Abstract:
A ready to use patch repair product is disclosed that includes a color change indicator therein. After the product has dried the color changes to signal that, if desired, the worker can perform other operations such as painting, sanding, etc on the surface. In one aspect of the invention, a substantially ammonia and ammonium salt free latex polymer is used as the resin binder component. This provides enhanced color stability in the stored product.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     Priority filing benefit of (1) International PCT application PCT/US00/12147 filed May 4, 2000, and published under PCT 21(2) in the English language and (2) U.S. provisional application Ser. No. 60/132,553 filed May 4, 1999 and Ser. No. 60/136,175 filed May 27, 1999. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to a spackling/repair product or powder that produces a color while containing water. After the product is applied and the product dries, the color changes from either red or blue to white. 
     BACKGROUND OF THE INVENTION 
     Spackling compounds, joint compounds and patch repair products have been used for years to provide the desired smooth or textured coating over imperfections in building members such as wall board, plaster and other construction surfaces. 
     Typically. these compounds comprise a resinous binder, limestone, clay, lubricant, stabilizers and thickeners that are mixed with water to provide a paste like product. The paste like product is applied to the desired building member substrate with a trowel or other tool. The product hardens via drying so that the construction worker can then perform other desired operations over the thus hardened product such as sanding, taping, painting, etc. 
     So as to provide a clear indication to the construction worker that the surface is ready for performance of such additional operations, it is desirable that the spackle, joint compound or repair product contain a color indicator whereby color of the product changes after the applied product has dried. 
     While the provision of a color change indicator in such a product would superficially appear to be an easy task, the problem is made much more complex by the additional requirement that the product must be color stable during its anticipated inventory or shelf life. Accordingly, there is an even more specific need for a hardenable spackle/repair product that will change color upon drying while exhibiting enhanced color stability during long storage periods. 
     SUMMARY OF THE INVENTION 
     In accordance with the invention a ready to use product or powder is provided containing a color change agent that produces a color while containing water. After the product is applied, and the product dries, the color changes, preferably from either red or blue to white. 
     This product indicates when the applied product has dried. This allows for sanding, painting or re-application at the proper time for maximum performance. All the problems associated with post-application performance due to incomplete drying of the compound can be avoided. 
     Color change indicators that have been evaluated include phenolphthalein (red) and thymolphthalein (blue). These well-known indicators may change color after an alkaline mixture or solution containing same approaches neutrality. Also indicators can change color when water is lost. Water loss leads to the insolubility and precipitation of indicator solids which are colorless. 
     One specific formulation that has been tested is as follows: 
     
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                 SAMPLE 
               
               
                   
                 RAW MATERIAL 
                 WT % 
                 2500 Grams 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Pluronic F-68 
                 0.1000 
                 2.5 
               
               
                   
                 Water 
                 14.0500 
                 351.25 
               
               
                   
                 Premix then Add 
               
               
                   
                 CMC 7H 
                 0.2500 
                 6.25 
               
               
                   
                 Ethylene Glycol 
                 0.5000 
                 12.5 
               
               
                   
                 Mix Thoroughly 
               
               
                   
                 UCAR 412 
                 6.0000 
                 150 
               
               
                   
                 Mix Thoroughly 
               
               
                   
                 Vicron 45-3 
                 71.2000 
                 1780 
               
               
                   
                 Mix Thoroughly Premix Then Add 
               
               
                   
                 Water 
                 4.08975 
                 122.4375 
               
               
                   
                 Attagel 40 
                 1.0000 
                 25 
               
               
                   
                 Premix Then Add 
               
               
                   
                 Water 
                 1.5000 
                 37.5 
               
               
                   
                 45% KOH 
                 0.5000 
                 12.5 
               
               
                   
                 Add 
               
               
                   
                 Phenolphthalein 
                 0.0025 
                 0.0625 
               
               
                   
                 W/o Preservative 
                 0.0000 
                 0 
               
               
                   
                   
                 100.0000 
                 2500 
               
               
                   
                   
               
               
                   
