WO2020062327A1 - 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用 - Google Patents

非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用 Download PDF

Info

Publication number
WO2020062327A1
WO2020062327A1 PCT/CN2018/109674 CN2018109674W WO2020062327A1 WO 2020062327 A1 WO2020062327 A1 WO 2020062327A1 CN 2018109674 W CN2018109674 W CN 2018109674W WO 2020062327 A1 WO2020062327 A1 WO 2020062327A1
Authority
WO
WIPO (PCT)
Prior art keywords
chain extender
aqueous polyurethane
polyurethane dispersion
parts
diisocyanate
Prior art date
Application number
PCT/CN2018/109674
Other languages
English (en)
French (fr)
Inventor
周操
张洁
李棒棒
贾海东
Original Assignee
上海万华科聚化工科技发展有限公司
万华化学集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海万华科聚化工科技发展有限公司, 万华化学集团股份有限公司 filed Critical 上海万华科聚化工科技发展有限公司
Publication of WO2020062327A1 publication Critical patent/WO2020062327A1/zh

Links

Classifications

    • 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
    • C08G18/65—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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • A61K8/89—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • 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
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/65—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
    • 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
    • C08G18/65—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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38

Definitions

  • the invention relates to a non-ionic silicon-containing modified aqueous polyurethane dispersion and its preparation, and its application in hair cleaning compositions such as shampoo.
  • silicone oil is generally added to shampoo to achieve hair smoothness, but there is a problem when using silicone oil: as the frequency of shampooing increases, silicone oil will deposit on the hair and make the hair look flat. , Lack of fullness. At present, no commercially available shampoo has both the functions of dry hair, smoothness and volume.
  • Chinese patent application CN107126378A introduces "The Use of a Surfactant Composition and a Detergent Made From It", which mainly relates to the application of anionic water-based polyurethane in shampoo, which has a styling effect, but it cannot achieve fullness and smoothness Slippery effect.
  • the present invention provides a non-ionic silicon-containing modified water-based polyurethane dispersion.
  • the non-ionic silicon-containing modified water-based polyurethane dispersion is applied to hair cleaning products, which helps to achieve dry and smooth hair at the same time. Volumizing effect.
  • One aspect of the present invention is to provide a non-ionic silicon-containing modified aqueous polyurethane dispersion prepared by reacting a raw material including a diisocyanate-terminated prepolymer, a macromolecular siloxane, and an amine chain extender;
  • the diisocyanate-terminated prepolymer is obtained by reacting reaction components including isocyanate, glycol chain extender, hydroxysiloxane, polyol, and hydrophilic chain extender;
  • the hydrophilic chain extender is mainly Mono- and / or diols of which the chain and / or side chains contain polyethylene oxide segments.
  • the non-ionic silicon-containing polyurethane provided by the present invention has a silicon-oxygen bond in the main chain of the polyurethane through the reaction of hydroxysiloxane and isocyanate.
  • the structure of the repeating unit of the polyurethane and the repeating unit of the macromolecular siloxane is very similar.
  • the hydrophilic polyethylene oxide segments introduced by the hydrophilic chain extender are distributed in the aqueous phase, while the hydrophobic silicone and the hard end portion of the polyurethane are in the polyurethane micelles.
  • the macromolecular siloxane can be well encapsulated into the interior of the polyurethane micelles, so there is no need to additionally emulsify the macromolecular siloxane.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion of the present invention is used in hair cleaning compositions, for example, in shampoo.
  • the polyurethane-coated macromolecular siloxane forms a protective film on the polyurethane and the hair while adsorbing it. On the scales of the hair, this makes the hair smooth.
  • a protective film can be formed on the surface of the hair, which supplements the natural gum that is lost by the hair and fills the hair. Hollow, this also increases the spacing between the hairs and makes the hair plump. Therefore, by adding the silicon-containing modified aqueous polyurethane dispersion of the present invention to a hair cleansing composition such as shampoo, the effects of dry hair, smoothness and fullness can be achieved at the same time.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion is prepared by reacting a mixed dispersion including a diisocyanate-terminated prepolymer and a macromolecular siloxane with the amine chain extender. ; More preferably, the diisocyanate-terminated prepolymer is not subjected to a dispersion treatment before forming the mixed dispersion with the macromolecular siloxane. That is to say, the mixed dispersion is formed by mixing and dispersing the diisocyanate-terminated prepolymer and the macromolecular siloxane without dispersing treatment.
  • the "mixed dispersion” herein refers to a mixture of a macromolecular siloxane and a diisocyanate-terminated prepolymer in a dispersing machine, for example, dispersing and mixing at a speed of 200-4000r / min. Water, such as distilled water, is added to the water. In a specific embodiment, water can be added slowly during the dispersion process.
  • the diisocyanate-terminated prepolymer that has not been subjected to the dispersion treatment can be understood as not having been subjected to the dispersion treatment in the disperser described above.
  • the macromolecular siloxane refers to a siloxane having an average molecular weight of 10,000 g / mol or more, and in some preferred embodiments, for example, 10,000 to 60,000 g / mol; and the hydroxy siloxane used is preferably The average molecular weight is below 10,000 g / mol. In some preferred embodiments, for example, the average molecular weight is 1000-10000 g / mol, and the diisocyanate obtained by using a combination of a macromolecular siloxane and a hydroxysiloxane that meets the above molecular weight requirements is obtained on the one hand.
  • the viscosity of the capped prepolymer will not be too large to cause dispersal into an emulsion.
  • the obtained silicon-containing modified polyurethane dispersion is applied to hair cleaning products, which can better improve the smoothness of hair.
  • the macromolecular siloxane is preferably selected from the group consisting of aminosiloxane, polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, (polydimethylsiloxane) Silicone) (methylvinylsiloxane) copolymer and poly (dimethylsiloxane) (diphenylsiloxane) (methylvinylsiloxane) copolymer It is preferred that the average molecular weight of the macromolecular siloxane is 10,000 g / mol to 60,000 g / mol, such as 10,000 g / mol, 20,000 g / mol, 40,000 g / mol, 60,000 g / mol, and the like.
  • the specific raw materials of the macromolecular siloxane may be corresponding raw materials commercially available, such as, but not limited to, sicare2422, sicare2420, sicare2
  • the macromolecular siloxane is an aminosiloxane, and more preferably, the aminosiloxane has an average molecular weight of 15,000-60000 g / mol, for example, 15000 g / mol, 20000 g / mol, 35000 g / mol, 50000 g / mol, 60,000 g / mol, etc. It is preferred that the macromolecular siloxane is an aminosiloxane. Due to the steric hindrance effect of the macromolecular siloxane amino group, the reaction efficiency with the isocyanate is low, no gelation will occur, and hydrophilicity will occur during mixing and dispersion with the polyurethane.
  • the macromolecular aminosiloxane will easily migrate into the polyurethane hydrophobic segment, and the macromolecular siloxane can be obtained inside the polyurethane micelles.
  • a more stable lotion which can improve the effect on hair dryness and volume.
  • the nitrogen content of the aminosiloxane is ⁇ 0.3% by weight, and if the nitrogen content is too high, it is easy to react with the diisocyanate prepolymer, increase the viscosity of the prepolymer, and increase the difficulty of dispersion.
  • the polymerization unit of the polyethylene oxide segment contains 90-100% by weight of ethylene oxide repeating units; corresponding commercially available raw materials may be used, for example, using YmerTM N120 from Perstrop, etc.
  • the reaction component for preparing the diisocyanate-terminated prepolymer further includes a dithiol chain extender.
  • a silicon-containing polyurethane containing sulfur element can be obtained.
  • the silicon-containing polyurethane is applied to a hair cleaning composition such as shampoo, it can be well adsorbed on the hair such as the surface of the hair, and has the characteristics of lasting function.
  • the dithiol chain extender is a compound containing two mercapto groups with a molecular weight of less than 500 g / mol (number average molecular weight); preferably, the dithiol chain extender is selected from 1,2-ethanedithiol, 1
  • 1,4-butanedithiol and 1,3-propanedithiol more preferably 1,4-butanedithiol, using a preferred dithiol chain extender, can Improves adhesion to hair (e.g., hair) and improves the durability of plumping effects.
