CA1162819A - Suspensions containing microfibrillated cellulose - Google Patents
Suspensions containing microfibrillated celluloseInfo
- Publication number
- CA1162819A CA1162819A CA000389140A CA389140A CA1162819A CA 1162819 A CA1162819 A CA 1162819A CA 000389140 A CA000389140 A CA 000389140A CA 389140 A CA389140 A CA 389140A CA 1162819 A CA1162819 A CA 1162819A
- Authority
- CA
- Canada
- Prior art keywords
- suspension
- cellulose
- microfibrillated cellulose
- oil
- finely divided
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/20—Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
- C09K8/206—Derivatives of other natural products, e.g. cellulose, starch, sugars
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 SUSPENSIONS CONTAINING
MICROFIBRILLATED CELLULOSE
Abstract of the Disclosure:
A suspension of a finely divided material in a liquid suspending medium which swells cellulose, the suspension containing microfibrillated cellulose in an amount sufficient to produce a stable, homogeneous suspension. The microfibrillated cellulose, a form of cellulose having a very large available surface area per unit of weight, acts to confer, among other benefits, greater stability on the suspension. The suspensions are useful in a variety of end use products including foods, cosmetics, pharmaceuticals, paints and drilling muds.
MICROFIBRILLATED CELLULOSE
Abstract of the Disclosure:
A suspension of a finely divided material in a liquid suspending medium which swells cellulose, the suspension containing microfibrillated cellulose in an amount sufficient to produce a stable, homogeneous suspension. The microfibrillated cellulose, a form of cellulose having a very large available surface area per unit of weight, acts to confer, among other benefits, greater stability on the suspension. The suspensions are useful in a variety of end use products including foods, cosmetics, pharmaceuticals, paints and drilling muds.
Description
A.F. Turba};-F.11. Snycler-9 I. n . S andbgrg 12 - 3- 2 This invention rQlates to s-tabls homoyeneous suspensions containing microfibrillated csllulose.
In our U.S. Patent ~,374,70~, -thsre is disclosec1 a n3w -typs oF celluloss, denominated microfibrillatsd csllulose, distinguished from prior cslluloses by a vastly increassd surface arsa, grQater liquid absorption charact~ristics and greater reactivity.
The microfibrillated cellulose there disclosed is prepared by repeatQdly passing a liquid suspsnsion of fibrous cellulose through a hiah pressure homo-gsnizsr until the celluloss suspension becomes substantially stable. The process convsrts th~
cellulose into microfibrillat_d cellulose without substantial chemical change.
It has besn discovered that the afor~mentioned microfibrillated cellulose has the uniqus capability of enhancing the homogeneity and stability of a wide varisty of suspensions. TheFressnce of microfibril-lated cellulos~ in suspensions of ths type used in foods, cosmstics, pharmaceuticals and such industrial products as paints and drilling muds has been found to confer a number o unusual pxoperty charactersistics on the resulting product. In some cases, suspensions may be made which were not previously possible.
The microfibrillated cellulose may ]~e formed in situ in the suspension in a single stage operation by mixing fibrous csllulose with the ingredients of the . ~
~62~
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 suspension and then passing the mixture through an homogenizer or alternatively, the microfibrillated cellulose may be separately prepared and added to the suspension after pre-paration.
Specifically, the invention involves a suspension of Einely divided material in a liquid suspending medium which swells cellulose, the suspension containing microfibrillated cellulose in an amount sufficient to produce a stable, homogen~ous suspension. The suspension is prepared in situ by mixing together a liquid which swells cellulose, a inely divided material suspendea in said liquid and fibrou~
cellulose to form a liquid suspension and repeatedly passing : the liquid suspension through a small diameter orifice in which the mixture is su~jected to a pressure drop of at least 3000 psi and a high velocity shearing action followed by a high velocity decelerating impact, the process o~ con-verting the cellulose into microfibrillated cellulose, the microfibrillated cellulose being present in an amount sufficient to form a stable homogeneous suspension of the liquid and suspended material. Alternatively, the suspension may be prepared by mixing together the liquid which swell~
cellulose, the finely divided material suspended in the liquid and the sepa:rately prepared microfibrillated cellulose in an amount sufficient to form a stable, homogeneous suspension of the liquid and suspended material.
~.F. Turba};-F.l~J. Snyd~r-I~.R. Sandberg 12-3-2 There is c~n obvious cost savings in preparing ths microfi~rillated celluloss and the suspension in a single stags operation. In aadiiion, chsre is also in certain instances a product advalltage wllich results in the use of the sin~le stags techniqus. Ths u.se of this singls stage tecnnique in ths pr~paration o certain food products is the subject of our U.S. Patent 4,341,~07. In certain products, ths heat build-up that accompanies -the fibrillation process is detrimental and for such heat sensitive systems the separate preparation of microfihrillated cellulose is necessary.
Ths term suspension as used herein is intencled to inclu~e within its scope, suspensions in wllich a finely dividsd solid, liquid or gas are mixed with, but undissolved in, a liquid. The term thus includes an emulsion in T~hich a liquid is disperssd in a second immiscible liquid, and a foam in which a gas is sntrapped in the liquid and stabilized.
The amount of microfibillated cellulose used in preparing the suspensions of the inve~tion will vary considerably depending on chs nature and intended use of the suspension. For example, it has been found that oil-in-T,~atsr emulsions may be rendered stable with l~o by ~ei~lt or less of microfibrillated cellulose.
Ths propsrties of latex paint suspension are enhancecl ~ith as little as 0.25% of _ ~ _ iZ~
A~Fo Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 microfibrillated cellulose while sand suspensions are stabi-lized with ~rom 2 to 3% of microfibrillated cellulose. At the other extreme, the microfibrillated cellulose may be present as the predominant or major ingredient of the S suspension. In general, the ~icrofibrillated cellulose should be present in an amount sufficient to accomplish its function of producing a stable, homogeneous suspension.
In most applications, this amount will range from about 0.25% to about 5~, the percentages being the weight of cellulose solids present as microfibrillated cellulose based on the total weight of the suspension.
The preparation of the microfibrillated cellulose, either in situ in the 3uspension or separately, is as.~is~ed by the addition to the starting mixture of a hydrophilic polymer which may be a cellulos~ ~ster or ether, a synthetic acid polymer (or copolymer), a natural ~um or a starch.
Ex~mples of such hydrophilic polymers are carboxymethyl cellulose, methyl cellulose (methocel), hydroxypropyl cellulose, polyacrylic acid, carageenin and guar gum.
Addition of the hydrophilic polymer to the liquid suspend-ing medium,pr.ior to cellulosic pulp addition, appears to prevent dewatering of the pulp (or other fibrous cellulose) under the high pre~sures of the ~ibrillation process and thus allows ~le slurry to pass through the homogenizer at ~5 higher slurry concentrations. Moxeover, the microfibrillated ~6Z8~
A.F. Turbak-F.W. Snyder-~.R. Sandberg 12-3-2 cellulose produced with the adclitive pre~ent also displays improved freeze-thaw stability and improved dewatering resistance under pressure and thus produces improved sus-pensions in accordance with the invention in those products where smoothn~ss is important, as for e2ample in hand creams, cosmetics and paints. The hydrophilic polymer will enhance the fibrillation process at levels as low as 0.1% by weight o~ the suspension, and may be used in amoun~s as high as 25~, depending on the nature of the suspension.
