US20020146492A1 - Starch phosphate ester for use as an expansion aid - Google Patents
Starch phosphate ester for use as an expansion aid Download PDFInfo
- Publication number
- US20020146492A1 US20020146492A1 US09/771,417 US77141701A US2002146492A1 US 20020146492 A1 US20020146492 A1 US 20020146492A1 US 77141701 A US77141701 A US 77141701A US 2002146492 A1 US2002146492 A1 US 2002146492A1
- Authority
- US
- United States
- Prior art keywords
- starch
- formulation
- phosphate monoester
- starch phosphate
- expanded
- 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.)
- Granted
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 177
- 235000019698 starch Nutrition 0.000 title claims abstract description 176
- 239000008107 starch Substances 0.000 title claims abstract description 154
- 229910019142 PO4 Inorganic materials 0.000 title claims description 69
- 239000010452 phosphate Substances 0.000 title claims description 69
- -1 phosphate ester Chemical class 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 238000009472 formulation Methods 0.000 claims abstract description 76
- 235000013305 food Nutrition 0.000 claims abstract description 40
- 235000011888 snacks Nutrition 0.000 claims abstract description 13
- 235000015496 breakfast cereal Nutrition 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 45
- 229920001542 oligosaccharide Polymers 0.000 claims description 16
- 150000002482 oligosaccharides Chemical class 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 230000001007 puffing effect Effects 0.000 claims description 4
- 235000015927 pasta Nutrition 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract description 8
- 235000021317 phosphate Nutrition 0.000 description 50
- 239000000047 product Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 235000013339 cereals Nutrition 0.000 description 18
- 235000013312 flour Nutrition 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 11
- 240000008042 Zea mays Species 0.000 description 10
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 10
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 10
- 235000005822 corn Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229920002261 Corn starch Polymers 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000008120 corn starch Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 235000019832 sodium triphosphate Nutrition 0.000 description 7
- 229920000856 Amylose Polymers 0.000 description 6
- 229920000881 Modified starch Polymers 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 244000075850 Avena orientalis Species 0.000 description 5
- 235000007319 Avena orientalis Nutrition 0.000 description 5
- 235000007558 Avena sp Nutrition 0.000 description 5
- 235000012438 extruded product Nutrition 0.000 description 5
- 235000019426 modified starch Nutrition 0.000 description 5
- 229920000945 Amylopectin Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000011868 grain product Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000026731 phosphorylation Effects 0.000 description 3
- 238000006366 phosphorylation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 229920002774 Maltodextrin Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000021374 legumes Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 239000001248 monostarch phosphate Substances 0.000 description 2
- 235000013807 monostarch phosphate Nutrition 0.000 description 2
- 230000035772 mutation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 235000005273 Canna coccinea Nutrition 0.000 description 1
- 240000008555 Canna flaccida Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000151018 Maranta arundinacea Species 0.000 description 1
- 235000010804 Maranta arundinacea Nutrition 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000294 Resistant starch Polymers 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000012419 Thalia geniculata Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009402 cross-breeding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000021254 resistant starch Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- SUZJDLRVEPUNJG-UHFFFAOYSA-K tripotassium 2,4,6-trioxido-1,3,5,2lambda5,4lambda5,6lambda5-trioxatriphosphinane 2,4,6-trioxide Chemical compound [K+].[K+].[K+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 SUZJDLRVEPUNJG-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
- C08B31/066—Starch phosphates, e.g. phosphorylated starch
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
- A23L29/219—Chemically modified starch; Reaction or complexation products of starch with other chemicals
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/117—Flakes or other shapes of ready-to-eat type; Semi-finished or partly-finished products therefor
- A23L7/13—Snacks or the like obtained by oil frying of a formed cereal dough
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/161—Puffed cereals, e.g. popcorn or puffed rice
- A23L7/165—Preparation of puffed cereals involving preparation of meal or dough as an intermediate step
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/161—Puffed cereals, e.g. popcorn or puffed rice
- A23L7/165—Preparation of puffed cereals involving preparation of meal or dough as an intermediate step
- A23L7/17—Preparation of puffed cereals involving preparation of meal or dough as an intermediate step by extrusion
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
- A23P30/30—Puffing or expanding
- A23P30/32—Puffing or expanding by pressure release, e.g. explosion puffing; by vacuum treatment
- A23P30/34—Puffing or expanding by pressure release, e.g. explosion puffing; by vacuum treatment by extrusion-expansion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
Definitions
- the present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products.
- the invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- Expansion is an important characteristic of a number of materials and is useful in a number of applications, including the preparation of sheets, shaped foam and loosefill products as well as in the preparation of food products.
- Food products in which expanded materials are useful include pasta, pet food, breakfast cereals and snacks.
- the expansion of food products is accomplished by a variety of means including extrusion, puffing, frying and baking.
- starch undergoes a melting, plasticizing and/or gelatinizing process.
- the structure of starch polymers in the plasticized or gelatinized state influence the product characteristics of expansion, crispness, bite, puff and texture as well as product-specific attributes such as the bowl life of cereals.
- Amylose is known to provide crunchiness and strength in expanded products, whereas increased amylopectin content typically results in a product with increased expansion, crispness and puffiness.
- Starches have been modified with the objective of affecting the expansion and texture of expanded products.
- pregelatinized starches have been used where the process conditions do not allow for complete gelatinization or complete disintegration of the granular structure of the starch.
- Wang, S. W. Starches and Starch Derivatives in Expanded Snacks, Cereal Foods World, Vol. 42, pg 743-745 (1997).
- crosslinked starches have been used under high shear conditions in order to reduce otherwise severe fragmentation of the starch polymers. Id.
- starches which have been modified to provide cold water soluble attributes are known to improve the expansion and texture of final expanded products.
- Such cold water soluble starches include hydroxypropylated or carboxymethylated starches. See U.S. Pat. No. 3,9566,990; Bhattacharyya, D., Singhal, R. s. and P. R. Kulkarni: Carboxymethyl Starch: an Expansion Aid, Carbohydrate Polymers 31, 79-82 (1996); and U.S. Pat. No. 5,480,669.
- Resistant starches have also been used to affect the expansion of food products. Id. While phosphorylated starches have been described for use in food products, they have not been described as an expansion aid.
- Starch phosphate monoesters have been described for use in a variety of food products, particularly as viscosifiers in order to improve texture and stability of non-expanded food.
- U.S. Ser. No. 09/633,832 the disclosure of which is incorporated herein by reference, describes the use of starch phosphate monoesters in protein-containing, low to intermediate moisture foods to improve the taste, texture, color and moisture retention of such foods.
- Texture in this case, refers to the texture of the food that is strongly affected by improved retention of moisture content during storage of the starch phosphate monoester-treated food product.
- starch phosphate monoesters may be advantageously used as expansion aids in foods, particularly breakfast cereals and snacks.
- the present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products.
- the invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- the present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products.
- the invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- starches and flours may be suitable for use herein and may be derived from any native source.
- a native starch or flour as used herein, is one as it is found in nature.
- starch or flours derived from a plant grown from artificial mutations and variations of the above generic composition which may be produced by known standard methods of mutation breeding are also suitable herein.
