Latex compositions containing aminosilane and anion exchange resin
阅读说明：本技术 含有氨基硅烷和阴离子交换树脂的乳胶组合物 (Latex compositions containing aminosilane and anion exchange resin ) 是由 A·艾拉 G·W·东布罗夫斯基 P·E·哈特奈特 O·M·普雷斯利 A·斯沃茨 Q·张 于 2019-10-08 设计创作，主要内容包括：本发明涉及一种组合物,其包含聚合物颗粒的水性分散液；b)阴离子交换树脂颗粒；以及c)氨基硅烷。相较于含有乳胶和氨基硅烷但不含阴离子交换树脂的组合物或含有乳胶和离子交换树脂但不含氨基硅烷的组合物,所述组合物在有色涂料配制品中实现了更理想的防污和去污性质的平衡。(The present invention relates to a composition comprising an aqueous dispersion of polymer particles; b) anion exchange resin particles; and c) an aminosilane. The compositions achieve a more desirable balance of stain release and stain release properties in pigmented coating formulations than compositions containing latex and aminosilane but not anion exchange resin or compositions containing latex and ion exchange resin but not aminosilane.)
1. A composition, comprising: a) an aqueous dispersion of polymer particles having an average particle size in the range of 50nm to 500 nm; b) from 0.01 to 7 weight percent, based on the weight of the polymer particles, of anion exchange resin particles having an average particle size in the range of from 0.1 μm to 50 μm; and c) from 0.05 to 5% by weight, based on the weight of the polymer particles, of an aminosilane which is a compound containing a primary, secondary or tertiary amino group or a quaternary ammonium group separated by 2 to 6 carbon atoms from a Si-O group or a group hydrolysable to a Si-O group.
2. The composition of claim 1, wherein the polymer particles are acrylic or styrene acrylic polymer particles, and wherein the aminosilane is represented by the structure:
wherein each R is independently H, C1-C3Alkyl, phenyl or 2-aminoethyl; r1Is C1-C3Alkyl or C (O) CH3(ii) a And each R2Independently is H, C1-C3Alkyl radical, C1-C3Alkoxy or O-C (O) CH3。
3. The composition of claim 2, wherein the aminosilane is represented by the structure:
wherein each R is independently H, C1-C3Alkyl or 2-aminoethyl; r1Is C1-C3An alkyl group; and each R2Independently is H, C1-C3Alkyl or C1-C3An alkoxy group.
4. The composition of claim 3, wherein the anion exchange resin particles are crosslinked porous polymer particles functionalized with an amine or quaternary ammonium salt.
5. The composition of claim 4, wherein the concentration of the anion exchange resin particles is in the range of 0.1 to 3 weight percent based on the weight of the polymer particles; and wherein the anion exchange resin particles are polystyrene-divinylbenzene anion exchange resin particles functionalized with quaternary ammonium salts.
6. The composition according to claim 5, wherein the aminosilane is N-methylaminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropylmethyldimethoxysilane, aminopropyldimethylethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane or N, N-dimethylaminopropyltrimethoxysilane.
7. The composition of any one of claims 1 to 6, wherein the polymer particles are functionalized with 0.2 to 5 weight percent of structural units of a phosphorus acid monomer, based on the weight of the polymer particles.
8. The composition of claim 6, wherein the phosphoric acid monomer is phosphoethyl methacrylate or an allyloxirane phosphate of the formula:
wherein y is 3 to 5 and X is Li, Na, K or NH4 +。
9. The composition of claim 8, wherein the phosphate monomer is phosphoethyl methacrylate and the dispersion of polymer particles has a bimodal distribution with one mode of volume average particle size in the range of 60nm to 100nm and another mode of volume average particle size in the range of 180nm to 300 nm.
10. The composition of claim 2, further comprising a pigment, a rheology modifier, and one or more additives selected from the group consisting of dispersants, surfactants, neutralizing agents, defoamers, extenders, opacifying polymers, and coalescing agents.
Background
The invention provides an aqueous coating composition comprising an anion exchange resin, a latex and an aminosilane; the compositions are useful for providing soil resistance and stain release.
