Abstract:
An improved method for dying leather with propylene glycol monomethyl ether (PGME) systems comprising adding polyacrylate resin base, C3 and C4 alcohols, and n-butyl acetate and negating the need for teflon dispersions, dibutyl phthalate, and improves the dye penetration, hastens the flash times, improve the dust free time, and improves the tape time.

Description:
[0001]     This application is a division of co-pending U.S. patent application Ser. No. 10/424,505, filed Apr. 28, 2003, which application is a continuation-in-part of U.S. patent application Ser. No. 10/158,441, filed May 30, 2002. 
     
    
     BACKGROUND OF THE INVENTION  
       [0002]     1. Field of the Invention  
         [0003]     This invention relates to leather coating compositions, particularly those compositions for dyeing, staining, or otherwise modifying the color of leather.  
         [0004]     2. Background of the Prior Art  
         [0005]     In recent years numerous advancements have been made in processes for coloring leather. U.S. Pat. No. 5,354,341 disclosed a mixture of at least 2 metal-free dyes having a trichromatic formulation that enhances the brilliance of the finished color on the leather. The dyes carry a single sulfo or carboxyl group and molecular weight of 450 to 700. The dyeing time routinely requires 30 to 180 minutes to dry.  
         [0006]     U.S. Pat. No. 5,376,147 likewise disclosed improvements in the trichromatic technique by employing dyes having two sulfo or carboxyl groups and molecular weights between 790 to 1100, but the dyeing process still required 30 to 180 minutes to dry.  
         [0007]     U.S. Pat. No. 6,290,866 disclosed that an aqueous coating composition comprising copolymerized acetoacetate or acetoacetamide monomer and copolymerized carboxylic acid monomer, in contact with metal oxide, hydroxide, or carbonate provided aesthetically pleasing and protective dried coatings on leather that had good embossability and wet-flex resistance. No enhancements in processing time at ambient temperature were noted; however, when drying at elevated temperatures of about 200° F. (93.3° C.), drying time still required at least 2.0 minutes.  
         [0008]     U.S. Pat. No. 6,387,291 discloses raising the glass transition temperature of the above-described aqueous coating compositions by increasing the amount of copolymerized acetoacetate or acetoacetamide. Again the leather products required 2 minutes or 120 seconds to dry at elevated temperatures of 93.3° C.  
         [0009]     U.S. Pat. No. 6,471,885 discloses a multistage emulsion polymer for an aqueous leather coating composition, said polymer containing copolymerized monoethylenically-unsaturated nonionic monomer which are predominantly acrylic, i.e. monomers selected from, e.g. esters of (meth) acrylic acid. It also contains copolymerized monoethylenically-unsaturated carboxylic acid monomer. Again, however, the coated leather required 120 seconds to dry at 90° C.  
         [0010]     Currently, state-of-the art aqueous coating compositions employed for dyeing leather employ dye mixtures of all types dispersed in propylene glycol monomethyl ether. Even with predominantly acrylic polymers, certain vehicles have been used for enhancing dye penetration, for example polytetrafluoroethylene, (i.e. teflon), and carboxylic acid derivatives such as dibutyl phthalate have been employed as an elastomeric plasticizer to help soften the leather. However, the enhanced dye penetration still requires, at ambient temperature, leather dyeing process times of 5 to 10 minutes and higher before dry surface is obtained. Also, the quality of the finish is not as soft and natural as desired, even though dibutyl phthalate is used.  
         [0011]     An improved leather dyeing process with enhanced drying or “flash time” while still providing aesthetically pleasing soft natural coatings with good wet-flex resistance is a long felt need in the industry.  
       DETAILED DESCRIPTION  
       [0012]     In the process of the present invention leathers are coated with dye mixtures prepared on a polyacrylate vehicle, dispersed in propylene glycol monomethyl ether, n-butyl acetate, and a mixture of C-3 and C-4 alcohols, thus negating the need for an aqueous composition, teflon dispersions and carboxylic acid derivatives such as dibutyl phthalate. The leather coating process results in improved dye penetration and processing at ambient conditions, surprisingly drying said leather in less than 1.0 minute, preferably 30 seconds.  
         [0013]     Compositions of the present invention may be applied to all types of leather such as, for example, mineral tanned or vegetable tanned leather including full-grain leather, buffed or corrected-grain leather, and split leather with or without a prior treatment with an impregnating resin mixture and with or without the application of subsequent coatings using conventional coatings application methods such as, for example, curtain coater and spraying methods such as, for example, air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, and air-assisted airless spray.  
         [0014]     The compositions of the present invention require at least one dye or pigment and a polyacrylate polymer vehicle. Additionally, conventional coating adjuvants may be contained in the composition. Such adjuvants may include, for example, emulsifiers, coalescing agents, buffers, neutralizers, thickeners, humectants, wetting agents, biocides, plasticizers, antifoaming agents, colorants, waxes, and anti-oxidants.  
         [0015]     The polyacrylate vehicle may include, for example, a (meth)acrylic ester monomer including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, aminoalkyl (meth)acrylates the polyacrylate and pigment will be substantially dissolved in from 30-65% by weight of a solvent, preferably n-butyl acetate capable of dissolving nitrocellulose (lacquer) as well as dyes and pigments, and which is compatible with leather.  
         [0016]     The quick-drying compositions of the present invention comprises polyacrylate resin, n-butyl acetate, dye or pigment, propylene glycol monomethyl ether and C-3/C-4 alcohols.  
         [0017]     In a preferred embodiment the composition of this invention may comprise an effective amount of dye or pigment constituents dispersed in, by weight, 20-32 parts propylene glycol monomethyl ether, preferably 28.0 parts; 10-15 parts isobutyl alcohol, preferably 12.0 parts; 8-12 parts isopropyl alcohol, preferably 10.0 parts; 3-5 parts n-butanol, preferably 4.0 parts; 20-25 parts n-butyl acetate, preferably 22.4 parts; 5-15 parts polyacrylate resin, preferably 5.5 parts. The overall amount of C3 and C4 alcohol is 21-32 parts.  
         [0018]     The dyes can be either metallic or metal-free colorants of the type readily available in the prior art.  
         [0019]     Especially preferred dye mixture and polyacrylate vehicle may be obtained from SPIES HECKER as Nos. 293 and 295.  
         [0020]     To a dye mixture and polyacrylate vehicle such as Spies Hecker 293 or 295 comprising 100 parts by weight is added an equal portion of 100 parts of a solvent mixture such as Spies Hecker 8581, comprising 50-60% by weight propylene glycol monomethyl ether, 20-30% C-4 alcohol (preferably isobutyl alcohol), 15-25% C-3 alcohol (preferably isopropyl alcohol), and if desired additional minor amounts of other C-3 or C-4 alcohols such as n-butanol and n-propanol.  
         [0021]     When coating the leather one must first clean the surface. The surface can be cleaned with ammonia water if extremely soiled. Then the leather may be cleaned (to return the leather to a bare state, removing all existing dyes, if desired) with the solvent mixture, such as SH 8581. Then the above-described composition of the invention is sprayed onto the leather, using 2-6 coats and allowing less than a minute, preferably 15-30 seconds flash time between coats.  
         [0022]     The materials become dust free in 30 seconds. “Dust-free” identifies the condition in which the coating sets to the point that dust will not become trapped in it.  
         [0023]     The materials exhibit tape time 30 seconds. Tape time is the condition where the materials are dry enough to tape on without leaving any tape marks.  
         [0024]     When a leather dye is sprayed onto the leather, the “overspray” created from the spraying operation will normally set on the areas surrounding the actual surface point sprayed. The compositions of the present invention will absorb into the surrounding area, such that blending or repair is invisible. This condition is commonly referred to as “zero overspray”.  
         [0025]     For purposes of this description and in the claims, parts and percentages are by weight unless otherwise specified. 
     
    
     EXAMPLE  
       [0026]     SURE COAT NO. 1601, having a toner color of black was acquired from SEM Products, Inc. and applied to the surface of a control leather strip and the results are reflected below in Table 1. However, prior to application, the leather surfaces were cleaned with SURE COAT NO. 3635 which was clear of toner.  
         [0027]     The Sure Coat specimen were cleaned with a clear Sure Coat prior to spraying the Sure Coat and toner.  
         [0028]     Two compositions (A and B) of the present invention was prepared, composition A by admixing 1.0 part SPIES HECKER 293 and 1.0 part SPIES HECKER 8581 and the composition B by admixing 1.0 part SPIES HECKER 295 and 1.0 part SPIES HECKER 8581. Two identical leather surfaces were selected as specimen A and B, and each was first cleaned with the SPIES HECKER 8581 by liberal application and immediate wiping with a cloth so that the 8581 did not evaporate on the surface. The specimen were taped for similar masking of graphic patterns to be dyed. Composition A was sprayed onto specimen A in six (6) coatings. Also six (6) coatings of composition B was sprayed onto specimen B. Flash times between each coating for each specimen was from 15 to 30 seconds, which was sufficient time to allow the coating to become dry to the touch prior to applying the subsequent coating. The taping was removed. Neither specimen A or B showed any build up of dye or pigment, unlike the Sure Coat system.  
         [0029]     The overspray for A and B was absorbed into the leather so that after merely 30 seconds no dust could be trapped within the coating. That is, it was dust free after 30 seconds.  
         [0030]     The specimen A and B were each dry enough in 30 seconds to tape over without leaving tape marks. The specimen did not require clear overcoating because the original coating completely penetrated the leather.  
         [0031]     Specimen A and B results and comparisons are as follows:  
                           TABLE 1                       TEST   SURE COAT   SPECIMEN A   SPECIMEN B                   Flash   300-600 seconds   30 seconds   30 seconds       time       Dust   1200 seconds   30 seconds   30 seconds       free       Tape   3,600 seconds   30 seconds   30 seconds       time       Final   Required to cover   Not required because   Not required because       clear   up surface   of dye absorption,   of dye absorption,       over-   imperfections   resulting in more   resulting in more       coat-   thus resulting in   natural appearance to   natural appearance to       ing   hiding natural   leather and more   leather and more           leather grain and   flexibility in the   flexibility in the           giving a   leather. However,   leather. However,           more vinyl-like   satin clear coating is   satin clear coating is           appearance.   possible for added   possible for added               durability without   durability without               losing appearance or   losing appearance or               texture flexibility.*   texture flexibility.                 *clear coating can be with for example SH 8070             
 
         [0032]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                   
               
               
                 SH 8581 
               
             
          
           
               
                   
                   
                   
                 WEIGHT 
               
               
                   
                 INGREDIENT 
                 CAS-NO 
                 PERCENT 
               
               
                   
                   
               
             
          
           
               
                   
                 Propylene glycol monomethyl 
                 107-98-2 
                 56.0 
               
               
                   
                 ether 
               
               
                   
                 Isobutyl alcohol 
                 78-83-1 
                 23.9 
               
               
                   
                 Isopropyl alcohol 
                 67-63-0 
                 20.0 
               
               
                   
                 n-butanol 
                 71-36-3 
                 0.1 
               
               
                   
                   
               
             
          
         
       
     
         [0033]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                   
               
               
                 SH 295 
               
             
          
           
               
                 INGREDIENT 
                 CAS-NO. 
                 PERCENT (WEIGHT) 
               
               
                   
               
               
                 n-Butyl acetate 
                 129-86-4 
                 44.1-45.7 
               
               
                 Polyacrylate resin 
                   
                 10.6-11.4 
               
               
                 n-Butanol 
                 71-38-3 
                 7.0-8.2 
               
               
                 Cellulose, acetate butanoate 
                 9004-38-8 
                 6.4-6.8 
               
               
                 Butyl glycolate 
                 7397-62-8 
                 4.7-4.9 
               
               
                 Mica 
                 12001-26-2 
                 4.2-8.2 
               
               
                 Xylene 
                 1330-20-7 
                 3.4-3.6 
               
               
                 2-Butoxyethyl acetate 
                 112-07-2 
                 3.0-3.2 
               
               
                 Titanium dioxide 
                 13463-67-7 
                 2.8-6.4 
               
               
                 White Spirit 
                 64742-82-1 
                 2.3-2.4 
               
               
                 Melamine resin 
                   
                 2.1-2.2 
               
               
                 Ethyl benzene 
                 100-41-4 
                 1.4-1.5 
               
               
                 Dipropylene glycol methyl ether 
                 34590-94-8 
                 1.5 
               
               
                 Isobutyl alcohol 
                 78-83.1 
                 1 
               
               
                 Chromium oxide 
                 1308-38-9 
                   0-1.2 
               
               
                 Iron oxide 
                 1309-37-1 
                   0-5.8 
               
               
                 Formaldehyde 
                 50-00-0 
                 0.1 
               
               
                 Suspected Human Carcinogen 
               
               
                   
               
             
          
         
       
     
         [0034]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                   
               
               
                 SH 293 
               
             
          
           
               
                 INGREDIENT 
                 CAS-NO. 
                 PERCENT (WEIGHT) 
               
               
                   
               
               
                 n-Butyl acetate 
                 123-88-4 
                 25.1-55.3 
               
               
                 Polyacrylate resin additives 
                   
                  5.9-48.0 
               
               
                 1-Ethoxy 2 Propanol 
                 52126-53-6 
                   0-10.3 
               
               
                 n-Butanol 
                 71-35-3 
                  0.1-10.9 
               
               
                 Cellulose acetate butanoate 
                 9004-36-5 
                   0-5.7 
               
               
                 Xylene 
                 1330-20-7 
                 1.9-5.5 
               
               
                 Aromatic hydrocarbons mixture 
                 54742-98 6 
                 0.3-9.4 
               
               
                 (C9-G12) 
               
               
                 1,2,4-Trimethyl-Benzene 
                 95-63-6 
                 0.3-5.2 
               
               
                 Butoxypropanol 
                 51331-86-8 
                   0-4.0 
               
               
                 White spirit 
                 64742-82.1 
                 1.2-3.9 
               
               
                 Aluminum 
                 7429-90-5 
                 1.3-3.6 
               
               
                 (inter alia) 
               
               
                   
               
             
          
         
       
     
         [0035]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                   
               
               
                 SURE COAT NO. 1601 
               
             
          
           
               
                   
                 COMPONENT 
                 PERCENT (WEIGHT) 
               
               
                   
                   
               
               
                   
                 PGME 
                  5-10 
               
               
                   
                 PTFE Dispersion 
                 1-5 
               
               
                   
                 Dibutyl phthalate 
                 1-5 
               
               
                   
                 C6-C13 acetates 
                 0-5 
               
               
                   
                 Colorant 
                 0-5 
               
               
                   
                 H 2 0 
                 &gt;50% 
               
               
                   
                   
               
             
          
         
       
     
         [0036]    
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                   
               
               
                 SH 8070 
               
             
          
           
               
                   
                 COMPONENT 
                 PERCENT (WEIGHT) 
               
               
                   
                   
               
             
          
           
               
                   
                 n-butyl acetate 
                 32.9 
               
               
                   
                 Polyester resin 
                 27.7 
               
               
                   
                 Polyacrylate resin 
                 13.7 
               
               
                   
                 Silica 
                 8.9 
               
               
                   
                 Xylene 
                 4.8 
               
               
                   
                 Methoxypropylene acetate 
                 3.6 
               
               
                   
                 Aromatic hydrocarbons C9-C12 
                 3.4 
               
               
                   
                 Ethyl benzene 
                 2 
               
               
                   
                 1,2,4-Trimethyl benzene 
                 1.7 
               
               
                   
                 2-(2H benzotriazol-2-yl)-4,6-DTPP