US20020055585A1 - Rheology modifier for use in aqueous compositions - Google Patents
Rheology modifier for use in aqueous compositions Download PDFInfo
- Publication number
- US20020055585A1 US20020055585A1 US09/882,418 US88241801A US2002055585A1 US 20020055585 A1 US20020055585 A1 US 20020055585A1 US 88241801 A US88241801 A US 88241801A US 2002055585 A1 US2002055585 A1 US 2002055585A1
- Authority
- US
- United States
- Prior art keywords
- composition according
- water
- polymer
- composition
- dmapma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F26/10—N-Vinyl-pyrrolidone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5272—Polyesters; Polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
Definitions
- This invention relates to rheology modifiers used to adjust the rheological properties of polymeric compositions, and, more particularly, to non-continuous, vinyl lactam polymeric compositions with two-phases therein, having advantageous rheology properties in commercial applications.
- Rheology modifiers are used generally to adjust or modify the rheological properties of aqueous compositions. Such properties include, without limitation, viscosity, flow rate, stability to viscosity change over time, and the ability to suspend particles in such aqueous compositions.
- the particular type of modifier used usually depends on the particular aqueous composition to be modified and on the end-use of the modified aqueous composition.
- Examples of conventional rheology modifiers include thickeners such as cellulosic derivatives, polyvinyl alcohol, sodium polyacrylate, and other water-soluble macromolecules, and copolymeric emulsions in which monomers with acid groups have been introduced onto the main chain. Such thickeners are used widely in fiber treatment and adhesives.
- the rheological properties of concentrated dispersions are critical to many important commercial applications. Examples include coatings, inks, films, oils, paints, food additives and pharmaceuticals. Accordingly, the microscopic and macroscopic dispersion structure and the resulting flow properties of such systems are of both scientific and practical interest.
- the art has established that sub-micron particles in such systems can have a dramatic effect on the rheology of a polymeric solution or fluid.
- Several physical critical parameters have been identified as influencing its rheology, including the dispersed particle volume fraction, particle size shape and distribution, the continuous phase viscosity and the fluid flow field. By altering or adjusting these microscopic parameters, certain macroscopic phenomena such as elasticity, shear thinning, thixotropic effect and shear thickening can be modified for a particular application or to exhibit a desired property.
- Polymeric compositions of vinyl lactam monomers generally are one-phase, soluble, high viscosity materials. These compositions are useful in a variety of commercial applications such as film formers, dye transfer inhibitors, dispersants, excipients and drug delivery. Aqueous gels of these monomers can also be prepared by light covalent or associative crosslinking of polymer chains resulting in one-phase materials of high viscosity which are effective thickeners in personal care formulations, particularly hair care products.
- Niessner in U.S. Pat. Nos. 5,149,750 and 5,180,804, disclosed finely divided, water-swellable gel-like, water-swellable copolymers by polymerization of comonomers in the presence of a surfactant.
- Liu in U.S. Pat. No. 5,997,855, described a homogeneous terpolymer for hair care use, however, without a crosslinking agent.
- Blankenburg in U.S. Pat. Nos. 5,635,169 and 6,107,397, described uncrosslinked aqueous copolymer dispersions of nonionic water-soluble monomers with N-vinyl groups and hydrophobic monomers.
- Steckler in U.S. Pat. No. 3,878,175, disclosed highly absorbent spongy gel polymer materials by simultaneous copolymerization and partial crosslinking of a comonomer mixture of an alkyl acrylate and a heterocyclic N-vinyl monomer containing a carbonyl functionality in the presence of a hydrophobic liquid diluent in which the final polymer is insoluble.
- Tseng in U.S. Pat. Nos. 5,393,854 and 5,717,045, disclosed a one-phase, aqueous gel of crosslinked copolymers of vinyl pyrrolidone and dimethylaminoethyl methacrylate for use in hair care products.
- the crosslinking agent was 1-vinyl-3-(E)-ethylidene pyrrolidone.
- the gels had a Brookfield viscosity of between 60,000 and 100,000.
- a particular object of the present invention is to provide a rheology modifier which is an aqueous polymeric composition of a water-soluble polymer, and including in situ-formed, minute resinous particles dispersed therein, that, under suitable light magnification, shows the presence of two-discrete phases therein, one being the water soluble polymer and the other being water-insoluble resinous particles.
- FIG. 1 is a photomicrograph of the aqueous polymeric composition of the invention showing the presence of two discrete phases therein.
- FIG. 2 is a graphical representation of Brookfield viscosity of the invention composition vs. ⁇ the volume fraction of particles in the composition.
- a rheology modifier for use in aqueous or alcoholic compositions which includes a stable, aqueous polymeric composition which forms a clear to translucent film upon application to a substrate comprising, by weight, 5-75% of (a) a water-soluble polymer having (b) in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein, and (c) 25-95% of water.
- the polymer is polyvinylpyrrolidone (PVP), poly(vinylcaprolactam) (PVCL), a copolymer of PVP and/or PVCL, and, optionally, one or more comonomers, including comonomers such as dimethylaminopropyl(meth)acrylamide (DMAPMA) and dimethylaminoethyl(meth)acrylate (DMAEMA).
- the polymer is a vinyl lactam polymer, optionally copolymerized with a methacrylate/acrylate and/or methacrylamide/acrylamide comonomer.
- the composition includes particles having a size of ⁇ 500 ⁇ , preferably ⁇ 100 ⁇ , and optimally between >1 nm and ⁇ 500 ⁇ .
- the composition includes a substantially water-insoluble polymer which is a crosslinked or branched polymer, neutralized and/or quaternized, and/or functionalized quaternized.
- the ratio of (a):(b) is 20-95% to 5-80%, preferably 20-75% to 25-80%
- the crosslinking agent is a substantially water-insoluble compound, preferably pentaerythritol triallyl ether (PETE), or pentaerythritol tetraacrylate (PETA), preferably at least partially soluble in water, and the crosslinking agent is present in an amount of 0.02-0.5% by weight of said composition, most preferably 0.05-0.3%.
- the composition prior to modification, has a Brookfield viscosity of 1,000 to 45,000 cps, preferably 2,000 to 20,000.
- a process for making a stable, aqueous polymeric composition which includes the steps of providing a reaction mixture of a water-soluble vinyl monomer, optionally with one or more water-soluble comonomers, a predetermined amount of a crosslinking agent and water, heating the mixture, then periodically adding a predetermined amount of an initiator, and polymerizing at about 30-130° C., optionally further including the step of diluting with water during or after the polymerization.
- the crosslinking agent is present in an amount of 0.02-0.5 wt. % based on monomers present, and preferably is PETE or PETA, and the initiator is an azo initiator.
- Another feature of the invention is the provision of formulations containing the above-described composition, made by such process, and films of the composition on a substrate.