Historically, reactive pigments such as ZnO or barium metaborate, or other cationic additives, have been used to improve the soil resistance of films prepared from aqueous coating compositions. It is believed that these pigments bind to the normally anionic stain molecules, thereby preventing the stain from penetrating into the film; however, according to US 5,527,619(Rokowski), reactive pigments "cause stability problems, such as viscosity increase and polymer gelation, and are known to be environmentally unfriendly. "
Antifouling is particularly challenging when the formulation designer also wants to achieve soil release: improvements in one property often come at the expense of the other; however, this balance has not been addressed until recently, in which case the development of a paint-and-primer-in-one formulation (paint-and-primer-in-one formulation) is required to provide both excellent stain resistance and stain release.
US 8,815,997B 2(Zhang) discloses an aqueous dispersion of phosphoric acid functionalized polymer particles in combination with anion exchange resin (IER) copolymer beads suitable for paint and primer in one application with improved soil resistance; however, Zhang's composition does not provide acceptable soil resistance without compromising stain release.
Other efforts to improve stain resistance have focused on improving the barrier properties of coatings through the use of hydrophobic and low molecular weight emulsion polymers. These attempts have been only partially successful; achieving the same antifouling properties as solvent based alkyds is still far from being achieved.
Accordingly, it would be advantageous to find an aqueous coating composition effective for improving the barrier and stain release properties of a coating formulation.
Disclosure of Invention
The present invention meets the need in the art by providing a composition comprising: a) an aqueous dispersion of polymer particles having an average particle size in the range of 50nm to 500 nm; b) from 0.01 to 7 weight percent, based on the weight of the polymer particles, of anion exchange resin particles having an average particle size in the range of from 0.1 μm to 50 μm; and c) from 0.05 to 5% by weight, based on the weight of the polymer particles, of an aminosilane which is a compound containing a primary, secondary or tertiary amino group or a quaternary ammonium group separated by 2 to 6 carbon atoms from a Si-O group or a group hydrolysable to a Si-O group. The compositions of the present invention provide effective stain resistance and stain release properties to coating formulations.
Detailed Description
The present invention is a composition comprising: a) an aqueous dispersion of polymer particles having an average particle size in the range of 50nm to 500 nm; b) from 0.01 to 7 weight percent, based on the weight of the polymer particles, of anion exchange resin particles having an average particle size in the range of from 0.1 μm to 50 μm; and c) from 0.05 to 5% by weight, based on the weight of the polymer particles, of an aminosilane which is a compound containing primary, secondary or tertiary amino groups or quaternary ammonium groups separated by 2 to 6 carbon atoms, preferably 3 carbon atoms, from Si-O groups or groups which can be hydrolyzed to Si-O groups.
The polymer particles preferably have an average particle size in the range of 70nm to 300 nm. As used herein, average particle size in the context of dispersed polymer particles refers to the z-average particle size as measured by a Brookhaven BI90 particle size analyzer or a comparable dynamic light scattering instrument. In another embodiment of the invention, the dispersion of polymer particles comprises a bimodal distribution: one mode is in the range of 60nm to 100nm and the other mode is in the range of 180nm to 300 nm.
Aqueous dispersions (latexes) of polymer particles include a variety of latexes such as acrylic, styrene-acrylic, and vinyl ester latexes. The solids content of the latex is preferably in the range of from 35, more preferably from 40 to 55, more preferably to 50 wt.%.
In one embodiment of the invention, the polymer particles are functionalized with structural units of a phosphorus acid monomer in an amount of 0.2 to 5 weight percent, based on the weight of the polymer particles. As used herein, the term "structural unit" designating a monomer refers to the residue of the monomer after polymerization. Suitable phosphorus acid monomers include phosphonate esters and dihydrogen phosphate esters of alcohols, wherein the alcohol contains or is substituted with a polymerizable vinyl or alkenyl group. Preferred dihydrogen phosphate esters are the phosphate esters of hydroxyalkyl acrylates and hydroxyalkyl methacrylates, including phosphoethyl methacrylate and phosphopropyl methacrylate, with phosphoethyl methacrylate being particularly preferred. Phosphoethyl methacrylate (PEM) is used herein to refer to the structure:
wherein R is H or
Another suitable class of phosphoric acid monomers is the allyloxirane phosphates of the formula:
wherein y is 3 to 5 and X is Li, Na, K or NH4 +. A commercially available example of allyloxirane phosphate is the Sipomer PAM-5000 monomer.