  • the hydroxysiloxane has the following structural formula (I):
  • the two R groups in the formula (I) are the same or different, and the R groups are selected from an alkyl group, and the specific type of the alkyl group is not particularly required); the value of n is 13-60.
  • the average molecular weight of the hydroxysiloxane is 1000-4000 g / mol, such as 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, and the like.
  • the isocyanate is selected from one or two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
  • the above combination is more preferably isophorone diisocyanate.
  • the glycol chain extender is a glycol compound having a number average molecular weight of less than 500 g / mol; in some preferred embodiments, it is preferably selected from 1,4-butanediol, 1,6-hexanediol, 1,4 -One or a combination of two or more of cyclohexanedimethanol, neopentyl glycol, 1,3-propanediol, and ethylene glycol; more preferably 1,4-cyclohexanedimethanol.
  • the number average molecular weight of the amine chain extender is less than 500 g / mol, which is an amine chain extender containing active hydrogen. In some preferred embodiments, it is preferably selected from, but not limited to, ethylene diamine, hexamethylene diamine, penta One or a combination of two or more of methylene diamine, diethylene triamine, isophorone diamine, hydroxyethyl ethylene diamine, 4,4-diphenylmethane diamine, and diethanolamine Is more preferably ethylenediamine. In the process of preparing the non-ionic silicon-containing modified polyurethane dispersion, an appropriate amount of an amine capping agent, such as monoethanolamine, may also be added.
  • an amine capping agent such as monoethanolamine
  • the average molecular weight of the polyol is 500-5000g / mol, for example, 500g / mol, 1000g / mol, 2000g / mol, 4000g / mol, 5000g / mol, etc .; preferably 500-3000g / ml, more preferably 1000-2000g / mol .
  • the polyol is selected from, but not limited to, polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol Polyethylene adipate glycol, Polyethylene adipate 1,4-butanediol ester glycol, Poly adipate neopentyl glycol ester glycol, Polyadipate 1,6- One or a combination of two or more of hexanediol ester diol and neopentyl glycol adipate 1,6-hexanediol ester diol; more preferably polypropylene glycol, preferably 500-3000 g / mol, especially polypropylene glycol having an average molecular weight of 1000-2000 g / mol.
  • Polyols can be selected from commercially available raw materials, such as DL2000 and DL1000 (Shandong),
  • the reaction components used to prepare the diisocyanate-terminated prepolymer also preferably include a catalyst.
  • the catalyst is preferably selected from the group consisting of dibutyltin dilaurate and / or organic bismuth catalysts. These The catalyst can use existing commercially available raw materials, such as, but not limited to, organic bismuth 8108, a leading company in the United States, dibutyltin dilaurate of Aladdin, Valikat Bi 2010 of Umicore, and the like.
  • the relationship between parts by weight of the main raw materials for the non-ionic silicon-containing modified aqueous polyurethane dispersion is as follows:
  • the isocyanate is 3-10 parts, preferably 4.5-8 parts, such as 3, 4, 5, 6, 8 and the like;
  • 0.2-8 parts of the glycol chain extender preferably 0.5-3 parts, such as 0.2, 0.5, 1, 3, 5, 8 parts, etc .;
  • 0-8 parts of the polyhydric alcohol preferably 0.05-5 parts, such as 0.05, 1, 3, 5, 6, 8 and the like;
  • hydrophilic chain extender 2-10 parts of the hydrophilic chain extender, preferably 4-8 parts, such as 2, 4, 6, 8, 10, etc .;
  • 0.05-4 parts of the amine chain extender preferably 0.2-1.5 parts, such as 0.05, 0.1, 0.2, 1, 1.5, 3, 4 parts, etc .;
  • 0.001-0.008 parts of the catalyst preferably 0.002-0.005 parts, such as 0.001, 0.002, 0.003, 0.005, 0.008 parts, etc .;
  • the dithiol chain extender is 0-5 parts, preferably 0.1-2 parts, such as 0.1, 0.2, 0.5, 1, 2 and the like.
  • water and an organic solvent are also used.
  • the total amount of water used is preferably 20-80 parts by weight, and preferably 30-60 parts by weight.
  • the total amount of organic solvents used is preferably 5-30 parts by weight. Parts are preferably 15-25 parts by weight.
  • the diisocyanate-terminated prepolymer in the specific preparation process of the diisocyanate-terminated prepolymer, it is usually performed in the presence of an organic solvent, and the diisocyanate-terminated prepolymer is usually diluted with an organic solvent when diluting the diisocyanate-terminated prepolymer;
  • the organic solvent may specifically be Organic solvents commonly used in the field such as methyl ethyl ketone, acetone, cyclohexanone and the like are not particularly limited, and acetone is preferably used as the solvent.
  • aqueous polyurethane dispersions for example, for diluting chain extenders such as amine chain extenders, and for diisocyanate-terminated prepolymers and macromolecules.
  • chain extenders such as amine chain extenders
  • diisocyanate-terminated prepolymers and macromolecules When the siloxane is mixed and dispersed to form a mixed dispersion, water is used for dispersion during the dispersion process, and usually adding some water during the specific operations such as dispersing or diluting the chain extender is well known to those skilled in the art and will not be described in detail.
  • the amount of the organic solvent and water can be specifically determined by those skilled in the art according to the needs of the reaction or preparation, which is not particularly limited; for example, in some embodiments, the total amount of the organic solvent may be 5-30 in the above-mentioned raw material formulation system.
  • the weight part is preferably 15-25 parts by weight, and the amount of water used may be, for example, 20-80 parts by weight, preferably 30-60 parts by weight.
  • Another aspect of the present invention provides a method for preparing the non-ionic silicon-containing modified aqueous polyurethane dispersion as described above, including the following steps:
  • the dithiol chain extender is further added to the reaction system of step (1); preferably a catalyst is added to the reaction system, preferably the catalyst is selected from dibutyltin dilaurate and / Or organic bismuth catalyst; the organic solvent used in this step may be, for example, acetone, methyl ethyl ketone, or cyclohexanone, which is commonly used in the preparation of diisocyanate-terminated prepolymers, which is not particularly limited.
  • the reaction temperature in step (1) is preferably 75-85 ° C, and the end point of the reaction is preferably the reaction until the NCO reaches a theoretical value or close to the theoretical value.
  • Step (2) After diluting the diisocyanate-terminated prepolymer with an organic solvent, it is mixed with the macromolecular siloxane and stirred well; the organic solvent may be, for example, acetone, methyl ethyl ketone, or cyclohexanone. Organic solvents commonly used for isocyanate-terminated prepolymers are not particularly limited. Step (2) can be specifically performed at 0-35 ° C, and the stirring time is, for example, 5-10min.
  • step (3) Disperse the solution obtained in step (2), add water for dispersion during specific operation, and disperse with water to obtain silicon-containing modified polyurethane (that is, a mixed dispersion of diisocyanate-terminated prepolymer and macromolecular siloxane) ), And then carry out a chain extension reaction with the amine chain extender, for example, and an amine chain extender diluted with water;
  • the reaction temperature in step (3) is preferably 20-45 ° C.
  • the reaction time is, for example, 5 to 15 minutes and the like, specifically, 10 minutes and the like.
  • the method for preparing a non-ionic silicon-containing modified aqueous polyurethane dispersion has the characteristics of simple production process, convenient operation, safety and non-toxicity, and the like.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion After the diisocyanate-terminated prepolymer is prepared, it is mixed and dispersed with the macromolecular siloxane without gelation. And can obtain a more stable emulsion.
  • the macromolecular siloxane is added after the reaction of the polyurethane prepolymer to obtain a diisocyanate-terminated prepolymer. At this time, the temperature is relatively low, gelation is not easy to occur, and a stable emulsion is easily obtained. It is preferable that the macromolecular siloxane is a macromolecular siloxane (aminosiloxane) containing an amino group.
  • the molecular siloxane contains an amino group, which easily reacts with an isocyanate and easily gels.