                 Pluronic F-68-Polyoxyalkylene glycol block copolymer; available BASF  
               
               
                   
                 CMC 7H-Carboxymethylcellulose; available Hercules  
               
               
                   
                 UCAR 412-Butyl acrylate/methyl methacrylate/methacrylic acid terpolymer; pH (8-9); available Union Carbide  
               
               
                   
                 Vicron 45-3-Ground limestone  
               
               
                   
                 Attagel 40-Attapulgus clay; available Engelhardt  
               
             
          
         
       
     
     The product is colored red to pink and turns white upon drying. 
     The pH of the above formula is preferably about 11-13 to promote enhanced stability of indicator color during the product application. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     In general, the color change patch repair or joint or spackling compositions comprise surfactant, water retained agent, free-thaw agent, resin binder, pigment, filters, pH adjustment agent and the desired color change indicator. As used throughout these compositions are referred to generically as “patch repair” compounds. 
     As to the surfactants that can be used, these can be chosen from a variety of commercially available compounds. These include the ethoxylated alkyl phenols, such as the Triton® products available from Union Carbide, the Tamol® products available from Rohm &amp; Haas and the polyoxyalkylene glycol block polymers available for example from BASF. 
     The water retaining agent or thickener is preferably a cellulosic ether such as carboxymethylcellulose CMC, hydroxyethylmethylcellulose (HEC), hydroxypropylmethylcellulose, alkali swellable and/or associative thickeners, etc. All of these are commercially available. The preferred thickeners are available from Aqualon, Wilmington Del. with the CMC 7H and Natrosol products particularly preferred. 
     The freeze thaw agent is normally ethylene glycol, although glycols in general can be mentioned. 
     The resinous binder component can be chosen from the groups of (I) polyvinyl esters and polymers derived therefrom and/or (II) acrylic resin binders. Exemplary binders falling within the designation (I) include poly(vinyl acetate), poly(vinyl alcohol); polyvinyl (butyral); poly(vinyl chloride) etc. 
     Exemplary binders falling within the group (II) designation include acrylic polymers and copolymers. Usually, these contain copolymerized acrylic unsaturated monomers preferably copolymerized with other ethylenically unsaturated monomers. Acrylic unsaturated monomers include lower alkyl esters of acrylic or methacrylic acid having an alkyl ester portion containing between 1 to 12 carbon atoms as well as aromatic derivatives of acrylic and methacrylic acid. Useful acrylic monomers include, for example, acrylic and methacrylic acid, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, propyl acrylate and methacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate and methacrylate, isodecylacrylate and methacrylate, benzyl acrylate and methacrylate, and various reaction products such as butyl, phenyl, and cresyl glycidyl ethers reacted with acrylic and methacrylic acids, hydroxy alkyl acrylates and methacrylates such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, as well as amino acrylates and methacrylates. 
     The acrylic monomers are preferably copolymerized with ethylenically unsaturated monomers other than acrylic monomers. Ethylenically unsaturated monomers other than said acrylic unsaturated monomers can include, for example, those monomeric materials exhibiting ethylenic double bond unsaturation such as polymerizable vinyl, allylic, fumaric, maleic, or like ethylenically unsaturated double bond functionality (carbon-to-carbon unsaturation) which can be copolymerized with the acrylic double bond unsaturation in said acrylic unsaturated monomers. 
     Ethylenically unsaturated monomers can include, for example, styrene alpha-methyl styrene and substituted alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene, dibutyl maleate, butadiene, vinyl chloride, vinylidene chloride, acrylamide and acrylonitrile and similar ethylenically unsaturated monomers. The ethylenically unsaturated monomers can be copolymerized with said monomers containing acrylic unsaturation by free radical induced addition polymerization using peroxy or azo catalysts, common redox catalysts, ultraviolet radiation, or the like. The acrylic copolymer of this invention can be synthesized by adding a monomer mixture over a period of time to an aqueous polymerization medium in the presence of a free radical initiator or azo catalyst to produce an acrylic latex copolymer. Ordinarily about 1-2% peroxide initiators based on the monomer weight is used in the polymerization of monomers. 
     At present, and in order to impact enhanced color stability to the product, it is preferred to use a resin binder latex that has substantially no NH 3  or ammonium salts contained in the latex. Most preferred is UCAR latex 412 which includes as the main polymeric component: 
     butyl acrylate(BA)/methyl methacrylate (MMA)/methacrylic acid (MA) polymer. 
     The BA repeat unit may be present in a molar amount of about 40-60% with the MMA present in an amount of about 40-60% and the MA present in an amount of about 0-5%. This particular latex comprises about 45 wt % polymer solids and water in an amount of about 53 wt %. In addition, it contains minor amounts of preservative, an anti-foam agent, anionic stabilizers and residues from free radical initiators. No ammonia or ammonium salts are used in the manufacture of this product. A nonylphenoxy poly(ethyleneoxyl)ethanol surfactant is reputedly present in this latex product in an amount of about 2 wt %. 
     Referring next to the pigments, these can be chosen from a variety of compounds including ground limestone, TiO 2 , satin white, etc. 
     Fillers such as fibers, glossy spheres, pearlites, vermiculites, talc, clays, etc., can also be added. 
     PH adjustment agents such as NaOH, KOH, K 2 CO 3  and other bases can be used to regulate pH of the product to preferably, alkalinity. 
     Exemplary color change agents include phenolpthalein (reddish pink) (PTL) and thymolphthalein (blue) as set forth above. Additionally, ortho-cresolphthalein (red), ethyl bis(2,4-dinitrophenyl)acetate (blue-green), p-nitrophenol (yellow), m-nitrophenol (yellow), m-dinitrophenyl (yellow), 1,2,5-trinitrophenol (orange), and 2,4,6-trinitrophenol (orange) may be mentioned. These color indicators possess color when maintained at an alkaline pH then lose color upon drying of the product. 
     
