United States Patent [19] [11] 3,954,999 Vidal et al. [45] May 4,1976

[54] DOUGH-IMPROVER COMPOSITION [56] References Cited [75] Inventors: Frederick l). Vidal, Englewood UNITED STATES PATENTS Cliffs; Albert B. Gerrity, Hazlet, 2,903,361 9/[959 Marks et al ...... 426/26

both of Ni; Walter Clavan, 3,578,462 5/l97l Smerak et al . . . . i . i . . , . , . . .. 426/226 X Jenkintown, Pa. 3,595,671 7/l971 Cooke et a1...... 426/23 Assignee: Pennwalt Corporation, Philadelphia, Pa. Primary Examiner-A. Louis Monacell Assistant Examiner-R. A. Yoncoskie I221 Filed: May 17, 1974 [211 Appl. No.: 470,767 [57] ABSTRACT A composition for improvement of dough comprising US. Cl ...... 426/61; 426/653 a powdery mixture of strong oxidizing agent, an or Int. Cl.2 ...... A2lD 2/08 ganic ?our and dough additive and an inert, hydrated Field of Search ...... 426/20, 22, 23, 36, salt. 426/26, 89, 147, 152, 226, 61, 94, 653 12 Claims, No Drawings 3,954,999 1 . 2 such as protease. amylase and lipoxidase; ascorbic acid DOUGH-IMPROVER COMPOSITION which serves as a dough conditioning agent or ?our maturing agent; and organic peroxides. for example. This invention relates to a composition in pulverulent peroxide and . which serve as form containing a strong oxidizing agent useful as a maturing and bleaching agents. additive for improving the handling properties of A unique additive of the combination of ingredients dough and the quality of bread and other bakery prod comprising the mixtures of the invention is an inert. ucts prepared therefrom. More particularly. this inven hydrated salt, that is. inert with respect to the active tion concerns a powdery mixture comprised ofa strong flour and dough treating ingredients and which is. of oxidizing agent (a flour and dough improver). a con course. edibly acceptable in food products. (i.e.. in the ventional flour and dough additive of an organic chemi minor proportions as will be added to ?our and dough cal nature. and a hydrated salt which is inert with re’ in utilizing the present compositions) and provides to gard to the other aforesaid ingredients and is edibly the claimed powdery mixture. when incorporated acceptable as a filler for flour additive compositions. therein in the proportions as set forth below. a Trauzl It has been noted in the flour additives art that com number (as de?ned in the Modified Trauzl Block Test positions comprised of concentrated powdery or gran u for hazard evaluation described below) of less than 40. lar mixtures ofa strong oxidizing agent with an organic Such hydrated salts include the edibly acceptable by material additive may present some hazard when con drated alkali metal and hydrated alkaline earth metal tacted with a ?ame or intense heat. This invention salts of inorganic or organic acids. Suitable hydrated provides a safer mixture comprised of said ingredients salts are CaHPO4.2H2O; MgSO4.7H2O; Na2HPO4.lZ with regard to reduction of any fire and/or explosive H2O; Ca(H2PO4)2.H-_,O'. Na2HPO4.7H2O; KNa tar decomposition potential. The composition of this in» trate.4H2O; sodium citrate.2H2O; calcium citrate.4 vention is a powdery mixture comprised of the strong H2O; calcium lactate.5H2O; N-a2CO3.l(lH-_,O; Nag. oxidizing agent. the organic additive, and an edibly SO4.I()H2O; MgCl-_,6H2O; FeCl;..6H._,O; CuSO..5H2O acceptable. inert hydrated salt. Advantageously. the and the like. Most of the foregoing hydrated salts pro inclusion of the salt in the composition embodied vide free-flowing. non-agglomerating powder mixtures herein does not diminish the efficacy of the active in for dough improvement which can be metered in small gredients in carrying out their improving and maturing quntities by dry chemical feeders without arching or functions in the Hour and resultant dough. Further uneven flow patterns over extended periods of time. details of the invention are presented hereinbelow. The preferred salts are CaHPO4.2H._,O and Ca(H Materials illustrative of the strong oxidizing agent 2PO4)T_,.H._,O. However. others from this illustrative portion of the pulverulent mixture of the invention group are less preferred because the powdery mixtures include the alkali metal and alkaline earth metal bro containing same must be added to the dough process mates. chlorites. period-ates, iodates. and peroxides, for manually as they make the powdery mixture exces example. . . sodium 35 sively damp causing