CA1106678A - Smoke colored food casing and method of producing same by use of the maillard reaction - Google Patents
Smoke colored food casing and method of producing same by use of the maillard reactionInfo
- Publication number
- CA1106678A CA1106678A CA304,864A CA304864A CA1106678A CA 1106678 A CA1106678 A CA 1106678A CA 304864 A CA304864 A CA 304864A CA 1106678 A CA1106678 A CA 1106678A
- Authority
- CA
- Canada
- Prior art keywords
- casing
- group
- reaction product
- amino acid
- food
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
-
- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
-
- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
- A22C13/0016—Chemical composition of synthetic sausage casings based on proteins, e.g. collagen
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Processing Of Meat And Fish (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Seasonings (AREA)
Abstract
SMOKE COLORED FOOD CASING AND METHOD OF
PRODUCING SAME BY USE OF THE MAILLARD REACTION
ABSTRACT OF THE DISCLOSURE
Food casing is treated with an aqueous solution of an amino acid and a reducing sugar which react in the casing by the Maillard reaction to form a reaction product which gives the casing a brown smoke color. The smoke color is water soluble and easily transfers to the surface of a food product subsequently stuffed in the casing. Alternately, a casing is treated directly with a Maillard reaction product to give the casing the transferable smoke color.
S P E C I F I C A T I O N
PRODUCING SAME BY USE OF THE MAILLARD REACTION
ABSTRACT OF THE DISCLOSURE
Food casing is treated with an aqueous solution of an amino acid and a reducing sugar which react in the casing by the Maillard reaction to form a reaction product which gives the casing a brown smoke color. The smoke color is water soluble and easily transfers to the surface of a food product subsequently stuffed in the casing. Alternately, a casing is treated directly with a Maillard reaction product to give the casing the transferable smoke color.
S P E C I F I C A T I O N
Description
~1~6 ~ 7 ~
Thls ~n~ention relate~ to methods of treating
Thls ~n~ention relate~ to methods of treating
2 food cssing w~th reRgents to imp~rt ~ water ~oluble smoke color to the caslng and also relates to the resultant lmproved tre~tet casln~, th~t ~an imp~rt smoke color to food products processed therein, Xn particular thi3 invention relsteR to fl method of coating a fibrous or non~fibrous regenerated celluloAe tubular food ca~ing w~h an aqueou~ 801ution of ~n amino ~cid and a reducing ~ugar hereinafter, referred to as unreacted Ma~llard re~gents, wh~ch react ~n situ in the casing to produce 8 water ~oluble brown smoke color in the ca~ing~ th~t ultimaeely ~ransfers rom the o~sing to ~he surface of ~ ~ub~equen~ly enc~sed mest product, giv~ng the mea~c produot ~ rich brown ~moke eolor.
An alternate embod~men~ of the invention i8 to coat the casing direotly wlth ~ Maill~rd reaetion product o~ ~n ~mino acid ~nd ~ reducing ~ugar, eliminating the need or in ~i~u reac~sn, 20 . Thl~ invention al~o relate~ ~o collagen c~Qing treased by the method~ of ~hi~ ~nveneion, Tubul~r ~ood ca~lng8 are used extensively ~: , for proce~sing 8 great ~ariety of meat product8 ~nd : other food item8, The ~ood casing~ ~re gener~lly thin-w~lled tublng of varlou3 d~ame~l:er~ prepllred ~y methods well known in the ~rt from recon~t~tuted ~naterlsl~"
; and p~rt~cularly cellulose derivatives ~uch ~8 segenerated cellulo~e. Celluloae food c~s~n~ m~y ~180 be prepared wi~h flbrouM web8 e~bedded ~n ~he ~, ~ 7 8 wall there~, such caslng3 commonly belng re~err~d ts aB l~rlbrouB ~ood ca3in~." Edlble rOoa caslng~ may be prep~red from collagen ~nd are known as "collagen caalng." Typlcal proce~ses ~or the production or collagen ca~ln~ are di~clo~ed ln U.S. Patenta 3,551,535 lssued December 29, 1970 and 3,782,977 lssued January 1, 1974 each to W. E. Henderson et al and U.S, Patent
An alternate embod~men~ of the invention i8 to coat the casing direotly wlth ~ Maill~rd reaetion product o~ ~n ~mino acid ~nd ~ reducing ~ugar, eliminating the need or in ~i~u reac~sn, 20 . Thl~ invention al~o relate~ ~o collagen c~Qing treased by the method~ of ~hi~ ~nveneion, Tubul~r ~ood ca~lng8 are used extensively ~: , for proce~sing 8 great ~ariety of meat product8 ~nd : other food item8, The ~ood casing~ ~re gener~lly thin-w~lled tublng of varlou3 d~ame~l:er~ prepllred ~y methods well known in the ~rt from recon~t~tuted ~naterlsl~"
; and p~rt~cularly cellulose derivatives ~uch ~8 segenerated cellulo~e. Celluloae food c~s~n~ m~y ~180 be prepared wi~h flbrouM web8 e~bedded ~n ~he ~, ~ 7 8 wall there~, such caslng3 commonly belng re~err~d ts aB l~rlbrouB ~ood ca3in~." Edlble rOoa caslng~ may be prep~red from collagen ~nd are known as "collagen caalng." Typlcal proce~ses ~or the production or collagen ca~ln~ are di~clo~ed ln U.S. Patenta 3,551,535 lssued December 29, 1970 and 3,782,977 lssued January 1, 1974 each to W. E. Henderson et al and U.S, Patent
3,956,512 issued May ll, 1976 to T. E. Higglns.
The many dlr~erent recipe~ and mode~ Or proces~lng that are u~ed by the processed rOo~ lndu~try to ~uit dl~erent t~ste~ and even reglonal pre~erences generally neces~itate3 the u~e o~ rood caslngs wlth a variety of characteri~tics. In some lnstances, ~or example, rood casings are requlred to have multl-~unctlonal uRe~ whereln they serve a~ contalner~ during the proce~lng of a food product encased thereln and then al~o serve as a protectlve wrapping for the ~inl3hed product. In the proce~sed meat industry, however~ the ~ood ca3ing~, especially those derived ~rom Ce~ 0138, used ln the preparation o~ many type~ :
Or meat product~, such as various types o~ ~ausages, bee~ rolls, hams and the like~ ar ~requently removed ~rom about the proce~sed meat product prior to sliclng and/or ~lnal packaglng.
Sur~ace appearance i3 an lmportant ractor - ~ ln the commercial and consumer acceptanee o~ most processed meat products and a common ~eature or most - varietles Or ~uch products lnvolve~ khe use o~
''smoklnæ" ~or lmparting a characterlati~ brown ~olor ll3sa 67~
thereto. In the past9 the 3moklng Or ~ood product3 waa generally accompll~he~ by the food proce~orc subJecting the rOo~ product to actual contact wlth smoke ~n a ga~eou~ or cloud-llke rorm. Such ~mo~lng proce3ses, however, have been consldered un~atlsractor~
ror a v~riety o~ rea~on3 lncludlng the lne~rlclencles and lack Or unl~ormlty o~ the ~moklng operatlon.
Because Or the shortcomlngs experlenced~ the trend ha~ been to employ varlous types o~ llquld aqueous solutions o~ smoke color~ commonly called "llquld smoke solutlons" that have been developed and used commerclally by the food processor ln the proce3sing o~ many typea o~ meat and other food product : The appllcation o~ liquld smoke solutions to meat productc 18 generally carried ou~ in a variety o~ ways, lncludlng spraylng or dlpping an encased food product during the processlng thereo~ or by lncorpor~ting the llquid ~moke solutlon ln the recipe lt~el~. The actual operation o~ ~moklng by spraylng or dipplng 18 not completely satl~actory due to the equlpment expenses and the limlted degree o~ control that ha~ been rOu~, and lncorporatlon Or llo,uld smoke solutions ln the meat recipe doe~ not always provlde the deqired sur~ace appearance becau~e Or dllution Or ~moke lngredients.
It haa al~o been ~ugge~ted, as ~or example dl3clo~ed ln U.S. ~atent No. 3,330,669 ~o ~ollenbe~k, that appl~cation o~ a vi~cous liquld ~moks ~olutlon to the ln~lde surface Or a tubular ~ood caslng by the 667~3 ~ood proce~or ~mm~diately prlor to the ~tu~lng thereo~ wlth a 3ausage emulsion re~ults ln preparatlon o~ proce~ed ~ood product~ that exhlblt good color arter cooklng and removal Or the caslng.
Hereto~ore, however, lt has been round that pro~lding casings to arrord speclal treatment or ~tructural characterlstlc~ to the ~ood product can be more unl~ormly and economically accompllshed by the casing manuracturer~ Thl~ 1~ especlally true wlth the advent and wlde commerclal use of automatic stur~lng and proce3 lng equlpment in the proces~ed ~ood industry.
Several methods Or provldln~ ~ood caslngs with coatlngs applled to a ~ur~ace thereof are known and de~crlbed ln the patsnt llterature. There 1~ -dl closed> ~or example, in U.S. Patent No. 3,451,827 a ~praylng mekhod ~or ap~lying a varlety o~ coatlng materlal~ over the internal ~ur~ace o~ small dlameter ca~ing~ and ln U.S. Patent No. 3,378,379 to Shlner et al, a "slugglng" method used ~or applying coating material~ to the internal surface of large diameter ~ -ca~lngs. Wh~le such technique~ and others have been used in preparing commercial quantltle~ o~ coated food caslng~, the caslng~ prepared thereby are~ ln ~eneral, u~ed to meet partlcular commercial re~u~rements and to the b~8t 0~ our knowledge none Or the ~oated ca~lnga ai~cloRe~ ln the art are completely ~ati~actory - ~or or ar~ lntended t~ speci~lcally ~mpar~ ~moke color to a meat product proc~3ed thereln. In U.S. P8tent ~o~. 3,360,383 to ROQ~ et al, ~d 3,383,223 snd 3,~17,312 to Rose, for example, ~re d~sclo~ed co~ting compositlons that employ liquid smokg solut1on~ ln amount0 that sre specifically required to insolubilize a protein material such as gelatin to prepare ca~$ngs that meet ~pec~l adhesion properties required for use in the proce~sing of dry sausagest which propertles would ~herefore limlt the sui~bility thereof for other ca~ing applications, Prep~ration of tubul~r food caslngs that could be used ~n ~he manufscture of a varlety of processet food products and would impart a desired ~moke colo~ ~o ehe processed product would be highly desirable, Especi~lly ~dvantageous would be food casings that coult be prepared u~ing conventional coat~ng meth~d~ ~nd that would impart the desir~d color to products that h~ve the casing removed prior to final packaging or cooking or that are sold wieh the caslng still in place, Brown dyes, such as chocolate Brown HT9 h~ve been considered for ~a~ing treatment~ but such dye is not con~idered ~afe for hum~n con~mption. A smoke color tye mix~ure, ~uch ~8 stflnge ~ ~ smoke color, can be u~ed to give B superflcial ~moke color ~o me~t productR, but, becau~e lt ~8 a dye mi~ure of pr~msry red ~nd blue dyes, which heve dlffering solublllty and dlffu~lv~ey, the ~urfcce colo~atlon of the me~t producta become~ blui~h a~ the ~ 7 ~
red dye dlffuses ~nto the meat product wi h ~tor~ge, Thus, the unQtable Stange' 8 smoke color ~ not a satisfactory coloring agent, The deflclencles of the aforementloned smoke coloring agentq have been overcome by the present invention, whLch provide~ a nonto~lc, safe and ~table smoke colorlng agene con~st~ng of a re~ction product of a reducing ~ugsr and an a~ino acid, In accordance with ehe present invention there i~ provided a tubular ~ood caæing that i8 su~table to impart smoke color to food product enca~ed or processed therein compris~ng ~ tubular cellulose food casing hsving incorporated therein a re~ction product of an smino acid and a reducing sugar in ~mount~
specified in more detail hereinafter~ I~ has been di~covered that the tl~bular food casings of the present inve~tlon may be used to ~mpart tran~ferable ~moke color to a wide variety of me~t products processed there~n without the need for ~ny further ~moking operation~ by ~ 20 the food processor, Moreover it has been found ehat :~ said casings may be preparod in the for~ of ~hirred casing stick3 wherein long continuou~ len~hs of tubular food casing are pleated and compres~ed into a substantially shortened form ~hereof~ or ~ ~hort ~egment~ of flsttened tubing, : ~ Al~o provided in accorda~nce with the present . ~ lnvention i8 a smoke colored coll~gen ca~ing, co~pri~ing a tubular collagen ~ood cssing h~ving ~ncorporated ther~in reaction product of n ~mino cid and G
7 ~
reduc~ng ~ugar ~n amount8 ~pecifled ln more detall hereinafter.
