Water-miscible fluorescent monomers as markers in aqueous coatings

Abstract

The present invention relates to a method for marking a coating composition, the method comprising adding a water-miscible fluorescent monomer to the coating composition. The fluorescent monomers of the invention are water-miscible compounds corresponding to: (Formula (I)) wherein: R2 and R3 are independently C1-C4 linear or branched alkyl groups; r1 is selected from the group consisting of a (meth) allyl group, a (meth) acryloyl group, a 2-hydroxy-3-(meth) allyloxypropyl group, a 1-hydroxy-3-(meth) allyloxypropyl group, a vinyl benzyl group, a 3-(meth) acrylamidopropyl group, and a 2-(meth) acryloyloxyethyl group or an alkyl group; x is an anionic counter ion preferably selected from the group consisting of a chloride ion, a bromide ion, a hydroxide ion, a methoxysulfate ion, a sulfate ion, a sulfonate ion, a carboxylate ion, a phosphate ion and a phosphonate ion; and R4 is independently selected from the group consisting of H, a hydroxyl group, an alkoxy group, an aryloxy group, an arylalkoxy group, an alkylaryloxy group, a (meth) allyloxy group, a vinylbenzyloxy group, a heteroaryl group,-NO2, Ci-C4alk-0-(CHR5CH20-) n,-CO2H or a salt thereof,-SO3H or a salt thereof,-PO3H2 or a salt thereof,-alkylene-C02H or a salt thereof,-alkylene-S03H or a salt thereof, and-alkylene-P03H2 or a salt thereof. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to water-miscible fluorescent monomers suitable for marking in water-based coatings.

[0002] Background and Summary of the Invention

[0003] It is well known to mark petroleum fuels with "silent" markers so that the fuel can be identified for tax purposes, manufacturing source, brand identification, and / or to prevent dilution and adulteration. Such markers are added to the fuel at low levels, typically at 100 ppm or less, where they are not easily detected by the naked eye. However, since the presence of such markers must be easily detected, simple chemical tests must be available to detect them. Typical petroleum markers react readily with reagents such as acids, bases, or, in the case of the markers described in U.S. Pat. No. 4,209,302, with acids and diazo reagents to produce chemicals that can be extracted in aqueous media and become highly colored by a chromogenic reaction.

[0004] The markers in U.S. Pat. No. 4,209,302 have also found non-fuel use as markers for asphalt additives, as described in U.S. Pat. No. 5,306,343. By using such markers, it can be determined whether contractors are indeed adding the proper amount of relatively expensive additives that increase the substantial life of the asphalt.

[0005] For similar reasons, it is desirable to label additives that are commonly used in water-based or water-processable materials and compositions. Additives in the form of aqueous solutions, dispersions, and emulsions are often added to concrete to improve its water resistance, strength, and long-term durability. Thus, it is desirable to have a tool or device to ensure that a particular additive is actually added to concrete in certain high-profile end-use applications, such as concrete structures for bridges or high-rise buildings.

[0006] Likewise, similar problems exist in the paint industry. It would be desirable to have a simple and economical method for brand / manufacturer identification. Paint companies are known to pay large amounts of money each year to settle paint failure claims. In many cases, paint manufacturers have no error proofing in identifying that their paints have indeed failed. As a result, claims are not disputed and are settled strictly based on receipts, which can be easily forged.

[0007] In order to avoid these problems, it is a potential solution to mark the coating. Solvent-based markers have been used in the prior art. Some marker compositions are integrated into polymers, requiring higher concentrations and compatibility of the marker in the polymeric system. These polymers are not easy to detect and need to be separated for detection. Some markers have unwanted side effects (such as toxicity) and / or require high dosage levels. Other markers do not have wide temperature or pH stability in coating formulations, and some markers may be removed from the composition of the mark during processing or use.