- Typical sources for the starches and flours are cereals, tubers, roots, legumes and fruits.
- the native source can be corn, pea, potato, sweet potato, banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high amylose varieties thereof.
- the term “waxy” is intended to include a starch or flour containing at least about 95% by weight amylopectin and the term “high amylose” is intended to include a starch or flour containing at least about 40% by weight amylose.
- Conversion products derived from any of the starches including fluidity or thin-boiling starches prepared by oxidation, enzyme conversion, acid hydrolysis, heat and or acid dextrinization, and or sheared products may also be useful herein.
- Chemically modified starches may also be used, provided such modification does not destroy the granular nature of the starch.
- Such chemical modifications are intended to include, without limitation, crosslinked starches, acetylated and organically esterified starches, hydroxyethylated and hydroxypropylated starches, phosphorylated and inorganically esterified starches, cationic, anionic, nonionic, and zwitterionic starches, and succinate and substituted succinate derivatives of starch.
- Such modifications are known in the art, for example in Modified Starches: Properties and Uses, Ed. Wurzburg, CRC Press, Inc., Florida (1986).
- the starch phosphate monoesters used in the formulations of the present invention may be prepared via methods known in the art. Traditional preparations of starch phosphate monoesters are described in U.S. Pat. No. 4,166,173, the disclosure of which is incorporated herein by reference. These preparations generally require the impregnation of the base starch with an alkali-metal phosphate, drying to a moisture content of less than 20% and heating in a continuous cooker, dextrinizer, convection oven or vacuum oven to effect the phosphorylation.
- starch phosphate monoester is intended to include, without limit, all equivalent terms, known to one of ordinary skill in the art, such as monostarch phosphate and includes regulatory definitions. Regulatory definitions of starch phosphate monoesters for use in food are often defined by the method in which they are made. In Europe, for example, a monostarch phosphate is defined to be a starch esterified with ortho-phosphoric acid or sodium or potassium ortho-phosphate or sodium tripolyphosphate. In the United States, a starch phosphate monoester is a food starch esterified by sodium trimetaphosphate or sodium tripolyphosphate and sodium trimetaphosphate.
- a particularly suitable method of preparing the starch phosphate monoesters of the present invention employs the fluidized bed technology described in U.S. Ser. No. 09/633,832.
- This application describes a process of impregnating the desired starch with a phosphate reagent, and optionally, an oligosaccharide. While in a fluidized state, the impregnated starch is then dried to a virtually anhydrous state, preferably 1 percent by weight of the starch or less, and then heated treated to effect phosphorylation. The impregnation of the starch by oligosaccharide and phosphate reagent may be done in any order. The pH of the resultant slurry may then adjusted to between about 3 and 12, preferably to between about 6 and 9.5.
- Phosphate reagent as used this particularly suitable method is defined as any phosphate reagent used for phosphorylating starch including ortho-, pyro-, meta- or tripolyphosphates.
- Illustrative phosphate reagents are the alkali metal phosphates such as sodium and potassium ortho-phosphate, phosphoric acid, phosphorus oxychloride, sodium and potassium tripolyphosphate and sodium and potassium trimetaphosphate.
- the reagent may be either a mono-, di- or trialkyl metal phosphate or combinations thereof.
- Impregnation by the phosphate reagent may be accomplished by adding the reagent in an amount of less than about 15% by weight of starch, preferably less than about 10%.
- the phosphate reagent may be added in the dry state to wet starch granules, or by dissolving the reagent in water to form an aqueous solution which is then mixed with the starch granules.
- Oligosaccharides suitable for the present invention include, but are not limited to, debranched starches, corn syrup solids, dextrose, fructose, maltose, particularly corn syrup solids with a DE of from about 20 to 40. Although oligosaccharide is intended to include monosaccharides, these generally add color and/or flavor which may be undesirable in many industrial applications. Therefore, particularly suitable oligosaccharides for the present invention are those which contain at least two sugar units joined by glycosidic bonds.
- the optional addition of the oligosaccharide to the starch may be achieved by adding the oligosaccharide either dry or as an aqueous solution.
- the oligosacchrides may be added to an agitated starch slurry or starch may be added to a stirred, aqueous solution of oligosaccharide.
- an aqueous solution of the oligosaccharide may be sprayed onto dry or wet starch granules.
- the impregnated starch is then subjected to a fluidized state and heat treated to effect the phosphorylation.
- the heat treatment may be carried out in one step, it is preferably carried out in two steps.
- the impregnated starch is subjected to the fluidized state and dried to virtually anhydrous conditions, particularly to less than about 1% moisture content by weight of starch, at less than about 140° C., particularly between 60° C. and 140° C., and most particularly between about 100° C. to about 125° C.
- the dried product is heated to between about 100° C. to about 185° C., particularly between about 120 to about 140° C. for between about 30 to about 300 minutes.
- the processing time is preferably less than about 45 minutes.
- the fluidized state is achieved by vigorous mixing of the solid starch particles in vacuum or in a gas whereby a uniform distribution of starch throughout the vacuum or gas may be attained. Vigorous mixing may be accomplished by using air or gas, at or above atmospheric pressures in a fluidized bed reactor or by sufficient mechanical agitation. Where pressurized gas is used to effect the fluidized state, the velocity of the gas must achieve a minimum rate such that the particles are free to move and exhibit a “fluidized state.”
- the fluidized state results in very efficient heat transfer and allows the starch to rapidly dry to a virtually anhydrous state at low temperature. Drying and heating the impregnated starch under fluidized conditions results in starch phosphate monoesters with high reaction efficiency, high levels of substitution and low levels of residual inorganic phosphate salt.
- the starch phosphate monoester preferably prepared according to the foregoing method, is then incorporated into a formulation suitable for use in expandable food products such as extruded breakfast cereals or snacks.
- Formulations containing about the starch phosphate monoester in the amounts of from about 0.1 to 50%, by weight of the formulation, more particularly from about 1 to 25% by weight and especially particularly from about 5 to about 20% show significant increases in expansion over formulations which substitute the non-derivatized native starch for the starch phosphate monoester.
- Increasing the content of starch phosphate monoester content in the formulation also increases the degree of expansion of the formulation.
- Extruded foods in which the starch phosphate monoesters may be advantageously incorporated include pasta, snacks, breakfast cereals and pet foods, particularly breakfast cereal and snack foods and most particularly in low moisture, ready-to-eat cereals and snacks.
- Formulation content or processing parameters may be adjusted according to principles well-known in the industry in order to achieve properties, such as degree of expansion, taste and sweetness, specific to the desired end product.
- Generally formulations may contain whole or partially milled grains and flours including corn, wheat oat, rice and barley, native or modified starch as described previously herein, sucrose, maltodextrins, corn syrup solids, other sweeneters and salt.
- Optional additives may include acidifier, antiforaming agents, antioxidants, binders/extenders, legumes, mold inhibitors, nuts, phosphate and other food chemcals, spices and herbs, and vegetables.
- the formulation can be processed by the use of any known technique suitable for expanding food products such as extrusion, puffing, frying, gun puffing, air impingement and baking.