- compositions herein may be dried if desired to provide the polymeric composition as a solid, and, if desired, the water soluble polymer extracted with a solvent.
- the dried stable polymeric composition thereby includes, by weight, (a) 20% to 95% of a water-soluble polymer, and (b) 5% to 80% of in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein.
- an aqueous or alcoholic polymeric composition having two phases therein, a water-soluble polymeric phase and a discrete, water-insoluble polymer particle phase which is generated in-situ during the polymerization of the monomers.
- the polymerization is carried out in aqueous solution of a vinyl lactam monomer, such as vinyl pyrrolidone or vinyl caprolactam.
- a comonomer may be present to form a copolymer.
- Suitable comonomers include methacrylate/acrylate monomers, such as dimethylaminoethyl(meth)acrylate (DMAEMA) and/or methacrylamide/acrylamide monomers, such as dimethylaminopropylacrylamide (DMAPMA).
- DMAEMA dimethylaminoethyl(meth)acrylate
- DMAPMA dimethylaminopropylacrylamide
- This stable, aqueous polymeric composition forms a clear to translucent film upon application to a substrate and comprises, by weight, 5-75% of (a) a water-soluble polymer having (b) in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein, and (c) 25-95% of water.
- Initiator was added in 5 separate shots at 0, 30, 60, 150 and 210 minutes. 0.2 g of Vazo® 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- Example 1 The process of Example 1 was repeated using 5 separate shots of 0.3 g each of Vazo® 67 in 1.0 g of IPA. A similar polymeric composition as in Example 1.
- Example 1 The process of Example 1 was repeated using 5 separate shots of 0.4 g each of Vazo® 67 in 1 g of IPA, and 0.3 g of crosslinker. A similar polymeric composition was obtained.
- Initiator was added at 0 and 30 minutes. 0.48 9 of Vazo® 67 in 1.5 g IPA was added for each shot and two 1.0 g IPA washes were made.
- the product was a 2-phase, polymerization composition with 40 to 70% resinous particles, whose soluble fraction had a weight average molecular weight of 1,200,000 to 1,500,000.
- Initiator was added at 0, 30, 60, 150 and 210 minutes. 0.44 g of Vazo 67 in 1.3 g IPA was added for each shot and two 0.7 g IPA washes were made.
- Initiator was added at 0, 30, 60, 150 and 210 minutes.
- 0.4 g of Vazo 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- Initiator was added at 0, 30, 60, 150 and 210 minutes. 0.16 g of Vazo® 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- Example 9 The solution of Example 9 was dried on a drum dryer to a solids of >95%. The Tg of the powder was 167° C. Then it was reconstituted in water and found to provide the same waterproofing as the original solution.
- Example 11 The precipitate obtained in Example 11 in three 8-dram vials was dried, in vacuo, in a 40° C. oven overnight. The result was a thin, generally clear film upon visual observation. This material was then exposed to either methanol, diethyl ether and n-heptane. After 24 hours, methanol had re-dispersed the material. Diethyl ether and n-heptane did not appear to effect the dried material. After 14 days, all samples exhibited a similar appearance to the original 24 hour observations. The particle size on the methanol dispersed material was measured using a Microtrak UPA and found to be about 4 microns.
- the UV absorbance of the cream was enhanced by the presence of the polymeric composition of the invention therein, as compared to similar formulations without this composition, generally an increase of about 2-3 SPF numbers.
- volume fraction, ⁇ , of particles in the composition of the invention is determined by the following procedure.
- the two-phase aqueous polymeric composition is prepared as in the examples above.
- FIG. 2 shows a plot of Brookfield viscosity vs. ⁇ , the volume fraction of particles in the 2-phase polymeric composition of the invention.
- the graph shows a dramatic increase in viscosity of the solution with an increase in the volume fraction of the particles therein, indicating it is an effective rheology modifier.
- compositions of the invention may be admixed, if desired, with one or more of the following commercially available rheology modifiers:
- Acrylic polymers crosslinked acrylic polymers, alginates, associative thickeners, carrageenan, microcrystalline cellulose, carboxymethylcellulose sodium, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, guar and guar derivatives, locust bea gum, organoclays, polyethylene, polyethylene oxide, polyvinylpyrrolidone, silica, water-swellable clay, xanthan gum and pigments (inorganic).
- Coatings cementitious compounds, contrast mediums, wrinkle masking, cryoprotectants, detergents, marking Instruments, flocculation moderators, personal care formulations such as skin/hair care, including shampoo, conditioner, gels and creams, pharmaceutical, such as bioadhesives, syrups and excipients), lubricating oil additives, lubricants, adhesives and cosmetics.
Abstract
Description
- This application is a continuation-in-part of co-pending U.S. patent applications Ser. Nos. 09/663,010, filed Sep. 15, 2000, and 09/784,268, filed Feb. 15, 2001.
- 1. Field of the Invention
- This invention relates to rheology modifiers used to adjust the rheological properties of polymeric compositions, and, more particularly, to non-continuous, vinyl lactam polymeric compositions with two-phases therein, having advantageous rheology properties in commercial applications.
- 2. Description of the Prior Art
- Rheology modifiers are used generally to adjust or modify the rheological properties of aqueous compositions. Such properties include, without limitation, viscosity, flow rate, stability to viscosity change over time, and the ability to suspend particles in such aqueous compositions. The particular type of modifier used usually depends on the particular aqueous composition to be modified and on the end-use of the modified aqueous composition. Examples of conventional rheology modifiers include thickeners such as cellulosic derivatives, polyvinyl alcohol, sodium polyacrylate, and other water-soluble macromolecules, and copolymeric emulsions in which monomers with acid groups have been introduced onto the main chain. Such thickeners are used widely in fiber treatment and adhesives.
- The rheological properties of concentrated dispersions are critical to many important commercial applications. Examples include coatings, inks, films, oils, paints, food additives and pharmaceuticals. Accordingly, the microscopic and macroscopic dispersion structure and the resulting flow properties of such systems are of both scientific and practical interest. The art has established that sub-micron particles in such systems can have a dramatic effect on the rheology of a polymeric solution or fluid. Several physical critical parameters have been identified as influencing its rheology, including the dispersed particle volume fraction, particle size shape and distribution, the continuous phase viscosity and the fluid flow field. By altering or adjusting these microscopic parameters, certain macroscopic phenomena such as elasticity, shear thinning, thixotropic effect and shear thickening can be modified for a particular application or to exhibit a desired property.
- Polymeric compositions of vinyl lactam monomers generally are one-phase, soluble, high viscosity materials. These compositions are useful in a variety of commercial applications such as film formers, dye transfer inhibitors, dispersants, excipients and drug delivery. Aqueous gels of these monomers can also be prepared by light covalent or associative crosslinking of polymer chains resulting in one-phase materials of high viscosity which are effective thickeners in personal care formulations, particularly hair care products.
