阅读说明：本技术 水性组合物 (Aqueous composition ) 是由 D·M·康纳 M·D·韦斯特梅耶 R·鲍曼 于 2019-10-01 设计创作，主要内容包括：一种组合物,其包含：(a)至少一种阴离子稳定的丙烯酸聚合物分散体,其中所述丙烯酸聚合物含有酸单体单元；以及(b)相对于所述组合物中的总聚合物的重量的至少一种聚氨基硅氧烷,其中含空间稳定基团的聚氨基硅氧烷共聚物具有带有仲胺或伯胺官能度的侧基；并且(ii)所述含空间稳定基团的聚氨基硅氧烷共聚物中的硅原子的至少一部分具有带有5个环氧乙烷单元到20个环氧乙烷单元的侧烷基-聚(环氧乙烷)链。(A composition, comprising: (a) at least one anionically stabilized acrylic polymer dispersion, wherein the acrylic polymer contains acid monomer units; and (b) at least one polyaminosiloxane, relative to the weight of total polymers in the composition, wherein the sterically-stabilizing group-containing polyaminosiloxane copolymer has pendant groups with secondary or primary amine functionality; and (ii) at least a portion of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer have pendant alkyl-poly (ethylene oxide) chains with 5 ethylene oxide units to 20 ethylene oxide units.)

1. A stable aqueous composition comprising:

(a) at least one anionically stabilized acrylic polymer dispersion, wherein the acrylic polymer contains at least a portion of polymerized acid monomer units; and

(b) at least one sterically stabilizing group-containing polyaminosiloxane copolymer, wherein (i) at least a portion of the silicon atoms in the polyaminosiloxane copolymer contain pendant groups having secondary or primary amine functionality; and (ii) at least a portion of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer have pendant alkyl-poly (alkylene oxide) chains.

2. The composition of claim 1, wherein the portion of the polymerized acid monomer units in the acrylic polymer is from 0.1 weight percent or more to 5.0 weight percent or less, based on the total weight of all monomers in the polymer; wherein the portion of silicon atoms in the polyaminosiloxane copolymer containing pendant groups having secondary or primary amine functionality is 60 mol% or more to 97 mol% or less, based on the total number of the polyaminosiloxane copolymer; and wherein the portion of silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer having pendant alkyl-poly (alkylene oxide) chains is 3 mol% or more to 17 mol% or less, based on the total number of the polyaminosiloxane copolymer.

3. The composition of claim 1, wherein the alkyl-poly (alkylene oxide) chain is a poly (ethylene oxide) chain.

4. The composition of claim 1, wherein the concentration of the steric stabilizing group-containing polyaminosiloxane copolymer is from 0.01 weight percent to 5.0 weight percent, based on the total weight of the polymers in the composition.

5. The composition of claim 1, wherein (i) at least 70 mole percent of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer have a pendant group with a secondary or primary amine functionality; and (ii) 5 to 20 mole percent of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer have pendant alkyl-poly (ethoxide) chains with 5 to 20 ethylene oxide units.

6. The composition of claim 1, wherein the pH of the composition ranges from 7 to 10.5, as determined by the procedure of ASTM E70.

7. The composition of claim 1, wherein the composition is a stable mixture that increases by no more than 5 microns as determined by the procedure of ASTM test D-1316.

8. The composition of any one of the preceding claims, wherein the composition contains less than 0.25 weight percent ammonia, based on the total weight of polymers in the composition, as determined by headspace gas chromatography.

9. The composition of any preceding claim, wherein the acrylic polymer is selected from the group consisting of (meth) acrylic polymers and styrene-acrylic copolymers.

10. The composition of any preceding claim, wherein the acrylic polymer is a monomer selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, and 2-hydroxyethyl methacrylate phosphate.

11. The composition of claim 10, wherein the monomer is present in the composition at a concentration of 0.1 weight percent to 5.0 weight percent based on the total weight of monomer units in the polymer.

12. The composition of any preceding claim, wherein the acrylic polymer has a glass transition temperature in a range of-55 degrees celsius to 35 degrees celsius as determined according to the procedure of ASTM E-1356-08.

13. The composition of any preceding claim, wherein the sterically-stabilized group-containing polyaminosiloxane copolymer is the product resulting from a condensation reaction of a mixture comprising:

(a)0 to 97 mole percent of a compound having the following structure (I):

Si(R¹)(R²)₂(CH₂)_XNH(CH₂)_YNH₂ (I)；

(b)0 to 97 mole percent of a compound having the following structure (II):

Si(R²)₃(CH₂)_XNH(CH₂)_YNH₂ (II)；

(c)0 to 97 mole percent of a compound having the following structure (III):

Si(R¹)(R²)₂(CH₂)_XNH₂ (III)；

(d)0 to 97 mole percent of a compound having the following structure (IV):

Si(R²)₃(CH₂)_XNH₂ (IV)；

(e)3 to 17 mole percent of a compound having the following structure (V):

Si(R¹)_x(R²)_3-x(CH₂)_a-O-(CH₂CH₂O)_bR³(V); and

(f)0 to 20 mole percent of a compound having the following structure (vi):

Si(R⁴)_y(R²)_4-y (VI)；

wherein in the above structures (I) to (VI), R¹Independently at each occurrence, selected from the group consisting of methyl and phenyl; r²Independently at each occurrence, selected from the group consisting of hydroxy, methoxy, and ethoxy; the values of x, y and a at each occurrence are independently selected from a number ranging from 0 to 2; and b is independently selected from a number ranging from 5 to 20; and wherein the mole percent values are relative to the total moles of compounds (a) through (f) and the sum of the mole percent values of compounds (a) through (f) total 100 mole percent; r³Is hydrogen, methyl or acetoxy; y is 0 to 3; r⁴Is C1 to C8 alkyl or phenyl.

14. The composition of claim 13, wherein the polyaminosiloxane is a product resulting from a condensation reaction of a mixture comprising:

(a)0 to 95 mole percent 3- (2-aminoethylamino) propyldimethoxy-methylsilane;

(b)0 to 95 mole percent of 3- (2-aminoethylamino) propyltrimethoxysilane;

(c)0 to 95 mole percent aminopropyldimethoxymethylsilane;

(d)0 to 95 mole percent aminopropyltrimethoxysilane;

(e)3 to 17 mole percent of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane; and

(f)0 to 20 mole percent of dimethoxydimethylsilane, diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane;

wherein the mole percent values are relative to the total moles of compounds (a) through (f) and the sum of the mole percent values of compounds (a) through (f) total 100 mole percent.

15. The composition of any preceding claim, comprising a coating, sealant or stone-made architectural paint (masonry finish).

Technical Field

The present invention relates to aqueous compositions, and more particularly, to aqueous compositions of anionically stabilized acrylic polymer dispersions and polyaminosiloxane copolymers.

Background

Formulations utilizing silanes and/or silicone additives have been used to date, for example, for preparing dispersions, coatings, sealants, stone-building paints (masonry finishes), and traffic signs. For example, U.S. provisional patent application No. 62/525851, filed by Katherine a. faber et al on 2017, 28/6, entitled "STORAGE OF STABLE rapid-setting COATING systems free OF VOLATILE BASEs (STORAGE STABLE quick setting COATING SYSTEM THAT IS FREE OF volalile-BASE"), discloses in example 5 the hydrolysis condensation products OF aminoethylaminopropyltrimethoxysilane in dispersion formulations containing anionically stabilized acrylic dispersions. The formulation has a neutral pH and is free of volatile base. The formulation performs well in achieving rapid solidification with 0.22% (%) polymeric polyamine.

However, the formulations disclosed in the above provisional patent application references consist of homopolymers of aminoethylaminopropyltrimethoxysilane that do not function to provide a stable dispersion because the aminosiloxane polymers disclosed in the above references are highly efficient flocculants and will coagulate immediately upon addition to the formulation. Thus, to prevent the occurrence of coagulation, the pH of a formulation containing such a silicone polymer must be significantly increased (i.e., to a pH of about 11), which is undesirable because the formulation needs to be diluted to an unacceptable level to obtain a formulation with a pH of 11, where the viscosity of the formulation becomes less than (<) 15 megapascals (MPa) (15,000 centipoise [ cps ]). In contrast, the viscosity of the formulations disclosed in the above references must be greater than (>) 15MPa (15,000cps) to provide very thick, water-resistant filler-like formulations such that the formulations achieve extended storage stability and rapid solidification without the need for volatile bases. Below a viscosity of < 15MPa (15,000cps), the formulations disclosed in the above references fail.

It would be advantageous to provide a formulation that does not rely on viscosity characteristics for the formulation to function in the applications mentioned above. Without viscosity limitation, formulations of this type having a viscosity of less than 15MPa (15,000cps) can be used in a wider number of applications, including paints, varnishes, exterior decorative systems, coatings (e.g., roof coatings) and traffic signs.

U.S. patent No. 5,672,379 discloses a method of producing an abrasion resistant traffic marking on a road surface by applying a layer of a traffic paint coating composition containing an aminosilane added to an aqueous vaporizable carrier maintained at a pH in the range of 7.5 to 11.0 on the road surface. The coating composition comprises dispersed particles of a latex binder bearing an acid-functional pendant moiety and an enamine-functional pendant moiety. The above patents disclose various aminosilane molecules and structures; and such aminosilanes are referred to as "small molecules". Also, while the above patents also refer to "oligomeric aminoalkylsilanes," oligomers would be difficult to produce because the aminosilane monomers disclosed in the patents need only be mixed with other aminosilane monomers in the composition and not with other non-aminosilane monomers, in accordance with the teachings of the above patents. None of the above patents teach the addition of a non-amino silane monomer to the composition.

Other formulations utilizing silanes and/or silicone additives have been disclosed in the prior art, including U.S. patent nos. 5,616,764 a; nos. 6,011, 109; and No. 4,246,029; and U.S. patent application publication nos. US20130129648a1, US20170119632a1, US20150159036a1, and US20040053810a 1. However, none of the known formulations or compositions include an aminosilane that, when added to a non-aminosilane material, provides a formulation that exhibits an enhancement in beneficial properties (e.g., fast setting properties). In addition, none of the above references provide compositions that can be used in a wide range of different applications (e.g., dispersions, coatings, sealants, stone building paints, and traffic signs).

Disclosure of Invention

The present invention relates to an aqueous acrylic formulation or composition comprising a stable latex or formulated product thereof; and a sterically stabilized hydrophilic aminosiloxane copolymer containing a sterically stabilizing group which may be used to impart rapid coagulation properties to the anionically stabilized latex or formulated products thereof. The compositions of the present invention may be used, for example, to provide dispersions, coatings, stone building paints, traffic signs, and the like. Advantageously, the compositions of the present invention set faster than similar conventional aqueous counterparts; and, accordingly, to provide a coating: (1) exhibits rapid setting, (2) is recoatable in a shorter time and (3) produces mar and scratch resistance earlier. And, particularly for coatings or sealants, the compositions of the present invention provide an early onset of resistance to water washout (e.g., from rain).

In one general embodiment, the present invention relates to a formulation or composition comprising: (a) at least one acrylic polymer, wherein the at least one acrylic polymer comprises an anionically stabilized acrylic polymer dispersion and wherein the at least one acrylic polymer contains acid monomer units; and (b) at least one sterically stabilizing group-containing polyaminosiloxane copolymer.

In another embodiment, the invention comprises a composition comprising: (a) at least one anionically stabilized acrylic polymer dispersion, wherein the acrylic polymer contains acid monomer units; and (b) at least one steric stabilizing group-containing polyaminosiloxane copolymer, wherein the steric stabilizing group-containing polyaminosiloxane copolymer is characterized by: (i) a certain percentage of the silicon atoms in the copolymer have pendant groups with secondary and/or primary amine functionality; and (ii) a certain percentage of the silicon atoms in the copolymer have pendant alkyl-poly (alkylene oxide), e.g., ethylene oxide, chains with a certain number of ethylene oxide units.