Smoke colored collagen ca~ings of this inventlon are cap~ble of impartlng tr~n~fer~ble ~moke color to food prGducts, such as meat product3, encased thereln, However, ln the pract~c~l u~e of edible collsgen casing, once the food product is encased therein, the ca~lng ~a not removed before human consumption, but conaumed with the encased meat produet, Therefore, transfer of the smoke color from an edible collagen casing to the encased food product surface i8 not critical, because in normal u~e, unlike in the use of peelable cellulose casing~, the consumer will not see the food product ' ~ sctu~l -surface. However, unlike tran fer of smoke color from an edible collagen casing~ transfer of smoke color from an in-edible coll~gen casing to the encased food produc~ i~ critical since the ~nedible casing must be removed before ~onsumption.
AL~o provided in ~ccordance with the pre~ent inventlon are methods of preparing tubul~r food casings that : ~re suitable or impartlng smoke color to fo~d products enca~ed or processed therein which compri~e~ ~n one embod~ment providing a tubul~r food cas ing ~nd applying thereto an aqueou~ ~olutlon of ~ reducing ~ugar and ~n amino acid wh$ch : ~ ~re c~used eo react in si~u in the cas~ng according to the well-known Mai1lsrd reac~on, The ~Saillard reaction product h~s a smoke brown color which i9 water ~sluble and can tr~n~fer to the surf~ce of ~ meat product which 1~ subsequently s~uffed in the trested c~6ing, The term~ "~ re~ction product" ~nd '~illard reaction product" a~ u~ed herein are ineended to er~compass any ~nd all re~ction product~ which ~re for~ed from the ~1~68 ~ 67 8 Maillard resetion, lncludlng any reduclng BUgar Gr amino acid ~n stoichiometric exce~s, but e~clud~ng any water or c~trste compounds here$nsfter described, In an alt~rnate embodiment of thls Inventlon the Maillard reaction product ~9 costed directly on the casing, obviatlng the requirement of in situ reactlon.
The undesirsble brownlng of food~tuffs, such a~ or~nge ~uice, due ~o the Malllard reaction between reduc~ng ~ugars and amino acid~ i~ known ~nd i~
discussed by Wolfrom et al~ in "J, Agr, Food Ch~m,", Vol, 22, No, 5, 1974 at page~ 796-~Q0, Al~o cee Green~hields et ~1, in "Process Biochemi~try", December 1972, pp. 11-16. In "The Science of Meat ant Meat Products", J,F. Prlce et ~1, ets.; 2nd ed.;
1971~ at pages 460-461, i~ iB dlsclosed that reducing ugars cause r~pid darkening of bacon on fry~ng, whieh i~ a~cribed o ehe Maillard reaction between glucose and amino group~, Neither Wolfrom et al, nor ~reenshields et al, nor Rrice e~ 81 di~clo~e the use of ~he ~llard reaction ~o color food ca~ing oæ meat products encased in the trea~ed casings.
The food casing~ of the present inventlon may be prepared rom tubul~r c~sings h~ving vari2d compo~
tlons~ suoh 88 those w~ known in ~he art a~ regenerated cellulose casings either wi~h or without ~lbrous reinforoement, The former i8 known in the tr~de as fibrous ~a~ng ~nd i~ reinforced with paper ~nd the llke, Other ~moke colored ca~ings c~n be prepared by the method~ o thl~ ~nvention, ~u~h as those ~ste from ~ 67 ~ 1l368 cellulo8e deriva~lves, collagen (edible and inedible), alginates, amylo3e, ~nsolubillzed polyvinyl slcohol tboeh f~brou~ reinforced ~nd unreinforced) And the llke, Wh~le the invention particul~rly relates to tubul~r food c~sings, food wrapping materials in other forms ~uch ~ ~heet form may be smoke colored by appropriaee modlfications of the treating methods of thls invent~on by those ~killed ~n ehe ~rt, The ca~ings of this invention csn be us d to enc~se me~t produ~t~ lncluding~ bue not limlted to cooked, smoked9 d~y or semidry ausages such as frankfurters, bologna~, ~al~mis, cervelats, Thuringer~, ant the like. CheeQe produc~s may also be enca~ed ln the casings of thi~ invention, In a preferred embodiment of this invention in~olving the use of unre~ctet Maillard reagents to coat cas~ng, spec~flc details of which are ~et forth hereinafter, an aqueous sslution of at lea~t one amino acid and st least one reducing ~ugar i8 fir~t formed, Optionally ~dded to this solution 1~ a cltsate :~ compound to lncrea~e the reaction r~e between the amino acid and reduc~ng sugar, The ~olution i~ ~hen coa~ed on tubula~ gel cas~ng before drylng, Durlng drying - at elevated temper~ture8 ehe M~illard reaction occurs : between ~the amino acid and the reducing sugar in .~
~itu ln th@ ca~lng, ~o give ~he finished c~sing ~
~moky brown color, The smoke colored casing c~n then be ~tuffed wl~h R food protuct ~uch ~B a meat emul~ion.
The ~moky brown color of the casing will .
~ 7 ~
transfer to the ~urf~ce o the enca~ed meat prsduct9 BO that if the easing 1~ separ~ted from the encased meat after cooking or other further proce3sing well-known ~ the art, the ~ur~ce of the meat wlll hsve a smoky b~own color.
In a preferred embod~ment of thls invention lnvolving the direct UBe of a M~illard react~on product to coat ca~ing, spec~flc detalls of which are 8et forth hereinAfter, ~n aqueous ~olution of ae le88t one ~mino acid and ~t lea~t one reduci~g su~ar i8 f~rs~ formed.
Optionally added to th~s ~olution i~ a ~itrate compound .
to increase ehe reactlon rate between the amino ~cid and reduclng sugar. The solutlon i~ then heated to react the amino acld and ~he reducing sug~r to form a Maillard reac~ion product and then further heated to evaporate the water contene to de~ired level3 and if needed se-d~lu~ed with water to ad~u~t color concentration befsre appllc~tion to the ca~ing. The re~ultant co~ting compo~iticn i~ then op~ionally mixed with an~block - -: 20 agent3 snd thickeners before ~he caslng ls coated, The Maillard reac~ion protuc~ containing composl~ion is then eo~ted on dried ~ubular food caslng giving the ca~ing a : ~m~ky brown col~r. The ~moke colDred casing c~n then b~
~tuffed with a food product ~ch as a meat emulsion. The ~moky brown color o~ the ca~ing will tr~ns~er to the ~rf~ce of ~he encased meat produc~, 80 that if ~he casing ie ~eparated ~om the encased ~neat after cook~ng or other further process~tlg well~known i~ the art, the ~urface o the ~e8t w~ll have a 8moky brown color.
. ,, , ~ ~ , ;7~
Many ~m~ no c~mpound~ ~re ~ultable fsr we ln th~ lnveQelon, E~emplary of the amino aclds which can be employed in the practice of this invention are 4~
aminobutyrle acld, glycine, ~lanine, ~rgln~ne, and the dimera and the trimers thereof, ~nd the like, Also useful are amino ~cid derivatives such a~ ~alt~ of amlno scid~
like mono~odium glut~mate ~nd lysine monohydrochlor~de.
The invention i3 not l~mited to tho~e ~mino ~clds or derivatlve~ ~pecified herein, but may include others selected by those skllled in the art, The amino acids or derivative~ may be u~ed ~ndividu~lly or as miactures of variou~ amino acid~, or aR IDixtures of amlno ~cid derivatives5 or ~s mixtures of amino ~cids and ~mino acid derivatives.
Exemplary of the reducing sug~r~ which can be employed in the prActice of thi~ invention are ~108e, arabino~e, de~trose (d-gluco~e) and the llke. The invention is not l~mited to those reducing sugars specified herein, bu~ may include other~ selected by those ~killed in the ar~.
The reduclng sugar~ m~y be u~ed individually or as mixture~
of variou~ reducing sugars~
If unreacted Maill~rd reage~t~ are u~ed to treat c~sing9 then the amount of ~he treAting 601ut~0n applied eo the ca~lng i~ from ~bout 5 to ~bout 50 ~lligr~ms per ~quare inch ~f ca~ing wall, preferably from about 15 eo about 30 ~g~/~q, in, Correspondlngly, the amount of ~he reduclng ~ugar appliet 1~ rom aboue 0,7 So ~bout 14.0 mg,/sq, ln. of ca~ing w~ll, preferably r~ a~out 3.7 ~o ~bout 7.5 mg,/~q, in., and the a~ino ~c~d ~ppl~ed i~ from : about 0,3 to ~bou~ 7,0 mg./~q. ln. of c~slng wal~
- - ~
.
`` 11368 3667~
psefer~bly from about 1.3 to about 2,7 ~g, /8q. ln.
If a coat~ng compo~ition containing a Maillard resctlon product i8 directly coa~ed on the caslng then the amount of the coating compos~eion applied ~hoult be from about 9 to about 35 mgs/~q, ~n, of casing wall, preferably from ~bout 10 ~o about 20 mgs/~q, in. tepending on whether additional ant~block and/or thlckenlng agent~
are employed, Cor~espond~ngly9 the amount of the MRillard reaction product ~pplied i3 from ~bout 2,7 to sbout 14 ~g./
~"1 0 Qq, in, of e~lng wall, prefer~blj from ~bout 3,5 to about 7,0 ~11g./5~, ill.
The c~sing cont~lning the brown ~moke color i8 subsequently gtuffed with a meat product. The smoke color transfer~ to ehe ~urface of the encssed meat product, The inal smoke colored ca~ing produced by the method~ of this lnvention ~hould contain a Maillard react~on product of an amino ~cid and ~ reducing sug~r at a level from ~bout 2.7 to about 14 mllligrams of reactlon produck per ~quare inch of casing w~ preferably about 3.5 to about 7.0 mg,~per ~q, in " in order to lmpar~ ~he smoke color to a food product encs~ed therein, The preferred level of Maillard reac~ion produ~t ~n the c~ing which ui~lmately ~ trsnsferred :~ to the ~urface of the enc~ed me~t psoduct 1~ dependent upon lndlYidual color preferenc~ o~ the ~onsumer~.
Some ~ould prefer ~ dsrk brown sausag~ whlle othor~
l~ght brown s~u~a~e.
The ~ethod o applying the treating a8~nts .
~ 7 ~
to the cas~ng cfln be selected irom varisu~ ~own techniques such as ~lugging, which iB al~o known a3 bubble ~oatLng (U,S. Patent 3,378,379 to Shiner et al and U.S. Pstents 3,360,383 to Rose et al; U.S. 3,383,223 to Ro~e; And U,S~ 3,427,16~ to Rose et al), dipping ~U.S. Patent 3,378,379), spraying (U.S, Patent 3,330,66Y
to Hollenbeck) os ln~ernally coating the caslng ~hile sh~rring by the method dlsclo~ed by Bridgeford in U.S.
Reissue 28,2~1.
The slugging method for co~ing the in~ide of a cA~ing lnvolveQ fllling a portion of th ca lng with the coating m~e~ial, ~3 ~hat ehe ~lug of coating materiAl generally reside3 ~t the bottom of a "U" shape formed by the casing draped over tws parallel rollers, ant then movlng the coneinuous indeflnite length of casing so ~hat the slug of co~tlng ~ateri~l remain~
conflned within the casing, while the casing moYe~ past ~he slug and i~ coated on lt3 inside wall by the coating materiAl conta$ned within the slug.
The dipplng method for coating a casing ~nvolves in it~ ~imples~ form immer~ing ~he cas~ng in a bath of treating solution for ~ suf~ic$ent period of ~me to coat the out~lde of the casing or in ~ oontinuous prOCe~8 psss~ng an indefinite length of oa~ing over guide rolls through a treatment bath.
The ~praying method m~y be u~ed ~o coat the outsld~ of the c~sing or the in31de urf~ce o~ ~he casing by the use of nozzle~ ~ueh a8 di~clo~ed by Hollenbeck, ~1368 ;7~3 Depending upon whlch embodlment of thi~ ~ nvention ~ cho~en, the tubular casing can be eLther eo~ted on it~
out~ide surfsce or on lts in~lde ~urface with the treating solution of the unreacted amino ~cids and re-ducing sug~r~ or the compo~ition already containing ~
Msillart re~ction product. The coat~ng on the cas~ng wall penetrates throughou~ the ca~ing to y1 eld ~ uniform r~dial distributi~n of the coa~ing ' 8 components in the casin~. Prefer~bly, the cas~g i~ coa~ed on lts inner surf3ce3 to mascimlze contact of ~he Malllard re~ction product wlth the ~ubsequently encased meac product~. If the easing i~ coated on itQ outaide wall, the coating will penetrate to the inside wall, ~o ~h~t subsequent transfer of the Maill~rt reaction product coloring agent ~o sn encased meat product wlll tske place. However, the surface of the caslng on which the ereating agents of thi~ ~nventlon was inieially coated will have ~ slightly hi~her concentration of the Maillard coloring agen~ thsn - -the opposLte surface which did not rece~ve the coating.
Of course, the ca3Lng m~y be co~ted on it~ outer wall and ~hen turned lnside-out for ~tuffing, if ~o deslred.
BecauRe the c~ing~ utilized in the practice of this invent~on ~re thin wslled generslly of a ehlckr~ess of about 1 mils to sbout 10 mil~, the differes~tial colo~ing agen~ concentra~ion beeween the inner and outer casing surfaces ha~ no ~ignlfic~nt effect on ~he colo~ of the ca~ing or ~he color tran~ferred to the encased me~t product .
