Patent Publication Number: US-4321279-A

Title: Buttered table syrup in polyolefin bottle

Description:
TECHNICAL FIELD 
     This invention relates to bottled buttered table syrup and to a method of bottling a buttered table syrup. 
     BACKGROUND OF INVENTION 
     In recent years there have been developed buttered table syrups which are stable and homogeneous. By the term &#34;buttered table syrup&#34; is meant a table syrup product having a sugar solids content of at least 65% by weight and butter in an amount of 1-5% by weight. By the term &#34;butter&#34; is meant whole butter or its equivalent such as butter fat or anhydrous butter oil. 
     Various emulsifiers are reported in the patent literature as being useful for buttered table syrups. 
     Pader, U.S. Pat. No. 3,057,734, discloses the use of water soluble proteins, gum arabic, and edible algin derivatives. For maximum emulsion stability, Pader prefers the polyhydric alcohol esters of alginic acid, e.g. propylene glycol ester of alginic acid. Pader also discloses that several other materials are not effective. Included among these are: fatty acid based emulsifiers such as &#34;Spans&#34; and &#34;Tweens&#34;; and gums other than gum arabic, gum arabic being useful with casein and its derivatives. 
     Topalian, U.S. Pat. No. 3,282,707 discloses the use of gum ghatti to stabilize a sugar syrup, and Smith, U.S. Pat. No. 3,362,833 discloses the use of gum ghatti and lecithin for the same purpose. 
     Daggy, U.S. Pat. No. 4,073,963, discloses the use of an emulsifier system for a buttered table syrup in which sodium stearoyl-2-lactylate and sorbitan monostearate are used. Daggy reports that several other materials are not useful. Among these are: xanthan gum, carrageenin gum, locust bean gum, guar gum, and pectin. 
     Difficulties have arisen, when stabilizers-emulsifiers such as carrageenan or lecithin alone are employed in stabilizing products such as table syrups, which must of necessity undergo prolonged storage in bottles or other containers prior to consumer use. Separation of the oil and aqueous phases has been noted when a table syrup employing an oil phase such as butter remains on the shelves of the retail outfit for several months. In many instances, there is at least partial separation of phases, which phases cannot be completely put into solution by the consumer by shaking the bottle. This separation constitutes an important disadvantage of buttered table syrups and has met with consumer dissatisfaction. 
     While the previously known emulsifiers are quite useful in providing storage-stable products in glass containers, a problem arises when these otherwise storage-stable buttered table syrup products are bottled in polyolefin bottles such as polypropylene or polyethylene bottles. We have found that, when a stable buttered table syrup is bottled in a plastic bottle of this type, a substantial and objectionable off-flavor develops after a relatively short period of time. 
     It is an object of the present invention to provide a pourable, stable table syrup which does not cause an objectionable off-flavor when bottled in a polyolefin bottle. It is a further object of the invention to provide a method of bottling, in a polyolefin bottle, a stable buttered table syrup which does not develop an objectionable off-flavor. 
     The present invention should provide a stabilized emulsion has improved stability against separation over prolonged periods of storage and is suitable for use as table syrup, topping, or the like. 
     The emulsion should further exhibit marked resistance to separation under repeated freeze-thaw cycles. 
     BRIEF SUMMARY OF THE INVENTION 
     The foregoing and other objects which will be apparent to those of ordinary skill in the art are achieved in accordance with the present invention by providing a bottled buttered table syrup comprising a polyolefin bottle containing a table syrup, said table syrup containing at least about 65% by weight sugar solids, butter in an amount of 1-5% by weight based on the weight of the syrup, and from 0.05 to 0.4% by weight of an emulsifier, said emulsifier comprising from 0.01 to 0.2% by weight, based on the weight of the syrup, of locust bean gum, from 0.01 to 0.2% by weight, based on the weight of the syrup, of carrageenin, and from 0.01 to 0.2% by weight, based on the weight of the syrup, of pectin, and by providing a method of bottling a table syrup in a polyolefin bottle which comprises filling a polyolefin container with said table syrup, and closing said container. 
     DETAILED DESCRIPTION 
     The buttered table syrups to which the present invention relate are known per se and are fully described in the prior art patents mentioned above, the disclosures of which are herein incorporated by reference. In general, the syrup is pourable at normal room temperature and contains at least 65% by weight sugar solids, from 1-5% butter, an emulsifier or stabilizer to provide a stable oil-in-water emulsion, and various conventional additives such as color, flavor, and the like. 
     The emulsifier system of the present invention includes three components: locust bean gum, carrageenin, and pectin, each of which, of course, is of food grade. Locust bean gum is used in an amount of 0.01 to 0.2% preferably 0.03 to 0.1% by weight, based on the weight of the table syrup. Carrageenin is used in an amount of 0.01 to 0.2%, preferably 0.03 to 0.1% by weight, same basis. Pectin is used in an amount of 0.01 to 0.2%, preferably 0.02 to 0.1% by weight, same basis. The total amount of the three components is 0.05 to 0.4%, preferably 0.1 to 0.3% by weight, same basis. The emulsifier system is conveniently provided by using a prepared aqueous, food grade, emulsifier such as &#34;Frimulsion 6G&#34;, a commercial product containing about 26% by weight locust bean gum, about 20% by carrageenin, and about 14% by weight pectin. 