- Conventional cooking-extruder expansion processes and equipment such as those disclosed in U.S. Pat. Nos. 3,054,677, 3,462,277 and Fast & Caldwell may be used to expand such formulations to give a breakfast cereal or snack product. See Fast, R. B., Caldwell, E. F., Breakfast Cereals and How They are Made, Amer. Asso. Of Cereal Chem., Inc., 2 nd ed. pg 215-278 (2000). Expansion techniques which do not require extrusion are intended to be included in this invention.
- a mixture of the formulation and water is processed in a cooker-extruder in which high pressure, temperature, and shear is generated. Under these process conditions, the formulation is melted, plasticized and/or at least partially gelatinized. The resultant material is expelled through a constricted opening, e.g. through a plurality of dies, under high temperature and pressure conditions.
- the material may be either directly or indirectly expanded.
- Direct expansion occurs when the process conditions result in instantaneous water evaporation and cooking of the product.
- Indirect expansion is achieved by processing the material, sometimes known as a half product, via known post-extrusion processes including frying, baking and microwave heating.
- Moisture content in this context refers to the total water content by weight present in the extruder during extrusion, including the water content of the formulation and water added during extrusion.
- total moisture content is generally in the range of from about 10% to about 30%, particularly from about 15 to about 20% and most particularly from about 17% to about 19%.
- total extruder moisture contents of up to 45% may be utilized.
- Expansion of the extruded products of this invention may be measured directly by measuring the dimensions of the product, or indirectly by measuring the bulk density of the product.
- These analytical methods are known in the art and described for example by Harper & Tribbelhorn. See Harper, J. M. and R. E. Tribbelhorn, Expansion of Native Cereal Starch Extrudates, Food Extrusion Science and Technology, Marcel Dekker, Inc., pg 653-666, (1992).
- Bulk density refers to the weight of the extruded product in a known volume and is inversely related to the degree of expansion measured directly.
- the present inventive formulation provides an expanded product which expands significantly even under variable extruder conditions such as total water content.
- an expanded corn starch phosphate monoester formulation provides an expanded product having a bulk density of 0.29 g/ml and 0.36 g/ml at extruder total water contents of 17% and 19%, respectively.
- This degree and type of expansion is much superior to the formulations containing the corresponding native corn starch which have high bulk densities of 0.51 g/ml and 0.55 g/ml produced at water contents of 17 and 19%, respectively.
- This example describes the preparation of starch phosphate monoesters useful in the formulations of the present invention.
- starch phosphate monoesters were prepared according to the method described in U.S. patent Ser. No. 09/633,832, incorporated herein by reference.
- Native starches which were used in the comparison formulations of Examples 1-4 and for the preparation of the corresponding starch phosphate monoesters included a high amylose corn starch (Sample I, HYLON® VII commercially available from National Starch and Chemical Co.), a waxy corn starch (Sample II, commercially available from National Starch and Chemical Co.), a potato starch (Sample III, commercially available from Emsland Staerke-Germany), and a wheat starch (Sample IV, commercially available from Midwest Grain Products Inc.).
- Impregnation of the starch with sodium tripolyphosphate was carried out using the following slurry impregnation method.
- One part native starch is slurried in two parts water by weight.
- the pH of the native starch slurry was adjusted to between 6.0 and 6.5 with HCl and stirred for 30 minutes.
- the slurry was then de-watered on a Buchner funnel and impregnated with a 3-10% aqueous sodium tripolyphosphate solution adjusted to a pH of between 6.0 to 6.5 to afford 2% sodium tripolyphosphate (anhydrous weight) impregnated starch cake.
- the impregnated starch (about 4 kg) was air dried to a moisture content of about 10-12%, ground, then dried in a pre-heated fluid bed reactor at a temperature of 220° F. until the starch had a moisture content of less than 1.0%. The dried starch was then heated to a temperature of 300° F. for 30 minutes, resulting in bound phosphorus levels of between 0.25 to 0.50% by weight.
- This example illustrates the superior expansion of cereals formulated with the starch phosphate monoesters of Example 1 over cereals formulated with the corresponding native starch.
- Cereals were formulated with the starch phosphate monoester (“SPM”) and corresponding native starch (“NS”) samples of Example 1 in the following proportions: 70% oat flour, 10% sugar, 5% corn flour and 15% starch sample. Cereals were formulated without starch in the following proportions: 70% oat flour, 10% sugar and 20% corn flour.
- SPM starch phosphate monoester
- NS native starch
- extrusion experiments were carried out on a co-rotating twin screw extruder (available from Werner & Pfeiderer) under the following conditions: screw design was chosen to provide medium shear; the screw speed was 250 rpm; L/d-ratio 21; the die diameter was 2 ⁇ 3 mm; water content was 17%; the feed rate was 13 kg/h, the barrel temperature was set to 60° C. in the mixing zone, to 150° C. in the heating/cooking zone, and the die plate was heated to 140° C.; and the die face cutter had 2 blades.
- This example demonstrates the ability of the starch phosphate monoesters to improve the expansion of cereal formulations irrespective of extrusion variables such as the extrusion total water content.
- the cereal formulation of native corn starch (“NS”) prepared according to Example 2 was extruded to form an expanded product having a bulk density of 0.51 gm/ml.
- the extruded NS formulation expanded providing a product with a bulk density of 0.55 g/ml.
- SPM phosphorylated corn starch
- Example 1 0.32% bound phosphorus by weight
- the SPM formulation showed improved expansion over the native corn starch formulation at both total extruder water content levels.
- the SPM formulation provided an expanded product having a bulk density of 0.29 g/ml, and at water content of 19%, a product having a bulk density of 0.36 g/ml.
- the SPM formulations display a increase in bulk density when higher extruder water contents are used, the expansion of the SPM formulation is still superior to that of the NS formulation.
- the example illustrates the superior expansion of cereal formulations containing from 5 to 15% over the starch phosphate monoester as compared to formulations containing the native starch.
- Formulations were prepared containing Hylon® VII starch phosphate monoester having a bound phosphorus level of 0.34%, prepared according to the method of Example 1 and compared to formulations containing Hylon® VII, the corresponding, non-phosphorylated native starch. The formulations are reported in Table 2 below. TABLE 2 Cereal Formulations (% wt) Ingredient 5% Starch* 10% Starch* 15% Starch* Oat flour 70% 70% 70% Sugar 10% 10% 10% Corn flour 15% 10% 5%
- the formulations were extruded and expanded according to the method described in Example 2. As reported in Table 2, at 5% the phosphorylated starch formulation expanded to give a bulk density of 0.465 g/ml compared to the native starch value of 0.481 g/ml. At 10% phosphorylated starch content the bulk densities of the expanded formulations were 0.370 g/ml, 0.437 g/ml; and at 15% the bulk densities were 0.332 and 0.405 g/ml for the phosphorylated starch and native starch, respectively.
- starch phosphate monoesters provide a consistently improved expanded cereal formulation, even at low levels of formulation content.
- This example illustrates the unexpectedly superior expansion of formulations containing the phosphorylated starch (“starch phosphate monoester) which had very little cold water swelling capacity as compared to carboxymethylated or hydroxypropylated starch, both of which demonstrate a high degree of cold water swelling.