[0008] Therefore, there is a need for new markers for use in the coatings industry, particularly those that can be physically added to the coating formulation at any stage of the preparation of the coated material and that can be detected in situ without destroying the coating.

[0009] The present invention addresses at least some of these needs. The present invention proposes a water-miscible fluorescent monomer to be physically added to the coating formulation at any stage of the coating material preparation. The water-miscible fluorescent monomer of the present invention may have the following formula (I). Preferably it is 4-methoxy-N-(3-N',N'-dimethylaminopropylnaphthalimide vinylbenzyl chloride quaternary salt (CASRN#371239-11-1) or N,N-dimethyl-N-[3-[N'-(4-methoxynaphthalimide)]]propyl-N-(2-hydroxy-3-allyloxy)propylammonium hydroxide (CASRN#276878-97-8).

[0010] (I)

[0011]

[0012] wherein R2 and R3 are independently C1-C4 straight or branched chain alkyl, preferably C1-C2 alkyl, more preferably C1 alkyl; and

[0013] R1 is selected from (meth)allyl, (meth)acryloyl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, vinylbenzyl, 3-(meth)acrylamidopropyl and 2-(meth)acryloyloxyethyl or alkyl; and

[0014] X is an anionic counterion preferably selected from the group consisting of chloride, bromide, hydroxide, methoxysulfate, sulfate, sulfonate, carboxylate, phosphate and phosphonate; and

[0015] R4 is independently selected from H, hydroxy, alkoxy, aryloxy, arylalkoxy, alkylaryloxy, (methyl)allyloxy, vinylbenzyloxy, heteroaryl, -NO2, Ci-C4alk -0-(CHR5CH20-) n , -CO2H or a salt thereof, -SO3H or a salt thereof, -PO3H2 or a salt thereof, -alkylene-C02H or a salt thereof, -alkylene-S03H or a salt thereof and -alkylene-P03H2 or a salt thereof.

[0016] These additives enable qualitative in situ detection of markers using UV light. The additives show no or minimal negative impact on the finished coating formulation properties. The reflectivity of the monomers can be easily detected using UV light in both unpigmented and pigmented systems. DETAILED DESCRIPTION

[0017] The embodiments of the invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Instead, the embodiments are selected and described to enable those skilled in the art to recognize and understand the principles and operations of the invention.

[0018] Use of the term "about" before any numerical value in this disclosure or the appended claims allows for some slight imprecision in the numerical value as may be understood in the art or may result from the method of measurement (e.g., such as chemical or physical measurements) used to obtain such numerical value, and any numerical value in this disclosure or the appended claims not preceded by the term "about" should be interpreted in the same manner.

[0019] The methods and compositions described in the present disclosure as "comprising" or "including" may include those listed steps and compounds, respectively, and may optionally include other steps and components. If the methods or compositions of the present disclosure are described as "consisting of", those methods or compositions have the listed steps or compounds, but do not include unlisted steps or compounds. The term "consisting essentially of" generally refers to a composition that includes the listed compounds, and may include other unlisted compounds, but not in large amounts. For example, such a composition may contain one or more other unlisted components, but in an amount not greater than about 1% (by weight) of the overall composition, greater than about 0.5% (by weight) of the overall composition, or greater than about 0.1% (by weight) of the overall composition. In a composition "consisting of the listed components", there are no measurable amounts of other components other than the listed components, or a method "consisting of certain steps" does not include other steps other than those listed.

[0020] The present invention relates to a method for marking a coating composition, the method comprising adding a water-miscible fluorescent monomer to the coating composition. The fluorescent monomer of the present invention is miscible with water. "Water-miscible" means that the compound is easily mixed with water at room temperature without forming a separate layer. Fluorescence means that the compound absorbs light of a given wavelength from a UV source and subsequently emits radiation of a different wavelength, preferably in the visible range.

