CN101400850B - Non-textile polymer compositions and methods - Google Patents

Non-textile polymer compositions and methods Download PDF

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Publication number
CN101400850B
CN101400850B CN2007800092158A CN200780009215A CN101400850B CN 101400850 B CN101400850 B CN 101400850B CN 2007800092158 A CN2007800092158 A CN 2007800092158A CN 200780009215 A CN200780009215 A CN 200780009215A CN 101400850 B CN101400850 B CN 101400850B
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composition
fabric
powder
dispersion
prepolymer
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CN101400850A (en
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C·F·亚瓦洛纳
J·M·兰贝尔
H·刘
S·梅诺
F·M·R·斯托帕
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Invista Technologies SARL Switzerland
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Invista Technologies SARL Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/698—Mixtures with compounds of group C08G18/40
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    • 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
    • C08J3/12—Powdering or granulating
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Abstract

Included are polymer compositions such as polyurethaneureas, polyamides and polyesters. The compositions may be in a variety of forms such as dispersions, powders, fibers, and beads. The compositions are useful in the preparation of many products including health and beauty products such as cosmetics, paint, household products such as fabric care compositions, apparel/footwear and textiles/furnishings.

Description

Non-textile polymer compositions and method
The cross reference of related application
The U. S. application the 60/865th that the present invention's requirement was submitted on November 9th, 2006; The U. S. application the 60/837th that No. 091 interests, requirement were submitted on August 11st, 2006; The U. S. application the 60/759th that No. 011 interests, requirement were submitted on January 18th, 2006; No. 853 interests merge to all these applications in this literary composition by reference.
Background of invention
Invention field
The present invention includes polymer composition, for example polyurethane-urea (polyurethaneureas), polyamide and polyester.Said composition can be various forms, for example dispersion, powder, fiber and particle (bead).Said composition is useful in the preparation of many products, comprises for example cosmetics of health care and cosmetics; Paint; Household products, for example Fabrid care composition, clothes/footwear and textiles/household goods.
The association area general introduction
Polymer, for example polyurethane-urea, polyamide and polyester always are used to prepare synthetic fiber.But these polymer have other character, and these character possibly provide the benefit that surmounts fibers form.So, polymer composition and method that the advantage that focuses on that these are extra need be provided are arranged.
The example of the suitable form of various polymerization thing is a powder.The fine powder of synthetic polymer (for example polyethylene, polyamide, polyurethanes and polysiloxanes) has been used in printing, coating and the cosmetic application.Though have many known granularities to reduce technology (for example solid state shear pulverizing, cryogenic grinding, gas atomization and high shear mixing and grinding) in this area and be used to produce in the polymer powder; But still need improved method, homogeneous granules meticulous to produce; Particularly for those elastomeric polymers, for example block polyurethanes and polyurethane-urea.
The polymer composition that people need improve, it can provide added benefit, not only is used for printing, coating and cosmetic application, and is used for other application, for example paint and fabric nursing.
Except that washing agent, use fabric softener to give usually and can wash fabric with flexibility and/or bulkiness.Fabric softener also make textile feel level and smooth, reduce Electrostatic Absorption, give exhilarating fragrance, reduce drying time, reduce wrinkling and make flatiron easier.But after washing, the benefit of these character passs in time usually and reduces.
Prevailing active component be called as quaternary ammonium compound based on long-chain fat type molecule, be in the nature CATION.So for preventing with washing agent (can be anion in essence) undesirable reaction to take place, fabric softener adds between fabric rinsing or dry period usually.
In order to reduce the time and the expense of fabric laundering, the Fabrid care composition that can add simultaneously with washing agent need be provided.The Fabrid care composition that can prolong the fragrance relevant with fabric softening compositions (fragrance substantiation) and be easy to the duration of benefits such as nursing also need be provided.
Summary of the invention
An embodiment provides the polyurethane-urea of powder type or aqueous dispersion form.These powder or dispersion provide separately, perhaps with washing agent or fabric softener composition fabric nursing character are provided.
In one embodiment, Fabrid care composition is a nonionic film forming dispersion form, and it comprises polyurethaneurea polymer and water.Said polymer is the product of prepolymer, and as cahin extension agent, wherein said prepolymer is glycol (glycol) or glycols (glycols) mixture and 4, the product of 4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate) with water.
Another embodiment is the non-film forming dispersion of nonionic, and it comprises water and polyurethaneurea polymer.Said polymer is the product of prepolymer and cahin extension agent, and said cahin extension agent comprises diamine chain extender and water, and wherein said polymer is glycol (polyol) or glycols mixture and 4, the product of 4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate).Said polymer can be filtered subsequently and grinding or spray drying so that powder to be provided.
Another embodiment provides and has prolonged spices or the method for aromatic substance duration on fabric or clothes.This method comprises the step that said fabric or clothes are contacted with the polyurethaneurea compositions of spices and powder or aqueous dispersion form.Said contact can be carried out in many ways; Include but not limited to; Before washing and/or dry fabric, said spices and polyurethane-urea are joined in washing agent or the fabric softener, they directly joined in the wash water (wash water), or during rinse cycle, they directly or with fabric softener composition are added.
Another embodiment provides the method that the character of expectation is provided to fabric or clothes.This method comprises the step that fabric is contacted with the polyurethane-urea of powder or aqueous dispersion form.The character that can be imparted into the said expectation on the fabric includes, but not limited to shape retention, easy care performance (that is, being easy to flatiron) and anti fouling performance.
The present invention also provides the block polyurethane urea compositions of fine powder form.The present invention also comprises the method for making this polyurethaneurea powder.In addition, some embodiments provide the powder with water imbibition and/or oil absorption.
The invention provides other polymer compositions and form.For example paint, cosmetics and Fabrid care composition etc. all are useful to these compositions for many compositions.
Detailed Description Of The Invention
So employed in the literary composition, term " powder " is meant the bulk material of being made up of the loose aggregation of subdivided solids particle.For fine powder, its full-size less than 1 millimeter and mean particle size less than 100 microns.But, also comprise having bigger granular size.For example, meal can have the granular size greater than 1 millimeter, and its mean particle size is in about 0.5mm arrives the scope of about 2mm.
So employed in the literary composition, term " film forming " is meant that under the synthesis condition that this literary composition discloses, when lacking other reagent, said material forms continuous film.
So employed in the literary composition, term " non-film forming " is meant that when lacking other reagent, said material does not form continuous film under the synthesis condition that this literary composition discloses.
So employed in the literary composition; Term " fabric " " be meant any Woven fabric, supatex fabric, knitted fabric, lint bundle, felted terxture, braided fabric or be combined into the binding material (bonded material) of (assembly) that said binding material includes but not limited to that those are used for clothes (clothes), coverlet, towel, curtain, the furniture decoration material with fabric (upholstery) and carpet by fiber and/or yarn.
So employed in the literary composition, term " fabric " care composition " refer to any fabric that is used to, particularly between the washing of said fabric or dry period, be used for fabric, to give the composition of said fabric beneficial property.These character comprise cleaning, remove oil stain and grease spot, make textile feel level and smooth, reduce Electrostatic Absorption, give exhilarating fragrance, reduce drying time, reduce wrinkling and make flatiron easier.
So employed in the literary composition, " be prone to nursing " about the term of fabric and refer to that fabric will have fold seldom after washing, can not need press or flatiron more easily.
Polyurethaneurea compositions
Said polyurethaneurea compositions in some embodiments possibly be aqueous dispersion, powder, fiber or particle form.When expecting powder type, filtration, drying that can be through said dispersion and grind or through spray drying, and segregation comes out from aqueous dispersion.The solids content of said dispersion can be different.For example, solids content (by weight) can account for said dispersion about 5% to about 50%, more specifically, account for about 20% to about 40% of said dispersion.Powder can have the mean particle size less than 100 microns, and for example about 50 to about 80 microns, and do not have granular size greater than 1.0mm, for example less than about 0.5mm.
Another the suitable method for preparing the polyurethaneurea powder in some embodiments is to carry out for the 6th, 475, No. 412 according to the United States Patent (USP) of authorizing Roach, by reference it is merged in this literary composition.Roach has disclosed a kind of elastic fibers of under specific process conditions, extruding so that the method for powder to be provided.
For preparing the anion film forming aqueous dispersion in some embodiments, prepare prepolymer, said prepolymer is capped glycol (capped glycol).Said prepolymer is the product of following material:
The polymer of at least a hydroxy terminal, for example number-average molecular weight is about 600 to about 3500 polyethers (comprising copolyether), Merlon or PEPA composition, for example, number-average molecular weight be about 1400 to about 2400 gather 1, the 4-butanediol ethere;
PIC, it is 4,4 '-with 2,4 '-(MDI) mixture of isomers of di-2-ethylhexylphosphine oxide (phenyl isocyanate), wherein 4,4 '-MDI isomers and 2,4 '-ratio of MDI isomers arrives about 35:65 for about 65:35; With
At least a diol compound; It has the hydroxyl that (i) can react with the MDI isomer mixture of said PIC; (ii) at least one can form the carboxylic acid group of salt after neutralization, and wherein said at least one carboxylic acid group can not react with the MDI isomer mixture of said PIC.
Said prepolymer is neutralized to form salt subsequently, for example through the adding triethylamine, and uses diamine chain extender and water to prolong chain (chain extended) at last, to form said aqueous dispersion.Can comprise additive, for example surfactant, antifoaming agent/antifoaming agent, anti-oxidant and thickener.
The said MDI isomer mixture that is used for anionic dispersions need not add solvent and can reduce said prepolymer viscosity.The speed that said MDI isomer mixture also can reduce to react.Said prepolymer can the batch-type method or is prepared with the continous mode method.
When containing glycol in some embodiments, the glycol that comprises hydroxyl and carboxylic acid group can be known as acidic glycol.The example of useful acidic glycol comprises 2,2-dihydroxymethyl acetate, 2,2-dihydromethyl propionic acid (DMPA), 2,2-dimethylolpropionic acid, 2,2-one methylol valeric acid and their combination.
Nonionic film forming dispersion in some embodiments comprises prepolymer, and said prepolymer is the polyester-urethane prepolymer of isocyanate terminated.This prepolymer is polymer polyol and the vulcabond for example 4 for example of hydroxy terminal; 4 '-product of di-2-ethylhexylphosphine oxide (phenyl isocyanate); Said polyol for example 1; 4-butanediol-ethylene glycol copolyether glycol or gather 1, the mixture of 4-butanediol ethere and ethoxylation polypropylene glycol.Make water prolong the chain of this prepolymer subsequently and it is dispersed in the water, perhaps be dispersed in it in water and make water prolong the chain of this prepolymer subsequently.
The non-film forming dispersion of nonionic in some embodiments comprises prepolymer, and said prepolymer is the polyester-urethane prepolymer of isocyanate terminated.This prepolymer also is a for example polybutadiene diol or gather 1 of polyol, 4-butanediol ethere and vulcabond for example 4,4 '-product of di-2-ethylhexylphosphine oxide (phenyl isocyanate).Can unite and make water and diamine chain extender prolong the chain of this prepolymer, said diamine chain extender is ethylenediamine or amine functional group (amine-functional) crosslinking agent (for example polyvinylamine) for example.Can select hydrophily or hydrophobic glycol production to have the polymer powder of different suction/oily abilities.And, can adjust said powder particle size through the viscosity of regulating said prepolymer, and said viscosity is to regulate through the solvent that use is used to dilute.
In some embodiments, polyurethaneurea powder is through using or do not use solvent, the prepolymer of isocyanate terminated is distributed to through high shear force makes in the aqueous medium that contains dispersant and cahin extension agent or crosslinking agent.High shear force is defined as the power that enough generations are not more than 500 microns particle.Said prepolymer can be through with polyol or polyol copolymer or polyol mixture (for example PTMEG, polyester-diol, PCDL, polybutadiene diol or their hydrogenated derivatives; Dimethyl silicone polymer with hydroxy terminal) processes with vulcabond (for example methylene-bis(4-phenyl isocyanate) (MDI)) reaction, to form prepolymer or " capped glycol " at NCO terminal.In polymer composition, the molar ratio of NCO/OH is 1.2 to 5.0.The example of cahin extension agent is an aliphatic diamine, for example ethylenediamine (EDA).The chain crosslinking agent be have at least three can with the primary amine of NCO radical reaction or the organic compound or the polymer of secondary amine functional groups.Organic solvent, water soluble or be insoluble in water, for example 1-methyl 2-Pyrrolidone (NMP) or xylene can be used to the said prepolymer of dilution before said dispersion steps.The formed polyurethaneurea polymer particulate that is dispersed in the water can use like this, perhaps can emanate out and is dried to pressed powder through filtration.Perhaps, also can use spraying process, it also can control granular size better.
The big I of particles of powder in some embodiments changes according to the difference of required application.For example, mean particle size possibly comprise that also mean particle size is less than 100 microns (μ m) less than 1 millimeter (mm).
In some embodiments; The block polyurethane urea that is used to make elastomer powder comprises: a) polyol or polyol copolymer or the number-average molecular weight polyol mixture between 500 to 5000; Include but not limited to; The dimethyl silicone polymer of PTMEG, polyester-diol, PCDL, polybutadiene diol or their hydrogenated derivatives and hydroxy terminal; B) vulcabond comprises aliphatic diisocyanate, aromatic diisocyanates and alicyclic diisocyanate; And c) aliphatic diamine (promptly; Diamine chain extender); Perhaps it and at least a mixture (said aliphatic diamine and alicyclic diamine all have 2 to 13 carbon atoms) that is selected from the diamines of aliphatic diamine and alicyclic diamine; The perhaps polymer at amino terminal perhaps has the organic compound or the polymer of at least three primary amine or secondary amine group; And the optional monoamine as chain terminating agent (primary amine or secondary amine).
The example that can be used for the PPG in some embodiments comprises that those have the glycols of two or more hydroxyls, and from the ring-opening polymerization and/or the ring-opening copolymerization of oxirane, expoxy propane, oxetanes, oxolane and 3-methyltetrahydrofuran, perhaps from the polycondensation of polyalcohol, said polyalcohol for example is glycol or diol mixture; Wherein the carbon atom in each molecule is less than 12, ethylene glycol, 1 for example, ammediol, 1; 4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 3-methyl isophthalic acid; 5-pentanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1; 9-nonanediol, 1,10-decanediol and 1,12-dodecanediol.For example; Can comprise Linear Double functional polyethers polyalcohol; What be specially molecular weight about 1700 to about 2100 gathers 1, the 4-butanediol ethere, and for example degree of functionality is that 2
Figure G2007800092158D0007100723QIETU
1800 (can be from INVISTA S.ar.l.of Wichita; KS and Wilmington, DE buys).
The PEPA that can be used comprises that those contain the esterdiol class of two or more hydroxyls (ester glycols); They are by having no more than 12 aliphatic polycarboxylic acid and the glycols of carbon atom in low molecular weight and each molecule, or the polycondensation of their mixture produces.The example of suitable polycarboxylic acids is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosane dicarboxylic acid and dodecanedicarboxylic acid.The suitable example that is used to prepare the glycols of PEPA is an ethylene glycol, 1, ammediol, 1,4-butanediol, 1; 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1; 7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1; 10-decanediol and 1, the 12-dodecanediol.For example, can comprise that melt temperature is about 5 ℃ and arrives about 50 ℃ Linear Double functional polyester polyalcohol.
The example of the polycarbonate polyol that can be used comprises that those have the carbonic acid ester glycols of two or more hydroxyls; They are by carbon atom in tool low molecular weight and each molecule no more than 12 phosgene, chloro-formate, dialkyl carbonate or diallyl carbonic acid ester and aliphatic polyol, or their mixture polycondensation generation.The suitable example that is used to prepare the glycols of said polycarbonate polyol is a diethylene glycol (DEG), 1, ammediol, 1,4-butanediol, 1; 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1; 7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1; 10-decanediol and 1, the 12-dodecanediol.For example, can comprise that melt temperature is about 5 ℃ and arrives about 50 ℃ Linear Double official's ability polycarbonate polyol.
The example of suitable vulcabond composition is 1; 6-two isocyanate group hexanes, 1; 12-two isocyanate group dodecanes, IPDI, trimethyl-hexamethylene diisocyanate, 1; 5-two isocyanate groups-2-methylpentane, two isocyanate groups-cyclohexane, methylene-two (4-cyclohexyl isocyanate), tetramethyl-XDI, two (isocyanate group methyl) cyclohexane, toluene di-isocyanate(TDI), di-2-ethylhexylphosphine oxide (4-phenyl isocyanate), phenylene vulcabond, XDI, and the mixture of these vulcabond.For example; Said vulcabond can be an aromatic diisocyanates, for example phenylene vulcabond, tolylene vulcabond (TDI), eylylene diisocyanate, biphenylene vulcabond, naphthalene diisocyanate, methyl diphenylene diisocyanate (MDI) and their combination.
The example of suitable two amine components (diamine chain extender) is an ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, 2,2-dimethyl-1; 3-propane diamine, 1,4-butanediamine, 1,5-pentanediamine, hexamethylene diamine, 1; 7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1; 10-decamethylene diamine, 1,12-dodecane diamines, 2-methyl isophthalic acid, 5-pentanediamine, cyclohexane diamine, the two methylamines of cyclohexane, IPD, xylylene amine and di-2-ethylhexylphosphine oxide (cyclohexylamine).Also can use the mixture of two kinds or more diamines.
The example of suitable amine terminal polymer is dimethyl silicone polymer, amine terminal acrylonitrile-butadiene copolymer, two (3-aminopropyl) terminal polyethylene glycol, two (2-aminopropyl) terminal polypropylene glycol and two (3-aminopropyl) terminal PolyTHFs at two (3-aminopropyl) terminals.
The suitable organic compound with at least three primary amine groups or secondary amine or the example of polymer be three-2-amino ethyl amine, gather (acid amides-amine) dendritic (poly (amido amine) dendrimers), polymine, polyvinylamine and PAH.
The example of suitable monoamine composition (d) comprises primary alkyl amine for example ethamine, butylamine, hexylamine, cyclohexylamine, monoethanolamine and 2-amino-2-methyl-1-propanol; With secondary dialkylamine N for example; N-diethylamide, N-ethyl-N-propylamine, N, N-diisopropylamine, the N-tert-butyl group-N-methylamine, the N-tert-butyl group-N-benzylamine, N, N-dicyclohexylamine, N-ethyl-N-isopropylamine, the N-tert-butyl group-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N; N-diethanol amine and 2; 2,6, the 6-tetramethyl piperidine.
When the polyurethaneurea powder of preparation in some embodiments, glycol at first with di-isocyanate reaction (randomly having catalyst) to form prepolymer or " capped glycol " at NCO-terminal.This reaction is carried out with the fusing form of mixed uniformly mixture usually, and applies heat 1 by 6 hours with 45 to 98 ℃ temperature.The amount of every kind of reacted constituent, i.e. the weight (Wdi) of weight of glycol (Wgl) and vulcabond, by the end-blocking rate (capping ratio CR) regulates, and is as follows, and CR is defined as the molar ratio of vulcabond and glycol:
CR＝(Wdi/MWdi)/(Wgl/MWgl)
Wherein MWdi is the molecular weight of vulcabond, and MWgl is the number-average molecular weight of glycol.According to the present invention, said end-blocking rate is between 1.2 to 5.0, specifically between 1.5 to 3.0.
After end capping reaction is accomplished; At this moment all hydroxyls on the glycol molecules (OH) all (NCO) are consumed with formation amino-formate bond (urethanebond), thereby form the viscosity polyester-urethane prepolymer that has terminal NCO group by the isocyanate group on the vulcabond.This prepolymer is added into subsequently and is distributed in the aqueous solution, and the said aqueous solution contains surfactant, for example dispersant and antifoaming agent/antifoaming agent, and randomly contain cahin extension agent, for example diamines.Perhaps, in being dispersed to aqueous medium before, this prepolymer can dilute with for example water-soluble N-Methyl pyrrolidone of organic solvent (NMP) or water-insoluble xylene.The effect of solid polymer particle high shear force during dispersion forms down and behind water and/or the diamine chain extender prolongation chain.These polyurethane-urea particles can be filtered subsequently and be dry.
Before disperseing said prepolymer, during or afterwards; Can be in said polyurethane-urea particle blast blending, for example anti-oxidant, pigment, colouring agent, spices, antiseptic (for example silver), active component (humidizer, UV-screener), surfactant, antifoaming agent/antifoaming agent, solvent or the like.In some cases, during disperseing said prepolymer, adding said additive, so that said additive-package is enclosed in the said polyurethane-urea particle, possibly be favourable.The sealing of said additive can be slowed down additive and diffused out said polymer substrate, thereby provides the delay of said additive to discharge or discharge (time release) in limited time.This postpone to discharge is the comparatively faster release of additive on being attracted to particle surface.The present invention can comprise that the additive with additive of sealing and surface adsorption combines, so that one or more additives discharge from particle surface fast, makes entrapped additive postpone to discharge.
Pigment also can be added in the polyurethaneurea compositions of some embodiments.Pigment can the mode similar with other additives be added.The example of pigment comprises carbon black and TiO 2For polyurethaneurea powder, shown in the following Table A of the effect of pigment:
The pigment type The powder color
Substrate does not add pigment White
Ultramarine blue Light blue
Ultramarine is pink Baby pink
Black oxide Grey
Orange oxide Light orange
The oxide yellow thing Yellow
The chrome green oxide Light green color
The additional embodiments of pigment is described hereinafter.
The polyurethane-urea particle
Embodiments more of the present invention are polyurethane-urea particles.A kind of process useful that is used to prepare this particle discloses in No. the 5th, 094,914, the United States Patent (USP) of authorizing Figuly etc. (" Figuly "), by reference its full content is merged in this literary composition.Can prepare block polyureas carbamate (polyureaurethane) composition, it can be any (for example those are based on the block polyureas carbamate of polyethers or polyester) that this literary composition is described.Can use solvent to prepare the solution that contains said polyureas carbamate.Can comprise multiple useful solvent, for example amide solvent includes but not limited to dimethylacetylamide (DMAc), dimethyl formamide (DMF) and N-Methyl pyrrolidone (NMP).Said polyureas carbamate solution subsequently can droplet form be introduced in the coagulating bath (coagulating bath), said coagulating bath is frozen into particle form with said polymer.Said coagulating bath can comprise the solvent that extracts said polymer solution, but is not the liquid of the solvent of said polymer, for example water.
Can prepare such particle, promptly diameter arrives about 4mm for about 1mm, and voidage is 60% to 90%, and on 5000X multiplication factor lower surface, does not have visible bore (proes).
Embodiments more of the present invention are polyureas carbamate particles, and it has granular size, voidage and surface holes than the more wide region of previous exposure.
Said voidage depends on the density of said particle:
Voidage=[1-(grain density/polymer volume density)] x100%
Some embodiments are voidages less than 60% polyureas carbamate particle.These particles can high viscosity solution prepares through using more.For example, Brookfield (Brookfield) viscosity for about 1000cps or higher, solids content be about 12% or the particle that produces of higher solution than using the identical particle manufacturing installation but the particle that uses the solution less than 1000cps to produce is more closely knit, more weigh and littler.In some embodiments, particle is by high viscosity (> 1000cps) but the formulations prepared from solutions of low relatively solids content (promptly < 10%).This can realize through the polymer that utilization has high mean molecule quantity, a tool side chain (branched), perhaps realizes through being utilized in the polymer that is associated together by crystallization, hydrogen bonding, the hard segment modes such as (hard segment association) of associating in the solution.For example, containing the solution of polyurethane-urea will be along with the aging and toughness more that becomes.
Can shear very rarely the polymer of (shear thin) through use; For example liquid crystal polymer or some elastic fibers goods; Perhaps has low average molecular weight through use; Or can association in solution, the polymer of hydrogen bonding or crystallization, prepare and have highly filled relatively low viscosity solution.
The method of the particle that another kind of preparation is littler, more closely knit is, makes particle by the solution that produces 60 to 90% voidages, but in removing solidifying of desolvating and dry run, allows some solvents to keep with said particle.The said particle of subsequent drying makes residual solvent that said polymer is dissolved (redissolve) again and precipitates into more closely knit structure again.
Voidage also can be produced greater than 90% particle.A kind of method relates to use and has low viscous polymer.But; Along with the lasting reduction of viscosity, in identical polymer product, can reach a such point; To such an extent as to be said polymer too rare it can not in said process of setting, keep said coating of particles; Thereby avalanche (collapse) (the method discloses in No. the 5th, 126,181, the United States Patent (USP) that is used to prepare smooth microporosity disk).On the other hand, possibly select or prepared polymer, polyurethane-urea particularly, its character is harder, dilutedly has still that enough hardness supports said grain shape and can avalanche even make.Especially, it is possible in polyurethane-urea family, coming synthetic or selecting goods harder but still that have an intrinsic very desirable elastic property (stretch and recover).The polyethylene glycol that for example uses low average molecular weight (for example mean molecule quantity is less than 1000 or less than 700) will enough can produce voidage greater than 90% particle as the polyurethane-urea of soft chain segment (soft segment), thus the sphere of keeping.
In addition; Other reactants or coreagent can be used to change the hardness of final polyureas carbamate particle, and for example be different from the cahin extension agent of EDA (ethylenediamine) or have the common cahin extension agent (coextenders) of EDA, or MDI (4; 4 ' with 2, isomers 4-) and their mixture.1,4-phenylene vulcabond or 1,4-phenylenediamine or their combination or mixture also produce than based on " tradition " MDI and the harder polyureas carbamate of the corresponding polyureas carbamate of EDA.The mixture that also should be appreciated that the polyureas carbamate with different hardness also can be used to adjust or regulate and reach the necessary hardness that requires greater than 90% voidage.Other polymer or additive can be mixed in the said solution and make the more required hardness and other requirements of high gap volume particle to reach.
Some embodiments are the particles that have the controlled size hole in its surface.Before being incorporated into coagulating bath, salt or other water-soluble materials (for example polyethylene glycol) micronized or nano-scale can mix with said polyureas carbamate solution.When said particle is solidified and in water, wash, said water-soluble material will produce the hole.
The present invention also provides the method for continuous or semicontinuous production particle.In batch-type, stirred reactor method, solvent can be accumulated (build up) in water or polymer non-solvent (polymer non-solvent).The viscosity of the particle that the excessive buildup of solvent can cause being produced causes them to stick together or even possibly make their coalescences.Solidifying of solvent in non-solvent (or water) accumulation yet possibly slowing down particle be not because have enough thermodynamics inducements (incentive) to make said solvent " drawn (pulled) " or be diffused in the non-solvent.When going out said particle or disk (disk) along with solvent diffuse, it is more and more concentrated and almost the same with solvent that non-solvent becomes.
Even the semicontinuous method of some embodiments can per 8 hours in shifts (shift) produce the particle of about 500 grams, increased by 10 times than batch-type, stirred reactor method.Particle can be after formation any time " results " after about 2-3 minute and being moved into be different from the container that they are formed, make the continuous production of the particle in " processing unit (plant) (process apparatus) " reach at least 38 hours in shifts.
In another embodiment, the water in said " processing unit (plant) " can be washed away continuously and particle can periodically or continuously be gathered in the crops, thereby said particle can be produced continuously.Compare with batch operation, inciting somebody to action more in the industry, the parent looks at the continuous or semicontinuous operation of use.
Can said particle be gathered in the crops and move to the different slots from the place that their form through many methods realizations and soak, extract residual DMAc solvent.A kind of method comprises uses the transportation system with conveyer belt.Said conveyer belt can be sieve or have hole to let water pass through them, simultaneously said particle is kept above that.The another kind of method that particle is shifted from said processing unit (plant) realizes through " waterfall ".This waterfall method lets said particle be collected in an end that forms local groove away from them through letting some water and a large amount of particles spill into another groove from the edge that forms groove.Because said particle swims in water/solvent mixture, so this method can easily realize.
The polyurethane-urea particle of some embodiments has very extensive applicability.This comprises and is used for textiles, clothes and shoes, furniture, cosmetics and other domestic. applications.As the bedding material, they for example can be included in comes the alternative fiber filler in the pillow.Particle can be included in the shoes, as the liner of sole.In addition, the combination of different size particle can be included in this identical sole, with adapt in the sole, at interior the end, different the pressure site, particularly particle on shoes outside and top can be included in fold or wadding has in " interlayer " structure of structure of soft thing.Cushioning effect also is useful for furniture liner and carpet wadding.For example, said particle can be included in the cellulosic cotton-wool material.Cushioning effect also is useful at headwear, the belt that is used for clothes, the belt that is used for luggage and comfortable grip device (comfort grip applications); Said headwear is the helmet or cap for example, and said comfortable grip device can for example found on club, ski pole, hammer, bicycle, grass mower, the steering wheel etc.
Said particle has very many useful qualitys.For example, after compression made its diameter reach four of green diameter/1 hour, said particle returned to 85% of its volume at once, and after 10 minutes, returns to about 97% of its volume.The size of particle maybe be different.Particle can have the diameter to 10mm greater than 0.1mm, and for example about .05mm is to about 8mm.The diameter of the individual particle that has prepared is 0.5mm, 0.8mm, 1.0mm, 2.5mm, 3.0mm, 4.0mm, 5.0mm and 8.0mm.
The density of individual particle can be in any suitable scope, for example from about 0.05g/cc to about 0.5g/cc, comprise about 0.1g/cc.Simultaneously, said particle has unique absorbent properties.For example, in the time of in being placed in water, the particle of the about 3mm of diameter will absorb about 14% of its weight in water.But, when the said particle of extruding in water, discharging then, said particle will absorb in water and reach about 350% of its weight.These absorbent properties have been showed other purposes, for example as the material delivery medium of spices, ointment and other fluid compositions for example.
Daiamid composition
Multiple different polyamide can use with some embodiments together.The example of suitable polyamide comprises nylon 6, nylon 12 and nylon 6,6.Said polyamide can any desirable form exist, and comprises fibers form and powder type.The method that a kind of suitable being used to prepares polyamide powder discloses in No. the 4th, 831,061, the United States Patent (USP) of authorizing Hilaire, by reference its content is merged in this literary composition.Such powder also can (size range of the powder of the said commercial acquisition of the trade name of ARKEMA
Figure G2007800092158D00141
be about 5 microns to about 20 microns from commercial acquisition.The more polyamide powder of large scale scope also can be provided, and for example mean particle size arrives in about 500 microns scope at about 50100 microns, comprises 100 microns.Also can comprise thicker powder, for example have mean particle size, comprise about 1mm at the powder of about 0.5mm to about 5mm.
Polymer blend
Multiple different polyester also can add in some embodiments.The example of polyester comprises polyalkylene terephthalates, gathers the naphthalenedicarboxylic acid alkylidene diol ester and gathers the M-phthalic acid alkylidene diol ester.The example of polyalkylene terephthalates is the fine linear contraction polymers of the one-tenth that in polymer chain, has carboxyl connection base (carboxyl linking radicals), for example PETG (" 2GT " or " PET "), polytrimethylene terephthalate (" 3GT " or " PTT ") and polybutylene terephthalate (PBT) (" 4GT ").
Said polymer blend can be any desirable form, comprises fiber, staple fibre (flock) and powder type.
As do not have the phase antirepresentation, and mention that " polyalkylene terephthalates " means and comprise copolyester, the polyester that promptly uses 3 kinds or more reactants to make, wherein every kind of reactant all has two and becomes ester groups.For example; Can use the copolymerization ethylene glycol terephthalate; The comonomer that wherein is used for making said copolyester is selected from linearity, ring-type and side chain aliphatic dicarboxylic acid with 4 to 12 carbon atoms (for example succinic acid, glutaric acid, adipic acid, dodecanedioic acid and 1,4-ring-hexane dicarboxylic acid); The aromatic dicarboxylic acid except that terephthalic acid (TPA) (for example M-phthalic acid and 2,6-naphthalenedicarboxylic acid) with 8 to 12 carbon atoms; Have 3 to 8 carbon atoms linearity, ring-type and side chain aliphatic diol (for example 1, ammediol, 1,2-propylene glycol, 1; 4-butanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1; Ammediol, 2-methyl isophthalic acid, ammediol and 1,4-cyclohexanediol); With the aliphatic series with 4 to 10 carbon atoms and aromatic oxide glycol (for example, quinhydrones two (2-ethoxy) ether, or molecular weight less than about 460 daltonian gathering (ethyleneether) glycol, comprise diethylidene ether glycol (diethyleneether glycol)).Usually, the content of said comonomer in said copolyester arrives in the scope of about 15 moles of % about 0.5.
Staple fibre
Be the polymer composition of staple fibre form in some embodiments.Staple fibre is a kind of very short accurate reduction or comminuted fibres, and it is used for producing the cover layer that is used for the similar staple on clothes, rubber, film or the paper.Staple fibre can be used as filler and is used for plastics, paper, rubber or analogous composition, increasing impact strength, to improve moldability, or on finished product, increases decorative appearance.Staple fibre normally length is about 0.040 inch fiber to about 0.250 inch (1mm is to 6.25mm).Diameter is usually between about 10 to about 100 microns.The staple fibre of different colours can be by multiple different synthetic and natural fabric preparations, and said synthetic and natural fabric be polyamide, polyester, cotton and artificial fibre for example.
Dyestuff information
Multiple different dyes, colouring agent and pigment can be used to add color to the composition of some embodiments.For example, some dyestuffs are the most useful for giving polyamide and polymer blend interpolation color, and pigment can be added in the polyureas carbamate composition.
The colouring agent that is used for some embodiments (comprising cosmetic composition) has the inorganic colourant that comprises synthetic and natural colorant and toner etc.Inorganic colourant comprises TiO 2, iron oxide and ultramarine.Synthetic toner comprises color lake, toner and pigment, and for example those are at United States Patent (USP) the 4th, 909, and the colouring agent that discloses in No. 853 merges to it in this literary composition by reference.The example of natural toner is a carmine pigment.
A kind of appropriate method that is used for preparing coloured nylon powder is included in dye beaker and dyes, and said dye beaker heats on electric hot plate with magnetic stirrer.This has guaranteed that said powder is stirred by said agitator fully, forms agglomerate and guarantees the level dyeing in whole batch preventing:
With phosphate buffer dye bath is adjusted to pH6.0
The Levegal SER (anion levelling agent) that adds 1% (by weight)
Add the dyestuff of dissolving in advance
Add nylon powder
Programming rate with 2 ℃/minute is warming up to boiling.Kept 30 minutes in this temperature.
Add 1g/l Sandacid GBV (acid donors (acid donor)-slow acid is released in the dye bath so that pH drops to pH5.0-5.5).
Kept 30 minutes in this temperature.
Cooling.
Dye bath and powder are toppled over through fine filter and rinsing.
Collect powder and drying in hot cupboard.
Comprise the nylon of fiber, staple fibre and powder type for any form, the most frequently used dyestuff is not use metal treatment and metallized ACID DYES.These two kinds of dyestuffs all can demonstrate the color fastness (colour fastness) of good color tone scope (shade range) and washing of opposing to a certain degree and UV.Said metallized dyestuff will show the best fastness of opposing UV and washing, but said tone range is limited to softer tone.Can only use ACID DYES (fastness of opposing UV and washing is not fine) without metal treatment; (it can provide the top performance of opposing washing perhaps to use narrow sp act ACID DYES; But for opposing UV, it has with said without the similar fastness performance of the ACID DYES of metal treatment) reach bright tone.These REACTIVE DYES often more costliness and depth of shade be limited, it depends on available amine terminal (amine ends) in nylon powder/staple fibre.
Comprise the polyester of fiber, staple fibre and powder type for any form, but DISPERSE DYES are unique dyestuffs that can standards for dyeing disperse dyeing polyester.But,, can use alkalescence (CATION) dyestuff or DISPERSE DYES so if you have cationic-dyeable look polyester.
The dyestuff kind of all these types all can obtain from bigger suppliers, for example Huntsman (being originally Ciba Textile Effects) and DyStar.The merchant that following table has been listed with supplier and class discrimination sells dyestuff.
Supplier Acid without metal treatment Acid through metal treatment Active acid Disperse CATION
Huntsman TectilonErionyl Lanaset EriofastLanasolLanaset Terasil Maxilon
Dystar Telon Isolan Stanalan Dianix Astazone
Spices
There is multiple spices material to be deposited on well or to be retained on the elastic fibers (that is the polyureas carbamate of block).These materials include, but not limited to two kinds like following proposition, kind A and kind B.
Kind A: hydroxyl material (alcohols, phenols or salicylate), the common logarithm (log of its octanol/water distribution coefficient (P) 10P) be 2.5 or bigger, and gas-chromatography Kovats index (measuring as non-polar stationary phase with dimethyl silicone polymer) is at least 1050.
Said octanol-water partition coefficient (perhaps its common logarithm " logP ") is well-knownly [to see Hansch and Leo, Chemical Reviews, 71,526-616, (1971) as hydrophobicity and water miscible index in document; Hansch, Quinlan and Lawrence, J.Organic Chemistry, 33,347-350 (1968)].When these numerical value can not obtain from document, can directly measure, perhaps utilize mathematical algorithm to estimate roughly.Provide the software of this estimation can be, for example " LogP " of Advanced Chemistry Design Inc from commercial acquisition.
Log 10P be 2.5 or bigger material certain hydrophobicity is arranged.
Kovats index is by the retention time in the gas Chromatographic Determination and [the seeing Kovats, Helv.Chim.Acta41,1915 (1958)] that calculate with reference to the retention time of alkane.In perfume industry, served as a mark (descriptor) use several years based on the index that uses non-polar stationary phase, its molecular size and boiling point with composition is relevant.In the perfume industry summary of Kovats index by T Shibamoto at " Capillary Gas Chromatography in Essential OilAnalysis (essential oil analyze in capillary gas chromatography) " P Sandra and C Bicchi (editor); Huethig (1987) provides in the 259-274 page or leaf.Suitable common nonpolar phase is 100% dimethyl polysiloxane, and its trade name is RP-1 (Hewlett-Packard), CP Si15CB (Chrompack) for example, OV-1 (Ohio Valley) and Rtx-1 (Restek).
The material of low Kovats index is volatile often, can not be retained in well on many fibers.
Kind A comprises that general formula is the alcohols of ROH; Wherein hydroxyl can be primary hydroxyl, secondary hydroxyl or tert-hydroxyl; The R base can be alkyl or alkenyl, randomly is branch or substituted, ring-type or acyclic, makes ROH have above-mentioned distribution coefficient and Ke Fazi characteristic.Has Kovats index and is normally monofunctional alkyl or the aralkyl alcohols of molecular weight in 150 to 230 scopes of 1050 to 1600 alcohols.
Kind A comprises that also general formula is the phenols of ArOH, and wherein the Ar group is represented phenyl ring, and said phenyl ring can be replaced by one or more alkyl or alkenyl, or by ester group-CO 2A replaces, and wherein A is an alkyl, like salicylate.ArOH has the distribution coefficient and the Kovats index of above definition.Usually, Kovats index is that such phenols of 1050 to 1600 is a molecular weight at 150 to 210 monohydroxy phenols.
The spices examples of material is 1-(2 '-tert-butyl group cyclohexyloxy)-Ding-2-alcohol, 3-methyl-5-(2 ' among the kind A; 2 '; 3 '-front three basic ring, penta-3-thiazolinyl)-penta-2-alcohol, 4-methyl-3-decene-5-alcohol, amyl salicylate, 2-ethyl-4 (2 '; 2 ', 3-front three basic ring penta-3 '-thiazolinyl) but-2-ene alcohol, baras camphor, carvacrol, citronellol, 9-decenol, dihydroeugenol, dihydro linalool (dihydrolinalol), dihydromyrcenol, dihydroterpineol, eugenol, geraniol, laurine, isoamyl salicylate, isonefolia, isoeugenol, linalool, menthol, nerolidol, nerol, patchone, phenoxanol, terpineol, tetrahydrogeraniol, tetrahydrolialool (tetrahydrolinalol), 2,6-Dimethyl-2-octanol (tetrahydromyrcenol), thymol, 2-methoxyl group-4-methylphenol, (4-isopropylcyclohexyl-)-methyl alcohol, salicylic acid benzene methyl, salicylic acid cyclohexyl, 1-Hexyl salicylate, Patchoulicalcohol and farnesol.
Kind B: ester, ether, nitrile, ketone or aldehyde have common logarithm (log 10P) be 2.5 or bigger octanol/water distribution coefficient (P), and gas-chromatography Kovats index (measuring as non-polar stationary phase with dimethyl silicone polymer) is at least 1300.
The spices of kind B has general formula R X, wherein X can be positioned at primary, the second month in a season or uncle position, and be a kind of of following group :-CO 2A ,-COA ,-OA ,-CN or-CHO.Radicals R and A are ring-type or acyclic alkyl, and randomly are substituted.Usually, to be no more than the material of 1600 kind B be the monofunctional compound of molecular weight in 160 to 230 scopes to Kovats index.
Among the kind B spices examples of material be 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-formaldehyde (carbaldehyde), 1-(5 ', 5 '-the dimethyl cyclohexenyl group)-amylene-1-ketone, alismone, 2-methyl-3-(4 '-tert-butyl-phenyl) propionic aldehyde, the 2-methyl hendecanal, 2-undecylene aldehyde, 2,2-dimethyl-3-(4 '-ethylphenyl)-propionic aldehyde, 3-(4 '-isopropyl phenyl)-2 methyl propanal, acetate 4-methyl-4-phenyl penta-2-base ester, Ananolide, allyl cyclohexyl ethoxyacetic acid ester, amyl benzoate, methyl ethyl ketone tripolymer, Benzophenone, 3-(4 '-tert-butyl-phenyl)-propionic aldehyde, carypohyllene, cis-jasmone, citral diethyl acetal, citronellal diethyl acetal, citronellyl acetate, phenethyl butyl ether, α-damascenone, dorinone, δ-damascenone, γ-decalactone, 2-n-hexyl-acid esters, dihydro jasmone, dihydroterpinyl acetate, amino toluene dimethyl phthalate, dipheny oxide, diphenyl methane, lauric aldehyde, laurylene-2-aldehyde, lauronitrile, 1-ethyoxyl-1-phenoxy group ethane, 3-(1 '-ethoxy ethoxy)-3; 7-dimethyl-octa-1,6-diene, 4-(4 '-methylpent-3 '-thiazolinyl)-hexamethylene-3-olefine aldehydr, three ring [5.2.1.0-2,6-] decane-2-carboxylic acid ethyl esters, 1-(7-isopropyl-5-methyl bicyclic [2.2.2] suffering-5-alkene-2-yl)-1-ethyl ketone (ethanone), allyl tricyclic decenyl ether, propionic acid tricyclodecenyl ester (tricyclodecenyl propanoate), peach aldehyde, n-methyl-n-phenyl-2-methylbutyryl amine, isobutyric acid tricyclodecenyl esters, geranyl acetate, hexyl-benzoate, α-Zi Luotong, β-ionone, isobutyl cinnamate, isobutyl quinoline, the different clove tree ester of acetate, 2; 2,7,7-tetramethyl three ring hendecane-5-ketone, cyclacet, 2-hexyl cyclopentanone, 4-acetate-3-amyl group oxinane, 2-hexyl ethyl acetoacetate, 8-isopropyl-6-methyl bicyclic [2.2.2] suffering-5-alkene-2-formaldehyde, 4-isopropyl-1-methyl bicyclic [2.2.2] suffering-5-alkene-2-carboxylate methyl ester, methyl cinnamate, the different methyl ionone of α, methyl naphthyl ketone, nerol oxide, nonyl lactone, nopyl acetate, to tert-butylcyclohexyl acetic acid esters, 4-isopropyl-1-methyl-2-[1 '-propenyl]-benzene, isobutyric acid ethyl phenoxy, phenethyl isoamyl ether, phenethyl isobutyrate,phenylethyl isobutyrate, trimethylace tonitric tricyclodecenyl esters, trimethylace tonitric phenethyl ester, the phenylacetaldehyde hexylene glycol, 2 that contracts; 4-dimethyl-4-phenyl oxolane, rose acetone (rose acetone), terpinyl acetate, 4-isopropyl-1-methyl-2-[1 '-propenyl]-benzene, neroline bromelia (yara), formic acid (4-isopropyl cyclohexadienyl) ethyl ester, amyl cinnamate, amyl cinnamic aldehyde, amyl cinnamic aldehyde dimethyl acetal, cinnamyl cinnamate, 1,2,3; 5,6,7; 8,8a-octathyro-1,2; 8,8-tetramethyl-2-acetonaphthone, ring-1,13-ethylenedioxy tridecane-1; 13-diketone, pentadacanolide, jasminolene, 1; 3,4,6; 7; 8-six hydrogen-4,6,6; 7; 8,8-pregnancy basic ring penta [g]-2-chromene, geranyl phenylacetic acid ester, 6-acetyl group-1-isopropyl-2,3; 3; 5 tetramethyl lindanes and 1,1,2; 4; 4,7-hexamethyl-6-acetyl group-1,2; 3, the 4-naphthane.
Though this is to the spices that can act on well with spandex composition and the extensive list of essence, recognize that in some embodiments, other spices also are useful.Spices can comprise the mixture of following material or material; Comprise natural (promptly; Obtain through extracting flowers, medicinal herbs, leaf, tree root, bark, trees, flower or plant), artificial (promptly; The mixture of different natural oils or oil component) with synthetic (that is synthetic method production) aromatic substance.
The non-limitative example of spices comprises: jasminolene; Amyl cinnamic aldehyde; Amyl salicylate; 1-Hexyl salicylate; Terpineol; 3,7-dimethyl-cis-2,6-octadiene-1-alcohol; 2,6-dimethyl-sec-n-octyl alcohol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadiene-1-alcohol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; 4-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde; Tricyclo decenyl propionate; Cyclacet; Anisaldehyde; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; Ethyl-3-methyl-3-phenyl glycidyl acid esters; 4-(p-hydroxybenzene)-Ding-2-ketone; 1-(2,6,6-trimethyl-2-cyclic ethylene-1-yl)-2-butene-1-ketone; Acetanisole; To methoxyl group-α-phenyl propylene; Methyl-2-n-hexyl-3-oxo-cyclopentane-carboxylic acid ester; Peach aldehyde, orange oil; Lemon oil; Grapefruit oil; Bergamot oil; Caryophyllus oil; γ-dodecalactone; Methyl-2-(2-phenyl-3-oxo-cyclopentyl) acetic acid esters; The betanaphthol methyl ether; Methyl β-naphthalenone; Cumarin; Capraldehyde; Benzaldehyde; Acetate 4-tert-butyl group cyclohexyl; Acetate α, the alpha-alpha-dimethyl phenethyl ester; Acetate aminomethyl phenyl methyl esters; The ring ethylene glycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; γ-methyl ionone (ionone gamma methyl); α-Zi Luotong; β-ionone; Petit grain pomelo oil (petitgrain); Vertofix coeur; 7-acetyl group-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; The methyl ionone; Methyl isophthalic acid, 6,10-trimethyl-2,5,9-cyclodoecatriene-1-base ketone; 7-acetyl group-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene; 4-acetyl group-6-the tert-butyl group-1,1-dimethyl indane; Benzophenone; 6-acetyl group-1,1,2,3,3,5-hexamethyl indane; 5-acetyl group-3-isopropyl-1,1,2,6-tetramethyl indane; The 1-lauric aldehyde; 7-hydroxyl-3,7-dimethyl octanal; 10-hendecane-1-aldehyde; Dissident's thiazolinyl hexahydrobenzaldehyde; The formyl tristane; Pentadacanolide; 16-hydroxyl-palmitoleic acid lactone; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-pregnancy basic ring penta-γ-2-chromene; Ambrane (ambroxane); Ten dihydros-3a, 6,6,9a-tetramethyl naphtho--[2,1b] furans; Cedrol; 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopentene-1-yl)-2-butene-1-alcohol; Caryophyllenol; Cedryl acetate; Vertenex; Pogostemon cablin; Olibanum resin; Cistus creticus; Labdanum oil; Vetiver oil; Copaiba balsam; Canada balsam; Laurine and indoles (indol); Phenylacetaldehyde and indoles; Geraniol; Geranyl acetate; Linalool; Bergamio; Tetrahydrolinalool; Citronellol; Citronellyl acetate; Dihydromyrcenol; Acetate dihydromyrcene ester; 2,6-Dimethyl-2-octanol; Terpinyl acetate; Nopol; Nopyl acetate; The 2-phenylethanol; Acetate 2-phenethyl ester; Phenmethylol; Phenylmethyl acetate; The salicylic acid benzene methyl; Ergol; The secondary ethyl ester (styrallyl acetate) of acetate benzene; Dimethyl benzyl carbinol; Trichloromethyl phenyl methyl aminomethyl phenyl methyl acetic acid ester; Isononyl acetate; Vetacetyl; Vetiverol; 2-methyl-3-(p-tert-butyl-phenyl)-propionic aldehyde; 2-methyl-3-(p-isopropyl phenyl)-propionic aldehyde; 3-(p-tert-butyl-phenyl)-propionic aldehyde; 4-(4-methyl-3-pentenyl)-3-cyclohexene formaldehyde; 4-acetoxy-3-amyl group oxinane; MDJ; The 2-n-fleuramone; 3-methyl-2-amyl group-cyclopentanone; The n-capraldehyde; The n-lauric aldehyde; 9-decenol-1; Phenoxyethyl isobutanoate; The phenylacetaldehyde dimethyl acetal; The phenylacetaldehyde diethyl acetal; Geranonitrile; Citronellyl nitrile; Cedryl acetate; The 3-Santalex; Methyl cypress base ether; The different ketone that comes into leaves; The anisaldehyde nitrile; Anisaldehyde; Piperonal; Eugenol; Vanillic aldehyde; Dipheny oxide; The laurine ionone; The methyl ionone; Different methyl ionone; Irone; Suitable-3-hexenol and ester thereof; Indan musk spices; Telralin musk spices; Isochroman musk spices; Macrocyclic ketone; Macrolide type (macrolactone) musk odorant; Astrotone ethyl and their combination.
Fabrid care composition
The polyurethaneurea compositions of the method preparation through above description provides the shape retention of surprising improvement to fabric.And they also make fabric nurse or provide easy care performance (easy care properties) easily.In other words, the fabric of handling with polyurethaneurea compositions has fold seldom after washing, and flatiron more easily.
Polyurethaneurea compositions in some embodiments also has surprising good water imbibition and oil absorption, in the time of particularly on being used for fabric.This is for the anti fouling performance particular importance.With after the polyurethaneurea compositions of some embodiments contacts, said polyurethane-urea will be from pollution-creating source (stain-causing sources) moisture absorption and oil suction at fabric, thereby has limited the absorption of fabric self.
Because said absorbability, said polyurethaneurea compositions also help to prolong by the duration of aromatic substance in the fabric of said composition contact.This also discharges said spices gradually subsequently by said polyurethaneurea compositions absorption and produces.
Fabrid care composition in some embodiments can comprise fabric softener or washing agent, and said polyurethaneurea compositions can be added in said fabric softener or the washing agent.These polyurethaneurea compositions also can be any form, for example dispersion or powder type.
Perhaps, said polyurethaneurea compositions can directly be added in the fabric, in the washing machine, in the wash water (for hand washing), or joins in the automatic drier.
And said powder or dispersion can be used as the substitute of fabric softener through home laundry (home laundering), to give the clothes anti fouling performance.Fabric softener usually is used for giving fabric fragrance or fragrance, and secondly is to give fabric softness.When using drum drying method (tumble drying), not to need the fabric-softening operation, because the fabric behind the drum drying is very soft.
Composition of detergent in some embodiments contains the surfactant of anionic, non-ionic or both sexes or their mixture usually, and usually contains the organic or inorganic builder in addition.
Fabric softener will comprise for example quaternary ammonium salt of active component usually.The example of non-cyclic quaternary ammonium salts comprises tallow base trimethyl ammonium chloride; Ditallow dimethyl ammonium chloride; Methylsulfuric acid ditallow Dimethyl Ammonium; Varisoft 432PPG (dihexadecyl dimethylammonium chloride); Two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride; Dioctadecyl dimethyl ammonium chloride; Two eicosyl alkyl dimethyl ammonium chlorides; Two docosyl alkyl dimethyl ammonium chlorides; Two (hydrogenated-tallow group) Dimethyl Ammonium of methylsulfuric acid; Double hexadecyl diethyl ammonium chloride; Double hexadecyl dimethyl acetic acid ammonium; Ditallow dipropyl ammonium phosphate; Ditallow dimethyl ammonium nitrate; With two (coconut-alkyl) alkyl dimethyl ammonium chloride.
Other optional members of Fabrid care composition in some embodiments are actually conventional ingredient, and account for about 0.1% to about 10% of said composition weight usually.This optional ingredients comprises; But be not limited to, colouring agent, spices, bacteriostatic agent, fluorescent whitening agent, opacifier, viscosity modifier, solid for example fabric regulator, the fabric of clay (clay) form help absorbent (fabric absorbency boosters), emulsifying agent, stabilizing agent, shrinkage control agent (shrinkagecontrollers), spotting agent, bactericide, fungicide, preservative agent etc.
Fabrid care composition in some embodiments can be through the conventional method preparation.Homogenization not necessarily.A kind of convenience and gratifying method are when about 150 ℉, the premix of preparation softening agent in water, and it is added in the hydrothermal solution of other compositions subsequently.After fabric regulating composition is cooled to about room temperature, can add heat-sensitive ingredients.
Fabrid care composition in some embodiments can be through being used in the wash cycle that joins conventional home laundry operation.Perhaps, said Fabrid care composition can be added in the washing agent before wash cycle, or directly joined in the fabric, perhaps when hand washing, went in wash water as a part of power of washing agent or fabric softening compositions, or directly joined in the wash water.
Said Fabrid care composition can any form known in the art be used; For example powder, liquid, solid tablet (solid tablet), enclosed liquid (for example using the composition of enclosed); Perhaps when being used for automatic drier, be used with the form of nonwoven sheet (non-woven sheet).
The addition of the Fabrid care composition in some embodiments can be to reach the required any amount of wanting of textile properties.For example, the addition of said Fabrid care composition can account for about 0.05% to about 1.5%, for example about 0.2% to about 1% of rinsing water-bath (aqueous rinsing bath) or wash water weight.
When existing with the aqueous dispersion form, polyurethaneurea compositions can account for about 0.1% to about 20%, for example about 5% to about 15% of said Fabrid care composition weight in some embodiments in Fabrid care composition.When existing with powder type, polyurethaneurea compositions can account for about 0.1% to about 20%, for example about 0.5% to about 10%, perhaps about 1% to about 5% of said Fabrid care composition weight in Fabrid care composition.
Perhaps, said polyurethaneurea powder or dispersion can replace said Fabrid care composition and be added into, rather than are added into as the composition of said Fabrid care composition, and the content that at this moment said polyurethaneurea compositions can 100% is added into.In this case, said polyurethaneurea compositions can be introduced directly in wash water or the washings, addition account for said washings or wash water weight about 0.05% to about 1.5%, particularly, about 0.2% to about 1%.
Cosmetic composition
Nylon (polyamide) and polyurethaneurea powder have many useful properties, make it and can add in the cosmetic composition.Oil absorption, water imbibition and absorption of perspiration are arranged in these character.When with contact skin, these character are used particularly useful for the absorption of perspiration of for example deodorant or antiperspirant.These character also are used for the sebum control of contact skin product, skin nursing and decorative cosmetic product having.
In one embodiment, the present invention provides the polymer powder with antimicrobial acivity, to reduce bacterial growth and foul smell.Through adding odour absorbents, zinc oxide for example, said powder can have the smell prevention ability of enhancing.
Powder in some embodiments has surprising good water imbibition and oil absorption.In one embodiment; Polyurethaneurea powder forms through the method for above description; It has specific granular size, and is adapted at being used as in deodorant and the Antipers pirant compositions water absorbing agent or absorbing sweat agent, perhaps in skin nursing or cosmetics (make-up) composition, is used as oil suction (sebum) agent.Other embodiment comprises powder with antibacterial additives to strengthen the smell protection, and the powder with bonus flavor to be providing charming fragrance, and is used for the powder that cosmetics or body care terminal (body care end) use.The non-limitative example of cosmetic composition that is added with powder, particle, fiber and the dispersion of some embodiments comprises deodorant, for example atomizing, adhesive type or roll daubing type antiperspirant; Cosmetics and colour cosmetic, for example powder (rouge (blush)/bronzer/outline-color (highlighter)), foundation cream, eye shadow cream, eyeliner, mascara, lipstick/lip gloss and nail polish; Skin care compositions and methods, for example health or facial NMF, shave glue and cream, the back of shaving are with glue and cream, soap slab and shower cream/abluent (body wash/cleaner); Treatment, for example shampoo, conditioning agent and approved product (styling product); Oral care product comprises toothpaste.
The polyamide of some embodiments and polyurethaneurea powder have extraordinary feel and sense of touch (touch property).For example, they touch sensation silk sliding (silky) and smooth (smooth) very along sliding (gliding).
Polyurethaneurea powder of the present invention demonstrates very high water and the sweat absorption value by multiple character decision, and demonstrates good oily absorption value simultaneously.Very high water absorption value is meant that (from Arkema, available from Lehmann and Voss&Co.Hamburg, Germany) compare, absorption value is greater than its three times with the NY-6 powder.Good oily absorption value is meant; Can compare favourably with nylon 12 (Arkema) and recently polymethyl methacrylate, polyethylene and the polyurethanes from KOBO (Kobo Products of South Plainfield, New Jersey and St.Agne France) is higher.Polyurethaneurea powder of the present invention demonstrates (immediately) water imbibition or the absorption of perspiration that is exceedingly fast.Fast water imbibition is meant than talcum fast 100 times.
Quick and a large amount of water of this civilian described polyurethaneurea powder absorbs and also helps anti-aging product and anti-wrinkle product.Said powder can be used as the filler of wrinkle of skin in anti-aging skin care compositions and methods.Said powder is hydrophilic, the compressible microsphere with Volume Changes effect (volumizing effect), with stretched skin, reduces or eliminates the appearance of wrinkle.
For the power applications in cosmetics and body care composition, be suitable less than 100 microns particles, so that on skin, feel smooth, and can not cause user's attention.Desirable mean particle size should be less than 50 microns.In one embodiment, polyurethaneurea powder comprise 90% less than 42 microns particle, this can be through filtering or parameter through the control spray-drying process realize.
Another embodiment is polyurethane-urea particle or powder, and it is as the agents for defoliating in cleaning agent, abrasive cleaner, the shower glue etc.Usually, for example peanut materials such as (comprising almond) has been used as agents for defoliating/abrasive cleaner/decorticating agent and has been included in the cosmetic composition.But these materials are hard often, and have very sharp hard edge, cause producing uncomfortable feeling.On the contrary, polyurethane-urea particle in some embodiments and powder can have the surface and the sliding feel of silk of very round sphere, circle, make them become " skin-friendly type (skin-friendly) " product more, have kept the effect of hard material simultaneously.Said powder or particle can be added in the cleanser compositions by any amount, to reach the effect of wanting.Granular size also can change, usually greater than about 100 microns, to let the consumer observe.
Another embodiment is the polyurethane-urea dispersion; But its film forming is with in Haircare composition (gel, atomizing articles for use (spray), shampoo, conditioning agent etc.), be used to perm retentivity (curlretention property) or anti-roll property (anti-frizz property).Can be used in the volatile hair dyeing by polyurethaneurea powder painted or that pigment is arranged.
Said polymer composition can be included in any composition, and its content accounts for 100% of said composition weight at most.Be included in the suitable content range (based on the weight of said composition) of nylon, polyester and polyurethane-urea in the composition, by weight, comprise 1-20%, 1-15%, 5-10% and 25-75%.Use amount depends on purposes and conceivable effect.
Paint composite
Some embodiments are the paint composites that contain polyurethane-urea, polyester and daiamid composition.Any form that said paint can be known in the art comprises latex, acrylic resin paint and oil based coating (oil based paint), and said oil based coating comprises priming paint (primer), sealer (sealer) and coating.Said polyurethane-urea, polyester and daiamid composition can be added in the paint in any form, to reach the effect of wanting.
Add the said polymer of powder, staple fibre or particle form, can be used to provides quality (texture) to said paint composite.In addition, if said powder, fiber or particle have been colored or are painted, they also will reach different paint effects.If to recent alternately paint technology (alternate painting techniques) and the interested words of artificial surface (faux finishes), this effect is extremely desirable.The composition of some embodiments provides optionally (alternative) surface features, for example quality and color, and do not need extra japanning step.And, through color being joined priming paint and the color that one or more are independent joins in said powder/granule/fiber, can reach two-color effect or multicolour effect.
Except the visual effect of color and quality, add staple fibre and in paint composite, also have other benefit.The paint composite that contains these staple fibres provides the covering in uneven zone on better wall/surface, higher pliability is provided, and resistance to rupture is provided.And in whole paint was used, they provided wallpaper effect (wall paper effect).
Except the visual effect of color and quality, add the polyurethane-urea dispersion and in paint composite, also have other benefit.The paint composite that contains these dispersions can provide better coverage (particularly on uneven surface), and resistance to rupture is provided.This is confirmed through embodiment.
Perhaps, can come skid resistance to be provided through the polymer that adds powder, staple fibre or particle form to said paint composite.Compare with the traditional paint composition, this realizes through increasing friction painted surface (friction painted surface).
Characteristics of the present invention and advantage will show through the description of following examples more fully, and these embodiment are illustrative, can not by any way it be interpreted as limitation of the present invention.
Embodiment
Embodiment 1
Obtain by
Figure G2007800092158D00282
E2538 glycol (by INVISTA from experimental
Figure G2007800092158D00281
elastic fibers production line; S.ar.1. provide) and the capped glycol prepolymer processed of
Figure G2007800092158D00283
125MDR, its end-blocking rate is 1.696.
Figure G2007800092158D00284
is the registration mark of the elastic fibers of INVISTA.This prepolymer of 300 grams mixes 10 minutes to reduce viscosity with the nmp solvent of 150 grams in plastic bottle.The mixture of this dilution is poured in the steel pipe, is used in the rustless steel container disperseing to be injected into.
Said container contains the deionized water of 2000 grams, the T DET N14 surfactant (can be from Harcros of Kansas City, Kansas buys) of 30 grams and the ethylenediamine cahin extension agent of 4.5 grams, and they are pre-mixed and are cooled to 5 ℃.It is 1/8 inch pipeline that said diluted prepolymer is injected under the air pressure of about 40psi through internal diameter; The high speed laboratory is with disperser (model HSM-100LC; Can be from Charles Ross&Son Company of Hauppauge, NewYork buys) with the speed running of 5000rpm.Being added in 15 minutes of the prepolymer of dilution accomplished, and formed oyster white dispersion was continued to disperse extra 5 minutes.After (backweighing) the said container of weighing show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 328 grams, the capped glycol prepolymer that is equivalent to 218.7 grams is added in the said dispersion.3 gram additive 65 (Additive65) foam control agents (from Dow Corning of Midland, Michigan buys) are added in the said dispersion, and before pouring plastic bottle into, let said dispersion mix other 30 minutes with the speed of 5000rpm.
Use Microtrac X100 particle size analyzer (Leeds, the mean particle size that Northrup) determines said dispersion is 52.83 microns, wherein 95% particle is less than 202.6 microns.
Embodiment 2
Use with embodiment 1 in identical composition and dispersion, just after said diluted prepolymer is dispersed in the aqueous mixtures, add the 4.5 ethylenediamine cahin extension agents that restrain again.After weigh said container show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 329 grams, the capped glycol prepolymer that is equivalent to 219 grams is added in the said dispersion.The mean particle size of measuring said dispersion is 33.45 microns, and wherein 95% particle is less than 64.91 microns.When by segregation, solid polymer particle can not form film.
Embodiment 3
Through with 500 the gram
Figure G2007800092158D00291
HLB2000 glycol (by Sartomer Company; Inc.at Exton; PA supply) 125MDR with 105.86 grams reacted 120 minutes with 90 ℃ in the agitated reactor of the 2000ml that is equipped with heating mantles and mechanical agitator, made the capped glycol prepolymer.This is reflected in the dried case that is full of nitrogen and carries out.After the reaction, measure like titration, the percetage by weight of the NCO group of said prepolymer is 2.98.This prepolymer is poured in the steel pipe, be used in the rustless steel container disperseing to be injected into.At room temperature; (can be with deionized water (2000 gram) from Harcros of KansasCity with the T DET N14 surfactant of 30 grams; Kansas buys) and 3 the gram additive 65 foam control agents (can be from Dow Corning ofMidland, Michigan buys) in said container, mix.It is 1/8 inch pipeline that said prepolymer is injected through internal diameter with the air pressure of about 80psi; The high speed laboratory is with disperser (model HSM-100LC; Can be from Charles Ross&Son Company of Hauppauge, NewYork buys) with the speed running of 5000rpm.In 15 minutes, accomplish the interpolation of the prepolymer of dilution, formed oyster white dispersion was continued to disperse extra 5 minutes.After weigh said container show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 422 grams.In said dispersion, add the ethylenediamine cahin extension agent of 4.5 grams, and let said dispersion mix other 30 minutes with 5000rpm.The mean particle size that determines formed dispersion is 49.81 microns, and wherein 95% particle is less than 309.7 microns.
Embodiment 4
Identical among program and the embodiment 3, just the diol mixture with
Figure G2007800092158D00294
HLB2000 glycol of
Figure G2007800092158D00293
that contain 250 grams 1,800 two pure and mild 250 grams forms said prepolymer.The prepolymer of totally 465 grams is disperseed.The mean particle size that determines formed dispersion is 13.67 microns, and wherein 95% particle is less than 38.26 microns.
Embodiment 5
In the glove box of blanket of nitrogen, carry out the preparation of said prepolymer.1800 glycol (can be from INVISTA for that adding about 382.5 restrains in 2000ml
Figure G2007800092158D00301
glass reaction still (it is equipped with air pressure to drive agitator, heating mantles and thermocouple thermometer); S.ar.l.; Of Wichita; KS and Wilmington; DE buys) and about 12.5 the gram 2,2-dihydromethyl propionic acid (DMPA).This mixture is heated to about 50 ℃ and stirring; Add subsequently about 105 the gram
Figure G2007800092158D00303
the M1 vulcabond (can be from BASF; Wyandotte, Michigan buys).Reactant mixture is heated to about 90 ℃ and lasting the stirring subsequently; And in the time of about 90 ℃, kept about 120 minutes; This afterreaction is accomplished, and the %NCO in the mixture drops to stable numerical value, conforms to the calculated value (the %NCO desired value is 1.914) of the prepolymer with isocyanates end group.Use the falling ball viscometer (by Duratech Corp., Waynesboro, VA sale) of model,, measure the viscosity of said prepolymer according to the universal method of ASTM D1343-69 in about 40 ℃ of operations as DV-8.Pass through S.Siggia; ＂ Quantitative Organic Analysis via FunctionalGroup (through the quantitative organic analysis of functional group) ＂; The third edition, Wiley & Sons, NewYork; Method among the pp.559-561 (1963) (its full content is integrated in this literary composition by reference) is measured the total content (according to the percetage by weight meter of NCO group) of isocyanate moiety in the said capped glycol prepolymer.
Embodiment 6
Use solvent-free prepolymer (as according to program of describing among the embodiment 5 and preparation of compositions) to make polyurethane-urea aqueous dispersion of the present invention.
In the stainless steel beaker of 2000ml, add the neopelex (SDBS) of the deionized water of about 700 grams, about 15 grams and the triethylamine (TEA) of about 10 grams.This mixture is cooled to about 5 ℃ with ice/water subsequently and also uses the high shear lab mixer (Ross, model 100LC) that has rotor/stator mixing head to mix about 30 seconds with the speed of about 5000rpm.The viscosity prepolymer that will prepare like the mode of embodiment 1 and be included in the tubular metal cylinder joins the bottom of mixing head described in the aqueous solution through the flexible tubing that is applied with air pressure.The temperature of said prepolymer is maintained between about 50 ℃ to about 70 ℃.Under the lasting mixing condition of about 5000rpm, water looses the prepolymer flow point that squeezes out and prolongs chain.After about 50 minutes, total amount is that the prepolymer of about 540 grams is added into and is dispersed in the water.Be right after after prepolymer is added into and disperses, add the additive 65 (can obtain) of about 2 grams to the mixture of said dispersion from Dow Midland Michigan.Reactant mixture is stirred other about 30 minutes subsequently, adds the diethylamine (DEA) of about 6 grams and stirring more thereafter.The solvent-free aqueous dispersion that is produced is creamy white and is stable.The viscosity of said dispersion is through adding and mixing the Hauthane HA thickener 900 that accounts for the about 2.0wt% of aqueous dispersion (can be from Hauthway, Lynn, Massachusetts buys) and regulate.Said viscosity dispersion is filtered with 40 microns Bendix metal cloth filters subsequently, and in room temperature storage, to be used for film casting or lamination (lamination).The solids content of said dispersion is 43%, and viscosity is about 25000 centipoises.
Embodiment 7
1,800 two pure and mild
Figure G2007800092158D00314
125MDR (can be from Dow Company by
Figure G2007800092158D00313
from the acquisition of commercialization
Figure G2007800092158D00312
elastic fibers production line; Midland; Michigan buys) the capped glycol prepolymer processed, its end-blocking rate is 1.688.
Figure G2007800092158D00315
is the registration mark of the elastic fibers of INVISTA.This prepolymer of 300 grams mixed in plastic bottle 10 minutes with the nmp solvent of 150 grams, to reduce viscosity.Diluted mixture is introduced in the steel pipe, is used in the rustless steel container disperseing to be injected into.The deionized water that contains 2000 grams in the said container, the ethylenediamine cahin extension agent of the T DET N14 surfactant (can be from Harcros of Kansas City, Kansas buys) of 30 grams and 3 grams, they are pre-mixed and are cooled to 5 ℃.It is 1/8 inch pipeline that diluted prepolymer is injected under the air pressure of about 40psi through internal diameter; Experiment is with dispersing mixer (model HSM-100LC at a high speed; Can be from Charles Ross&SonCompany of Hauppauge, New York buys) with the speed running of 5000rpm.In 15 minutes, accomplish the interpolation of diluted prepolymer, formed oyster white dispersion was continued to disperse extra 5 minutes.After weigh said container show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 347 grams, the capped glycol prepolymer that is equivalent to 231 grams is added in the said dispersion.In dispersion, add 3 gram additive 65 foam control agents (can be from DowCorning of Midland, Michigan buys), and before pouring plastic bottle into, let said dispersion mix other 30 minutes with 5000rpm.
Through use Microtrac X100 particle size analyzer (Leeds, the mean particle size that Northrup) determines said dispersion is 32.59 microns, wherein 95% particle is less than 65.98 microns.Use buchner funnel and filter paper solids filtered polymer beads under reduced pressure; With water rinse filter cake 3 times, and 60-65 ℃ of drying 4 hours.Said particle does not form film between filtration and dry period.The service test chamber is with
Figure G2007800092158D00322
blender (Blender700 model 33BL79; By Dynamics Inc.; New Hartford, Connecticut makes) be easy to the filter cake of said drying is ground to form fine powder.In business practice, said solid particle will through known drying means for example spray drying process directly from said dispersion segregation come out.As through what GPC measured, the weight average molecular weight of dried powder is 352550, and number-average molecular weight is 85200.
Embodiment 8
In embodiment 8, use with embodiment 7 in identical composition and dispersion, the solvent that just is used to dilute said capped glycol prepolymer is changed into xylene, and the amount of ethylenediamine cahin extension agent is increased to 4.5 and restrains.After weigh said container show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 339 grams, the capped glycol prepolymer that is equivalent to 226 grams is added in the dispersion.
The mean particle size that determines said dispersion is 22.88 microns, and wherein 95% particle is less than 46.97 microns.When by segregation, said solid polymer particle does not form film.
Embodiment 9
In embodiment 9, use with embodiment 7 in identical composition and dispersion, be that said ethylenediamine cahin extension agent is by the branched polyethylenimine of same amount [GPC measures Mn and is about 600 (from Aldrich)] replacement.After weigh said container show that the total amount that is added into the capped glycol of the dilution in the said dispersion is 340 grams, the capped glycol prepolymer that is equivalent to 227 grams is added in the said dispersion.
The mean particle size that determines said dispersion is 58.12 microns, and wherein 95% particle is less than 258.5 microns.When by segregation, said solid polymer particle does not form film.
Embodiment 10
Use the glove box of dry nitrogen atmosphere to prepare said prepolymer.2000ml of the two independent
Figure G2007800092158D00331
glass reactor (equipped with a pressure-driven stirrer, heating mantle and thermocouple thermometer) were added 220.0 g of
Figure G2007800092158D00332
1800 diol (commercially available from INVISTA) and 220.0 g of
Figure G2007800092158D00333
HP4000D diol (commercially available from BASF).This diol mixture is heated to 50 ℃ and stirring, adds
Figure G2007800092158D00334
125MDR (can buy from Dow Chemical) of 75.03 grams thereafter.Reactant mixture is heated to 90 ℃ and lasting the stirring subsequently, and keeps 120 minutes at 90 ℃.From reactor, take a sample; Measure it and have 2.170 and 2.169% NCO, assay method such as S.Siggia, ＂ QuantitativeOrganic Analysis via Functional Group (through the quantitative organic analysis of functional group) ＂ respectively; The third edition; Wiley&Sons, New York, the method among the pp.559-561 (1963).
The deionized water that in the stainless steel beaker of 3000ml, adds 1600 grams, the additive 65 (can buy) of the TDET N14 surfactant (can be from Harcros of Kansas City, Kansas buys) of 15 grams and 5 grams from Dow Corning.This mixture also mixed 30 seconds with 5000rpm with blender (Ross, model 100LC) with the high shear laboratory with rotor/stator mixing head with icing/be water-cooled to 10 ℃ subsequently.More than the viscosity prepolymer in two reactors of preparation is introduced into the bottom that joins mixing head described in the aqueous solution in the tubular metal cylinder and through the flexible tubing that is applied with air pressure.The temperature of said prepolymer is maintained between 50-70 ℃.Under the lasting mixing condition of 5000rpm, water looses the prepolymer flow point that squeezes out and prolongs chain.After 5 minutes, total amount is that the prepolymer of 616 grams is added into and is distributed in the water.After said prepolymer is added into and disperses, this dispersed mixture was mixed other 40 minutes.It is light blue that the solvent-free aqueous dispersion that is produced is that oyster white arrives, and solids content is 28.84wt%, and viscosity is 44 centipoises.Under environmental condition, said dispersion by curtain coating (cast) on polyethylene sheets, and in fume hood dried overnight, to form the elasticity continuous film.Measure through GPC, the weight average molecular weight of this film is 127900, number-average molecular weight is 41000.
Embodiment 11
Program and condition and the foregoing description 10 basic identical; Just surfactant changes
Figure G2007800092158D00341
N1-9 (can be from Stepan of Northfield, Illinois buys) into.Have 2.156 with 2.136%NCO, from said two reactors, totally 640 the gram prepolymer be dispersed in the water.The solids content of formed solvent-free dispersion is 26.12%, and viscosity is 51 centipoises.Weight average molecular weight by the curtain coating and the elastic membrane of drying is 133900, and number-average molecular weight is 44400.
Embodiment 12
Use solvent-free prepolymer (as according to program of describing among the embodiment 5 and preparation of compositions) to make polyurethane-urea aqueous dispersion of the present invention.
The deionized water that in the stainless steel beaker of 2000ml, adds about 700 grams, the triethylamine (TEA) of the neopelex (SDBS) of about 15 grams and about 10 grams.This mixture also uses the high shear lab mixer (Ross, model 100LC) that has the rotor/stator mixing head to mix about 30 seconds with the speed of about 5000rpm with icing/be water-cooled to about 5 ℃ subsequently.Saidly prepare and be included in the viscosity prepolymer in the tubular metal cylinder, be added into the bottom of mixing head described in the aqueous solution through the flexible tubing that is applied with air pressure like the mode among the embodiment 1.The temperature of said prepolymer is maintained between about 50 ℃ to about 70 ℃.Under the lasting mixing condition of about 5000rpm, water looses the prepolymer flow point that squeezes out and prolongs chain.After about 50 minutes, total amount is that the prepolymer of about 540 grams is added into and is dispersed in the water.Be right after after prepolymer is added into and disperses, in said dispersed mixture, add the additive 65 (can obtain) of about 2 grams and the diethylamine (DEA) of about 6 grams from Dow Midland Michigan.Subsequently, reactant mixture is stirred other about 30 minutes.The solvent-free aqueous dispersion that is produced is creamy white and is stable.The viscosity of said dispersion is through adding and mixing the Hauthane HA thickener 900 that accounts for the about 2.0wt% of aqueous dispersion (can be from Hauthway, Lynn, Massachusetts buys) and regulate.Said viscosity dispersion is filtered with 40 microns Bendix metal cloth filters subsequently, and in room temperature storage, to be used for film casting or lamination.The solids content of said dispersion is 43%, and viscosity is about 25000 centipoises.Soft, the toughness and flexible of the film of dispersion curtain coating thus.
Embodiment 13-fabric test
Composition of the present invention is to be tested with cotton
Figure G2007800092158D00351
fabric (97% cotton/3%
Figure G2007800092158D00352
elastic fibers).The contrast of this embodiment is a fabric of using the non-concentrated ConfortTM fabric softener washing that is provided by Unilever.Through 40 ℃, with the program 4 (program4) of
Figure G2007800092158D00353
program control automatic washing machine, with the ArielTM liquid detergent washing (using gauge load fabric (standard load fabric)) that can obtain from Procter and Gamble to reach the load of 2.5kg; And, every kind of composition shown in the table 1 is used for cotton
Figure G2007800092158D00354
fabric with the fabric softener composition rinsing of 18g.After drum dried, any deposit on the assessment fabric face.Neither one demonstrates the deposit of any powder or film in these three kinds of fabrics.
Composition in the table 1 is following:
(a) only with fabric softener fabric treated (contrast)
(b) with Unimer (synthetic wax disperses the to improve) fabric treated of dispersion, film forming anion polyurethane urea water and the 2%wt of the 1%wt of fabric softener, embodiment 6
(c) with the polyurethaneurea powder of the 1%wt of fabric softener, embodiment 5 and the Unimer of 2%wt (synthetic wax disperses to improve) fabric treated.
To comprise the composition (b) of said fabric softener and (c) mix and to produce homogeneous dispersion (do not have sedimentation, also do not have agglomeration).
Estimate the easy care performance (easy care) of every kind of fabric.Use standard testing method AATCCTM124/ISO15487 to come to measure DP rate (durable pressrating) (" DP leads ") before and afterwards in flatiron." DP leads " is the tolerance to the fabric three-dimensional smoothness.Sliding compliance (irongliding) of flatiron or easy flatiron property (ease of ironing) are measured as, and when the angle of ironing board was about 20 °, flatiron slided the time through the length-specific of fabric.The easy care performance result is as shown in table 1.
Figure G2007800092158D00361
The result of table 1 demonstrates, and compares with contrast (flatiron then increase by 0.5 unit), and two kinds of fabrics handling with powder or dispersion demonstrate improve (having increased by 1 unit after the flatiron) that better DP leads.
And, show that with the fabric (b) of compositions-treated of the present invention with (c) flatiron slides sooner at said fabric face.
Composition (a) and (b) and spices/aromatic substance (c) have also been assessed.Let three people hear each fabric individually.Everyone perceives, and with the fabric (b) of compositions-treated of the present invention with (c) denseer fragrance is arranged.
Also tested the absorbability (humidity disposal ability (moisture management)) of fabric, said fabric comprises the fabric that those are crossed with compositions-treated of the present invention.Confirm with the fabric after powder of the present invention or the dispersion processing and the difference of untreated comparing with fabric after measuring these character.
For above-mentioned every kind of fabric (a) and (b) with (c), on the surface of fabric, apply Linseed oil and water respectively one (about 30 microlitres).Mensuration by the time that absorbs fully, and is that unit record is in table 2 with the second up to each droplet.The surface area of droplet when also having measured the 60th second after fabric absorbs fully, and with square centimeter (cm 2) be that unit record is in table 2.
Figure G2007800092158D00362
As shown in table 2, dispersion of the present invention (b) is compared with contrast (a) with powder (c), and the absorbability of improving is provided.Use (c) of powder type to demonstrate sizable improvement.
Embodiment 14-100% cotton Woven fabric (cotton woven fabric) test
Also after with the compositions-treated in some embodiments, tested 100% cotton Woven fabric.The contrast of this embodiment is the fabric softener that concentrates, and it is the Softian that is provided by Colgate Palmolive TMUltra.The every kind of composition that shows in the table 3, all pass through in 40 ℃, with
Figure G2007800092158D0037101554QIETU
The program 4 of program control automatic washing machine, use Ariel TMLiquid detergent washing (with the gauge load fabric to reach the load of 2.5kg), and, be used for 100% COTTON FABRIC with the fabric softener composition rinsing of 18g.After drum dried (dry) with moderate temperature, any deposit on the assessment fabric face.There is not a kind of fabric to demonstrate any powder or the deposit of film.
The composition of table 3 is following:
(e) only with fabric softener fabric treated (contrast)
(f) with said dispersion (a kind of non-ionic polyurethane urea dispersion) fabric treated of 10wt% among fabric softener and the embodiment 10
Mix the composition (f) that comprises said fabric softener and produce homogeneous dispersion (do not have sedimentation, also do not have agglomeration).
Increment (growth) for test fabric at first calculates accessible amount of tension or maximum tension amount.Through at first regulating fabric sample, subsequently on constant rate of stretch tension draftomter, circulation three times between 0-30N, and measure said accessible amount of tension.Said maximum tension amount is passed through computes:
Maximum tension amount %=(ML-GL) x100/GL
Wherein: ML is when 30N, to be the length of unit with mm; And
GL is measuring length (gauge length) 250mm.
The single sample of every kind of fabric is stretched to subsequently said " accessible amount of tension " 80% and the about 30min of maintenance.With the lax about 60min of the said fabric sample of relief, and according to following formula mensuration with calculate increment:
Increment %=L2/Lx100
Wherein: " increment " represented with the percentage after lax;
The length (is unit with cm) that the lax back of L2=increases; And
L=original length (is unit with cm).
Measure fabric (e) and each fabric increment (f).The result is presented in the table 3.
Figure G2007800092158D00381
The fabric increment is the tolerance to shape retention.Increment numerical value representative expendable prolongation amount during wearing.The increment proof fabric of low numerical value has the ability of better its original shape of recovery.
Present embodiment also tested fabric (e) and (f) after washing and rinse cycle in the difference of release aspect the fragrance.In the gas sample container of sealing, place every kind of fabric sample of one to two gram.Carry out fabric loading (fabric stressing) through using steel ball bearing to shake.Using gases sampling pump (with the speed of 50cc per minute running 20 minutes), extract out from the top of said gas sample container through TenexTM probe tube, the volatile compound that will from sample, discharge.Said Tenex TMPipe is held back said VOC (VOC) and is used for analyzing.Said Tenex TMPipe is heated subsequently and discharges said volatile organic matter and be used in the GC/MS analyzing.VOC among the table 3a measures the result and shows, uses the fabric of the fabric softener rinsing of the dispersion (a kind of non-ionic polyurethane urea dispersion) that contains embodiment 10 to discharge more fragrance.
Figure G2007800092158D00382
Embodiment 15-elastic fibers/cotton mixed goods test
Also tested after using the compositions-treated of some embodiments, elastic fibers/cotton mixes Woven fabric.The contrast of this embodiment is the fabric softener that the concentrates (Softlan that is provided by Colgate Palmolive TMUltra).The every kind of composition that shows in the table 4; All pass through 40 ℃, with the program 4 of
Figure G2007800092158D00391
program control automatic washing machine, use ArielTM liquid detergent washing (using the gauge load fabric) to reach the load of 2.5kg; And, be used for cotton/elastic fibers mixed goods with the fabric softener composition rinsing of 18g.After drum dried (dry) with moderate temperature, any deposit on the assessment fabric face.There is not a kind of said fabric to demonstrate any powder or the deposit of film.
The composition of table 4 is following:
(g) only with fabric softener fabric treated (contrast)
(h) with dispersion (a kind of non-ionic polyurethane urea dispersion) fabric treated of the 10wt% of fabric softener and embodiment 10.
Mix the composition (h) that comprises said fabric softener and produce homogeneous dispersion (do not have sedimentation, also do not have agglomeration).Measure fabric (g) and (h) every kind fabric increment.The result is presented in the table 4.
The fabric increment is the tolerance to shape retention.Increment numerical value representative expendable prolongation amount during wearing.The increment proof fabric of low numerical value has the ability of better its original shape of recovery.
Also, two kinds of
Figure G2007800092158D00393
elastic fiberss/cotton mixed goods have been tested with after the compositions-treated of some embodiments.The contrast of this embodiment is the fabric softener that the concentrates (Soupline that is provided by ColgatePalmolive TMUltra).The every kind of composition that shows among table 4a and the 4b, all through 40 ℃, use Miele TMThe standardization program of commercial laundering, use
Figure G2007800092158D00394
Gel detergent (can from Henkel Corporation obtain) washing (using the gauge load fabric) and with the fabric softener composition rinsing of 30ml to reach the load of 2.5kg, be used for cotton and
Figure G2007800092158D00395
The elastic fibers mixed goods.After drum dried (dry) with moderate temperature, any deposit on the assessment fabric face.The said fabric of neither one demonstrates any powder or the deposit of film.For following fabric; CK is a kind of circular knitted fabric with 95% cotton-5%
Figure G2007800092158D00401
elastic fibers, and WOV is grey parallel stretching (weft stretch) Woven fabric with 97% cotton-3% elastic fibers.
Composition among table 4a and the 4b is following:
(i) only with the fabric softener fabric treated (contrast-CK)
(j) with dispersion (a kind of non-ionic polyurethane urea dispersion) fabric treated of the 10wt% (3% active component) of fabric softener and embodiment 10 (processing-CK)
(k) only with the fabric softener fabric treated (contrast-WOV)
(1) with dispersion (a kind of non-ionic polyurethane urea dispersion) fabric treated of the 10wt% (3% active component) of fabric softener and embodiment 10 (processing-WOV)
Figure G2007800092158D00403
Figure G2007800092158D00404
Embodiment 16-paint is anti-skidding
This embodiment tests " anti-skidding " property of the composition of some embodiments.These tests are to accomplish according to ASTM D4518-91 (be described below, it has been done change).The paint of being tested (it also is contrast) is a kind of solvent-free, lacklustre (matte), white vinyl acetate base paint (base paint), can buy from Akzo Nobel.The purpose that adds composition as shown in the table and mean particle size is in order to increase static friction.The result who produces is as calculating and be presented at the confficient of static friction in the table 5 according to said method of testing.
Completion is at the process of measurement of the lip-deep static friction that is coated, to be determined at the resistance that slides on the surface (paint) that is coated through measuring said static friction.For each paint sample, prepare skin of paint through using paint roller (paint roller).Said paint contains particle as shown in table 5.Painted dry one day with relief.Cover second layer paint, let its dry one day more thereafter.
Change to ASTM D4518-91 is meant through using rounded edge aluminium block (block) to replace the bloom of identical weight and polished surface.On the inclined-plane that said is placed on painted surface.During measuring, clean said aluminium block with acetone.
In order to obtain the identical constant speed of clinoplain, use the INSTRON dynamometer to carry out following program:
Absolute inclined-plane (absolute ramp)-0 to 300% prolongs (extension), and 480mm/min (～1.5+/-0.5 °/s)
The Kevlar yarn is used to avoid yarn to prolong (yarn extension) and good repeatability is provided.
Based on the length (X) on the height (h) on plane and plane (30cm), calculate angle of inclination (a) through trigonometry.Confficient of static friction is following to be measured:
Static friction=tan a; And
Static friction=tan (sin -1H/X)
Figure G2007800092158D00411
Table 5 confirms, compares with contrast or rubber texturizing agent, and the polymer composition of some embodiments provides suitable or better skid resistance.For institute's inventive compositions to some extent, 5% addition has all produced better effect.
Embodiment 17-paint breaks
Carry out the pliability test of paint composite based on BS EN ISO6860:1995.Paint composite prepares as shown in table 6, and it comprises and can buy to such an extent that unglazed white substrate is coated with lacquer from Akzo Nobel.Every kind of paint all is coated about 30 mil thick on cardboard substrate.Subsequently, each substrate is folded on the conical mandrel, to be determined at following minimum bend diameter that can reach of situation that paint does not break.
Can the result from table 6 find out that the said paint that contains the dispersion of some embodiments has sizable pliability.
Figure G2007800092158D00422
Embodiment 18-elongation at break (elongation) and Young's modulus
Mix paint sample according to the composition of describing in the table 7 and 8.Said paint composite be applied to can be antiseized (releasable) substrate on to form film.The wide 1cm of each sample, the long 5cm that cut down from these films.Use dynamometer to test three kinds of films of corresponding each composition.Carry out initial testing, to measure percentage elongation and the power of every kind of material when rupturing.Go out constraint rate (constrain) and Young's modulus (or elastic modelling quantity) by this data computation.The result is presented in the table 7 and 8.
Figure G2007800092158D00431
Figure G2007800092158D00441
Can see from table 7 and 8 that institute's inventive compositions demonstrates comparison has improvement according to (priming paint).Specifically, institute's inventive compositions has lower Young's modulus, and this shows that it has higher elastic properties of materials.
Embodiment 19-percentage elongation
Also use
Figure G2007800092158D00442
Material Testing Machine to test every kind of three kinds of paint sample of the dispersion that contains some embodiments; To be determined in the 3rd circulation maximum elongation rate of paint 1 and 3 when 4N and the maximum elongation rate of paint 2 when 1N.From previous test of elongation rate described in embodiment 18, select maximum power, so that it is in the Hookean region (horizontal zone of stress-strain diagram) of material.This test is to be used for measuring when applying identical power the difference of percentage elongation.The result is presented in the table 9.
Figure G2007800092158D00451
Table 9 confirms, adds the extensibility that the polyurethane-urea dispersion of being invented has been improved all three kinds of base paints.After adding the dispersion of being invented, the percentage elongation of base paint increases to twice at least.
Absorption-the time of embodiment 20-oil and water
In order to test the absorbability of comparing powder composition of the present invention with commercially available powder composition, several kinds of compositions have been tested, to measure the various needed times of Linseed oil, water and synthetic perspiration that absorb.In each test, on the powder of being invented He be purchased, respectively place Linseed oil, water or a synthetic perspiration.The time of this drop of record absorption is as shown in table 10.
Figure G2007800092158D00461
As shown in table 10, to compare with silica with nylon, the powder of being invented provides oil and water faster absorption, and compares with the polyurethanes powder that is purchased, and soak time similar or that improve is provided.
Absorption-the quality of embodiment 21-oil and water
In order to test the absorbability of comparing powder composition of the present invention with commercially available powder composition; Present embodiment has been tested several kinds of compositions, to measure among Linseed oil, water and the synthetic perspiration each according to the absorbed quality of method of testing ASTM D281-95 (having done change for water and synthetic perspiration).The result is presented in the table 11.
Figure G2007800092158D00471
As shown in table 11, composition of the present invention can absorb the same with the powder that is purchased or than its more quality.
Embodiment 22-the composition that comes off (Exfoliating Compositions)
The rational agents for defoliating of admixture is more prevalent in the cosmetic cleaning article.Early production depends on the grinding effect of broken shuck in the standard cosmetic base (standard cosmetic bases), and for the consumer, its perceptual image sand paper is the same.Current, have many derive from natural and route of synthesis can be used for making up the agents for defoliating of chemicals.Every type granular size and Grinding Quality can be controlled by strictness; Make the falling-off effect that to realize ideal through accurate preparation; And can produce stable, first-class product for the better understanding of the rheological equationm of state is feasible, said agents for defoliating is evenly distributed in the product.
Polyethylene (PE) spheroid is prevailing polymer agents for defoliating.The polyethylene spheroid of different size scope all can obtain.Can obtain the commercial sample of following level other polyethylene (PE) spheroid from A&E Connock (Perfumery&Cosmetics) Ltd:
65/100 mesh size (about 150-230 μ m),
35/48 mesh size (about 300-500 μ m),
24/32 mesh size (about 600-700 μ m),
14/16 mesh size (about 1200-1400 μ m).
Preparation has the following polyureas carbamate powder of following granular size to contrast with the PE spheroid:
The polyurethaneurea powder of the method preparation through Roach: 25-200 μ m
The polyurethaneurea powder of embodiment 7: 300-800 μ m
The polyurethaneurea powder of embodiment 3: 500-1000 μ m
Every kind of powder was joined in the shower gels (the Silk Glow Softening Silk Shower that is provided by Dove) with 15% (by weight); And with made, (Silk Glow Douche Gommage QuotidienneSoie Dove) compares as the product that comes off of agents for defoliating to contain oxidic polyethylene.
The composition that has by the polyurethaneurea powder of the method for Roach preparation does not provide any real decortication effect, because this particles of powder size is too little.Through contrast, embodiment 3 and 7 powder mix well with said shower gels and produce falling-off effect.Because the compressibility of said polyurethaneurea powder so they have soft more sense of touch, and is provided at the gentle more decortication effect on the skin.
Embodiment 23-film forming polymer
In cosmetics industry,, in face cosmetic, sunscreen product and the hair care goods, use many film forming polymers particularly at nail polish, mascara-eyeliner.Chemical composition that can be acrylate copolymer, polyurethanes, polyvinylpyrrolidone vinyl acetate, polyacrylic acid (carbomer (carbomer)).These can be used as typing with (styling) polymer or be used as thickener, and gloss, adhesion, wear resistence and the flexible transparent flexible film with different stage is provided.Embodiment 5,6 and 10 polyurethane-urea aqueous dispersion also can be used to provide these effects.
The major advantage of these compositions is improved elastic and pliability, softness and charming sense of touch and good wear resistence.As mentioned below; Two kinds of polyurethane polymer dispersions that test can be buied from Noveon: UR425 and UR450, and with said polyurethaneurea compositions relatively.
By the said film that is purchased dispersion curtain coating 20 mil thick of dispersion and embodiment 6.Compare their elastic property, it is presented in the table 12.
Figure G2007800092158D00491
The dispersion of embodiment 6 is compared with being purchased material, obviously shows extraordinary elastic property, because Young's modulus is much lower.The motion that this dispersion can produce high prescription elasticity (formula elasticity) and will comply with skin better.
Though described and thought preferred implementation of the present invention now; But those skilled in the art will recognize; Can make a change above that and modify and without prejudice to essence of the present invention, and applicant's expection change and modification that all are such comprises within the scope of the invention.

Claims (9)

1. Fabrid care composition, it comprises:
(a) washing agent or fabric softener composition; With
(b) polyurethane-urea of powder or aqueous dispersion form;
The percentage by weight of wherein said washing agent or fabric softener composition is greater than the percentage by weight of said polyurethane ester aqueous dispersion; Wherein said polyurethane-urea comprises the product of the polyester-urethane prepolymer and the cahin extension agent of isocyanate terminated; Said prepolymer is the product of PTMEG polymer or copolyether diol polymer, vulcabond and optional acidic glycol; Said vulcabond is the aromatic diisocyanates that is selected from phenylene vulcabond, tolylene vulcabond (TDI), eylylene diisocyanate, biphenylene vulcabond, naphthalene diisocyanate, methyl diphenylene diisocyanate (MDI) and their combination.
2. the composition of claim 1, wherein said washing agent or fabric softener are suitable in the washing machine.
3. the composition of claim 1, wherein said washing agent or fabric softener are suitable for hand washing.
4. the composition of claim 1, the form of wherein said washing agent or fabric softener is selected from powder, liquid, solid tablet, enclosed liquid and nonwoven sheet.
5. the composition of claim 1, wherein said cahin extension agent is selected from diamine chain extender, water and their combination.
6. the composition of claim 1, wherein said aqueous dispersion is selected from anionic dispersions and nonionic dispersion.
7. the composition of claim 1, wherein said acidic glycol is selected from 2,2-dihydroxymethyl acetate, 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid and their combination.
8. the composition of claim 1, wherein said polymer is to gather 1, the 4-butanediol ethere; Said vulcabond is 4; 4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate) or 4,4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate) and 2,4 '-mixture of di-2-ethylhexylphosphine oxide (phenyl isocyanate); And said acidic glycol is 2,2-dihydromethyl propionic acid or do not have said acidic glycol.
9. the composition of claim 1, wherein said polyurethane ester aqueous dispersion account for said Fabrid care composition about 0.1% to about 20% weight.
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