caking or agglomeration and loss bromate. sodium iodate. . calcium of the free-?owing characteristics essential to continu iodate. magnesium bromate. magnesium iodate. so ous mechanical feeding. Salts representative of this dium peroxide, . sodium chlorite. type are Na2CO3.lt)H2O and Na2SO..l0H2O. In addi potassium periodate. and the like. The most widely tion. some salts. for example. MgClrtiHgO. are less used oxidizing agents for ?our and dough are potassium preferred because they are very hygroscopic. and if the bromate. potassium iodate. calcium iodate and calcium powdery mixture containing same is inadvertently left peroxide. exposed to a humid atmosphere. liquid lakes will be The organic constituent of the composition embod~ formed. Although certain other hydrated salts. such as ied herein is composed of at least on organic material AI2(SO4)_-,.9H2O and AI2(SO4);,.ISH2O provide free used in flour and dough treatment. For example. a 45 ?owing mixtures. the hazard evaluation test results widely-used organic substance for flour addition is a (Trauzl Block Test and Flame test, described hereinbe flour maturing agent in particulate form. fully de low) for the oxidizing agent'containing mixtures are scribed in U.S. Pat. No. 2.903.36l. selected from the unexpectedly poor. Many available hydrated salts are class of amides. amidines and mixed ester-amides of edibly unacceptable for the present compositions. for azodicarbonic acid. which compounds may be repre example. barium citrate.7H-_,O. sodium tetraborate. l0 sented by the structural formula H2O. sodium metasilicate.9H._,O. and it is apparent that most of the hydrated salts disclosed in U.S. Pat. No. 3.7932 l 6 for making a calcium hypochlorite sanitizing composition flame resistant (a much different system 55 than involved in the present invention) are unsuitable for the present compositions. where in the case of amides. R3 and R‘ are each an The proportions of the aforesaid constituents in the oxygen atom. and R' and R2 are each NH: groups. substantially homogenous. pulverulent mixture of the either substituted or unsubstituted; in the case of ami invention will range as follows: generally from about 10 dines. R' and R2 are as above and R"g and R ' are each an to about I00 parts by weight of the organic ?our addi NH radical; in the case of the mixed ester-amides. R“ tive constituent per H10 parts by weight of the oxidizing and R' are each oxygen. R' is NHL“ substituted or un agent constituent. and an amount of hydrated salt suffi substituted. and R2 is alkoxy. The preferred flour ma~ cient to provide a moisture content of at least about l5 turing agent from this class is . parts by weight of H20. preferably from about l5 to ()thcr organic llour additives include gluthathione about St) parts H20. and more preferably from about and L-cysteinc. either in the form ofthc H(‘l hydrate or It! to 40 parts H2O. per l(l() parts by weight of the cy steinesN-carbamide. which serve as dough condition oxidizing agent. The compositions may have included ing aids to reduce llour mixing requirements; enzymes therein. in addition. non-hydrated inert ?llers. gener 3,954,999 3 4 ally up to about I to 5 parts of filler pcr IOU parts by Some of the following examples are illustrative of the weight of oxidizing agent. Representative of such ?llers compositions of the invention. Their safer properties are tricalcium phosphate. sodium chloride, magnesium are shown by comparison with the compositions con carbonate. silicon dioxide and microcrystalline cellu taining only an anhydrous ?ller or inadequate propor lose. It is understood. however. that the upper limit of 5 tions of hydrated salt. Amounts of ingredients are in ?ller. as well as the upper limit of hydrated salt. is one weight percents. of practicality due to be extra bulk such materials pro EXAMPLE 1 vide to the mixtures. The usual form in which the mix tures of the invention are supplied to the baking indus Potassium bronialc 195"; | 56.7% try is as individual packages or envelopes of powder A/ltdllllll'h?ltll?lidk.