The following examples illustrate the practice of the invention. Unless otherwise indicated, all parts and percentages are by weight.
Ea~Ar~E 1 A 4~ cellulose slurry in approximately 3 gallon3 of water was prepared using prehydroly~ed kraft pulp which had been cut to pas~ through a 0.125 inch screen. The starting temperature of the sluxry was 25C. The sluxry was passed ~hrough a Manton-Gaulin (trademar~) homogenizer at 8000 lbs~sq. in. (gauge) ten consecutive tLmes until a stable suspension or gel-point was reached.
Microfibrillated cellulose can be used to adjust the rheology of paint to reduce dripp~ng. In addition, the i2~
A.F. Turbak-~.W. Snyder-K.R. Sandberg 12-3-2 microfibrillated cellulose assi.sts in ~he coverage of the surface to be painted and thus reduces the required levels of titanium dioxide pigment. This is illustrated by E~amples 2-7.
The microfibrillated cellulose of Example 1 was added as a 4~ slurry in water to a commercial latex enamel white paint. A comparison of the drip length o ths paint at various solid levels with and without various percentages of microfibrillated cellulose addition is set forth in Table I.
: ~ TABLE I
: ~ _ Drip Length ~ % MFC % Pigment ~ Solids % Vehicle (Inches) ; 2 0 15.97 }5.97 84~03 8.8 3 0.25 15.72 15.97 84.03 ~.2 4 0 15.34 15.34 84.66 8.5 0.50 14.84 15.34 84,66 6.0 6 0 14.06 14.06 85.93 12.0 7 ~0 13.06 14.06 85.93 4.0 It will be apparent from Table I that an amount o~ micro-fibrillated cellulose as low as 0.25% seduces dripping of the paint and that at a level of 1%, dripping as measured by drip length is one third of that of an equivalent solids ~1~2~
A.F. Turbak-F.W. Snyder K.R. Sandberg 12-3-2 percent paint without microfibrillated cellulose.
Microfibrillated cellulose acts as a non-ionic emulsifying agent as well as a stabilizer for emulsions.
This is illustrated by the following examples.
A 4.7% solids microfibrillated cellulose slurry in water was prepared as in Example 1 from sulfite pulp. The slurry was then intimately mixed wi~h food grade soybean oil and additional water in a blender. Table II sets forth the results of a series of experiments with ana without microfibrillated cellulose and with various quantities of microfibrillated celluloseJ oil and added water to prepare an oil-in-watar emulsion.
.
~6~
A.F~ Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 _ g _ .
TAB~
a~ .
x MFC Slurry Oil Water Added Grams Grams Grams ~ M~C ~ Oil Result 8 0 40 160 0 20 Stable emul-~ion not possible 9 10~640 150 0.25 20 l 44 150 0.54 20 n 11 40 40 120 0.94 20 Stable emulsion 12 40 80 80 0 . 94 40 n 13 70 251 30 0.94 71.5 n 14 50 64 51 1.42 38.8 "
10 15 85 1~6 15 1~ 45 63.8 "
16 85 100 15 2.0 50 It is apparent from the data in Table II that small amounts of microfibrillated cellulose are able to stabilize emulsions containing up to 71.5~ oil.
To demonstrate that stable emulsions can be made in situ (i.e. without separate preparation of the micro-fibrillated cellulose), a 20% by weight .~table smul-~ion was prepared from 80 grams of pulp which had been cut to pass through a 0.125 inch screen, 800 grams of a liquid vegetable oi:L (a food grade oil sold under the trademark _ g _ A.F. Turbak-F.W. Snyder-R.R. Sandberg 12-3-2 Crisco) and 3112 grams of water. The entire mixture was passed through an homogenizer at 8000 psig for ten passes.
The final emulsion contained about 2~ micro~ibrillated cellulose and was stable on ~he shelf at room temperature for at least six months.
Microfibrillated cellulose i5 also capable o use in relatively small, economical proportions for the pre-paration of stable emulsions of dense solids such as sand and coal for pipeline coal slurry pumping. The following examples demonstrate the usefulness of microfibrillated cellulose for use as "packer ~luidsn of the type used ~or preventing settling of suspended material during shutdown of drilling operations.
A 2% suspension in water of cellulosic pulp cut to pass through a 0.125 inch screen was prepared as a control.
To 100 grams of this suspension was added about 10 grams o~ ordinary sand. The mlxture was shaken and allowed to stand. As e~ected~ the sand settled rapidly to the bottom -no suspending action was noted.
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 EXA~PLE l9 To a sample of lO0 grams of a 2% slurry of micro-fibrillated cellulose in water, about lO grams of sand was added and the mix~urP was shaken. Upon standing, the sand remained suspended for over three months. Unlike most polymeric thickened suspensions~ the suspension was stable even if heated to 100C.
A second experiment was performed in which a layer of the sand was placed on top of a layer of the mlcro-fibrillated cellulose. Again, the sand did not settlethrough the microfi~rillated cellulose and did not pene-trate it appreciably o~er a period of months~
Microfibrillated cellulose thus may be used at low concentrations (2 to 3%) and therefore in~xpensivsly in drilling operations and for enhancing the stability of suspensions of relatively dense solids.
There is currently an active interest in the food industry in the use of gums, or other substitute for oil, to produce "no-oil" salad dressings. It has been found that microfibrillated cellulose may be substituted for oil to produce a low calorie salaa dressing. The product obtained from mixing a commercial Italian dxessing mix yields a stable suspension o~ spices which are uniformly AoF~ Turbak-F.W. Snyder-R.R. Sandberg 12-3-2 distributed throughout the mix. A commercial Thousand Island mix with microfibrillat:ed cellulose yields a crsamy stable suspension similar to the texture of its oil base counterpart. Commercial preparations of Italian salad dressings generally require shaking before use. The corresponding product made with microfibrilla~ed cellulose does not~
EXAMPL~ 20 _ A vinegar solution was approximated by preparing a 5% [V/V) acetic acid solution. Fifty-~ive milliliters of this vinegar was added tv 25 ml of wa~er in a cruet. In place of oil, 150 ml of a 1.7% microfibrillated cellulose was substituted. An envelope of dried Italian salad mix was added and the entire mixture well shaken. A stable dispersion of the spices resulted. The color and texture of the material resembled very closely an authentic Italian dressing.
For comparison purposes, the equivalent amoun~ 12.60 grams) of cellulosic sulfite pulp, cut to pass through a 0.125 inch screen, was added to the same composition in place of microfibrillated cellulose. The cellulosic pulp quickly settled and did not suspend the spices.
A.P. Turbak-F.W. Snyder-R~R. Sandberg 12-3-2 A commercially available dry Thousand Island dressing mix was added to approximately 225 ml of a 2% slurry in water of microfibrillated cellulose and mixed well. A
smooth consistency was obtained which appeared quite similar to a regular Thousand Island dressing. The suspension was stable to settling.
The following e~amples illustrate further uses of microfibrillated cellulose as an aid for emulsifying oils or fats in foods.
