Abstract:
Provided among other things is a glove formed by latex dipping having one or more textured finger tips wherein: the texture at the finger tips results from forming the glove on a former having the following properties: 
                                   (micrometer)                                           Ra   Av. roughness   about 7-14         Rsm   Mean width of roughness   about 500-720         Rpc   Peak count   about 15-20                                         
the glove being non-chlorinated, wherein the glove is a (i) single dip nitrile glove or (ii) a dipped glove with a textured layer formed of polymer latex, and comprising a multivalent metal ion salt of an organic acid with log P of about 4 to about 15.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application claims benefit of U.S. provisional patent application Ser. No. 62/063,531, filed Oct. 14, 2014 and provisional patent application Ser. No. 62/100,610, filed Jan. 7, 2015. Each of the aforementioned patent applications is herein incorporated in its entirety by reference. 
     
    
       [0002]    The present application relates generally to nitrile gloves with molded texture at the finger tips, polymeric gloves with molded texture at the fingertips and containing a multivalent metal ion salt of an organic acid with log P of about 4 to about 15, and a method of making. 
         [0003]    In seeking to produce texture on the surface of a single dip polymeric glove by a texture structure found at the surface of the dipping former, it is extremely difficult to produce a glove that has good grip while being reliably formed without holes. It has now been unexpectedly found that good grip can be obtained by carefully selecting certain roughness parameters for the former. 
       SUMMARY 
       [0004]    Provided is a glove formed by latex dipping having one or more textured finger tips wherein: the texture at one or more finger tips results from forming the glove on a former having the following properties at the corresponding finger tip regions: 
         [0000]                                                          (micrometer)                                        Ra   Av. roughness   about 7-14           Rsm   Mean width of roughness   about 500-720           Rpc   Peak count   about 15-20                        
the glove being non-chlorinated, wherein the glove is a (i) single dip nitrile glove or (ii) a dipped glove with a textured layer formed of polymer latex (e.g., natural rubber latex or another rubber latex, or mixtures), and comprising a multivalent metal ion salt of an organic acid with log P of about 4 to about 15.
 
         [0005]    Provided is a method of making such a glove comprising: coating a glove former with coagulant; applying a coagulable elastomer formulation to the coagulant coated former so that the former is coated with coagulated elastomer; and curing the elastomer coating, wherein former has the following properties at the corresponding finger tip regions: 
         [0000]    
       
         
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 (micrometer) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Ra 
                 Av. roughness 
                 about 7-14 
               
               
                   
                 Rsm 
                 Mean width of roughness 
                 about 500-720 
               
               
                   
                 Rpc 
                 Peak count 
                 about 15-20 
               
               
                   
                   
               
             
          
         
       
     
         [0006]    Also provided is a former for making a glove (such as a single dip nitrile glove) having one or more textured finger tips wherein the former has the following properties at the corresponding finger tip regions: 
         [0000]    
       
         
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 (micrometer) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Ra 
                 Av. roughness 
                 about 7-14 
               
               
                   
                 Rsm 
                 Mean width of roughness 
                 about 500-720 
               
               
                   
                 Rpc 
                 Peak count 
                 about 15-20 
               
               
                   
                   
               
             
          
         
       
     
     
    
     
       DESCRIPTION OF THE DRAWINGS 
         [0007]    So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only illustrative embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments. 
           [0008]      FIG. 1  depicts a glove with texture; 
           [0009]      FIG. 2  shows the texture in expanded view; 
           [0010]      FIG. 3  shows an exemplary method of making; and 
           [0011]      FIG. 4  shows a former for imparting texture. 
       