- Hylon® VII Starch was phosphorylated according to the method described herein in Example 1 (0.44% bound phosphorus).
- a carboxymethylated sample of Hylon® VII Starch having a carboxyl group content of 3-3.5% by weight was also prepared according to the method described in Rutenberg, et al. which is incorporated herein by reference. Rutenberg, M. W. and D. Solarek: Starch Derivatives: Production and Use P. 312-388 in: Starch—Chemistry and Technology, pg 312-388, Academic Press (1984). Briefly, Hylon® VII Starch was slurred in alcohol at 35% solids.
- hydroxypropylated sample of Hylon® VII Starch having a bound hydroxypropyl group content of 3-3.5% by weight was also prepared according to the method described in Rutenberg et al. as well as U.S. Pat. No. 4,863,655, which is incorporated herein by reference. Id.
- Each derivatized starch was mixed into a cereal formulation of 10% derivatized starch, 10% sugar, 10% corn flour and 70% oat flour and expanded according to the procedure described herein in Example 2.
- the measured bulk densities for the expanded formulations of phosphorylated (starch phosphate monoester), hydroxypropylated and carboxymethylated Hylon® VII were 4.36 g/ml, 5.74 g/ml and 0.620 g/ml, respectively.
- the expanded formulation containing phosphorylated Hylon® VII Starch advantageously displayed a lower bulk density as compared to other derivatized starches known in the art, despite the fact that the phosphorylated sample displays none of the cold water swelling properties believed to aid the hydroxypropylated and carboxymethylated derivatives in their expansion properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Nutrition Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Grain Derivatives (AREA)
- General Preparation And Processing Of Foods (AREA)
- Jellies, Jams, And Syrups (AREA)
- Confectionery (AREA)
Abstract
Description
- The present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products. The invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- Expansion is an important characteristic of a number of materials and is useful in a number of applications, including the preparation of sheets, shaped foam and loosefill products as well as in the preparation of food products. Food products in which expanded materials are useful include pasta, pet food, breakfast cereals and snacks. The expansion of food products is accomplished by a variety of means including extrusion, puffing, frying and baking.
- The expansion processes which are used for making expanded products affect the physical and structural properties of starch. Under the process conditions of known food expansion, starch undergoes a melting, plasticizing and/or gelatinizing process. The structure of starch polymers in the plasticized or gelatinized state influence the product characteristics of expansion, crispness, bite, puff and texture as well as product-specific attributes such as the bowl life of cereals.
- Another important parameter is the relative amylose-amylopectin content of starch. Amylose is known to provide crunchiness and strength in expanded products, whereas increased amylopectin content typically results in a product with increased expansion, crispness and puffiness.
- Starches have been modified with the objective of affecting the expansion and texture of expanded products. For instance, pregelatinized starches have been used where the process conditions do not allow for complete gelatinization or complete disintegration of the granular structure of the starch. Wang, S. W.: Starches and Starch Derivatives in Expanded Snacks, Cereal Foods World, Vol. 42, pg 743-745 (1997). In addition, crosslinked starches have been used under high shear conditions in order to reduce otherwise severe fragmentation of the starch polymers. Id.
- Further, starches which have been modified to provide cold water soluble attributes are known to improve the expansion and texture of final expanded products. Such cold water soluble starches include hydroxypropylated or carboxymethylated starches. See U.S. Pat. No. 3,9566,990; Bhattacharyya, D., Singhal, R. s. and P. R. Kulkarni: Carboxymethyl Starch: an Expansion Aid, Carbohydrate Polymers 31, 79-82 (1996); and U.S. Pat. No. 5,480,669. Resistant starches have also been used to affect the expansion of food products. Id. While phosphorylated starches have been described for use in food products, they have not been described as an expansion aid.
- Starch phosphate monoesters have been described for use in a variety of food products, particularly as viscosifiers in order to improve texture and stability of non-expanded food. In particular, U.S. Ser. No. 09/633,832, the disclosure of which is incorporated herein by reference, describes the use of starch phosphate monoesters in protein-containing, low to intermediate moisture foods to improve the taste, texture, color and moisture retention of such foods. Texture, in this case, refers to the texture of the food that is strongly affected by improved retention of moisture content during storage of the starch phosphate monoester-treated food product.
- Surprisingly, it has now been discovered that, irrespective of the amylose/amylopectin content of the native starch structure or modification of the native starch structure, starch phosphate monoesters may be advantageously used as expansion aids in foods, particularly breakfast cereals and snacks.
- The present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products. The invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- The present invention is directed to the use of starch phosphate esters as an expansion and/or texture aid in food or industrial products. The invention further provides the formulations and improved expanded products containing starch phosphate esters, particularly extruded breakfast cereals and snacks.
- All starches and flours (hereinafter “starch”) may be suitable for use herein and may be derived from any native source. A native starch or flour as used herein, is one as it is found in nature. Also suitable are starches and flours derived from a plant obtained by standard breeding techniques including crossbreeding, translocation, inversion, transformation or any other method of gene or chromosome engineering to include variations thereof. In addition, starch or flours derived from a plant grown from artificial mutations and variations of the above generic composition which may be produced by known standard methods of mutation breeding are also suitable herein.
- Typical sources for the starches and flours are cereals, tubers, roots, legumes and fruits. The native source can be corn, pea, potato, sweet potato, banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high amylose varieties thereof. A used herein, the term “waxy” is intended to include a starch or flour containing at least about 95% by weight amylopectin and the term “high amylose” is intended to include a starch or flour containing at least about 40% by weight amylose.
- Conversion products derived from any of the starches, including fluidity or thin-boiling starches prepared by oxidation, enzyme conversion, acid hydrolysis, heat and or acid dextrinization, and or sheared products may also be useful herein.
- Chemically modified starches may also be used, provided such modification does not destroy the granular nature of the starch. Such chemical modifications are intended to include, without limitation, crosslinked starches, acetylated and organically esterified starches, hydroxyethylated and hydroxypropylated starches, phosphorylated and inorganically esterified starches, cationic, anionic, nonionic, and zwitterionic starches, and succinate and substituted succinate derivatives of starch. Such modifications are known in the art, for example in Modified Starches: Properties and Uses, Ed. Wurzburg, CRC Press, Inc., Florida (1986).
- The starch phosphate monoesters used in the formulations of the present invention may be prepared via methods known in the art. Traditional preparations of starch phosphate monoesters are described in U.S. Pat. No. 4,166,173, the disclosure of which is incorporated herein by reference. These preparations generally require the impregnation of the base starch with an alkali-metal phosphate, drying to a moisture content of less than 20% and heating in a continuous cooker, dextrinizer, convection oven or vacuum oven to effect the phosphorylation.
- Additional methods of preparing starch phosphate monoesters using fluidizied bed methodology are described in U.S. Pat. No. 3,843,377 and WO 99/64467, the disclosures of which are incorporated herein by reference. These methods disclose the use of a fluidized bed reactor in order to heat treat and phosphorylate starch in the presence of urea under semi-dry conditions of less than 5% moisture at temperatures of between 100° C. to 175° C. for between 20 to 60 minutes.