       
         
               
             
               
               
               
             
               
             
               
               
               
             
           
               
                   
               
             
             
               
                 Exemplary compositions are as follows: 
               
             
          
           
               
                   
                 surfactant 
                 0-10% 
               
               
                   
                 thickeners 
                 0-10% 
               
               
                   
                 freeze-thaw 
                 0-10% 
               
               
                   
                 resin binder 
                 1-50% 
               
               
                   
                 pigments 
                 1-80% 
               
               
                   
                 water 
                 10-50%  
               
               
                   
                 fillers 
                 0-80% 
               
               
                   
                 pH adjustment agent 
                 .01-10%   
               
               
                   
                 color change indicator 
                 0.00001-10%     
               
               
                   
                 (The foregoing add up to 100 wt %) 
               
             
          
           
               
                 Preferred compositions are as follows: 
               
             
          
           
               
                   
                 surfactant 
                 .05-5.0%  
               
               
                   
                 thickeners 
                 .1-5.0% 
               
               
                   
                 freeze-thaw 
                 .1-2.0% 
               
               
                   
                 resin binder 
                  1-50.00% 
               
               
                   
                 pigments 
                  40-80.00% 
               
               
                   
                 water 
                  15-40.00% 
               
               
                   
                 fillers 
                 1-20% 
               
               
                   
                 pH adjustment agent 
                 .25-5%   
               
               
                   
                 color change indicator 
                 .001-5%    
               
               
                   
                 (The foregoing add up to 100 wt %) 
               
               
                   
                   
               
             
          
         
       
     
     The compositions most preferred at this time (i.e., best mode) is as follows: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 water 
                 18.48 
                 wt % 
               
               
                   
                 surfactant 
               
               
                   
                 Tamol 850 
                 0.57 
                 wt % 
               
               
                   
                 Pluronic F68 
                 0.21 
                 wt % 
               
               
                   
                 clay 
               
               
                   
                 attagel 40 
                 1.92 
                 wt % 
               
               
                   
                 calcium carbonate 
               
               
                   
                 microwhite 100 
                 42.14 
                 wt % 
               
               
                   
                 vicron 45-3 
                 20.73 
                 wt % 
               
               
                   
                 thickeners 
               
               
                   
                 CMC 7H 
                 0.06 
                 wt % 
               
               
                   
                 Natrosol 250* 
                 0.13 
                 wt % 
               
               
                   
                 pH adjustment cmpd. 
               
               
                   
                 K 2 CO 3  (45%) 
                 0.34 
                 wt % 
               
               
                   
                 freeze-thaw 
               
               
                   
                 ethylene glycol 
                 0.99 
                 wt % 
               
               
                   
                 color indicator 
               
               
                   
                 PTL 
                 0.02 
                 wt % 
               
               
                   
                   
               
             
          
         
       
     
     * -modified hydroxylethylcellulose—Aqualon Div. Hercules  
     pH=11.8-12.8; density 14.8-15.00 lbs/gal; color=pink 
     In accordance with the invention, the artisan applies the repair composition to the requisite structural surface and, with the aid of a trowel or other tool, provides a smooth or textured surface. As applied, the product is in its colored (e.g. pink when PTL is used as the color indicator) state. Upon drying, the color changes to white thereby indicating to the artisan that additional treatments etc. may be performed on the thus treated surface. 
    
    
     The invention will be further described in the following illustrative examples which are not to be construed to limit the invention. 
     In the examples the following product identifications are used, in addition to those reported above. 
     U CAR 353—Union Carbide; vinyl acetate/butylacrylate latex 
     U CAR 413—Union Carbide; butyl acrylate/methyl methacrylate methacrylic acid latex 
     EXAMPLES 
     In order to assess the color stability of the spackling/repair product of the invention, the following tasks were conducted. 
     Example 1 
     A spackle formulation including UCAR 353, and phenolphthalein (PTL), as the color change indicator, was prepared. The formulation had the following major ingredients (all ingredients reported in gram units): 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Pluronic F-68 
                 0.30 
               
               
                   
                 water 
                 63.58 
               
               
                   
                 U CAR 353 
                 19.2 
               
               
                   
                 Ethylene glycol 
                 1.5 
               
               
                   
                 attagel 40 
                 3.0 
               
               
                   
                 PTL 
                 0.03 
               
               
                   
                 KOH (45%) 
                 1.5 
               
               
                   
                 Vicron 45-3 
                 210 
               
               
                   
                   
               
             
          
         
       
     
     Initially the pH of the mixture was about 12.68 but dropped to an unacceptable level of 9.57 within 1 day. 
     Example 2 
     Another product having the following formulation was prepared: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Pluronic F-68 
                 2.5 
                 grams 
               
               
                   
                 CMC 7-H 
                 6.25 
                 grams 
               
               
                   
                 water 
                 511.19 
                 grams 
               
               
                   
                 ethylene glycol 
                 12.5 
                 grams 
               
               
                   
                 U CAR 413 
                 150 
                 grams 
               
               
                   
                 Vicron 45-3 
                 1780 
                 grams 
               
               
                   
                 attagel 40 
                 25 
                 grams 
               
               
                   
                 KOH (45%) 
                 12.5 
                 grams 
               
               
                   
                 PTL 
                 0.0625 
                 grams 
               
               
                   
                   
               
             
          
         
       
     
     The initial color of the product was pinkish but after about 4 weeks storage of the product at 120° F. in a closed container, the color substantially faded. 
     Example 3 
     In an attempt to maintain the desired color level, the amount of PTL in the formulation was increased: 
     The formulation was as follows: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 U CAR 413 
                 106 
                 grams 
               
               
                   
                 water 
                 281.8 
                 grams 
               
               
                   
                 Pluronic F-68 
                 2.5 
                 grams 
               
               
                   
                 Ethylene glycol 
                 15.00 
                 grams 
               
               
                   
                 attagel 40 
                 25.00 
                 grams 
               
               
                   
                 Vicron 45-3 
                 1110.00 
                 grams 
               
               
                   
                 CMC 7H 
                 2.1 
                 grams 
               
               
                   
                 KOH (45%) 
                 4.4 
                 grams 
               
               
                   
                 PTL 
                 0.25 
                 grams 
               
               
                   
                   
               
             
          
         
       
     
     Initially, the product had a very bright pink appearance and a pH of 11.01. About 5½ weeks after storage at 120° F., rapid dissipation of the color was noted. 
     Example 4 
     In another attempt to enhance color stability of the product, the amount of the KOH (pH regulator) in the formulation was increased. The following composition was prepared: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 water 
                 240 
                 grams 
               
               
                   
                 ethylene glycol 
                 15 
                 grams 
               
               
                   
                 CMC 7H 
                 2.1 
                 grams 
               
               
                   
                 Vicron 45-3 
                 1,110.00 
                 grams 
               
               
                   
                 U CAR 413 
                 106 
                 grams 
               
               
                   
                 Pluronic F-68 
                 2.50 
                 grams 
               
               
                   
                 attagel 40 
                 20.00 
                 grams 
               
               
                   
                 KOH (45%) 
                 6.2 
                 grams 
               
               
                   
                 PTL 
                 0.25 
                 grams 
               
               
                   
                   
               
             
          
         
       
     
     The initial pH of the product increased to a pH of greater than 12. After 5½ weeks storage at 120° F. the color had faded to about 45-50% of its original intensity. 
     Example 5 
     To inhibit color fading, an ammonia free polymer was used as the resin binder. This polymer was given the original designation U CAR 413 “ammonia free” but has now been reclassified as U CAR 412. The previously available U CAR 413 had been synthesized to include a small amount (up to about 1 wt %) of NH 4 OH to raise the product pH. The manufacturer has indicated that the U CAR 412 manufacturing process now eliminates this step hence the latex polymer is referred to as “substantially ammonia free.” Reference to ammonia free in this context means free of NH 3  and/or any of its ammonium salt forms. This phrase shall denote polymer latexes having less than about 0.5 wt % of NH 3  or NH 4  salt in the latex. 
     This new formulation included the following: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 water 
                 240 
                 grams 
               
               
                   
                 CMC 7H 
                 15 
                 grams 
               
               
                   
                 Vicron 45.3 
                 1,110.00 
                 grams 
               
               
                   
                 U CAR 412 
                 106 
                 grams 
               
               
                   
                 (No NH 4 OH) 
               
               
                   
                 Pluronic F 68 
                 2.5 
                 grams 
               
               
                   
                 attagel 40 
                 25.00 
                 grams 
               
               
                   
                 KOH (45%) 
                 4.40 
                 grams 
               
               
                   
                 PTL 
                 0.25 
                 grams 
               
               
                   
                   
               
             
          
         
       
     
     The product was bright pink and exhibited excellent color uniformity. It dried within 1-1½ hours after being placed over a plurality of small hammer dents. 
     The initial pH of the product was 11.1. After 7 weeks storage at 120° F. the product surprisingly retained 85-90% of its original depth of pink color. The viscosity of the product was also stable. 
     Example 6 
     An additional batch of the U CAR 412 (NH3 or NH 4 OH) was obtained from the manufacturer. This latex, as received, had a pH of 8.85. (The manufacturer indicated that an amine biocide was incorporated into the latex and this most probably resulted in the higher latex polymer pH). Spackling compositions incorporating this polymer latex and the other ingredients as given in Example 5 above were made. Initial pH of the product was 11.38. No significant change from the original pink color could be detected after 6 weeks storage at 120° F. 
     Discussion of Results 
     Improvement in product color stability was observed after changing to a substantially ammonia free latex polymer. This is counterintuitive since PTL is known to provide a pink to red color in alkaline media with a change to colorless at a neutral pH. Quite obviously, one would think that the presence of NH 3  in the polymer latex would elevate product pH thereby leading to increased color stability. 
     While the above description and examples describe specific embodiments of the invention, these are not intended to limit the scope of the invention. The invention is intended to cover equivalents and modifications of those disclosed, specific embodiments.