A 2% microfibrillated cellulose slurry was addad to a ground pork sausage mixture in an amount equal to 0.2%
total cellulose based on final product weight, Upon frying, there was considerably less shrinkage of the sausage link and far less fat rendered as compared to the same ground mixture wi~h no added microfibrillated cellulose.
. .
A 2.5~ microfibrillated cellulose slurry in water was added in the proportion of 1/3 slurry by weight to 2/3 by weight of ground chuck hamburger. This results in a product having 0.83~ added cellulose based on final product weight i.e.
~ii2~
A.F. ~urbak-F.W. Snyder-K.R. Sa~dberg 12-3-2 27 g of hamburger, 12.67 g adcled H20 and 0.33 g of cellulose.
On cooking the product remaining weighed 24 ~ or there was only a 3 gram loss from the original 27 g of hamburger which comes to an 11% weight loss on frying. By comparison a control weighing 40 grams ended up at 26 g after identical frying conditions which corresponds to a 34% weight loss. Not only did the hamburger containing microfibrillated cellulose lose less weight, but it was far juicier and did not have the extremely mealy taste of the control. Thus, addition of the 0.83~ cellulose as microfibrillated cellulose served both to reduce cooking losses and to improve overall taste and acceptance of the final product.
EXAMP~E 24 _ . . .
A 2% microfibrillated cellulose slurry in water was added to a commercial meat emul~ion used for making hot dogs in an amount equal to 2~ cellulose based on total weight of product. After stuffing, smoking and cooking the resultant wieners had a juicier taste and an improved smoke flavor retention as compared wi~h an equivalent wiener without microfibrillated cellulose. FurtherJ thera is considerably less ~ormation of fat globules throughout the fi~al product.
Palate response was excellent.
In our U.S. Patent ~,374,70~, -thsre is disclosec1 a n3w -typs oF celluloss, denominated microfibrillatsd csllulose, distinguished from prior cslluloses by a vastly increassd surface arsa, grQater liquid absorption charact~ristics and greater reactivity.
The microfibrillated cellulose there disclosed is prepared by repeatQdly passing a liquid suspsnsion of fibrous cellulose through a hiah pressure homo-gsnizsr until the celluloss suspension becomes substantially stable. The process convsrts th~
cellulose into microfibrillat_d cellulose without substantial chemical change.
It has besn discovered that the afor~mentioned microfibrillated cellulose has the uniqus capability of enhancing the homogeneity and stability of a wide varisty of suspensions. TheFressnce of microfibril-lated cellulos~ in suspensions of ths type used in foods, cosmstics, pharmaceuticals and such industrial products as paints and drilling muds has been found to confer a number o unusual pxoperty charactersistics on the resulting product. In some cases, suspensions may be made which were not previously possible.
The microfibrillated cellulose may ]~e formed in situ in the suspension in a single stage operation by mixing fibrous csllulose with the ingredients of the . ~
~62~
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 suspension and then passing the mixture through an homogenizer or alternatively, the microfibrillated cellulose may be separately prepared and added to the suspension after pre-paration.
Specifically, the invention involves a suspension of Einely divided material in a liquid suspending medium which swells cellulose, the suspension containing microfibrillated cellulose in an amount sufficient to produce a stable, homogen~ous suspension. The suspension is prepared in situ by mixing together a liquid which swells cellulose, a inely divided material suspendea in said liquid and fibrou~
cellulose to form a liquid suspension and repeatedly passing : the liquid suspension through a small diameter orifice in which the mixture is su~jected to a pressure drop of at least 3000 psi and a high velocity shearing action followed by a high velocity decelerating impact, the process o~ con-verting the cellulose into microfibrillated cellulose, the microfibrillated cellulose being present in an amount sufficient to form a stable homogeneous suspension of the liquid and suspended material. Alternatively, the suspension may be prepared by mixing together the liquid which swell~
cellulose, the finely divided material suspended in the liquid and the sepa:rately prepared microfibrillated cellulose in an amount sufficient to form a stable, homogeneous suspension of the liquid and suspended material.
~.F. Turba};-F.l~J. Snyd~r-I~.R. Sandberg 12-3-2 There is c~n obvious cost savings in preparing ths microfi~rillated celluloss and the suspension in a single stags operation. In aadiiion, chsre is also in certain instances a product advalltage wllich results in the use of the sin~le stags techniqus. Ths u.se of this singls stage tecnnique in ths pr~paration o certain food products is the subject of our U.S. Patent 4,341,~07. In certain products, ths heat build-up that accompanies -the fibrillation process is detrimental and for such heat sensitive systems the separate preparation of microfihrillated cellulose is necessary.
Ths term suspension as used herein is intencled to inclu~e within its scope, suspensions in wllich a finely dividsd solid, liquid or gas are mixed with, but undissolved in, a liquid. The term thus includes an emulsion in T~hich a liquid is disperssd in a second immiscible liquid, and a foam in which a gas is sntrapped in the liquid and stabilized.
The amount of microfibillated cellulose used in preparing the suspensions of the inve~tion will vary considerably depending on chs nature and intended use of the suspension. For example, it has been found that oil-in-T,~atsr emulsions may be rendered stable with l~o by ~ei~lt or less of microfibrillated cellulose.
Ths propsrties of latex paint suspension are enhancecl ~ith as little as 0.25% of _ ~ _ iZ~
A~Fo Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 microfibrillated cellulose while sand suspensions are stabi-lized with ~rom 2 to 3% of microfibrillated cellulose. At the other extreme, the microfibrillated cellulose may be present as the predominant or major ingredient of the S suspension. In general, the ~icrofibrillated cellulose should be present in an amount sufficient to accomplish its function of producing a stable, homogeneous suspension.
In most applications, this amount will range from about 0.25% to about 5~, the percentages being the weight of cellulose solids present as microfibrillated cellulose based on the total weight of the suspension.
The preparation of the microfibrillated cellulose, either in situ in the 3uspension or separately, is as.~is~ed by the addition to the starting mixture of a hydrophilic polymer which may be a cellulos~ ~ster or ether, a synthetic acid polymer (or copolymer), a natural ~um or a starch.
Ex~mples of such hydrophilic polymers are carboxymethyl cellulose, methyl cellulose (methocel), hydroxypropyl cellulose, polyacrylic acid, carageenin and guar gum.
Addition of the hydrophilic polymer to the liquid suspend-ing medium,pr.ior to cellulosic pulp addition, appears to prevent dewatering of the pulp (or other fibrous cellulose) under the high pre~sures of the ~ibrillation process and thus allows ~le slurry to pass through the homogenizer at ~5 higher slurry concentrations. Moxeover, the microfibrillated ~6Z8~
A.F. Turbak-F.W. Snyder-~.R. Sandberg 12-3-2 cellulose produced with the adclitive pre~ent also displays improved freeze-thaw stability and improved dewatering resistance under pressure and thus produces improved sus-pensions in accordance with the invention in those products where smoothn~ss is important, as for e2ample in hand creams, cosmetics and paints. The hydrophilic polymer will enhance the fibrillation process at levels as low as 0.1% by weight o~ the suspension, and may be used in amoun~s as high as 25~, depending on the nature of the suspension.
The following examples illustrate the practice of the invention. Unless otherwise indicated, all parts and percentages are by weight.