The compositions of the present invention containing a sterically stabilized group-containing polyaminosiloxane copolymer are more advantageous for achieving rapid setting than known compositions and methods using aminosilanes, because their inclusion of polyether diol groups in the polymer backbone imparts steric stability to the resulting accelerator compounds. This imparted stability enables the use of such accelerators at higher concentrations in the composition, which helps to shorten the drying time of the composition. In addition, because the pH at which the formulation is used can be reduced, more desirable formulations can be obtained, and thus formulations with lower odor and higher solids content can be prepared. Furthermore, some embodiments of the present invention allow these sterically-stabilized aminosiloxane additives to be used at neutral pH as coagulants that will induce coagulation without pH-triggered base volatilization (e.g., ammonia flashing after application of the composition).

In a preferred embodiment, the present invention comprises, for example, a formulation or composition comprising a siloxane containing an aminosilane copolymerized with a silane monomer that does not contain an amino group (e.g., dimethyldimethoxysilane). Stabilizing groups (such as poly (ethylene glycol)) are part of the polymer used in the composition; such stabilizing groups reduce the charge density of the aminosilicone and increase stability. Thus, when the composition is used as a coagulant, the compositions of the present invention are less prone to induce undesirable flocculation when added to an anionically stabilized latex or formulated products thereof. The aminosilanes of the present invention can be used at lower pH and therefore their dispersions or formulations require less base, which in turn reduces the odor of the composition and increases the solids content of the composition.

Detailed Description

Definition of

With respect to aqueous compositions, "stable", "stability", "stabilization" or "product stability" refers herein to the ability to: mixing a coagulant into the dispersion or formulated product thereof; and maintaining suitable processability of the mixture for the time required to apply the mixture. The mixture containing both the coagulant and the dispersion or its formulation product should maintain flow and viscosity; and should not coagulate into solids, form large agglomerates, form grit, or micro-agglomerates within the time required to apply the mixture. Typically, application of the mixture takes at least 5 minutes (min) to several hours (hr). Large agglomerated agglomerates in the mixture can be seen during mixing; and micro-agglomeration on a grit or micron scale can be detected by using a fineness test procedure, such as that described in ASTM test D-1316. The fineness of the mixture should not increase by > 5 micrometers (um) as described in ASTM test D-1316.

With respect to aqueous compositions, "dry time" herein refers to the time required to reach "stage D full dry time" as described in ASTM test D5895-13. One skilled in the art will recognize that many factors (e.g., temperature, humidity, formulation composition, solids, and composition application thickness) may affect the drying of the aqueous dispersion or its formulation product. However, as mentioned above, the "dry time" of the aqueous composition of the present invention follows the description in ASTM test D5895-13.

With respect to aqueous compositions, "set" or "set time" or "time to set" refers herein to the time required for the dispersion or formulated product thereof to provide resistance to mechanical deformation or water scouring.

With respect to aqueous compositions, "water-scouring" is meant herein the resistance of the composition to dissipation, loss of cohesion or adhesion to a substrate due to rain or other natural or simulated precipitation.

With respect to aqueous compositions, "rapid setting" means that the time required for a dispersion or formulated product thereof containing an accelerator to provide resistance to mechanical deformation or water scouring is reduced compared to the comparative time required for a dispersion or formulated product thereof not containing an accelerator to provide resistance to mechanical deformation or water scouring; wherein in one embodiment, the time is reduced by at least > 25%, and in another embodiment, > 35%; wherein coagulation is measured in terms of time to achieve stage D through-dry time as described in ASTM test D5895-13; wherein the tests were carried out under the same drying conditions and at the same film thickness for both the aqueous composition containing the coagulant and the comparative aqueous composition not containing the coagulant.

With regard to aqueous compositions, "flocculation" means herein the process by which particles or colloids dispersed in a liquid or dispersion come out of suspension from such liquid or dispersion and stick to each other; and spontaneously form irregular larger-sized clusters, flocs, aggregates or agglomerates. Flocculation is the result of insufficient stability of the composition and is undesirable prior to application of the composition. Flocculation is synonymous with agglomeration and coagulation.

With respect to aqueous compositions, "micro-flocculation" or "micro-agglomeration" refers herein to hard or soft-package agglomeration that occurs after the coagulant is added to the composition and before the composition is applied. Micro-agglomeration will result in defects in products containing such micro-agglomeration. Also, while the size of the micro-agglomerates is < 50 μm and will not impede the mixing or flow of the product, the presence of such micro-agglomerates causes visual imperfections in the product or reduces the final mechanical integrity of the product. Moreover, such micro-agglomeration may negatively impact the application of the product in, for example, spray applications.

With respect to aqueous compositions, "gel" or "gelation" herein refers to the following states: upon addition of a coagulant to the dispersion or its formulated product, the high volume fraction of the dispersion or its formulated product has coagulated into a hard or soft packet; and the dispersion or its formulated product cannot be easily mixed. The occurrence of gels or gelatinations prior to application of the dispersion or its formulated product would render the dispersion or its formulated product unusable.

In general, the present invention relates to a stable aqueous composition comprising: (a) at least one acrylic polymer, wherein the at least one acrylic polymer comprises an anionically stabilized acrylic polymer dispersion and wherein the at least one acrylic polymer contains acid monomer units; and (b) at least one sterically stabilizing group-containing polyaminosiloxane copolymer. The compositions of the present invention exhibit advantageous properties and benefits including, for example, increased stability, rapid setting, no flocculation, low pH, minimal use of alkali, low odor, and high solids content.

As component (a), the formulations or compositions of the present invention contain at least one anionically stabilized acrylic polymer dispersion and serve as a medium in water. The anionically stabilized acrylic polymer dispersions useful in the present invention may comprise, for example, polymers (e.g., (meth) acrylic polymers), styrene-acrylic copolymers, and mixtures or blends thereof.

Exemplary (meth) acrylic polymers present in the acrylic polymer dispersion comprise polymers including polymerized monomers selected from the group consisting of: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, benzyl 2-propylacrylate, t-butyl acrylate, ethyl 2-propylacrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, 3- (trimethoxysilyl) propyl acrylate, di (ethylene glycol) ethyl ether acrylate, trimethylolpropane triacrylate, 1, 3-butanediol diacrylate, 1, 6-hexanediol diacrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile, isobutyl methacrylate, n-hydroxy (meth) acrylate, ethylhexyl (meth) acrylate, n-heptyl (meth) acrylate, ethyl (meth) acrylate, 2-methylheptyl (meth) acrylate, ethyl acrylate, n-ethylhexyl (meth) acrylate, n-heptyl (meth) acrylate, n-hexyl (meth) acrylate, n-ethylhexyl (meth) acrylate, n-, Octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 3- (trimethoxysilyl) propyl methacrylate, glycidyl (meth) acrylate, alkyl crotonate, di-n-butyl maleate, dioctyl maleate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, dodecyl (meth, 2-methoxy (meth) acrylate, 2- (2-ethoxy) ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-propylheptyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol (meth) acrylate, benzyl (meth) acrylate, 2, 3-epoxycyclohexylmethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methylpropanediol (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and copolymers and combinations thereof.

Exemplary (meth) acrylic polymers present in the acrylic polymer dispersion may also include polymers including polymerized (meth) acrylic monomers copolymerized with vinyl esters of vinyl halides (e.g., vinyl chloride), alkanoic acids having 1C to 12C atoms, non-limiting examples of which include vinyl acetate, vinyl propionate, vinyl valerate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl versatate, and mixtures thereof. The vinyl versatate may comprise vinyl esters of alpha-branched monocarboxylic acids having 9 and 10C atoms in the carboxylic acid moiety, respectively, for exampleOr(trade name of Momentive, Mayer corporation). A preferred vinyl ester monomer may be vinyl acetate. In one embodiment, the vinyl ester monomer (a) may be generally present at 0 weight percent (percent by weight) (or weight-percent) [ wt% ], based on the total weight of the monomers]) To 20 wt% and in another embodiment, from 0 wt% to 10 wt%.

The anionically stabilized acrylic polymer dispersions useful in the present invention may have a concentration of polymerized acid monomer units. Exemplary acid monomer units of the (meth) acrylic polymer present in the acrylic polymer dispersion may comprise acrylic acid, methacrylic acid, itaconic acid, phosphoric acid, 2-hydroxyethyl methacrylate, and mixtures thereof. For example, in one general embodiment, the anionically stabilized acrylic polymer dispersions useful in the present invention can have a concentration of polymerized acid monomer units in the polymerized acid monomer ranging from 0.1 wt% or more to 5.0 wt% or less, based on the total weight of all monomers in the polymer; and in another embodiment, the polymerized acid monomer is 0.5 wt% to 3.0 wt% or less. Dispersions containing < 0.1% by weight of acid monomer are not sufficiently stable; and dispersions containing > 5.0 wt% acid monomer will have undesirable water sensitivity and require excessive concentrations of the sterically stabilized group-containing polyaminosiloxane copolymer (i.e., coagulant) to be cost effective.

In one embodiment, the anionically stabilized acrylic polymer dispersions useful in the present invention may also generally have an average particle size of 65 nanometers (nm) or more to 500nm or less as determined by 90 degree light scattering using a Malvern Zetasizer Nano ZS 90; and in another embodiment, an average particle diameter of 100nm or more to 350nm or less is formed. Polymer dispersions having average particle diameters outside the above ranges may not stabilize the dispersion because particles larger than 500nm are difficult to adequately stabilize and particles smaller than 65nm are difficult to produce at polymer solids that are practical for use. The anionically stabilized acrylic polymer dispersions may consist of bimodal, trimodal and multimodal particle sizes.

Additionally, in one embodiment, the anionically stabilized acrylic polymer dispersions useful in the present invention can generally have an average glass transition temperature of from-55 degrees Celsius (. degree. C.) or higher to 35 ℃ or lower, and in another embodiment from-40 ℃ to 20 ℃, as determined according to ASTM E-1356-082014. Within the above ranges, the polymer dispersion composition can be formulated to form a composition that can undergo film formation to convert the composition into a continuous material after application.

Additionally, the anionically stabilized acrylic polymer dispersions useful in the present invention can generally have a concentration of silicone copolymer from 0.1 wt% or more to < 5.0 wt% in one embodiment, from 0.3 wt% to 2.5 wt% in another embodiment, and from 0.5 wt% to 1.5 wt% in yet another embodiment, based on the total weight of polymers in the composition. At concentrations of > 5.0 wt% siloxane copolymer, there is no significant additional advantage to using more siloxane copolymer to provide a useful, stable, and cost-effective silane. At concentrations of siloxane copolymer below < 0.1 wt.%, accelerated setting may not be detectable.

Generally, the amount of anionically stabilized acrylic polymer used in the composition may range from 3 wt% to 65 wt% in one embodiment, based on the total weight of the components in the composition; in another embodiment, from 5 wt% to 60 wt%; in yet another embodiment, from 7 wt% to 55 wt%. The preferred amount of polymer used in the formulation may also depend on the amount and type of other optional ingredients used in the formulation.

The compositions of the invention contain as component (b) at least one polyaminosiloxane copolymer containing sterically stabilising groups which can be used as setting accelerator. The sterically stabilized group-containing polyaminosiloxane copolymer may comprise, for example, a copolymer comprising polymerized monomers selected from the group consisting of aminosilane monomer mixtures. Exemplary aminosilane monomers present in the mixture may include N-methylaminopropyl-trimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, and mixtures thereof. Exemplary commercial embodiments of some of the above compounds and mixtures thereof that may be used in the present invention may include one or more of the aminosilane monomers described in table I, as follows:

TABLE I

In a preferred embodiment, the composition of the invention comprises, consists essentially of, or consists of: anionically stabilized dispersions of acrylic polymers containing a sterically stabilized polyaminosiloxane copolymer, such as aqueous aminosilicone polyalkyleneoxide silane copolymers; and the sterically stabilized group-containing polyaminosiloxane copolymer may be the product of hydrolytic condensation polymerization of: (i) an amino-functional silane; (ii) a polyalkylene glycol silane; (iii) optionally, an alkyl (or phenyl) silane; or mixtures thereof. For example, in one general embodiment, the polyaminosiloxane copolymers useful in the present invention may comprise compounds of the following structure (I):

in the above structure (I), R¹Can be, for example, aminopropyl, aminomethyl, aminoethyl, aminoisobutyl, aminoethylaminopropyl, ethylaminoisobutyl, methylaminopropyl, diethylenediaminopropyl, phenylaminopropyl, aminobutyl, aminoethylaminoisobutyl; r²May be, for example, methoxypoly (ethylene oxide) propyl, hydroxypoly (ethylene oxide) propyl or acetoxypoly (ethylene oxide) propyl; r³May be, for example, methyl or phenyl; r⁴May be, for example, hydroxy, methoxy or ethoxy.

