阅读说明：本技术 用于控制风化的涂料组合物 (Coating compositions for controlling weathering ) 是由 J-P·勒孔特 J·夫约尔凯 S·萨尔瓦蒂 于 2019-09-23 设计创作，主要内容包括：本公开提供一种用于控制多孔建筑材料中的风化的涂料组合物。所述涂料组合物包括丙烯酸聚合物水性乳液和水包油硅基乳液,其中在所述丙烯酸聚合物水性乳液中的所述丙烯酸聚合物的Tg为15℃至60℃。所述水包油硅基乳液包括由选自由以下组成的组的化合物形成的油相：烷氧基硅烷、硅酮树脂、聚二甲基硅氧烷、聚甲基氢硅氧烷以及其组合,其中所述水包油硅基乳液基的所述油相为所述涂料组合物中的所述丙烯酸聚合物水性乳液提供唯一的聚结剂。本公开另外包括一种用于控制多孔建筑材料中的风化的含水组合物,其中所述含水组合物包括所述涂料组合物和水,所述水足以提供按所述含水组合物的总重量计固体含量为2至25wt％的所述含水组合物。(The present disclosure provides a coating composition for controlling weathering in porous building materials. The coating composition includes an aqueous acrylic polymer emulsion and an oil-in-water silicon-based emulsion, wherein the acrylic polymer in the aqueous acrylic polymer emulsion has a Tg of 15 ℃ to 60 ℃. The oil-in-water, silicon-based emulsion includes an oil phase formed from a compound selected from the group consisting of: an alkoxysilane, a silicone resin, a polydimethylsiloxane, a polymethylhydrosiloxane, and combinations thereof, wherein the oil phase of the oil-in-water silicon-based emulsion base provides the sole coalescent agent for the aqueous acrylic polymer emulsion in the coating composition. The present disclosure additionally includes an aqueous composition for controlling weathering in porous building materials, wherein the aqueous composition includes the coating composition and water sufficient to provide the aqueous composition with a solids content of 2 to 25 wt%, based on the total weight of the aqueous composition.)

1. A coating composition for controlling efflorescence in porous building materials comprising:

25 weight percent (wt%) to 95 wt% of an aqueous emulsion of an acrylic polymer, based on the total weight of the coating composition, wherein the acrylic polymer has a Tg of 15 ℃ to 60 ℃; and

from 75 wt% to 5 wt%, based on the total weight of the coating composition, of an oil-in-water, silicon-based emulsion, wherein the oil-in-water, silicon-based emulsion comprises an oil phase formed from a compound selected from the group consisting of: an alkoxysilane, a silicone resin, a polydimethylsiloxane, a polymethylhydrosiloxane, and combinations thereof, wherein the oil phase of the oil-in-water silicon-based emulsion base provides the sole coalescent agent for the aqueous acrylic polymer emulsion in the coating composition.

2. The coating composition of claim 1, wherein the wt% of the aqueous acrylic polymer emulsion and the oil-in-water silicone-based emulsion in the coating composition increases to 100 wt%.

3. The coating composition of claim 1, wherein the acrylic polymer in the aqueous acrylic polymer emulsion has a Tg of 25 ℃ to 55 ℃.

4. The coating composition of claim 1, wherein the alkoxysilane is selected from the group consisting of Si (OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And combinations thereofGroup of each R¹Independently selected from an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and wherein each R is independently selected from an alkyl group having 1 to 6 carbon atoms.

5. The coating composition of claim 4, wherein the alkoxysilane is R¹Si(OR)₃。

6. The coating composition of claim 5, wherein R¹Has 8 carbon atoms and R has 2 carbon atoms to provide triethoxy (octyl) silane.

7. The coating composition of claim 1, wherein the silicone resin is selected from the group consisting of Si (OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And any combination thereof, wherein each R is R¹Independently selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and each R is independently an alkyl group having 1 to 6 carbon atoms.

8. The coating composition of claim 1, wherein the polymethylhydrosiloxane is selected from compounds having the formula:

R⁴(R⁵)₂Si—(O—SiR⁵H)_a—(O—SiR⁵R⁶)_b—Si(R⁵)₂R⁴ (I)；

or

(OSiR(R⁵)H)_c(OSiR⁵R⁶)_d (II)

Wherein;

R⁴is hydrogen or has 1 to 4An alkyl group of carbon atoms;

R⁵is an alkyl group having 1 to 4 carbon atoms;

R⁶is an alkyl group having 1 to 18 carbon atoms;

a is an integer of 0 to 35;

b is an integer of 0 to 32; and

c and d are each independently an integer of 1 to 10.

9. The coating composition of claim 1, wherein the organosiloxane is selected from compounds having the formula;

(R⁷)₃Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—SiR⁷ ₃ (I)；

or

HO(R⁷)₂Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—Si(R⁷)₂OH (II)

Wherein;

R⁷is an alkyl group having 1 to 4 carbon atoms;

R⁸is an alkyl group having 1 to 18 carbon atoms;

a is an integer of 0 to 35;

b is an integer of 0 to 32; and

c and d are each independently an integer of 1 to 10.

10. The coating composition of any one of claims 1 to 9, wherein the aqueous acrylic polymer emulsion has an acid level of up to 2 weight percent acid monomer based on dry weight of the acrylic polymer.

11. The coating composition of any one of claims 1 to 10, wherein the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, butyl methacrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, alpha-methylstyrene, vinyl acetate, hexyl acrylate, and combinations thereof.