     It is primarily intended that the stable emulsion, which is an important part of the present invention, be adapted for food use, specifically for use as a table syrup, the quantities of some of the ingredients therein will be subject to variations in accordance with the particular use to which the syrup is to be adapted and the grade and flavor of the product to be manufactured. Table syrup in its most preferred form is a cane-corn syrup blend in which, in the present invention, butter and maple syrup or maple flavor are incorporated; it will be apparent that the amount of butter in the syrup, as well as the amount of maple syrup or maple flavor will vary in accordance with consumer preference and the retail price at which the syrup is to be marketed. In addition, if the syrup is to be utilized to pour over ice cream and for general fountain use, as well as a topping for pancakes, waffles and the like, it may be desirable to increase the sugar solids content of the aqueous phase of the emulsion well beyond 65 percent up to about 80 percent or more, providing the syrup or topping is still pourable. 
     Consequently, while in its most preferred form the syrup is contemplated as having about 2 percent butter or other oil by weight of the emulsion, the amount of oil will vary to a preferred range of about 1 to 5 percent to a broad range of about 1 to 10 percent. In addition, where maple syrup is used as a flavoring ingredient, the most preferred amount of such maple syrup used is presently about 2 percent by weight of the finished emulsion. It will, of course, be apparent that a more expensive product would incorporate greater amounts of maple syrup, which is relatively expensive compared to a cane-corn syrup blend. Artificial flavors may be used to replace the costly maple syrup. While, as stated, the percentage of sugar solids in the aqueous phase will generally be at least about 65 percent, increased viscosity requirements will result in increased sugar content. The sugar content should not be so high that crystallization will occur at conventional storage temperatures or that the syrup will become nonpourable and must and must be spooned from its container. 
     One of the properties of polyolefin material is that it is a poor gas barrier. Therefore the protection of the fat particles from oxidation must be accomplished to prevent stale flavor notes. 
     The emulsifier system of the present invention provides both a stable oil and water emulsion as well as preventing the development of off-flavors. The following hypothosis is used to explain this latter phenomena of the invention. However, the hypothosis of the existence and mechanism by which the invention prevents the development of off-flavor is not designed to limit the scope of the present invention, but is advanced only as a means of explaining the effects produced. 
     The emulsifier of this invention has the ability to stabilize a homogeneous buttered syrup with much larger fat particle sizes than conventional propylene glycol ester of alginic acid. By obtaining larger fat particles, the surface area to volume ratio of fat is reduced. This may act to decrease the available sight for oxidation of the fat. In addition, the emulsifier system of the present invention may have antioxident powers through physically protecting (or coating) the fat particles or through chemically altering or binding precursors that form the compounds responsible for the stale flavor notes. 
     It is presently believed that a combination of any two of the three emulsifiers, carrageenin, pectin, and locust bean will provide product stability and eliminate any off-flavor notes. Emulsions made with conventional prior art emulsifiers, such as propylene glycol alginate, produce particles sizes of the range of one micron. An emulsion made with a commercially available pectin marketed by the Hercules Company, known as HMBB Rapid Set Pectin produces an average fat particle size of 7 microns. An emulsion made with commercially avialable carrageenan also from Hercules, known as Type J, produces an average particle size of approximately one micron. An emulsion made with a commmercially available combination of locust gum and carrageenan, marketed by the Hercules Company and sold under the Trademark of Genulacta PL-93 had an average particle size of seven microns. It has been determined that the average particle size using the &#34;Frimulsion 6G&#34; emulsifying system is in the range of 7 microns. It is therefore believed that it is desirable to have an average fat particle size of greater than 4 microns and more preferably greater than 6 microns but less than 9 microns. 
     A preferred method of preparing the buttered table syrup is as follows. A gum pre-solution is made by dispersing and dissolving the emulsifier in soft water at about 49° C. to 60° C. (approximately 120°-140° F.) and held for about one hour to solubilize the emulsifiers with the weight of the water being about 10 to 100 times the total weight of the locust bean gum, carrageenin and pectin. A blend of sugar syrups, flavor, etc, is made up and heated to a temperature of about 71° C. to 82° C. (approximately 160°-180° F.). The gum pre-solution and sugar syrup blend are admixed and blended for about 5-10 minutes. Melted whole butter, heated to a temperature of about 60° C. (approximately 140° F.) maximum, is then added and blended for an additional 5-10 minutes. The blend is then heated to a temperature of about 71° C. to 85° C. (approximately 160°-185° F.), adjusted, if necessary, to a desired sugar solid content by the addition of water, and homogenized at a single stage homogenizer pressure of approximately 4000 psi. The product is then bottled at about 77° C. to 80° C. (approximately 170°-175° F.). These are conventional steps used by the table syryp industry. Deviations from anyone of the listed processing conditions is within the contemplation of this invention. 
    
    
     EXAMPLE I 
     The procedure described above is followed. The sugar solids content is adjusted to 70°-71° Brix by the addition of water. 
     The following formulation is used: 
     
         ______________________________________                                    
Gum presolution       Parts by wt                                         
______________________________________                                    
Emulsifier System (Frimulsion 6G)                                         
                      0.200                                               
26 wt % locust bean gum                                                   
20 wt % carrageenin                                                       
14 wt % pectin                                                            
Soft Water            3.128                                               
Sugar Blend                                                               
Liquid sugar syrup    73.600                                              
42 DE corn syrup      20.527                                              
Flavor and color      0.400                                               
Sodium Benzoate       0.050                                               
Citric Acid           0.016                                               
Tri sodium citrate    0.069                                               
Whole Butter          2.000                                               
                      100.000                                             
______________________________________                                    
 
    
     The product is bottled in two types of containers: polyacrylonitrile, and polypropylene. As a comparison, a similar table syrup is prepared using 0.2% of a commercially available propylene glycol ester of alginic acid, known as PGA for short notation and &#34;Kelcoloid O&#34; as the tradename, and bottled in the two types of plastic bottles. Neither product produces an objectionable off-taste when stored in the polyacrylonitrile container. An objectionable off-flavor develops in the table syrup in the polypropylene container stabilized with propylene glycol ester of alginic acid. However, no such off-flavor is produced in the table syrup in the polypropylene container stabilized with the three-component stabilizer system of the present invention. 
     EXAMPLE II 
     The following seven systems were tested to develope a theory of the present invention. The reasoning behind choosing systems 1-4 was to store these systems under various conditions and determine whether the stale flavor development is due to the oxidation of butter fat or a combination reaction and whether ascorbyl palmitate, an antioxidant and weighing agent, would act to inhibit formation of these off-notes. Systems 5, 6, and 7 are attempts at finding out how each ingredient in the Frimulsion preparation functions separately and to determine if use of only one or two of its more functional ingredients could produce a system with similarly improved flavor stability. 
     
                                           TABLE 1                                 
__________________________________________________________________________
          System                                                          
               System                                                     
                    System                                                
                         System                                           
                              System                                      
                                   System                                 
                                        System                            
          #1   #2   #3   #4   #5   #6   #7                                
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Liquid Sugar and                                                          
Corn Syrup                                                                
          90.5 92.0 90.5 90.5 92.0 92.0 92.0                              
Butter    2.0  2.0  --   2.0  2.0  2.0  2.0                               
PGA       0.40 --   0.40 0.40 --   --   --                                
Frimulsion 6G                                                             
          --   0.10 --   --   --   --   --                                
Pectin    --   --   --   --   0.20 --   --                                
Carrageenan                                                               
          --   --   --   --   --   0.20 --                                
Genulacta PL-93                                                           
          --   --   --   --   --   --   0.20                              
Preservatives                                                             
          0.09 0.09 0.09 0.09 0.09 0.09 0.09                              
Buffering Agent                                                           
          0.12 0.12 0.12 0.12 0.12 0.12 0.12                              
Acidulent 0.01 0.01 0.01 0.01 0.01 0.01 0.01                              
Flavors and Color                                                         
          0.17 0.17 0.17 0.17 0.17 0.17 0.17                              
Salt      0.3  0.3  0.3  0.3  0.3  0.3  0.3                               
Water     6.42 5.27 8.42 6.42 5.17 5.17 5.17                              
Ascorbyl Palmitate                                                        
          --   --   --   0.002                                            
                              --   --   --                                
Approximate Totals                                                        
          100.00%                                                         
               100.00%                                                    
                    100.00%                                               
                         100.00%                                          
                              100.00%                                     
                                   100.00%                                
                                        100.00%                           
__________________________________________________________________________
 
    
     To obtain results in a relative short period of time on a stabilized butter-syrup in plastic, an accelerated controlled environment test was developed. This was accomplished with the aid of four glass desiccators, a vacuum pump, an O 2  and a N 2  gas source, twenty-four 400 milliliter beakers. The procedure consisted of: 
     (1) Filling the labelled 400 ml beakers with their respective syrups in amounts predetermined so as to duplicate in the beaker the surface area to syrup volume found in 12 ounce polypropylene bottles. 
     (2) Placing the beakers in their respective desiccators and sealing the desiccators. 
     (3) Hooking up tygon tubing between the desiccators, the vacuum pump and the appropriate gas source (either O 2  or N 2 ) through the use of a &#34;T&#34; connector. 
     (4) Evacuating the gas from the desiccator with the vacuum pump and replacing it with either O 2  or N 2 , depending upon the desiccator designation I-IV as follows: 
     Four desiccators were utilized with the following contents and placed in storage @100° F. 
     
         ______________________________________                                    
Desiccator I                                                              
         Desiccator II                                                    
                    Desiccator III                                        
                                Desiccator IV                             
O.sub.2  N.sub.2    N.sub.2     O.sub.2                                   
environment                                                               
         environment                                                      
                    environment environment                               
______________________________________                                    
#1A  #1B     #2A    #2B   #1A   #1B   #2A   #2B                           
#3A  #3B     #5A    #5B   #3A   #3B   #5A   #5B                           
#4A  #4B     #6A    #6B   #4A   #4B   #6A   #6B                           
______________________________________                                    
 
    
     Each beaker contained 74 ml of the indicated syrup. Beaker labelled &#34;A&#34; lacked polypropylene beads while Beakers labelled &#34;B&#34; contained 146 polypropylene beads each. 
     (5) Repetition of step 4 five additional times to maximize the concentration of the designated gas inside the desiccator. 
     (6) Quickly removing the hose from the desiccator and plugging the glass tube in the top with a secondary rubber stopper while maintaining a flow of the same gas as contained in the desiccator over the glass tube opening during the execution of this step. 
     (7) Repeating steps 3-7 with the remaining three desiccators. 
     (8) Placing all of the desiccators into storage at 100° F. for a period of three weeks. 
     The occurence of emulsion spearation in Systems #5 and #6 caused their elimination from the study. In addition, when System #7 was permitted to cool, it formed a stable gel exhibiting very poor flow characteristics. Because of this, System #7 was also eliminated from the study. However, preliminary indications are that when Genulacta PL-93, a commercially available combination of locust bean gum and carrageenan, marketed by Hercules, is employed at a 0.10% by weight basis, a flowable stable syrup is obtained. 
     Results from the accelerated 140° F. stability study, the one month analysis in the conventional storage study and from the accelerated controlled environment study are recorded in the data section. These results indicate that the stale flavor was not due to migration of monomers from the polypropylene bottle or a reaction with the polypropylene resin. The stale flavor was probably due to oxidation of the butter fat and propylene glycol ester of algenic acid probably did not contribute to this reaction. The addition of 0.002% ascorbyl palmitate significantly reduced production of the oxidized stale flavor. Also indicated was that the presence of sunlight caused the development of an off flavor described as being both stronger and different from the stale note produced under the conditions previously discussed. The presence of ascorbyl palmitate in the sunlight exposed samples also helped reduce the additional off flavors that otherwise developed with sunlight exposure. 
     
         __________________________________________________________________________
DATA SECTION                                                              
                                           Controlled O.sub.2             
                                                     Controlled N.sub.2   
                   Evaluation of Flavor and Stability Following           
                                           Environment                    
                                                     Environment          
          140° F. Storage                                          
                   Month Storage Under the Following Conditions           
                                           Saturated with                 
                                                     Saturated with       
          Evaluated                                                       
                   Room           Window   H.sub.2 O and                  
                                                     H.sub.2 and stored   
Sample    after 2 weeks                                                   
                   Temperature                                            
                          100° F.                                  
                                  Exposure @ 100° F. for           
                                                     @ 100° F. for 
                                                     a                    
Description                                                               
          and 4 weeks                                                     
                   Contrasted Against a Refrigerated Control              
                                           3 week period                  
                                                     3 week               
__________________________________________________________________________
                                                     period               
#1-A (stored in                                                           
glass)                                     good stability                 
0.4% PGA  good stability                                                  
                   no change                                              
                          no change                                       
                                  development of                          
                                           sl. stale note                 
                                                     good stability       
2.0% Butter                       off flavors                             
                                           developing                     
                                                     clean flavor         
#1-B (stored              stale off                                       
in plastic)                                                               
          --       no change                                              
                          flavor  same as above                           
                                           same as above                  
                                                     same as above        
same as #1-A              development                                     
#2-A (stored in                                                           
glass)    slight separation       similar off                             
                                           *fair stability                
                                                     slight separation    
0.1% Frimulsion                                                           
          following 2 week                                                
                   no change                                              
                          no change                                       
                                  flavor as above                         
2.0% Butter                                                               
          period increasing       (but slightly less)                     
                                           slight sour note               
                                                     clean flavor         
          with time*                       developing                     
#2-B (stored              slight separation                               
in plastic)                                                               
          --       no change                                              
                          very slight stale                               
                                  same as #1                              
                                           same as above                  
                                                     same as above        
same as #2-A              flavor note*                                    
                                  above                                   
#3-A (stored in                                                           
glass)                                                                    
0.4% PGA  good stability                                                  
                   no change                                              
                          raisin flavor                                   
                                  no change                               
                                           clean     clean                
0.0% Butter               note                                            
#3-B (stored                                                              
in plastic)                                                               
          --       no change                                              
                          raisin flavor                                   
                                  slight raisin                           
                                           clean     clean                
same as #3-A              development                                     
                                  note                                    
#4-A (stored in                                                           
glass)                                     very slight                    
system #1 plus                                                            
          good stability                                                  
                   no change                                              
                          no change                                       
                                  no change                               
                                           sour note clean                
0.002A ascorbyl                            not stale                      
palmitate                                                                 
#4-B (stored              possibly a                                      
                                  slight                                  
in plastic)                                                               
          --       no change                                              
                          slight stale                                    
                                  off flavor                              
                                           same as above                  
                                                     clean                
same as #4-A              note    note                                    
__________________________________________________________________________
 *Note:                                                                   
 Frimulsion used in this study was old. Previously made in using Frimulsio
 exhibites good stability after 13 months storage