  • the macromolecular siloxane is added after the diisocyanate-terminated prepolymer is prepared and added before the prepolymer is dispersed, which can ensure the reverse conversion process to obtain a more stable emulsion; on the other hand, if the macromolecular silicone The alkane is added after the diisocyanate-terminated prepolymer is dispersed, which is not conducive to the reverse conversion process. It is difficult for the macromolecular siloxane to be completely coated inside the polyurethane micelles, and the stability of the obtained emulsion is not good.
  • the solid content of the prepared non-ionic silicon-containing modified aqueous polyurethane dispersion is 20-40 wt%, such as 20 wt%, 30 wt%, 40 wt%, and the like.
  • the average particle diameter of the non-ionic silicon-containing modified aqueous polyurethane dispersion is preferably in the range of 30-150 nm, and more preferably in the range of 40-100 nm.
  • a surfactant composition includes at least a nonionic silicon-containing modified aqueous polyurethane dispersion, and the nonionic silicon-containing modified aqueous polyurethane dispersion.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion described above or the non-ionic silicon-containing modified aqueous polyurethane dispersion prepared by the method described above.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion provided by the present invention has a hydrophilic group of a polyethylene oxide segment and a non-ionic hydrophilic group, and can be used with various types of surfactants and / or conditioning agents. Agent without affecting its performance (especially viscosity). Therefore, the present invention is based on the silicon-containing modified aqueous polyurethane dispersion, and also provides a surfactant composition in combination with other surfactants.
  • the other surfactants are not particularly limited in type, for example, in the application
  • the hair cleansing composition (such as shampoo) can be applied in combination with various surfactants allowed in the art; the other surfactants are preferably selected from, but not limited to, sodium lauryl sulfate, alkyl ammonium Compounds, alkyl betaines, alkyl aminopropyl betaines, alkyl sulfobetaines, alkyl glycines, alkyl carboxyglycines, alkyl glycosides, acyl taurates and acyl glutamates One or two or more combinations; preferably, the alkyl and acyl groups have 8-19 carbon atoms, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 Carbon atoms; in some preferred embodiments, the other surfactant is more preferably selected from the group consisting of sodium lauryl sulfate and / or cocamidopropyl betaine.
  • a hair cleansing composition which contains the above-mentioned surfactant composition; preferably, the surfactant is a non-ionic silicon-containing modified aqueous polyurethane dispersion and the other surface-active properties described above.
  • the hair cleansing composition further contains one or at least two of a conditioner, a thickener, and an antidandruff agent.
  • the mass percentages of the non-ionic silicon-containing modified aqueous polyurethane dispersion and the other surfactants in the hair cleaning composition are preferably 1-20%, 14-20, respectively. %.
  • the hair cleansing composition may also contain other components allowed in the art, such as preservatives, fragrances and / or functional components, etc., which are not described in detail here.
  • the hair cleansing composition contains each component in the following mass percentages: the non-ionic silicon-containing modified aqueous polyurethane dispersion 1-20%, and the other surfactants 14-20 %, Conditioner 0.1-1%, thickener 0.1-3%, anti-dandruff agent 0.1-3%, preservative 0.3-0.5%, flavor 0-3%, water 33.5-92.45%;
  • the type of the conditioning agent is not particularly limited, and various types of conditioning agents allowed in the field can be used.
  • the thickener is preferably selected from, but not limited to, sodium chloride, cocoamide MIPA, PEG-150 distearate, ammonium chloride, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyacrylic acid, One or a combination of at least two of polyacrylate, polyurethane, and high molecular weight polyethylene oxide (number average molecular weight 6000-1000 g / mol), more preferably sodium chloride.
  • inorganic salts such as sodium chloride for thickening.
  • the inorganic salts have the function of electrostatic shielding and can reduce the electrostatic repulsion between the hydrophilic groups of the surfactant.
  • the electric double layer structure of the micelle is compressed, so that the surface area of the hydrophilic head of the surfactant is reduced, the stacking parameters are increased, and the micellar structure is changed accordingly, from spherical to rod-shaped, and one-dimensional growth forms flexibility.
  • the linear micelles caused a transient three-dimensional network structure, and the apparent viscosity showed a sudden increase.
  • the hydrophilic group of the non-ionic silicon-containing modified aqueous polyurethane dispersion of the present invention is a non-ionic type, which is a non-ionic polyurethane, and does not cause the static electricity of the inorganic salt to the surfactant due to the use of the inorganic salt in the formulation system.
  • the shielding effect is significantly weakened, and it will not be neutralized and demulsified due to the combination with other types of indicated active agents.
  • the micelles of the anionic polyurethane are also two-electron layers, which will significantly reduce the electrostatic shielding effect of the inorganic salt on the surfactant.
  • the cationic polyurethane it is easy to work with hair cleaning compositions such as shampoos. Neutralization of the anionic surfactant caused demulsification and could not be used.
  • the antidandruff agent is preferably selected from, but not limited to, one or a combination of at least two of ganbolin, zinc pyrithione (ZPT), piroctone ethanolamine salt (OCT), and triclosan (DP-300), More preferred is ZPT.
  • the preservative can be any preservative that is permitted in the field of daily chemicals, such as but not limited to carson, paraben, sodium benzoate, salicylic acid, DMDM hydantoin, phenoxyethanol, etc. One or a combination of two or more of these is preferably sodium benzoate.
  • the fragrance may be artificially synthesized or / and natural fragrance, and more preferably, natural fragrance is used.
  • Another aspect of the present invention also provides an application for cleaning or caring for hair using the hair cleansing composition described above.
  • the non-ionic silicon-containing modified aqueous polyurethane dispersion of the present invention is used in hair cleaning compositions, for example, in shampoo.
  • the polyurethane-coated macromolecular siloxane forms a protective film on the polyurethane and the hair while adsorbing it. On the scales of the hair, this makes the hair smooth.
  • a protective film can be formed on the surface of the hair, which supplements the natural gum that is lost by the hair and fills the hair. Hollow, this also increases the spacing between the hairs and makes the hair plump. Therefore, by adding the non-ionic silicon-containing modified aqueous polyurethane dispersion of the present invention to a hair cleaning composition such as shampoo, the effects of dry hair, smoothness and fullness can be achieved at the same time.
  • a dithiol chain extender is used to prepare a silicon-containing polyurethane containing sulfur element, which can be well adsorbed on the hair surface To play a lasting role.
  • the production process of the non-ionic aqueous polyurethane dispersion of the present invention is simple, easy to operate, safe and non-toxic.
  • a silicon-oxygen bond is incorporated in the main chain of the polyurethane.
  • the hydrophilic polyethylene oxide segments are distributed in the water phase, while the hydrophobic siloxane It is similar to the hard end of polyurethane in the interior of the polyurethane micelles, and is compatible with the macromolecular siloxane, so it does not need to demulsify the macromolecular siloxane.
  • the hydrophilic group of the non-ionic silicon-containing polyurethane of the present invention is a polyethylene oxide segment, which is a non-ionic hydrophilic group, and can be used with various types of surfactants and conditioners without affecting its performance. (Especially viscosity), when formulating hair cleansing compositions such as shampoos, the combination can be flexibly formulated. For example, when using inorganic salts such as sodium chloride for thickening, it will not significantly reduce the electrostatic shielding effect of inorganic salts on surfactants as with anionic polyurethane, and it will not be as easy as using cationic polyurethane with shampoos. The anionic surfactant neutralizes and breaks the emulsion, making it unusable.
  • raw materials or equipment used in the following examples or comparative examples are commercially available raw materials or equipment, for example:
  • PPG1000 Shandong Bluestar Dongda Chemical Co., Ltd .
  • PPG2000 Shandong Bluestar Dongda Chemical Co., Ltd .