Ea~Ar~E 1 A 4~ cellulose slurry in approximately 3 gallon3 of water was prepared using prehydroly~ed kraft pulp which had been cut to pas~ through a 0.125 inch screen. The starting temperature of the sluxry was 25C. The sluxry was passed ~hrough a Manton-Gaulin (trademar~) homogenizer at 8000 lbs~sq. in. (gauge) ten consecutive tLmes until a stable suspension or gel-point was reached.
Microfibrillated cellulose can be used to adjust the rheology of paint to reduce dripp~ng. In addition, the i2~
A.F. Turbak-~.W. Snyder-K.R. Sandberg 12-3-2 microfibrillated cellulose assi.sts in ~he coverage of the surface to be painted and thus reduces the required levels of titanium dioxide pigment. This is illustrated by E~amples 2-7.
The microfibrillated cellulose of Example 1 was added as a 4~ slurry in water to a commercial latex enamel white paint. A comparison of the drip length o ths paint at various solid levels with and without various percentages of microfibrillated cellulose addition is set forth in Table I.
: ~ TABLE I
: ~ _ Drip Length ~ % MFC % Pigment ~ Solids % Vehicle (Inches) ; 2 0 15.97 }5.97 84~03 8.8 3 0.25 15.72 15.97 84.03 ~.2 4 0 15.34 15.34 84.66 8.5 0.50 14.84 15.34 84,66 6.0 6 0 14.06 14.06 85.93 12.0 7 ~0 13.06 14.06 85.93 4.0 It will be apparent from Table I that an amount o~ micro-fibrillated cellulose as low as 0.25% seduces dripping of the paint and that at a level of 1%, dripping as measured by drip length is one third of that of an equivalent solids ~1~2~
A.F. Turbak-F.W. Snyder K.R. Sandberg 12-3-2 percent paint without microfibrillated cellulose.
Microfibrillated cellulose acts as a non-ionic emulsifying agent as well as a stabilizer for emulsions.
This is illustrated by the following examples.
A 4.7% solids microfibrillated cellulose slurry in water was prepared as in Example 1 from sulfite pulp. The slurry was then intimately mixed wi~h food grade soybean oil and additional water in a blender. Table II sets forth the results of a series of experiments with ana without microfibrillated cellulose and with various quantities of microfibrillated celluloseJ oil and added water to prepare an oil-in-watar emulsion.
.
~6~
A.F~ Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 _ g _ .
TAB~
a~ .
x MFC Slurry Oil Water Added Grams Grams Grams ~ M~C ~ Oil Result 8 0 40 160 0 20 Stable emul-~ion not possible 9 10~640 150 0.25 20 l 44 150 0.54 20 n 11 40 40 120 0.94 20 Stable emulsion 12 40 80 80 0 . 94 40 n 13 70 251 30 0.94 71.5 n 14 50 64 51 1.42 38.8 "
10 15 85 1~6 15 1~ 45 63.8 "
16 85 100 15 2.0 50 It is apparent from the data in Table II that small amounts of microfibrillated cellulose are able to stabilize emulsions containing up to 71.5~ oil.
To demonstrate that stable emulsions can be made in situ (i.e. without separate preparation of the micro-fibrillated cellulose), a 20% by weight .~table smul-~ion was prepared from 80 grams of pulp which had been cut to pass through a 0.125 inch screen, 800 grams of a liquid vegetable oi:L (a food grade oil sold under the trademark _ g _ A.F. Turbak-F.W. Snyder-R.R. Sandberg 12-3-2 Crisco) and 3112 grams of water. The entire mixture was passed through an homogenizer at 8000 psig for ten passes.
The final emulsion contained about 2~ micro~ibrillated cellulose and was stable on ~he shelf at room temperature for at least six months.
Microfibrillated cellulose i5 also capable o use in relatively small, economical proportions for the pre-paration of stable emulsions of dense solids such as sand and coal for pipeline coal slurry pumping. The following examples demonstrate the usefulness of microfibrillated cellulose for use as "packer ~luidsn of the type used ~or preventing settling of suspended material during shutdown of drilling operations.
A 2% suspension in water of cellulosic pulp cut to pass through a 0.125 inch screen was prepared as a control.
To 100 grams of this suspension was added about 10 grams o~ ordinary sand. The mlxture was shaken and allowed to stand. As e~ected~ the sand settled rapidly to the bottom -no suspending action was noted.
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 EXA~PLE l9 To a sample of lO0 grams of a 2% slurry of micro-fibrillated cellulose in water, about lO grams of sand was added and the mix~urP was shaken. Upon standing, the sand remained suspended for over three months. Unlike most polymeric thickened suspensions~ the suspension was stable even if heated to 100C.
A second experiment was performed in which a layer of the sand was placed on top of a layer of the mlcro-fibrillated cellulose. Again, the sand did not settlethrough the microfi~rillated cellulose and did not pene-trate it appreciably o~er a period of months~
Microfibrillated cellulose thus may be used at low concentrations (2 to 3%) and therefore in~xpensivsly in drilling operations and for enhancing the stability of suspensions of relatively dense solids.
There is currently an active interest in the food industry in the use of gums, or other substitute for oil, to produce "no-oil" salad dressings. It has been found that microfibrillated cellulose may be substituted for oil to produce a low calorie salaa dressing. The product obtained from mixing a commercial Italian dxessing mix yields a stable suspension o~ spices which are uniformly AoF~ Turbak-F.W. Snyder-R.R. Sandberg 12-3-2 distributed throughout the mix. A commercial Thousand Island mix with microfibrillat:ed cellulose yields a crsamy stable suspension similar to the texture of its oil base counterpart. Commercial preparations of Italian salad dressings generally require shaking before use. The corresponding product made with microfibrilla~ed cellulose does not~
EXAMPL~ 20 _ A vinegar solution was approximated by preparing a 5% [V/V) acetic acid solution. Fifty-~ive milliliters of this vinegar was added tv 25 ml of wa~er in a cruet. In place of oil, 150 ml of a 1.7% microfibrillated cellulose was substituted. An envelope of dried Italian salad mix was added and the entire mixture well shaken. A stable dispersion of the spices resulted. The color and texture of the material resembled very closely an authentic Italian dressing.
For comparison purposes, the equivalent amoun~ 12.60 grams) of cellulosic sulfite pulp, cut to pass through a 0.125 inch screen, was added to the same composition in place of microfibrillated cellulose. The cellulosic pulp quickly settled and did not suspend the spices.
A.P. Turbak-F.W. Snyder-R~R. Sandberg 12-3-2 A commercially available dry Thousand Island dressing mix was added to approximately 225 ml of a 2% slurry in water of microfibrillated cellulose and mixed well. A
smooth consistency was obtained which appeared quite similar to a regular Thousand Island dressing. The suspension was stable to settling.
The following e~amples illustrate further uses of microfibrillated cellulose as an aid for emulsifying oils or fats in foods.
A 2% microfibrillated cellulose slurry was addad to a ground pork sausage mixture in an amount equal to 0.2%
total cellulose based on final product weight, Upon frying, there was considerably less shrinkage of the sausage link and far less fat rendered as compared to the same ground mixture wi~h no added microfibrillated cellulose.
. .
A 2.5~ microfibrillated cellulose slurry in water was added in the proportion of 1/3 slurry by weight to 2/3 by weight of ground chuck hamburger. This results in a product having 0.83~ added cellulose based on final product weight i.e.