Generally, the amino-functional silane present in the hydrolytic condensation polymerization can be 97 mole percent (mol%) to 66 mol% in one embodiment, and 93 mol% to 70 mol% in another embodiment.

In one embodiment, the amino group (R) of the amino-functional silane¹) Can be primary amine (-NH)₂) (ii) a OrSecondary amines (-NH-R), where R may be a C1 to C8 alkylamine, e.g. methylamine, ethylamine or propylamine, ethylenediamine (-NH-CH)₂-CH₂-NH₂) Or diethylenetriamine and mixtures thereof; or C3 alkylarylamines, such as aniline (-NH-phenyl), and mixtures thereof.

The primary amino unit of the amino functional group may comprise, for example, aminopropyl, aminomethyl, aminoethyl or aminoisobutyl and mixtures thereof. The secondary amino units of the amino functional group can comprise, for example, aminoethylaminopropyl, methylaminopropyl, ethylaminoisobutyl, triaminodiethylenepropyl, phenylaminopropyl, methylaminomethyl, ethylaminomethyl, phenylaminomethyl, aminoethylaminoisobutyl, and mixtures thereof.

In one embodiment, the equivalent weight of the silane monomer of the composition can be, for example, < 250 grams per mole (g/mol), in another embodiment, from 80g/mol to 240g/mol, and in yet another embodiment, from 100g/mol to 230 g/mol.

Generally, the polyalkylene glycol silane may be present in the hydrolytic condensation polymerization in an embodiment in a range of from 3 to 15 mole percent, and in another embodiment in a range of from 6 to 12 mole percent.

In one embodiment, the polyalkylene glycol silane of the composition may have an average molecular weight of, for example, 200 daltons (Da) to 2,000Da, in another embodiment 250Da to 1,750Da, and in yet another embodiment 300Da to 1,500 Da.

The alkylene group of the polyalkyleneoxide silane may comprise units of ethylene oxide, propylene oxide and mixtures thereof. The polyalkylene group of the polyalkyleneoxide silane may be not terminated by OH or by an alcohol (such as methanol, ethanol, propanol, butanol, and mixtures thereof); or capped with a C1 to C4 alkyl group (e.g., methyl, ethyl, propyl, butyl, and mixtures thereof); or end-capped with acetoxy or acetate end groups.

Typically, the compositions of the present invention may optionally comprise C1 to C8 alkylsilanes, phenylsilanes, C1 to C8 alkylphenylsilanes, or mixtures thereof. For example, the above compound may comprise dimethoxydimethylsilane, diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane, dimethoxy (methyl) phenylsilane, diethoxy (methyl) phenylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, octyltrimethoxysilane, and a mixture thereof. In one embodiment, the amount of the above-described compound when used may be from 0 mol% to 20 mol%, in another embodiment, from 0.01 mol% to 15 mol%, and in yet another embodiment, from 0.1 mol% to 10 mol%.

In one general embodiment, the sterically stabilizing group-containing polyaminosiloxane copolymer component (b) may be characterized as follows: (α) at least a portion of the silicon atoms in the sterically stabilizing group-containing polyaminosiloxane copolymer have pendant groups with primary or secondary amine functionality; and (β) at least a portion of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer have pendant alkyl-poly (ethylene oxide) chains with a number of ethylene oxide units.

For example, at least 70 mole percent of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer may have pendant groups with primary or secondary amine functionality in one embodiment, in another embodiment, 70 mole percent to 95 mole percent, and in yet another embodiment, 85 mole percent to 90 mole percent, based on moles of total polymer in the composition.

For example, at least 5 to 20 mol% of the silicon atoms in the steric stabilizing group-containing polyaminosiloxane copolymer may have pendant alkyl-poly (ethylene oxide) chains, in another embodiment, 5 to 15 mol%, and in yet another embodiment, 5 to 10 mol%, based on the weight of the total polymers in the smart composition. In one embodiment, the pendant alkyl-poly (ethylene oxide) chain may have from 5 ethylene oxide units to 30 ethylene oxide units, in another embodiment, from 6 ethylene oxide units to 20 ethylene oxide units, and in yet another embodiment, from 7 ethylene oxide units to 15 ethylene oxide units.

In a preferred embodiment, the sterically stabilized group-containing polyaminosiloxane copolymer may be characterized by: (α) at least 70 mol% of the silicon atoms in the copolymer have pendant groups with both secondary and primary amine functionality; and 5 to 20 mol% of the silicon atoms in the (β) copolymer have pendant alkyl-poly (ethylene oxide) chains with 5 to 20 ethylene oxide units.

The one or more primary pendant groups on the silicon atom of the sterically stabilized group-containing polyaminosiloxane copolymer may comprise, for example, 2-aminoethyl, 3-aminopropyl, 4-aminodimethylbutyl, 3- (2-aminoethylamino) propyl, propyl (diethylenetriamine) and mixtures thereof.

The one or more secondary pendant groups on the silicon atom of the sterically stabilizing group-containing polyaminosiloxane copolymer may comprise, for example, 3- (2-aminoethylamino) propyl, propyl (diethylenetriamine), N-ethyl- γ -aminoisobutyl, methyl, ethyl, propyl, phenyl and mixtures thereof.

The one or more pendant alkyl-poly (ethylene oxide) chain groups on the silicon atoms of the sterically stabilizing group-containing polyaminosiloxane copolymer may comprise, for example, hydroxyl, methyl or alkyl terminated polyethylene oxide, polypropylene oxide, polybutylene oxide, and mixtures thereof.

In one embodiment, one or more pendant alkyl-poly (ethylene oxide) chain groups on the silicon atoms of the steric stabilizing group-containing polyaminosiloxane copolymer may comprise a chain having from 5 ethylene oxide units to 20 ethylene oxide units, in another embodiment from 5 ethylene oxide units to 35 ethylene oxide units, and in yet another embodiment from 4 ethylene oxide units to 100 ethylene oxide units.

One skilled in the art will recognize that the concentration of ethylene oxide units will affect the desired concentration of pendant alkyl-poly (ethylene oxide) chain groups on the silicon atoms of the polyaminosiloxane copolymer to provide a balance of properties related to dispersion stability and film solidification.

In one embodiment, the sterically stabilizing group-containing polyaminosiloxane copolymer may be present in the composition, typically in an amount ranging from 0.01 wt% to 5 wt%; in another embodiment, 0.025 wt% to 4 wt%; and in yet another embodiment, 0.08 wt% to 3 wt%.

Optionally, the compositions of the present invention may be formulated with a wide variety of one or more additives to achieve performance of a particular function while maintaining the superior benefits/characteristics of the compositions of the present invention. For example, optional components useful in the aqueous coating compositions of the present invention may include pigments, fillers, dispersants, coalescents, pH adjusters, plasticizers, defoamers, surfactants, thickeners, biocides, co-solvents, and combinations thereof. The choice of additives in the composition will be influenced by a number of factors, including the nature of the acrylic polymer dispersion and the intended use of the coating composition.

In one embodiment, the formulation may include an inorganic filler, sometimes referred to as a pigment or extender. The inorganic filler is typically dispersed in the formulation in particulate form. Suitable fillers include, for example, any one or a combination of more than one selected from the group consisting of: metal oxides (e.g., titanium oxide, zinc oxide, iron oxide, etc.), calcium carbonate, nepheline syenite, aluminosilicate, feldspar, diatomaceous earth, calcined diatomaceous earth, talc, sand, silica, alumina, clay, kaolin, mica, pyrophyllite, perlite, barite, sodium potassium aluminosilicate, and calcium metal silicate. In a preferred embodiment, the inorganic filler may be any one or any combination of more than one selected from the group consisting of metal oxides, calcium carbonate and sodium potassium aluminosilicate.

The concentration of inorganic filler can be, for example, 0 volume percent (vol%) or > 0 vol%, such as in a general embodiment, greater than or equal to (≧)0.1 vol%, in another embodiment, 10 vol% or more, in another embodiment, 30 vol% or more, in yet another embodiment, 50 vol% or more, in even yet another embodiment, 75 vol% or more, where vol% is relative to the total volume of the formulation.

In another embodiment, the formulation optionally may include one or more rheology modifiers. Rheology modifiers can be used to adjust the viscosity of the formulation. Exemplary suitable thickeners useful in the present invention may comprise hydrophobically modified ethylene oxide urethane (HEUR) polymers, hydrophobically modified alkali soluble emulsion (HASE) polymers, hydrophobically modified hydroxyethyl cellulose (HMHEC), hydrophobically modified polyacrylamides, and mixtures thereof. Other rheology modifiers may comprise nonionic size exclusion thickeners including any one thickener or any combination of more than one thickener selected from the group consisting of hydroxyethylcellulose, hydroxyethylmethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, and combinations thereof. HEUR polymers are linear reaction products of diisocyanates with polyethylene oxides capped with hydrophobic hydrocarbon groups. HASE polymers are homopolymers of (meth) acrylic acid, or copolymers of (meth) acrylic acid, (meth) acrylate esters, or maleic acid modified with hydrophobic vinyl monomers.

Rheology modifiers can be present in the formulation at concentrations of, for example, examples comprising (0) wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% or more, and 0.9 wt% or more; also, the rheology modifier can be present in the formulation at a concentration of 1.0 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, 0.1 wt% or less, relative to the weight of the total formulation. In a preferred embodiment, the wt% of the rheology modifier may be determined according to the concentration of the component added to the formulation according to the formulation composition.

In yet another embodiment, the composition may optionally contain one or more volatile bases and/or one or more non-volatile bases. Exemplary volatile bases include, but are not limited to: ammonia; lower alkylamines, such as dimethylamine and diethylamine; ethanolamine; morpholine; aminopropanol; 2-amino-2-methyl-1-propanol; 2-dimethylaminoethanol; and combinations thereof. In other preferred embodiments, the volatile base may be ammonia. Exemplary non-volatile bases include, but are not limited to, alkali metal hydroxides, such as sodium hydroxide.

Generally, one or more volatile bases and/or non-volatile bases can be incorporated into the composition in an effective amount to maintain the pH of the aqueous vaporizable vehicle of the composition in the range of 7.2 to 10.5 or in the range of 7.5 to 10.5. In some embodiments, one or more volatile bases and/or non-volatile bases can be incorporated into the composition at a concentration of between 0 wt% and 5.0 wt%. In certain embodiments, one or more volatile bases and/or non-volatile bases can be incorporated into the composition at a concentration of between 0.1 wt% and 2.5 wt%.

In a preferred embodiment, the desired pH of the aqueous vaporizable carrier of the formulation of the invention can be obtained by addition of: volatile bases, such as ammonia; non-volatile bases such as sodium hydroxide; or a mixture of a volatile base and a non-volatile base.

In yet another embodiment, a suitable dispersant may be added to the composition, including, for example, a polyacid dispersant and a hydrophobic copolymer dispersant. The polyacid dispersants may generally comprise, for example, a polycarboxylic acid, such as polyacrylic acid or polymethacrylic acid, in part or in whole in its ammonium form; an alkali metal; an alkaline earth metal; ammonium lower alkyl quaternary ammonium salts; and combinations thereof. The hydrophobic copolymer dispersant may comprise, for example, a copolymer of acrylic acid, methacrylic acid, or maleic acid with a hydrophobic monomer.

In even yet another embodiment, suitable coalescing agents that aid in film formation during drying can be added to the composition, including, for example, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, and combinations thereof.

In yet another embodiment, other suitable additives that may optionally be incorporated into the composition may include, for example, wetting and spreading agents, leveling agents, conductivity additives, adhesion promoters, antiblocking agents, anticratering and antisurfactant agents, antifreeze agents, corrosion inhibitors, antistatic agents, flame and intumescent additives, dyes, optical brighteners and fluorescent additives, UV absorbers and light stabilizers, chelating agents, cleaning additives, cross-linking agents, matting agents, flocculants, wetting agents, biocides, lubricants, fragrances, oils, waxes and slip agents, soil resistance agents, and combinations thereof.

In one embodiment, the optional compound, when used in the compositions of the present invention, may be present in an amount generally ranging from 0 wt% to about 0.2 wt%; in another embodiment, 0 wt% to 0.5 wt%; and in yet another embodiment, 0 wt% to 1.5 wt%.