    
    
       [0012]    To facilitate understanding, identical reference numerals have been used, where possible, to designate comparable elements that are common to the figures. The figures are not drawn to scale and may be simplified for clarity. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. 
       DETAILED DESCRIPTION 
       [0013]    The glove has one or more textured finger tips. texturing can be on one side, since the gripping side of a finger is on one side. However, it will often be convenient to form the grip on both sides. Grip texture can be at a finger tip, such as about 50% of the way down to the first knuckle crease. Or, texture can be found further down the finger. In embodiments, 2, 3, 4 or 5 fingers have texture. Texture can be formed more generally, but is particularly useful at the finger tips. 
         [0014]      FIG. 1  depicts the palm side of a glove  10  with texture at  12  at the finger tips. 
         [0015]      FIG. 2  shows the texture in expanded view. Each line on the superimposed scale is 1 mm. While the vertical scale is not apparent, the surface was created with, and the thus a reverse image of, a former with the Ra, Rsm, Rpc, Rz, Rmax, Rp and Rv parameters of the narrower ranges recited below. 
         [0016]    In embodiments elastomeric layer is primarily acrylonitrile butadiene copolymer (NBR or “nitrile”) by polymer content weight (e.g. 80% or more), thus forming for the purposes of this application a “nitrile glove.’ Other polymers may be natural rubber latex (including Guayule latex), other synthetic rubber latex, or the like, and combinations thereof. The synthetic rubber latex may be selected, for example, from the group comprised of polychloroprene, polyisoprene, polyurethane, styrene-butadiene, butyl, and combinations thereof. The nitrile can include carboxylated acrylonitrile butadiene copolymer. In embodiments, it is highly carboxylated. 
         [0017]    The texture at the finger tips results from forming the glove on a former having one or more of the following values (from about value A to about value B): 
         [0000]    
       
         
               
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 or 
               
               
                   
                 (micrometer) 
                 (micrometer) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Ra 
                 Av. roughness 
                  7-14 
                  8-12 
               
               
                 Rsm 
                 Mean width of roughness 
                 500-720 
                 610-700 
               
               
                 Rpc 
                 Peak count 
                 15-20 
                 16-19 
               
               
                   
               
             
          
         
       
     
         [0018]    In embodiments, Ra is about 9, 10, 11 or 12. In embodiments, Rsm is about 500, 630, 650 or 670. In embodiments, Rpc is about 17, 18 or 19. 
         [0019]    In embodiments, the former of the invention and used in the invention has one or more of the following roughness properties (from about value A to about value B): 
         [0000]    
       
         
               
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 or 
               
               
                   
                 (micrometer) 
                 (micrometer) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Rz 
                 Mean roughness depth 
                 30-50 
                 30-45 
               
               
                 Rmax 
                 Largest roughness depth 
                 40-70 
                 40-65 
               
               
                 Rp 
                 Height of the highest peak 
                  8-22 
                 10-20 
               
               
                 Rv 
                 Depth of deepest valley 
                 16-35 
                 18-30 
               
               
                   
               
             
          
         
       
     
         [0020]    In embodiments, Rz is 34, 38, 40 or 42. In embodiments, Rmax is about 47, 53 or 60. In embodiments, Rp is about 13, 15, 17 or 20. In embodiments, Rv is 20, 21, 24 or 27. 
         [0021]    The above parameters are as measured by a Perthometer (Mahr GmbH, Göttingen, Germany), with the stylus running at constant speed across 0.22 in (5.6 mm) length of surface. The Roughness profile R describes the departure from the mean line. The average roughness is calculated as described is the arithmetic average of the absolute values of the roughness profile ordinates. 
         [0022]    In embodiments, the former is ceramic. 
         [0023]    Gloves formed on the above formers can be tested for falling within the claims by reverse molding. For example, the glove can be treated with a release agent if needed, inverted, and used as a mold for a self-curing polymer mixture that solidifies to sufficient hardness to allow for measurement with the Perthometer device. Perthometer values within the above ranges indicate that the former used falls within the above values. 
         [0024]    It is believed that better results are obtained in the manufacturing process if the temperature of the leaching process is about 50° C., such as about 45 to about 55° C. The temperature of the gelling (vulcanization) oven can about 120 to about 160° C., such as 125°, 135°, 145° or 155°. 
         [0025]    It is believed that better results are obtained in the manufacturing process if the coagulant used in the dipping step includes a fatty acid salt. For example, the following can be used: 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                 Material 
                 % W/W 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Water 
                 70 
               
               
                   
                 Calcium nitrate 
                 24.5 
               
               
                   
                 calcium stearate 
                 5.5 
               
               
                   
                   
               
             
          
         
       
     
         [0026]    In methods of the invention, the coagulant composition can for example comprise multivalent metal ion salt of an organic acid with log P of about 4 to about 15. In all embodiments with an organic acid salt, the organic acid can a for example C14 to C30 fatty acid (whether or not within the log P parameters). In all embodiments with an organic acid salt, the organic acid can be a for example C16 to C20 fatty acid. In all embodiments with an organic acid salt, the multivalent metal ion can be for example Ca, Mg, Zn or Al. In all embodiments with an organic acid salt, the multivalent metal ion can be Ca. In all embodiments with an organic acid salt, such a salt can for example comprises about 5 to about 50% by wt (e.g., 18%) of coagulant compounds in the coagulant composition. 
         [0027]    In embodiments, the gloves of the invention comprise a multivalent metal ion salt of an organic acid consistent with any of the above (e.g., C14-C30, even if not with above log P range). The amount present can be the residue remaining after a post-dipping leaching or washing. 
         [0028]    In embodiments of the gloves that contain the fatty acid salt (by any definition herein), the polymer of the outer layer can be natural rubber latex (including Guayule latex), other synthetic rubber latex, or the like, and combinations thereof. In embodiments, such a glove is a single dip glove. 
         [0029]      FIG. 3  shows an exemplary process for forming the article of the invention. Step  202  (optional) is cleaning the textured former. Step  204  is applying coagulant to the former. In the illustrative embodiment, the coagulant is composition is dried at 60-80° C. In step  206 , the former is dipped in elastomer composition (compound). In step  208  (optional), the dipped former is dried, for example if a glove with the fingers pointing down. 
         [0030]    In step  210  (optional), the article on the dipped former is leached. For example, leaching can be conducted at a moderately elevated temperature that effects some cross-linking. In step  212 , the article on the former is cured. In step  214  (optional), the article (typically after stripping from the former) is washed and dried. 
       Principle of the Test Method 
       [0031]    The method uses a 1.0 kg or 1.5 kg weight (e.g., metallic), and measures “Pull Force” needed to grip test bar for lifting the weight, and a “Catch Force” needed to re-grip the test bar after letting it slip. 
         [0032]    The test is used to measure the pinch grip performance of glove in grip force (kgf) in a systematic pattern of a pinch grip task. The subject uses only the tips of the first finger and thumb to grip the grip bar. Sufficient grip force between the finger and thumb is required to enable the grip bar to be held in control so that it can then be pulled down in a fixed distance without slipping (“Pull Force”). The pulling down action effectively lifts a specific mass (1.0 kg or/and 1.5 kg) on the other side of a pulley. The grip bar is then released, allowed to slip and then re-gripped (“Catch Force”). Finally the grip bar is returned to the stationary initial position in a controlled manner. The grip bar is wetted with water or covered with oil when performing wet or oil pinch grip test respectively. 
         [0000]    
       
         
               
             
               
               
             
               
             
               
               
             
               
             
               
               
             
               
             
               
               
             
               
             
               
               
             
           
               
                 TABLE 
               
               
                   
               
               
                 Test Procedure 
               
               
                   
               
             
             
               
                 General 
               
             
          
           
               
                 a) 
                 Apply minimum grip force around a grip bar which is sufficient to 
               
               
                   
                 lift up a certain load. 
               
               
                 b) 
                 The tester shall use only the tips of the first finger and thumb 
               
               
                   
                 to grip the grip 
               
               
                 c) 
                 Preferably use the same size and same side of gloves when 
               
               
                   
                 conductingthe test. 
               
               
                 d) 
                 The tester shall perform the test by using the dominant hand. 
               
               
                 e) 
                 The wrist shall be rested on a support (e.g., the lower height 
               
               
                   
                 indicator block) when re-gripping the slipping grip bar. 
               
             
          
           
               
                 Test Procedure - Dry 
               
             
          
           
               
                 a) 
                 2 × 500 g standard weights are slotted onto the mass-holder 
               
               
                   
                 to provide a 1.0 kg load. 
               
               
                 b) 
                 The grip bar is cleaned with ethanol and dried to remove any 
               
               
                   
                 contamination. 
               
               
                 c) 
                 The tester shall follow the procedure in Table D (below). 
               
               
                 d) 
                 Repeat Table D steps until three repetitions have been performed 
               
               
                   
                 for the same glove specimen. 
               
               
                 e) 
                 3 × 500 g standard weights are slotted onto the mass-holder 
               
               
                   
                 to provide a 1.5 kg load. 
               
               
                 f) 
                 Repeat Table D steps for lifting up the load of 1.5 kg and until 
               
               
                   
                 three repetitions have been performed for the same glove specimen. 
               
               
                 g) 
                 Unless otherwise specified, two tests on each sample should be 
               
               
                   
                 carried out. 
               
             
          
           
               
                 Test Procedure - Wet 
               
             
          
           
               
                   
                 The same procedure is repeated, but adding the following after 
               
               
                   
                 step b): 
               
               
                 b-1) 
                 Approximately 1.0 ml of water is dripped onto a gauze using a 
               
               
                   
                 pipettor. 
               
               
                 b-2) 
                 Both sides of the grip bar are then wiped with the wetted gauze. 
               
             
          
           
               
                 Test Procedure - Oil 
               
             
          
           
               
                   
                 The same procedure is repeated, but adding the following after 
               
               
                   
                 step b): 
               
               
                 b-1*) 
                 Approximately 1.0 ml of oil (Shell Rimula × 15 W-40) is dripped 
               
               
                   
                 onto a gauze using a pipettor. 
               
               
                 b-2*) 
                 Both sides of the grip bar are then wiped with the wetted gauze. 
               
             
          
           
               
                 Test Procedure - IPA 
               
             
          
           
               
                   
                 The same procedure is repeated, but adding the following after 
               
               
                   
                 step b): 
               
               
                 b-1 ∂ ) 
                 Approximately 1.0 ml of isopropyl alcohol is dripped onto a gauze 
               
               
                   
                 using a pipettor. 
               
               
                 b-2 ∂ ) 
                 Both sides of the grip bar are then wiped with the wetted gauze. 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
             
           
               
                   
                 TABLE D 
               
               
                   
                   
               
               
                   
                 Task 
                 Action 
               
               
                   
                   
               
             
             
               
                   
                 1 
                 Tester uses only the tips of the first finger and thumb to 
               
               
                   
                   
                 grip the grip bar at the pre-marked position 
               
               
                   
                   
                 The gloved hand applies just sufficient grip force to pull 
               
               
                   
                   
                 the grip bar down vertically 
               
               
                   
                 2 
                 The gloved hand&#39;s wrist reaches the lower height 
               
               
                   
                   
                 indicator and stops 
               
               
                   
                   
                 Tester releases grip allowing the grip bar to slip through 
               
               
                   
                   
                 the fingers whilst keeping the wrist at the lower height 
               
               
                   
                   
                 indicator 
               
               
                   
                 3 
                 Tester re-grips grip bar and stops its movement whilst 
               
               
                   
                   
                 keeping the wrist at the lower height indicator 
               
               
                   
                   
                 Tester moves grip bar up vertically 
               
               
                   
                 4 
                 Tester releases grip when the grip bar reaches its initial 
               
               
                   
                   
                 stationary position 
               
               
                   
                   
               
             
          
         
       
     
         [0033]    With gloves of the invention, the following oil grip values were obtained: 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                   
               
               
                 1.0 kg Load 
               
             
          
           
               
                   
                 Catch Force 
                 Max Pull Down 
               
               
                   
                 (Kgf) 
                 Force (Kgf) 
               
               
                   
                   
               
               
                   
                 4.25 
                 1.85 
               
               
                   
                   
               
             
          
         
       
     
         [0034]    With gloves of the invention, the following dry grip values were obtained: 
         [0000]    
       
         
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 1.0 kg Load 
                 1.5 kg Load 
               
             
          
           
               
                 Catch Force 
                 Max Pull Down 
                 Catch Force 
                 Max Pull Down 
               
               
                 (Kgf) 
                 Force (Kgf) 
                 (Kgf) 
                 Force (Kgf) 
               
               
                   
               
               
                 0.12 
                 0.15 
                 0.35 
                 0.22 
               
               
                   
               
             
          
         
       
     
         [0035]    With gloves of the invention, the following wet grip values were obtained: 
         [0000]    
       
         
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 1.0 kg Load 
                 1.5 kg Load 
               
             
          
           
               
                 Catch Force 
                 Max Pull Down 
                 Catch Force 
                 Max Pull Down 
               
               
                 (Kgf) 
                 Force (Kgf) 
                 (Kgf) 
                 Force (Kgf) 
               
               
                   
               
               
                 0.16 
                 0.17 
                 0.5 
                 0.28 
               
               
                   
               
             
          
         
       
     
         [0036]    With gloves of the invention, the following IPA grip values were obtained: 
         [0000]    
       
         
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 1.0 kg Load 
                 1.5 kg Load 
               
             
          
           
               
                 Catch Force 
                 Max Pull Down 
                 Catch Force 
                 Max Pull Down 
               
               
                 (Kgf) 
                 Force (Kgf) 
                 (Kgf) 
                 Force (Kgf) 
               
               
                   
               
               
                 1.12 
                 0.31 
                 4.55 
                 1.42 
               
               
                   
               
             
          
         
       
     
         [0037]    In embodiments, gloves of the invention achieve grip values of about 1.5× the values listed above (rounded to the nearest 0.01 value) or less, or about 1.4× or less, or about 1.3× or less, or about 1.2× or less, or about 1.1× or less. In embodiments, gloves of the invention achieve grip values of about 0.5× the values listed above (rounded to the nearest 0.01 value) or more, or about 0.7× or more, or about 0.85× or more. These values apply to gloves of any of the embodiments described above. 
         [0038]    Formers for use in the invention can be manufactured by casting, selectively sandblasted to form texture, or the like.  FIG. 4  depicts a former of the invention in the form of a glove former  310 , with the palm side having texture at  312  at the finger tips. 
         [0039]    All ranges recited herein include ranges therebetween, and can be inclusive or exclusive of the endpoints. Optional included ranges are from integer values therebetween (or inclusive of one original endpoint), at the order of magnitude recited or the next smaller order of magnitude. For example, if the lower range value is 0.2, optional included endpoints can be 0.3, 0.4, . . . 1.1, 1.2, and the like, as well as 1, 2, 3 and the like; if the higher range is 8, optional included endpoints can be 7, 6, and the like, as well as 7.9, 7.8, and the like. One-sided boundaries, such as 3 or more, similarly include consistent boundaries (or ranges) starting at integer values at the recited order of magnitude or one lower. For example, 3 or more includes 4 or more, or 3.1 or more. 
         [0040]    This invention described herein is of textured gloves, methods of forming the same, and formers for making the gloves. Although some embodiments have been discussed above, other implementations and applications are also within the scope of the following claims. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the following claims. 
         [0041]    Publications and references, including but not limited to patents and patent applications, cited in this specification are herein incorporated by reference in their entirety in the entire portion cited as if each individual publication or reference were specifically and individually indicated to be incorporated by reference herein as being fully set forth. Any patent application to which this application claims priority is also incorporated by reference herein in the manner described above for publications and references.