12. The coating composition of claim 11, wherein the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and butyl acrylate.

13. The coating composition of claim 11, wherein the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and 2-ethylhexyl acrylate.

14. An aqueous composition for controlling efflorescence in porous building materials comprising:

the coating composition of any one of claims 1 to 13; and

water in an amount sufficient to provide said aqueous composition with a solids content of from 2 to 25 wt%, based on the total weight of the aqueous composition.

15. The aqueous composition of claim 14, wherein the coating composition and the water of the aqueous composition are increased to 100 wt% based on the total weight of the aqueous composition.

16. A porous building material at least partially coated with the aqueous composition of any one of claims 14 or 15.

17. The porous building material of claim 16, wherein the porous building material is an inorganic porous building material.

18. The porous building material of claim 17, wherein the inorganic porous building material is a cement-based porous building material.

Technical Field

The present disclosure relates generally to coating compositions, and more particularly to coating compositions for controlling weathering in porous building materials.

Background

Efflorescence is a phenomenon describing the migration and precipitation of salts to the surface of porous building materials, such as concrete, wherein the salts form specks, powdery and/or crystalline deposits. Efflorescence occurs when the absorbed moisture dissolves salts in the porous building material. The salt then migrates to the surface of the porous building material. Once at the surface, the water evaporates and the salt remains on the surface of the porous building material in the form of a white paint.

It is known to reduce efflorescence by reducing water movement in porous building materials. Typically, this can be done by coating or by impregnation with a silicon-based material. The silicone-based impregnation provides protection against invisible water penetration and gives the surface of the porous building material an unmodified appearance. However, it has been observed that silicone-based impregnation solutions are sometimes not effective in preventing efflorescence.

Accordingly, there is a need to protect porous building materials to provide protection not only against water ingress which can lead to freeze-thaw damage, swelling, warping or impaired mechanical properties (as observed for fiber cement boards), but also against observable efflorescence despite effective reduction of water penetration after treatment of the surface with silicone-based water repellents.

Another approach is to use acrylic-based protection in an attempt to reduce water penetration in porous building materials. Acrylic-based protection is based on the formation of a film at the porous building material surface and results in some surface appearance modification. Even without the addition of pigments/fillers to the acrylic, the surface of the porous building material will have a clear visual gloss. For some applications, it is desirable to provide protection to porous structures so that the appearance of the material is unmodified (i.e., has a "natural appearance") and does not have a visual sheen.

Thus, there is a need in the art for a coating composition for reducing the absorption of water and at the same time controlling the efflorescence in porous building materials, which not only helps to protect the porous building materials from efflorescence, but also does not change the appearance of the porous building materials.

Disclosure of Invention

The present disclosure provides a coating composition for reducing water absorption and simultaneously controlling weathering in porous building materials, which not only helps to protect the porous building materials from weathering, but also does not change the appearance of the porous building materials. Specifically, the coating composition includes an aqueous acrylic polymer emulsion, wherein the acrylic polymer in the aqueous acrylic polymer emulsion has a Tg of 15 ℃ to 60 ℃; and an oil-in-water silicon-based emulsion, wherein the oil phase of the oil-in-water silicon-based emulsion provides the sole coalescent agent for the aqueous emulsion of acrylic polymer in the coating composition. The present disclosure additionally includes an aqueous composition for controlling weathering in porous building materials, wherein the aqueous composition includes a coating composition and water sufficient to provide an aqueous composition having a solids content of 2 to 25 weight percent (wt%), based on the total weight of the aqueous composition.

Specifically, a coating composition for controlling weathering in porous building materials includes 25 wt% to 95 wt%, based on the total weight of the coating composition, of an aqueous emulsion of an acrylic polymer, wherein the acrylic polymer in the aqueous emulsion of an acrylic polymer has a Tg of 15 ℃ to 60 ℃; and 75 wt% to 5 wt%, based on the total weight of the coating composition, of an oil-in-water, silicon-based emulsion. The oil-in-water silicon-based emulsion comprises an oil phase formed from a compound selected from the group consisting of: alkoxysilanes, silicone resins, polydimethylsiloxanes, polymethylhydrosiloxanes, and combinations thereof. The oil phase of the oil-in-water silicon-based emulsion provides the only coalescent for the aqueous emulsion of acrylic polymer in the coating composition.

The coating compositions of the present disclosure can have various embodiments. For example, the wt% of the acrylic polymer aqueous emulsion and the oil-in-water silicone based emulsion in the coating composition is increased to 100 wt%. Thus, a coating composition for controlling efflorescence in a porous building material may consist essentially of or may consist of: 25 to 95 weight percent, based on the total weight of the coating composition, of an aqueous emulsion of an acrylic polymer, wherein the acrylic polymer has a Tg of 15 to 60 ℃; and 75 wt% to 5 wt%, by total weight of the coating composition, of an oil-in-water, silicon-based emulsion, wherein the oil-in-water, silicon-based emulsion comprises an oil phase formed from a compound selected from the group consisting of: alkoxysilanes, silicone resins, polydimethylsiloxanes, polymethylhydrosiloxanes, and combinations thereof, wherein the oil phase of the oil-in-water silicon-based emulsion base provides the sole coalescent agent for the acrylic polymer aqueous emulsion in the coating composition.