In yet another embodiment, the composition may optionally comprise a combination of other aqueous polymer dispersions, including polyurethane dispersions, mechanical dispersions of polyolefins, epoxy dispersions, polysiloxane dispersions, and combinations thereof.

In one embodiment, the optional compound, when used in the compositions of the present invention, may be present generally in an amount ranging from 0 wt% to about 1 wt%; in another embodiment, 0 wt% to 2.5 wt%; and in yet another embodiment, 0 wt% to 5.0 wt%.

In one broad embodiment, the process for preparing the composition or formulation of the present invention comprises mixing, blending or blending (a) at least one anionically stabilized dispersion of an acrylic polymer; and (b) at least one sterically stabilizing group-containing polyaminosiloxane copolymer. One or more additional optional components may be added to the formulation as desired. For example, in one embodiment, components (a) and (b) may be mixed together at the desired concentrations discussed above and at a temperature of about 5 ℃ to about 50 ℃; in another embodiment, from about 15 ℃ to about 25 ℃. The order of mixing the components is not critical, and two or more components may be mixed together and then the remaining components added. The formulation components may be mixed together by any known mixing process and equipment.

In another embodiment, the process for preparing the compositions or formulations of the present invention comprises mixing, blending or blending (a) at least one anionically stabilized dispersion of an acrylic polymer with additional optional components (e.g., pigments, extenders, dispersants, rheology modifiers) may be pre-mixed in the formulation and (b) at least one sterically stabilizing group-containing polyaminosiloxane copolymer may be added to the formulation components and may be mixed together by any known mixing process and equipment.

The compositions of the present invention produced by the process of the present invention have several advantageous properties and benefits compared to known formulations. For example, some of the properties/benefits exhibited by the compositions of the present invention may include, for example, increased stability, rapid setting, no flocculation, low pH, low alkali demand, low odor, and high solids content.

For example, in one embodiment, the viscosity of the composition of the present invention may generally range from 1 millipascal-second (mPa-s) to 5,000 mPa-s; in another embodiment, from 5mPa-s to 4,000 mPa-s; and in yet another embodiment, from 50mPa-s to 3,000 mPa-s. The viscosity of the composition can be measured by any of the conventional viscosity measurement methods known in the art.

In general, "product stability" is a requirement for successful application of the product to a substrate. Products that do not have stability may become too viscous to be applied by any of a variety of conventional application methods that may be used in a particular application. Furthermore, products that do not have stability may contain agglomerates that may lead to visual and/or mechanical defects in the final application product. One skilled in the art will recognize that the stability required for a fast setting composition may vary widely depending on the type of formulation, the intended use, and the method of application. For example, product application using a nebulizer may require the formulation to maintain viscosity and flowability; and there is no grit or agglomeration that could clog the atomizer nozzle. Spray application can be fast and can be designed to minimize the residence time between the accelerator and the coating. The stability of the composition can be measured by: (1) combining the coagulant and the product by a mixing process; (2) after mixing, the time for the composition to equilibrate and defoam; and (3) the product was then tested for grit and flocculation. Conventional grind fineness gauge instruments can be used to verify the stability of the combined equilibrium mixture, as such fineness gauges are typically used to indicate the fineness of grind or to detect the presence of coarse particles or agglomerates. Flocculation, coagulation or grit typically forms immediately after mixing and a 5 minute equilibration time is sufficient before the fineness of the mixture is tested using a grind gauge (such as the NPIRI blade fineness gauge) and using a test method such as that described in ASTM test D-1316. The size of the stable mixture should not increase by > 5 micrometers (μm) relative to a formulation without aminosilicone.

In one embodiment, the stability of the compositions of the present invention may generally range from 0 to 2 fineness difference from NPRIR; in another embodiment, 0 to 1; and in yet another embodiment, 0 (no change in fineness).

Conventional, non-fast setting aqueous products utilizing anionic polymer dispersions (e.g., acrylic emulsions) coalesce through particle-particle and/or particle-filler interactions to build mechanical properties of the final product. Build-up of properties occurs after sufficient water evaporation has occurred to concentrate the dispersion and destabilize it, thereby collapsing the polymer particles.

With respect to the product, "rapid solidification" refers to the ability of the product to achieve resistance to mechanical defects and/or resistance to water scouring faster than would otherwise occur if the product were solidified by water evaporation. The ability to reduce such set times is valuable to the formulator and the user. For example, faster setting allows for the use of water-based products in cooler and/or more humid conditions that enable application in less weather-favorable seasons or where rain is expected. Rapid solidification may also reduce the time to achieve resistance to mechanical defects. This property is valuable to the formulator and the user because of the fast setting product: (1) resistance to scratching due to dirt or debris that may be encountered, for example, during external application of the product, may be rapidly developed; (2) blocking or stacking resistance can be provided earlier; and/or (3) may be earlier recoated with additional surface coatings.

One skilled in the art will recognize that the set time of the product can vary widely, and many factors such as temperature, humidity, formulation pigment volume concentration, product solids, product thickness, or substrate conditions will have an effect on the set time of the product. For example, it is desirable that compositions for traffic or pavement marking have a short set time to minimize interference with traffic. Other products may require a higher degree of operability after initial use. For example, an exterior finish system may be expected to be about 1 hour to render or polish before setting. Thus, rapid setting is a comparison of time between comparative formulations with and without an accelerator; that is, the time required to set the product by a particular method and achieve resistance to mechanical defects and/or resistance to water scour is compared to the time required to set the product by water evaporation and achieve resistance to mechanical defects and/or resistance to water scour.

Those skilled in the art will also recognize that rapid solidification can be measured by a comparative pass-fail water flush test (such as the test described in U.S. patent No. 7,897,669B2 or U.S. patent No. 4,571, 415A). Alternatively, more gauges (e.g., linear or circular mechanical drying time recording devices) may be used to measure the set time. The rapid setting of the compositions of the present invention can be measured by the method described in ASTM D-5895-13 using such a recording apparatus. The test determines the various stages of drying by dragging a Teflon ball stylus through the composition as it dries. The test was completed at "through dry time" when the stylus rose out of the coating (formed from the composition) and there was no tearing or pattern formation on the surface of the coating. When the set time was measured using a circular mechanical drying time recorder, the set time was noted as "stage D".

In general, the "fast setting" characteristic of the compositions of the present invention may be defined herein as a reduction in relative "through dry time" based on relative percentages of the composition. A 100% reduction on a relative dry time basis is immediate drying, in one embodiment, the reduction in relative dry time may be greater than 25%; in another embodiment, greater than 35%; and in yet another embodiment, greater than 40%. In another embodiment, the reduction in relative total dry time may be less than 90%. Other embodiments of the reduction in relative full dry time may include ranges of, for example, 25% to 90%, 35% to 90%, and 40% to 90%.

In one embodiment, the pH of the composition of the present invention may range generally from 7 to 10.5; in another embodiment, 7.2 to 10, and in yet another embodiment, 8 to 9.5. The pH of the composition can be measured by the method described in ASTM E70. Typically, no base is required to adjust the pH of the composition, and if a base is used, the amount of base used should be minimized. In one embodiment, if a base is used to adjust the pH of the composition, the amount of base used may generally be an amount sufficient to provide a pH of the composition in the range of 7 to 10.5; in another embodiment, 7.2 to 10, and in yet another embodiment, 8 to 9.5. In one embodiment, if a base is used to adjust the pH of the composition, the amount of base can be, for example, 0 wt% to 2 wt%; in another embodiment, 0.01 wt% to 1.0 wt%, and in yet another embodiment, 0.01 wt% to 0.5 wt%.

The solids content of the formulations of the present invention may depend on the function of the desired application in which the formulations of the present invention are to be used. For example, for clear varnish coating end uses, the varnish may contain very low solids and may contain little, if any, extender. For other applications, such as for sealants or exterior finishes typically containing extenders and fillers, a high solids content can be used to maximize build-up upon application and minimize drying time and shrinkage upon drying. By way of illustration of the invention, but not limitation, in one embodiment, the solids content of the composition of the invention may range generally from 20% to 80%; in another embodiment, 30% to 75%; and in yet another embodiment, 35% to 70%. Generally, the solids content is defined as the weight percent of the volatile content of the composition. The solids content can be measured, for example, by various tests, such as those described in ASTM D2369-10 (2015)).

In another embodiment, it is desirable to minimize and keep the odor of the composition of the present invention at as low a level as possible. As known to those skilled in the art, odor is directly related to the concentration of volatile base present in the formulation and the pH of the formulation. The higher the pH of the formulation, the more intense the formulation will have as compared to a formulation with a lower pH and equivalent volatile base concentration.

The present invention can be compared to aminosilanes or aminosiloxanes known in the art to act as accelerators and which do not have polyether diol groups to enhance stability and increase formulation latitude. By "increased formulation latitude" is meant herein a formulation containing an aminosilicone composition of the present invention that achieves a stable, fast-setting mixture with less restriction such that the mixture maintains its ability to be applied to a substrate. For example, the pH of the formulations of the present invention are used in a range less than other known aminosilanes/siloxanes and the viscosity of the formulations of the present invention need not be very high (e.g., > 15MPa [15,000cps ]]). For example, it is known in the art to use amino-functional silanes or siloxanes such as aminopropyltrimethoxysilane (e.g., Silquest available from Meiji Co., Ltd.)^TMA-1110) or condensation products of such silanes are added to the formulation such that upon application a pH triggered flocculation is induced. Known aminosilane materials may also be used as part of a polyamine admixture to accelerate setting to provide adhesion; and accelerated solidification is achieved. Typically, known aminosilane materials are used in the formulation at a desired concentration of 0.5 wt% to 2.0 wt%, based on the weight of the polymer solids of the formulation. However, the addition of aminosilane in sufficient concentration to effect coagulation also requires a significant excess of pH neutralizing agent to prevent coagulation of the formulation.

It has also been found that, for example, when a hydrolytic condensation product of aminopropyltrimethoxysilane is used in the formulation, ammonia (or a mixture of ammonia bases and non-volatile bases) must be added to the formulation to provide a pH ≧ 11.0 in order to prevent the formulation from coagulating, so that the formulation has a consistency ranging from gritty to gelled. To achieve a pH of 11.0 or more, the amount of alkaline solution that must be added to the formulation may exceed 10% of the total formulation weight. Such an amount of base in the formulation undesirably reduces the solids content of the formulation. Also, if a volatile base is used in the formulation, the volatile base may have a very strong impact on the odor of the formulation.

Using the compositions of the present invention, it has surprisingly been found that aminosiloxane compositions exhibiting the steric stability imparted by polyether diol functionality reduces the pH required to achieve a stable mixture with an anionic dispersion or a product formulated with an anionic dispersion. Moreover, it has also been unexpectedly found that the polyether diol functionality of the composition comprising the aminosiloxane coagulant advantageously provides rapid solidification with a more desirable formulation pH, odor, and solids content. For example, compositions having higher solids content advantageously do not require dilution to unacceptable levels. The compositions also advantageously have a lower amine/ammonia odor. Also, compositions having a lower pH are advantageous because the compositions may be less corrosive. In addition, the inclusion of more polyether diol functional silane in the aminosiloxane composition helps to stably add the composition to the coating at a pH as low as 7.

In one preferred embodiment, for example, an aminosiloxane copolymer comprising about 3m0 l% of an ethoxylated silane, 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane, stabilizes the composition against grit and gelation when the coating composition of the acrylic anion stabilized dispersion or formulation is at a pH of about 9.5 (11.0 relative to the aminosilane or aminosiloxane without the ethoxylated silane in the copolymer; this is the difference between adding 1% ammonia or 10% ammonia to the coating composition). In another embodiment, a composition comprising about 7 mole% of an ethoxylated silane in an aminosiloxane provides a formulation having a pH of about 9.0; and in another embodiment, a composition comprising about 10 mol% of an ethoxylated silane provides a formulation having a pH of about 7. Aminosiloxane copolymers containing 10 mol% of ethoxylated silanes can achieve rapid solidification in dispersions or formulations that do not contain ammonia or other volatile bases. Thus, the formulations of the present invention achieve coagulation without pH-triggered base volatilization. On the other hand, compositions containing about 18 mol% of ethoxylated silane provided sufficient stability performance to the composition, but did not have any rapid setting action (i.e., set time equal to control).