~ii2~
A.F. ~urbak-F.W. Snyder-K.R. Sa~dberg 12-3-2 27 g of hamburger, 12.67 g adcled H20 and 0.33 g of cellulose.
On cooking the product remaining weighed 24 ~ or there was only a 3 gram loss from the original 27 g of hamburger which comes to an 11% weight loss on frying. By comparison a control weighing 40 grams ended up at 26 g after identical frying conditions which corresponds to a 34% weight loss. Not only did the hamburger containing microfibrillated cellulose lose less weight, but it was far juicier and did not have the extremely mealy taste of the control. Thus, addition of the 0.83~ cellulose as microfibrillated cellulose served both to reduce cooking losses and to improve overall taste and acceptance of the final product.
EXAMP~E 24 _ . . .
A 2% microfibrillated cellulose slurry in water was added to a commercial meat emul~ion used for making hot dogs in an amount equal to 2~ cellulose based on total weight of product. After stuffing, smoking and cooking the resultant wieners had a juicier taste and an improved smoke flavor retention as compared wi~h an equivalent wiener without microfibrillated cellulose. FurtherJ thera is considerably less ~ormation of fat globules throughout the fi~al product.
Palate response was excellent.
2~
A~Fo Turbak-F.W. Snyder-R~R. Sandberg 12-3-2 . . .
Example 24 was repeatedl using a commercial bologna emulsion with 3~ cellulose based on ~inal product. As compared with the same bologna without microfibrillated cellulose, the resulting bologna ~as vastly improved response to lowered formation of fat pockets which is onei Gf the major problems in the industry. The product was al50 juicier and had better flavor retention than the control.
EXA~PLE 2 6 . _ A low calorie whipped dassert topping was made by mixing together 2~2% cellulosic pulp, 6%~ sugar, 8% soybean oil and 83.8% water. The mixed ingredients formed ~ sluxry - which was passed through an homoge~izer having an 8000 psig pressure for ten passes. A whipped topping was producad with a smooth, consistent texture. ~he topping mayJ but need not be, further whipped in a blender.
In the cosmetics industry, particularly in the area of skin care t a few basic materials ar~ incorporated into different oil based formulations. The most common of these materials are! glycerine and propylene glycol which are used as moisturizing ingredients. When microfibrillated cellulose is produced in glycerol or propylene glycol sufficient body ~;2~
~.~. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 is imparted to the moisturizer so that expensive oils are not required. This not only Lowers the costs, but also is an advantage for controlling oily skin. The translucent glycerine-cellulose (MFC) and propylene glycol-cellulose ; 5 (MFC) give a stable suspension of smooth consistency quite like a commercial hand cream. The high absorbency of the microfibrillated cellulose may additionally be used to carry other agents as a slow release vehicle. The other agents may be bacteriostats or other special skin care agents.
~ . . .
A 2~ slurry of cellulosic pulp in glycerine was passed through a Manton-Gaulin homogenizer for 950 seconds at 8000 psig for 12 passe~ to a final ~emperature of 135C.
The result was a stable suspension of smooth consistency quite similar to a commercial hand craam. To this suspension base may be added various aroma contributing ingredien~s, lancin,other softening oils, cleansing agents or bacteriQcides as d~sired~
. . .
Example 27 was repeated, usins however propylene glycol as the liquicl carrier. The resulting product was similar to the glycerine based product.
g ~.F. rLurbal;-F. r~ . Sn~Jrler-T~. R. Sandherg 12-3-2 A 2~ slurry oS fluffed sulfi-te pulp in water eontaining 0.5% sodium earboxymethyl eellulose was pass~d throu~h the homogenizsr at ~000 psig for 600 seeonds or 10 passes to a final tsrilp~ra-turs of 100C.
A tllic}~ opaque paste was obtainQd whieh had an exeellent eonsisteney for cosmetie ersam i~as~d uses, showing c~hat wacer ean also D9 UsQ(l in addition to glyeols.
Various aroma concributing ingredients, lanolin, other softsning oilst eleansing agents or ~acteriocides may b~ added to this base as in l.xampls 27.
The mierofi}~rilled e~llulose useful in the invention is more speeifically defined as cellulose having a water retention value over 280%, a settling volume afc~r 60 minutes in a 0.5~ by wsight suspension in water of greater than 60% and a rate o degradation inerease by hydrolysis at 60C in ons molar h~drochloric aeid at least twics as great as eellulose beaten to a Canadian Standard Freelless value of 50 ml. Further and more detailed information concerning microfibrillated cellulose, as well as its preparation, may be found in our aforesaid U.S. Patent 4~374r702 ' ..' _,~
A~Fo Turbak-F.W. Snyder-R~R. Sandberg 12-3-2 . . .
Example 24 was repeatedl using a commercial bologna emulsion with 3~ cellulose based on ~inal product. As compared with the same bologna without microfibrillated cellulose, the resulting bologna ~as vastly improved response to lowered formation of fat pockets which is onei Gf the major problems in the industry. The product was al50 juicier and had better flavor retention than the control.
EXA~PLE 2 6 . _ A low calorie whipped dassert topping was made by mixing together 2~2% cellulosic pulp, 6%~ sugar, 8% soybean oil and 83.8% water. The mixed ingredients formed ~ sluxry - which was passed through an homoge~izer having an 8000 psig pressure for ten passes. A whipped topping was producad with a smooth, consistent texture. ~he topping mayJ but need not be, further whipped in a blender.
In the cosmetics industry, particularly in the area of skin care t a few basic materials ar~ incorporated into different oil based formulations. The most common of these materials are! glycerine and propylene glycol which are used as moisturizing ingredients. When microfibrillated cellulose is produced in glycerol or propylene glycol sufficient body ~;2~
~.~. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2 is imparted to the moisturizer so that expensive oils are not required. This not only Lowers the costs, but also is an advantage for controlling oily skin. The translucent glycerine-cellulose (MFC) and propylene glycol-cellulose ; 5 (MFC) give a stable suspension of smooth consistency quite like a commercial hand cream. The high absorbency of the microfibrillated cellulose may additionally be used to carry other agents as a slow release vehicle. The other agents may be bacteriostats or other special skin care agents.
~ . . .
A 2~ slurry of cellulosic pulp in glycerine was passed through a Manton-Gaulin homogenizer for 950 seconds at 8000 psig for 12 passe~ to a final ~emperature of 135C.
The result was a stable suspension of smooth consistency quite similar to a commercial hand craam. To this suspension base may be added various aroma contributing ingredien~s, lancin,other softening oils, cleansing agents or bacteriQcides as d~sired~
. . .
Example 27 was repeated, usins however propylene glycol as the liquicl carrier. The resulting product was similar to the glycerine based product.
g ~.F. rLurbal;-F. r~ . Sn~Jrler-T~. R. Sandherg 12-3-2 A 2~ slurry oS fluffed sulfi-te pulp in water eontaining 0.5% sodium earboxymethyl eellulose was pass~d throu~h the homogenizsr at ~000 psig for 600 seeonds or 10 passes to a final tsrilp~ra-turs of 100C.