- The term “starch phosphate monoester” is intended to include, without limit, all equivalent terms, known to one of ordinary skill in the art, such as monostarch phosphate and includes regulatory definitions. Regulatory definitions of starch phosphate monoesters for use in food are often defined by the method in which they are made. In Europe, for example, a monostarch phosphate is defined to be a starch esterified with ortho-phosphoric acid or sodium or potassium ortho-phosphate or sodium tripolyphosphate. In the United States, a starch phosphate monoester is a food starch esterified by sodium trimetaphosphate or sodium tripolyphosphate and sodium trimetaphosphate.
- A particularly suitable method of preparing the starch phosphate monoesters of the present invention employs the fluidized bed technology described in U.S. Ser. No. 09/633,832. This application describes a process of impregnating the desired starch with a phosphate reagent, and optionally, an oligosaccharide. While in a fluidized state, the impregnated starch is then dried to a virtually anhydrous state, preferably 1 percent by weight of the starch or less, and then heated treated to effect phosphorylation. The impregnation of the starch by oligosaccharide and phosphate reagent may be done in any order. The pH of the resultant slurry may then adjusted to between about 3 and 12, preferably to between about 6 and 9.5.
- “Phosphate reagent” as used this particularly suitable method is defined as any phosphate reagent used for phosphorylating starch including ortho-, pyro-, meta- or tripolyphosphates. Illustrative phosphate reagents are the alkali metal phosphates such as sodium and potassium ortho-phosphate, phosphoric acid, phosphorus oxychloride, sodium and potassium tripolyphosphate and sodium and potassium trimetaphosphate. The reagent may be either a mono-, di- or trialkyl metal phosphate or combinations thereof.
- Impregnation by the phosphate reagent may be accomplished by adding the reagent in an amount of less than about 15% by weight of starch, preferably less than about 10%. The phosphate reagent may be added in the dry state to wet starch granules, or by dissolving the reagent in water to form an aqueous solution which is then mixed with the starch granules. These impregnation techniques are described in U.S. Pat. Nos. 4,166,173 and 4,216,310 which are incorporated herein by reference.
- The optional use of oligosaccharide in the preferred method of making the starch phosphate monoesters may include the addition of any oligosaccharide. The source may be the same as or different from that of the starch component and may be derived from any native source, including those listed above. As defined herein, oligosaccharide contains from one to twenty sugar units joined by glycosidic bonds. Oligosaccharide is intended to include monosaccharides, disaccharides, oligosaccharides, corn syrup solids, and maltodextrins. Oligosaccharides suitable for the present invention include, but are not limited to, debranched starches, corn syrup solids, dextrose, fructose, maltose, particularly corn syrup solids with a DE of from about 20 to 40. Although oligosaccharide is intended to include monosaccharides, these generally add color and/or flavor which may be undesirable in many industrial applications. Therefore, particularly suitable oligosaccharides for the present invention are those which contain at least two sugar units joined by glycosidic bonds.
- In the preferred method of preparing starch phosphate monoesters, the optional addition of the oligosaccharide to the starch may be achieved by adding the oligosaccharide either dry or as an aqueous solution. In particular, the oligosacchrides may be added to an agitated starch slurry or starch may be added to a stirred, aqueous solution of oligosaccharide. In addition, an aqueous solution of the oligosaccharide may be sprayed onto dry or wet starch granules.
- According to the preferred preparation, the impregnated starch, impregnated with phosphate and optionally with oligosaccharides, is then subjected to a fluidized state and heat treated to effect the phosphorylation. Though the heat treatment may be carried out in one step, it is preferably carried out in two steps. First, the impregnated starch is subjected to the fluidized state and dried to virtually anhydrous conditions, particularly to less than about 1% moisture content by weight of starch, at less than about 140° C., particularly between 60° C. and 140° C., and most particularly between about 100° C. to about 125° C. Secondly, while still in the fluidized state, the dried product is heated to between about 100° C. to about 185° C., particularly between about 120 to about 140° C. for between about 30 to about 300 minutes. At temperatures higher than about 150° C., the processing time is preferably less than about 45 minutes.
- The fluidized state is achieved by vigorous mixing of the solid starch particles in vacuum or in a gas whereby a uniform distribution of starch throughout the vacuum or gas may be attained. Vigorous mixing may be accomplished by using air or gas, at or above atmospheric pressures in a fluidized bed reactor or by sufficient mechanical agitation. Where pressurized gas is used to effect the fluidized state, the velocity of the gas must achieve a minimum rate such that the particles are free to move and exhibit a “fluidized state.” The fluidized state results in very efficient heat transfer and allows the starch to rapidly dry to a virtually anhydrous state at low temperature. Drying and heating the impregnated starch under fluidized conditions results in starch phosphate monoesters with high reaction efficiency, high levels of substitution and low levels of residual inorganic phosphate salt.
- The starch phosphate monoester, preferably prepared according to the foregoing method, is then incorporated into a formulation suitable for use in expandable food products such as extruded breakfast cereals or snacks. Formulations containing about the starch phosphate monoester in the amounts of from about 0.1 to 50%, by weight of the formulation, more particularly from about 1 to 25% by weight and especially particularly from about 5 to about 20% show significant increases in expansion over formulations which substitute the non-derivatized native starch for the starch phosphate monoester. Increasing the content of starch phosphate monoester content in the formulation also increases the degree of expansion of the formulation.
- Extruded foods in which the starch phosphate monoesters may be advantageously incorporated include pasta, snacks, breakfast cereals and pet foods, particularly breakfast cereal and snack foods and most particularly in low moisture, ready-to-eat cereals and snacks. Formulation content or processing parameters may be adjusted according to principles well-known in the industry in order to achieve properties, such as degree of expansion, taste and sweetness, specific to the desired end product. Generally formulations may contain whole or partially milled grains and flours including corn, wheat oat, rice and barley, native or modified starch as described previously herein, sucrose, maltodextrins, corn syrup solids, other sweeneters and salt. Optional additives may include acidifier, antiforaming agents, antioxidants, binders/extenders, legumes, mold inhibitors, nuts, phosphate and other food chemcals, spices and herbs, and vegetables.
- The amount of starch phosphate monoester which can be added and used in any given food will also be determined by the amount that can be tolerated from a functional standpoint. In other words, the amount of starch phosphate monoester used generally will be as high as will be acceptable in organoleptic evaluation of the food. Generally the starch phosphate monoester may be used in food applications at about 0.1 to 50%, by weight of the food, more particularly from about 1 to 25% by weight and especially particularly from about 5 to about 20%.
- The formulation can be processed by the use of any known technique suitable for expanding food products such as extrusion, puffing, frying, gun puffing, air impingement and baking. Conventional cooking-extruder expansion processes and equipment such as those disclosed in U.S. Pat. Nos. 3,054,677, 3,462,277 and Fast & Caldwell may be used to expand such formulations to give a breakfast cereal or snack product. See Fast, R. B., Caldwell, E. F., Breakfast Cereals and How They are Made, Amer. Asso. Of Cereal Chem., Inc.,2 nd ed. pg 215-278 (2000). Expansion techniques which do not require extrusion are intended to be included in this invention.