Without being bound by any particular theory, it is believed that the sterically stabilized aminosilicone additive switches the electrostatic anionic particle stabilization to a weaker steric stabilization that would otherwise collapse earlier during drying due to the more dense packing of the particles.

The compositions of the present invention can be used in a wide variety of applications including, for example, dispersions, coatings, sealants, and stone building paints. For example, the coating may be an exterior coating, such as a roof coating, a water-based traffic sign, an exterior finish system, flashing for liquid applications, and a sealant.

In a preferred embodiment, the composition of the present invention may be used, for example, as a coating composition to form a coating on a substrate. Substrates useful in the present invention can comprise, for example, metals such as aluminum, copper, steel, zinc, tin, and mixtures thereof. The substrate may also comprise building and masonry materials such as wood, brick, concrete, gypsum board, slate, marble, granite, cast stone, glass block, and mixtures thereof. The substrate may also comprise roofing materials such as asphalt, modified asphalt, silicone, ethylene propylene diene monomer rubber, thermoplastic polyolefins, and combinations thereof. The substrate may also comprise road and pavement materials such as asphalt, concrete, gravel, cobbles, paving materials (e.g., bricks and ingots), grass, and combinations thereof. The substrate may also comprise an article coated with an organic coating or a silicone coating.

The coating composition may be produced by mixing the components in a first step. The mixture is homogenized by mixing by any of the methods known to those skilled in the art and may be carried out at a temperature and product consistency suitable for the product application. The coating can then be applied as a second step using methods such as spraying, brushing, rolling, troweling, dipping, and knife coating. After the second step is applied, the coating may be dried; and the drying step may typically occur at ambient conditions, for example, 5 ℃ to 45 ℃. Alternatively, the drying step may be carried out in a factory application setting, wherein the article may be baked at an elevated temperature of 30 ℃ to 95 ℃.

In various applications, the thickness of the coating used may depend on the function of the coating composition. For example, in one embodiment, a coating having a thickness of 25 micrometers (μm) to 13 millimeters (mm) may be produced for coating applications. In another embodiment, a stone architectural paint having a thickness of, for example, 50 μm to 26mm, can be produced for masonry applications. In yet another embodiment, a sealant having a thickness of, for example, 0.5mm to 1 centimeter (cm) may be produced for sealant applications.

The coatings produced by the processes described above have several beneficial properties including, for example, the following benefits: faster wash-through resistance, earlier time scratch resistance, earlier time recoating, longer application window relative to poorer drying conditions, such as at low temperature (e.g., 5 ℃) or at high relative humidity (e.g., 85%).

Examples of the invention

The following examples are provided to illustrate the invention in further detail, but should not be construed to limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated.

The various materials used in the examples are explained in table II below:

TABLE II raw materials

Test method

Coagulation measured using a dry time recorder

The dispersion or coating samples were tested for coagulation according to ASTM D-5895-13(2013) and tested using a Gardner instrument DG 9300 drying time recorder. Generally, the steps for testing the process of setting of a dispersion or coating are as follows: a test panel of Leneta scrub test patterns P121-10N is provided. A 15.2cm BYK 20MIL wet film applicator was used to apply a film of the sample to the test panel. Then, the above-mentioned dry time recorder was placed on the test panel so that the radius of the stylus used in the recorder was located at the center of the film of the sample to be tested; and thereafter, the test is started. The measured set time of the film sample was recorded as the time interval from the stylus rising out of the film sample and resting on the surface of the film sample without tearing or patterning the surface of the sample.

Agglomeration measurement

Measurement of fineness of dispersions or coatings by use of G-2NPIRI blade fineness tester instability due to addition of aminosilicone (i.e., flocculation) was tested according to ASTM D1316-06 (2011). "NPIRI" stands for national institute for printing ink. A lower score of the NPIRI value indicates a higher degree of fineness. In the comparative example, an increase in NPIRI value is essentially indicative of gel formation due to undesirable flocculation (i.e., the composition is unstable).

The dispersion or coating samples were tested for instability using the following general procedure: a sample of bubble-free composition was placed into the deep end of the channel of the screed fineness gauge such that the sample level slightly overflowed the channel. The blade is then drawn across the blade finery parallel to the channel (or groove). Then, the surface of the blade fineness gauge pattern was visually observed immediately. The end point of the test was recorded as the position on the film sample where the length of the scratch was > 10 millimeters (mm).

Instability can also be evident without testing by a fine gauge blade finesse. If the sample in which the aminosilicone is added to the composition results in visually noticeable grit or larger type of agglomeration, or if the aminosilicone is added the sample is coagulated.

General procedure for producing dispersions

General procedure for producing anionic dispersions of acrylic Polymer DA

The anionic dispersion of ammonia-free pH 7 anionically stabilized acrylic polymer dispersion (referred to herein as "acrylic polymer DA") was prepared by emulsion polymerization in a four-neck one-liter round bottom reaction flask equipped with a condenser, mechanical stirrer, thermocouple, monomer feed line, and nitrogen inlet.

A monomer emulsion was also prepared in a second vessel separate from the reaction flask by mixing 75.0 grams (g) of deionized water with 13.0 grams of water containing a 23.0% solution of sodium dodecylbenzenesulfonate, then adding 148.5 grams of butyl acrylate, then 148.5 grams of methyl methacrylate and 3.0 grams of methacrylic acid.

155.0g of deionized water was added to the reaction flask, and the flask was heated to 83 ℃ under a nitrogen purge while the contents of the flask were stirred. Then, the following components were added to the flask: water containing 0.68g of a 23.0% sodium dodecylbenzenesulfonate solution; a solution containing 0.09g of sodium carbonate dissolved in 10.0g of deionized water; and a solution containing 1.5g of sodium persulfate dissolved in 10.0g of deionized water. The monomer emulsion was fed to the reaction flask at a rate of 6.5 grams per minute (g/min) and the temperature of the flask was maintained at 83 ℃ during the monomer emulsion feed.

After the monomer emulsion addition was complete, the reaction flask temperature was maintained at 83 ℃ for 10 minutes. Then, the reaction flask was cooled to 70 ℃, and water containing 0.5g of a 0.15 wt% ferrous sulfate solution was added to the flask. By adding 0.14g of water in 70% t-butyl hydroperoxide solution dissolved in 6.3g of deionized water, followed by 0.22g of reducing agent (Bruggolite)^TMFF 6M; bruggolite (Bruggolite) is a trademark of bruggangman brother) in 6.3g of deionized water to track residual monomer. The reaction flask was cooled to 35 ℃ and 0.42g of potassium hydroxide dissolved in 8.1g of deionized water was added. The resulting dispersion was cooled to room temperature (about 22 ℃) and the resulting cooled dispersion was filtered through a 325 mesh stainless steel screen.

The resulting dispersion contained a solids content of 51.1% by weight and particles having an average particle diameter of 152 nm. The dispersion had a Tg of 13 ℃ and a pH of 7.2. And the dispersion is free of volatile base. The composition of the polymer particles in the dispersion was 49.5 wt% butyl acrylate, 49.5 wt% methyl methacrylate and 1.0 wt% methacrylic acid. The dispersion contained 0.51% by weight of sodium dodecylbenzenesulfonate.

For producing propaneGeneral procedure for anionic dispersions of ethylenic Polymer DB

An ammonia-containing, anionically stabilized acrylic polymer dispersion having a pH of 9 (referred to herein as "acrylic polymer DB") was prepared according to the procedure described above for the preparation of acrylic polymer DA (except that sodium persulfate was replaced by 1.5g of ammonium persulfate, potassium hydroxide and dilution water were replaced by 2.3g of water containing 29% ammonium hydroxide solution).

The resulting dispersion had a solids content of 51.3 wt%, an average particle size of 154nm, a Tg of 15 ℃, a pH of 9.0 and contained 0.11% volatile base by total weight of the dispersion. The composition of the polymer particles in the dispersion was 49.5 wt% butyl acrylate, 49.5 wt% methyl methacrylate and 1.0 wt% methacrylic acid. The dispersion contained 0.51% by weight of sodium dodecylbenzenesulfonate.

General procedure for the production of anionic dispersions of acrylic polymers DC:

an ammonia-containing, anionically stabilized acrylic polymer dispersion (referred to herein as "acrylic polymer DC") having a pH of 9 and in which the polymer was free of acid monomers was prepared according to the procedure described above for preparing acrylic polymer DB (except that all methacrylic monomers were replaced with 3.0g of methyl methacrylate, the amount of sodium dodecylbenzenesulfonate in the monomer emulsion was reduced to 2.0g, and the total amount of ammonia added to the composition was 1.1 g).

The resulting dispersion had a solids content of 52.0 wt%, an average particle size of 175nm, a Tg of 11 ℃, a pH of 9.0 and contained 0.06% volatile base by total weight of the dispersion. The composition of the polymer particles in the dispersion was 49.5 wt% butyl acrylate and 50.5 wt% methyl methacrylate. The dispersion contained 0.11 wt% sodium dodecylbenzenesulfonate.

General procedure for producing anionic dispersions of acrylic polymers DD

An amino-containing pH 9 anionically stabilized acrylic polymer dispersion (referred to herein as "acrylic polymer DD") in which the particle size is increased and the glass transition temperature is decreased relative to acrylic polymer DA was prepared according to the above procedure for preparing acrylic polymer DB with the following changes: no sodium dodecylbenzenesulfonate was added to the reactor; after adding ammonium persulfate, 58.0g of acrylic polymer seed acrylic polymer DB was added to the reactor and the composition of the monomer emulsion was changed to: 75.0g of deionized water, 1.5g of water containing 23.0% sodium dodecylbenzenesulfonate, 249.0g of butyl acrylate, 46.5g of methyl methacrylate, and 4.5g of methacrylic acid. The ammonia added to the acrylic polymer DD was increased to 2.7g of water containing 29% ammonium hydroxide solution.

The resulting dispersion had a solids content of 53.0 wt%, an average particle size of 332nm, a Tg of-32 deg.C, a pH of 9.0 and contained 0.14% volatile base based on the total weight of the dispersion. The composition of the polymer particles in the dispersion was 83.0 wt% butyl acrylate, 15.5 wt% methyl methacrylate and 1.5 wt% methacrylic acid. The dispersion contained 0.10 wt% sodium dodecylbenzenesulfonate.

General procedure for producing anionic dispersions of acrylic polymers DE

An ammoniated pH 9 anionically stabilized acrylic polymer dispersion containing fatty alcohol ether sulfate surfactant (referred to herein as "acrylic polymer DE") was prepared according to the procedure described above for preparing acrylic polymer DB with the following changes: sodium dodecylbenzenesulfonate added to the reactor with 0.1g of 30% 12EO fatty alcohol ether sulfate solution (Disponil)^TMFES-993; disponil is a trademark of basf corporation) and the composition of the monomer emulsion was modified to: 75.0g of deionized water, 2.1g of water containing 30% 12EO fatty alcohol ether sulfate solution, 249.0g of butyl acrylate, 46.5g of methyl methacrylate and 4.5g of methacrylic acid. The ammonia added to the acrylic polymer DE was increased to 2.3g of water containing 29% ammonium hydroxide solution.

The resulting dispersion had a solids content of 52.2 wt%, an average particle size of 262nm, a Tg of-32 deg.C, a pH of 9.0 and contained 0.12% volatile base based on the total weight of the dispersion. The composition of the polymer particles in the dispersion was 83.0 wt% butyl acrylate, 15.5 wt% methyl methacrylate and 1.5 wt% methacrylic acid. The dispersion contained 0.11 wt% 12EO fatty alcohol ether sulfate.

General procedure for producing anionic dispersions of acrylic Polymer DF

An amino-containing pH 9 anionically stabilized acrylic polymer dispersion (referred to herein as "acrylic polymer DF") in which the polymer contained the alternative acid monomer 2-hydroxyethyl phosphate methacrylate was prepared according to the procedure described above for preparing acrylic polymer DB with the following variations: all methacrylic acid was replaced by 0.9g of 2-hydroxyethyl phosphomethacrylate and 2.1g of methyl methacrylate. The ammonia added to the acrylic polymer DF was reduced to 0.05g of water containing 29% ammonium hydroxide solution.