  • N120 Ymer TMN120, Perstorp
  • CHDM 1,4-cyclohexanedimethanol, Kailing Chemical
  • KF6001 Shin-Etsu Chemical Silicone Co., Ltd., with a number average molecular weight of 1870 g / mol;
  • KF6002 Shin-Etsu Chemical Silicone Co., Ltd., with a number average molecular weight of 3205 g / mol;
  • HMDI Dicyclohexylmethane diisocyanate
  • IPDI isophorone diisocyanate, Bayer GmbH
  • Organic bismuth 8108 a leading company in the United States;
  • DMPA 2,2-Dimethylolpropionic acid, Guangzhou Jieluhua Biological Co., Ltd .;
  • Sicare 2422 Silok Silicone Co., Ltd., nitrogen content ⁇ 0.05%, molecular weight 25000g / mol (number average molecular weight);
  • the particle size testing instrument is Malvern laser particle size analyzer, mastersizer 2000.
  • Disperser zoncn, H32A02D2K.
  • the formula of the shampoo is shown in the following table.
  • the preparation method includes the following steps: According to the ratio, add the components in Table 1 in order with stirring at room temperature of 1500r / min, adjust the pH to 5.5-6, and stir for 15-30 minutes to Completely dispersed.
  • Tress compression volume test Unused hair tress is washed with 15 wt% ammonium lauryl sulfate aqueous solution and placed at 25 degrees Celsius. After drying at 50% humidity, use MTT175 (DIASTRONMTT175) to test the hair tress pulled through the 1cm hole Compression work at 15 cm; repeat the above test operation after washing with the tested shampoo. Take the difference between the two compression powers to characterize the effect of the sample on the abundance of the tresses.
  • Abundance test 5 women use 2 weeks (three to five times a week) to evaluate the score (1-5 points system). The softness of the hair is 1 point, and the hair is 5 points.
  • Dandruff 5 women were evaluated for scoring (1-5 points) after 2 weeks (three to five times a week). Dandruff was severely scored as 1 point, and almost no dandruff was scored as 5 points.
  • Persistence The performance of five women after two days of use is compared with the performance immediately after washing, with 5 being the best.
  • Application Example 1-3 has a prominent abundance in the hair tress and consumer evaluation, and has good smoothness and product appearance, and is not prone to dandruff. Compared with the comprehensive performance of the application example Poor, can not take into account the fullness, smoothness, durability is also poor, and even some appearances are worse; and application example 3 has a better comprehensive effect and a longer lasting effect.

Abstract

一种非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用，该非离子型含硅水性聚氨酯分散体应用于毛发清洁产品中，有助于同时达到干发爽滑和丰盈的效果。所述含硅改性水性聚氨酯分散体，采用包括二异氰酸酯封端预聚物、大分子硅氧烷和胺扩链剂的原料反应制得；其中，所述二异氰酸酯封端预聚物采用包括异氰酸酯、二元醇扩链剂、羟基硅氧烷、多元醇和亲水扩链剂的反应组分反应得到；所述亲水扩链剂为主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇。

Description

非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用 技术领域
本发明涉及一种非离子型含硅改性水性聚氨酯分散体及其制备，以及其在洗发水等毛发清洁组合物中的应用。
背景技术
随着人类社会的进步，人们对于清洁用品的需求越来越多的同时，也对清洁用品的性能提出了更高的要求。洗发水是人们在日常生活中经常使用的清洁用品，除了满足清洁这一最基本的要求之外，对其提出了更高的要求。对于头发细的人通常使用“丰盈”洗发水，以增加头发的体积。但是，常规的丰盈洗发香波具有某些缺点，例如，由于有效成分在头发上沉积过多而不能提供真正的丰盈效果。与丰盈洗发香波相关的,另一个缺点是它们提高头发丰盈度的同时,头发会很毛躁,不顺滑。目前一般会在洗发水中加入硅油来达到头发的顺滑感，但在使用硅油时会存在一个问题：随着洗发频率的增加,硅油会沉积在发丝上，使头发看起来很扁塌，缺乏丰盈感。目前市售的洗发水还没有能同时拥有干发爽滑和丰盈这两项功能的。
中国专利申请CN107126378A介绍了《一种表面活性剂组合物及由其制成的清洁剂的使用》，其中主要涉及阴离子水性聚氨酯在洗发水的应用,起到定型的效果，但是无法同时达到丰盈和顺滑的功效。
因而，如何改善现有洗发产品，以使得其同时能够达到干发爽滑和丰盈的这两项功能显得非常有必要。
发明内容
有鉴于此，本发明提供一种非离子型含硅改性水性聚氨酯分散体，该非离子型含硅改性水性聚氨酯分散体应用于毛发清洁产品中，有助于同时达到干发爽滑和丰盈的效果。
本发明为达到其目的，采用的技术方案如下：
本发明一方面提供一种非离子型含硅改性水性聚氨酯分散体，采用包括二异氰酸酯封端预聚物、大分子硅氧烷和胺扩链剂的原料反应制得；
