intended for use in air filters, upholstery, curtains and the like, or in garments such as T-shirts, underwear, socks and the like.

The amount of particles present in or on the substrate may vary depending on the nature of the substrate and its intended application. In some embodiments, for example, the dry solids addition level is from about 0.001 wt% to about 20 wt%, in some embodiments, from about 0.01 wt% to about 10 wt%, and in some embodiments, from about 0.1 wt% to about 4 wt%. The term "solids addition level" refers to the value obtained by subtracting the weight of untreated substrate from the weight of treated substrate (after drying), dividing this calculated weight by the weight of untreated substrate, and then multiplying by 100%.

Various publicly known ones can be usedAny of the application techniques applies the colloidal dispersion to a substrate. Suitable techniques for applying the dispersion to a substrate include printing, dipping, spraying, melt extrusion, solvent coating, powder coating, and the like. The application can result in the incorporation of metal-coated silica particles and/or metal-bearing silicate particles into the matrix of the substrate and/or coating onto the surface of the substrate. In some embodiments, the particles are coated onto one or more surfaces of the substrate. When applied to a substrate, the thickness of the resulting coating can be minimal, such that it is nearly invisible to the naked eye. In some embodiments, the thickness is less than about 2 μm (2 × 10)^-6m), in some embodiments, from about 5 nanometers to about 1 μm in thickness. In some embodiments, the thickness is from about 10 nanometers to about 500 nanometers, or from about 20 nanometers to about 200 nanometers.

The amount of colloidal dispersion applied to any particular substrate or surface may depend on factors such as surface structure, material, absorption capacity, substrate location, and the like. For example, 0.1 kg/m²To 10 kg/m²For example 0.2 kg/m²To 5kg/m²Or 0.5kg/m²To 2 kg/m²In an amount of 100ppm to 1000ppm by weight of metal ions, 1% to 10% by weight of silica and containing particles having a size of, for example, 3 nm to 20 nm.

In some embodiments, the methods of the invention comprise applying the colloidal dispersions as provided herein to a wall, textile, wallpaper, glass, toilet and/or countertop, for example in a toilet facility, industrial building, public building, at home, in a vehicle such as an automobile, airplane, train, or any confined space where odor reduction is desired.

In some embodiments, a pad or cloth to which the composition of the invention has been applied is provided, for example by dipping the fabric into a solution of the colloidal dispersion, drying the fabric, and cutting an appropriately sized piece of fabric, the pad or cloth having air deodorising properties. The mat or cloth may be placed in a confined space such as a room, cabinet, refrigerator, lavatory, etc. to reduce or eliminate any malodour in the confined space.

In another embodiment, the colloidal dispersion as provided herein is used as an aerosol odor neutralizer/deodorizer. The dispersion may be mixed with a propellant to eject the particles into the air to remove gases and odorous compounds. However, in some embodiments, no propellant is used, i.e. the colloidal dispersion contains water as the only liquid carrier and is sprayed into the air, for example by using a suitable spray.

Thus, in some embodiments, there is provided a spray bottle containing a colloidal dispersion as disclosed herein and optionally a propellant for use in confined spaces such as toilets, cloakrooms, washrooms, kitchens, smoking rooms, for example as an air freshener.

The amount of colloidal dispersion required to contact the gaseous phase of a confined space (e.g., air containing odorous compounds) in order to significantly reduce the odor within the space can depend on a variety of factors such as the metal used, the metal content in the dispersion, the particle content in the dispersion, the level of odorous compounds within the space, and the like. For example, to significantly reduce the content of odorous compounds in the gas phase, about 1 g/m will be used³To about 1 kg/m³E.g. about 1 g/m³To about 500 g/m³E.g. about 1 g/m³To about 100 g/m³Or about 1 g/m³To about 50 g/m³It may be sufficient to eject into the gas phase an amount of colloidal dispersion as disclosed herein.

In some embodiments, there is provided a liquid composition for producing a surface coating, the composition comprising silica particles having a particle size of from 3 nm to 100 nm, the particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles; and a liquid carrier for the particles.

In some embodiments, there is provided a liquid composition for producing a surface coating, the composition comprising silica particles having a particle size of from 3 nm to 100 nm, the particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles; and a liquid carrier for the particles.