In additional embodiments, the aqueous acrylic polymer emulsion of the coating composition includes an acrylic polymer having a Tg of 25 ℃ to 55 ℃. For the various embodiments, the aqueous acrylic polymer emulsion may have an acid level of up to 2 weight percent acid monomer based on the dry weight of the acrylic polymer. Additionally, the acrylic polymer of the aqueous acrylic polymer emulsion may be formed from a nonionic monomer selected from the group consisting of: methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, butyl methacrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, alpha-methylstyrene, vinyl acetate, hexyl acrylate, and combinations thereof. In one embodiment, the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and butyl acrylate. In additional embodiments, the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and 2-ethylhexyl acrylate. Other examples of nonionic monomers for the acrylic polymer used to form the aqueous acrylic polymer emulsion are also possible.

For the various embodiments, the oil phase of the oil-in-water, silicon-based emulsion may be formed from an alkoxysilane, wherein the alkoxysilane is selected from the group consisting ofSi(OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And combinations thereof, wherein each R¹Independently selected from an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and wherein each R is independently selected from an alkyl group having 1 to 6 carbon atoms. In a more specific embodiment, the alkoxysilane is R¹Si(OR)₃. In one embodiment, R¹Has 8 carbon atoms and R has 2 carbon atoms to provide triethoxy (octyl) silane.

For the various embodiments, the oil phase of the oil-in-water, silicon-based emulsion may be formed from a silicone resin, wherein the silicone resin is formed from a silicone resin selected from the group consisting of Si (OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And any combination thereof, wherein each R is R¹Independently selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and each R is independently an alkyl group having 1 to 6 carbon atoms.

For various embodiments, the oil phase of the oil-in-water, silicon-based emulsion may be formed from polymethylhydrosiloxane, wherein the polymethylhydrosiloxane is selected from compounds having the formula: r⁴(R⁵)₂Si—(O—SiR⁵H)_a—(O—SiR⁵R⁶)_b—Si(R⁵)₂R⁴(I) (ii) a Or (OSiR (R)⁵)H)_c(OSiR⁵R⁶)_d(II) wherein; r⁴Is hydrogen or alkyl having 1 to 4 carbon atoms; r⁵Is an alkyl group having 1 to 4 carbon atoms; r⁶Is an alkyl group having 1 to 18 carbon atoms; a is an integer of 0 to 35; b is an integer of 0 to 32; and c and d are each independently an integer of 1 to 10.

For the various embodiments, the oil phase of the oil-in-water silicon-based emulsion may be prepared from an organosiloxaneWherein the organosiloxane is selected from compounds having the formula; (R)⁷)₃Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—SiR⁷ ₃(I) (ii) a Or HO (R)⁷)₂Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—Si(R⁷)₂OH (II) wherein; r⁷Is an alkyl group having 1 to 4 carbon atoms; r⁸Is an alkyl group having 1 to 18 carbon atoms; a is an integer of 0 to 35; b is an integer of 0 to 32; and c and d are each independently an integer of 1 to 10.

Embodiments of the present disclosure also include aqueous compositions for controlling efflorescence in porous building materials. In accordance with the present disclosure, an aqueous composition includes a coating composition as described herein and water in an amount sufficient to provide the aqueous composition with a solids content of 2 to 25 weight percent based on the total weight of the aqueous composition. For the various examples, the coating composition of the aqueous composition and water were increased to 100 wt% based on the total weight of the aqueous composition.

The aqueous compositions of the present disclosure may be used with porous building materials. For example, the aqueous compositions of the present disclosure can be used to at least partially coat porous building materials. Examples of the porous building material may include an inorganic porous building material, wherein the inorganic porous building material may be a cement-based porous building material.

Detailed Description

The present disclosure provides a coating composition for reducing water absorption and simultaneously controlling weathering in porous building materials, which not only helps to protect the porous building materials from weathering, but also does not change the appearance of the porous building materials. Specifically, the coating composition includes an aqueous acrylic polymer emulsion, wherein the acrylic polymer in the aqueous acrylic polymer emulsion has a Tg of 15 ℃ to 60 ℃; and an oil-in-water, silicon-based emulsion, wherein the oil phase of the oil-in-water, silicon-based emulsion provides the sole coalescent agent for the aqueous emulsion of acrylic polymer in the coating composition. The present disclosure additionally includes an aqueous composition for controlling weathering in porous building materials, wherein the aqueous composition includes a coating composition and water sufficient to provide an aqueous composition having a solids content of 2 to 25 weight percent based on the total weight of the aqueous composition.

When the components of the coating composition are described as being present in weight percent, it is understood to mean that the weight of the coating composition is 100%, and the sum of all components (including any optional additives) will be 100 weight percent. For example, a coating composition having from 25 wt% to 95 wt% of an aqueous acrylic polymer emulsion, based on the total weight of the coating composition, and from 75 wt% to 5 wt% of an oil-in-water, silicon-based emulsion, based on the total weight of the coating composition, is understood to encompass coating compositions wherein the amount of the aqueous acrylic polymer emulsion and the oil-in-water, silicon-based emulsion, together, will be 100 weight percent, or the sum of the amounts of the aqueous acrylic polymer emulsion, the oil-in-water, silicon-based emulsion, and the optional one or more additives, together, will be 100 weight percent. Thus, when the acrylic polymer aqueous emulsion is 90 weight percent, for example, the oil-in-water silicon-based emulsion can be any amount greater than 5 and up to 10 weight percent. In the case when the oil-in-water, silicon-based emulsion is less than 10 weight percent, the optional additives are present in the coating composition in an amount sufficient to total 100 weight percent. Additionally, both the acrylic polymer aqueous emulsion and the oil-in-water silicon-based emulsion of the present disclosure are water-based continuous emulsions comprising a dispersed phase and a non-dispersed (continuous) phase, wherein the dispersed phase is the acrylic polymer or the silicon-based compound and the non-dispersed phase is water or an aqueous solution or mixture.