The resulting dispersion had a solids content of 49.8 wt%, an average particle size of 160nm, a Tg of 13 ℃, a pH of 9.1 and contained 0.14% volatile base by total weight of the dispersion. The composition of the polymer particles in the dispersion was 49.5 wt% butyl acrylate, 50.2 wt% methyl methacrylate and 0.3 wt% 2-hydroxyethyl methacrylate phosphate. The dispersion contained 0.52 wt% sodium dodecylbenzenesulfonate.

General procedure for the production of anionic dispersions of acrylic Polymer DG

An amino-containing pH 9 anionically stabilized acrylic polymer dispersion (referred to herein as "acrylic polymer DG") in which the polymer glass transition temperature was increased was prepared according to the procedure described above for the preparation of acrylic polymer DB with the following changes: the total amount of methyl methacrylate was increased to 177g and the total amount of BA was reduced to 120 g.

The resulting dispersion had a solids content of 51.2 wt%, an average particle size of 158nm, a Tg of 33.7 ℃, a pH of 9.2 and contained 0.10% volatile base by total weight of the dispersion. The composition of the polymer particles in the dispersion was 40.0 wt% butyl acrylate, 59.0 wt% methyl methacrylate and 1.0 wt% methacrylic acid. The dispersion contained 0.51% by weight of sodium dodecylbenzenesulfonate.

General procedure for the production of siloxanes

General procedure for the production of aqueous amino-functional siloxanes SA

Aqueous amino-functional siloxanes (referred to herein as "siloxane SA") were prepared by hydrolytic condensation polymerization in a 200 milliliter (mL) round bottom reaction flask equipped with a magnetic stirrer. To the reaction flask was added 3.3g of 3- (2-aminoethylamino) propyldimethoxymethylsilane, 12.8g of 3- (2-aminoethylamino) propyltrimethoxysilane, 6.5g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 2.0g of dimethoxydimethylsilane. The contents of the flask were then stirred. The flask was fitted with a 100mL addition funnel and 25.0g of deionized water was added to the flask at a rate of 0.5 mL/min (mL/min). After the water addition was complete, mixing was maintained for one hour. The flask was then transferred to a rotary evaporator and the solution in the flask was concentrated under reduced pressure. The resulting amino-functional siloxane solution had a solids content of 47.7%. The composition of the siloxane polymer was 16.5 mol% 3- (2-aminoethylamino) -propyldimethoxymethylsilane, 57.1 mol% 3- (2-aminoethylamino) propyltrimethoxysilane, 9.8 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 16.5% dimethoxydimethylsilane.

General procedure for the production of aqueous amino-functional siloxanes SB

An aqueous amino-functional siloxane (referred to herein as "siloxane SB") was prepared using the procedure described above for the preparation of siloxane SA except that 0.0g of 3- (2-aminoethylamino) -propyldimethoxymethylsilane, 12.5g of 3- (2-aminoethylamino) propyltrimethoxysilane, and 10.5g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane were added to the flask. The resulting amino-functional siloxane solution had a solids content of 47.2%. The composition of the siloxane polymer was 63.3m0 l% 3- (2-aminoethylamino) propyltrimethoxysilane, 18.0 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 18.7% dimethoxydimethylsilane.

For producing aqueous ammoniaGeneral procedure for radical-functional siloxane SC

An aqueous amino-functional siloxane (referred to herein as "siloxane SC") was prepared using the procedure described above for the preparation of siloxane SA, except that no 3- (2-aminoethylamino) propyltrimethoxysilane and dimethoxydimethylsilane were added to the flask. Instead, 22.5g of 3- (2-aminoethylamino) propyldimethoxymethylsilane and 5.0g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane were added to the flask. The resulting amino-functional siloxane solution had a solids content of 49.3%. The composition of the siloxane polymer was 93.0 mol% 3- (2-aminoethylamino) propyldimethoxymethylsilane and 7.0 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane.

General procedure for the production of aqueous amino-functionalized siloxanes SD

An aqueous amino-functional siloxane (referred to herein as "siloxane SD") was prepared using the procedure described above for the preparation of siloxane SA (except that 25.0g of aminopropyltriethoxysilane was used in place of all other silane monomers). The resulting amino-functional siloxane solution had a solids content of 49.8%. The composition of the siloxane polymer was 100 mol% aminopropyltriethoxysilane.

General procedure for the production of aqueous amino-functional siloxanes SE

An aqueous amino-functional siloxane (referred to herein as "siloxane SE") was prepared using the procedure described above for the preparation of siloxane SA, except that all silane monomers were replaced with 27.5g of 3- (2-aminoethylamino) propyltrimethoxysilane and 27.5g of aminopropyltriethoxysilane, and 50.0g of water was added. The resulting amino-functionalized silicone solution had a solids content of 44.0%. The composition of the siloxane polymer was 49.9 mol% 3- (2-aminoethylamino) propyltrimethoxysilane and 50.1 mol% aminopropyltriethoxysilane.

General procedure for the production of aqueous amino-functionalized siloxanes SF

An aqueous amino-functional siloxane (referred to herein as "siloxane SF") was prepared using the procedure described above for the preparation of siloxane SA (except that 25.0g of aminopropyldimethoxymethylsilane was used in place of all other silane monomers). The resulting amino-functional siloxane solution had a solids content of 43.7%. The composition of the siloxane polymer was 100 mol% aminopropyldimethoxymethylsilane.

General procedure for the production of aqueous amino-functional siloxane SG

An aqueous amino-functional siloxane (referred to herein as "siloxane SG") was prepared using the procedure described above for the preparation of siloxane SA except that 3- (2-aminoethylamino) propyltrimethoxysilane was not added and instead 22.5g of 3- (2-aminoethylamino) propyldimethoxymethylsilane, 2.3g of dimethoxydimethylsilane and 5.0g of 2- [ methoxy (polyvinyloxy) 9-12 propyl ] trimethoxysilane were added. The resulting amino-functionalized silicone solution had a solids content of 48.0%. The composition of the siloxane polymer was 82.0 mol% 3- (2-aminoethylamino) propyl-dimethoxymethylsilane, 3.0 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 15.0% dimethoxydimethylsilane.

General procedure for the production of aqueous amino-functional siloxanes SH

An aqueous amino-functional siloxane (referred to herein as "siloxane SH") was prepared using the procedure described above for the preparation of siloxane SA except that all monomers were replaced with 39.1g of 3-aminopropyldiethoxymethylsilane and 10.1g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] -trimethoxysilane and 50.0g of water was added. The resulting amino-functional siloxane solution had a solids content of 43.0%. The composition of the silicone polymer was 93.0 mol% 3-aminopropyldiethoxymethylsilane and 7.0 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane.

General procedure for generating aqueous amino-functional siloxanes SI

An aqueous amino-functional siloxane (referred to herein as "siloxane SI") was prepared using the procedure described above for the preparation of siloxane SA except that 33.8g of 3-aminopropyldimethoxymethylsilane and 21.2g of dimethoxydimethylsilane were used in place of all other silane monomers and 50.0g of water was added. The resulting amino-functionalized silicone solution had a solids content of 60.0%. The composition of the siloxane polymer was 50 mol% 3-aminopropyldiethoxymethylsilane and 50 mol% dimethoxydimethylsilane.

General procedure for production of aqueous amino-functionalized siloxanes SJ

An aqueous amino-functional siloxane (referred to herein as "siloxane SJ") was prepared as an exemplary SA, except that 25.0g of 3- (2-aminoethylamino) propyltrimethoxysilane was used in place of all other silane monomers. The resulting amino-functionalized silicone solution had a solids content of 48.0%. The composition of the siloxane polymer was 100 mol% 3- (2-aminoethylamino) propyltrimethoxysilane.

General procedure for the production of aqueous amino-functional siloxanes SK

An aqueous amino-functional siloxane (referred to herein as "siloxane SK") was prepared using the procedure described above for the preparation of siloxane SA except that all monomers were replaced with 39.1g of 3-aminopropyldiethoxymethylsilane, 10.1g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 8.7g of dimethyldimethoxysilane and 50.0g of water was added. The resulting amino-functionalized silicone solution had a solids content of 48.30%. The composition of the siloxane polymer was 73.0 mol% 3-aminopropyldiethoxymethylsilane, 5.3 mol% 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane and 24.7% dimethyldimethoxysilane.

General procedure for producing acrylic coatings

General procedure for the production of acrylic coating CA

Acrylic coatings free of ammonia or volatile base (referred to herein as "acrylic coating CA") were prepared by mixingAdded sequentially to a1 liter vessel to prepare: 73.2g of deionized water, 3.0g of a 30% solids, ammonia and formaldehyde free polyacid pigment dispersant (e.g., TAMOL)^TM851 dispersing agent; TAMOL is a trademark of Rohm and Haas corporation), 0.9g of a defoaming agent (e.g., DEE FO^TM1015; DEE Fo is a trademark of the Ming Rabdosia group), 268.2g of a ground calcium carbonate filler (e.g., SNOWHITE) having a median particle size of 12 microns^TM12 calcium carbonate; SNOWHITE is a trademark of the Europe group) and 45.0g of a titanium dioxide pigment (e.g., Ti-Pure)^TMR-960, Ti-Pure is a trademark of Kesime). The above components were mixed together for 20 minutes using a 6.4em Cowels serrated dispersing blade operating at 1,500 Revolutions Per Minute (RPM). The mixing speed was then reduced to 350 RPM. To the vessel were added 303.2g of acrylic polymer DA and 3.6g of a coalescing agent (e.g., 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, UCAR)^TM Filmer IBT，UCAR^TMIs a trademark of the dow chemical company). In a separate vessel, by mixing 8.4g of propylene glycol with 1.1g of high molecular weight hydroxyethylmethylcellulose CAS #9032-42-2 (e.g., WALOCEL)^TMMT 30000PV, WALOCEL is a trademark of dow chemical company) to prepare a rheology modifier premix. The rheology modifier premix was then added to the vessel and the contents of the vessel were mixed at 350RPM for 10 minutes. The resulting formulation had a solids content of 65.7 wt% and a pH of 7.9. The formulation is free of ammonia and volatile amines.

General procedure for the production of acrylic coating CB

An acrylic coating having a higher pH than the acrylic coating CA prepared as described above and containing ammonia (herein referred to as "acrylic coating CB") was prepared according to the procedure described above for preparing acrylic coating CA, except that 70.8g of deionized water was added to the formulation and the dispersion was replaced with 305.6g of an anionic dispersion of acrylic polymer DB. The resulting formulation had a solids content of 65.7 wt% and a pH of 9.0. The formulation contained 0.05% ammonia, based on the total weight of the coating.

General procedure for the production of acrylic coating CC

An acrylic paint (referred to herein as "acrylic paint CC") having a higher pH than acrylic paint CA, containing ammonia, having a larger particle size polymer dispersion of particles, and a lower glass transition temperature was prepared according to the procedure described above for preparing acrylic paint CA, except that 80.6g of deionized water was added to the formulation and the dispersion of preparation example 1 was replaced with 295.8g of the anionic dispersion of acrylic polymer DD added to the formulation. The resulting formulation had a solids content of 65.7 wt% and a pH of 9.0. The formulation contained 0.06% ammonia by total weight of the coating.

Examples of the invention

Inventive example 1

In inventive example (inventive example) 1, the inventive composition was prepared using a neutral pH binder that did not contain ammonia or volatile base. In inventive example 1, no pigments, fillers, or other coating formulation ingredients were used to prepare the inventive composition. The composition of the invention example 1 was prepared by adding 50g of the dispersion of acrylic polymer DA to a 100mL vessel. Then, 1.09g of the aqueous amino-functional siloxane SA was added to the container using a pipette. The silicone (silicone SA) was homogenized into a dispersion (acrylic polymer DA) by mixing the contents of the container for approximately 30 seconds (sec) using a 15.2cm tongue depressor. The tongue depressor was removed and the mixture was defoamed by allowing the container to stand for about 5 minutes. Inventive example 1 contained 2.0% aminosilicone on dry weight adhesive. The setting time of inventive example 1 was 113 minutes and the NPIRI value < 1.