In some embodiments, there is provided a liquid composition for producing a surface coating, the composition comprising silicate particles, for example silicate particles having a particle size of less than 3 nm or less than 2 nm, bearing ions of one or more metals selected from copper, silver, zinc and iron at the surface of the particles; and a liquid carrier for the particles.

The liquid carrier may include, for example, solvents and resin types used in conventional paints. For example, the solvent may include mineral spirits, aromatic solvents, alcohols, esters, and ketones, or water. The resin may be selected from natural resins such as linseed oil, coconut oil and soybean oil, and synthetic resins such as alkyd resins, acrylic resins, epoxy resins and polyurethanes.

In some embodiments, the particles of the present invention are contained in paints, latexes, binders, etc., or other liquid formulations, to be applied as a surface coating or as an impregnate, varnish, lacquer, etc.

Thus, in some embodiments, the colloidal dispersions of the present invention are used as paint additives to provide paints with anti-odor properties. For example, in some embodiments, a paint is provided that is suitable for use in painting a surface (e.g., a wall, ceiling, floor, or appliance surface, etc.) in a confined space (e.g., a garbage room, public washroom, restaurant kitchen, closet, greenhouse, etc.).

Thus, in some embodiments, a paint formulation is provided that contains the particles of the present invention in addition to conventional ingredients (e.g., pigments, resins, solvents). Such paint formulations may be obtained by mixing the colloidal dispersion of the invention with conventional paint formulations, for example, 50 ml to 500 ml, or 100 ml to 450 ml, or 150 ml to 400ml, or 200 to 300 ml of the colloidal dispersion as described herein may be mixed with conventional paint formulations to obtain an anti-odor paint formulation with a final volume of 1 litre.

It is to be understood that the "particles of the invention" are silica particles having a particle size of 3 nm to 100 nm, said particles having adsorbed on the surface of the particles ions of one or more metals selected from the group consisting of copper, silver, zinc and iron, or small species (less than 3 nm) formed in the aqueous silicate solution containing metal ions selected from the group consisting of ions of copper, silver, zinc and iron, i.e. silicate particles carrying said metal ions as mentioned above. In some embodiments, the particles used are silica particles having a particle size of 3 nm to 100 nm, said particles having ions of one or more metals selected from copper, silver, zinc and iron adsorbed on the surface of the particles. In some other embodiments, the particles used are small silicate particles bearing one or more metal ions selected from copper, silver, zinc and iron.

In addition to the colloidal dispersion of the invention, the odor control paint may contain any conventional ingredients, such as binders, e.g., synthetic resins; a carrier, such as water or an organic solvent; a pigment; and any additional additives such as fungicides, UV screeners, rust inhibitors, and the like. The paint may be of the emulsion (latex) type, i.e. with water as a carrier, or may be an oil-based paint.

It is believed that when using the colloidal dispersion of the invention, for example for painting walls, it may be sufficient to apply the colloidal dispersion in a top coat only, in combination with a conventional paint in an under coat. In some embodiments, the colloidal dispersion is also applied in one or more lower layers. Thus, in some embodiments, such as when treating walls or other surfaces previously damaged by, for example, smoke or mold attack, the treatment may include first applying the colloidal dispersion of the present invention as a primer coating, followed by applying a barrier coating containing the colloidal dispersion of the present invention mixed with a conventional barrier paint, and finally applying a topcoat containing the colloidal dispersion of the present invention mixed with a conventional paint formulation.

For example, in some embodiments, a colloidal dispersion as described herein is applied as a surface primer; followed by an odor barrier paint formulation comprising 5 to 50 volume percent, such as 10 to 40 volume percent, or 20 to 30 volume percent, of the colloidal dispersion of the present invention in any conventional barrier paint formulation, and finally an odor barrier top coat comprising 5 to 50 volume percent, such as 10 to 40 volume percent, or 20 to 30 volume percent, of the colloidal dispersion of the present invention in any conventional paint formulation.