[0021] The water-miscible fluorescent monomer should be stable in the temperature range of -20°C to 50°C, preferably -10°C to 40°C. The water-miscible fluorescent monomer should also be stable in the pH range of 7 to 11, preferably 8 to 9.5. "Stable" means that the monomer is part of the formulation and does not separate and / or cause stratification during formulation stability studies. The water-miscible fluorescent monomer of the present invention corresponds to the following formula (I).

[0022] (I)

[0023]

[0024] wherein R2 and R3 are independently C1-C4 straight or branched chain alkyl, preferably C1-C2 alkyl, more preferably C1 alkyl; and

[0025] R1 is selected from (meth)allyl, (meth)acryloyl, 2-hydroxy-3-(meth)allyloxypropyl,

[0026] 1-hydroxy-3-(methyl)allyloxypropyl, vinylbenzyl, 3-(methyl)acrylamidopropyl and

[0027] 2-(meth)acryloyloxyethyl or alkyl; and

[0028] X is an anionic counterion preferably selected from the group consisting of chloride, bromide,

[0029] hydroxide ions, methoxysulfate ions, sulfate ions, sulfonate ions, carboxylate ions, phosphate ions, and phosphonate ions; and

[0030] R4 is independently selected from H, hydroxy, alkoxy, aryloxy, arylalkoxy, alkylaryloxy, (methyl)allyloxy, vinylbenzyloxy, heteroaryl, -NO2, Ci-C 4alk -0-(CHR5CH20-) n , -CO2H or a salt thereof, -SO3H or a salt thereof, -PO3H2 or a salt thereof, -alkylene-C02H or a salt thereof, -alkylene-S03H or a salt thereof and -alkylene-P03H2 or a salt thereof.

[0031] Preferably, the water-miscible fluorescent monomer of the present invention is 4-methoxy-N-(3-N',N'-dimethylaminopropyl naphthalimide vinylbenzyl chloride quaternary salt (CASRN#371239-11-1) or N,N-dimethyl-N-[3-[N'-(4-methoxynaphthalimide)]]propyl-N-(2-hydroxy-3-allyloxy)propylammonium hydroxide (CASRN#276878-97-8).

[0032] Preferably, the water-miscible fluorescent monomer is added in an amount of 5 ppm to 200 ppm by weight of the coating composition, more preferably in the range of at least 10 ppm, 25 ppm, 50 ppm or even 75 ppm to 175 ppm, 150 ppm or even 125 ppm, most preferably about 100 ppm.

[0033] The fluorescent monomeric markers of the present invention can be added to any paint / coating that is compatible with water. Such water-based interior / exterior coatings are well known in the art.

[0034] The fluorescent monomer marker of the present invention can be added at any stage of the coating / paint preparation, and can be added alone or together with one or more other components of the coating / paint.

[0035] The fluorescent monomers of the present invention should not substantially alter the properties of the coating, other than fluorescence. For example, the coating's whiteness and yellowness (as measured using ASTM E 313), gloss / sheen (as measured using ASTM D523), opacity at 3 mil coating (as measured using ASTM D2805), viscosity (as measured using a Stormer viscometer and ASTM D562) should all be within 5%, 4%, 3%, 2%, 1% of the values ​​obtained from similar formulations, except in the absence of the fluorescent marker. Preferably, these properties are not altered by the presence of the fluorescent marker.

[0036] In practice, the fluorescent marker of the present invention is added to a paint / coating, and the coating is subsequently applied to a surface in any manner generally known in the art. Once applied, the marker can be detected by irradiating a UV light source on the surface of the coating to determine whether the desired fluorescence is observed. It is believed that the intensity of the fluorescence can be measured by methods known in the art (such as by using a spectrometer), and such intensity can be related to the amount of fluorescent monomer present. In this way, the dilution of the coating can be detected.