其中，所述二异氰酸酯封端预聚物采用包括异氰酸酯、二元醇扩链剂、羟基硅氧烷、多元醇和亲水扩链剂的反应组分反应得到；所述亲水扩链剂为主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇。
本发明所提供的非离子型含硅聚氨酯，通过羟基硅氧烷和异氰酸酯反应在聚氨酯的主链上接入了硅氧键，聚氨酯的重复单元和大分子硅氧烷的重复单元的结构很类似，在分散成乳液的过程中，由所述亲水扩链剂所引入的亲水的聚氧化乙烯链段分布在水相中，而疏水的硅氧烷和聚氨酯硬端部分在聚氨酯胶束的内部；由于相似相容，大分子硅氧烷能够很好地被包覆进聚氨酯胶束的内部，因而不需要额外去乳化大分子硅氧烷。
本发明的非离子型含硅改性水性聚氨酯分散体，应用于毛发清洁组合物中，例如应用于洗发水中，聚氨酯包覆的大分子硅氧烷在聚氨酯和头发上形成保护膜的同时吸附在头发的毛鳞片上，这样使得头发具有顺滑性；同时由于聚氨酯和头发表面极易形成氢键，从而在头发表面能形成一层保护膜，补充头发流失的天然胶质，填补了头发中空洞，这样也增加了发丝之间的间距，使得头发变得丰盈。因而，在毛发清洁组合物例如洗发水中添加本发明的含硅改性水性聚氨酯分散体，能同时达到干发爽滑和丰盈的效果。
较佳的一些实施方案中，所述非离子型含硅改性水性聚氨酯分散体采用包括二异氰酸酯封端预聚物和大分子硅氧烷的混合分散物与所述胺扩链剂反应制得；较优选所述二异氰酸酯封端预聚物为在与所述大分子硅氧烷形成所述混合分散物之前是未经过分散处理的。也就是说，所述混合分散物是采用没有经过分散处理的二异氰酸酯封端预聚物和大分子硅氧烷混合剪切分散而形成的。采用这种方案，大分子硅氧烷和二异氰酸酯封端预聚物在混合分散时，能得到大分子硅氧烷更完全的包覆在聚氨酯胶束内部的稳定性较佳的乳液；将其应用于毛发 清洁产品中时能达到较好的效果。此处所述的“混合分散物”是指将大分子硅氧烷和二异氰酸酯封端预聚物的混合物在分散机中分散混合，例如在200-4000r/min的转速分散混合，在分散过程中加入水，例如蒸馏水，在具体实施方式中可将水在分散过程中缓慢加入其中。而未经过分散处理的二异氰酸酯封端预聚物，可以理解为未经过前面所述的在分散机中分散处理。
本发明中，所述大分子硅氧烷是指平均分子量10000g/mol以上的硅氧烷，较佳的一些实施方案中，例如为10000-60000g/mol；而所用的羟基硅氧烷较佳的为平均分子量10000g/mol以下，较佳的一些实施方案中，例如平均分子量为1000-10000g/mol，采用符合上述分子量要求的大分子硅氧烷和羟基硅氧烷组合，一方面得到的二异氰酸酯封端预聚物粘度不会过大而造成无法分散成乳液，另一方面所得的含硅改性聚氨酯分散体应用于毛发清洁产品中，能更好改善毛发的顺滑性。
一些实施方案中，所述大分子硅氧烷优选选自氨基硅氧烷、聚二甲基硅氧烷、聚二乙基硅氧烷、聚甲基苯基硅氧烷、(聚二甲基硅氧烷)(甲基乙烯基硅氧烷)共聚物和聚(二甲基硅氧烷)(二苯基硅氧烷)(甲基乙烯基硅氧烷)共聚物中的一种或两种以上的混合物；优选所述大分子硅氧烷的平均分子量为10000g/mol-60000g/mol，例如10000g/mol、20000g/mol、40000g/mol、60000g/mol等。大分子硅氧烷的具体原料可以采用市售的相应原料，例如但不限于斯洛柯公司的sicare2422，sicare2420，sicare2400，sicare2429等。
在一些较佳的实施方案中，所述大分子硅氧烷为氨基硅氧烷，更优选所述氨基硅氧烷具有15000-60000g/mol的平均分子量，例如15000g/mol、20000g/mol、35000g/mol、50000g/mol、60000g/mol等。优选大分子硅氧烷为氨基硅氧烷，由于大分子硅氧烷氨基的位阻效应，与异氰酸酯反应的效率较低，不会发生凝胶，在与聚氨酯混合分散过程中，会发生亲水基团向水相迁移和疏水基团向油相迁移的过程(相反转过程)，大分子氨基硅氧烷会容易迁移到聚氨酯疏水链段中，能得到大分子硅氧烷在聚氨酯胶束内部的稳定性更佳的乳液，从而能提升在毛发干发爽滑和丰盈方面的效果。更进一步优选所述氨基硅氧烷的 含氮量≤0.3wt％，而若含氮量太高，容易和二异氰酸酯预聚体反应，增加预聚体的粘度，增加分散的难度。
在一些优选实施方式中，所述亲水扩链剂中，所述聚氧化乙烯链段的聚合单元中含有90-100wt％的环氧乙烷重复单元；可以采用市售的相应原料，例如采用Perstrop公司的YmerTM N120等。
优选的一些实施方案中，制备所述二异氰酸酯封端预聚物的反应组分还包括二元硫醇扩链剂。采用该方案能获得含有硫元素的含硅聚氨酯，将这种含硅聚氨酯应用于毛发清洁组合物例如洗发水中时，可以很好的吸附在毛发例如头发表面上，具有持久发挥作用的特点。所述二元硫醇扩链剂为分子量小于500g/mol(数均分子量)的含有两个巯基的化合物；优选所述二元硫醇扩链剂选自1,2-乙二硫醇、1,4-丁二硫醇和1,3-丙二硫醇中的一种或两种以上的组合，更优选为1，4-丁二硫醇，采用优选的二元硫醇扩链剂，可以提高在毛发(例如头发)上的附着力，提高丰盈效果的持续性。
一些实施方式中，所述羟基硅氧烷具有如下结构式(I)：
Figure PCTCN2018109674-appb-000001
式(I)中的两个R基团相同或不同，所述R基团选自烷基,烷基的具体种类并无特殊要求)；n的取值为13-60。优选所述羟基硅氧烷的平均分子量为1000-4000g/mol，例如1000g/mol、2000g/mol、3000g/mol、4000g/mol等。
在一些优选实施方式中，所述异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或两种以上的组合，更优选为异佛尔酮二异氰酸酯。
所述二元醇扩链剂为数均分子量小于500g/mol的二元醇化合物；在一些优选实施方式中，优选选自1，4-丁二醇、1，6-己二醇、1,4- 环己烷二甲醇、新戊二醇、1，3-丙二醇和乙二醇中的一种或两种以上的组合；更优选为1,4-环己烷二甲醇。
所述胺扩链剂的数均分子量小于500g/mol，为含有活泼氢的胺扩链剂，在一些优选实施方式中，优选选自但不限于乙二胺、六亚甲基二胺、五亚甲基二胺、二亚乙基三胺、异佛尔酮二胺、羟乙基乙二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或两种以上的组合，更优选为乙二胺。在制备非离子型含硅改性水性聚氨酯分散体过程中，还可以加入适量的胺封端剂，例如单乙醇胺等。
所述多元醇的平均分子量为500-5000g/mol，例如500g/mol、1000g/mol、2000g/mol、4000g/mol、5000g/mol等；优选500-3000g/ml，更优选1000-2000g/mol。一些优选实施方式中，所述多元醇选自但不限于聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或两种以上的组合；更优选为聚丙二醇，优选使用具有500-3000g/mol特别是1000-2000g/mol的平均分子量的聚丙二醇。多元醇具体可以选用市售的相应原料，例如东大的DL2000，DL1000(山东蓝星东大化工有限责任公司)。
制备所述二异氰酸酯封端预聚物所用的反应组分还优选包括催化剂，在一些优选实施方式中，本发明优选所述催化剂选自二丁基二月桂酸锡和/或有机铋催化剂，这些催化剂可以采用现有市售原料，例如但不限于美国领先公司的有机铋8108，阿拉丁的二丁基二月桂酸锡，优美科的Valikat Bi 2010等。
一些优选实施方式中，所述非离子型含硅改性水性聚氨酯分散体的主要制备原料的重量份关系如下：
所述异氰酸酯3-10份，优选4.5-8份，例如3、4份、5份、6份、8份等；
所述二元醇扩链剂0.2-8份，优选0.5-3份，例如0.2、0.5、1、3、5、8份等；
所述羟基硅氧烷2-10份，优选3-6份，例如2、3、4、6、8、10份等；
所述多元醇0-8份，优选0.05-5份，例如0.05、1、3、5、6、8份等；
所述亲水扩链剂2-10份，优选4-8份，例如2、4、6、8、10份等；
所述胺扩链剂0.05-4份，优选0.2-1.5份，例如0.05、0.1、0.2、1、1.5、3、4份等；
所述大分子硅氧烷2-10份，优选5-8份，例如2、4、5、7、8、10份等；
所述催化剂0.001-0.008份，优选0.002-0.005份，例如0.001、0.002、0.003、0.005、0.008份等；
所述二元硫醇扩链剂0-5份，优选0.1-2份，例如0.1、0.2、0.5、1、2份等。
具体实施方式中，还会用到水和有机溶剂，所用的水的总量较佳为20-80重量份优选30-60重量份；用到的有机溶剂的总量较佳为5-30重量份优选15-25重量份。
本领域技术人员所知晓的，在二异氰酸酯封端预聚物具体制备过程中，通常在有机溶剂存在下进行，在稀释二异氰酸酯封端预聚物时通常用有机溶剂来稀释；有机溶剂具体可以采用领域常用的有机溶剂例如丁酮、丙酮、环己酮等，不作特别限定，较佳的使用丙酮为溶剂。本领域技术人员所了解的，在制备水性聚氨酯分散体的过程中，通常还会用到水，例如用于稀释扩链剂比如胺扩链剂，以及将二异氰酸酯封端预聚物和大分子硅氧烷混合分散形成混合分散物时在分散过程中用水进行分散等，通常会在分散或稀释扩链剂等具体操作时加入一些水是本领域技术人员所熟知的，不作赘述。有机溶剂和水的用量本领域技术人员根据反应或制备需要而能具体确定，对此不作特别限定；例如，在一些实施方案中，有机溶剂的总用量在上述原料配方体系中可以是5-30重量份优选15-25重量份，水的用量例如可以是20-80重量份优选30-60重量份。
本发明另一方面提供一种制备如上文所述的非离子型含硅改性水性聚氨酯分散体的方法，包括如下步骤：
(1)将所述异氰酸酯、所述二元醇扩链剂、所述羟基硅氧烷、所述多元醇和所述亲水扩链剂在有机溶剂存在下混合反应制备所述二异氰酸酯封端预聚物；优选在步骤(1)的反应体系中还加入所述二元硫醇扩链剂；优选所述反应体系中添加有催化剂，优选所述催化剂选自二丁基二月桂酸锡和/或有机铋催化剂；该步骤所用的有机溶剂例如可以是丙酮、丁酮或环己酮等制备二异氰酸酯封端预聚物常用的有机溶剂，对此不作特别限定。步骤(1)的反应温度优选为75-85℃，反应终点优选为反应至NCO达到理论值或接近理论值。
(2)将所述二异氰酸酯封端预聚物用有机溶剂稀释后，与所述大分子硅氧烷混合搅拌均匀；该有机溶剂可以例如为丙酮、丁酮或环己酮等本领域稀释二异氰酸酯封端预聚物所常用的有机溶剂，对此不作特别限定。步骤(2)具体可以在0-35℃下进行，搅拌时间例如为5-10min。
(3)将步骤(2)所得溶液分散，具体操作时加入用于分散的水，用水分散得到含硅改性的聚氨酯(即二异氰酸酯封端预聚物和大分子硅氧烷的混合分散物)，之后将其与所述胺扩链剂，比如将其和用水稀释的胺扩链剂进行扩链反应；步骤(3)的反应温度优选为20-45℃。反应时间例如为5-15min等，具体如10min等。
(4)对步骤(3)反应得到的乳液脱溶剂。脱溶剂的具体操作方式为本领域所熟知，不作赘述，例如通过减压蒸馏等方式达到脱除溶剂的目的。
本发明制备非离子型含硅改性水性聚氨酯分散体的方法，具有生产工艺简单，便于操作和安全无毒等特点。
本发明在制备所述非离子型含硅改性水性聚氨酯分散体过程中，在制得二异氰酸酯封端预聚物后，再和大分子硅氧烷混合搅拌并分散，不会发生凝胶，且能得到较为稳定的乳液。大分子硅氧烷是在聚氨酯预聚体反应完得到二异氰酸酯封端预聚物之后加入的，此时温度 较低，不容易发生凝胶，易于得到稳定乳液。优选大分子硅氧烷为含有氨基的大分子硅氧烷(氨基硅氧烷)，由于大分子硅氧烷氨基的位阻效应，与异氰酸酯反应的效率较低，不会发生凝胶，在聚氨酯的分散过程中，会发生亲水基团向水相迁移和疏水基团向油相迁移的过程(相反转过程)，大分子硅氧烷会容易迁移到聚氨酯疏水链段中，能得到大分子硅氧烷在聚氨酯胶束内部的稳定性更佳的乳液。而如果大分子硅氧烷在聚氨酯预聚体反应阶段加入的话，由于大分子硅氧烷自身的粘度很大，会降低反应效率，而且此时温度较高，容易发生凝胶；特别是如果大分子硅氧烷含有氨基，容易和异氰酸酯反应，容易发生凝胶。而将大分子硅氧烷在二异氰酸酯封端预聚物制得后且在该预聚物分散之前加入，可确保发生相反转过程，得到稳定性较佳的乳液；反之，若大分子硅氧烷是在二异氰酸酯封端预聚物分散完之后加入，不利于发生相反转过程，大分子硅氧烷较难被全部包覆进聚氨酯胶束内部，得到的乳液稳定性欠佳。
一些实施方式中，所制得的所述非离子型含硅改性水性聚氨酯分散体的固含量为20-40wt％，例如20wt％、30wt％、40wt％等。
所述的非离子型含硅改性水性聚氨酯分散体的平均粒径优选在30-150nm范围内，更优选在40-100nm范围内。
本发明另一方面还提供一种表面活性剂组合物，所述表面活性剂组合物中至少包括非离子型含硅改性水性聚氨酯分散体，所述非离子型含硅改性水性聚氨酯分散体为上文所述的非离子型含硅改性水性聚氨酯分散体或上文所述的方法制得的非离子型含硅改性水性聚氨酯分散体。
本发明提供的非离子型含硅改性水性聚氨酯分散体，其亲水基团为聚氧化乙烯链段，为非离子型亲水基团，可以和各种类型的表面活性剂和/或调理剂使用，且不会影响其性能(尤其是粘度)。因而，本发明基于所述含硅改性水性聚氨酯分散体，还提供一种和其他表面活性剂组合的表面活性剂组合物，所述其他表面活性剂并无特别的种类局限，例如在应用于毛发清洁组合物(比如洗发水)时可以和本领域 所允许使用的各种表面活性剂组合应用；所述其他表面活性剂优选选自但不限于月桂醇聚醚硫酸酯钠、烷基氨氧化物、烷基甜菜碱、烷基氨基丙基甜菜碱、烷基磺基甜菜碱、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基糖苷、酰基牛磺酸盐和酰基谷氨酸盐中的一种或两种以上的组合；其中优选所述烷基和酰基分别具有8-19个碳原子，例如8、9、10、11、12、13、14、15、16、17、18、19个碳原子；在一些较佳的实施方式中，更优选所述其他表面活性剂选自月桂醇聚醚硫酸酯钠和/或椰油酰胺基丙基甜菜碱。
本发明另一方面还提供一种毛发清洁组合物，其中含有上文所述的表面活性剂组合物；优选该表面活性剂是非离子型含硅改性水性聚氨酯分散体和所述的其他表面活性剂组合的，优选所述毛发清洁组合物中还含有调理剂、增稠剂、去屑剂中的一种或至少两种。在一些较佳实施方式中，所述非离子型含硅改性水性聚氨酯分散体和所述其他表面活性剂在所述毛发清洁组合物中的质量百分比优选分别为1-20％、14-20％。该毛发清洁组合物还可以含有本领域所允许使用的其他组分，例如防腐剂、香精和/或功效性组分等，对此不作一一赘述。
优选的一些实施方式中，所述毛发清洁组合物中含有如下质量百分比的各组分：所述非离子型含硅改性水性聚氨酯分散体1-20％，所述其他表面活性剂14-20％，调理剂0.1-1％，增稠剂0.1-3％，去屑剂0.1-3％，防腐剂0.3-0.5％，香精0-3％，水33.5-92.45％；
所述调理剂的种类并没有特别的限定，在该领域所允许使用的各种类型的调理剂均可以使用。在一些优选实施方式中，优选选自但不限于聚季铵盐、瓜儿胶、季铵化蛋白中的一种或至少两种的组合，更优选聚季铵盐；
所述增稠剂优选选自但不限于氯化钠、椰油酰胺MIPA、PEG-150二硬脂酸酯、氯化铵，羟乙基纤维素、羟丙基甲基纤维素、聚丙烯酸、聚丙烯酸酯、聚氨酯和高分子量的聚氧化乙烯(数均分子量6000-1000g/mol)中的一种或至少两种的组合，更优选氯化钠。在配置毛发清洁组合物例如洗发水时，较优选的使用氯化钠等无机盐来进 行增稠，无机盐有静电屏蔽的作用，可以减小表面活性剂的亲水基团间的静电斥力，胶团的双电层结构被压缩，使得表面活性剂亲水头面积减小，堆积参数就会增大了，胶束结构也会随之发生改变，从球形变为棒状，一维增长形成柔性的线状胶束，促使体系出现瞬时的三维网络结构，表观粘度表现出突增的现象。本发明的非离子型含硅改性水性聚氨酯分散体其亲水基团为非离子型，为一种非离子聚氨酯，不会由于配方体系中使用无机盐而使得无机盐对表面活性剂的静电屏蔽作用被显著减弱，也不会由于与其他类型的表明活性剂组合使用而发生中和导致破乳等现象。然而，使用阴离子聚氨酯时，阴离子聚氨酯的胶束也是双电子层，会显著地减少无机盐对表面活性剂的静电屏蔽作用；而使用阳离子聚氨酯时，则很容易和毛发清洁组合物例如洗发水中的阴离子表面活性剂发生中和作用，从而破乳，无法使用。
所述去屑剂优选选自但不限于甘宝素、吡啶硫酮锌(ZPT)、吡罗克酮乙醇胺盐(OCT)和三氯生(DP-300)中的一种或至少两种的组合，更优选ZPT。
所述防腐剂采用具有日用化学品领域所允许使用的防腐试剂均可，例如但不限于卡松、尼泊金酯、苯甲酸钠、水杨酸、DMDM乙内酰脲、苯氧乙醇等中的一种或两种以上的组合，优选苯甲酸钠。
所述香精采用人工合成或/和天然香精均可，较优选采用天然香精。
本发明另一方面还提供一种应用，使用上文所述的毛发清洁组合物清洁或护理毛发。
本发明提供的技术方案具有如下有益效果：
本发明的非离子型含硅改性水性聚氨酯分散体，应用于毛发清洁组合物中，例如应用于洗发水中，聚氨酯包覆的大分子硅氧烷在聚氨酯和头发上形成保护膜的同时吸附在头发的毛鳞片上，这样使得头发具有顺滑性；同时由于聚氨酯和头发表面极易形成氢键，从而在头发表面能形成一层保护膜，补充头发流失的天然胶质，填补了头发中空洞，这样也增加了发丝之间的间距，使得头发变得丰盈。因而，在 毛发清洁组合物例如洗发水中添加本发明的非离子型含硅改性水性聚氨酯分散体，能同时达到干发爽滑和丰盈的效果。
一些优选方案中在制备本发明的非离子型含硅改性水性聚氨酯分散体时，使用二元硫醇扩链剂，制得含有硫元素的含硅聚氨酯，可以很好地吸附在头发表面上，从而发挥持久的作用。
另外，本发明非离子型水性聚氨酯分散体的生产工艺简单，便于操作，安全无毒。通过羟基硅氧烷和异氰酸酯的反应在聚氨酯的主链上接入了硅氧键，在分散成乳液的过程中，亲水的聚氧化乙烯链段分布在水相中，而疏水的硅氧烷和聚氨酯硬端部分在聚氨酯胶束的内部，相似相容，大分子硅氧烷能够很好地被包覆进聚氨酯胶束的内部，因而不需要额外去乳化大分子硅氧烷。
本发明的非离子型含硅聚氨酯的亲水基团为聚氧化乙烯链段，其为非离子型亲水基团，可以和各种类型的表面活性剂以及调理剂使用，而不影响其性能(尤其是粘度)，用于配制毛发清洁组合物例如洗发水时，可以灵活调配组合。例如当使用氯化钠等无机盐来进行增稠，不会像使用阴离子聚氨酯那样显著地减少无机盐对表面活性剂的静电屏蔽作用，也不会像使用阳离子聚氨酯那样很容易和洗发水中的阴离子表面活性剂发生中和作用，从而破乳，无法使用。
具体实施方式
为了更好的理解本发明的技术方案，下面结合实施例进一步阐述本发明的内容，但本发明的内容并不仅仅局限于以下实施例。
以下实施例或对比例中所用的原料或设备若未特别说明，均为市售原料或设备，例如：
PPG1000：山东蓝星东大化工有限公司；
PPG2000：山东蓝星东大化工有限公司；
N120：Ymer TMN120,柏斯托；
CHDM：1,4-环己烷二甲醇，凯凌化工；
KF6001：信越化学有机硅有限公司，数均分子量为1870g/mol；
KF6002：信越化学有机硅有限公司，数均分子量为3205g/mol；
HMDI：二环己基甲烷二异氰酸酯；
IPDI：异佛尔酮二异氰酸酯，拜耳有限公司；
有机铋8108：美国领先公司；
DMPA:2，2-二羟甲基丙酸，广州结露华生物有限公司；
sicare 2422：斯洛柯有机硅有限公司，含氮量<0.05％，分子量为25000g/mol(数均分子量)；
EDA：乙二胺，廊裕化学；
粒径测试仪器为马尔文激光粒度仪，mastersizer 2000。
分散机：zoncn，H32A02D2K。
实施例1：硅改性的聚氨酯1
将48克PPG1000、9克CHDM、71克N120、73克KF6001加入到带有冷凝器和搅拌器的四口烧瓶中，再加入65克的IPDI、0.05克有机铋8108、26.6克丙酮，在75℃反应1.5小时，NCO值为1.97％(理论值为2.07％)；
降温至20℃后，加入266克丙酮和100克sicare 2422；
在高速(1400转/min)剪切分散下加入726克水，搅拌5min后得粗乳液；然后加入3.2克EDA和13克去离子水的混合溶液，搅拌反应10min，反应温度为35℃；
之后将粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到粒径(指平均粒径)d＝40nm和固含为30wt％的水性聚氨酯乳液。
实施例2：硅改性的聚氨酯2
将2克PPG2000、45克CHDM、109克N120、154克KF6002加入到带有冷凝器和搅拌器的四口烧瓶中，再加入167克的HMDI、0.07克有机铋8108、38.6克丙酮，在75℃反应1.5小时，NCO值为2.60％(理论值为2.67％)；
降温至20℃后，加入243克丙酮和140克sicare 2422；
在高速(1500转/min)剪切分散下加入1036克水，搅拌5min后得粗乳液，然后加入8克EDA和40克去离子水的混合溶液，继续搅 拌10min，反应温度为40℃；
粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到粒径(指平均粒径)d＝60nm和固含为30wt％水性聚氨酯乳液。
实施例3：硅改性的聚氨酯3
将1克PPG1000、39.1克CHDM、5克1,4-丁二硫醇，109克N120、90克KF6001加入到带有冷凝器和搅拌器的四口烧瓶中，再加入141克的IPDI、0.07克有机铋8108、38.6克丙酮，在75℃反应1.5小时，NCO值为3.15％(理论值为3.26％)；
降温至20℃后，加入386克丙酮和140克sicare 2422；
在1500转/min剪切分散下加入1036克水，搅拌5min后得粗乳液，然后加入8克EDA和40克去离子水的混合溶液，继续搅拌10min，反应温度为40℃；
粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到平均粒径d＝60nm和固含为30wt％水性聚氨酯乳液。
对比例1：(在预聚物制备反应过程中加入氨基硅氧烷)
将48克PPG1000，9克CHDM，71克N120，73克KF6001加入到带有冷凝器和搅拌器的四口烧瓶中，再加入65克的IPDI和100克sicare 2422，0.05克有机铋8108，26.6克丙酮在75℃反应1.5小时，发现发生凝胶现象。
对比例2：(在二异氰酸酯封端预聚物分散后加入氨基硅氧烷)
将48克PPG1000，9克CHDM，71克N120，73克KF6001加入到带有冷凝器和搅拌器的四口烧瓶中，再加入65克的IPDI，0.05克有机铋8108，26.6克丙酮在75℃反应1.5小时，NCO值为1.97％(理论值为2.07％)；
降温至20℃后，加入266克丙酮；在高速剪切下加入726克水，搅拌反应5min后得粗乳液；
然后加入3.2克EDA和13克去离子水的混合溶液，然后加入100 克sicare 2422，继续搅拌10min；粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到粒径d＝40nm和固含为30wt％水性聚氨酯乳液，静置两小时之后发现分层的现象。
对比例3：聚氨酯10(未使用羟基硅氧烷和大分子硅氧烷)
将87克PPG1000、9克CHDM、71克N120、65克的IPDI、0.05克有机铋8108、23.2克丙酮，在75℃反应1.5小时，NCO值为2.3％(理论值为2.38％)；
降温至20℃后，加入232克丙酮；
在1400转/min剪切分散下加入450克水，搅拌5min后得粗乳液；然后加入3.2克EDA和13克去离子水的混合溶液，搅拌反应10min，反应温度为35℃；
之后将粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到平均粒径d＝45nm和固含为30wt％的水性聚氨酯乳液。
对比例4：阴离子聚氨酯
将30克PPG1000、30克CHDM、10克DMPA、80克N120、90克KF6001加入反应装置中，再加入141克的IPDI、0.08克有机铋8108、38.1克丙酮，在75℃反应1.5小时，NCO值为3.8％(理论值为2.89％)；
降温至20℃后，加入381克丙酮和140克sicare 2422；
在1400转/min剪切分散下加入450克水，搅拌5min后得粗乳液；然后加入8克EDA和32克去离子水的混合溶液，搅拌反应10min，温度为35度；
之后将粗乳液在45℃、0.01MPa真空条件下脱去溶剂丙酮，得到平均粒径d＝45nm和固含为30wt％的阴离子水性聚氨酯乳液。
应用例(洗发水)
洗发水配方如下表所示，其制备方法包括以下步骤：按照比例，室温下1500r/min搅拌下依次加入表1中的各组分，并调整pH值至 5.5-6，搅拌15-30分钟至完全分散即可。
表1(各组分用量为质量比分比％)
Figure PCTCN2018109674-appb-000002
测试方法
A.发束丰盈测试