- In such processes requiring extrusion, a mixture of the formulation and water is processed in a cooker-extruder in which high pressure, temperature, and shear is generated. Under these process conditions, the formulation is melted, plasticized and/or at least partially gelatinized. The resultant material is expelled through a constricted opening, e.g. through a plurality of dies, under high temperature and pressure conditions.
- Depending upon the process conditions, the material may be either directly or indirectly expanded. Direct expansion occurs when the process conditions result in instantaneous water evaporation and cooking of the product. Indirect expansion is achieved by processing the material, sometimes known as a half product, via known post-extrusion processes including frying, baking and microwave heating.
- To achieve a directly expanded product, temperature and pressure ahead of the dies are maintained high enough to cause sudden release of pressure when the plasticized material is forced through the dies, with sudden conversion of at least some of the moisture to steam in the extruded material to develop bubbles in the resulting product. The development of bubbles and simultaneous cooling process creates a “foam type” of cell structure which defines the morphology of the expanded product. The expansion of the formulation is thus sensitive to moisture content in the extruder which in turn affects the energy required to extrude the formulation.
- Moisture content in this context refers to the total water content by weight present in the extruder during extrusion, including the water content of the formulation and water added during extrusion. For the production of directly expanded products extruder total moisture content is generally in the range of from about 10% to about 30%, particularly from about 15 to about 20% and most particularly from about 17% to about 19%. For indirect expansion, total extruder moisture contents of up to 45% may be utilized.
- Expansion of the extruded products of this invention may be measured directly by measuring the dimensions of the product, or indirectly by measuring the bulk density of the product. These analytical methods are known in the art and described for example by Harper & Tribbelhorn. See Harper, J. M. and R. E. Tribbelhorn, Expansion of Native Cereal Starch Extrudates, Food Extrusion Science and Technology, Marcel Dekker, Inc., pg 653-666, (1992). Bulk density refers to the weight of the extruded product in a known volume and is inversely related to the degree of expansion measured directly.
- The present inventive formulation provides an expanded product which expands significantly even under variable extruder conditions such as total water content. For instance, an expanded corn starch phosphate monoester formulation provides an expanded product having a bulk density of 0.29 g/ml and 0.36 g/ml at extruder total water contents of 17% and 19%, respectively. This degree and type of expansion is much superior to the formulations containing the corresponding native corn starch which have high bulk densities of 0.51 g/ml and 0.55 g/ml produced at water contents of 17 and 19%, respectively.
- The following examples are presented to further illustrate and explain the present invention and should not be taken as limiting in any regard. All parts and percentages are given by weight and all temperatures in degrees Celcius (° C.) unless otherwise noted.
- Measurement of Bound Phosphorus on Starch:
- The phosphorus content of starch samples was measured on acid-hydrolyzed starch samples by Inductive Couple Plasma-Atomic Emission (“ICP-AE”) Spectroscopy.
- Measurement of Bulk Density:
- A known mass of an extruded and expanded formulated starch sample was introduced into a 500 ml beaker, and the volume of the sample determined. The bulk density was then obtained by dividing the measured mass (in grams) of the extruded product by the defined volume (in mls).
- Preparation of the Starch Phosphate Monoester
- This example describes the preparation of starch phosphate monoesters useful in the formulations of the present invention.
- The starch phosphate monoesters (“SPM”) were prepared according to the method described in U.S. patent Ser. No. 09/633,832, incorporated herein by reference. Native starches (“NS”) which were used in the comparison formulations of Examples 1-4 and for the preparation of the corresponding starch phosphate monoesters included a high amylose corn starch (Sample I, HYLON® VII commercially available from National Starch and Chemical Co.), a waxy corn starch (Sample II, commercially available from National Starch and Chemical Co.), a potato starch (Sample III, commercially available from Emsland Staerke-Germany), and a wheat starch (Sample IV, commercially available from Midwest Grain Products Inc.).
- Impregnation of the starch with sodium tripolyphosphate was carried out using the following slurry impregnation method. One part native starch is slurried in two parts water by weight. The pH of the native starch slurry was adjusted to between 6.0 and 6.5 with HCl and stirred for 30 minutes. The slurry was then de-watered on a Buchner funnel and impregnated with a 3-10% aqueous sodium tripolyphosphate solution adjusted to a pH of between 6.0 to 6.5 to afford 2% sodium tripolyphosphate (anhydrous weight) impregnated starch cake.
- The impregnated starch (about 4 kg) was air dried to a moisture content of about 10-12%, ground, then dried in a pre-heated fluid bed reactor at a temperature of 220° F. until the starch had a moisture content of less than 1.0%. The dried starch was then heated to a temperature of 300° F. for 30 minutes, resulting in bound phosphorus levels of between 0.25 to 0.50% by weight.
- Expansion of Starch Phosphate Monoester-Containing Formulations
- This example illustrates the superior expansion of cereals formulated with the starch phosphate monoesters of Example 1 over cereals formulated with the corresponding native starch.
- Cereals were formulated with the starch phosphate monoester (“SPM”) and corresponding native starch (“NS”) samples of Example 1 in the following proportions: 70% oat flour, 10% sugar, 5% corn flour and 15% starch sample. Cereals were formulated without starch in the following proportions: 70% oat flour, 10% sugar and 20% corn flour.
- The extrusion experiments were carried out on a co-rotating twin screw extruder (available from Werner & Pfeiderer) under the following conditions: screw design was chosen to provide medium shear; the screw speed was 250 rpm; L/d-ratio 21; the die diameter was 2×3 mm; water content was 17%; the feed rate was 13 kg/h, the barrel temperature was set to 60° C. in the mixing zone, to 150° C. in the heating/cooking zone, and the die plate was heated to 140° C.; and the die face cutter had 2 blades.
- The extruded product was cut at the die and air dried. Bulk density refers to the weight of the extruded product in a known volume. The results are presented in Table 1.
TABLE 1 Bulk density of extruded formulations containing native and phosphorylated starches % bound SPM phosphorus NS formulation formulation on SPM Bulk density Bulk density Sample (by weight) (g/ml) (g/ml) Sample I 0.25 0.51 0.33 Sample II 0.25 0.36 0.27 Sample III 0.50 0.37 0.28 Sample IV 0.46 0.56 0.46 No starch in formulation Formulation Bulk Density = 0.51 g/ml - It is common knowledge that expansion is inversely related to the bulk density of the extruded cereal products. The data in Table 1 show that, the formulations of the present invention, prepared with the starch phosphate monesters (“SPM”), demonstrate significantly improved expansion over formulations containing the corresponding native starch (“NS”) as reflected in the lower bulk density of the expanded cereal products of the present invention. This is true irrespective of the botanical source of the starch phosphate monester sample.
- Expansion of Formulations of Varying Water Content
- This example demonstrates the ability of the starch phosphate monoesters to improve the expansion of cereal formulations irrespective of extrusion variables such as the extrusion total water content.
- At a total extruder water content of 17%, the cereal formulation of native corn starch (“NS”) prepared according to Example 2 was extruded to form an expanded product having a bulk density of 0.51 gm/ml. At a water content of 19%, the extruded NS formulation expanded providing a product with a bulk density of 0.55 g/ml.