Coa~cln~ composl~ons of unre~cted Maillard 113~8 ~ 7 ~
reagents suit~ble for use ~n accordance with the embodiment~ of ~he present lnvention are preferably homogeneous aqueous ~olutions of the ~mino acid~ ~nd reducing sugars.
The molar ratio of the ~educing sugar to the amlno aclt in the unreacted Maillard reagents aqueous treatlng ~olution u~ed to ccat food casing~ within the practlce of this invent~on should be from about9 10 to 1, to about~ 1 to 10, preferably about, 1 to 1, to abou~, 1 ~o 5, In the prepara~ion of the unrea ted Maillard reagents treatlng solution the amount of water used should be that minimum amount wh~ch i~ just suffic$ent to dis~olve 811 the components of the solution, that i~ from about 40 to about 70 weigh~ percent water based upon the total weight o the flnal solution, preferably from about 40 ~o about 50 weight percent water, In the alternate embodiment of thi~ invention, the composition u~ed ~o dlrectly coat csC~ng~ with a ~aillard reaction produet 1~ prepared by flrs~ prep~ring an ~queo-~s 601ution of an amlno acid and a reducing sugar in the ~ame proportlon~ of amino acid, reducing 6ugar ~nt w~ter ~8 outl~ned above for ~he embodiment of thi~
inventlon dlrected to unre~cted Maillard reagents, and then hea~ng the ~olutlon to a ~emperature ln the rsnge of from a~ou~ 60C ~o abou~ 110C for abou~ ~ ~inute~ to sbout 30 ~nu~e~ to cause ~he M~illard reactlon ~o eake place, preferAbly from ~bouE 90C to ~bout 100C for about 10 to ~bout 20 m~nu~es, ~nd then ~dditionally ~3 -~6~ii7~3 heating ~or ~ ~uff~clent amount of t~me to evaporate the water eo from about 5 to ~bout 10 we~ght percen~ w~ter The M~lllard reaction product conta~n$ng compositlon iB
then re-dlluted wlth water, before coa~lng the cssing, to ~ water c~ntent of about 25 to about 50 weight percent, preferably nbout 30 to about 35 weight percent, Casing can also be coated with ~n unevaporated Maillard react~on product containing compo~ition, lf a l~ghter color i8 de6ired Color concentration iB readily controlled by those skilled in the art by proper evaporat~on and/or re-dilutlon, Potasslum citrate may be added hS pota~ium c~trate hydrate to the aqueou~ solution of an amino acid and a redu~ing sugar in order to increase the r~te of the color development in the casing by the ln 8itU
Malllard reac~ion~ If potassium citrate i~ used, the molar ratio of po~assiu~ citra~e to reduc~ng ~ugar in the aqueou~ treating solution used to coat the casings ~hould be from abou~, 1 to 2~, to about, 1 to 19 p~eferably ~bou~, 3 ~o 4. Sodium citrate a ~dium cltr~te hydrate may be added ~nstead of potasslum cltrate ~n the same molsr ratio~ with the sEme effect~
With respec~ to ~he prep~rat~on of the coa~lng c~mpo~ition ~lready containing a Maill~rd reac~ion produet, the M~ sd reaction r~te i~ no~ ~s ~mpo~tane ln the case of c~ng tre~tment wi~h an unreaeted ~olut~on o a redueing sugar ~nd ~n amino ac~d where the G~sing has to be he~ted to develop the color in s~tu, ~nd prefer~bly dr~ed at ~he ~ame time. Thu~9 in the ~-$~6~7~3 emb~d~ment of this lnventisn lnYo1~ing casing tre~tm2nt w1th unreacted Ma~llard reagents the rate of color deve10pment ha3 to be co~ordinated with caslng drying, whil~ ln the embodiment of th~s invention involv~ng the direct use of ~ Maillard reaction product to co~t the caslng, color de~elopment i~ not gener~lly co-ordinated with ca3ing drying. In fact the Maill~rd reac~ion product i9 preferably eoated on pre~iou~1y dried ca~ing~
Therefore, ~ince color development rate con~rol i8 not critical in the prep~ration of the coAtlng compo~ition contalning the Maillard rea tlon product, the use of pota~s~um o~ sodium citrate i8 optional and the concentration u~ed i8 generally 1~88 ~han thA~ used in the prep~ration of the unreacted M~illard treat~ng - ~olutlonO If used, the amount of potasAium or sodium citrate sdted ln hydrate form to prepare the coating compos~E~on cont~ining the Mai~1srd reaction product~
i3 expressed as ~ molar ratio of ~he pot~ssium or ~odium citrate to reducing sugar u~ed 2nd i~ on the order of from ~bout, O to 1, to ~bout~ l to 1, preferably about 3 to 4, Op~ona11y, prior to the oo~ting ~tep, ; th~ckener~ and antib10ck agen~ are ~dded to the coating compo~ition contaln~ng the Mail1art reaction product which al~o con~ins sbout 25 ~o about 50 weight percen~
wa~er f The ~hickeners are ~dded to lncrea~e the ~scosley of ~he mi~t~re ln osder to obtaln ~ ~hicker coa~n~ on the cssing, lf it 1~ de~ired to supp1y 1ncreased co10r to the c~ing. Th~ckeners wh~ch can be lB
1136~
eDployed lnclude, but ~re not l~mited to aqueous cellulose gum ~olu~ions ~uch aa solutions of c~rbo~ymethylcellulose, methylcellulo~e, and the llke ant aqueous ~olutions of pectin, vegetable gum or tarch and the like. Antiblock agent~ are ~dded to prevent the treated casing from st~ck-~g to itself. Any comp~tlble antiblock agent can be employed such a~ a water emul~on of food gr~de minersl oil, vegetable oil, s$1icone oil, And ehe like. If a mlnersl o~l emulsion i~ employed, the final co~ting compo~i~ion containing ~he Maillard reaction product i8 2n emul~ion with the Maillard reaction product dlssolved in the water pha~e. In the practice of thi~ invention : the difference be~ween ~ 301ution and an emul~lcn i8 not critical, The amount of antiblock and thickening agents employed in the coating c~mpositio~ i~ dependent upon the type of ~gent~, P~eferably about 5 ~o about 15 weight percent ant~block a~ent ~nd about 0.5 to about 2 weight percent thickeners are used~ If dry casing i8 coated with such ~ mixture contaln~ng the ~dditional antlblock and thiokening ~gents, then addition~l drying af~er co~ting will be nece~s~ry ~n order to bring the ~o~ture con~ent of the tre~ted cssing back down to a de~ired level of fr~m about 3 to about 15 weight perrent. ~-Antiblock and thlckening agents may al~ be employed, if desired, w$th the unreaeted ~llard ;- se~gent~ coatlng 801ution.
In the well~know~ conventional ~ethod~ for psepar~ng ~egener~ ed cellulo~e c~slng (non-fi~rou~
or fibrou~ ca~ing) or collagen caslng, the final c~s~ng :-~ 7 processlng step 1~ a drylng step whlch encompas3e~
pas~ing the unf~nl~hed casing commonly known a~ gel ca~ing through a ho~ ~ir dryer whereln the gel c~sing 1~ dr~et to a de~lred molsture content, typ~cally be~ween about 3 weight percent to about 15 weight percene moisture.
The ca3~ng c~n be coatet wlth an aqueou~
solution ~f the unreacted Maillard reagent~ prlor to the drying o~ the gel c~ing or after the drying 8tep.
Preferably, the casing i~ coated immediately pr~or to the drying step 80 that the elevated temperature of the drylng step can serve to both dry the gel casing ~nd cause the Malllard reaction between the a~ino acid and the reduclng ~ugar of the coat$ng to occur in ~itu in the cs~lng, producing reaction product~ wh~ch give the casing a rich smoky brown color which iB readily tran~fer~ble from the casing to ~he surface of d meat produc~ which is subsequently stuffed in the ca3ing. The drying tempera-ture and time are lnterdependent and should range ~rom about 80C or abou~ 24 hours to a~ou~ 120C for ~bout 5 minutes, and preferably from abou~ 100C to about 110C
for about lO to about 15 mlnutes, If the casing 1~ coated af~er ~he drying step, then an addit~onal heating step i8 re~uired at from ~bout 30C to about 1209C for ~bou~ 1 m~nute to about 30 days to c~u~e the Maillard zeac~on to e~ke pl~ce~ ~nd prefer~bly Crom about 7~C ~o ab~ut 90C for about 15 mlnutes to ~bout 10 hourA, The drying t~e ~nd ~emperature ~re in~er-dependent f~ctorR in~ofar a~ ~ffeeting the drying of ~0 ~ 7 the ca~ing to de ired mol~ture levels aa well a~
affect~ng the Malllard re~ct~on. If the caRl~g i~
coated sfter drying requlr~ng sn additional hest~ng 8tep~
the in~erdependent hestlng ~ime and temperature should be selected by those skilled ln the art to be ~ufficlent to ~chieve ln 61tu Maillard reaction ~n ~he cas~ng while maintainLng de~ired final moisture levels in the ca~ing end minimlzing the neces ity of re-moi~turizing the casing.
lQ If it i~ deslred to coat casing with ~ coatlng composition already c3ntalning ~ Maillard reaction produce, thi3 al~o can be performed before or ~fter ~he casing ~rying ~tep. ~ecau~e the ~aillard reagents in this instance are pre-reacted, the heat from the drying step is not needed eo cause the reaction to take place in s~u ln the cas~ng9 and therefore, ~he ca~ing i8 preferably coated after the try~ng step. EYe~ if eoated after drying, some additional drying may be nece~sry depending on ehe water con~en~ of the co~ting compositlon containing ~he Maillard reaction product, Thi~
additional dryLng can be performed at from abou~ 80~C for abou~ 10 minute~ to about 120C for about l minute, and preferably from about 90C to abou~ 1~0C for ~bout 2 to : ~bou~ S minutes, Csa~ing compositlon8 of unreacted M ~llard reagen~s or tho~e con~aining a Ma~ rd reaction product can ~l~o be u3ed in con3unrtlon wit~ liquld ~moke which : i~ well. known ln the art a8 a ~moke color~ng and flavor-lng agent fo~ meat product~.
~ 6 ~7 ~
Sultable coating compo~tions may al80 conta~n those ~ngred~ents that are known ln the art as u~ful for ~mpartin~ a variety of desirable characterlstic3 to food casing~, such a~ lmproved ~hlrrflbillty, peelability, pliabillty and the like.
The following examples sre set forth ~9 being merely lllu~trat~ve o ~he invention snd are not ~ntended, in ~ny manner, tG be l~mitative thereof.
Unless otherwi3e lndieated, all part~ and percentage~
are by weight.
E ~ LE I
This example illustrate~ the treatment of fibro~s cas~ng with unreacted Maillard reagent~ which react in situ in the casing to give transferable smoke color.
200 gr~m~ of glycine, 400 grams of xylose and 300 grams of po~a~slu~ citrate hydrate are d~olved ln 800 grams of water at room tempera~ure, 23C.
The ~olution i~ coa~ed on the inside wsLl of ~ubul~r ibrou~ gel casing havlng a c~mposltion of cellulose Z5 welght percent, water 65 welght pe~cent snd glyce~lne 10 welgh~ percent~ ~t room temper~eure by h~ slugging method, The ~olutlon is unifor~ly applied to the ea~in8 a~ a lev~l of 25 mllllgra~3 of ~olu~ion per squsre inch of ca~ng w~ The coat~ng solution pene~r~tes throughout the c~sing wall. The ca~ing i~
then hot air dried at 105C or 15 m~nuteg. The dried 7~
caYlng ha~ a ~ifor~ ~moky bro~m color, The finished cssing ha~ ~ compositlon, excludlng the sol~ds of the treating solution of this lnvention, of cellulose 71. 2 weight percent, waeer 6 weight percent snd glycer~ne 22,8 welght percent. The f~n~shed smoke colored ca~lng ha~ an amount of the Ma~llard react~on products of the amino acid glycine and the reducing ~ugar xylose sf 9,0 m~lligram~ per square lnch of casing wall, EXAMPLE II
This example illustrate~ the transfe~ability of the smoke color from a food ca~lng, treated with Maillard reagents reacted in sltu, to an enca~ed pro~
cessed meat product.
The moke Golored f~brous c~sing prepared as in Example I, i~ stufed with bologna emulsion, The bologn~ 18 fur~her proce~sed by stepc well-known in ~he - art, but without ~ conventional ~moking step. The c~sing ~8 ~hen peelet from the inished bologna rev2al ~ ing a bologn~ w~th ~ ~mske brown colored surface~ A
: 20 control sample s~uffed in an untreated casing and proce~ed u~der s~mllar condlt~on~ doe8 not have She smoke color, :
Th~ ample lllustrates ~he treatment of non-f~brou~ cellulo~e ca~ng with a co~ting composit~on 113~8 6 6~ ~
~lre~dy cont~inlng ~ M~illard reaction product ~h~ch gives the casing ~ transferable brown amoke color.