- The prior art in this field is represented by the following patents.
- Niessner, in U.S. Pat. Nos. 5,149,750 and 5,180,804, disclosed finely divided, water-swellable gel-like, water-swellable copolymers by polymerization of comonomers in the presence of a surfactant.
- Liu, in U.S. Pat. No. 5,997,855, described a homogeneous terpolymer for hair care use, however, without a crosslinking agent.
- Kopolow, in U.S. Pat. No 5,130,121, described personal care compositions containing a stabilized cosmetically-active product obtained by in situ polymerization of a water-soluble vinyl monomer in the presence of discrete microdroplets of a cosmetically-active oil in water.
- Blankenburg, in U.S. Pat. Nos. 5,635,169 and 6,107,397, described uncrosslinked aqueous copolymer dispersions of nonionic water-soluble monomers with N-vinyl groups and hydrophobic monomers.
- Steckler, in U.S. Pat. No. 3,878,175, disclosed highly absorbent spongy gel polymer materials by simultaneous copolymerization and partial crosslinking of a comonomer mixture of an alkyl acrylate and a heterocyclic N-vinyl monomer containing a carbonyl functionality in the presence of a hydrophobic liquid diluent in which the final polymer is insoluble.
- Markus, in U.S. Pat. No. 2,810,716, described a process for making swellable resins by copolymerizing monomers in the presence of a water-soluble non-redox divalent-ion containing salt.
- Tseng, in U.S. Pat. Nos. 5,393,854 and 5,717,045, disclosed a one-phase, aqueous gel of crosslinked copolymers of vinyl pyrrolidone and dimethylaminoethyl methacrylate for use in hair care products. The crosslinking agent was 1-vinyl-3-(E)-ethylidene pyrrolidone. The gels had a Brookfield viscosity of between 60,000 and 100,000.
- These references illustrate the desire of the art to produce a continuous network of polymer molecules, or microgel, which is a one-phase system, and of high viscosity.
- Accordingly, it is an object of this invention to provide a new and improved rheology modifier composition to adjust the rheological properties of commercial products.
- A particular object of the present invention is to provide a rheology modifier which is an aqueous polymeric composition of a water-soluble polymer, and including in situ-formed, minute resinous particles dispersed therein, that, under suitable light magnification, shows the presence of two-discrete phases therein, one being the water soluble polymer and the other being water-insoluble resinous particles.
- FIG. 1 is a photomicrograph of the aqueous polymeric composition of the invention showing the presence of two discrete phases therein.
- FIG. 2 is a graphical representation of Brookfield viscosity of the invention composition vs. Φ the volume fraction of particles in the composition.
- What is described herein is a rheology modifier for use in aqueous or alcoholic compositions which includes a stable, aqueous polymeric composition which forms a clear to translucent film upon application to a substrate comprising, by weight, 5-75% of (a) a water-soluble polymer having (b) in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein, and (c) 25-95% of water.
- Preferably, the polymer is polyvinylpyrrolidone (PVP), poly(vinylcaprolactam) (PVCL), a copolymer of PVP and/or PVCL, and, optionally, one or more comonomers, including comonomers such as dimethylaminopropyl(meth)acrylamide (DMAPMA) and dimethylaminoethyl(meth)acrylate (DMAEMA). Preferably, the polymer is a vinyl lactam polymer, optionally copolymerized with a methacrylate/acrylate and/or methacrylamide/acrylamide comonomer.
- In this invention, the composition includes particles having a size of <500μ, preferably <100μ, and optimally between >1 nm and <500 μ.
- Suitably, the composition includes a substantially water-insoluble polymer which is a crosslinked or branched polymer, neutralized and/or quaternized, and/or functionalized quaternized. The ratio of (a):(b) is 20-95% to 5-80%, preferably 20-75% to 25-80%, and the crosslinking agent is a substantially water-insoluble compound, preferably pentaerythritol triallyl ether (PETE), or pentaerythritol tetraacrylate (PETA), preferably at least partially soluble in water, and the crosslinking agent is present in an amount of 0.02-0.5% by weight of said composition, most preferably 0.05-0.3%.
- In this invention, the composition, prior to modification, has a Brookfield viscosity of 1,000 to 45,000 cps, preferably 2,000 to 20,000.
- As a feature of the invention, there is provided herein a process for making a stable, aqueous polymeric composition which includes the steps of providing a reaction mixture of a water-soluble vinyl monomer, optionally with one or more water-soluble comonomers, a predetermined amount of a crosslinking agent and water, heating the mixture, then periodically adding a predetermined amount of an initiator, and polymerizing at about 30-130° C., optionally further including the step of diluting with water during or after the polymerization.
- Suitably, the crosslinking agent is present in an amount of 0.02-0.5 wt. % based on monomers present, and preferably is PETE or PETA, and the initiator is an azo initiator.
- Another feature of the invention is the provision of formulations containing the above-described composition, made by such process, and films of the composition on a substrate.
- The compositions herein may be dried if desired to provide the polymeric composition as a solid, and, if desired, the water soluble polymer extracted with a solvent. The dried stable polymeric composition thereby includes, by weight, (a) 20% to 95% of a water-soluble polymer, and (b) 5% to 80% of in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein.
- In accordance with this invention, there is provided herein an aqueous or alcoholic polymeric composition having two phases therein, a water-soluble polymeric phase and a discrete, water-insoluble polymer particle phase which is generated in-situ during the polymerization of the monomers. In the preferred forms of the invention, the polymerization is carried out in aqueous solution of a vinyl lactam monomer, such as vinyl pyrrolidone or vinyl caprolactam. Optionally a comonomer may be present to form a copolymer. Suitable comonomers include methacrylate/acrylate monomers, such as dimethylaminoethyl(meth)acrylate (DMAEMA) and/or methacrylamide/acrylamide monomers, such as dimethylaminopropylacrylamide (DMAPMA).
- This stable, aqueous polymeric composition forms a clear to translucent film upon application to a substrate and comprises, by weight, 5-75% of (a) a water-soluble polymer having (b) in situ-formed, substantially water-insoluble resinous particles of said polymer substantially uniformly dispersed therein, and (c) 25-95% of water.
- The invention will now be illustrated in more detail by reference to the following examples.
- 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines was added 87.15 g of vinyl pyrrolidone monomer, (VP), 697 g DI water and 0.275 g (0.25% based upon monomer) of pentaerythritol triallyl ether (PETE) as crosslinker.
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. In a separate container weighed out 22.69 g of dimethylaminopropyl methacrylamide (DMAPMA).
- 5. With kettle temperature at 70° C., stop subsurface nitrogen purge and purged above surface. Precharged 1.1 g DMAPMA from container.
- 6. Started continuous addition of the remaining DMAPMA (21.86 g) over 210 minutes at a flow rate 0.11 ml/minute. Once the DMAPMA flow started, initiated with first shot of Vazo® 67 in isopropanol (IPA) (Time 0).
- 7. Initiator was added in 5 separate shots at 0, 30, 60, 150 and 210 minutes. 0.2 g of Vazo® 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- 8. Held the reaction temperature overnight at 70° C.
- 9. When residual VP level was below 400 ppm, diluted the batch with 266.7 g of DI water.
- 10. Cooled batch to 50° C.
- 11. Neutralized the batch with conc. HCI to pH of 6.2-6.8 at 50° C. Room temperature pH was 6.8-7.2. Required approximately 14 g of conc. HCl.
- 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
- 13. A two-phase, aqueous polymeric composition as shown in the Figure was obtained.
- The process of Example 1 was repeated using 5 separate shots of 0.3 g each of Vazo® 67 in 1.0 g of IPA. A similar polymeric composition as in Example 1.
- The process of Example 1 was repeated using 5 separate shots of 0.4 g each of Vazo® 67 in 1 g of IPA, and 0.3 g of crosslinker. A similar polymeric composition was obtained.
- Results
- The results of these tests, shown in Table 1 below establish that the 2-phase polymeric composition of the invention exhibits advantageous viscosity properties.
TABLE 1 Results The results of these tests, shown in Table 1 below establish that the 2-phase polymeric composition of the invention exhibits advantageous viscosity properties. Ex. Crosslinker Initiator Viscosity No. (%) (g/shot) (cps) 1 0.25 0.2 28,200 2 0.25 0.3 13,000 3 0.3 0.4 12,800 - 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines was added 131.81 g of VP, 756 g DI water and 0.197 g PETE (0.15% based upon monomer).
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. Initiator was added at 0 and 30 minutes. 0.48 9 of Vazo® 67 in 1.5 g IPA was added for each shot and two 1.0 g IPA washes were made.
- 5. Held the reaction temperature overnight at 70° C.
- 6. When residual VP was below 400 ppm, diluted the batch with 320.04 g DI water.
- 7. Cooled batch to 50° C.
- 8. Added 0.15 to 0.19% BTC 50 NF as preservative.
- 9. The product was a 2-phase, polymerization composition with 40 to 70% resinous particles, whose soluble fraction had a weight average molecular weight of 1,200,000 to 1,500,000.
- 1. To a 2-l, kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines was added 96.00 g of VP, 702.7 g DI water and 0.36 g PETE (0.30% based upon monomer).
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. In a separate container weighed out 24.0 g DMAPMA and 74.7 g DI water. Purged with nitrogen.
- 5. When kettle temperature was at 70° C., stopped subsurface nitrogen purge and purged above surface. Precharged 4.94 g DMAPMA/water from container.
- 6. Started continuous addition of the remaining DMAPMA/water (93.76 9) over 210 minutes. Flow rate 0.48 ml/minute. Once DMAPMA/water flow started, initiated with first shot of Vazo® 67 in IPA (Time 0).
- 7. Initiator was added at 0, 30, 60, 150 and 210 minutes. 0.44 g of Vazo 67 in 1.3 g IPA was added for each shot and two 0.7 g IPA washes were made.
- 8. Held the reaction temperature overnight at 70° C.
- 9. When residual VP was below 400 ppm, diluted the batch with 297.5 g DI water.
- 10. Cooled batch to 50° C.
- 11. Neutralized the batch with 19.56 g diethyl sulfate (DES) over 60 minutes; at flow rate of 0.28 g/ml.
- 12. Stirred for 2 hours.
- 13. Product.
- 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines was added 87.15 g of HPVP, 630 g DI water and 0.33 g PETE (0.30% based upon monomer).
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. Weighed out 22.69 g DMAPMA and 67 g DI water. Purged with nitrogen.
- 5. When kettle temperature was at 70° C., stopped subsurface nitrogen purge and purged above surface. Precharged 4.23 g DMAPMA/water from container.
- 6. Started a continuous addition of the remaining DMAPMA/water (85.46 g) over 210 minutes. Flow rate 0.40 ml/minute. Once DMAPMA/water flow started, initiated with first shot of Vazo® 67 in IPA (Time 0).
- 7. Initiator was added at 0, 30, 60, 150 and 210 minutes. 0.4 g of Vazo 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- 8. Held the reaction temperature overnight at 70° C.
- 9. When residual VP was below 400 ppm, diluted the batch with 266.7 g DI water.
- 10. Cooled batch to 50° C.
- 11. Neutralized the batch with benzophenone-4, 5 to 99 mole % (2 to 38.6 g respectively). Continued neutralization with sulfuric acid to pH of 6.8 to 7.8 at 50° C.
- 12. Cooled and discharged.
- 13. Product.
- 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines was added 104.58 g of HPVP, 756 g DI water and 0.59 g pentaerythritol tetraacrylate (0.30% based upon monomer).
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. In a separate container, weighed out 27.23 g DMAPMA and 80.4 g DI water. Purged with nitrogen.
- 5. When kettle temperature was at 70° C., stopped subsurface nitrogen purge and purged above surface. Precharged 5.38 g DMAPMA/water from container.
- 6. Started continuous addition of the remaining DMAPMA/water (102.25 g) over 210 minutes. Flow rate 0.52 ml/minute. Once DMAPMA/water flow started, initiated with first shot of Vazo®67 in IPA (Time 0).
- 7. Initiator was added at 0, 30, 60, 150 and 210 minutes. 0.16 g of Vazo® 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- 8. Held the reaction temperature overnight at 70° C.
- 9. When VP was below 400 ppm, diluted the batch with 266.7 g DI water.
- 10. Cooled batch to 50° C.
- 11. Neutralized the batch with conc. sulfuric acid to pH of 6.6 to 7.8 at 25° C.
- 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
- 13. Product.
- 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator and feed lines was added 130.7 g vinyl caprolactam, 128.7 g DI water, 171.6 g ethanol, and 0.88 g PETE (0.6% based upon monomer).
- 2. Purged with nitrogen for 30 minutes.
- 3. Heated to 70° C.
- 4. In a syringe pump was added 32.98 g DMAPMA and 171.6 g DI water.
- 5. At 70° C. added 40 ml of the DMAPMA/water mixture to the kettle and added the first shot of initiator, 0.075 g Vazo® 67 in 0.75 g ethanol. Washed with 0.75 g ethanol.
- 6. Started addition of the remaining DMAPMAlwater mixture (Time 0) from the syringe pump at a rate of 0.34 ml/min, added over 480 minutes.
- 7. At time 60, 120, 180, 240, 300, 360, 420 and 480 minutes added a shot of Vazo® 67, 0.075 g in 0.75 g ethanol. Washed with 0.75 g ethanol.
- 8. Held at 70° C. overnight.
- 9. Cooled reaction to 30° C. and added 415.6 g DI water.
- 10. Mixed until uniform and then added 544.4 g DI water and 15.38 g hydrochloric acid.
- 11. Mixed for 2 hours. Adjusted pH to 6.6 to 7.8 with hydrochloric acid, if necessary.
- 12. Added 0.15 to 0.19% BTC-50 NF as preservative.
- 13. Product.
- 1. To a 2-l kettle fitted with a nitrogen inlet tube, thermocouple, agitator, and feed lines is added 87.15 g of HPVP, 630 g DI water and 0.33 g (0.30% based upon monomer) pentaerythritol triallyl ether.
- 2. Purged with nitrogen subsurface for 30 minutes.
- 3. Heated to 70° C.
- 4. In a separate container, weighed out 22.69 g DMAEMA and 67 g DI water. Purged with nitrogen.
- 5. When kettle temperature was at 70° C., stopped subsurface nitrogen purge and purged above surface. Precharged 4.23 g DMAEMA/water from container.
- 6. Started continuous addition of the remaining DMAEMA/water (85.46 g) over 210 minutes. Flow rate 0.40 ml/minute. Once DMAEMA/water flow started initiator addition with first shot of Vazo 67 in IPA (Time 0).
- 7. Initiator was added at 0, 30, 60, 150, and 210 minutes. 0.4 g of Vazo 67 in 1.0 g IPA was added for each shot and two 0.5 g IPA washes were made.
- 8. Held the reaction temperature overnight at 70° C.
- 9. When VP was below 400 ppm, diluted the batch with 266.7 g DI water.
- 10. Cooled batch to 50° C.
- 11. Neutralized the batch with conc. HCl to pH of 6.2 to 6.8 at 50° C. Room temperature pH will be 6.8 to 7.2. Required approximately 14 g of conc. HCl.
- 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
- The solution of Example 9 was dried on a drum dryer to a solids of >95%. The Tg of the powder was 167° C. Then it was reconstituted in water and found to provide the same waterproofing as the original solution.
- 95.2 g of approximately 10% solids polyvinylpyrrolidone/PETE was diluted in 2-liters of distilled water and stirred until thoroughly mixed. A second solution was prepared by taking 500 ml of the first solution and diluting in 2-liters of distilled water. Stirred until thoroughly mixed. Poured the second solution into four 16 oz. jars and centrifuged at ˜2250 rpm for about 90 minutes. A white precipitate was observed on the bottom of each 16 oz. jar. The precipitate was removed, via pipette, and placed into four 8-dram vials, respectively. The four 8-dram vials were centrifuged at ˜3000 rpm for 60 minutes. The particle size on the precipitate was measured using a Microtrak UPA and found to be about 4 nm.
- The precipitate obtained in Example 11 in three 8-dram vials was dried, in vacuo, in a 40° C. oven overnight. The result was a thin, generally clear film upon visual observation. This material was then exposed to either methanol, diethyl ether and n-heptane. After 24 hours, methanol had re-dispersed the material. Diethyl ether and n-heptane did not appear to effect the dried material. After 14 days, all samples exhibited a similar appearance to the original 24 hour observations. The particle size on the methanol dispersed material was measured using a Microtrak UPA and found to be about 4 microns.
- An aqueous solution of 119.64 g of vinyl pyrrolidone monomer, 0.36 g pentaerythritol trially ether (PETE), 0.6 g of Vazo 67, and 480 g water was charged to a kettle and purged with nitrogen. The reaction mixture was then heated to 65° C. while stirring at 650 rpm. Within 25 minutes the product became so viscous that the reaction was stopped. The product was a continuous gel only.
- An aqueous solution of 119.64 g of vinyl pyrrolidone monomer, 0.36 g pentaerythritol triallyl ether (PETE), 0.23 g of Vazo 67, and 480 g water was charged to a kettle and purged with nitrogen. The reaction mixture was then heated to 65° C. while stirring at 650 rpm. After 2 hours at 65° C., the reaction was heated to 95° C. for 1 hour. The product was a viscous solution only.
-
Ingredient Parts by Weight VP/DMAPMA/PETE (Ex. 1) 2.00 PV-OH (88% hydrolyzed) 8.00 Sequrez ® 755 (glyoxyl) 0.75 Water 89.25 100.00 -
Ingredient Parts by Weight VP/DMAPMA/PETE/BENZO-4 (Ex. 6) 2.00 PV-OH (88% hydrolyzed) 8.00 Sequrez ® 755 (glyoxyl) 0.75 Water 89.25 100.00 -
Ingredients Wt. % PHASE A Deionized water 15.69 Disodium EDTA 0.10 Acrylates/Steareth-20 Methacrylate Copolymer 1.00 Acrylates Copolymer 1.00 Hexylene Glycol 1.00 Glyceryl Polymethacrylate and Propylene 0.50 Glycol and PVM/MA Copolymer VP/DMAPMNPETE/Benzophenone-4 50.00 Copolymer (Ex. 6) PHASE B Glyceryl Stearate and Behenyl Alcohol and 5.00 Palmitic and Stearic Acid and Lecithin and Lauryl and Myristyl Alcohol and Cetyl Alcohol Oxybenzone 3.00 Octyl Salicylate 3.00 Tridecyl Neopentanoate 2.00 Octyl Palmitate 6.00 Myristyl Myristate 1.00 PHASE C Deionized Water 5.00 NaOH, 10% Solution 1.26 PHASE D Diazolidinyl Urea and Iodopropynyl Butylcarbamate 0.50 Methyl Paraben 0.20 Hexylene Glycol 1.00 PHASE E Fragrance 0.25 - Procedure
- 1. Combine ingredients in Phase A and heat to 70-75° C.
- 2. Combine ingredients in Phase B and mix and heat to 70-75° C.
- 3. Add Phase B to Phase A under homogenization.
- 4. Add Phase C to the batch under homogenization and homogenize for 15 minutes.
- 5. Switch to propeller mixing and cool to 45° C.
- 6. Add Phase D at 45° C. Add Phase E at 40° C. QS with water.
- The UV absorbance of the cream was enhanced by the presence of the polymeric composition of the invention therein, as compared to similar formulations without this composition, generally an increase of about 2-3 SPF numbers.
- Clear Styling/Conditioning Gel
Ingredients Wt. % Deionized Water 74.60 Ethanol (190 Proof) 5.00 VP/DMAPMA/PETE Copolymer (Ex. 1) 20.00 Dimethicone Copolyol 0.10 Caprylyl Pyrrolidone 0.10 Panthenol 0.10 2,4-Dihydroxy-N-(3-hydroxypropyl)- 3,3-Dimethyl Butanamide Diazolidinyl Urea and Iodopropynyl Butylcarbamate 0.10 Perfume qs - Manufacturing Procedure
- 1. In a vessel, add ethanol to water and stir until homogeneous.
- 2. Next, add VP/DMAPMA/PETE copolymer to the mixture and stir well until homogeneous.
- 3. Add dimethicone copolyol, panthenol and caprylyl pyrrolidone to the mixture and stir well after each addition until homogeneous.
- 4. Next, add diazolidinyl urea and iodopropynyl and butylcarbamate and stir well until homogeneous.
-
Ingredients Wt. % Deionized Water 81.73 Emulsifying Wax NF 4.00 Cetearyl Alcohol and Ceteareth-20 2.00 Propylene Glycol 1.00 VP/DMAPMA/PETE Neutralized with 10.00 Benzophenone-4 (Ex. 6) Glycerin 99.7% 0.50 Lauryl Pyrrolidone 0.25 Citric Acid FCC, USP, Anhydrous 0.02 Propylene Glycol and Diazolidinyl Urea and 0.50 Iodopropynyl butylcarbamate - Manufacturing Procedure
- 1. Heat the water, propylene glycol, glycerin, and citric acid to 80-85° C. using continuous addition with a propeller stir rod.
- 2. Add the VP/DMAPMA/PETE neutralized with Benzophenone-4 and stir to homogeneous.
- 3. Combine in a separate vessel lauryl pyrrolidone, emulsifying wax NF, cetearyl alcohol and ceteareth-20, heating to 80-85° C. mixing until homogeneous.
- 4. Add, product step 3, to the water phase with good agitation. Mix with continuous agitation for 10-20 minutes or longer. Maintain temperature at 80-85° C. during this step.
- 5. Begin cooling with continuous agitation until approximately 45° C. Do not force cool.
- 6. Switch to a paddle mixing rod. Continue slow agitation and cool until a temperature of 30-35° C. is reached. At 30-35° C. add the propylene glycol and diazolidinyl urea and iodopropynyl butylcarbamate and continue mixing until 25° C. is reached.
- A 5% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric acid (Ex. 1) was thoroughly mixed with a 5% aqueous polymer solution of polyvinyl alcohol (PVOH). The Brookfield viscosity of each solution, and mixtures thereof, was determined to demonstrate the effect of rheology modification by the composition of the invention. Under visual inspection, the solutions appeared to be homogeneous. The results are presented in Table 2 below.
TABLE 2 Test Solution Brookfield Viscosity (cps) Percent Scale 5% LV, 62, 10 RPM 1470 48.9 VP/DMAPMA/ PETE/Sulfuric Acid in Water (A) 5% PVOH in LV, 00, 30 RPM 5.2 26.0 water (B) 50/50 (w/w) LV, 62, 20 RPM 464 27.6 mixture of A and B - A 5% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric acid (Ex. 1) was thoroughly mixed with a 5% aqueous polymer solution of poly-2-ethyl-2-oxazoline (PEO). The Brookfield viscosity of each solution, and mixtures thereof, was performed to demonstrate the effect of rheology modification. Under visual inspection, the solution appeared to be homogeneous. The results are presented in Table 3 below.
TABLE 3 Test Solution Brookfield Viscosity (cps) Percent Scale 5% VP/DMAPMA/ LV, 62, 10 RPM 1470 48.9 PETE/Sulfuric Acid in Water 5% PEO in water LV, 00, 30 RPM 4.0 21.3 50/50 (w/w) mixture LV, 62, 20 RPM 339 22.6 - A 1% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric acid (Ex. 1) was thoroughly mixed with a 1% aqueous polymer solution of Kelcoloid HVF Algin (HVF), an alginate. The Brookfield viscosity of each solution and their combination was performed to demonstrate the effect of rheology modification. Under visual inspection, the solution exhibited turbidity. The results are presented in Table 4 below.
TABLE 4 Test Solution Brookfield Viscosity (cps) Percent Scale 1% VP/DMAPMA/ LV, 00, 6 RPM 60 58.8 PETE/Sulfuric Acid in Water 1% HVF in water LV, 62, 30 RPM 709 71.4 50/50 (w/w) mixture LV, 61, 30 RPM 20 10.4 - A 1% aqueous polymer solution of PVP/PETE (Ex. 4) was thoroughly mixed with a 1% aqueous polymer solution of Kelcoloid HVF Algin (HVF). The Brookfield viscosity of each solution and their combination was performed to demonstrate the effect of rheology modification. Under visual inspection, the solution appeared to be homogeneous. The results are presented in Table 5 below.
TABLE 5 Test Solution Brookfield Viscosity (cps) Percent Scale 1% PVP/PETE in LV, 00, 12 RPM 12.4 24.8 Water 1% HVF in water LV, 62, 30 RPM 709 71.4 50/50 (w/w) mixture LV, 61, 12 RPM 129.5 26.1 - The volume fraction, Φ, of particles in the composition of the invention is determined by the following procedure.
- (1) The two-phase aqueous polymeric composition is prepared as in the examples above.
- (2) The known amount of the composition is passed through a resin bed to remove insoluble particles.
- (3) A water soluble solution remains.
- (4) The solution is subjected to light to determine its differential Refractive Index.
- (5) The amount of soluble polymer which passed through the resin bed is determined.
- (6) Φ=1; (#5/#2).
- FIG. 2 shows a plot of Brookfield viscosity vs. Φ, the volume fraction of particles in the 2-phase polymeric composition of the invention. The graph shows a dramatic increase in viscosity of the solution with an increase in the volume fraction of the particles therein, indicating it is an effective rheology modifier.
- The compositions of the invention may be admixed, if desired, with one or more of the following commercially available rheology modifiers:
- Acrylic polymers, crosslinked acrylic polymers, alginates, associative thickeners, carrageenan, microcrystalline cellulose, carboxymethylcellulose sodium, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, guar and guar derivatives, locust bea gum, organoclays, polyethylene, polyethylene oxide, polyvinylpyrrolidone, silica, water-swellable clay, xanthan gum and pigments (inorganic).
- Product applications of the rheology modifier of the invention include the following:
- Coatings, cementitious compounds, contrast mediums, wrinkle masking, cryoprotectants, detergents, marking Instruments, flocculation moderators, personal care formulations such as skin/hair care, including shampoo, conditioner, gels and creams, pharmaceutical, such as bioadhesives, syrups and excipients), lubricating oil additives, lubricants, adhesives and cosmetics.