A tllic}~ opaque paste was obtainQd whieh had an exeellent eonsisteney for cosmetie ersam i~as~d uses, showing c~hat wacer ean also D9 UsQ(l in addition to glyeols.
Various aroma concributing ingredients, lanolin, other softsning oilst eleansing agents or ~acteriocides may b~ added to this base as in l.xampls 27.
The mierofi}~rilled e~llulose useful in the invention is more speeifically defined as cellulose having a water retention value over 280%, a settling volume afc~r 60 minutes in a 0.5~ by wsight suspension in water of greater than 60% and a rate o degradation inerease by hydrolysis at 60C in ons molar h~drochloric aeid at least twics as great as eellulose beaten to a Canadian Standard Freelless value of 50 ml. Further and more detailed information concerning microfibrillated cellulose, as well as its preparation, may be found in our aforesaid U.S. Patent 4~374r702 ' ..' _,~
Claims (17)
1. A suspension of a finely divided material in a liquid suspending medium which swells cellulose, said suspension containing microfibrillated cellulose in an amount sufficient to produce a stable, homogeneous suspension.
2. The suspension of Claim 1 in which the liquid suspending medium is water.
3. The suspension of Claim 1 in which the finely divided material is a solid.
4. The suspension of Claim 1 in the form of an emulsion in which the finely divided material is a liquid which is immiscible in the liquid suspending medium.
5. The suspension of Claim 1 containing a hydrophilic polymer.
6. The suspension of Claim 6 in which the hydrophilic polymer is selected from the group consisting of cellulose esters and ethers, synthetic acid polymers, natural gums and starches.
7. The suspension of Claim 1 in which the micro-fibrillated cellulose is present in an amount ranging from 0.25% to the major ingredient of the suspension, said pro-portions being based on the weight of cellulose solids present as microfibrillated cellulose as compared to the total weight of the suspension.
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2
A.F. Turbak-F.W. Snyder-K.R. Sandberg 12-3-2
8. The suspension of Claim 3 in which the finely divided material is a dense solid.
9. The suspension of Claim 8 in which the dense solid is sand
10. The suspension of Claim 8 in which the dense solid is coal.
11. The suspension of Claim 1 in which the suspension is a paint.
12. The suspension of Claim 3 in which the suspension is an oil-free salad dressing.
13. The suspension of Claim 4 in which the emulsion is an oil-in-water emulsion.
14. The suspension of Claim 1 in which the suspension is a cosmetic base.
15. The suspension of Claim 1 in which the suspension is an oil or fat containing food.
16. The suspension of Claim 15 in which the food is a ground meat product.
17. The suspension of Claim 15 in which the food is a whipped topping.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/202,740 US4378381A (en) | 1980-10-31 | 1980-10-31 | Suspensions containing microfibrillated cellulose |
| US202,740 | 1980-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162819A true CA1162819A (en) | 1984-02-28 |
Family
ID=22751071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389140A Expired CA1162819A (en) | 1980-10-31 | 1981-10-30 | Suspensions containing microfibrillated cellulose |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4378381A (en) |
| JP (1) | JPS603855B2 (en) |
| CA (1) | CA1162819A (en) |
| ES (1) | ES9200009A1 (en) |
| FI (1) | FI68529C (en) |
| MX (1) | MX7152E (en) |
| NO (1) | NO158810C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8231764B2 (en) | 2009-05-15 | 2012-07-31 | Imerys Minerals, Limited | Paper filler method |
| US10053817B2 (en) | 2010-04-27 | 2018-08-21 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
| US10253457B2 (en) | 2010-11-15 | 2019-04-09 | Fiberlean Technologies Limited | Compositions |
| US10294371B2 (en) | 2009-03-30 | 2019-05-21 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US10301774B2 (en) | 2009-03-30 | 2019-05-28 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose suspensions |
| US10577469B2 (en) | 2015-10-14 | 2020-03-03 | Fiberlean Technologies Limited | 3D-formable sheet material |
| US10794006B2 (en) | 2016-04-22 | 2020-10-06 | Fiberlean Technologies Limited | Compositions comprising microfibrilated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
| US11155697B2 (en) | 2010-04-27 | 2021-10-26 | Fiberlean Technologies Limited | Process for the production of gel-based composite materials |
| US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
| US11970817B2 (en) | 2009-05-15 | 2024-04-30 | Fiberlean Technologies Limited | Paper filler composition |
Families Citing this family (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487634A (en) * | 1980-10-31 | 1984-12-11 | International Telephone And Telegraph Corporation | Suspensions containing microfibrillated cellulose |
| US4831127A (en) * | 1983-07-12 | 1989-05-16 | Sbp, Inc. | Parenchymal cell cellulose and related materials |
| JPS60260517A (en) * | 1984-06-08 | 1985-12-23 | Daicel Chem Ind Ltd | Composition for food and drug |
| JPS61197654U (en) * | 1985-05-31 | 1986-12-10 | ||
| JPS6239507A (en) * | 1985-08-13 | 1987-02-20 | Daicel Chem Ind Ltd | Cosmetic for keeping skin in good state |
| US4865863A (en) * | 1985-12-31 | 1989-09-12 | The Procter & Gamble Company | Co-milling fiber for use in foods |
| JPS62277144A (en) * | 1986-05-23 | 1987-12-02 | Shiseido Co Ltd | Water-in-oil type emulsion composition |
| US4774099A (en) * | 1986-05-30 | 1988-09-27 | The Procter & Gamble Company | Process for making brownies containing cellulosic fiber |
| JPS6328443A (en) * | 1986-07-21 | 1988-02-06 | Shiseido Co Ltd | Oil-in-water type emulsion composition |
| US4840800A (en) * | 1987-11-16 | 1989-06-20 | Harris Robert L | Soybean fiber in insect rearing media |
| US5006360B1 (en) * | 1988-06-27 | 1992-04-28 | Low calorie fat substitute compositions resistant to laxative side effect | |
| US5011701A (en) * | 1988-12-30 | 1991-04-30 | Kraft General Foods, Inc. | Low calorie food products having smooth, creamy, organoleptic characteristics |
| US5106644A (en) * | 1990-05-25 | 1992-04-21 | Procter & Gamble Company | Food products containing reduced calorie, fiber containing fat substitute |
| US5215757A (en) * | 1991-03-22 | 1993-06-01 | The Procter & Gamble Company | Encapsulated materials |
| US5254357A (en) * | 1991-06-28 | 1993-10-19 | Langner Bruce J | Process for making a fiber beverage |
| US5385640A (en) * | 1993-07-09 | 1995-01-31 | Microcell, Inc. | Process for making microdenominated cellulose |
| US5487419A (en) * | 1993-07-09 | 1996-01-30 | Microcell, Inc. | Redispersible microdenominated cellulose |