The anion exchange resin particles are water-insoluble particles, preferably water, functionalized with basic groups capable of exchanging anionsInsoluble porous particles. Examples of suitable basic groups include amines, quaternary ammonium salts, and aminophosphino groups. Examples of anion exchange resins include polystyrene, polyacrylic acid or phenolic resins crosslinked with a suitable crosslinking agent such as divinylbenzene or allyl methacrylate. Commercial examples of anion exchange resins include DOWEXTM1X2 resin and AMBERLITETMIRA-900Cl resins, which are polystyrene-divinylbenzene anion exchange resins functionalized with quaternary ammonium chloride.
The concentration of anion exchange resin in the composition is preferably in the range of from 0.1, more preferably from 0.3 to 5, more preferably to 3 wt% based on the weight of the polymer particles. The average particle size of the anion exchange resin particles is preferably in the range of from 0.75 μm, more preferably from 1 μm and most preferably from 2 μm to 20 μm, more preferably to 10 μm; as used herein, the average particle size of the anion exchange resin is the D50 median particle size diameter measured using a Mastersizer 3000 particle size analyzer or a comparable laser light scattering device.
Aminosilanes are compounds which contain a primary, secondary or tertiary amino group or a quaternary ammonium group which is separated from a Si-O group or a group which can be hydrolyzed to a Si-O group (e.g.SiH or SiCl group) by 2 to 6 carbon atoms, preferably 3 carbon atoms. More preferably, the aminosilane is illustrated by the following structure:
wherein each R is independently H, C1-C3Alkyl, phenyl or 2-aminoethyl; r1Is C1-C3Alkyl or C (O) CH3(ii) a And each R2Independently is H, C1-C3Alkyl radical, C1-C3Alkoxy or O-C (O) CH3。
Examples of suitable aminosilanes include N-methylaminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropylmethyldimethoxysilane, aminopropyldimethylethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N, N-dimethylaminopropyltrimethoxysilane.
The compositions of the invention are particularly useful in pigmented coating compositions, for example further comprising TiO2The latex composition of (3) provides stain resistance. The composition advantageously further comprises a pigment, a rheology modifier and one or more additives selected from the group consisting of dispersants, surfactants, neutralizing agents, defoamers, extenders, opacifying polymers and coalescents.
It has surprisingly been found that an aqueous composition comprising a combination of an aminosilane, an anion exchange resin and a latex shows a significant improvement in the balance between detergency and soil resistance compared to a composition comprising a latex and an aminosilane but no anion exchange resin or a composition comprising a latex and an ion exchange resin but no aminosilane. It has further been found that polymer particles functionalized with a phosphoric acid monomer, preferably a PEM, further improve the balance of soil resistance and stain resistance.
Comparative example 1 preparation of latex
A monomer emulsion (ME1) was prepared from deionized water (670g), Disponil FES 993 emulsifier (FES 993, 22.5g), butyl acrylate (BA, 825g), methyl methacrylate (MMA, 645g) and glacial methacrylic acid (MAA, 30 g). To a 5 liter 4-necked flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and inlets for monomer emulsion and initiator solution, was added deionized water (750g) and FES 993(5.77 g). The contents of the flask were stirred and heated to 82 ℃. A seed charge consisting of a portion of ME1(76.3g) was added to the flask, followed by an initiator solution consisting of deionized water (10g) and sodium persulfate (3.75 g). The seed charge and initiator solution were rinsed into the flask with deionized water. The polymerization of the seed charge was monitored with a thermocouple and when the temperature of the reaction mixture peaked, the remainder of ME1 and a second initiator solution consisting of deionized water (200g), sodium persulfate (0.75g) and sodium carbonate (10.5g) were fed monotonically into the reactor over 150 minutes while controlling the reactor temperature at 85 ℃. After the feed was complete, the ME1 and initiator solution were combined with deionized waterThe flask was rinsed and the reactor was held at 85 ℃ for 10 minutes. The reactor was cooled to 80 ℃ and then a solution of ferrous sulfate heptahydrate (0.02g) and ethylenediaminetetraacetic acid tetrasodium salt (0.02g) in deionized water (5g) was added to the flask and rinsed with deionized water. Residual monomer in the reaction mixture was polymerized by feeding a solution of tert-butyl hydroperoxide (4g) in deionized water (20 g); another solution of erythorbic acid (2.2g) in deionized water (20g) was added to the flask over 20 minutes while the reaction mixture was cooled to 55 ℃. After the feed was complete, the reaction mixture was cooled to 30 ℃ and neutralized to pH 8 using ammonium hydroxide solution. After neutralization, it will be made of KATHONTMA solution of LX 1400 preservative (0.36g), FES 993(21.73g) and deionized water (8.19g) was added to the flask. The resulting latex was filtered to remove coagulum. The resulting latex had a measured solids of 45.7%.
Comparative example 2 preparation of latex with milled ion exchange resin
The procedure of comparative example 1 was followed except DOWEX which was milled to 0.75% of the median particle size of 4-6 μmTM1X2 ion exchange resin (as taught in US 8,815,997B 2) was added to the final latex. The chloride form of the resin was used.
Comparative example 3 preparation of latex with aminosilane
The procedure of comparative example 1 was followed except that 1 wt% 2-aminoethyl-3-aminopropyltrimethoxysilane (2.29g, 1 wt% based on latex solids) was added to a portion of the final latex (500 g).
2-aminoethyl-3-aminopropyltrimethoxysilane
EXAMPLE 1 preparation of latex with milled ion exchange resin and 2-aminoethyl-3-aminopropyltrimethoxysilane
The procedure of comparative example 2 was followed except that 1 wt% 2-aminoethyl-3-aminopropyltrimethoxysilane, based on latex solids, was added to the final latex.
Comparative example 4-preparation of PEM functionalized latex
The procedure was performed as described in comparative example 1, except that the monomers constituting ME1 were BA (825g), MMA (637.5g) and phosphoethyl methacrylate (PEM, 60% activity, 22.5 g); and a second initiator solution was composed of sodium persulfate (0.75g) and sodium carbonate (2.5g) in deionized water (200 g).
Comparative example 5-preparation of PEM functionalized latex with milled ion exchange resin.
The procedure of comparative example 4 was followed except that Dowex 1X2 ion exchange resin (as taught in US 8,815,997B 2) milled to 0.75% of median particle size of 4-6 μm was added to the final latex. The chloride form of the resin was used.
Comparative example 6 preparation of PEM functionalized latex with aminosilane
The procedure of comparative example 4 was followed except that 1 wt% 2-aminoethyl-3-aminopropyltrimethoxysilane, based on latex solids, was added to the final latex.
EXAMPLE 2 preparation of PEM functionalized latex with milled ion exchange resin and 2-aminoethyl-3-aminopropyltrimethoxysilane
The procedure of comparative example 5 was followed except that 1% 2-aminoethyl-3-aminopropyltrimethoxysilane, based on latex solids, was added to the final latex.
As shown in table 1, paint formulations were prepared by adding the components to the container in the order listed (comparative examples 1a-6a and examples 1a-2 a). The amounts used were the same as the formulations prepared using the binders of comparative examples 1-6 and examples 1-2, unless otherwise noted. PVC refers to pigment volume concentration. RM-3000 refers to ACRYSOLTMRM-3000 rheology modifier; the Ultra EF means ROPAQUETMAn Ultra EF opaque polymer; RM-995 refers to ACRYSOLTMRM-995 rheology modifier; the dispersant is TAMOLTM2011 dispersing agent (ROPAQUE, TAMOL and ACRYSOL are trademarks of The Dow Chemical Company or its subsidiary companies).
TABLE 1 Room semi-gloss paint formulations
Name of Material
Weight (g)
Horizontal (%)
PVC
Grinding
Kronos 4311TiO2
310.02
19.92
Dispersing agent
6
0.6
AMP-75
0.6
15-S-40(20％)
20.01
A-2434
1.00
RM-3000
15
Minex 10 bulking agent
18.62
2.37
ASP-170 bulking agent
18.62
2.40
Dilution control
Latex emulsion
*
Water (W)
50.02
Where grinding is added
Ultra EF
20
3.3
A-2434
0.5
Propylene glycol
6
Texanol
5.02
2
RM-3000
*
RM-995
*
Water (W)
*
Table 2 shows the final added water, adhesive, ACRYSOL used in the semi-optical formulationTMRM-3000 rheology modifier and ACRYSOLTMRM-995 rheology modifier.
TABLE 2 semi-gloss paint formulations
Latex example number
Water (g)
Latex (g)
RM-995(g)
RM-3000(g)
Paint example number
Comparative example 1
36.4
535.7
5.6
20
Comparative example 1a
Comparative example 2
9.25
548.9
5.6
20
Comparative example 2a
Comparative example 3
33.4
526.4
5.2
24
Comparative example 3a
Example 1
29.4
546.4
5.2
28
Example 1a
Comparative example 4
41.4
535.7
2.4
19
Comparative example 4a
Comparative example 5
42.2
546.4
2.4
18
Comparative example 5a
Comparative example 6
42.9
535.7
2.4
17
Comparative example 6a
Example 2
42.2
540.4
2.4
18
Example 2a
And (3) carrying out mark pen stain resistance test:
flat room test paints were painted on a white Leneta Penopac WB plain white chart with a 75 μm (3 mil) Bird film applicator and dried at 25 ℃ and 50% relative humidity for 7 days. A Marker stain (Blue Hydrophilic crayon wash Marker) was applied to the dried film across the width of the film and the Marker was allowed to dry for 4 days. To evaluate the marquee stain resistance, test and control paints were painted side-by-side perpendicular to the marquee stain using a 75 μm (3 mil) Bird film applicator and the films were allowed to dry overnight; a second coating was then similarly applied using a 178 μm (7 mil) "U" shaped straddle rod film applicator, and the film was then dried overnight.
The mark pen stain resistance was measured using an X-Rite spectrophotometer model Ci 7. This apparatus was used to measure the color change of both the unstained and stained areas of a substrate covered with a paint coating as described above. The value used to represent the degree of smudging of the marker is Delta E (Δ E), which is the total color difference represented by the sum of the facts of the 'L', 'a' and 'b' values, such that:
ΔE＝(ΔL 2+Δa 2+Δb2)1/2
'L' is a measure of color intensity; l-100 is equivalent to white and L-0 is equivalent to black; "a" is a measure of the hue of red and green, where positive equals red and negative equals green; "b" is a measure of the hue of yellow and blue, where positive equals yellow and negative equals blue. When measuring the Δ Ε of the test paint and the control, a lower Δ Ε indicates better marker stain resistance.
Stain removal test
Stain removal testing was performed according to ASTM method D4828.
Table 3 illustrates the stain resistance to blue marker and stain release to red wine of the adhesives functionalized with MAA.
TABLE 3-Delta E Mark resistance and stain removal results for paint coatings with binders functionalized with MAA
Examples of the invention
Delta E blue Mark stain resistance
Delta E red wine stain removal
Comparative example 1a
9.7
10.4
Comparative example 2a
5.7
10.9
Comparative example 3a
9.9
4.0
Example 1a
4.7
7.3
When an anion exchange resin is present in the acrylic resin binder (comparative example 2a), the stain resistance is improved compared to comparative example 1a without anion exchange resin; however, the red wine stain removal performance of comparative example 2a was not improved compared to comparative example 1 a. In contrast, when aminosilane was present in the acrylic adhesive (comparative example 3a), the stain release was significantly improved compared to comparative example 1a, but the stain release was not improved.
When both ion exchange resin and aminosilane were present in the acrylate based binder (example 1a), the stain resistance was further reduced compared to comparative example 2a, showing a surprising synergistic effect. In addition, the stain release in example 1a was significantly better than comparative example 1 a; thus, the presence of both the ion exchange resin and the aminosilane in the formulation, an improvement in both antifouling and stain release properties was observed.
TABLE 4-Delta E anti-Mark pen stain and stain release results for paint coatings with PEM functionalized binders
Examples of the invention
Delta E blue Mark stain resistance
Delta E red wine stain removal
Comparative example 4a
13.6
1.0
Comparative example 5a
5.9
1.3
Comparative example 6a
7.4
0.7
Example 2a
3.7
0.9
The data shows that an excellent balance of stain release and soil release properties can be achieved when the milled anion exchange resin and aminosilane are present in PEM functionalized binder example 2 a.