- While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which:
Claims (23)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/882,418 US6458888B1 (en) | 2000-09-15 | 2001-06-15 | Rheology modifier for use in aqueous compositions |
KR1020037003705A KR100794088B1 (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
CA002422098A CA2422098C (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
JP2002526968A JP5384778B2 (en) | 2000-09-15 | 2001-08-23 | Polymer composition |
AU8524801A AU8524801A (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
DE60129571T DE60129571D1 (en) | 2000-09-15 | 2001-08-23 | POLYMER COMPOSITION |
MXPA03001943 MX238220B (en) | 2000-09-15 | 2001-08-23 | Polymeric composition. |
AT01964390T ATE368067T1 (en) | 2000-09-15 | 2001-08-23 | POLYMER COMPOSITION |
CNB018157599A CN1285652C (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
EP01964390A EP1317502B1 (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
PCT/US2001/026417 WO2002022722A1 (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
BRPI0113853-7A BR0113853B1 (en) | 2000-09-15 | 2001-08-23 | stable stable and dry aqueous polymeric composition, formulation, film, process for making the stable aqueous polymeric composition and process for making a water resistant polymeric coating or a strongly swellable polymeric gel. |
ES01964390T ES2291343T3 (en) | 2000-09-15 | 2001-08-23 | POLYMER COMPOSITIONS. |
AU2001285248A AU2001285248B2 (en) | 2000-09-15 | 2001-08-23 | Polymeric composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/663,010 US6620521B1 (en) | 2000-09-15 | 2000-09-15 | Water-resistant color inkjet receptive films |
US09/784,268 US6548597B2 (en) | 2000-09-15 | 2001-02-15 | Polymeric composition |
US09/882,418 US6458888B1 (en) | 2000-09-15 | 2001-06-15 | Rheology modifier for use in aqueous compositions |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/663,010 Continuation-In-Part US6620521B1 (en) | 2000-09-15 | 2000-09-15 | Water-resistant color inkjet receptive films |
US09/784,268 Continuation-In-Part US6548597B2 (en) | 2000-09-15 | 2001-02-15 | Polymeric composition |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020055585A1 true US20020055585A1 (en) | 2002-05-09 |
US6458888B1 US6458888B1 (en) | 2002-10-01 |
Family
ID=46277751
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/882,418 Expired - Lifetime US6458888B1 (en) | 2000-09-15 | 2001-06-15 | Rheology modifier for use in aqueous compositions |
Country Status (1)
Country | Link |
---|---|
US (1) | US6458888B1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060286384A1 (en) * | 2005-06-17 | 2006-12-21 | Crawford Emmett D | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
US20130004667A1 (en) * | 2010-01-11 | 2013-01-03 | Isp Investments Inc. | Compositions comprising a reactive monomer and with a urea or urethane functional group |
US10202341B2 (en) | 2010-01-11 | 2019-02-12 | Isp Investments Llc | Compositions comprising a reactive monomer and with a urea or urethane functional group |
EP3126151B1 (en) | 2014-03-31 | 2020-04-29 | Hewlett-Packard Development Company, L.P. | Printable recording media |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7108860B2 (en) * | 2002-06-06 | 2006-09-19 | Playtex Products, Inc. | Sunscreen compositions |
EP2782337A3 (en) * | 2002-10-15 | 2014-11-26 | Verance Corporation | Media monitoring, management and information system |
WO2006042064A2 (en) * | 2004-10-11 | 2006-04-20 | Hagquist James Alroy E | Composition inhibiting the expansion of fire, suppressing existing fire, and methods of manufacture and use thereof |
US7854754B2 (en) * | 2006-02-22 | 2010-12-21 | Zeltiq Aesthetics, Inc. | Cooling device for removing heat from subcutaneous lipid-rich cells |
US9132031B2 (en) | 2006-09-26 | 2015-09-15 | Zeltiq Aesthetics, Inc. | Cooling device having a plurality of controllable cooling elements to provide a predetermined cooling profile |
US8192474B2 (en) | 2006-09-26 | 2012-06-05 | Zeltiq Aesthetics, Inc. | Tissue treatment methods |
US20080287839A1 (en) | 2007-05-18 | 2008-11-20 | Juniper Medical, Inc. | Method of enhanced removal of heat from subcutaneous lipid-rich cells and treatment apparatus having an actuator |
US8523927B2 (en) | 2007-07-13 | 2013-09-03 | Zeltiq Aesthetics, Inc. | System for treating lipid-rich regions |
WO2009026471A1 (en) | 2007-08-21 | 2009-02-26 | Zeltiq Aesthetics, Inc. | Monitoring the cooling of subcutaneous lipid-rich cells, such as the cooling of adipose tissue |
US8603073B2 (en) | 2008-12-17 | 2013-12-10 | Zeltiq Aesthetics, Inc. | Systems and methods with interrupt/resume capabilities for treating subcutaneous lipid-rich cells |
EP4066797A1 (en) | 2009-04-30 | 2022-10-05 | Zeltiq Aesthetics, Inc. | Device for removing heat from subcutaneous lipid-rich cells |
WO2010144392A1 (en) | 2009-06-08 | 2010-12-16 | Isp Investments Inc. | The manipulation of cloud point for two-phase, aqueous polymeric systems |
WO2011091293A1 (en) * | 2010-01-21 | 2011-07-28 | Zeltiq Aesthetics, Inc. | Compositions for use with a system for improved cooling of subcutaneous lipid-rich tissue |
MX2012008660A (en) | 2010-01-25 | 2013-02-26 | Zeltiq Aesthetics Inc | Home-use applicators for non-invasively removing heat from subcutaneous lipid-rich cells via phase change coolants, and associated devices, systems and methods. |
US8676338B2 (en) | 2010-07-20 | 2014-03-18 | Zeltiq Aesthetics, Inc. | Combined modality treatment systems, methods and apparatus for body contouring applications |
WO2012103242A1 (en) | 2011-01-25 | 2012-08-02 | Zeltiq Aesthetics, Inc. | Devices, application systems and methods with localized heat flux zones for removing heat from subcutaneous lipid-rich cells |
US9545523B2 (en) | 2013-03-14 | 2017-01-17 | Zeltiq Aesthetics, Inc. | Multi-modality treatment systems, methods and apparatus for altering subcutaneous lipid-rich tissue |
US9844460B2 (en) | 2013-03-14 | 2017-12-19 | Zeltiq Aesthetics, Inc. | Treatment systems with fluid mixing systems and fluid-cooled applicators and methods of using the same |
WO2015117032A1 (en) | 2014-01-31 | 2015-08-06 | Zeltiq Aesthestic, Inc. | Treatment systems for treating glands by cooling |
US10675176B1 (en) | 2014-03-19 | 2020-06-09 | Zeltiq Aesthetics, Inc. | Treatment systems, devices, and methods for cooling targeted tissue |
USD777338S1 (en) | 2014-03-20 | 2017-01-24 | Zeltiq Aesthetics, Inc. | Cryotherapy applicator for cooling tissue |
US10952891B1 (en) | 2014-05-13 | 2021-03-23 | Zeltiq Aesthetics, Inc. | Treatment systems with adjustable gap applicators and methods for cooling tissue |
US10568759B2 (en) | 2014-08-19 | 2020-02-25 | Zeltiq Aesthetics, Inc. | Treatment systems, small volume applicators, and methods for treating submental tissue |
US10935174B2 (en) | 2014-08-19 | 2021-03-02 | Zeltiq Aesthetics, Inc. | Stress relief couplings for cryotherapy apparatuses |