| CA2168212C (en) | 1993-07-26 | 1999-12-14 | Domingo C. Tuason | Fat-like agents for low calorie food compositions |
| US6083582A (en) * | 1996-11-13 | 2000-07-04 | Regents Of The University Of Minnesota | Cellulose fiber based compositions and film and the process for their manufacture |
| US5817381A (en) * | 1996-11-13 | 1998-10-06 | Agricultural Utilization Research Institute | Cellulose fiber based compositions and film and the process for their manufacture |
| TW408153B (en) * | 1998-01-09 | 2000-10-11 | Asahi Chemical Ind | Cellulose-containing composite, process for its preparation and use thereof |
| US6602994B1 (en) | 1999-02-10 | 2003-08-05 | Hercules Incorporated | Derivatized microfibrillar polysaccharide |
| US6506435B1 (en) * | 1999-11-03 | 2003-01-14 | Regents Of The University Of Minnesota | Cellulose fiber-based compositions and their method of manufacture |
| US6699977B1 (en) | 2000-06-09 | 2004-03-02 | Cp Kelco Aps | Low methoxyl pectins, processes thereof, and stabilized aqueous systems comprising the same |
| WO2003030916A1 (en) | 2001-10-12 | 2003-04-17 | Regents Of The University Of Minnesota | Medical and nutritional applications of highly refined cellulose |
| US20080193590A1 (en) * | 2002-11-06 | 2008-08-14 | Fiberstar Inc., Incorporated | Highly refined cellulose neutraceutical compostions and methods of use |
| US20050233044A1 (en) * | 2004-04-19 | 2005-10-20 | Don Rader | Encapsulated organic solution particles |
| US20070087061A1 (en) * | 2005-10-14 | 2007-04-19 | Medafor, Incorporated | Method and composition for creating and/or activating a platelet-rich gel by contact with a porous particulate material, for use in wound care, tissue adhesion, or as a matrix for delivery of therapeutic components |
| US20070086958A1 (en) * | 2005-10-14 | 2007-04-19 | Medafor, Incorporated | Formation of medically useful gels comprising microporous particles and methods of use |
| US9045716B2 (en) | 2006-11-08 | 2015-06-02 | Cp Kelco U.S., Inc. | Surfactant thickened systems comprising microfibrous cellulose and methods of making same |
| US8772359B2 (en) * | 2006-11-08 | 2014-07-08 | Cp Kelco U.S., Inc. | Surfactant thickened systems comprising microfibrous cellulose and methods of making same |
| US7888308B2 (en) * | 2006-12-19 | 2011-02-15 | Cp Kelco U.S., Inc. | Cationic surfactant systems comprising microfibrous cellulose |
| SE532840C2 (en) * | 2008-02-14 | 2010-04-20 | Lars Eriksson | biofuel |
| US20100016575A1 (en) * | 2008-07-15 | 2010-01-21 | Zhi-Fa Yang | Bacterial cellulose-containing formulations lacking a carboxymethyl cellulose component |
| WO2011030295A1 (en) * | 2009-09-08 | 2011-03-17 | Cp Kelco U.S., Inc. | Methods to improve the compatibility and efficiency of powdered versions of microfibrous cellulose |
| FI123869B (en) * | 2010-04-07 | 2013-11-29 | Teknologian Tutkimuskeskus Vtt | Process for producing paint or varnish |
| FI126259B (en) | 2011-02-11 | 2016-09-15 | Upm Kymmene Corp | Microfibrillated cellulose for use in the treatment of atopic dermatitis and psoriasis |
| DE102011117136A1 (en) * | 2011-10-25 | 2013-04-25 | JeNaCell GmbH | A process for the generation of dried cellulose and cellulosic material as well as ready-to-use cellulose products prepared by this process |
| GB2502955B (en) * | 2012-05-29 | 2016-07-27 | De La Rue Int Ltd | A substrate for security documents |
| US9359678B2 (en) | 2012-07-04 | 2016-06-07 | Nanohibitor Technology Inc. | Use of charged cellulose nanocrystals for corrosion inhibition and a corrosion inhibiting composition comprising the same |
| US9222174B2 (en) | 2013-07-03 | 2015-12-29 | Nanohibitor Technology Inc. | Corrosion inhibitor comprising cellulose nanocrystals and cellulose nanocrystals in combination with a corrosion inhibitor |
| EP2877496B1 (en) * | 2012-07-27 | 2017-03-01 | Koninklijke Coöperatie Cosun U.A. | Anti-cracking agent for water-borne acrylic paint and coating compositions |
| PL2877497T3 (en) | 2012-07-27 | 2017-07-31 | Koninklijke Coöperatie Cosun U.A. | Structuring agent for liquid detergent and personal care products |
| DK2877550T3 (en) | 2012-07-27 | 2023-05-30 | Cellucomp Ltd | Plant-derived cellulosic compositions for use as drilling mud |
| EP2970514A1 (en) | 2013-03-15 | 2016-01-20 | Koninklijke Coöperatie Cosun U.A. | Stabilization of suspended solid particles and/or gas bubbles in aqueous fluids |
| WO2014154348A1 (en) * | 2013-03-25 | 2014-10-02 | Borregaard As | Composition comprising water-soluble polymer and microfibrillated cellulose, product and method for oilfield applications |
| US20160074289A1 (en) * | 2013-04-22 | 2016-03-17 | Nissan Chemical Industries, Ltd. | Thickening composition |
| SE537668C2 (en) * | 2013-04-26 | 2015-09-29 | Stora Enso Oyj | Process for treating a food product with a solution comprising a nanofibrillated polysaccharide and mono-treated product |
| FI126755B (en) * | 2014-04-28 | 2017-05-15 | Kemira Oyj | Procedure for a suspension of microfibrillar cellulose, microfibrillar cellulose and its use |
| WO2016025873A1 (en) | 2014-08-15 | 2016-02-18 | Halosource, Inc. | Granular filtration media mixture and uses in water purification |
| WO2016176759A1 (en) | 2015-05-01 | 2016-11-10 | Fpinnovations | A dry mixed re-dispersible cellulose filament/carrier product and the method of making the same |
| RU2693105C2 (en) | 2015-05-20 | 2019-07-01 | Шлюмбергер Текнолоджи Б.В. | Water influx elimination agent for use in oil fields |
| AU2016342130B2 (en) | 2015-10-19 | 2019-07-11 | Unilever Plc | Composition comprising an oil phase |
| US10689564B2 (en) | 2015-11-23 | 2020-06-23 | Schlumberger Technology Corporation | Fluids containing cellulose fibers and cellulose nanoparticles for oilfield applications |
| US11286313B2 (en) | 2016-06-30 | 2022-03-29 | Betulium Oy | Parenchymal cellulose composition |
| US10662366B2 (en) | 2016-08-09 | 2020-05-26 | Schlumberger Technology Corporation | Compositions and methods for servicing subterranean wells |
| WO2018064284A1 (en) | 2016-09-30 | 2018-04-05 | Novaflux, Inc. | Compositions for cleaning and decontamination |
| JP6743738B2 (en) | 2017-03-27 | 2020-08-19 | 信越化学工業株式会社 | Laminated body and manufacturing method thereof |
| JP6662337B2 (en) | 2017-03-27 | 2020-03-11 | 信越化学工業株式会社 | Semiconductor device, method of manufacturing the same, and laminate |
| EP3775133A4 (en) | 2018-04-03 | 2021-12-15 | Novaflux, Inc. | Cleaning composition with superabsorbent polymer |
| CA3156824A1 (en) | 2019-10-03 | 2021-04-08 | Novaflux Inc. | Oral cavity cleaning composition, method, and apparatus |
| EP3825375A1 (en) | 2019-11-20 | 2021-05-26 | Covestro Deutschland AG | Wet bonding of storage stable 1k spray adhesives based on polychloroprene |