Inventive example 2

In inventive example 2, the composition of the present invention was prepared using the above procedure as described in inventive example 1, except that the amount of silicone SA of inventive example 1 was increased to a total of 2.15g in order to further accelerate the set time. Inventive example 2 contained 4.0% aminosilicone on dry weight adhesive. The setting time of inventive example 2 was 43 minutes and the NPIRI value < 1.

Inventive example 3

In inventive example 3, the inventive composition was prepared using a neutral pH coating that did not contain ammonia or volatile base. Inventive example 3 was prepared using the above procedure as described in inventive example 1 by adding 50g of acrylic paint CA to a 100mL container. Then, 0.42g of aqueous ammonia-functional siloxane SA was added to the container using a pipette. The silicone was homogenized into a dispersion by mixing the contents of the container for about 30 seconds using a 15.2cm tongue depressor. The tongue depressor was removed and the mixture was defoamed by allowing the container to stand for about 5 minutes. Inventive example 3 contained 1.8% aminosilicone on dry weight adhesive. The setting time for inventive example 3 was 89 minutes and the NPIRI value was 7.

Inventive example 4

In inventive example 4, using the above procedure as described in inventive example 3 to prepare the inventive composition, the amount of the water-dispersible amino-functional siloxane SA was increased to a total of 0.66g in order to further accelerate the setting time. Inventive example 4 contained 2.9% aminosilicone on dry weight adhesive. The setting time for inventive example 4 was 72 minutes and the NPIRI value was 7.

Inventive example 5

In inventive example 5, the composition of the invention was prepared using a pH 9 coating without a volatile base. The aqueous amino-functional siloxane of example 5 of the present invention requires monomers that are sterically less stable and have an increased pH. Inventive example 5 was prepared using the procedure described above as described in inventive example 3, except that acrylic coating CA was replaced with acrylic coating CB and silicone SA was replaced with 0.25g of silicone SC. Inventive example 5 contained 1.1% aminosilicone on dry weight adhesive. The setting time for inventive example 5 was 51 minutes and the NPIRI value was 7.

Example 60 of the invention

In inventive example 6, the inventive composition was prepared in a coating formulation containing a dispersion with a lower glass transition acrylic polymer and containing larger particles. Inventive example 6 was prepared using the procedure described above as described in inventive example 3, except that the acrylic coating CA was replaced by the acrylic coating CC and 0.16g of silicone SA was added to the formulation. Inventive example 6 contained 0.7% aminosilicone on dry weight adhesive. The setting time for inventive example 6 was 128 minutes and the NPIRI value was 7.

Inventive example 7

In inventive example 7, the inventive composition was prepared in a coating formulation with ammonia where the aminosiloxane contained a low mol% of ethoxylated silane. Inventive example 7 was prepared using the procedure described above as described in inventive example 3, except that acrylic paint CA was replaced with acrylic paint CB and 0.25g of water containing 29% ammonium hydroxide solution was mixed into acrylic paint CB to increase the pH to 9.7 prior to addition of the aminosilicone. Also, siloxane SA was replaced with 0.22g of siloxane SG. Inventive example 7 contained 1.0% aminosilicone on dry weight adhesive. The setting time for inventive example 7 was 39 minutes and the NPIRI value was 7. The formulation contained 0.19% ammonia, based on the total weight of the coating.

Inventive example 8

In inventive example 8, the composition of the invention was prepared in a dispersion containing a fatty alcohol ether sulfate surfactant. Inventive example 8 was prepared according to the procedure used to prepare inventive example 1, except that acrylic polymer DA was replaced with acrylic polymer DE and 0.21g of silicone SA was added to the formulation. Inventive example 8 contained 0.4% aminosilicone on dry weight adhesive. The setting time for inventive example 8 was 174 minutes and the NPIRI value was < 1.

Inventive example 9

In inventive example 9, the primary amine group aminopropyl on a silane monomer was used to prepare the inventive composition. Inventive example 9 was prepared using the procedure described above as described in inventive example 3, except that the acrylic coating CA was replaced by the acrylic coating CC and the aminosilane was replaced by 0.13g of siloxane SH added to the formulation. Inventive example 9 contained 0.6% aminosilicone on dry weight adhesive. The setting time for inventive example 9 was 95 minutes and the NPIRI value was 7.

Inventive example 10

In inventive example 10, a composition according to the invention was prepared according to the procedure used to prepare inventive example 1, except that dispersion DA was replaced by dispersion DF containing 2-hydroxyethyl methacrylate phosphate. In inventive example 10, 50.0g of dispersion DF were mixed with a total of 0.64g of aqueous amino-functional siloxane SA. Inventive example 10 contained 1.3% aminosilicone on dry weight adhesive. The setting time for inventive example 10 was 46 minutes and the NPIRI value was < 1.

Inventive example 11

In inventive example 11, a composition of the present invention was prepared according to the procedure used to prepare inventive example 1, except that acrylic polymer DA was replaced with acrylic polymer DG containing a polymer having a higher glass transition temperature. A coalescing agent is added to the formulation to reduce the film forming temperature below ambient temperature. In inventive example 11, 50.0g of dispersion DG are mixed with 2.0g of Texanol and a total of 0.50g of siloxane SA. Inventive example 11 contained 0.9% aminosilicone on dry weight adhesive. The setting time of inventive example 11 was 96 minutes and the NPIRI value was < 1.

Inventive example 12

In inventive example 12, the primary amine aminopropyl groups on silane monomers were used at lower concentrations to prepare the inventive compositions. Inventive example 12 was prepared using the procedure described above as described in inventive example 3, except that the acrylic coating CA was replaced by the acrylic coating CC and the aminosiloxane was replaced by 0.22g of siloxane SK added to the formulation. Inventive example 12 contained 0.9 aminosilicone on dry weight adhesive. The setting time for inventive example 12 was 108 minutes and the NPIRI value was 7.

Inventive example 13

In inventive example 13, a composition of the invention was prepared using a formulation of an aqueous polymer dispersion containing polysiloxane particles. Inventive example 13 was prepared using the procedure described above as described in inventive example 3, except that the acrylic coating CA was replaced with the acrylic coating CC, 1.0g of dow corning IE-6683 emulsion was mixed into the acrylic coating CC prior to addition of the aminosilicone, and a total of 0.40g of silicone SA was added to the formulation. Dow Corning IE-6683 emulsion is a 40% active nonionic silane-siloxane type emulsion. Inventive example 13 contained 0.6% aminosilicone on dry weight adhesive. The setting time for inventive example 13 was 85 minutes and the NPIRI value was 7.

Inventive example 14

In inventive example 14, a composition of the invention was prepared using a formulation of an aqueous polymer dispersion containing polyethylene particles. Inventive example 14 was prepared using the above procedure as described in inventive example 3, except that: acrylic coating CA is replaced by acrylic coating CC; 1.0g of Michem emulsion 62330 was mixed into acrylic paint CC before the aminosilicone was added; and a total of 0.43g of silicone SA was added to the formulation.Emulsion 62330 was a 30% solids anionic paraffin/polyethylene co-emulsion. Inventive example 14 contained 0.6% aminosilicone on dry weight adhesive. The setting time for inventive example 14 was 82 minutes and the NPIRI value was 7.

Inventive example 15

In inventive example 15, the composition of the present invention was prepared using a dispersion containing an aqueous polyurethane polymer dispersion. Inventive example 15 was prepared using the above procedure as described in inventive example 1, except that: the dispersion of inventive example 1 was replaced by acrylic polymer DB; 5.0g of Witcobond 418-49 were mixed into the acrylic polymer DB before the addition of the aminosilicone; and a total of 1.0g of silicone SA was added to the formulation. Witcobond 418-49 is a 60% solids, aqueous, aliphatic polyester polyurethane dispersion with anionic stability. Inventive example 15 contained 1.8% aminosilicone on dry weight adhesive. The setting time of inventive example 15 was 120 minutes and the NPIRI value < 1.

Comparative example

Comparative example A

This comparative example (comparative example) a is a control experiment in which the coagulation and fineness of the dispersion of acrylic polymer DA were tested without addition of aminosiloxane. No pigments, fillers, or other coating formulation ingredients were used in this comparative example a. The composition of comparative example a was prepared using the procedure described above as described in inventive example 1, which resulted in an increased time for setting the acrylic polymer DA, except that no silicone SA was added. Comparative example a contained 0.0% aminosilicone on dry weight adhesive. The setting time of comparative example A was 263 minutes and the NPIRI value was < 1.

Comparative example B

This comparative example B is a control experiment in which the setting and fineness of the acrylic coating CA were tested without addition of aminosiloxane. Comparative example B was prepared using the procedure described above as described in inventive example 3, which resulted in an increased time for setting the acrylic coating CA, except that no siloxane SA was added. Comparative example B contained 0.0% aminosilicone on dry weight adhesive. The clotting time for comparative example B was 157 minutes and the NPIRI value was 7.

Comparative example C

This comparative example C used an aminosiloxane having a composition that did not accelerate the coagulation of the acrylic polymer DA. Comparative example C was prepared using the procedure described above as described in inventive example 1, except that the siloxane SA was replaced with 0.33g of an aqueous amino-functional siloxane SB. Comparative example C contained 0.6% aminosilicone on dry weight adhesive. The setting time of comparative example C was 258 minutes and the NPIRI value was < 1.

Comparative example D

This comparative example D used an aminosiloxane having a composition that did not accelerate the setting of the acrylic coating CA. Comparative example D was prepared using the procedure described above as described in inventive example 3, except that the siloxane SA was replaced with 0.39 siloxane SB. Comparative example D contained 1.7% aminosilicone on dry weight adhesive. The clotting time for comparative example D was 153 minutes and the NPIRI value was 7.

Comparative example E

This comparative example E is a control experiment in which the setting and fineness of the acrylic coating CB were tested without addition of aminosiloxane. Comparative example E was prepared using the procedure described above as described in inventive example 3, which increased the time for curing the acrylic coating CB, except that the acrylic coating CA was replaced by the acrylic coating CB and no silicone SA was added to the formulation. Comparative example E contained 0.0% aminosilicone on dry weight adhesive. The clotting time for comparative example E was 174 minutes and the NPIRI value was 7.

Comparative example F

This comparative example F is a control experiment in which the coagulation and fineness of the acrylic polymer DB were tested without addition of aminosiloxane. No pigments, fillers, or other coating formulation ingredients were used in this comparative example F. Comparative example F was prepared using the procedure described above as described in inventive example 1, except that the dispersion of inventive example 1 was replaced with acrylic polymer DB and no silicone SA was added to the formulation; this increases the time for solidifying the acrylic polymer DB. Comparative example F contained 0.0% aminosilicone on dry weight adhesive. The setting time of comparative example F was 244 minutes and the NPIRI value was < 1.

Comparative example G

This comparative example G demonstrates the need for acid monomers in the composition of the acrylic polymer dispersion. In the absence of such acid monomers, gels are formed when the aminosilicone is combined with the dispersion. Comparative example G was prepared using the procedure described above as described in inventive example 1, except that acrylic polymer DA was replaced with 50.0G of acrylic polymer DC and 0.53G of siloxane SA was added. Comparative example G contained 1.0% aminosilicone on dry weight adhesive. The NPIRI value of comparative example G was > 20 because significant gels and agglomerates were formed when the aminosilicone was mixed into the dispersion.

Comparative example H

This comparative example H further demonstrates the need for acid monomers in the composition of the acrylic polymer dispersion. Additional ammonia was added to the dispersion to increase the pH. Even with higher pH dispersions, but without the acid monomer, gels will form when the aminosilicone is combined with the dispersion. Comparative example H was prepared using the procedure described above as described in comparative example G, except that 0.25G of ammonia was added to the dispersion of comparative example G to increase the pH to 10.3 before adding a total of 0.33G of siloxane SA. Comparative example H contained 0.6% aminosilicone on dry weight adhesive. Comparative example H had an NPIRI value of > 20 because significant gels and agglomerates formed when the aminosilicone was mixed into the dispersion.

Comparative example I

This comparative example E is a control experiment in which the setting and fineness of the acrylic coating CC were tested without addition of aminosilicone. Comparative example I was prepared using the procedure described above as described in inventive example 3, which increased the time for curing the acrylic coating CC, except that the acrylic coating CA was replaced by the acrylic coating CC and no silicone SA was added to the formulation. Comparative example I contains 0.0% aminosilicone on dry weight adhesive. The clotting time for comparative example I was 212 minutes and the NPIRI value was 7.

Comparative example J

This comparative example J was tested on coatings having aminosiloxane homopolymers without ethoxylated silanes. Comparative example J was prepared using the procedure described above as described in inventive example 3, except that acrylic coating CA was replaced with acrylic coating CC and silicone SA was replaced with 0.22g of silicone SD. Comparative example J contained 1.0% aminosilicone on dry weight adhesive. Comparative example J had an NPIRI value of > 20 because significant agglomeration formed when the aminosilicone was mixed into the dispersion.

Comparative example K

This comparative example K was tested on coatings having aminosiloxane copolymers without ethoxylated silanes. Comparative example K was prepared using the procedure described above as described in inventive example 3, except that acrylic coating CA was replaced by acrylic coating CC and silicone SA was replaced by 0.30g of silicone SE. Comparative example K contains 1.2% aminosilicone on dry weight adhesive. The NPIRI value of comparative example K was > 20 because significant agglomeration formed when the aminosilicone was mixed into the dispersion.

Comparative example L

This comparative example L was tested on coatings with aminosiloxane copolymers that did not contain ethoxylated silanes and ammonia was added to increase the formulation pH to 10.7. Comparative example L was prepared using the procedure described above as described in inventive example 3, except that: acrylic coating CA is replaced by acrylic coating CC; 0.45g of water containing 29% ammonium hydroxide solution was mixed into the acrylic paint CC to increase the pH to 10.7 before addition of the aminosilicone and the silicone SA was replaced by 0.30g of silicone SF. Comparative example L contained 1.2% aminosilicone on dry weight adhesive. The NPIRI value of comparative example L was > 20 because significant agglomeration formed when the aminosilicone was mixed into the dispersion.

Comparative example M

This comparative example M was tested on coatings with a large addition of ammonia load, but still insufficient to stabilize the formulation to flocculation due to the presence of the ethoxylated silane free aminosiloxane homopolymer. Comparative example M was prepared using the procedure described above as described in inventive example 3, except that acrylic paint CA was replaced by acrylic paint CC and 2.1g of water containing 29% ammonium hydroxide solution was mixed into acrylic paint CC to increase the pH to 11.2 prior to addition of the aminosilicone. Also, siloxane SA was replaced with 0.21g of siloxane SF. Comparative example M contained 0.9% aminosilicone on dry weight adhesive. The NPIRI value of comparative example M was > 18, indicating that micro-agglomerates were formed when the aminosilicone was mixed into the dispersion. The formulation contained 1.27% ammonia, based on the total weight of the coating.

Comparative example N

This comparative example N is a control experiment in which the coagulation and fineness of the acrylic polymer DE were tested without addition of aminosiloxane. No pigments, fillers, or other coating formulation ingredients were used in this comparative example N. Comparative example N was prepared using the procedure described above as described in inventive example 1, which would increase the time for setting the acrylic polymer DE, except that the dispersion of inventive example 1 was replaced with the acrylic polymer DE and no siloxane SA was added to the formulation. Comparative example N contains 0.0% aminosilicone on dry weight adhesive. The clotting time for comparative example N was 268 minutes and the NPIRI value < 1.

Comparative example O

This comparative example O was tested on a coating having an aminosiloxane homopolymer as described in the above-mentioned U.S. provisional patent application No. 62/525851 (attorney docket No. 80618:). Comparative example O was prepared using the procedure described above as described in inventive example 3, except that acrylic paint CA was replaced with acrylic paint CC and silicone SA was replaced with 0.30g of silicone SJ. Comparative example O contains 1.3% aminosilicone on dry weight adhesive. The NPIRI value of comparative example O was > 20 because significant agglomeration formed when the aminosilicone was mixed into the dispersion.

Comparative example P

This comparative example P was tested on coatings of aminosiloxane copolymers without ethoxylated silanes and the mol% of aminosilane was reduced by the addition of non-functional silanes.

Comparative example P was prepared using the procedure described above as described in inventive example 3, except that the siloxane SA was replaced with 0.22g of siloxane SI. Comparative example P contains 1.2% aminosilicone on dry weight adhesive. The set time for comparative example P was 193 minutes and the NPIRI value was 15, indicating that micro-agglomerates were formed when the aminosilicone was mixed into the dispersion.

Comparative example Q

This comparative example Q is a control experiment in which the coagulation and fineness of the acrylic polymer DF were tested without addition of aminosiloxane. No pigments, fillers, or other coating formulation ingredients were used in this comparative example Q. Comparative example Q was prepared using the procedure described above as described in inventive example 1, which would increase the time for setting the acrylic polymer DF, except that the dispersion of inventive example 1 was replaced with the acrylic polymer DF and no silicone SA was added to the formulation. Comparative example Q contains 0.0% aminosilicone on dry weight adhesive. The setting time of comparative example Q was 199 minutes and the NPIRI value < 1.

Comparative example R

This comparative example R is a control experiment in which the coagulation and fineness of the acrylic polymer DG were tested without addition of aminosiloxane. No pigment or filler was used in comparative example R, but a coalescing agent was added to reduce the film forming temperature below ambient. Comparative example R was prepared using the procedure described above as described in inventive example 1, except that the dispersion of inventive example 1 was replaced by acrylic polymer DG and 2.0g of Texanol was mixed into the adhesive before application. No siloxane SA was added to the formulation, which increased the time for setting the acrylic polymer DG. Comparative example R contains 0.0% aminosilicone on dry weight adhesive. The setting time of comparative example R was 168 minutes and the NPIRI value < 1.

Comparative example S

This comparative example S is a control experiment demonstrating the need to copolymerize aminosilane monomers with ethoxylated silane monomers. A premix of monomers in the same molar ratio as the silicone SC is added to the acrylic polymer DA and the result is a significant flocculated acrylic polymer DA. Comparative example S was prepared by mixing 4.5g of 3- (2-aminoethylamino) -propyldimethoxymethylsilane and 1.0g of 2- [ methoxy (polyethyleneoxy) 9-12 propyl ] trimethoxysilane in a one ounce vial. In a separate vessel, 50.0g of acrylic polymer DA was mixed with 0.26g of the silane monomer mixture. The agglomerates form immediately upon addition of the large grit. The NPIRI value of comparative example S was > 20 because significant agglomerates were formed when the silane monomer siloxane was mixed into the dispersion. The results of testing the above-described compositions in the inventive examples and comparative examples using the test patterns described above are shown in table III.

TABLE III-results of the tests

Discussion of results

Comparative example a similar compositions with different aminosiloxane levels were used as compared to inventive example 1 and inventive example 2. Comparison of comparative example a, inventive example 1 and inventive example 2 demonstrates that the set time is reduced by adding aminosilicones to the dispersion samples. The dispersion without aminosiloxane additive (comparative example a) and the dispersion with aminosiloxane additive (inventive example 1) established that rapid setting can be achieved when the setting time characteristics of the dispersion are reduced. Example 2 of the present invention further demonstrates that even more rapid set times of the dispersion can be achieved by increasing the concentration of aminosilicone in the dispersion. The invention example 1 also demonstrates rapid solidification in a composition that does not contain a volatile base.

Comparative example C a silicone composition outside the scope of the invention was used; and therefore, comparative example C did not set quickly because the amino content of the siloxane in comparative example C was low.

Comparative example B similar compositions with different aminosiloxane levels were used as compared to inventive example 3 and inventive example 4. Comparison of comparative example B, inventive example 3, and inventive example 4 demonstrates that set time is reduced by adding an aminosilicone to a dispersion formulated into a coating composition. Comparative example B the set time for the coating established without the aminosiloxane additive and inventive example 3, which is an aminosiloxane additive-containing coating, demonstrates that rapid set is achieved with reduced set time. Inventive example 4 further demonstrates that even more rapid set times of the dispersion can be achieved by increasing the concentration of aminosilicone in the dispersion.

Comparative example D used a siloxane outside the scope of the present invention; and, therefore, comparative example D did not set quickly because the amino content of the siloxane was low.

In inventive example 6, a dispersion with a glass transition temperature of-32 ℃ was used. Inventive example 6 demonstrates that rapid solidification can be achieved with dispersions of softer polymers having lower glass transition temperatures than the dispersions of inventive example 3.

The dispersion of inventive example 7 has low polyethylene oxide levels and can be compared to comparative example E and comparative example O. Inventive example 7, comparative example E, and comparative example O demonstrate that pendant alkyl-poly (ethylene oxide) chains are required to achieve stability and show the lower range of pendant alkyl-poly (ethylene oxide) chains. Comparative example E shows the set time of the dispersion without aminosilicone. Inventive example 7 demonstrates rapid solidification with an aminosiloxane-containing composition having low levels of silicon atoms with pendant alkyl-poly (ethylene oxide) chains. Comparative example O shows that flocculation occurs when the aminosiloxane does not contain pendant alkyl-poly (ethylene oxide) chains.

Inventive example 8 uses a dispersion stabilized with a surfactant other than sodium dodecylbenzenesulfonate. Inventive example 8 demonstrates that dispersions containing a surfactant other than sodium dodecylbenzenesulfonate (i.e., the surfactant used in the other inventive examples) can achieve rapid solidification. The dispersion in inventive example 8 was stabilized with 12EO fatty alcohol ether sulfate (Disponil FES-993).

The dispersion of example 9 of the invention with a siloxane within the compositional range of the invention may be compared to the dispersion of comparative example I (which is a comparative composition without the aminosiloxane).

The dispersion of inventive example 10 used an alternative synergistic acid in the binder. The dispersion of example 10 of the present invention demonstrates that acid monomers other than methacrylic acid are suitable for the composition of the present invention; and the acid level in the polymer composition may be lower than methacrylic acid present in other compositions of the present examples.

In inventive example 11, a dispersion with a glass transition temperature of 33 ℃ was used. The dispersion of example 11 of the present invention demonstrates that rapid solidification can be achieved by adding a coalescent agent to the dispersion with a higher temperature film forming dispersion.

In inventive example 12, aminosiloxane SK was used and it was demonstrated that a lower range of aminosilanes could be used. The dispersion of inventive example 12 may be compared to the dispersion of comparative example I to show the difference in set time.

Comparative examples G and H demonstrate the effect of combining an aminosiloxane with an adhesive when no acid is present in the adhesive. In the absence of acid monomer in the adhesive, a significant amount of coagulum formed immediately upon combining the aminosilicone with the dispersions of comparative examples G and H; and the dispersion is difficult to mix. In comparative example H, ammonia was added to the formulation to increase the pH of the formulation, which should improve the stability of the formulation by reducing the loading of the aminosilicone. Reduced coagulum for comparative example H relative to comparative example G; however, the dispersion of comparative example H still failed due to the presence of coagulum and agglomeration in the dispersion.

The compositions of comparative example J, comparative example K, and comparative example L demonstrate the need to have pendant alkyl-poly (ethylene oxide) chains on the aminosiloxane. When the aminosilicone does not contain pendant alkyl-poly (ethylene oxide) chains, a significant amount of coagulum forms in the formulation immediately upon combining the aminosilicone. To stabilize the formulation of comparative example L, the formulation also contained additional ammonia to increase the pH of the formulation, which in turn reduced the packing on the aminosilicone.

Comparative example M shows that even with significant amounts of ammonia added to the formulation, the formulation still had too much micro-flocculation. Comparative example M used a composition comparable to comparative example L, except that ammonia was added to the composition to increase the pH to > 11 prior to addition of the aminosilicone. At pH > 11 and dilution, the stability of the formulation (comparative example M) was improved relative to the comparative example L level; however, comparative example M also demonstrates that the formulation of comparative example M needs to have pendant alkyl-poly (ethylene oxide) chains when flocculation is increased from the control coating (comparative example I).

Comparative example P demonstrates the need for pendant alkyl-poly (ethylene oxide) chains in aminosilicones. The decrease in aminosilane level in comparative example P was so low that the set time of the formulation of comparative example P was not increased (see, e.g., comparative example D for CA set time). In addition, micro-flocculation was observed in the formulation of comparative example P.

Inventive example 13, inventive example 14, and inventive example 15 use different types of polymer dispersions of inventive formulations. For example, inventive example 13 was bonded to polysiloxane, inventive example 14 was bonded to polyolefin, and inventive example 15 was bonded to polyurethane dispersion.