In addition to the oil-in-water silicon-based emulsion, the coating compositions of the present disclosure do not include another coalescent agent. Coalescing agents are used to aid in the formation of a film in a film-forming composition, as is typical in the art. Coalescents aid in film formation, particularly by lowering the minimum film-forming temperature (MFFT) of one or more polymers dispersed in the composition. Reducing the MFFT of the one or more polymers contributes to their better coalescence, with the coalescing agent acting as a transient plasticizer for the one or more polymers. Thus, the coalescing agent facilitates film formation at a temperature below the MFFT of the polymer or polymers present in the composition.

Surprisingly, the use of oil-in-water silicon-based emulsions as provided in the present disclosure has not been recognized, nor has they been used as coalescents in coating compositions for controlling weathering in porous building materials. In addition, the use of oil-in-water silicon-based emulsions as provided in the present disclosure exhibits low volatility and does not include Volatile Organic Compounds (VOCs), both of which are highly environmentally beneficial. Thus, in addition to the oil-in-water silicon-based emulsion as provided in the present disclosure, the coating compositions of the present disclosure do not include any additional coalescent agent or agents, as they are not required.

For the present disclosure, the oil-in-water silicon-based emulsion includes an oil phase formed from a compound selected from the group consisting of: alkoxysilanes, silicone resins, polydimethylsiloxanes, polymethylhydrosiloxanes, and combinations thereof, wherein the oil phase of the oil-in-water, silicon-based emulsion provides the sole coalescent agent for the aqueous acrylic polymer emulsion in the coating composition. As used herein, an oil-in-water silicon-based emulsion refers to an emulsion having a water-based continuous phase in which an oil phase is dispersed. As discussed herein, the oil phase is formed from the silicon-based compounds provided herein, and the non-dispersed phase is water or an aqueous solution or mixture.

For the various embodiments, the alkoxysilane is selected from the group consisting of Si (OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And combinations thereof, wherein each R¹Independently selected from an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and wherein each R is independently selected from an alkyl group having 1 to 6 carbon atoms. In a more specific embodiment, the alkoxysilane is R¹Si(OR)₃. In one embodiment, R¹Has 8 carbon atoms and R has 2 carbon atoms to provide triethoxy (octyl) silane. Representative, non-limiting examples of commercial alkoxysilanes that can be used in the oil-in-water, silicon-based emulsions in the present disclosure include those under the trade name DOWSIL^TMOFS 6341 and DOWSIL^TMThose sold by OFS 6403.

Unless otherwise indicated, the term "substituted" as used with respect to another group (e.g., alkyl) means that one or more hydrogen atoms in the alkyl group have been replaced with another substituent. Examples of such substituents include alkyl groups having 1 to 6 carbon atoms, halogen atoms such as chlorine, fluorine, bromine and iodine; halogen atom-containing groups such as chloromethyl group, perfluorobutyl group, trifluoroethyl group, and nonafluorohexyl group; an oxygen atom; oxygen atom-containing groups such as (meth) acrylic acid and carboxyl groups; a nitrogen atom; nitrogen atom-containing groups such as amine, amino-functional group, amido-functional group, and cyano-functional group; a sulfur atom; and groups containing sulfur atoms, such as mercapto groups.

For the various embodiments, the silicone resin is composed of a material selected from the group consisting of Si (OR)₄、R¹Si(OR)₃、(R¹)₂Si(OR)₂And any combination thereof, wherein each R is R¹Independently selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, and each R is independently an alkyl group having 1 to 6 carbon atoms.

The silicone resin may also contain reactive groups such as silanol groups (hydroxyl groups bonded to silicon atoms) OR alkoxy groups (OR groups bonded to silicon atoms). The amount of silanol groups present on the silicone resin may be in the range of 0.1 to 35 mole% of silanol groups [ ≡ SiOH]SiOR groups, alternatively from 2 to 30 mol% of alkoxy groups, alternatively from 5 to 20 mol% of alkoxy groups. The alkoxy groups may be present on any siloxy unit within the silicone resin. The mole fraction and alkoxy group content of the various siloxy units may be determined by²⁹Si NMR techniques are readily determined.

The molecular weight of the silicone resin is not limited. The silicone resin may have an M of at least 1,000 g/mole_n(number average molecular weight), alternatively at least 2,000 g/mole of M_nOr alternatively at least 5,000 g/mol of M_n. The number average molecular weight can be readily determined using Gel Permeation Chromatography (GPC) techniques.

Representative, non-limiting examples of hydrolysis-condensation reactions that may be used in the commercial production of oil-in-water, silicon-based emulsions in the present disclosure include those under the trade name DOWSIL^TMMR 2404 resin, DOWSIL^TM3037 resin, DOWSIL^TM3074 resin, DOWSIL^TM2403 resin and DOWSIL^TM2405 those sold as resins.

For the various embodiments, the polymethylhydrosiloxane is selected from compounds having the formula: r⁴(R⁵)₂Si—(O—SiR⁵H)_a—(O—SiR⁵R⁶)_b—Si(R⁵)₂R⁴(I) (ii) a Or (OSiR (R)⁵)H)_c(OSiR⁵R⁶)_d(II) wherein; r⁴Is hydrogen or alkyl having 1 to 4 carbon atoms; r⁵Is an alkyl group having 1 to 4 carbon atoms; r⁶Is an alkyl group having 1 to 18 carbon atoms; a is an integer of 0 to 35; b is an integer of 0 to 32; and c and d are each independently an integer of 1 to 10.

For the various embodiments, the organosiloxane is selected from compounds having the formula; (R)⁷)₃Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—SiR⁷ ₃(I) (ii) a Or HO (R)⁷)₂Si—(O—Si(R⁷)₂)_a—(O—SiR⁷R⁸)_b—Si(R⁷)₂OH (II) wherein; r⁷Is an alkyl group having 1 to 4 carbon atoms; r⁸Is an alkyl group having 1 to 18 carbon atoms; a is an integer of 0 to 35; b is an integer of 0 to 32; and c and d are each independently an integer of 1 to 10. Representative, non-limiting examples of commercial polymethylhydrosiloxanes that can be used in the oil-in-water, silicon-based emulsions in the present disclosure include those under the trade name DOWSIL^TM6-3570 polymer and Xiameter OFX-5625 fluid.

As seen herein, the oil-in-water silicon-based emulsions of the present disclosure are more generally formed from a silane-based emulsion, a silicone-based emulsion, or a mixture of both a silane-based emulsion and a silicone-based emulsion. As seen above, examples of silanes used in the oil phase of the silane-based emulsion may include alkoxysilanes, while examples of silicone-based emulsions may include the silicone resins, polydimethylsiloxanes, and/or polymethylhydrosiloxanes provided herein. As noted, the coating compositions of the present disclosure may include a combination of two or more of these compounds for use in the oil phase of the oil-in-water, silicon-based emulsions of the present disclosure. For various embodiments, the ratio of silane-based compound to silicone-based compound in the oil phase of the oil-in-water silicon-based emulsion can range from 0:1 to 1:0 (silane: silicone). Ratios within this range are also possible and include 0:1, 0.01:0.99, 0.05:0.95, 0.1:0.9, 0.2:0.8, 0.3:0.7, 0.4:0.6, 0.5:0.5, 0.6:0.4, 0.7:0.3, 0.8:0.2, 0.9:0.1, 0.95:0.05, 0.99:0.01, and 1:0.

Forming the oil-in-water silicon-based emulsion of the present disclosure may include forming a mixture by combining one or more silane-based compounds and one or more silicone-based compounds in a desired ratio as provided herein and mixing and homogenizing with water or a water-based solution to form the oil-in-water silicon-based emulsion of the present disclosure. As used herein, water may include deionized water, while a water-based solution may include water and one or more hydrophilic additives. Such hydrophilic additives include, but are not limited to, low molecular weight alcohols such as methanol, ethanol, propanol, isopropanol, and the like. One or more of the foam control agent and/or the pH control agent may be included with the oil-in-water silicon-based emulsion as desired.

Mixing to form the oil-in-water, silicon-based emulsion can be accomplished by known methods and can occur as a batch, semi-continuous, or continuous process. Forming the oil-in-water silicon-based emulsions of the present disclosure may include adding 30 to 900 parts of water or water-based solution per 100 parts of one or more silane-based compounds and/or one or more silicone-based compounds. This allows the oil phase content (e.g., the "solids" content) of the oil-in-water silicon-based emulsion to be 11% to 79% by volume. The oil phase content may have an average volume particle size of 0.3 to 10 μm. The viscosity of the oil-in-water, silicon-based emulsions of the present disclosure can range from 5 centipoise to 500 centipoise as measured using a Brookfield viscometer (Brookfield viscometer); the viscosity changes significantly for different application methods.

The process of combining and mixing the components of the oil-in-water silicon-based emulsion may occur in a single-step or multi-step process. Thus, the components may all be combined and subsequently mixed via any of the techniques described herein. Alternatively, one or more portions of the components may be combined first, mixed, and then additional quantities of the components combined and mixed in addition. Those skilled in the art will be able to select the optimum portion of the components for combing and mixing, depending on the selection of the amounts used in forming the oil-in-water silicon-based emulsion and the particular mixing technique utilized.

The coating composition of the present disclosure also includes from 25 wt% to 95 wt%, based on the total weight of the coating composition, of an aqueous emulsion of an acrylic polymer. As used herein, an acrylic polymer aqueous emulsion refers to a water-based emulsion, wherein the acrylic polymer of the acrylic polymer aqueous emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, butyl methacrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, alpha-methylstyrene, vinyl acetate, hexyl acrylate, and combinations thereof. The use of the term "(meth)" followed by another term such as methacrylate refers to both acrylates and methacrylates. Preferably, the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and butyl acrylate. Preferably, the acrylic polymer of the aqueous acrylic polymer emulsion is formed from a nonionic monomer selected from the group consisting of: methyl methacrylate and 2-ethylhexyl acrylate.

The acrylic polymer is substantially uncrosslinked, i.e., the acrylic polymer comprises less than 1 weight percent, preferably less than 0.2 weight percent, and more preferably 0 percent, of copolymerized polyethylenically unsaturated monomer, based on the weight of the polymer. The polyethylenically unsaturated monomers include, for example, allyl (meth) acrylate, diallyl phthalate, 1, 4-butanediol di (meth) acrylate, 1, 2-ethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and divinylbenzene.

The aqueous acrylic polymer emulsion has an acid level of acid monomer of up to 2 weight percent based on the dry weight of the acrylic polymer. Acid monomers include carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydride; and sulfur and phosphorus containing acid monomers. Preferred acid monomers are carboxylic acid monomers. A more preferred monomer is (meth) acrylic acid. The acid level can be calculated by determining the number of milliequivalents per gram of acid in the acrylic acid polymer and multiplying by the molecular weight of the potassium hydroxide.

For various embodiments, the acrylic polymer may have a glass transition temperature ("Tg") of 15 ℃ to 60 ℃. In additional embodiments, the Tg of the acrylic polymer in the aqueous emulsion of acrylic polymer is from 25 ℃ to 55 ℃. The Tg of an acrylic polymer can be calculated using the Fox equation (T.G.Fox, U.S. physical society of America, Inc. (Bull. am. Physics Soc.), Vol.1, No. 3, p.123 (1956)), wherein the Tg of a copolymer of monomers M1 and M2 is calculated using the following equation,

1/Tg (calculated) ═ w (M1)/Tg (M1) + w (M2)/Tg (M2)

Wherein Tg (calculated) is the glass transition temperature calculated for the copolymer; w (M1) is the weight fraction of monomer M1 in the copolymer; w (M2) is the weight fraction of monomer M2 in the copolymer; tg (M1) is the glass transition temperature of homopolymer of M1; tg (M2) is the glass transition temperature of the homopolymer of M2, all temperatures in Kelvin. The glass transition temperature of homopolymers can be found, for example, in "Handbook of polymers" (edited by j. brandrup and e.h. immergut, international scientific press (Interscience Publishers). The contribution of copolymerized graft-linking monomers is excluded herein in calculating Tg. The calculated Tg is calculated from the total overall composition of the acrylic polymer particles.

Polymerization techniques for acrylic polymers used to prepare aqueous emulsions of acrylic polymers include emulsion polymerization, which is well known in the art (e.g., the examples disclosed in U.S. Pat. Nos. 4,325,856; 4,654,397; and 4,814,373). Conventional surfactants may be used, such as anionic and/or nonionic emulsifiers, for example alkali metal or ammonium alkyl sulfates, alkyl sulfonic acids, fatty acids and ethoxylated alkylphenols. The amount of surfactant used may be from 0.1 to 6 weight percent based on the weight of the total monomers. Either a thermal or redox initiation process may be used. Conventional free radical initiators such as hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, ammonium and/or alkali metal persulfates may be used, typically at levels of 0.01 to 3.0 weight percent based on the weight of the total monomers. Redox systems using the same initiators coupled with suitable reducing agents (e.g., sodium formaldehyde sulfoxylate, sodium bisulfite, erythorbic acid, hydroxylamine sulfate, and sodium bisulfite) can be used at similar levels, optionally in combination with metal ions such as iron and copper, optionally additionally including metal complexing agents. The monomer mixture for a certain stage can be added neat or in the form of an emulsion in water. The monomer mixture for a stage can be added in a single addition or in multiple additions using homogeneous or different compositions or continuously over the reaction period allotted to the stage; preferred are emulsions in which one or more of the polymeric monomers are added in a single addition. Additional ingredients such as free radical initiators, oxidizing agents, reducing agents, chain transfer agents, neutralizing agents, surfactants, and dispersants may be added before, during, or after any stage.

The acrylic polymer particles may have an average particle diameter of 40 to 400 nanometers (measured using a Brookhaven Instruments particle size analyzer). The solids content of the aqueous acrylic polymer emulsions of the present disclosure can be from 30 to 70 weight percent based on the total weight of the aqueous acrylic polymer emulsion. The viscosity of the aqueous acrylic polymer emulsions of the present disclosure can be from 10 centipoise to 5000 centipoise as measured using a brookfield viscometer; the viscosity changes significantly for different application methods. The pH of the aqueous acrylic polymer emulsion of the present disclosure can be from 3 to 11 as measured at 23 ℃.

The coating composition can be prepared by techniques well known in the coating art. The acrylic polymer aqueous emulsion and the oil-in-water silicon-based emulsion may be added together with other coating aids as needed under low shear agitation. In addition to the aqueous acrylic polymer emulsion and the oil-in-water silicon-based emulsion, the coating composition may contain inorganic fillers (e.g., quartz), bactericides when water is present, untreated and treated silica, metal hydroxide micropowder (e.g., aluminum hydroxide micropowder, calcium hydroxide micropowder, and magnesium hydroxide micropowder), bisamides, plate-like fillers (e.g., mica), dimethylpolysiloxane, epoxy-functional diorganopolysiloxane, and amino-functional diorganopolysiloxane, and pigments, curing agents, buffers, corrosion inhibitors, neutralizing agents, humectants, wetting agents, antifoaming agents, UV absorbers, optical brighteners, light or heat stabilizers, biocides, dispersants, colorants, colorant dispersions, waxes, water repellents, pigments, extenders, antioxidants, and dyes may be added to the coating composition. Additional components that may also be included in the coating composition may be preservatives, freeze/thaw additives, and various thickeners.

The present disclosure also provides aqueous compositions for controlling efflorescence in porous building materials. The aqueous composition comprises a coating composition as described herein and water in an amount sufficient to provide the aqueous composition with a solids content of 2 to 25 wt%, based on the total weight of the aqueous composition. Thus, for the purposes of this disclosure, a coating composition as described herein can be considered to be a concentrated form of an aqueous composition, wherein the coating composition is diluted with water or an aqueous composition to obtain an aqueous composition. As with the coating composition, embodiments of the present disclosure include coating compositions wherein the aqueous composition and water are increased to 100 wt% based on the total weight of the aqueous composition.

Mixing to form an aqueous composition having a solids content of from 2 to 25 wt.%, based on the total weight of the aqueous composition, can be accomplished by known methods and can occur as a batch, semi-continuous, or continuous process. The aqueous compositions forming the present disclosure may comprise water or an aqueous composition of the coating composition as provided herein to obtain a solids content of from 2 to 25 wt% based on the total weight of the aqueous composition. As will be appreciated, the solids content to obtain the aqueous composition will depend on the solids content of each of the aqueous acrylic polymer emulsion and the oil-in-water silicon-based emulsion.

The process of combining and mixing the aqueous acrylic polymer emulsion and the oil-in-water silicon-based emulsion may occur in a single or multi-step process. Thus, the components may all be combined and subsequently mixed via any of the techniques described herein. Alternatively, one or more portions of the components may be combined first, mixed, and then additional quantities of the components combined and mixed in addition. Those skilled in the art will be able to select the optimum portion of the components for combing and mixing, depending on the selection of the amounts used in forming the aqueous composition and the particular mixing technique utilized.

As discussed herein, embodiments of the aqueous composition can be used to control efflorescence in porous building materials. The aqueous compositions of the present disclosure may be used with porous building materials. For example, the aqueous compositions of the present disclosure can be used to at least partially coat porous building materials. Examples of the porous building material may include an inorganic porous building material, wherein the inorganic porous building material may be a cement-based porous building material.

In providing the coating of the present disclosure, the aqueous composition of the present disclosure is applied to a porous building material and dried or allowed to dry. The aqueous composition is typically applied to porous building materials, such as wood and/or inorganic porous substrates, such as those made with cement or gypsum. Examples of such inorganic porous substrates include concrete, mortar, drywall and mortar, which are new and are surfaces or weathered surfaces that have not been previously painted or treated, previously printed, painted or primed. The aqueous compositions of the present disclosure may be applied to porous building materials using conventional coating application methods, such as paintbrushes, paint rollers, gravure rollers, curtain coaters, and spraying methods, such as air atomized sprays, air assisted sprays, airless sprays, high volume low pressure sprays, and air assisted airless sprays. Drying of the aqueous composition may be carried out at ambient conditions, for example at 5 ℃ to 35 ℃, or the coating may be dried at elevated temperatures, for example at 35 ℃ to 100 ℃.

The following examples are provided to illustrate the present disclosure.

Examples of the invention

In examples, various terms and names of materials are used, including, for example, the following:

TABLE 1 bill of materials

The high density flat Fiber Cement (FC) boards used in the examples were prepared using the Hatscheck process and air cured. The thickness of the FC plate was 0.8 cm. FC plates are stored at room temperature (23 ℃) at a relative humidity of 40 to 50%. The following paint tests were performed at room temperature (23 ℃) at a relative humidity of 40 to 50%.

For each of the following coating tests, the FC panel was impregnated with an aqueous composition formed from the coating compositions provided in tables 2 and 4 below. To prepare the aqueous compositions of each of the examples and comparative examples, each of the oil-in-water, silicon-based emulsions and the aqueous emulsions of acrylic polymers of the coating compositions seen in tables 2 and 4 were diluted with deionized water to obtain aqueous compositions, wherein the solids content of the aqueous compositions was 15 weight percent (wt%) based on the total weight of the aqueous compositions. The coating composition was mixed at room temperature using an overhead stirrer with blades at a rotational speed of 200RPM for approximately 5 minutes.

The aqueous composition formed from each of the examples and comparative examples was applied to an FC board to give 150g/m²The amount of coverage of (c). Each of the FC panels treated with the aqueous compositions formed from each of the examples and comparative examples was dried for 7 days. After 7 days, each of the FC plates was visually inspected. For the examples and comparative examples seen in table 1, treating FC panels with an aqueous composition formed from a coating composition containing greater than 50 wt% of an acrylic emulsion (e.g., example 3, example 4, and comparative example C) produced a glossy appearance on the FC panels. Treatment of FC boards with aqueous compositions formed from coating compositions containing 0 to 50 wt.% of acrylic emulsions maintains their original matte appearance (e.g., examples 1 and 2)。

TABLE 2 coating compositions-examples (Ex)1-4 and Comparative Examples (CE) A-C

Water absorption test

The water uptake value of each of the FC plates treated with the aqueous compositions formed from each of examples 1-4 and comparative examples A-C was evaluated using the Cobb test (a modified version of ISO 535-2714). The water uptake into the FC plate at different contact times with water is expressed in kg/m 2. The gloss and efflorescence of each of the FC panels treated with the aqueous compositions formed from each of examples 1-4 and comparative examples a-C was visually evaluated. The results are provided in table 3.

Weathering test

The weathering resistance of each of the FC panels treated with the aqueous compositions formed from each of examples 1-4 and comparative examples a-D was evaluated as follows. Exposure of the reference or treated FC plate to water does potentially result in water penetration into the plate, followed by dissolution of calcium hydroxide present in the plate matrix and migration to the plate surface. In addition, the application of low temperatures at the top surface of the FC plate may drive the precipitation of calcium hydroxide or calcium carbonate (formed in situ as the calcium hydroxide reacts with carbon dioxide dissolved in water), resulting in an accelerated weathering process. Two test methods were used in this study-forced condensation and forced precipitation

Forced condensation method

The FC panel was placed on top of a refrigerated cold pack at-18 ℃ to form an assembly. The assembly was placed in a climate chamber where the relative humidity was set to > 80%. The cold surface causes cold water to be forced to condense at the surface of the FC plate. The cold packs were replaced daily. The FC panels were left in the climate chamber for one week (7 days). After drying the FC panels, the efflorescence was assessed visually.

Forced precipitation

The FC plate was placed horizontally on a laboratory bench. Cold water (0.5 ℃, melted from ice or stored in a refrigerator) is applied to the upper surface of the FC plate. The low temperature of the water on the upper surface forces the precipitation of calcium hydroxide solution (which migrates from the interior of the FC plate to the surface of the FC plate due to hydration conditions) or calcium carbonate (which forms in situ after the calcium hydroxide reacts with carbon dioxide dissolved in the water). Weathering was assessed visually overnight after complete evaporation of the cold water applied to the surface of the FC plate.

After drying the water applied at the plate surface, the appearance of the FC plate was evaluated. The results are provided in table 3.

Table 3-water absorption results from Cobb test and weathering according to forced precipitation test.

Weathering: +++: the surface is obviously white on the whole surface; ++: white marks are evident on all surfaces; +: the surface bears some white markings. 0: no sign of white mark)

The data seen in table 3 shows that by treating FC panels with either a pure silane/siloxane formulation (comparative example a) or an aqueous composition formed from the coating composition of the present disclosure (examples 1-3), the absorption of water is significantly reduced, provided that the acrylic polymer content is no greater than 75 wt%, based on the total weight of the coating composition (e.g., example 4). Table 3 also shows that some whitening of the FC plate surface occurred due to the lack of the weathering test described above. Whitening of the FC plate surface was observed with untreated FC plates (comparative example D) and FC plates treated with an aqueous composition formed from a coating composition having an aqueous acrylic polymer emulsion content of less than 25 weight percent based on the total weight of the coating composition (comparative example B). The data in Table 3 show that better protection of FC plates from water ingress and resultant weathering is obtained as a result of treatment with aqueous compositions formed from coating compositions having at least 25 weight percent of an aqueous acrylic polymer emulsion based on the total weight of the coating composition (examples 1-4).

Table 4 provides additional examples (example 6) and comparative examples (comparative example E-comparative example H) of coating compositions. The coating compositions of each of example 6 and comparative examples D to G were prepared according to the ratios provided in table 4 (ratios based on the total weight of the coating composition) by mixing the components at room temperature using an overhead stirrer at a rotational speed of 200RPM for about 10 minutes. Each of comparative examples E to H additionally included 8 wt% (based on the total weight of polymer content in the aqueous acrylic polymer emulsion) of a coalescent agent. An aqueous composition having a solids content of 10% was prepared using deionized water with the coating composition using each of example 6 and comparative examples E-H seen in table 4.

TABLE 4 coating compositions EXAMPLE 6 and COMPARATIVE EXAMPLES (CE) E-H

For each of the following coating tests, FC panels were impregnated with the aqueous composition prepared from each of the coating compositions of example 6 and comparative examples E through H. Applying the aqueous composition to an FC plate to give 110g/m²The amount of coverage of (c). Each of the FC panels treated with the aqueous compositions formed from example 6 and comparative examples E through H was dried for 7 days. After 7 days, each of the FC plates was visually inspected. Each FC panel treated with the aqueous compositions formed using example 6 and comparative examples D through G retained its original matte appearance.

Weathering test

The weathering resistance of each of the FC panels treated with each of the aqueous compositions formed using example 6 and comparative examples E to H was evaluated as follows. The long term durability against weathering of FC panels treated with aqueous compositions formed using the coating compositions of example 6 and comparative examples E through H was evaluated by subjecting the treated FC panels to UV exposure. FC plates treated with the aqueous compositions described herein were irradiated in a dry closed box with an ULTRA-VITALUX high pressure UV lamp (300W, OSRAM) for 10 weeks. After 10 weeks of exposure to UV light, they were then tested according to the forced precipitation weathering test to assess weathering resistance. The results are provided in table 5.

TABLE 5 weathering test after 10 weeks UV exposure

The appearance of the fiber cement board after 10 weeks UV exposure and weathering test (ice cube test).	Efflorescence
		Comparative example E	+++
Comparative example F	++
		Comparative example G	+
Comparative example H	+
		Example 6	0

Weathering: +++: the surface is obviously white on the whole surface; ++: white marks are evident on all surfaces; +: the surface bears some white markings. 0: no sign of white mark)

As seen from table 5, the FC panels treated with the aqueous composition formed from example 6 showed excellent weathering resistance even after 10 weeks of exposure to UV light before undergoing the forced precipitation weathering test. Even after 14 weeks of UV exposure, FC panels treated with the aqueous composition formed from example 6 showed no signs of efflorescence when tested by the forced sedimentation test. As seen with the FC panels treated with the aqueous compositions formed from comparative examples E through H, the FC panels with the aqueous composition containing the coalescing agent showed clear signs of efflorescence. In contrast, example 6 shows FC panels treated with an aqueous composition containing only an aqueous emulsion of an acrylic polymer, where the acrylic polymer has a Tg greater than 15 ℃, and the oil-in-water silicon-based emulsion of the present disclosure, without additional coalescent agent, shows no signs of efflorescence.