‘ 27 5"; designed to be added to the yeast broth or dough and of [)icalclum phosphate. Anhydrous I43’) such amount of provide from about 5 to about IUU ppm Microcryslalline Cellulose I“A\icel") LIV/l of oxidiring agent per IOU pounds of flour. The mix tures can. of course. be shipped in bulk quantities to Trauzl No — I15; the mill or bakery where the compositions can be ap Flame test — Violent decomposition — ignition — portioned for use in the desired amount. smoke propagation to complete decomposition — Another embodiment of this invention comprises a Rating — It); powdery mixture of the strong oxidizing agent with the Impact Sensitivity - Positive —- report at I8 inches; described inert. hydrated salt in the proportions as Flow properties —- Excellent. above disclosed. This mixture is adapted for shipment to the mill or bakery where it is subsequently mixed EXAMPLE 2 with the organic flour and dough additive(s), whereby the hydrated salt provides a greater margin of safety for Potassium bromate [95%) 40% Alodicarbonamidc 10% the overall mixture of ingredients. Salt INaL'I) MM Several standard tests which have been developed to gauge the fire hazards and explosive (decomposition) tendencies of substances are useful in evaluating the Trauzl No. — 5(); compositions of this invention The first of these is the Flame test — Vigorous decomposition — propaga Modi?ed Trauzl Block Test which measures the sensi tion to complete decomposition — Rating — 8; tivity of the test sample to a blasting cap shock and the Impact Sensitivity —— Positive at 35 inches; potential energy released under these conditions. Flow Properties — Good. Quantitative measurement is made by measuring the EXAMPLE 3 degree ofexpansion of a lead block into which (1 grams of substance in a sample vial is placed in contact with a Potassium hronialc (95'12 l Sll ‘fr No. 8 electric blasting cap. The volume of the lead Ayodicarbonamidc 14 '/r block is measured before and after detonation to the Dicalcium phospI‘tate.2H._,O 85% Aluminum sulfate. l 8H ._.() ItxS'? nearest half milliliter using water as a reference me» Microcrystallinc Cellulose (“AviccF'j l.tl’./| dium. The increase in the volume of the block is re ported as the “Trauzl number". The minimum expan sion is the result obtained using water as the test mate Trauzl No. —— 65; rial, which gives an expansion of 7.0 ml.‘ or a Trauzl Flame test — Vigorous decomposition — propaga number of'7. The maximum expansion which can be tion to complete decomposition — Rating — 6; sustained by the lead block. before rupturing, is I 15 ml. Impact Sensitivity — Negative at 20 inches; or a Trauzl number of 1 15. For the kind of composi Flow Properties — Good. tions involved herein. Trauzl numbers of less than 40 EXAMPLE 4 are regarded as designating safe materials. Another test for gauging safety of the tablets is the Potassium bromatc (95% i 40% “Impact Sensitivity" test in which the test apparatus. a Alodicarbonamidc ZII'A DuPont Impact testing machine, is set at a desired Sodium (‘hloridc I954 height. A 30 milligram sample is placed in the center of Calcium laetatc.5H._.O I‘J'rl the drop test cup. The cup is placed on the anvil, under Sllicun Llltthltlt.‘ ("(‘abusil'? 2% the plunger pin assembly and the weight dropped. This operation is repeated at several different heights. A Flame test — Vigorous decomposition — propaga report and/or smoke and obvious decomposition of the 55 tion to complete decomposition; smoke — Rating sample is considered a positive result. If none of these __ 7; properties is observed. the result is considered nega Flow Properties - Good. tive. Yet another test for evaluating safety ofthe composi— EXAMPLE 5 tions is the flame test in which the flame of a Bunsen (ill burner is held to the sample for ?ve seconds‘ then Sample a Sample b withdrawn. and observations noted. A hazard evalua Potassium bromatc (9“; 1 4t ‘,4 4W; tion rating system has been devised in accordance with A/odicarbonamtdc Ill ‘2? Ztl'? nicalclum phosphate-CH4) I 4.5"? li'tl this test. lfsing a numbering system of I through IU. the (‘alcium lactate EH30 23.5’) 24’; best flame rating [most resistant to decomposition and Microcrystallinc ('cllulosc ignition) is assigned the number I; the poorest rating I"A\iccl"l Ill‘: (least resistant to decomposition and ignition) is as signed the number It). 3,954,999 5 . 