| WO2022212913A1 (en) | 2021-04-01 | 2022-10-06 | Novaflux Inc. | Oral cavity cleaning composition, method, and apparatus |
| US20220412010A1 (en) | 2021-06-09 | 2022-12-29 | Soane Materials Llc | Articles of manufacture comprising nanocellulose elements |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3023104A (en) * | 1960-07-05 | 1962-02-27 | American Viscose Corp | Food compositions incorporating cellulose crystallite aggregates |
| US3067037A (en) * | 1960-12-02 | 1962-12-04 | American Viscose Corp | Foamable products containing disintegrated cellulose crystallite aggregates |
| NL7512017A (en) * | 1975-10-13 | 1977-04-15 | Claasen Antonius Bernardus | METHOD OF PACKAGING FOODS. |
| US4143163A (en) * | 1976-06-30 | 1979-03-06 | Maxfibe, Inc. | Coated fibrous cellulose product and process |
| US4299856A (en) * | 1980-01-09 | 1981-11-10 | Wm. B. Reily & Company, Inc. | Method for preparing a suspension salad dressing or juice product |
-
1980
- 1980-10-31 US US06/202,740 patent/US4378381A/en not_active Expired - Lifetime
-
1981
- 1981-09-23 FI FI812964A patent/FI68529C/en not_active IP Right Cessation
- 1981-10-26 MX MX819723U patent/MX7152E/en unknown
- 1981-10-29 NO NO813664A patent/NO158810C/en unknown
- 1981-10-30 CA CA000389140A patent/CA1162819A/en not_active Expired
- 1981-10-30 ES ES506718A patent/ES9200009A1/en not_active Expired
- 1981-10-30 JP JP56173161A patent/JPS603855B2/en not_active Expired
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10975242B2 (en) | 2009-03-30 | 2021-04-13 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US10294371B2 (en) | 2009-03-30 | 2019-05-21 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US10982387B2 (en) | 2009-03-30 | 2021-04-20 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose suspensions |
| US10301774B2 (en) | 2009-03-30 | 2019-05-28 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose suspensions |
| US11970817B2 (en) | 2009-05-15 | 2024-04-30 | Fiberlean Technologies Limited | Paper filler composition |
| US10100464B2 (en) | 2009-05-15 | 2018-10-16 | Fiberlean Technologies Limited | Paper filler composition |
| US11732411B2 (en) | 2009-05-15 | 2023-08-22 | Fiberlean Technologies Limited | Paper filler composition |
| US8231764B2 (en) | 2009-05-15 | 2012-07-31 | Imerys Minerals, Limited | Paper filler method |
| US11377791B2 (en) | 2009-05-15 | 2022-07-05 | Fiberlean Technologies Limited | Paper filler composition |
| US11162219B2 (en) | 2009-05-15 | 2021-11-02 | Fiberlean Technologies Limited | Paper filler composition |
| US11155697B2 (en) | 2010-04-27 | 2021-10-26 | Fiberlean Technologies Limited | Process for the production of gel-based composite materials |
| US10633796B2 (en) | 2010-04-27 | 2020-04-28 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| US10100467B2 (en) | 2010-04-27 | 2018-10-16 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| US10053817B2 (en) | 2010-04-27 | 2018-08-21 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| US11655594B2 (en) | 2010-11-15 | 2023-05-23 | Fiberlean Technologies Limited | Compositions |
| US10253457B2 (en) | 2010-11-15 | 2019-04-09 | Fiberlean Technologies Limited | Compositions |
| US11136721B2 (en) | 2010-11-15 | 2021-10-05 | Fiberlean Technologies Limited | Compositions |
| US11932740B2 (en) | 2015-10-14 | 2024-03-19 | Fiberlean Technologies Limited | 3D-formable sheet material |
| US10577469B2 (en) | 2015-10-14 | 2020-03-03 | Fiberlean Technologies Limited | 3D-formable sheet material |
| US11384210B2 (en) | 2015-10-14 | 2022-07-12 | Fiberlean Technologies Limited | 3-D formable sheet material |
| US10801162B2 (en) | 2016-04-05 | 2020-10-13 | Fiberlean Technologies Limited | Paper and paperboard products |
| US11274399B2 (en) | 2016-04-05 | 2022-03-15 | Fiberlean Technologies Limited | Paper and paperboard products |
| US11732421B2 (en) | 2016-04-05 | 2023-08-22 | Fiberlean Technologies Limited | Method of making paper or board products |
| US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
| US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
| US10794006B2 (en) | 2016-04-22 | 2020-10-06 | Fiberlean Technologies Limited | Compositions comprising microfibrilated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
| US11572659B2 (en) | 2016-04-22 | 2023-02-07 | Fiberlean Technologies Limited | Compositions comprising microfibrillated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| FI68529C (en) | 1985-10-10 |
| ES9200009A1 (en) | 1992-06-01 |
| FI812964L (en) | 1982-05-01 |
| US4378381A (en) | 1983-03-29 |
| NO158810B (en) | 1988-07-25 |
| NO158810C (en) | 1988-11-02 |
| NO813664L (en) | 1982-05-03 |
| MX7152E (en) | 1987-11-13 |
| JPS57107234A (en) | 1982-07-03 |
| FI68529B (en) | 1985-06-28 |
| JPS603855B2 (en) | 1985-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1162819A (en) | Suspensions containing microfibrillated cellulose | |
| US4487634A (en) | Suspensions containing microfibrillated cellulose | |
| US4500546A (en) | Suspensions containing microfibrillated cellulose | |
| US4452722A (en) | Suspensions containing microfibrillated cellulose | |
| US4452721A (en) | Suspensions containing microfibrillated cellulose | |
| US4464287A (en) | Suspensions containing microfibrillated cellulose | |
| CA1149219A (en) | Food products containing microfibrillated cellulose | |
| CN104921047B (en) | Microcapsule mustard essence and preparation method thereof | |
| US4276312A (en) | Encapsulation of materials | |
| US4143163A (en) | Coated fibrous cellulose product and process | |
| AU654443B2 (en) | Emulsifier, emulsifying composition and powdery composition | |
| Gaonkar | Surface and interfacial activities and emulsion characteristics of some food hydrocolloids | |
| US4198400A (en) | Water-reconstitutable juice and soup compositions | |
| EP0051230B1 (en) | Suspensions containing microfibrillated cullulose, and process for their preparation | |
| US6689405B1 (en) | Fat-like agents for low calorie food compositions | |
| CA1102698A (en) | Fibrous cellulose product and process | |
| US5795614A (en) | Method of making a reduced fat emulsified dressing | |
| NO914601L (en) | FATTY VOLUME CONCENTRATOR FOR Aqueous FOODS INCLUDING MICROCrystalline CELLULOSE AND GALACTOMANANUM GUM | |
| CN102746534A (en) | Alginate matrix particles | |
| TW304868B (en) | ||
| EP0377312B1 (en) | Low oil mayonnaise | |
| US4129663A (en) | Pourable salad dressing composition | |
| DE60028880T2 (en) | Liquefied sago starch and its uses | |
| US3691281A (en) | Microcrystalline collagen,method of making same and foods,pharmaceuticals and cosmetics containing same | |
| JPH0224512B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |