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Title:
DERIVATIZED MICROFIBRILLAR POLYSACCHARIDE
Document Type and Number:
WIPO Patent Application WO/2000/047628
Kind Code:
A2
Abstract:
A method for producing derivatized microfibrillar polysaccharide, including but not limited to cellulose, derivatized by steric and/or electrostatic forces, where the electrostatic forces are provided by anionic charge or by a combination of both anionic and cationic charge, by stabilizing and/or microfibrillating a polysaccharide starting material. A method of modifying the rheological properties of a composition of matter using derivatized microfibrillar polysaccharide. Method of improving coatings, paper manufacture, and the stability of emulsions, dispersions, and foams using a derivatized microfibrillar polysaccharide. Compositions that include derivatized microfibrillar polysaccharide, including paper compositions, comestible compositions, non-comestible spreadable compositions, and emulsions, dispersion, and foams.

Inventors:
CASH MARY JEAN
CHAN ANITA N
CONNER HERBERT THOMPSON
COWAN PATRICK JOSEPH
GELMAN ROBERT ALAN
LUSVARDI KATE MARRITT
THOMPSON SAMUEL ANTHONY
TISE FRANK PEINE
Application Number:
PCT/US2000/003319
Publication Date:
August 17, 2000
Filing Date:
February 08, 2000
Export Citation:
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Assignee:
HERCULES INC (US)
International Classes:
A01N25/00; A23L27/60; A23L29/00; A23L1/00; A23L29/20; A61F13/00; A61K8/00; A61K8/73; A61Q11/00; A61Q17/04; A61Q19/00; A61Q19/08; C08B1/00; C08B1/08; C08B3/06; C08B5/14; C08B11/08; C08B11/12; C08B11/20; C08B15/00; C08B37/00; C09K3/00; D21H17/24; D21H17/26; D21H19/10; D21H21/10; D21H21/16; D21H21/18; D21H21/20; (IPC1-7): C08B11/20; C08B1/00; C08B1/02
Domestic Patent References:
WO1999038892A11999-08-05
WO1996024720A11996-08-15
Foreign References:
FR2716887A11995-09-08
EP0859011A11998-08-19
EP0845495A21998-06-03
Other References:
FERRY, J.D.: "Viscoelastic Properties of Polymers", 1980, JOHN E. WILEY & SONS
Attorney, Agent or Firm:
Edwards, David (DE, US)
Download PDF:
Claims:
WHAT I/WE CLAIM IS:
1. A derivatized microfibrillar polysaccharide, derivatized to comprise substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality comprises anionic charge.
2. The derivatized microfibrillar polysaccharide of claim 1, wherein the polysaccharide in said derivatized microfibrillar polysaccharide comprises at least one of cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, agar, xanthan, starch, amylose, amylopectin, alternan, gellan, mutan, dextran, pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murein, bacterial capsular polysaccharides, and derivatives thereof.
3. The derivatized microfibrillar polysaccharide of claim 2, wherein said polysaccharide is at least one of cellulose, chitin, chitosan, pectin, agar, starch, carrageenan, and derivatives thereof.
4. The derivatized microfibrillar polysaccharide of claim 3, comprising derivatized microfibrillar cellulose.
5. The derivatized microfibrillar polysaccharide of claim 4, wherein said cellulose is obtained from at least one of chemical pulps, mechanical pulps, thermal mechanical pulps, chemicalthermal mechanical pulps, recycled fibers, newsprint, cotton, soybean hulls, pea hulls, corn hulls, flax, hemp, jute, ramie, kenaf, manila hemp, sisal hemp, bagasse, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables, and fruits.
6. The derivatized microfibrillar polysaccharide of claim 5, wherein said cellulose is obtained from at least one of purified, optionally bleached wood pulps produced from sulfite, kraft, or prehydrolyzed kraft pulping processes; purified cotton linters; fruits; and vegetables.
7. The derivatized microfibrillar cellulose of claim 4, comprising at least one of hydroxyethyl cellulose, ethylhydroxyethyl cellulose, carboxymethylcellulose, carboxymethylhydroxyethyl cellulose, hydroxypropylhydroxyethyl cellulose, methyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethylhydroxyethyl cellulose, hydrophobically modified carboxymethylhydroxyethyl cellulose, hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobically modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose, hydrophobically modified carboxymethylmethyl cellulose, nitrocellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulfate, cellulose phosphate, and cellulose phosphonate.
8. The derivatized microfibrillar cellulose of claim 4, wherein said derivatized microfibrillar cellulose forms a gel throughout the concentration range of between about 0.01 % and about 100% in water.
9. The derivatized microfibrillar cellulose of claim 8, wherein said derivatized microfibrillar cellulose forms a gel throughout the concentration range of between about 0.01 % and about 50 % in water.
10. The derivatized microfibrillar cellulose of claim 4, wherein said derivatized microfibrillar cellulose forms a gel at at least one point in the concentration range of from about 0.05 % up to about 0.99% in water.
11. The derivatized microfibrillar polysaccharide of claim 1, further comprising a solvent, wherein said derivatized microfibrillar polysaccharide is substantially insoluble in said solvent.
12. The derivatized microfibrillar polysaccharide of claim 11, wherein said solvent is water, alcohol, or oil.
13. The derivatized microfibrillar polysaccharide of claim 12, wherein said solvent is water.
14. The derivatized microfibrillar polysaccharide of claim 13, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic functionality.
15. The derivatized microfibrillar polysaccharide of claim 1, wherein said derivatized microfibrillar polysaccharide is derivatized microfibrillar cellulose having a degree of substitution of less than about 0.5.
16. The derivatized microfibrillar polysaccharide of claim 15, wherein said degree of substitution is less than about 0.35.
17. The derivatized microfibrillar polysaccharide of claim 16, wherein said degree of substitution is less than about 0.2.
18. The derivatized microfibrillar polysaccharide of claim 17, wherein said degree of substitution is less than about 0.18.
19. The derivatized microfibrillar polysaccharide of claim 18, wherein said degree of substitution is less than about 0.1.
20. The derivatized microfibrillar polysaccharide of claim 15, wherein said degree of substitution is between about 0.02 and about 0.5.
21. The derivatized microfibrillar polysaccharide of claim 20, wherein said degree of substitution is between about 0.05 and about 0.2.
22. The derivatized microfibrillar polysaccharide of claim 1, derivatized to comprise substituents that provide electrostatic functionality in the form of anionic charge, wherein the degree of substitution representing substituents that provide electrostatic functionality in the form of anionic charge is at least about 0.02.
23. The derivatized microfibrillar polysaccharide of claim 1, wherein said anionic charge is provided by carboxyl, sulfate, sulfonate, phosphonate, or phosphate groups, or combinations thereof.
24. The derivatized microfibrillar polysaccharide of claim 14, wherein said electrostatic functionality is provided by both anionic and cationic charge.
25. The derivatized microfibrillar cellulose of claim 24, wherein said electrostatic functionality is provided by substituents that contain both anionic and cationic charge in the same substituent.
26. The derivatized microfibrillar cellulose of claim 24, wherein said electrostatic functionality is provided both by substituents having anionic charge and by substituents having cationic charge.
27. The derivatized microfibrillar polysaccharide of claim 13, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide steric functionality.
28. The derivatized microfibrillar polysaccharide of claim 27, having a molar substitution of less than about 3.0.
29. The derivatized microfibrillar polysaccharide of claim 28, wherein said molar substitution is less than about 1.5.
30. The derivatized microfibrillar polysaccharide of claim 29, wherein said molar substitution is less than about 1.0.
31. The derivatized microfibrillar polysaccharide of claim 30, wherein said molar substitution is less than about 0.5.
32. The derivatized microfibrillar polysaccharide of claim 28, wherein said molar substitution is between about 0.5 and 3.0.
33. The derivatized microfibrillar polysaccharide of claim 27, wherein said substituents comprise at least one of hydroxyethyl groups; hydroxypropyl groups; methyl groups; ethyl groups; straightor branchedchain alkyl, alkenyl, or alkynyl groups having from about 4 to about 30 carbons; aryl, arylalkyl, arylalkenyl, cyclic, and herterocyclic hydrocarbons having from about 4 to about 30 carbons; or combinations thereof.
34. The derivatized microfibrillar polysaccharide of claim 33, further wherein said derivatized microfibrillar polysaccharide is a derivatized microfibrillar cellulose.
35. The derivatized microfibrillar cellulose of claim 4, comprising carboxymethylcellulose.
36. The derivatized microfibrillar cellulose of claim 34, having a degree of substitution of less than about 0.35.
37. The derivatized microfibrillar cellulose of claim 36, wherein said degree of substitution is less than about 2.0.
38. The derivatized microfibrillar cellulose of claim 37, wherein said degree of substitution is between about 0.02 and about 0.2.
39. The derivatized microfibrillar cellulose of claim 38, wherein said degree of substitution is between about 0.10 and about 0.2.
40. The derivatized microfibrillar polysaccharide of claim 4, wherein said derivatized microfibrillar cellulose forms a gel at a concentration of less than about 1 % in water.
41. Microfibrillar carboxymethylcellulose having a degree of substitution of between about 0.10 and about 0.20.
42. A comestible composition of matter comprising derivatized microfibrillar polysaccharide derivatized to comprise substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality is provided by anionic charge.
43. The comestible composition of matter of claim 42, in the form of a low fat, reduced fat, or fatfree mayonnaise.
44. The comestible composition of matter of claim 42, in the form of a salad dressing.
45. The comestible composition of matter of claim 42, further comprising a pharmaceutically active ingredient.
46. The comestible composition of claim 45, wherein said derivatized microfibrillar polysaccharide at least partially provides controlled, sustained, or delayed release of said pharmaceutically active ingredient.
47. A noncomestible composition of matter comprising derivatized microfibrillar polysaccharide derivatized to comprise substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality is provided by anionic charge.
48. The noncomestible composition of matter of claim 47, in the form of a wound care product.
49. The noncomestible composition of matter of claim 48, wherein said wound care product is a wound dressing.
50. The noncomestible composition of matter of claim 48, wherein said wound care product is an ostomy ring.
51. The noncomestible composition of matter of claim 47, in the form of a skin care lotion or cream.
52. The noncomestible composition of matter of claim 47, in the form of a sunscreen lotion or cream.
53. The noncomestible composition of matter of claim 47, in the form of an oral care composition.
54. The noncomestible composition of matter of claim 53, wherein said oral care product is a toothpaste.
55. The noncomestible composition of matter of claim 47, further comprising a fertilizer, herbicide, fungicide, or pesticide.
56. The noncomestible composition of matter of claim 55, wherein said derivatized microfibrillar polysaccharide at least partially provides controlled, sustained, or delayed release of said fertilizer, herbicide, or pesticide.
57. The noncomestible composition of matter of claim 47, in the form of a drilling fluid.
58. A paper composition comprising derivatized microfibrillar cellulose derivatized to comprise groups that provide electrostatic and/or steric functionality, further wherein said electrostatic functionality comprises the presence of anionic charge.
59. The paper composition of claim 58, wherein said derivatized microfibrillar cellulose is microfibrillar carboxymethylcellulose.
60. A method for producing derivatized microfibrillar polysaccharide, said method comprising at least one of the following: a) a derivatizing step of treating a microfibrillar polysaccharide to obtain a derivatized microfibrillar polysaccharide; b) a microfibrillizing step of treating a derivatized nonmicrofibrillar polysaccharide to produce a derivatized microfibrillar polysaccharide; or, c) microfibrillizing and derivatizing a nonmicrofibrillar polysaccharide substantially simultaneously, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic and/or steric functionality, further wherein said electrostatic functionality is provided by anionic charge.
61. The method of claim 60, wherein the polysaccharide is at least one of cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, agar, xanthan, starch, amylose, amylopectin, alternan, gellan, mutan, dextran, pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murein, bacterial capsular polysaccharides, and derivatives thereof.
62. The method of claim 61, wherein said polysaccharide is at least one of cellulose, chitin, chitosan, pectin, agar, starch, carrageenan, and derivatives thereof.
63. The method of claim 62, wherein the polysaccharide is cellulose and said derivatized microfibrillar polysaccharide is derivatized microfibrillar cellulose.
64. The method of claim 63, wherein said cellulose is obtained from at least one of chemical pulps, mechanical pulps, thermal mechanical pulps, chemicalthermal mechanical pulps, recycled fibers, newsprint, cotton, soybean hulls, pea hulls, corn hulls, flax, hemp, jute, ramie, kenaf, manila hemp, sisal hemp, bagasse, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables, and fruits.
65. The method of claim 64, wherein said cellulose is obtained from at least one of purified, optionally bleached wood pulps produced from sulfite, kraft, or prehydrolyzed kraft pulping processes; purified cotton linters; fruits; and vegetables.
66. The method of claim 60, comprising the steps of : a) derivatizing cellulose with monochloroacetic acid or a salt thereof under alkaline conditions to produce carboxymethylcellulose; b) suspending the carboxymethylcellulose in water to form a suspension; and c) homogenizing said suspension to produce microfibrillated carboxymethylcellulose.
67. The method of claim 60, wherein said derivatizing step comprises contacting a nonmicrofibrillar polysaccharide with a swelling agent.
68. The method of claim 67, further wherein said contacting takes place under alkaline conditions.
69. The method of claim 68, wherein said swelling agent is an anionic reagent.
70. The method of claim 69, wherein the polysaccharide is cellulose.
71. The method of claim 70, further wherein said alkaline conditions comprise contacting the cellulose with said anionic reagent in the presence of an alkaline reagent which is at least one of sodium hydroxide, an oxide or hydroxide of an alkali metal or alkaline earth metal, an alkali silicate, an alkali aluminate, an alkali carbonate, an amine, ammonium hydroxide, tetramethyl ammonium hydroxide, or combinations thereof.
72. The method of claim 60, wherein said derivatizing step takes place at high solids.
73. The method of claim 60, wherein said anionic charge comprises the presence of carboxyl, sulfate, sulfonate, phosphonate, or phosphate groups, or combinations thereof.
74. The method of claim 73, wherein said derivatizing step comprises carboxymethylation of the cellulose.
75. The method of claim 63, wherein said derivatized microfibrillar cellulose comprises at least one of hydroxyethyl cellulose, ethylhydroxyethyl cellulose, carboxymethylcellulose, carboxymethylhydroxyethyl cellulose, hydroxypropylhydroxyethyl cellulose, methyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethylhydroxyethyl cellulose, hydrophobically modified carboxymethylhydroxyethyl cellulose, hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobically modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose, hydrophobically modified carboxymethylmethyl cellulose, nitrocellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulfate, cellulose phosphate, and cellulose phosphonate.
76. The method of claim 60, wherein said microfibrillizing step comprises applying energy to said polysaccharide under conditions sufficient to produce microfibrillar polysaccharide.
77. The method of claim 76, further comprising enzymetreating said non microfibrillar polysaccharide prior to said microfibrillizing step.
78. The method of claim 76, comprising applying at least one of homogenization, pumping, mixing, heat, steam explosion, pressurizationdepressurization cycle, impact, grinding, ultrasound, microwave explosion, and milling to said non microfibrillar polysaccharide.
79. The method of claim 78, comprising passing said nonmicrofibrillar polysaccharide through a homogenizer under conditions sufficient to produce microfibrillar polysaccharide.
80. The method of claim 79, wherein said conditions comprise passing said nonmicrofibrillar polysaccharide through a pressure differential of at least about 3,000 psi.
81. The method of claim 80, further comprising passing said nonmicrofibrillar polysaccharide through said homogenizer at least three times.
82. The method of claim 60, wherein said derivatized microfibrillar polysaccharide forms a gel throughout a concentration range of from about 0.01 % to about 100% in water.
83. The method of claim 82, wherein said derivatized microfibrillar polysaccharide forms a gel throughout a concentration range of between about 0.01 % and about 50 % in water.
84. The method of claim 60, wherein said derivatized microfibrillar polysaccharide forms a gel at at least one point in the concentration range of from about 0.05 % to about 0.99% in water.
85. The method of claim 84, wherein said derivatized microfibrillar polysaccharide forms a gel at a concentration of about 0.9% in water.
86. The method of claim 60, wherein said derivatized microfibrillar polysaccharide is substantially insoluble in the solvent of use.
87. The method of claim 86, wherein the solvent of use is water.
88. The method of claim 87, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic functionality.
89. The method of claim 88, wherein said derivatized microfibrillar polysaccharide is derivatized microfibrillar cellulose having a degree of substitution of less than about 0.5.
90. The method of claim 89, wherein said degree of substitution is less than about 0.35.
91. The method of claim 90, wherein said degree of substitution is less than about 0.2.
92. The method of claim 91, wherein said degree of substitution is less than about 0.18.
93. The method of claim 92, wherein said degree of substitution is less than about 0.1.
94. The method of claim 89, wherein said derivatized microfibrillar cellulose has a degree of substitution of between about 0.02 and about 0.5.
95. The method of claim 94, wherein said degree of substitution is between about 0.05 and about 0.2.
96. The method of claim 86, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise a steric substituent.
97. The method of claim 96, further wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic functionality.
98. The method of claim 96, wherein said derivatized microfibrillar polysaccharide has a molar substitution of less than about 3.0.
99. The method of claim 98, wherein said molar substitution is less than about 1.5.
100. The method of claim 99, wherein said molar substitution is less than about 1.0.
101. The method of claim 100, wherein said molar substitution is less than about 0.5.
102. The method of claim 98, wherein said molar substitution is between about 0.5 and 3.0.
103. The method of claim 63, wherein said derivatized microfibrillar cellulose is a carboxymethylcellulose.
104. The method of claim 103, wherein said carboxymethylcellulose has a degree of substitution of less than about 0.35.
105. The method of claim 104, wherein said degree of substitution is less than about 2.0.
106. The method of claim 105, wherein said degree of substitution is between about 0.02 and about 2.0.
107. The method of claim 106, wherein said degree of substitution is between about 0.1 and about 0.2.
108. Derivatized microfibrillar polysaccharide produced by the method of claim 60.
109. Derivatized microfibrillar cellulose produced by the method of claim 63.
110. The derivatized microfibrillar cellulose of claim 63, derivatized to comprise substituents that provide steric functionality.
111. The derivatized microfibrillar cellulose of claim 110, wherein said substituents comprise at least one of hydroxyethyl groups; hydroxypropyl groups; methyl groups; ethyl groups; straightor branchedchain aliphatic groups having from about 4 to about 30 carbons; or combinations thereof.
112. The derivatized microfibrillar cellulose of claim 109, derivatized to comprise substituents that provide electrostatic functionality by anionic charge.
113. The derivatized microfibrillar cellulose of claim 112, wherein said anionic charge comprises the presence of carboxyl, sulfate, sulfonate, phosphonate, or phosphate groups, or combinations thereof.
114. The derivatized microfibrillar cellulose of claim 113, wherein said anionic charge comprises the presence of carboxyl groups.
115. The derivatized microfibrillar cellulose of claim 112, wherein said electrostatic functionality is provided by both anionic and cationic charge.
116. The derivatized microfibrillar cellulose of claim 115, wherein said electrostatic functionality is provided by substituents that contain both anionic and cationic charge in the same substituent.
117. The derivatized microfibrillar cellulose of claim 115, wherein said electrostatic functionality is provided both by substituents having anionic charge and by substituents having cationic charge.
118. A method of modifying the rheological properties of a composition of matter, said method comprising the step of incorporating, into said composition of matter, derivatized microfibrillar polysaccharide that is derivatized to comprise substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality is provided by anionic charge.
119. The method of claim 118, wherein said composition comprises a liquid.
120. The method of claim 119, wherein said liquid is water.
121. The method of claim 120, comprising using said derivatized microfibrillar polysaccharide in an amount effective to provide scale control and/or corrosion control.
122. The method of claim 118, wherein said derivatized microfibrillar polysaccharide is derivatized microfibrillar cellulose.
123. The method of claim 119, wherein said rheological properties are at least one of viscosity, suspension stability, gel insensitivity to temperature, shear reversible gelation, yield stress, and liquid retention.
124. The method of claim 118, wherein said composition of matter is a food, pharmaceutical, neutraceutical, personal care, fiber, paper, paint, coating, or construction composition. <BR> <BR> <P>.
125. The method of claim 124, wherein said composition of matter is an oral<BR> care product.
126. The method of claim 124, wherein said composition of matter is a cream or lotion for epidermal application.
127. The method of claim 124, wherein said composition of matter is moisturizing, night, antiage, or sunscreen cream or lotion.
128. The method of claim 124, wherein said composition of matter is a food spread.
129. The method of claim 128, wherein said food spread is a reduced fat, low fat, or fat free food spread.
130. The method of claim 129, wherein said food spread is a reduced fat, low fat, or fat free mayonnaise.
131. The method of claim 124, wherein said composition of matter is a drilling fluid.
132. A method of improving the physical and/or mechanical properties of a coating composition by incorporating, into said coating composition, an effective amount of a derivatized microfibrillar polysaccharide derivatized to comprise substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality is provided by anionic charge.
133. The method of claim 132, wherein said physical and/or mechanical properties include at least one of film forming, leveling, sag resistance, strength, durability, dispersion, flooding, floating, and spatter.
134. A method of improving at least one of sizing, strength, scale control, drainage, dewatering, retention, clarification, formation, adsorbency, film formation, membrane formation, and polyelectrolyte complexation during paper manufacture, said method comprising the step of using a derivatized microfibrillar cellulose during said manufacture, wherein said derivatized microfibrillar cellulose is derivatized by electrostatic and/or steric substituents, further wherein said electrostatic substituents comprise the presence of either anionic charge or both anionic and cationic charge.
135. The method of claim 134, wherein said derivatized microfibrillar cellulose is used as a drainage aid and/or as a sizing agent.
136. The method of claiml34, wherein said derivatized microfibrillar cellulose is microfibrillated carboxymethylcellulose.
137. The method of claim136, comprising using said microfibrillated carboxymethylcellulose in a papermaking machine to increase the rate of drainage and/or dewatering during paper manufacture.
138. The method of claiml37, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of cationic polyacrylamides; polydiallyldimethylammonium chloride; cationic starch; derivatives of cellulose containing ammonium or mono, di, or trialkyl ammonium substituents; derivatives of guar gum containing ammonium or mono, di, or trialkyl ammonium substituents; resins formed by the reaction of amines and/or polyamines with epichlorohydrin; and combinations thereof.
139. The method of claiml37, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : aluminum salts; hydrolyzed or partially hydrolyzed aluminum salts; complexes of hydrolyzed or partially hydrolyzed aluminum salts with organic or inorganic species; and combinations thereof.
140. The method of claiml37, further wherein said microfibrillated carboxymethylcellulose is used in the presence of: at least one polymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; at least one copolymer or terpolymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; and combinations thereof.
141. The method of claiml36, comprising using said microfibrillated carboxymethylcellulose in a papermaking machine for retention of organic and/or inorganic dispersed particles in a sheet of paper during its manufacture.
142. The method of claim141, wherein said dispersed particles comprise at least one of pulp fines, fillers, sizing agents, pigments, clays, detrimental organic particulate materials, detrimental inorganic particulate materials, and combinations thereof.
143. The method of claiml41, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : cationic polyacrylamides; polydiallyldimethylammonium chloride; cationic starch; derivatives of cellulose containing ammonium or mono, di, or trialkyl ammonium substituents; derivatives of guar gum containing ammonium or mono, di, or trialkyl ammonium substituents; resins formed by the reaction of amines and/or polyamines with epichlorohydrin; and combinations thereof.
144. The method of claiml41, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : aluminum salts; hydrolyzed or partially hydrolyzed aluminum salts; complexes of hydrolyzed or partially hydrolyzed aluminum salts with organic or inorganic species; and combinations thereof.
145. The method of claiml41, further wherein said microfibrillated carboxymethylcellulose is used in the presence of: at least one polymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; at least one copolymer or terpolymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; and combinations thereof.
146. The method of claiml36, comprising using said microfibrillated carboxymethylcellulose in a papermaking machine to improve the uniformity of formation of a sheet of paper during its manufacture.
147. The method of claiml46, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : cationic polyacrylamides; polydiallyldimethylammonium chloride; cationic starch; derivatives of cellulose containing ammonium or mono, di, or trialkyl ammonium substituents; derivatives of guar gum containing ammonium or mono, di, or trialkyl ammonium substituents; resins formed by the reaction of amines and/or polyamines with epichlorohydrin; and combinations thereof.
148. The method of claim 146, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : aluminum salts; hydrolyzed or partially hydrolyzed aluminum salts; complexes of hydrolyzed or partially hydrolyzed aluminum salts with organic or inorganic species; and combinations thereof.
149. The method of claiml46, further wherein said microfibrillated carboxymethylcellulose is used in the presence of: at least one polymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; at least one copolymer or terpolymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; and combinations thereof.
150. The method of claim36, comprising using said microfibrillated carboxymethylcellulose in a papermaking machine to improve the strength of a sheet of paper produced on a papermachine.
151. The method of claim 150, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : cationic polyacrylamides; polydiallyldimethylammonium chloride; cationic starch; derivatives of cellulose containing ammonium or mono, di, or trialkyl ammonium substituents; derivatives of guar gum containing ammonium or mono, di, or trialkyl ammonium substituents; resins formed by the reaction of amines and/or polyamines with epichlorohydrin; and combinations thereof.
152. The method of claim150, further wherein said microfibrillated carboxymethylcellulose is used in the presence of at least one of : aluminum salts; hydrolyzed or partially hydrolyzed aluminum salts; complexes of hydrolyzed or partially hydrolyzed aluminum salts with organic or inorganic species; and combinations thereof.
153. The method of claiml50, further wherein said microfibrillated carboxymethylcellulose is used in the presence of: at least one polymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; at least one copolymer or terpolymer of ethylene oxide, ethyleneimine, allylamine, or vinylamine; and combinations thereof.
154. A method for improving the stability of an emulsion, dispersion, or foam system, said method comprising the step of including, in the system, a derivatized microfibrillar polysaccharide derivatized by electrostatic and/or steric substituents, further wherein said electrostatic substituents comprise the presence of anionic charge.
155. The method of claiml54, wherein said derivatized microfibrillar polysaccharide is added to the system.
156. The method of claim1 55, wherein said system comprises an emulsion, further wherein said emulsion is produced by processing of an emulsion formulation.
157. The method of claim156, further wherein said derivatized microfibrillar polysaccharide is added prior to completion of processing of said emulsion formulation.
158. The method of claim156, wherein a nonmicrofibrillated polysaccharide is added prior to completion of processing of said emulsion formulation, and said emulsion formulation is processed under conditions sufficient to microfibrillate said non microfibrillated polysaccharide.
159. The method of claim158, further wherein said nonmicrofibrillated or only partially microfibrillated polysaccharide is nonderivatized or only partially derivatized, and said emulsion formulation is further processed under conditions sufficient to derivatized said nonderivatized polysaccharide, or to complete derivatization of said only partially derivatized polysaccharide, respectively.
160. The method of claim156, wherein a nonderivatized or only partially derivatized polysaccharide is added prior to completion of processing of said emulsion formulation, and the emulsion formulation is processed under conditions sufficient to derivatize said nonderivatized polysaccharide, or to complete derivatization of said only partially derivatized polysaccharide, respectively.
161. The method of claim 160, further wherein said nonderivatized or only partially derivatized polysaccharide is nonmicrofibrillated or only partially microfibrillated, and said emulsion formulation is further processed under conditions sufficient to microfibrillate said nonderivatized polysaccharide, or to complete microfibrillation of said only partially derivatized polysaccharide, respectively.
162. The method of claim155, wherein said system is a waterinoil or oilin water emulsion.
163. The system produced by the method of claim 154.
164. A system comprising an emulsion, dispersion, or foam containing a derivatized microfibrillar polysaccharide, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic and/or steric functionality, further wherein said electrostatic functionality is provided by anionic charge.
165. A polyelectrolyte complex comprising a derivatized microfibrillar polysaccharide comprising substituents that provide electrostatic and/or steric functionality, wherein said electrostatic functionality comprises anionic charge.
Description:
INTERNATIONAL SEARCH REPORT Intem2-mial Application No PCT/US 00/03319 C. (Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. P, X RIEDEL B ET AL:"NOVEL 1-7,22, POLYANION-POLYCATION-MICROFIBRIDE BLEND 23, NONWOVENS BASED ON CELLULOSE DERIVATIVES"35-39, CHEMICAL FIBERS INTERNATIONAL, DE, DEUTSCHER 41, FACHVERLAG,47-49, vol. 49, no. 1, March 1999 (1999-03), 60-67, pages 55-57, XP000827376 72-76, ISSN: 0340-3343 78-80, 82-85, 103-109, 112-114, 165 *The whole document* X FR 2 716 887 A (ELF ATOCHEM S. A.) 1-7, 8 September 1995 (1995-09-08) 11-23, 35-39, 47, 60-73, 75,76, 78-81, 86-95, 108,109, 112,113, 118, 122-124, 132-135. 165 page 8, line 17-20; claims 1,6-8; examples 1,1BIS X WO 96 24720 A (GENERALE SUCRIERE) 1-6, 15 August 1996 (1996-08-15) 8-23, 35-40, 42-44, 47,58, 60-65, 67-73, 76, 78-95, 108,109, 112-114, 118-120, 122-124, 130, 132-135, 137,146, 150, 154-156, 162-165 page 10-page 12; claims 1-3; examples 12,13 2 2 INTERNATIONAL SEARCH REPORT Intem ; al Application No PCT/US00/03319 C. (Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT CategorytCategory Citation of document with indication, where appropriate, of the relevant passages Relevant to claim No. X CHEMICAL ABSTRACTS, vol. 129, no. 9,1-23, 31 August 1998 (1998-08-31) 35-41, Columbus, Ohio, US; 47, abstract no. 110334,60-66, XP002140693 72-76, 78-95, 103-109, 112-114, 165 abstract X & JP 10 165823 A (NISSHIN SPINNING CO., LTD.) 23 June 1998 (1998-06-23) A EP 0 859 O11 A (A. R. D.) 48-57, 19 August 1998 (1998-08-19) 126,127, cited in the application 131 page 8-page 9; claim 17 A EP 0 845 495 A (LUMOS) 24-26, 3 June 1998 (1998-06-03) 115-117, cited in the application 136, 138-145, 147-149, 151-153, 157-161 page 3, line 38-44; example 5 2 Inttcnational application No. PCT/US 00/03319 INTERNATIONAL SEARCH REPORT PCT/US 00/03319 Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This Intemational Search Report has not been established in respect of certain claims under Article 17 (2) (a) for the following reasons: 1.7 Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. faims Nos.: because they relate to parts of the International Application that do not comply with the prescribed requirements to such an extent that no meaningful International Search can be carried out, specifically: 3.! Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4 (a). Box 11 Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this intemational application, as follows: See additional sheet 1. As all required additional search fees were timely paid by the applicant, this International Search Report covers all searchable claims. 2. As at) saarchabte ctaims couid be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. As only some of the required additional search fees were timely paid by the applicant, this International Search Report covers only those claims for which fees were paid, specifically claims Nos.: 4. ga No required additional search fees were timely paid by the applicant. Consequently, this International Search Report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: IN TOTAL: 112-117,136-153. IN PART: 118-135,154-165 Remark on Protest n The additional search fees were accompanied by the applicant's protest. u g No protest accompanied the payment of additional search fees. LJ FURTHER INFORMATION CONTINUED FROM 1. Claims: IN TOTAL: 66,73,74,88-95,103-107, 112-117,136-153. IN PART: 1-22,36-40,42-58,60-65, 67-72,75-87,97,108,109,118-135,154-165 The part of the claims relating to microfibrillar polysaccharides derivatized to provide ELECTROSTATIC functionality comprising anionic charge.

2. Claims: IN TOTAL: 27-34,96,98-102,110,111; IN PART: 1-22, 36-40,42-58,60-65,67-72,75-87,97,108,109,118-135, 154-165 The part of the claims relating to microfibrillar polysaccharides derivatized to provide STERIC functionality. INTERNATIONAL SEARCH REPORT Intemattnal Application No .,ormationonpaten « am. ! ymembersPCT/US 00/03319 Patent document Publication Patent family Publication cited in search report date member (s) date WO 9938892 A 05-08-1999 FR 2774380 A 06-08-1999 AU 2170199 A 16-08-1999 FR 2716887 A 08-09-1995 AT 158602 T 15-10-1997 AU 1895695 A 18-09-1995 CN 1142238 A 05-02-1997 DE 69500771 D 30-10-1997 DE 69500771 T 07-05-1998 EP 0748348 A 18-12-1996 FI 963384 A 30-08-1996 WO 9523824 A 08-09-1995 JP 9509694 T 30-09-1997 US 6103790 A 15-08-2000 WO 9624720 A 15-08-1996 FR 2730251 A 09-08-1996 FR 2730252 A 09-08-1996 BR 9607594 A 07-07-1998 CA 2209790 A 15-08-1996 CN 1173904 A 18-02-1998 EP 0726356 A 14-08-1996 JP 3042892 B 22-05-2000 JP 11501684 T 09-02-1999 US 5964983 A 12-10-1999 JP 10165823 A 23-06-1998 NONE EP 0859011 A 19-08-1998 FR 2759376 A 14-08-1998 EP 0845495 A 03-06-1998 GB 2323100 A 16-09-;, 98 DE 845495 T 24-09-1998