- In comparison, the corresponding phosphorylated corn starch, prepared according to Example 1 (0.32% bound phosphorus by weight) (“SPM”) formulation showed improved expansion over the native corn starch formulation at both total extruder water content levels. At 17% total extruder water content, the SPM formulation provided an expanded product having a bulk density of 0.29 g/ml, and at water content of 19%, a product having a bulk density of 0.36 g/ml. Thus, even though the SPM formulations display a increase in bulk density when higher extruder water contents are used, the expansion of the SPM formulation is still superior to that of the NS formulation.
- Accordingly, the improved expansion of the cereal formulations containing the starch phosphate monoester occurs despite variation in extruder variables such as total water content.
- Expansion Over a Range of Starch Phosphate Monoester Content
- The example illustrates the superior expansion of cereal formulations containing from 5 to 15% over the starch phosphate monoester as compared to formulations containing the native starch.
- Formulations were prepared containing Hylon® VII starch phosphate monoester having a bound phosphorus level of 0.34%, prepared according to the method of Example 1 and compared to formulations containing Hylon® VII, the corresponding, non-phosphorylated native starch. The formulations are reported in Table 2 below.
TABLE 2 Cereal Formulations (% wt) Ingredient 5% Starch* 10% Starch* 15% Starch* Oat flour 70% 70% 70% Sugar 10% 10% 10% Corn flour 15% 10% 5% - The formulations were extruded and expanded according to the method described in Example 2. As reported in Table 2, at 5% the phosphorylated starch formulation expanded to give a bulk density of 0.465 g/ml compared to the native starch value of 0.481 g/ml. At 10% phosphorylated starch content the bulk densities of the expanded formulations were 0.370 g/ml, 0.437 g/ml; and at 15% the bulk densities were 0.332 and 0.405 g/ml for the phosphorylated starch and native starch, respectively.
- Therefore, the starch phosphate monoesters provide a consistently improved expanded cereal formulation, even at low levels of formulation content.
- Expansion of Starch Phosphate Monoesters Compared to the Expansion of Other Derivitized Starches
- This example illustrates the unexpectedly superior expansion of formulations containing the phosphorylated starch (“starch phosphate monoester) which had very little cold water swelling capacity as compared to carboxymethylated or hydroxypropylated starch, both of which demonstrate a high degree of cold water swelling.
- Hylon® VII Starch was phosphorylated according to the method described herein in Example 1 (0.44% bound phosphorus). For comparison purposes a carboxymethylated sample of Hylon® VII Starch having a carboxyl group content of 3-3.5% by weight was also prepared according to the method described in Rutenberg, et al. which is incorporated herein by reference. Rutenberg, M. W. and D. Solarek: Starch Derivatives: Production and Use P. 312-388 in: Starch—Chemistry and Technology, pg 312-388, Academic Press (1984). Briefly, Hylon® VII Starch was slurred in alcohol at 35% solids. Then 15% by weight of the starch of a 50% sodium hydroxide solution was added to the slurry and incubated for 10-30 minutes. After heating the slurry to 70° C., 15% (weight on starch) sodium salt of chloroacetic acid was added to the slurry. After stirring for 18 hours the reaction mixture was cooled to room temperature and the pH adjusted to neutral. The carboxymethylated starch was then filtered out of solution, washed with an alcohol/water mixture and dried.
- In addition, a hydroxypropylated sample of Hylon® VII Starch having a bound hydroxypropyl group content of 3-3.5% by weight was also prepared according to the method described in Rutenberg et al. as well as U.S. Pat. No. 4,863,655, which is incorporated herein by reference. Id.
- Each derivatized starch was mixed into a cereal formulation of 10% derivatized starch, 10% sugar, 10% corn flour and 70% oat flour and expanded according to the procedure described herein in Example 2. The measured bulk densities for the expanded formulations of phosphorylated (starch phosphate monoester), hydroxypropylated and carboxymethylated Hylon® VII were 4.36 g/ml, 5.74 g/ml and 0.620 g/ml, respectively.
- Thus, the expanded formulation containing phosphorylated Hylon® VII Starch advantageously displayed a lower bulk density as compared to other derivatized starches known in the art, despite the fact that the phosphorylated sample displays none of the cold water swelling properties believed to aid the hydroxypropylated and carboxymethylated derivatives in their expansion properties.
Claims (19)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/771,417 US6461656B1 (en) | 2001-01-26 | 2001-01-26 | Starch phosphate ester for use as an expansion aid |
JP2002011174A JP2002291420A (en) | 2001-01-26 | 2002-01-21 | Starch phosphate for use as a baking aid |
EP02001056A EP1226762A3 (en) | 2001-01-26 | 2002-01-21 | Starch phosphate ester for use as an expansion aid |
CN02102427A CN1366839A (en) | 2001-01-26 | 2002-01-21 | Starch phosphate as puffing adjuvant |
KR1020020003275A KR20020063113A (en) | 2001-01-26 | 2002-01-21 | Starch phosphate ester for use as an expansion aid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/771,417 US6461656B1 (en) | 2001-01-26 | 2001-01-26 | Starch phosphate ester for use as an expansion aid |
Publications (2)
Publication Number | Publication Date |
---|---|
US6461656B1 US6461656B1 (en) | 2002-10-08 |
US20020146492A1 true US20020146492A1 (en) | 2002-10-10 |
Family
ID=25091740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/771,417 Expired - Fee Related US6461656B1 (en) | 2001-01-26 | 2001-01-26 | Starch phosphate ester for use as an expansion aid |
Country Status (5)
Country | Link |
---|---|
US (1) | US6461656B1 (en) |
EP (1) | EP1226762A3 (en) |
JP (1) | JP2002291420A (en) |
KR (1) | KR20020063113A (en) |
CN (1) | CN1366839A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060240169A1 (en) * | 2003-03-12 | 2006-10-26 | Heydtmann Patricia C | Puffed pet food for diet control |
US20080063775A1 (en) * | 2006-07-28 | 2008-03-13 | Penford Food Corporation | High amylose dog chew formulation |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006020806A2 (en) * | 2004-08-12 | 2006-02-23 | Cargill, Incorporated | Food products comprising starch phosphorylated with sodium trimetaphosphate that retain dietary fiber and methods of making said food products |
US8741370B2 (en) * | 2005-03-18 | 2014-06-03 | Mgpi Processing, Inc. | Expanded products with high protein content |
WO2007081655A2 (en) * | 2006-01-05 | 2007-07-19 | Tate & Lyle Ingredients Americas, Inc. | Extrudable food composition |
KR100758582B1 (en) * | 2006-04-26 | 2007-09-13 | 조남지 | The composition of fat replacement |
JP2009537159A (en) * | 2006-05-24 | 2009-10-29 | バイエル・クロップサイエンス・アーゲー | Use of modified wheat flour to reduce baking loss |