[0037] Example

[0038] The method of the present invention is demonstrated in the following examples. Low pigment volume concentration (PVC) and medium PVC formulation coatings were evaluated. These coatings used the following materials:

[0039] Table 1

[0040]

[0041] The contents of the low PVC paint formulations (Table 2) and the medium PVC paint formulations (Table 3) of the examples of the present invention and the comparative examples are as follows:

[0042] Table 2 Low PVC paint formulations

[0043]

[0044]

[0045] Table 3 Medium PVC paint formulation

[0046]

[0047]

[0048] The procedure used to prepare the low PVC paint formulation is as follows. TM 8590 (0.05 wt%) was slowly added to a certain amount of water (9.85 wt%) in a Dispermat mixing device with continuous stirring at 400 RPM to 500 RPM. LXE (0.10 wt%); gradually added under continuous stirring 363 (0.30 wt%), OROTAN TM 731A (1.00 wt%) and ECOSURF TM EH 9 (0.30 wt%). After 15 minutes, TiO2 (R902) (18.00 wt%) was added and stirred at 1000 RPM. After 10 minutes, Omya carb (10.00 wt%) was added and the speed was adjusted to 1500 RPM to 1700 RPM. The abrasive matrix was prepared at a high speed of 20 m / sec for 45 minutes for paint dispersion. Once dispersion was complete, water (3.65 wt%) was then added to dilute the paint. Propylene glycol (2.00 wt%) and pure acrylic binder PRIMAL were added. TM AC 369S (38.00 wt%) and ROPAQUE TM Ultra E (12.00 wt%), and stirred at 700 RPM. Add defoamer DOWSIL TM8590 (0.05 wt%). Add the abrasive matrix to the thickener solution under stirring at 700 RPM. Add the coalescing additive [UCAR TM Filmer IBT / TEXANOL TM ](1.00 wt%). Add thickener [ACRYSOL TM RM 2020 NPR] (1.00 wt%) and ACRYSOL TM RM 825 (0.5 wt%) was added and the remaining water (2.00 wt%) was used to adjust the viscosity as needed. A neutralizer solution was added to adjust the pH (8.5-9.5) and obtain the final paint composition. Fluorescent monomers were added to the finished formulation and the final formulation was mixed for another 10 to 15 minutes.

[0049] The procedure used to prepare the medium PVC paint formulation is as follows. TM 8590 (0.05 wt%) was slowly added to a certain amount of water (17.85 wt%) in a Dispermat mixing device with continuous stirring at 400 RPM to 500 RPM. LXE (0.20 wt%); added gradually 363 (1.00 wt%), OROTAN TM 1288 (1.00 wt%), pine oil (0.30 wt%), TERGITOL TM 15 S 40 (70%) (0.40 wt%), NATRASOL was slowly added under continuous stirring TM 250 HBR (0.20 wt%), UCAR TM MF 90 (0.20 wt%). After 15 minutes, TiO2 (R902) (15.00 wt%) was added with stirring at 1000 RPM, and after 10 minutes, Calcite-4.00 wt%, China clay (10.00 wt%) and Talc (13.50 wt%) were added at a speed of 1500 to 1700 RPM. The abrasive matrix was prepared at a high speed of 20 m / sec for 45 minutes for paint dispersion. Once dispersion was complete, the paint was then diluted with additional water (5.95 wt%). Diethylene glycol (1.00 wt%) and styrene acrylic binder PRIMAL were gradually added with stirring at 700 RPM. TM AS 511 (20.00 wt%) and ROPAQUE TM Ultra E (5.00 wt%). Add defoamer DOWSIL TM 8590 (0.05 wt%). Add the abrasive matrix to the thickener solution under stirring at 700 RPM. Add the coalescing additive (UCARTM Filmer IBT / (1.50 wt%) and thickener ACRYSOL TM DR 110 (0.80 wt%) and the remaining water (2.00 wt%) was used to adjust the viscosity to the desired correct KU viscosity and obtain the final paint composition. The fluorescent monomer was added to the finished formulation and the final formulation was mixed for another 10 to 15 minutes.