The colloidal dispersion used may be, for example, one containing 5% SiO₂And 100-500 ppm or 200-400 ppm of a metal ion as defined herein, e.g. 5% SiO₂And 300ppm Cu²⁺。

In some embodiments, the odor-inhibiting paint can be a ready-to-use mixture containing the particles of the present invention. However, it is also contemplated that the colloidal dispersion of the present invention may be provided separately and mixed with conventional paint prior to application of the paint.

In some embodiments of the invention, the method for treating a surface comprises applying a surface coating to the surface (e.g., applying a paint, varnish, lacquer, adhesive, or any type of solvent-resin mixture to the surface), optionally allowing the coating to at least partially dry, and applying the nanoparticles of the invention to the optionally partially dried surface, e.g., by spraying or brushing.

For example, in some embodiments, a surface coating is applied to a wall, ceiling or floor, e.g., by applying a conventional paint formulation, and the particles of the present invention, e.g., in the form of a colloidal dispersion in a liquid carrier such as water, are applied to a wet paint surface, e.g., by spraying, after which the surface is allowed to dry.

The granules of the invention may be present, for example, at about 0.01 kg/m²To 5kg/m²(ii) a For example 0.1 kg/m²To 3 kg/m²(ii) a For example 0.5kg/m²To 2 kg/m²Is applied to the surface. For example, in some embodiments, the colloidal dispersions of the present invention are used that contain from about 100ppm to about 1000ppm of a metal as mentioned herein and from about 1% to about 20% SiO₂Wherein the particles have a size of about 3 nm to about 50 nm, for example about 3 nm to about 10 nm, or about 5 nm. The granules of the invention may be present, for example, at about 0.01 kg/m²To 5kg/m²(ii) a For example 0.1 kg/m²To 3 kg/m²(ii) a For example 0.5kg/m²To 2 kg/m²Is applied to the surface.

In some further embodiments, the colloidal dispersions of the present invention are usedA body comprising from about 100ppm to about 500ppm of a metal as mentioned herein, and from about 3% to about 10% SiO₂Wherein the particles have a size of about 3 to about 10 nm.

In some of the above embodiments, the colloidal dispersion contains copper as the metal. In some other specific embodiments, the colloidal dispersion contains zinc as the metal. In a further embodiment, the colloidal dispersion contains iron as the metal.

In some embodiments, a method is provided for treating a woven or non-woven material, e.g., a fabric such as cotton, wool, or any synthetic fabric, by contacting the material with metal-coated silica particles, e.g., in the form of a colloidal dispersion. The material may be immersed in a liquid formulation containing the particles in a liquid carrier, such as water optionally containing a surfactant, and allowed to dry. Thus, in some embodiments, woven or nonwoven materials having improved odor-resistant properties are provided. Such materials may be present in, for example, garments such as sportswear, underwear, socks, pants, T-shirts, work clothes, and the like; footwear, such as athletic shoes, boots, and the like; an insole for footwear; and in textiles for interior decoration, such as curtains or upholstery textiles.

Thus, in some embodiments, there is provided a nonwoven or woven material bearing at its surface a plurality of metal-coated silica particles of the present invention.

In some embodiments, an object is provided, for example, selected from garments, such as sportswear, underwear, socks, pants, T-shirts, work-wear, and the like; footwear, such as athletic shoes, boots, and the like; an insole for a shoe or boot; or interior trim, such as curtains, sofa covers, mattress covers, pillow cases, etc., comprising a nonwoven or woven material treated as mentioned above, i.e., carrying a plurality of metal coated particles as disclosed herein.

In the following, examples of metal-coated silica particles and colloidal dispersions thereof that can be used in embodiments of the method of the present invention are described. Useful silver-coated silica particles, colloidal dispersions thereof and methods for their preparation are described in WO 2011/037523.

In the examples, stock solutions containing 9000 ppm of salts of some representative metals according to the present invention were used, as shown in table 2.

TABLE 2 stock solutions containing 9000 ppm of metals.

Metal	Salt (salt)	Molar weight (g)	pH	Appearance/remarks
					Cu	CuCl2.2H2O	170.48	4.1	Clear, blue color
Fe	FeCl3.6H2O	270.30	1.6	Clear, orange
					Zn	C4H6O4Zn.2H2O	219.51	5.8	Some sediment, clear supernatant