US20100112176A1 (en) * | 2008-10-31 | 2010-05-06 | Quaker Oats Co. | Expansion of Extruded Cereals with Good Source of Fiber |
US20100189843A1 (en) * | 2009-01-23 | 2010-07-29 | Wei Luke Xie | Hydroxypropylated Starch as a Processing Aid to Improve Resistant Starch Total Dietary Fiber (TDF) Retention in Direct Expansion Extrusion Applications |
AU2010285965B2 (en) * | 2009-08-18 | 2013-08-29 | Glico Nutrition Co., Ltd. | Food product containing starch gel |
US9963581B2 (en) * | 2009-08-18 | 2018-05-08 | Glico Nutrition Co., Ltd. | Food product containing starch gel, starch granule, production method and use thereof |
EP2587937A2 (en) * | 2010-06-29 | 2013-05-08 | Tate & Lyle Ingredients Americas LLC | Hydroxypropyl substituted starches as source of soluble fiber |
CN103012604B (en) * | 2012-12-19 | 2015-09-02 | 北京林业大学 | Chestnut starch phosphomonoester and preparation method thereof |
KR101416607B1 (en) * | 2012-12-26 | 2014-07-08 | 주식회사농심 | Preparation meohod of the instant dry puffing rice |
CN107594482A (en) * | 2017-09-11 | 2018-01-19 | 浙江海洋大学 | A kind of aquatic products expanding processing auxiliary agent |
CN110200035A (en) * | 2019-05-20 | 2019-09-06 | 贾新会 | A kind of food expander |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2884413A (en) * | 1956-04-06 | 1959-04-28 | Corn Products Co | Orthophosphate esters of starch |
US3054677A (en) | 1959-06-26 | 1962-09-18 | Quaker Oats Co | Method of making shredded cereal product |
US3462277A (en) | 1966-09-26 | 1969-08-19 | Quaker Oats Co | Method of shaping a cereal product |
US3600193A (en) * | 1968-03-28 | 1971-08-17 | Milk Research Inc | Food compositions for preparing snack food products |
US3843377A (en) | 1972-06-12 | 1974-10-22 | Krause Milling Co | Art of manufacturing modified amylaceous materials with condensed phosphates and urea |
US3966990A (en) | 1974-02-11 | 1976-06-29 | A. E. Staley Manufacturing Company | Granular modified starch binder for dough forming of puffable food products |
US4166173A (en) | 1978-05-15 | 1979-08-28 | National Starch And Chemical Corporation | Process for phosphorylating starch in alkali metal tripolyphosphate salts |
US4216310A (en) * | 1979-04-19 | 1980-08-05 | National Starch And Chemical Corporation | Continuous process for phosphorylating starch |
ES2003767A6 (en) * | 1986-12-30 | 1988-11-16 | Leng D Or Sa | Method of making an edible potato dough sheet |
US5165950A (en) * | 1991-08-28 | 1992-11-24 | American Amaranth, Inc. | Microwave expandable half product and process for its manufacture |
AU664327C (en) | 1993-03-24 | 2003-01-30 | Brunob Ii B.V. | Method for increasing expansion and improving texture of fiber fortified extruded food products |
US5747092A (en) * | 1996-04-25 | 1998-05-05 | Nabisco Technology Company | Production of crispy wheat-based snacks having surface bubbles |
JP4594524B2 (en) * | 1998-06-10 | 2010-12-08 | コオペラティ・アヴェベ・ユー・エイ | Dextrinization of starch |
US6242033B1 (en) * | 1999-02-16 | 2001-06-05 | Eugene H. Sander | High protein cereal |
US6428836B1 (en) * | 2000-08-07 | 2002-08-06 | National Starch And Chemical Investment Holding Corporation | Starch phosphate ester composition, process and method of use in food |
-
2001
- 2001-01-26 US US09/771,417 patent/US6461656B1/en not_active Expired - Fee Related
-
2002
- 2002-01-21 KR KR1020020003275A patent/KR20020063113A/en not_active Application Discontinuation
- 2002-01-21 CN CN02102427A patent/CN1366839A/en active Pending
- 2002-01-21 JP JP2002011174A patent/JP2002291420A/en active Pending
- 2002-01-21 EP EP02001056A patent/EP1226762A3/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060240169A1 (en) * | 2003-03-12 | 2006-10-26 | Heydtmann Patricia C | Puffed pet food for diet control |
US7678406B2 (en) * | 2003-03-12 | 2010-03-16 | Nestec S.A. | Puffed pet food for diet control |
US20080063775A1 (en) * | 2006-07-28 | 2008-03-13 | Penford Food Corporation | High amylose dog chew formulation |
US7722911B2 (en) * | 2006-07-28 | 2010-05-25 | Penford Food Corporation | High amylose dog chew formulation |
Also Published As
Publication number | Publication date |
---|---|
CN1366839A (en) | 2002-09-04 |
EP1226762A2 (en) | 2002-07-31 |
JP2002291420A (en) | 2002-10-08 |
EP1226762A3 (en) | 2003-07-23 |
KR20020063113A (en) | 2002-08-01 |
US6461656B1 (en) | 2002-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6461656B1 (en) | Starch phosphate ester for use as an expansion aid | |
Singh et al. | Potato starch and its modification | |
Ma et al. | Research progress on properties of pre-gelatinized starch and its application in wheat flour products | |
CA2562605C (en) | Production of low calorie, extruded, expanded foods having a high fiber content | |
EP1161155B1 (en) | Ingredients for expanded foods | |
EP0512249B1 (en) | Extruded foods containing high amylose starch | |
Shrestha et al. | Starch modification to develop novel starch-biopolymer blends: State of art and perspectives | |
CN100355789C (en) | Sago-based gelling starches | |
Landerito et al. | Preparation and properties of starch phosphates using waxy, common, and high‐amylose corn starches. II. Reactive extrusion method | |
US20100189843A1 (en) | Hydroxypropylated Starch as a Processing Aid to Improve Resistant Starch Total Dietary Fiber (TDF) Retention in Direct Expansion Extrusion Applications | |
AU2004298399C1 (en) | Slowly digestible starch product | |
WO2010051181A1 (en) | Expansion of extruded cereals with good source of fiber | |
GB2111816A (en) | Starch-based snack products | |
Butt et al. | A comprehensive review on scope, characteristics and applications of instant starches in food products. | |
EP1955600A1 (en) | Expanded, low-salt snack product comprising high-amylopectin starch | |
Sethi et al. | Starch gelatinization and modification | |
US20070275123A1 (en) | Stable starches for contributing dietary fiber to food compositions | |
Mhaske et al. | Starch, Modified Starch, and Extruded Foods | |
Nel et al. | Preparation and Properties of Starch Phosphates Using Waxy, Common, and High-Amylose Corn Starches. II. Reactive Extrusion Method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BINDZUS, WOLFGANG;ALTIERI, PAUL A.;REEL/FRAME:011498/0818 Effective date: 20010125 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: BRUNOB II B.V., NETHERLANDS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION;REEL/FRAME:021096/0293 Effective date: 20080401 Owner name: BRUNOB II B.V.,NETHERLANDS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION;REEL/FRAME:021096/0293 Effective date: 20080401 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
SULP | Surcharge for late payment |
Year of fee payment: 7 |
|
AS | Assignment |
Owner name: CORN PRODUCTS DEVELOPMENT, INC., ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NATIONAL STARCH LLC;BRUNOB II B.V.;REEL/FRAME:027645/0724 Effective date: 20111219 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20141008 |