ES2892598T3 (en) | 2015-10-19 | 2022-02-04 | Zeltiq Aesthetics Inc | Vascular treatment methods to cool vascular structures |
US10524956B2 (en) | 2016-01-07 | 2020-01-07 | Zeltiq Aesthetics, Inc. | Temperature-dependent adhesion between applicator and skin during cooling of tissue |
US10765552B2 (en) | 2016-02-18 | 2020-09-08 | Zeltiq Aesthetics, Inc. | Cooling cup applicators with contoured heads and liner assemblies |
US11382790B2 (en) | 2016-05-10 | 2022-07-12 | Zeltiq Aesthetics, Inc. | Skin freezing systems for treating acne and skin conditions |
US10555831B2 (en) | 2016-05-10 | 2020-02-11 | Zeltiq Aesthetics, Inc. | Hydrogel substances and methods of cryotherapy |
US10682297B2 (en) | 2016-05-10 | 2020-06-16 | Zeltiq Aesthetics, Inc. | Liposomes, emulsions, and methods for cryotherapy |
US11076879B2 (en) | 2017-04-26 | 2021-08-03 | Zeltiq Aesthetics, Inc. | Shallow surface cryotherapy applicators and related technology |
CN112789013A (en) | 2018-07-31 | 2021-05-11 | 斯尔替克美学股份有限公司 | Method, device and system for improving skin |
CN113039252A (en) | 2018-09-13 | 2021-06-25 | 艾利丹尼森公司 | Universal printable topcoat for graphics |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5997855A (en) * | 1994-12-28 | 1999-12-07 | Isp Investments Inc. | Personal care composition containing a clear homogeneous polymer of an N-vinyl lactam |
-
2001
- 2001-06-15 US US09/882,418 patent/US6458888B1/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060286384A1 (en) * | 2005-06-17 | 2006-12-21 | Crawford Emmett D | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
US20130004667A1 (en) * | 2010-01-11 | 2013-01-03 | Isp Investments Inc. | Compositions comprising a reactive monomer and with a urea or urethane functional group |
US10202341B2 (en) | 2010-01-11 | 2019-02-12 | Isp Investments Llc | Compositions comprising a reactive monomer and with a urea or urethane functional group |
EP3126151B1 (en) | 2014-03-31 | 2020-04-29 | Hewlett-Packard Development Company, L.P. | Printable recording media |
Also Published As
Publication number | Publication date |
---|---|
US6458888B1 (en) | 2002-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6458888B1 (en) | Rheology modifier for use in aqueous compositions | |
US5280095A (en) | Fine particulate crosslinked type N-vinylamide resin and microgel, process for preparing same, and use thereof | |
US6361768B1 (en) | Hydrophilic ampholytic polymer | |
AU770521B2 (en) | Liquid dispersion polymer compositions, their preparation and their use | |
CN1953998B (en) | Conditioning/styling tetrapolymers | |
US20080182773A1 (en) | Thickeners Based on Polymers Comprising Amine Groups | |
JP2014193905A (en) | Liquid dispersion polymer compositions, their preparation and their use | |
CA2390952C (en) | Compositions and process for retaining active ingredients comprising networked structured polymers | |
JP4808829B2 (en) | Use of W / O emulsions containing water-swellable cross-linked polymers as thickeners, such emulsions and cosmetic or pharmaceutical formulations | |
US6541565B2 (en) | Polymeric system for delivering an active material | |
JP2004043785A (en) | Thickener and cosmetic obtained by formulating the same | |
US6548597B2 (en) | Polymeric composition | |
TWI287571B (en) | Thickener, cosmetic preparation containing the same, and process for producing the same | |
EP1145708A2 (en) | Cosmetic and use thereof | |
JPH09157130A (en) | Water soluble thickener and cosmetic material blended with the same | |
JP2001115135A (en) | Water-soluble thickener and cosmetic comprising the same | |
US6617372B2 (en) | Process of making polymeric hydrogel products | |
JP3625893B2 (en) | Hairdressing fee | |
AU2001285248B2 (en) | Polymeric composition | |
JPH1087438A (en) | Heir cosmetic composition | |
AU2001285248A2 (en) | Polymeric composition | |
AU2001285248A1 (en) | Polymeric composition | |
US20220192965A1 (en) | Cosmetic composition for hair | |
JP2004277384A (en) | External preparation composition | |
MXPA06011126A (en) | Liquid dispersion polymer compositions, their preparation and their use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ISP INVESTMENTS INC., DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOOD, DAVID K.;KOPOLOW, STEPHEN L.;TALLON, MICHAEL;AND OTHERS;REEL/FRAME:011913/0348;SIGNING DATES FROM 20010612 TO 20010614 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT, Free format text: SECURITY AGREEMENT;ASSIGNORS:ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC;HERCULES INCORPORATED;AQUALON COMPANY;AND OTHERS;REEL/FRAME:026918/0052 Effective date: 20110823 |
|
AS | Assignment |
Owner name: VERONA, INC., NEW JERSEY Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774 Effective date: 20110823 Owner name: ISP CHEMICAL PRODUCTS, INC., NEW JERSEY Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774 Effective date: 20110823 Owner name: ISP CAPITAL, INC., NEW JERSEY Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774 Effective date: 20110823 |
|
AS | Assignment |
Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, OHIO Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320 Effective date: 20130314 Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, O Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320 Effective date: 20130314 Owner name: AQUALON COMPANY, DELAWARE Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320 Effective date: 20130314 Owner name: ISP INVESTMENTS INC., DELAWARE Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320 Effective date: 20130314 Owner name: HERCULES INCORPORATED, DELAWARE Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320 Effective date: 20130314 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: ISP INVESTMENTS LLC, DELAWARE Free format text: CONVERSION;ASSIGNOR:ISP INVESTMENTS INC.;REEL/FRAME:041556/0499 Effective date: 20160818 |
|
AS | Assignment |
Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT, CANADA Free format text: SECURITY AGREEMENT;ASSIGNORS:AVOCA, INC.;HERCULES LLC;ISP INVESTMENTS LLC;AND OTHERS;REEL/FRAME:043084/0753 Effective date: 20170630 Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT, Free format text: SECURITY AGREEMENT;ASSIGNORS:AVOCA, INC.;HERCULES LLC;ISP INVESTMENTS LLC;AND OTHERS;REEL/FRAME:043084/0753 Effective date: 20170630 |
|
AS | Assignment |
Owner name: AVOCA LLC, NORTH CAROLINA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504 Effective date: 20200110 Owner name: PHARMACHEM LABORATORIES LLC, NEW JERSEY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504 Effective date: 20200110 Owner name: HERCULES LLC, DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504 Effective date: 20200110 Owner name: ISP INVESTMENTS LLC, NEW JERSEY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504 Effective date: 20200110 |