100 gr~ms of monosodium glutamate, 200 grams of te~trose and 25 grams of sodium citrate hydr~te are dl~solved Ln 750 gr~ms of w~ter and heated ~t 90C for 10 minutes to cause the MaLllard reaction to take place, The solution i8 then further heated eo evaporate the w~ter, le~ving ~ dark brown pa~te.
Sufficien~ water i8 then added ~o re-dilute the pa~te so that the composi~ion conta~ning the Maillard reaction product to ~e coated on he casing has a wa~er content based on total weighe of ~11 component~ of 40 weight percent, The coating compo~ition i~ then coated on the ~nside wa~l of dried tubular non-fibrous cellulose casing having a compo8ition of cellulose 70,3 wei~ht percent, water 12.1 wei~ht percent ~nd glycerlne 17.6 weight percent, at 23C room temperature by ~he ~lugging method, The coating ~ompo~ition i~ un~formly applied to the casing a~ ~ concentration of 20 milligr~ms of coseing composi~ion per square inch of casing waLl which i~ equiv~lent by excluding citrate and water ~o 11.0 m$11igrams of the Maillard reactlsn produc~ per ; square inch, The trested cssing has a rich moky brown colDr .
, ~ 7 EXAMPLE TY
Th~ example ~llu~tsate~ the transferablllty of the 3moke color from ~ food caslng, tre~tet w~th a coatlng compos~tion already containing a Maillard seact~on product, to an encased proce~qed meat product, The smoke c~l~red no~ fibrou~ cellulose casing prepared as in Example III, ~8 stuffed w$th fran~furter emul~lonO
The fr~nkfur~er 1s proce~sed ~t 25% rel~ti~e humidity with a dry bulb temper~ture maintained ~t 140F for 30 minute~ The temper~ture i8 then r~ised from 140~ to 180F ove~ a period of 30 mlnutes~ 3nd : then maintalnet at 180F un~il an intern~l frankfurter product t2mperature of 160F i8 reached. The p~otuct ~ i~ then cold eap-water shower~d to an internal temper-: ature of 120F and iB held in a 40F cooler for two hours prior to peellng, The ca~Lng ~ ehen peeled from the finished fr~nkfurter reveal1ng a ~ran~fur er with a smoke brown colored ~urface, A c3n~rol ~ample ~uffed in an untrea~ed c~sing and proees~ed under ~1milar condit10ns does no~ hflve ~he smoke color, :: EXAMPLE:V
~h1s example illu8~rat~ the t~e~tmen~ of celluloRe ca~lng w~h a coa~ing composl~on ~lready : con ~n~ng a M~ rd react~on produc~ ~nd whish Bl~O `
, ~ 67 8 contalns antiblock and thlckening ~gentR.
103 gram~ of 4-~minobutyric ~c~d, 150 grams of xylo8e, and 50 gram~ of sodium citrate hydrate are d~solved in 500 grams of water, The solut~on is heatet at 90C for 5 minutes to csuse the M~illard reaction to occ~r and then further heated S4 evaporate the water unt~l the water content i8 10 weight percent.
To 43 gr~ms of this compo~ition containing a Maillard reac~on product are ~ddet 15 gram8 of ~ 50% food grade mineral oil in water emul~ion as an antlblock agent, 28 gr~ms of a 3% ~queous solution of methylcellulose as a thickener 9 and 20 gm~ of propylene glycol a~ an inert diluent~ The resul~ing mixture i8 coated uniformly on dry cellulose casing by the slugging method to give a ~urface coating of ~he mixture of 20 mg/sq, in. of casing wall, which is equivalent to 7,0 mg/sq, in. of ~he Ma~llard re~ction product, The casing i8 re-dried to a 15 weight percent moi~ture level and i9 ~tuffed wieh frankurter emulslon, The ~uffed easing ~ conventionally proce~sed without ~pplicat~on of smoke and i8 ~hen peeled from ~he frankfurter, The fran~fur~er has a brswn smoke color on it~ surface, while a con~rol ~rankfurter ~imilarly processed while encased in an un~rested c~sing doe~ not, .
EXAMPLE VI
__ Thi~ example illu~tr~te~ the ~reakmenS o~ sollagen ca~ng wl~h unreae~ed Maillard re~gent~ wh~ch reac~ in ~itu in the ca~ing o glve the c~ing ~ ~moke colo~, An unre~cted M~ rd reagen~ solution i8 prepared ~ în E~cample I and applled to a ~ubular collagen gel cas~ng by ~praylng and dried as in E~cample I. The drled casing ha~ a smoky brown color, EXAMPLE VII
This e~ample ~llu~tra~es the treatment of collagen ca~ing with ~ coating composition already cont~ining a Maillard reaction produc~ which gives the casing a smoke color, A coating compo~ition i~ prepared ~18 in Example III and Dpp'l ied to a dr$ed 'cubular coll~gen c~sing by ~praying so that the Maillard re~ction product iR coated on the csslng At a level a~ ln Example III.
The treated ca3~ng ha~ a rlch smoky brown color, EXA~tPLE VIII
Thi~ exalDple illustrates the treatment of cellulose casing with a coating composition containing Maill~rd re~ction produet ~nd liquid smoke, A dark brown pa6te is prep~red a~ in Ex~mple III.
To 4 . O grams of thls dark brown p~ste are added 2, O gr~m~
- ~ of a 5~7. fvod grade Dliner~l oll in water eD~ulslon as an ; ~ ant~bIock agent ~nd 10 gram~ of liq--ld smoke" ~he resulting co~ing compo3~tion i8 ~pplied ~o ~h~ lnterior wall of at tubul~r cellulo~e casing at a level o abou~c .~
,~' 1~368 7~
30 mllligsam~ of coating compo3itlon per s~uare inch ~f cssing wall which ~ equ~valent to about 8 mg, of ~he Maillard reactlon product and to about 19 mg. of llquld smoke per ~q, ~n. of casing wall, The treated CaBing has a smoky brown color snd ~ smoke odor, A frankfurt~r processed in the treuted casing 8180 haA a ~moky brown color ~nd a smoke odor, EXAMPLE IX
This e~cample illu~trates the treatment of fibrou~ casing with a coating compo3itlon eontaining a Maillard reaction product and liqu~d smoke.
A dark brown paste i8 prepared as ~n Example III, To 4,0 grams of this dark brown pas~e are added 2,0 grams of a 50% food grade minersl oil ~n water emul6ion a~ an antiblock agent and 10 gram6 of l~qu~ d smoke, The resulting coating compo~itioTl is appl led to the ~nterior wall of ~ 'cubular fibrou~ casing at ~ level o about 39 mllligram3 of co8ting compositlon per ~quare inoh of casing w~ll which is equivalene to about 8 mg. o~ ~he Maillard reaction product and to about 19 ~g, of liquid s2noke per ~q, ~n. of casing wall, The treated c~ing ha~ 8 ~moky brown color and a smoke odor. A bologna proce~sed lr, ~he tre~ted ca~ing also ha~ ~ smoky brow~
color ant ~ 8moke odor,
The many dlr~erent recipe~ and mode~ Or proces~lng that are u~ed by the processed rOo~ lndu~try to ~uit dl~erent t~ste~ and even reglonal pre~erences generally neces~itate3 the u~e o~ rood caslngs wlth a variety of characteri~tics. In some lnstances, ~or example, rood casings are requlred to have multl-~unctlonal uRe~ whereln they serve a~ contalner~ during the proce~lng of a food product encased thereln and then al~o serve as a protectlve wrapping for the ~inl3hed product. In the proce~sed meat industry, however~ the ~ood ca3ing~, especially those derived ~rom Ce~ 0138, used ln the preparation o~ many type~ :
Or meat product~, such as various types o~ ~ausages, bee~ rolls, hams and the like~ ar ~requently removed ~rom about the proce~sed meat product prior to sliclng and/or ~lnal packaglng.
Sur~ace appearance i3 an lmportant ractor - ~ ln the commercial and consumer acceptanee o~ most processed meat products and a common ~eature or most - varietles Or ~uch products lnvolve~ khe use o~
''smoklnæ" ~or lmparting a characterlati~ brown ~olor ll3sa 67~
thereto. In the past9 the 3moklng Or ~ood product3 waa generally accompll~he~ by the food proce~orc subJecting the rOo~ product to actual contact wlth smoke ~n a ga~eou~ or cloud-llke rorm. Such ~mo~lng proce3ses, however, have been consldered un~atlsractor~
ror a v~riety o~ rea~on3 lncludlng the lne~rlclencles and lack Or unl~ormlty o~ the ~moklng operatlon.
Because Or the shortcomlngs experlenced~ the trend ha~ been to employ varlous types o~ llquld aqueous solutions o~ smoke color~ commonly called "llquld smoke solutlons" that have been developed and used commerclally by the food processor ln the proce3sing o~ many typea o~ meat and other food product : The appllcation o~ liquld smoke solutions to meat productc 18 generally carried ou~ in a variety o~ ways, lncludlng spraylng or dlpping an encased food product during the processlng thereo~ or by lncorpor~ting the llquid ~moke solutlon ln the recipe lt~el~. The actual operation o~ ~moklng by spraylng or dipplng 18 not completely satl~actory due to the equlpment expenses and the limlted degree o~ control that ha~ been rOu~, and lncorporatlon Or llo,uld smoke solutions ln the meat recipe doe~ not always provlde the deqired sur~ace appearance becau~e Or dllution Or ~moke lngredients.
It haa al~o been ~ugge~ted, as ~or example dl3clo~ed ln U.S. ~atent No. 3,330,669 ~o ~ollenbe~k, that appl~cation o~ a vi~cous liquld ~moks ~olutlon to the ln~lde surface Or a tubular ~ood caslng by the 667~3 ~ood proce~or ~mm~diately prlor to the ~tu~lng thereo~ wlth a 3ausage emulsion re~ults ln preparatlon o~ proce~ed ~ood product~ that exhlblt good color arter cooklng and removal Or the caslng.
Hereto~ore, however, lt has been round that pro~lding casings to arrord speclal treatment or ~tructural characterlstlc~ to the ~ood product can be more unl~ormly and economically accompllshed by the casing manuracturer~ Thl~ 1~ especlally true wlth the advent and wlde commerclal use of automatic stur~lng and proce3 lng equlpment in the proces~ed ~ood industry.
Several methods Or provldln~ ~ood caslngs with coatlngs applled to a ~ur~ace thereof are known and de~crlbed ln the patsnt llterature. There 1~ -dl closed> ~or example, in U.S. Patent No. 3,451,827 a ~praylng mekhod ~or ap~lying a varlety o~ coatlng materlal~ over the internal ~ur~ace o~ small dlameter ca~ing~ and ln U.S. Patent No. 3,378,379 to Shlner et al, a "slugglng" method used ~or applying coating material~ to the internal surface of large diameter ~ -ca~lngs. Wh~le such technique~ and others have been used in preparing commercial quantltle~ o~ coated food caslng~, the caslng~ prepared thereby are~ ln ~eneral, u~ed to meet partlcular commercial re~u~rements and to the b~8t 0~ our knowledge none Or the ~oated ca~lnga ai~cloRe~ ln the art are completely ~ati~actory - ~or or ar~ lntended t~ speci~lcally ~mpar~ ~moke color to a meat product proc~3ed thereln. In U.S. P8tent ~o~. 3,360,383 to ROQ~ et al, ~d 3,383,223 snd 3,~17,312 to Rose, for example, ~re d~sclo~ed co~ting compositlons that employ liquid smokg solut1on~ ln amount0 that sre specifically required to insolubilize a protein material such as gelatin to prepare ca~$ngs that meet ~pec~l adhesion properties required for use in the proce~sing of dry sausagest which propertles would ~herefore limlt the sui~bility thereof for other ca~ing applications, Prep~ration of tubul~r food caslngs that could be used ~n ~he manufscture of a varlety of processet food products and would impart a desired ~moke colo~ ~o ehe processed product would be highly desirable, Especi~lly ~dvantageous would be food casings that coult be prepared u~ing conventional coat~ng meth~d~ ~nd that would impart the desir~d color to products that h~ve the casing removed prior to final packaging or cooking or that are sold wieh the caslng still in place, Brown dyes, such as chocolate Brown HT9 h~ve been considered for ~a~ing treatment~ but such dye is not con~idered ~afe for hum~n con~mption. A smoke color tye mix~ure, ~uch ~8 stflnge ~ ~ smoke color, can be u~ed to give B superflcial ~moke color ~o me~t productR, but, becau~e lt ~8 a dye mi~ure of pr~msry red ~nd blue dyes, which heve dlffering solublllty and dlffu~lv~ey, the ~urfcce colo~atlon of the me~t producta become~ blui~h a~ the ~ 7 ~
red dye dlffuses ~nto the meat product wi h ~tor~ge, Thus, the unQtable Stange' 8 smoke color ~ not a satisfactory coloring agent, The deflclencles of the aforementloned smoke coloring agentq have been overcome by the present invention, whLch provide~ a nonto~lc, safe and ~table smoke colorlng agene con~st~ng of a re~ction product of a reducing ~ugsr and an a~ino acid, In accordance with ehe present invention there i~ provided a tubular ~ood caæing that i8 su~table to impart smoke color to food product enca~ed or processed therein compris~ng ~ tubular cellulose food casing hsving incorporated therein a re~ction product of an smino acid and a reducing sugar in ~mount~
specified in more detail hereinafter~ I~ has been di~covered that the tl~bular food casings of the present inve~tlon may be used to ~mpart tran~ferable ~moke color to a wide variety of me~t products processed there~n without the need for ~ny further ~moking operation~ by ~ 20 the food processor, Moreover it has been found ehat :~ said casings may be preparod in the for~ of ~hirred casing stick3 wherein long continuou~ len~hs of tubular food casing are pleated and compres~ed into a substantially shortened form ~hereof~ or ~ ~hort ~egment~ of flsttened tubing, : ~ Al~o provided in accorda~nce with the present . ~ lnvention i8 a smoke colored coll~gen ca~ing, co~pri~ing a tubular collagen ~ood cssing h~ving ~ncorporated ther~in reaction product of n ~mino cid and G
7 ~
reduc~ng ~ugar ~n amount8 ~pecifled ln more detall hereinafter.
Smoke colored collagen ca~ings of this inventlon are cap~ble of impartlng tr~n~fer~ble ~moke color to food prGducts, such as meat product3, encased thereln, However, ln the pract~c~l u~e of edible collsgen casing, once the food product is encased therein, the ca~lng ~a not removed before human consumption, but conaumed with the encased meat produet, Therefore, transfer of the smoke color from an edible collagen casing to the encased food product surface i8 not critical, because in normal u~e, unlike in the use of peelable cellulose casing~, the consumer will not see the food product ' ~ sctu~l -surface. However, unlike tran fer of smoke color from an edible collagen casing~ transfer of smoke color from an in-edible coll~gen casing to the encased food produc~ i~ critical since the ~nedible casing must be removed before ~onsumption.
AL~o provided in ~ccordance with the pre~ent inventlon are methods of preparing tubul~r food casings that : ~re suitable or impartlng smoke color to fo~d products enca~ed or processed therein which compri~e~ ~n one embod~ment providing a tubul~r food cas ing ~nd applying thereto an aqueou~ ~olutlon of ~ reducing ~ugar and ~n amino acid wh$ch : ~ ~re c~used eo react in si~u in the cas~ng according to the well-known Mai1lsrd reac~on, The ~Saillard reaction product h~s a smoke brown color which i9 water ~sluble and can tr~n~fer to the surf~ce of ~ meat product which 1~ subsequently s~uffed in the trested c~6ing, The term~ "~ re~ction product" ~nd '~illard reaction product" a~ u~ed herein are ineended to er~compass any ~nd all re~ction product~ which ~re for~ed from the ~1~68 ~ 67 8 Maillard resetion, lncludlng any reduclng BUgar Gr amino acid ~n stoichiometric exce~s, but e~clud~ng any water or c~trste compounds here$nsfter described, In an alt~rnate embodiment of thls Inventlon the Maillard reaction product ~9 costed directly on the casing, obviatlng the requirement of in situ reactlon.
The undesirsble brownlng of food~tuffs, such a~ or~nge ~uice, due ~o the Malllard reaction between reduc~ng ~ugars and amino acid~ i~ known ~nd i~
discussed by Wolfrom et al~ in "J, Agr, Food Ch~m,", Vol, 22, No, 5, 1974 at page~ 796-~Q0, Al~o cee Green~hields et ~1, in "Process Biochemi~try", December 1972, pp. 11-16. In "The Science of Meat ant Meat Products", J,F. Prlce et ~1, ets.; 2nd ed.;
1971~ at pages 460-461, i~ iB dlsclosed that reducing ugars cause r~pid darkening of bacon on fry~ng, whieh i~ a~cribed o ehe Maillard reaction between glucose and amino group~, Neither Wolfrom et al, nor ~reenshields et al, nor Rrice e~ 81 di~clo~e the use of ~he ~llard reaction ~o color food ca~ing oæ meat products encased in the trea~ed casings.
The food casing~ of the present inventlon may be prepared rom tubul~r c~sings h~ving vari2d compo~
tlons~ suoh 88 those w~ known in ~he art a~ regenerated cellulose casings either wi~h or without ~lbrous reinforoement, The former i8 known in the tr~de as fibrous ~a~ng ~nd i~ reinforced with paper ~nd the llke, Other ~moke colored ca~ings c~n be prepared by the method~ o thl~ ~nvention, ~u~h as those ~ste from ~ 67 ~ 1l368 cellulo8e deriva~lves, collagen (edible and inedible), alginates, amylo3e, ~nsolubillzed polyvinyl slcohol tboeh f~brou~ reinforced ~nd unreinforced) And the llke, Wh~le the invention particul~rly relates to tubul~r food c~sings, food wrapping materials in other forms ~uch ~ ~heet form may be smoke colored by appropriaee modlfications of the treating methods of thls invent~on by those ~killed ~n ehe ~rt, The ca~ings of this invention csn be us d to enc~se me~t produ~t~ lncluding~ bue not limlted to cooked, smoked9 d~y or semidry ausages such as frankfurters, bologna~, ~al~mis, cervelats, Thuringer~, ant the like. CheeQe produc~s may also be enca~ed ln the casings of thi~ invention, In a preferred embodiment of this invention in~olving the use of unre~ctet Maillard reagents to coat cas~ng, spec~flc details of which are ~et forth hereinafter, an aqueous sslution of at lea~t one amino acid and st least one reducing ~ugar i8 fir~t formed, Optionally ~dded to this solution 1~ a cltsate :~ compound to lncrea~e the reaction r~e between the amino acid and reduc~ng sugar, The ~olution i~ ~hen coa~ed on tubula~ gel cas~ng before drylng, Durlng drying - at elevated temper~ture8 ehe M~illard reaction occurs : between ~the amino acid and the reducing sugar in .~
~itu ln th@ ca~lng, ~o give ~he finished c~sing ~
~moky brown color, The smoke colored casing c~n then be ~tuffed wl~h R food protuct ~uch ~B a meat emul~ion.
The ~moky brown color of the casing will .
~ 7 ~
transfer to the ~urf~ce o the enca~ed meat prsduct9 BO that if the easing 1~ separ~ted from the encased meat after cooking or other further proce3sing well-known ~ the art, the ~ur~ce of the meat wlll hsve a smoky b~own color.
In a preferred embod~ment of thls invention lnvolving the direct UBe of a M~illard react~on product to coat ca~ing, spec~flc detalls of which are 8et forth hereinAfter, ~n aqueous ~olution of ae le88t one ~mino acid and ~t lea~t one reduci~g su~ar i8 f~rs~ formed.
Optionally added to th~s ~olution i~ a ~itrate compound .
to increase ehe reactlon rate between the amino ~cid and reduclng sugar. The solutlon i~ then heated to react the amino acld and ~he reducing sug~r to form a Maillard reac~ion product and then further heated to evaporate the water contene to de~ired level3 and if needed se-d~lu~ed with water to ad~u~t color concentration befsre appllc~tion to the ca~ing. The re~ultant co~ting compo~iticn i~ then op~ionally mixed with an~block - -: 20 agent3 snd thickeners before ~he caslng ls coated, The Maillard reac~ion protuc~ containing composl~ion is then eo~ted on dried ~ubular food caslng giving the ca~ing a : ~m~ky brown col~r. The ~moke colDred casing c~n then b~
~tuffed with a food product ~ch as a meat emulsion. The ~moky brown color o~ the ca~ing will tr~ns~er to the ~rf~ce of ~he encased meat produc~, 80 that if ~he casing ie ~eparated ~om the encased ~neat after cook~ng or other further process~tlg well~known i~ the art, the ~urface o the ~e8t w~ll have a 8moky brown color.
. ,, , ~ ~ , ;7~
Many ~m~ no c~mpound~ ~re ~ultable fsr we ln th~ lnveQelon, E~emplary of the amino aclds which can be employed in the practice of this invention are 4~
aminobutyrle acld, glycine, ~lanine, ~rgln~ne, and the dimera and the trimers thereof, ~nd the like, Also useful are amino ~cid derivatives such a~ ~alt~ of amlno scid~
like mono~odium glut~mate ~nd lysine monohydrochlor~de.
The invention i3 not l~mited to tho~e ~mino ~clds or derivatlve~ ~pecified herein, but may include others selected by those skllled in the art, The amino acids or derivative~ may be u~ed ~ndividu~lly or as miactures of variou~ amino acid~, or aR IDixtures of amlno ~cid derivatives5 or ~s mixtures of amino ~cids and ~mino acid derivatives.
Exemplary of the reducing sug~r~ which can be employed in the prActice of thi~ invention are ~108e, arabino~e, de~trose (d-gluco~e) and the llke. The invention is not l~mited to those reducing sugars specified herein, bu~ may include other~ selected by those ~killed in the ar~.
The reduclng sugar~ m~y be u~ed individually or as mixture~
of variou~ reducing sugars~
If unreacted Maill~rd reage~t~ are u~ed to treat c~sing9 then the amount of ~he treAting 601ut~0n applied eo the ca~lng i~ from ~bout 5 to ~bout 50 ~lligr~ms per ~quare inch ~f ca~ing wall, preferably from about 15 eo about 30 ~g~/~q, in, Correspondlngly, the amount of ~he reduclng ~ugar appliet 1~ rom aboue 0,7 So ~bout 14.0 mg,/sq, ln. of ca~ing w~ll, preferably r~ a~out 3.7 ~o ~bout 7.5 mg,/~q, in., and the a~ino ~c~d ~ppl~ed i~ from : about 0,3 to ~bou~ 7,0 mg./~q. ln. of c~slng wal~
- - ~
.
`` 11368 3667~
psefer~bly from about 1.3 to about 2,7 ~g, /8q. ln.
If a coat~ng compo~ition containing a Maillard resctlon product i8 directly coa~ed on the caslng then the amount of the coating compos~eion applied ~hoult be from about 9 to about 35 mgs/~q, ~n, of casing wall, preferably from ~bout 10 ~o about 20 mgs/~q, in. tepending on whether additional ant~block and/or thlckenlng agent~
are employed, Cor~espond~ngly9 the amount of the MRillard reaction product ~pplied i3 from ~bout 2,7 to sbout 14 ~g./
~"1 0 Qq, in, of e~lng wall, prefer~blj from ~bout 3,5 to about 7,0 ~11g./5~, ill.
The c~sing cont~lning the brown ~moke color i8 subsequently gtuffed with a meat product. The smoke color transfer~ to ehe ~urface of the encssed meat product, The inal smoke colored ca~ing produced by the method~ of this lnvention ~hould contain a Maillard react~on product of an amino ~cid and ~ reducing sug~r at a level from ~bout 2.7 to about 14 mllligrams of reactlon produck per ~quare inch of casing w~ preferably about 3.5 to about 7.0 mg,~per ~q, in " in order to lmpar~ ~he smoke color to a food product encs~ed therein, The preferred level of Maillard reac~ion produ~t ~n the c~ing which ui~lmately ~ trsnsferred :~ to the ~urface of the enc~ed me~t psoduct 1~ dependent upon lndlYidual color preferenc~ o~ the ~onsumer~.
Some ~ould prefer ~ dsrk brown sausag~ whlle othor~
l~ght brown s~u~a~e.
The ~ethod o applying the treating a8~nts .
~ 7 ~
to the cas~ng cfln be selected irom varisu~ ~own techniques such as ~lugging, which iB al~o known a3 bubble ~oatLng (U,S. Patent 3,378,379 to Shiner et al and U.S. Pstents 3,360,383 to Rose et al; U.S. 3,383,223 to Ro~e; And U,S~ 3,427,16~ to Rose et al), dipping ~U.S. Patent 3,378,379), spraying (U.S, Patent 3,330,66Y
to Hollenbeck) os ln~ernally coating the caslng ~hile sh~rring by the method dlsclo~ed by Bridgeford in U.S.
Reissue 28,2~1.
The slugging method for co~ing the in~ide of a cA~ing lnvolveQ fllling a portion of th ca lng with the coating m~e~ial, ~3 ~hat ehe ~lug of coating materiAl generally reside3 ~t the bottom of a "U" shape formed by the casing draped over tws parallel rollers, ant then movlng the coneinuous indeflnite length of casing so ~hat the slug of co~tlng ~ateri~l remain~
conflned within the casing, while the casing moYe~ past ~he slug and i~ coated on lt3 inside wall by the coating materiAl conta$ned within the slug.
The dipplng method for coating a casing ~nvolves in it~ ~imples~ form immer~ing ~he cas~ng in a bath of treating solution for ~ suf~ic$ent period of ~me to coat the out~lde of the casing or in ~ oontinuous prOCe~8 psss~ng an indefinite length of oa~ing over guide rolls through a treatment bath.
The ~praying method m~y be u~ed ~o coat the outsld~ of the c~sing or the in31de urf~ce o~ ~he casing by the use of nozzle~ ~ueh a8 di~clo~ed by Hollenbeck, ~1368 ;7~3 Depending upon whlch embodlment of thi~ ~ nvention ~ cho~en, the tubular casing can be eLther eo~ted on it~
out~ide surfsce or on lts in~lde ~urface with the treating solution of the unreacted amino ~cids and re-ducing sug~r~ or the compo~ition already containing ~
Msillart re~ction product. The coat~ng on the cas~ng wall penetrates throughou~ the ca~ing to y1 eld ~ uniform r~dial distributi~n of the coa~ing ' 8 components in the casin~. Prefer~bly, the cas~g i~ coa~ed on lts inner surf3ce3 to mascimlze contact of ~he Malllard re~ction product wlth the ~ubsequently encased meac product~. If the easing i~ coated on itQ outaide wall, the coating will penetrate to the inside wall, ~o ~h~t subsequent transfer of the Maill~rt reaction product coloring agent ~o sn encased meat product wlll tske place. However, the surface of the caslng on which the ereating agents of thi~ ~nventlon was inieially coated will have ~ slightly hi~her concentration of the Maillard coloring agen~ thsn - -the opposLte surface which did not rece~ve the coating.
Of course, the ca3Lng m~y be co~ted on it~ outer wall and ~hen turned lnside-out for ~tuffing, if ~o deslred.
BecauRe the c~ing~ utilized in the practice of this invent~on ~re thin wslled generslly of a ehlckr~ess of about 1 mils to sbout 10 mil~, the differes~tial colo~ing agen~ concentra~ion beeween the inner and outer casing surfaces ha~ no ~ignlfic~nt effect on ~he colo~ of the ca~ing or ~he color tran~ferred to the encased me~t product .
Coa~cln~ composl~ons of unre~cted Maillard 113~8 ~ 7 ~
reagents suit~ble for use ~n accordance with the embodiment~ of ~he present lnvention are preferably homogeneous aqueous ~olutions of the ~mino acid~ ~nd reducing sugars.
The molar ratio of the ~educing sugar to the amlno aclt in the unreacted Maillard reagents aqueous treatlng ~olution u~ed to ccat food casing~ within the practlce of this invent~on should be from about9 10 to 1, to about~ 1 to 10, preferably about, 1 to 1, to abou~, 1 ~o 5, In the prepara~ion of the unrea ted Maillard reagents treatlng solution the amount of water used should be that minimum amount wh~ch i~ just suffic$ent to dis~olve 811 the components of the solution, that i~ from about 40 to about 70 weigh~ percent water based upon the total weight o the flnal solution, preferably from about 40 ~o about 50 weight percent water, In the alternate embodiment of thi~ invention, the composition u~ed ~o dlrectly coat csC~ng~ with a ~aillard reaction produet 1~ prepared by flrs~ prep~ring an ~queo-~s 601ution of an amlno acid and a reducing sugar in the ~ame proportlon~ of amino acid, reducing 6ugar ~nt w~ter ~8 outl~ned above for ~he embodiment of thi~
inventlon dlrected to unre~cted Maillard reagents, and then hea~ng the ~olutlon to a ~emperature ln the rsnge of from a~ou~ 60C ~o abou~ 110C for abou~ ~ ~inute~ to sbout 30 ~nu~e~ to cause ~he M~illard reactlon ~o eake place, preferAbly from ~bouE 90C to ~bout 100C for about 10 to ~bout 20 m~nu~es, ~nd then ~dditionally ~3 -~6~ii7~3 heating ~or ~ ~uff~clent amount of t~me to evaporate the water eo from about 5 to ~bout 10 we~ght percen~ w~ter The M~lllard reaction product conta~n$ng compositlon iB
then re-dlluted wlth water, before coa~lng the cssing, to ~ water c~ntent of about 25 to about 50 weight percent, preferably nbout 30 to about 35 weight percent, Casing can also be coated with ~n unevaporated Maillard react~on product containing compo~ition, lf a l~ghter color i8 de6ired Color concentration iB readily controlled by those skilled in the art by proper evaporat~on and/or re-dilutlon, Potasslum citrate may be added hS pota~ium c~trate hydrate to the aqueou~ solution of an amino acid and a redu~ing sugar in order to increase the r~te of the color development in the casing by the ln 8itU
Malllard reac~ion~ If potassium citrate i~ used, the molar ratio of po~assiu~ citra~e to reduc~ng ~ugar in the aqueou~ treating solution used to coat the casings ~hould be from abou~, 1 to 2~, to about, 1 to 19 p~eferably ~bou~, 3 ~o 4. Sodium citrate a ~dium cltr~te hydrate may be added ~nstead of potasslum cltrate ~n the same molsr ratio~ with the sEme effect~
With respec~ to ~he prep~rat~on of the coa~lng c~mpo~ition ~lready containing a Maill~rd reac~ion produet, the M~ sd reaction r~te i~ no~ ~s ~mpo~tane ln the case of c~ng tre~tment wi~h an unreaeted ~olut~on o a redueing sugar ~nd ~n amino ac~d where the G~sing has to be he~ted to develop the color in s~tu, ~nd prefer~bly dr~ed at ~he ~ame time. Thu~9 in the ~-$~6~7~3 emb~d~ment of this lnventisn lnYo1~ing casing tre~tm2nt w1th unreacted Ma~llard reagents the rate of color deve10pment ha3 to be co~ordinated with caslng drying, whil~ ln the embodiment of th~s invention involv~ng the direct use of ~ Maillard reaction product to co~t the caslng, color de~elopment i~ not gener~lly co-ordinated with ca3ing drying. In fact the Maill~rd reac~ion product i9 preferably eoated on pre~iou~1y dried ca~ing~
Therefore, ~ince color development rate con~rol i8 not critical in the prep~ration of the coAtlng compo~ition contalning the Maillard rea tlon product, the use of pota~s~um o~ sodium citrate i8 optional and the concentration u~ed i8 generally 1~88 ~han thA~ used in the prep~ration of the unreacted M~illard treat~ng - ~olutlonO If used, the amount of potasAium or sodium citrate sdted ln hydrate form to prepare the coating compos~E~on cont~ining the Mai~1srd reaction product~
i3 expressed as ~ molar ratio of ~he pot~ssium or ~odium citrate to reducing sugar u~ed 2nd i~ on the order of from ~bout, O to 1, to ~bout~ l to 1, preferably about 3 to 4, Op~ona11y, prior to the oo~ting ~tep, ; th~ckener~ and antib10ck agen~ are ~dded to the coating compo~ition contaln~ng the Mail1art reaction product which al~o con~ins sbout 25 ~o about 50 weight percen~
wa~er f The ~hickeners are ~dded to lncrea~e the ~scosley of ~he mi~t~re ln osder to obtaln ~ ~hicker coa~n~ on the cssing, lf it 1~ de~ired to supp1y 1ncreased co10r to the c~ing. Th~ckeners wh~ch can be lB
1136~
eDployed lnclude, but ~re not l~mited to aqueous cellulose gum ~olu~ions ~uch aa solutions of c~rbo~ymethylcellulose, methylcellulo~e, and the llke ant aqueous ~olutions of pectin, vegetable gum or tarch and the like. Antiblock agent~ are ~dded to prevent the treated casing from st~ck-~g to itself. Any comp~tlble antiblock agent can be employed such a~ a water emul~on of food gr~de minersl oil, vegetable oil, s$1icone oil, And ehe like. If a mlnersl o~l emulsion i~ employed, the final co~ting compo~i~ion containing ~he Maillard reaction product i8 2n emul~ion with the Maillard reaction product dlssolved in the water pha~e. In the practice of thi~ invention : the difference be~ween ~ 301ution and an emul~lcn i8 not critical, The amount of antiblock and thickening agents employed in the coating c~mpositio~ i~ dependent upon the type of ~gent~, P~eferably about 5 ~o about 15 weight percent ant~block a~ent ~nd about 0.5 to about 2 weight percent thickeners are used~ If dry casing i8 coated with such ~ mixture contaln~ng the ~dditional antlblock and thiokening ~gents, then addition~l drying af~er co~ting will be nece~s~ry ~n order to bring the ~o~ture con~ent of the tre~ted cssing back down to a de~ired level of fr~m about 3 to about 15 weight perrent. ~-Antiblock and thlckening agents may al~ be employed, if desired, w$th the unreaeted ~llard ;- se~gent~ coatlng 801ution.
In the well~know~ conventional ~ethod~ for psepar~ng ~egener~ ed cellulo~e c~slng (non-fi~rou~
or fibrou~ ca~ing) or collagen caslng, the final c~s~ng :-~ 7 processlng step 1~ a drylng step whlch encompas3e~
pas~ing the unf~nl~hed casing commonly known a~ gel ca~ing through a ho~ ~ir dryer whereln the gel c~sing 1~ dr~et to a de~lred molsture content, typ~cally be~ween about 3 weight percent to about 15 weight percene moisture.
The ca3~ng c~n be coatet wlth an aqueou~
solution ~f the unreacted Maillard reagent~ prlor to the drying o~ the gel c~ing or after the drying 8tep.
Preferably, the casing i~ coated immediately pr~or to the drying step 80 that the elevated temperature of the drylng step can serve to both dry the gel casing ~nd cause the Malllard reaction between the a~ino acid and the reduclng ~ugar of the coat$ng to occur in ~itu in the cs~lng, producing reaction product~ wh~ch give the casing a rich smoky brown color which iB readily tran~fer~ble from the casing to ~he surface of d meat produc~ which is subsequently stuffed in the ca3ing. The drying tempera-ture and time are lnterdependent and should range ~rom about 80C or abou~ 24 hours to a~ou~ 120C for ~bout 5 minutes, and preferably from abou~ 100C to about 110C
for about lO to about 15 mlnutes, If the casing 1~ coated af~er ~he drying step, then an addit~onal heating step i8 re~uired at from ~bout 30C to about 1209C for ~bou~ 1 m~nute to about 30 days to c~u~e the Maillard zeac~on to e~ke pl~ce~ ~nd prefer~bly Crom about 7~C ~o ab~ut 90C for about 15 mlnutes to ~bout 10 hourA, The drying t~e ~nd ~emperature ~re in~er-dependent f~ctorR in~ofar a~ ~ffeeting the drying of ~0 ~ 7 the ca~ing to de ired mol~ture levels aa well a~
affect~ng the Malllard re~ct~on. If the caRl~g i~
coated sfter drying requlr~ng sn additional hest~ng 8tep~
the in~erdependent hestlng ~ime and temperature should be selected by those skilled ln the art to be ~ufficlent to ~chieve ln 61tu Maillard reaction ~n ~he cas~ng while maintainLng de~ired final moisture levels in the ca~ing end minimlzing the neces ity of re-moi~turizing the casing.
lQ If it i~ deslred to coat casing with ~ coatlng composition already c3ntalning ~ Maillard reaction produce, thi3 al~o can be performed before or ~fter ~he casing ~rying ~tep. ~ecau~e the ~aillard reagents in this instance are pre-reacted, the heat from the drying step is not needed eo cause the reaction to take place in s~u ln the cas~ng9 and therefore, ~he ca~ing i8 preferably coated after the try~ng step. EYe~ if eoated after drying, some additional drying may be nece~sry depending on ehe water con~en~ of the co~ting compositlon containing ~he Maillard reaction product, Thi~
additional dryLng can be performed at from abou~ 80~C for abou~ 10 minute~ to about 120C for about l minute, and preferably from about 90C to abou~ 1~0C for ~bout 2 to : ~bou~ S minutes, Csa~ing compositlon8 of unreacted M ~llard reagen~s or tho~e con~aining a Ma~ rd reaction product can ~l~o be u3ed in con3unrtlon wit~ liquld ~moke which : i~ well. known ln the art a8 a ~moke color~ng and flavor-lng agent fo~ meat product~.
~ 6 ~7 ~
Sultable coating compo~tions may al80 conta~n those ~ngred~ents that are known ln the art as u~ful for ~mpartin~ a variety of desirable characterlstic3 to food casing~, such a~ lmproved ~hlrrflbillty, peelability, pliabillty and the like.
The following examples sre set forth ~9 being merely lllu~trat~ve o ~he invention snd are not ~ntended, in ~ny manner, tG be l~mitative thereof.
Unless otherwi3e lndieated, all part~ and percentage~
are by weight.
E ~ LE I
This example illustrate~ the treatment of fibro~s cas~ng with unreacted Maillard reagent~ which react in situ in the casing to give transferable smoke color.
200 gr~m~ of glycine, 400 grams of xylose and 300 grams of po~a~slu~ citrate hydrate are d~olved ln 800 grams of water at room tempera~ure, 23C.
The ~olution i~ coa~ed on the inside wsLl of ~ubul~r ibrou~ gel casing havlng a c~mposltion of cellulose Z5 welght percent, water 65 welght pe~cent snd glyce~lne 10 welgh~ percent~ ~t room temper~eure by h~ slugging method, The ~olutlon is unifor~ly applied to the ea~in8 a~ a lev~l of 25 mllllgra~3 of ~olu~ion per squsre inch of ca~ng w~ The coat~ng solution pene~r~tes throughout the c~sing wall. The ca~ing i~
then hot air dried at 105C or 15 m~nuteg. The dried 7~
caYlng ha~ a ~ifor~ ~moky bro~m color, The finished cssing ha~ ~ compositlon, excludlng the sol~ds of the treating solution of this lnvention, of cellulose 71. 2 weight percent, waeer 6 weight percent snd glycer~ne 22,8 welght percent. The f~n~shed smoke colored ca~lng ha~ an amount of the Ma~llard react~on products of the amino acid glycine and the reducing ~ugar xylose sf 9,0 m~lligram~ per square lnch of casing wall, EXAMPLE II
This example illustrate~ the transfe~ability of the smoke color from a food ca~lng, treated with Maillard reagents reacted in sltu, to an enca~ed pro~
cessed meat product.
The moke Golored f~brous c~sing prepared as in Example I, i~ stufed with bologna emulsion, The bologn~ 18 fur~her proce~sed by stepc well-known in ~he - art, but without ~ conventional ~moking step. The c~sing ~8 ~hen peelet from the inished bologna rev2al ~ ing a bologn~ w~th ~ ~mske brown colored surface~ A
: 20 control sample s~uffed in an untreated casing and proce~ed u~der s~mllar condlt~on~ doe8 not have She smoke color, :
Th~ ample lllustrates ~he treatment of non-f~brou~ cellulo~e ca~ng with a co~ting composit~on 113~8 6 6~ ~
~lre~dy cont~inlng ~ M~illard reaction product ~h~ch gives the casing ~ transferable brown amoke color.
100 gr~ms of monosodium glutamate, 200 grams of te~trose and 25 grams of sodium citrate hydr~te are dl~solved Ln 750 gr~ms of w~ter and heated ~t 90C for 10 minutes to cause the MaLllard reaction to take place, The solution i8 then further heated eo evaporate the w~ter, le~ving ~ dark brown pa~te.
Sufficien~ water i8 then added ~o re-dilute the pa~te so that the composi~ion conta~ning the Maillard reaction product to ~e coated on he casing has a wa~er content based on total weighe of ~11 component~ of 40 weight percent, The coating compo~ition i~ then coated on the ~nside wa~l of dried tubular non-fibrous cellulose casing having a compo8ition of cellulose 70,3 wei~ht percent, water 12.1 wei~ht percent ~nd glycerlne 17.6 weight percent, at 23C room temperature by ~he ~lugging method, The coating ~ompo~ition i~ un~formly applied to the casing a~ ~ concentration of 20 milligr~ms of coseing composi~ion per square inch of casing waLl which i~ equiv~lent by excluding citrate and water ~o 11.0 m$11igrams of the Maillard reactlsn produc~ per ; square inch, The trested cssing has a rich moky brown colDr .
, ~ 7 EXAMPLE TY
Th~ example ~llu~tsate~ the transferablllty of the 3moke color from ~ food caslng, tre~tet w~th a coatlng compos~tion already containing a Maillard seact~on product, to an encased proce~qed meat product, The smoke c~l~red no~ fibrou~ cellulose casing prepared as in Example III, ~8 stuffed w$th fran~furter emul~lonO
The fr~nkfur~er 1s proce~sed ~t 25% rel~ti~e humidity with a dry bulb temper~ture maintained ~t 140F for 30 minute~ The temper~ture i8 then r~ised from 140~ to 180F ove~ a period of 30 mlnutes~ 3nd : then maintalnet at 180F un~il an intern~l frankfurter product t2mperature of 160F i8 reached. The p~otuct ~ i~ then cold eap-water shower~d to an internal temper-: ature of 120F and iB held in a 40F cooler for two hours prior to peellng, The ca~Lng ~ ehen peeled from the finished fr~nkfurter reveal1ng a ~ran~fur er with a smoke brown colored ~urface, A c3n~rol ~ample ~uffed in an untrea~ed c~sing and proees~ed under ~1milar condit10ns does no~ hflve ~he smoke color, :: EXAMPLE:V
~h1s example illu8~rat~ the t~e~tmen~ of celluloRe ca~lng w~h a coa~ing composl~on ~lready : con ~n~ng a M~ rd react~on produc~ ~nd whish Bl~O `
, ~ 67 8 contalns antiblock and thlckening ~gentR.
103 gram~ of 4-~minobutyric ~c~d, 150 grams of xylo8e, and 50 gram~ of sodium citrate hydrate are d~solved in 500 grams of water, The solut~on is heatet at 90C for 5 minutes to csuse the M~illard reaction to occ~r and then further heated S4 evaporate the water unt~l the water content i8 10 weight percent.
To 43 gr~ms of this compo~ition containing a Maillard reac~on product are ~ddet 15 gram8 of ~ 50% food grade mineral oil in water emul~ion as an antlblock agent, 28 gr~ms of a 3% ~queous solution of methylcellulose as a thickener 9 and 20 gm~ of propylene glycol a~ an inert diluent~ The resul~ing mixture i8 coated uniformly on dry cellulose casing by the slugging method to give a ~urface coating of ~he mixture of 20 mg/sq, in. of casing wall, which is equivalent to 7,0 mg/sq, in. of ~he Ma~llard re~ction product, The casing i8 re-dried to a 15 weight percent moi~ture level and i9 ~tuffed wieh frankurter emulslon, The ~uffed easing ~ conventionally proce~sed without ~pplicat~on of smoke and i8 ~hen peeled from ~he frankfurter, The fran~fur~er has a brswn smoke color on it~ surface, while a con~rol ~rankfurter ~imilarly processed while encased in an un~rested c~sing doe~ not, .
EXAMPLE VI
__ Thi~ example illu~tr~te~ the ~reakmenS o~ sollagen ca~ng wl~h unreae~ed Maillard re~gent~ wh~ch reac~ in ~itu in the ca~ing o glve the c~ing ~ ~moke colo~, An unre~cted M~ rd reagen~ solution i8 prepared ~ în E~cample I and applled to a ~ubular collagen gel cas~ng by ~praylng and dried as in E~cample I. The drled casing ha~ a smoky brown color, EXAMPLE VII
This e~ample ~llu~tra~es the treatment of collagen ca~ing with ~ coating composition already cont~ining a Maillard reaction produc~ which gives the casing a smoke color, A coating compo~ition i~ prepared ~18 in Example III and Dpp'l ied to a dr$ed 'cubular coll~gen c~sing by ~praying so that the Maillard re~ction product iR coated on the csslng At a level a~ ln Example III.
The treated ca3~ng ha~ a rlch smoky brown color, EXA~tPLE VIII
Thi~ exalDple illustrates the treatment of cellulose casing with a coating composition containing Maill~rd re~ction produet ~nd liquid smoke, A dark brown pa6te is prep~red a~ in Ex~mple III.
To 4 . O grams of thls dark brown p~ste are added 2, O gr~m~
- ~ of a 5~7. fvod grade Dliner~l oll in water eD~ulslon as an ; ~ ant~bIock agent ~nd 10 gram~ of liq--ld smoke" ~he resulting co~ing compo3~tion i8 ~pplied ~o ~h~ lnterior wall of at tubul~r cellulo~e casing at a level o abou~c .~
,~' 1~368 7~
30 mllligsam~ of coating compo3itlon per s~uare inch ~f cssing wall which ~ equ~valent to about 8 mg, of ~he Maillard reactlon product and to about 19 mg. of llquld smoke per ~q, ~n. of casing wall, The treated CaBing has a smoky brown color snd ~ smoke odor, A frankfurt~r processed in the treuted casing 8180 haA a ~moky brown color ~nd a smoke odor, EXAMPLE IX
This e~cample illu~trates the treatment of fibrou~ casing with a coating compo3itlon eontaining a Maillard reaction product and liqu~d smoke.
A dark brown paste i8 prepared as ~n Example III, To 4,0 grams of this dark brown pas~e are added 2,0 grams of a 50% food grade minersl oil ~n water emul6ion a~ an antiblock agent and 10 gram6 of l~qu~ d smoke, The resulting coating compo~itioTl is appl led to the ~nterior wall of ~ 'cubular fibrou~ casing at ~ level o about 39 mllligram3 of co8ting compositlon per ~quare inoh of casing w~ll which is equivalene to about 8 mg. o~ ~he Maillard reaction product and to about 19 ~g, of liquid s2noke per ~q, ~n. of casing wall, The treated c~ing ha~ 8 ~moky brown color and a smoke odor. A bologna proce~sed lr, ~he tre~ted ca~ing also ha~ ~ smoky brow~
color ant ~ 8moke odor,
Claims (64)
1. A casing suitable for imparting smoke color to food products encased therein, prepared by treating the casing with a reaction product of a reducing sugar and an amino compound selected from the group consisting of an amino acid, an amino acid derivative, and a mixture of an amino acid and an amino acid derivative, in an amount sufficient to give the casing a smoke color which is water soluble and readily transferable to a food product.
2. The casing of Claim 1 wherein the casing is a tubular food casing.
3. The casing of Claim 1 wherein the casing is a cellulose casing.
4. The casing of Claim 1 wherein the casing is a fibrous cellulose casing.
5. The casing of Claim 1 wherein the casing is a collagen casing.
6. The casing of Claim 1 wherein the casing is an insolubilized polyvinyl alcohol casing.
7. The casing of Claim 1 wherein the casing is a fibrous insolubilized polyvinyl alcohol casing.
8. The casing of Claim 1 wherein said amino compound is selected from the group consisting of 4-aminobutyric acid, glycine, lysine monohydrochloride, alanine, arginine, and monosodium glutamate.
9. The casing of Claim 1 wherein said reducing sugar is selected from the group consisting of xylose, arabinose and dextrose.
10. The casing of Claim 1 wherein the casing has liquid smoke additionally incorporated therein.
11. The casing of Claim 1 which comprises from about 2.7 to about 14 milligrams of said reaction product per square inch of casing wall.
12. The casing of Claim 1 which additionally comprises a citrate selected from the group consisting of potassium citrate and sodium citrate.
13. The casing of Claim 1 wherein a food product is encased therein.
14. A meat sausage with a smoke color surface coating prepared by the steps of providing a food casing, treating said casing with a reaction product of a reducing sugar and an amino compound selected from the group consisting of an amino acid, an amimo acid derivative, and a mixture of an amino acid and an amino acid derivative, drying the casing by heating at elevated temperatures to form said reaction product as a coating on said casing, stuffing the so-coated casing with said meat sausage and contacting the coating with water so as to solubilize and transfer the reaction product to the sausage.
15. The meat sausage of Claim 14 wherein said amino compound is selected from the group consisting of 4-aminobutyric acid, glycine, lysine monohydrochloride, alanine, arginine, and monosodium glutamate.
16. The meat sausage of Claim 14 wherein said reducing sugar is selected from the group consisting of xylose, arabinose, and dextrose.
17. In a method for manufacturing a tubular food casing the improvement which comprises treating the casing prior to drying with an aqueous solution of a reducing sugar and an amino compound selected from the group consisting of an amino acid, an amino acid derivative, and a mixture of an amino acid and an amino acid derivative, drying the casing by heating at elevated temperatures so that simultaneously with drying the said solution components react in situ in the casing to form a reaction product which gives the dried casing a smoke color which is water soluble find readily transferable to a food product.
18. The method of Claim 17 wherein the casing is a cellulose casing.
19. The method of Claim 17 wherein the casing is a fibrous cellulose casing.
20, The method of Claim 17 wherein the casing is a collagen casing.
21. The method of Claim 17 wherein the casing is an insolubilized polyvinyl alcohol casing.
22. The method of Claim 17 wherein the casing is a fibrous insolubilized polyvinyl alcohol casing.
23. The method of Claim 17 wherein the casing is treated by slugging.
24. The method of Claim 17 wherein the casing is treated by dipping.
25. The method of Claim 17 wherein the casing is treated by spraying.
26. The method of Claim 17 wherein said aqueous treating solution comprises a molar ratio of a reducing sugar to an amino compound of from about, 10 to 1, to about, 1 to 10.
27. The method of Claim 17 wherein the treated casing is heated and dried at a temperature and during a period of time from about 80°C for about 24 hours to about 120°C for about 5 minutes.
28. The method of Claim 17 wherein the concentration of said reaction product in the casing is from about 2.7 to about 14 milligrams per square inch of casing wall.
29. The method of Claim 17 wherein the amount of treating solution applied to the casing is from about 5 to about 50 milligrams per square inch of casing wall.
30. The method of Claim 17 wherein the aqueous treating solution additionally comprises a citrate compound.
31. The method of Claim 17 wherein an antiblocking agent is mixed with said aqueous treating solution prior to casing treatment.
32. The method of Claim 17 wherein a thickening agent is mixed with said aqueous treating solution prior to casing treatment.
33. The method of Claim 26 wherein said aqueous treating solution comprises from about 40 to about 70 weight percent water based upon the total weight of the solution.
34. The method of Claim 26 wherein said amino compound is selected from the group consisting of 4-aminobutyric acid, glycine, lysine monohydrochloride, alanine, arginine, and monosodium glutamate.
35. The method of Claim 26 wherein said reducing sugar is selected from the group consisting of xylose, arabinose and dextrose.
36. The method of Claim 30 wherein said citrate compound is selected from the group consisting of potassium citrate and sodium citrate.
37. The method of Claim 30 wherein the molar ratio of said citrate compound to said reducing sugar is from about, 1 to 20, to about, 1 to 1.
38. The method of Claim 31 wherein the antiblocking agent comprises an aqueous emulsion selected from the group consisting of a food grade mineral oil emulsion, a vegetable oil emulsion and silicone oil emulsion.
39. The method of Claim 32 wherein the thickening agent is selected from the group consisting of carboxymethylcellulose, methyl cellulose, pectin, vegetable gum and starch.
40. In a method for manufacturing a tubular food casing the improvement which comprises treating the casing with a reaction product of a reducing sugar and an amino compound selected from the group consisting of an amino acid, an amino acid derivative, and a mixture of an amino acid and an amino acid derivative, in an amount sufficient to give the casing a smoke color which is water soluble and readily transferable to a food product.
41. The method of Claim 40 wherein the casing is a cellulose casing.
42. The method of Claim 40 wherein the casing is a fibrous cellulose casing.
43. The method of Claim 40 wherein the casing is a collagen casing.
44. The method of Claim 40 wherein the casing is an insolubilized polyvinyl alcohol casing.
45. The method of Claim 40 wherein the casing is a fibrous insolubilized polyvinyl alcohol casing.
46. The method of Claim 40 wherein the casing is treated by slugging.
47. The method of Claim 40 wherein the casing is treated by dipping.
48. The method of Claim 40 wherein the casing is treated by spraying.
49. The method of Claim 40 wherein said reaction product is formed from an aqueous solution initially comprising a molar ratio of a reducing sugar to an amino compound of from about, 10 to 1, to about, l to 10.
50. The method of Claim 40 wherein said reaction product is in a treating mixture comprising from about 25 to about 50 weight percent water.
51. The method of Claim 40 wherein from about 2.7 to about 14 milligrams of reaction product per square inch of casing wall are added to the casing.
52. The method of Claim 40 wherein an antiblocking agent is mixed with said reaction product prior to casign treatment.
53. The method of Claim 40 wherein a thickening agent is mixed with said reaction product prior to casing treatment.
54. The method of Claim 49 wherein said aqueous solution comprises from about 40 to about 70 weight percent water based upon the total weight of the solution.
55. The method of Claim 49 wherein said amino compound is selected from the group consisting of 4-aminobutyric acid, glycine, lysine monohydrochloride, alanine, arginine, and monosodium glutamate.
56. The method of Claim 49 wherein said reducing sugar is selected from the group consisting of xylose, arabinose and dextrose.
57. The method of Claim 49 wherein said aqueous solution additionally comprises a citrate compound.
58. The method of Claim 49 wherein said aqueous solution is heated to a temperature of from about 60°C to about 110°C for about 5 minutes of about 30 minutes to cause the formation of said reaction product.
59. The method os Claim 50 wherein said casing is treated with from about 9 to about 35 milligrams of said treating mixture per square inch of casing wall.
60. The method of Claim 52 wherein the antiblocking agent comprises an aqueous emulsion selected from the group consisting of a food grade mineral oil emulsion, a vegetable oil emulsion and a silicone oil emulsion.
61. The method of Claim 53 wherein the thickening agent selected from the group consisting of carboxymethylcellulose, methyl cellulose, pectin, vegetable gum and starch.
62. The method of Claim 57 wherein said citrate compound is selected from the group consisting of potassium citrate and sodium citrate.
63. The method of Claim 57 wherein the molar ratio of said citrate compound to said reducing sugar is from about, 0 to 1, to about, 1 to 1.
64. The casing of C Claim 1 wherein the casing is a wrap of sheeting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81084377A | 1977-06-28 | 1977-06-28 | |
| US810,843 | 1977-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106678A true CA1106678A (en) | 1981-08-11 |
Family
ID=25204851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA304,864A Expired CA1106678A (en) | 1977-06-28 | 1978-06-06 | Smoke colored food casing and method of producing same by use of the maillard reaction |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS5910788B2 (en) |
| AR (1) | AR218497A1 (en) |
| AT (1) | AT366236B (en) |
| AU (1) | AU3747978A (en) |
| BE (1) | BE868516A (en) |
| BR (1) | BR7804068A (en) |
| CA (1) | CA1106678A (en) |
| DE (1) | DE2828296C3 (en) |
| DK (1) | DK289178A (en) |
| ES (1) | ES471176A1 (en) |
| FI (1) | FI64266C (en) |
| FR (1) | FR2395912A1 (en) |
| GB (1) | GB2000424B (en) |
| IT (1) | IT1097355B (en) |
| NL (1) | NL7806898A (en) |
| NO (1) | NO154152C (en) |
| NZ (1) | NZ187687A (en) |
| PH (1) | PH13562A (en) |
| SE (1) | SE439095B (en) |
| ZA (1) | ZA783674B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57193288A (en) * | 1981-05-26 | 1982-11-27 | Fuji Electric Co Ltd | Spot welding method |
| JPH08323482A (en) * | 1995-05-31 | 1996-12-10 | Nec Toyama Ltd | Spot resistance welding machine |
| CA2271361A1 (en) | 1999-05-07 | 2000-11-07 | Peter Taylor | Edible casing film formulation |
| MXPA05009795A (en) * | 2003-03-13 | 2006-01-27 | Vector Usa Inc | A film having a liquid absorbed therein. |
| ES2294649T3 (en) | 2004-04-15 | 2008-04-01 | Reg Macquarrie | COMPOSITIONS OF EDIBLE FILMS TO PROCESS MEAT PRODUCTS. |
| ES2304846B1 (en) * | 2006-05-11 | 2009-10-23 | Viscofan, S.A. | COLORING CLIP FOR MEAT DRINKS AND PROCEDURE OF OBTAINING. |
| ES2632365T3 (en) * | 2008-07-07 | 2017-09-12 | Naturin Gmbh & Co. | Non-edible collagen casing ready to fill long-lasting stabilized, and manufacturing procedure |
| DE102009059320A1 (en) * | 2009-12-23 | 2011-06-30 | Cofresco Frischhalteprodukte GmbH & Co. KG, 32427 | Substrate with antimicrobial coating, an antimicrobial packaging material, and method of making the same |
| DE202013101887U1 (en) * | 2013-04-30 | 2014-07-31 | Planetpac Gmbh | Food browning coating and film and casing coated therewith |
| KR20220039857A (en) | 2016-05-24 | 2022-03-29 | 다이니폰 인사츠 가부시키가이샤 | Lighting control device |
| KR102569648B1 (en) | 2018-11-19 | 2023-08-24 | 주식회사 엘지화학 | Substrate |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US28281A (en) | 1860-05-15 | Improvement in cotton-presses | ||
| GB1053001A (en) * | 1900-01-01 | |||
| GB448813A (en) * | 1934-05-08 | 1936-06-16 | Ireks Ag | Improvements in and relating to processes for the production of preparations for nutritive, seasoning and other purposes |
| GB485148A (en) * | 1936-10-30 | 1938-05-16 | Wolff & Co | Method of manufacturing tubes, especially artificial sausage skins |
| US2477767A (en) * | 1948-08-05 | 1949-08-02 | Transparent Package Company | Food casing |
| NL123697C (en) * | 1957-07-13 | 1900-01-01 | ||
| DE1492636B2 (en) * | 1961-10-09 | 1976-10-14 | Johnson & Johnson, New Brunswick, NJ. (V.St.A.) | METHOD OF MANUFACTURING AN EDIBLE SAUSAGE HUGE WITH IMPROVED COOKING PROPERTIES |
| US3378379A (en) | 1963-05-21 | 1968-04-16 | Union Carbide Corp | Food casing and method of producing same |
| US3330669A (en) | 1964-03-27 | 1967-07-11 | Wisconsin Zinn Malting Corp | Smoke flavoring process |
| US3360383A (en) | 1964-09-08 | 1967-12-26 | Tee Pak Inc | Casing for preparation of dry sausages |
| US3383223A (en) | 1964-09-16 | 1968-05-14 | Tee Pak Inc | Casing for dry sausages |
| US3551535A (en) | 1964-12-01 | 1970-12-29 | Union Carbide Corp | Freezing-mixing process for making homogeneous collagen mixtures |
| US3451827A (en) | 1965-11-22 | 1969-06-24 | Tee Pak Inc | Method of coating the interior of a sausage casing |
| US3427169A (en) | 1965-12-23 | 1969-02-11 | Tee Pak Inc | Casing for dry sausages |
| SE344668B (en) * | 1966-05-14 | 1972-05-02 | J Sato | |
| DE1815843A1 (en) | 1967-12-27 | 1969-12-18 | Ajinomoto Kk | Process for improving the stability of Maillard reaction products |
| DE1947599C3 (en) * | 1968-09-24 | 1973-09-27 | Kyowa Hakko Kogyo Co. Ltd., Tokio | Process for the preparation of a coloring agent for food and beverages |
| US3617318A (en) | 1969-01-10 | 1971-11-02 | Corson G & W H | Magnesia-containing refractory products and methods of making same |
| US3782977A (en) | 1971-09-01 | 1974-01-01 | Union Carbide Corp | Method for preparing collagen compositions |
| JPS522745B2 (en) * | 1972-08-12 | 1977-01-24 | ||
| GB1464376A (en) * | 1973-02-26 | 1977-02-09 | Unilever Ltd | Foodstuffs containing vegetable protein |
| US3860728A (en) * | 1973-04-05 | 1975-01-14 | Devro Inc | Caramel-containing collagen sausage casing and smoked sausage |
| US3894158A (en) * | 1973-04-24 | 1975-07-08 | Devro Inc | Manufacture of edible collagen casings using liquid smoke |
| US3956512A (en) | 1975-04-28 | 1976-05-11 | Union Carbide Corporation | Collagen compositions and the method of preparing the same |
| US4171381A (en) * | 1978-01-27 | 1979-10-16 | Union Carbide Corporation | Smoke colored food casing and method of producing same by use of a Maillard reaction product and an albumin |
-
1978
- 1978-06-06 CA CA304,864A patent/CA1106678A/en not_active Expired
- 1978-06-26 FI FI782023A patent/FI64266C/en not_active IP Right Cessation
- 1978-06-27 NL NL7806898A patent/NL7806898A/en not_active Application Discontinuation
- 1978-06-27 SE SE7807276A patent/SE439095B/en not_active IP Right Cessation
- 1978-06-27 NZ NZ187687A patent/NZ187687A/en unknown
- 1978-06-27 IT IT25035/78A patent/IT1097355B/en active
- 1978-06-27 JP JP53077091A patent/JPS5910788B2/en not_active Expired
- 1978-06-27 AR AR272738A patent/AR218497A1/en active
- 1978-06-27 FR FR7819118A patent/FR2395912A1/en active Granted
- 1978-06-27 ZA ZA00783674A patent/ZA783674B/en unknown
- 1978-06-27 AU AU37479/78A patent/AU3747978A/en active Pending
- 1978-06-27 DK DK289178A patent/DK289178A/en not_active Application Discontinuation
- 1978-06-27 BE BE188890A patent/BE868516A/en not_active IP Right Cessation
- 1978-06-27 BR BR7804068A patent/BR7804068A/en unknown
- 1978-06-27 NO NO782220A patent/NO154152C/en unknown
- 1978-06-27 GB GB7828047A patent/GB2000424B/en not_active Expired
- 1978-06-27 AT AT0467478A patent/AT366236B/en not_active IP Right Cessation
- 1978-06-27 ES ES471176A patent/ES471176A1/en not_active Expired
- 1978-06-27 PH PH21313A patent/PH13562A/en unknown
- 1978-06-28 DE DE2828296A patent/DE2828296C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2828296B2 (en) | 1980-10-02 |
| DE2828296A1 (en) | 1979-01-04 |
| FI64266C (en) | 1983-11-10 |
| JPS5910788B2 (en) | 1984-03-12 |
| PH13562A (en) | 1980-06-26 |
| ZA783674B (en) | 1979-07-25 |
| FR2395912A1 (en) | 1979-01-26 |
| BE868516A (en) | 1978-12-27 |
| NO782220L (en) | 1978-12-29 |
| FI64266B (en) | 1983-07-29 |
| ES471176A1 (en) | 1979-01-16 |
| ATA467478A (en) | 1981-08-15 |
| FR2395912B1 (en) | 1985-05-03 |
| GB2000424B (en) | 1982-01-27 |
| AU3747978A (en) | 1980-01-03 |
| DE2828296C3 (en) | 1981-06-04 |
| NO154152B (en) | 1986-04-21 |
| BR7804068A (en) | 1979-04-10 |
| DK289178A (en) | 1978-12-29 |
| IT7825035A0 (en) | 1978-06-27 |
| NZ187687A (en) | 1980-11-28 |
| NL7806898A (en) | 1979-01-02 |
| AT366236B (en) | 1982-03-25 |
| AR218497A1 (en) | 1980-06-13 |
| IT1097355B (en) | 1985-08-31 |
| SE439095B (en) | 1985-06-03 |
| GB2000424A (en) | 1979-01-10 |
| JPS5411252A (en) | 1979-01-27 |
| FI782023A (en) | 1978-12-29 |
| SE7807276L (en) | 1978-12-29 |
| NO154152C (en) | 1986-08-06 |
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| MKEX | Expiry |