[0050] The properties of these formulations were then tested as shown in the table:

[0051] Table 4 Low PVC formulations

[0052]

[0053] Table 5 Medium PVC formulation

[0054]

[0055]

[0056] The formulations shown in Tables 4 and 5 were aged at 55°C for 30 days and then the properties were remeasured as shown in Tables 6 and 7, respectively.

[0057] Table 6 Low PVC formulations after heat aging

[0058]

[0059] Table 7 Medium PVC formulations after heat aging

[0060]

[0061]

[0062] Based on laboratory-scale evaluation of finished paints prepared without and with the proposed water-miscible fluorescent monomer, it can be seen that the fluorescent monomer is stable under high shear mixing and does not separate out. The finished paint does not have any specific changes in its properties during the wet stage, and the cured films and formulations are stable under accelerated heat aging studies and do not interfere with the required optical properties and washability.

[0063] The intention of the present invention is to ensure that fluorescent monomer molecules are easily detected using UV lamp / torch without any extraction. The following drawings show a qualitative representation of the evaluation process as summarized in Table 8, where the number of "+" symbols indicates the relative fluorescence intensity compared to the control, and "+ / =" indicates marginal improvement, "=" and "= / -" indicate more or less similar without actual difference:

[0064]

[0065]

[0066] Paintings with monomer doses (100ppm to 0ppm) in visible light

[0067]

[0068] Paintings with monomer dose (100ppm to 0ppm) during UV light exposure

[0069]

[0070] Table 8 - Reflection intensity classification

[0071] Comparison 100ppm 75ppm 50ppm 25ppm Paint (without additives) NIL NIL NIL NIL Paint (containing FM2) +++ ++ + + / ＝ Paint (containing FM1) ++ + / ＝ ＝ ＝ / -

[0072]

Claims

1. A method for marking a paint or coating, the method comprising adding a water-miscible fluorescent monomer to the paint or coating, and then exposing the paint or coating to an ultraviolet light source and observing whether the paint or coating exhibits fluorescence.

2. The method of claim 1, wherein the paint or coating is applied to a substrate and subsequently exposed to the UV light source.

3. The method according to claim 1, wherein the fluorescent monomer miscible with water corresponds to in: R2 and R3 are independently C1-C4 straight or branched chain alkyl; R1 is selected from (meth)allyl, (meth)acryloyl, 2-hydroxy-3-(meth)allyloxypropyl, 1-hydroxy-3-(meth)allyloxypropyl, vinylbenzyl, 3-(meth)acrylamidopropyl and 2-(meth)acryloyloxyethyl or alkyl; X is an anionic counterion preferably selected from the group consisting of chloride, bromide, hydroxide, methoxysulfate, sulfate, sulfonate, carboxylate, phosphate and phosphonate; and R4 is independently selected from H, hydroxy, alkoxy, aryloxy, arylalkoxy, alkylaryloxy, (methyl)allyloxy, vinylbenzyloxy, heteroaryl, -NO2, Ci-C 4alk -0-(CHR5CH20-) n , -CO2H or a salt thereof, -SO3H or a salt thereof, -PO3H2 or a salt thereof, -alkylene-C02H or a salt thereof, -alkylene-S03H or a salt thereof and -alkylene-P03H2 or a salt thereof.

4. The method according to claim 3, wherein the fluorescent monomer miscible with water is selected from the group consisting of: 4-methoxy-N-(3-N',N'-dimethylaminopropylnaphthalimide vinylbenzyl chloride quaternary salt or N,N-dimethyl-N-[3-[N'-(4-methoxynaphthalimide)]]propyl-N-(2-hydroxy-3-allyloxy)propylammonium hydroxide.

5. The method according to claim 3, wherein R2 and R3 are independently C1-C2 alkyl. 6 . The method of claim 1 , wherein the fluorescent monomer miscible with water is added in an amount ranging from 10 ppm to 200 ppm by weight.

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