6 earth metal bromate. iodate, chlorite. periodate or Potassium hrolnatc 495“? l 4| ‘ii peroxide; and the organic chemical ?our and dough A1odicarbonainide It] ‘i Dicalcium phosphate Ill!) l4 5'; additive is selected from the group consisting ol~ am~ Magneslulu chloride Mia) 1.1.59} ides, amidines and mixed estenamides of azodicar_ Mycrocryslalhnc Cellulose IAN honic acid, gluthathione, L». HCl hydrate. cys teine—N-carbamide. ascorbic acid. organic peroxide. Trauzl No. — 2H5; and enzymes. ' Flame test — Mild decomposition A— some propaga 3. A composition according to claim 2 in which the tion — Rating » 3.5; oxidizing agent is selected from the group consisting of lmpaet Sensitivity a Negative at 35 inches; potassium bromate. potassium iodate. . Flow Properties — Fair but tendency for stickiness sodium iodate, calcium bromate. calcium iodate. mag» due to formation ol‘ liquid lakes. ncsium bromate. magnesium iodate. sodium peroxide, calcium peroxide, sodium chlorite and potassium peri EXAMPLE 7 odate. 4. A composition according to claim 2 in which the Potassium hromate (95’) | 4| '% organic ?our and dough additive is azodiearhonamide. A1ridicarbonamidc Ill ‘w DIL'illCltllll phosphate 2H4) I] 5"; 5. A composition according to claim 3 in which the Aluminum sult'ate lts'll._,() l4 5"} hydrated salt is selected from the group consisting of Microclyslalhnc cellulose l I)’; C'aHPO,,.2H2O; MgS().,.7H2O; NaZHPOPIZHQO; (‘at H ll) ._,P()t)i_,. H2O; NagHPOp'lHgO; KNa tartrateAHzO: so~ dium citrate.2H2O; calcium citrate-1H4); calcium lac Flame test — Mild decomposition ~ slight propaga tate.5Hi_,(); Na2CO". I()H2O; M12504. ltJHilO; tion (5 seconds) — RatingI ~ 2.5; MgClThHlO; FeClw?HgO, and (‘uS()_,.5Hi_,(). impact Sensitivity — Negative at 30 inches; 6. A composition according to claim 5 in which the Flow Properties —— (iood. organic ?our and dough additive is azodicarbonamide. 7. A composition according to claim 6 in which the EXAMPLE 8 strong oxidizing agent is selected from the group con< sisting of potassium bromate, potassium iodate. cal cium iodate and calcium peroxide. A/odicarhonamide 21m [)lcalciuni phosphate EH20 lunniillcdi .17’) 8. A composition for improving ?our and dough Silicon dioxide l"('al\osil"l 3'! comprising a powdery mixture of strong oxidizing agent and an inert. cdibly acceptable hydrated salt wherein Trauzl No. — 2t); the proportion of said hydrated salt in the mixture provides about 15 parts up to about 50 parts by weight Flame test — Moderate decomposition — no propa gation — no ignition ~ slight smoke —— Rating —— of water per ltltl parts by weight ot‘the strong oxidizing '1. agent. and a Trauzl num her for the mixture of less than Impact Sensitivity -— Negative at 35 inches; 40 when from about l() to about ltti] parts by weight, Flow Properties ~ Excellent. per 100 parts by weight of the oxidizing agent, of on ganic flour and dough additive is mixed. therewith. EXAMPLE 9 9. A composition according to claim 8 in which the strong oxidizing agent is an alkali metal or alkaline Polasslum hrinnatc ("5'1' | 41W earth metal bromate. iodate, chlorite. periodate or Azodiearbonaniide 2t)‘; peroxide. Magnesuun chloI idc (\H_,(1 1X") Sillcon dioxide 2'; 45 It). A composition according to claim 9 in which the oxidizing agent is selected from the group consisting of potassium bromate. potassium iodate. sodium bromate. 'l‘rauzl No. — 3|: sodium iodate, calcium hromate, calcium iodate. mag» Flame test — Slow decomposition — no propagation ncsium bromate. magnesium iodate. sodium peroxide. ~— Rating — l.5; calcium peroxide. sodium chlorite and potassium peri Impact Sensitivity —- Negative at 35 inches; odate. Flow Properties ~ Poor - blend slightly sticky. ll. A composition according to claim It) in which the We Claim: hydrated salt in selected from the group consisting of 1. A composition for improving ?our and dough CaHPOPZHQO; MgSOr'IHQO: Na._,HPO,,; l EH20; Ca( H comprising a powdery mixture of strong oxidizing i_,P(),,)2.H2O; Na-3HPO4J'H2O; K'Na tartrateAHZO; so agent. organic flour and dough additive. and an inert, dium citrateQHQO; calcium citrate.~lH._,O; calcium lac~ edibly acceptable. hydrated salt wherein the proportion tate.5H2O; Na2CO_-,. l ()HQO; NagSOv IOHiJO; of said hydrated salt in the mixture provides about 15 MgClrt’iHgO', FeClmoHzO; and (11804.5 H20. parts up to about 50 parts by weight of water per 100 12. A composition according to claim 11 in which the parts by weight of the strong oxidizing agent and a till strong oxidizing agent is selected from the group con» Tran/l number for the mixture ot‘ less than 40. sisting of potassium bromate. potassium iodate. cal 2. A composition according to claim 1 in which the cium iodate and calcium peroxide. strong o\idi/ing agent is an alkali metal or alkaline