发束压缩体积测试：未使用过的发束采用15wt％十二烷基硫酸铵 水溶液洗发后置于25摄氏度，50％湿度干燥后，使用MTT175(DIA STRON MTT175)测试头发束在1cm孔拉动15cm时的压缩功；采用被测试的洗发水进行洗涤后重复上述测试操作。取两次压缩功的差值来表征样品对发束的丰盈效果。
B.消费者测试感官评估实验
丰盈度测试：5位女性使用2周后(一周三到五次)进行打分评价(1-5分制)，头发软榻无丰盈效果为1分，头发丰盈度好为5分。
顺滑度测试：5位女性使用2周(一周三到五次)后进行打分评价(1-5分制)，干发缠结现象严重、难梳理、阻力非常大为1分，无缠结、极易梳理、几乎无阻力为5分。
头屑：采用5位女性使用2周(一周三到五次)后进行打分评价(1-5分制)，头屑现象严重为1分，几乎无头屑产生为5分。
持久性：采用5位女性使用两天之后的性能与刚洗完之后的性能对比，5分为最佳。
评价结果
Figure PCTCN2018109674-appb-000003
*：对比应用例4的粘度无法达到正常的粘度，正常粘度为1000-5000，该样品只能达到500，未进行这些测试。
由评价结果可以看出，应用例1-3在发束及消费者评价均具有比 较突出的丰盈度，且具有很好的顺滑度和产品外观，同时不易起头屑，而对比应用例综合性能不佳，无法兼顾丰盈度、顺滑度，持久性也较差，甚至有些外观也较差；而应用例3综合效果更佳，效果更持久。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。

Claims (14)

  1. 一种非离子型含硅改性水性聚氨酯分散体，其特征在于，采用包括二异氰酸酯封端预聚物、大分子硅氧烷和胺扩链剂的原料反应制得；
    其中，所述二异氰酸酯封端预聚物采用包括异氰酸酯、二元醇扩链剂、羟基硅氧烷、多元醇和亲水扩链剂的反应组分反应得到；所述亲水扩链剂为主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇；
    制备所述二异氰酸酯封端预聚物的反应组分优选还包括二元硫醇扩链剂；
    所述大分子硅氧烷的平均分子量为10000g/mol以上，优选为10000-60000g/mol；
    所述羟基硅氧烷的平均分子量为10000g/mol以下，优选1000-10000g/mol；
    优选的，所述非离子型含硅改性水性聚氨酯分散体采用包括二异氰酸酯封端预聚物和大分子硅氧烷的混合分散物与所述胺扩链剂反应制得，所述二异氰酸酯封端预聚物为在与所述大分子硅氧烷形成所述混合分散物之前是未经过剪切分散处理的。
  2. 根据权利要求1所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，
    所述大分子硅氧烷选自氨基硅氧烷、聚二甲基硅氧烷、聚二乙基硅氧烷、聚甲基苯基硅氧烷、(聚二甲基硅氧烷)(甲基乙烯基硅氧烷)共聚物和聚(二甲基硅氧烷)(二苯基硅氧烷)(甲基乙烯基硅氧烷)共聚物中的一种或两种以上的混合物；
    优选所述大分子硅氧烷为氨基硅氧烷，更优选所述氨基硅氧烷具有15000-60000g/mol的平均分子量；更进一步优选所述氨基硅氧烷的含氮量≤0.3wt％。
  3. 根据权利要求1或2所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，所述亲水扩链剂中，所述聚氧化乙烯链段的聚合单元中含有90-100wt％的环氧乙烷重复单元。
  4. 根据权利要求1-3任一项所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，所述二元硫醇扩链剂为数均分子量小于500g/mol的含有两个巯基的化合物；
    优选所述二元硫醇扩链剂选自1,2-乙二硫醇、1,4-丁二硫醇和1,3-丙二硫醇中的一种或两种以上的组合，更优选为1，4-丁二硫醇。
  5. 根据权利要求1-4任一项所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，
    所述羟基硅氧烷具有如下结构式(I)：
    Figure PCTCN2018109674-appb-100001
    式(I)中的两个R基团相同或不同，所述R基团选自烷基；n的取值为13-60；
    优选结构式(I)的羟基硅氧烷的平均分子量为1000-4000g/mol。
  6. 根据权利要求1-5任一项所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，
    所述异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或两种以上的组合，优选为异佛尔酮二异氰酸酯；
    所述二元醇扩链剂为数均分子量小于500g/mol的二元醇化合物；优选选自1，4-丁二醇、1，6-己二醇、1,4-环己烷二甲醇、新戊二醇、1，3-丙二醇和乙二醇中的一种或两种以上的组合；优选为1,4-环己烷二甲醇；
    所述胺扩链剂的数均分子量小于500g/mol，为含有活泼氢的胺扩链剂，优选选自乙二胺、六亚甲基二胺、五亚甲基二胺、二亚乙基三胺、异佛尔酮二胺、羟乙基乙二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或两种以上的组合，更优选为乙二胺。
  7. 根据权利要求1-6任一项所述的非离子型含硅改性水性聚氨酯 分散体，其特征在于，
    所述多元醇的平均分子量为500-5000g/mol，优选500-3000g/ml，更优选1000-2000g/mol；
    优选所述多元醇选自聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或两种以上的组合，更优选为聚丙二醇。
  8. 根据权利要求1-7任一项所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，制备所述非离子型含硅改性水性聚氨酯分散体的原料主要包括如下重量份的各组分：
    所述异氰酸酯3-10份，优选4.5-8份；
    所述二元醇扩链剂0.2-8份，优选0.5-3份；
    所述羟基硅氧烷2-10份，优选3-6份；
    所述多元醇0-8份，优选0.05-5份；
    所述亲水扩链剂2-10份，优选4-8份；
    所述胺扩链剂0.05-4份，优选0.2-1.5份；
    所述大分子硅氧烷2-10份，优选5-8份；
    所述二元硫醇扩链剂0-5份，优选0.1-2份。
  9. 根据权利要求8所述的非离子型含硅改性水性聚氨酯分散体，其特征在于，制备所述二异氰酸酯封端预聚物所用的反应组分还包括催化剂，优选所述催化剂选自二丁基二月桂酸锡和/或有机铋催化剂；用量优选为0.001-0.008份，进一步优选0.002-0.005份。
  10. 一种制备如权利要求1-9任一项所述的非离子型含硅改性水性聚氨酯分散体的方法，其特征在于，包括如下步骤：
    (1)将所述异氰酸酯、所述二元醇扩链剂、所述羟基硅氧烷、所述多元醇和所述亲水扩链剂在有机溶剂存在下混合反应制备所述二异氰酸酯封端预聚物；优选在步骤(1)的反应体系中还加入所述二元硫醇扩链剂；优选所述反应体系中添加有催化剂，优选所述催化剂选自二丁基二月桂酸锡和/或有机铋催化剂；步骤(1)的反应温度优 选为75-85℃；
    (2)将所述二异氰酸酯封端预聚物稀释后，与所述大分子硅氧烷混合搅拌均匀；
    (3)将步骤(2)所得溶液分散得到含硅改性的聚氨酯，将其与所述胺扩链剂进行扩链反应，反应温度优选为20-45℃；
    (4)对步骤(3)反应得到的乳液脱溶剂。
  11. 根据权利要求10所述的方法，其特征在于，所制得的非离子型所述含硅改性水性聚氨酯分散体的固含量为20-40wt％，平均粒径为30-150nm，优选为40-100nm。
  12. 一种表面活性剂组合物，其特征在于，所述表面活性剂组合物中至少包括非离子型含硅改性水性聚氨酯分散体，所述非离子型含硅改性水性聚氨酯分散体为权利要求1-9任一项所述的非离子型含硅改性水性聚氨酯分散体或权利要求10-11任一项所述的方法制得的非离子型含硅改性水性聚氨酯分散体；
    优选所述表面活性剂组合物中还包括其他表面活性剂，所述其他表面活性剂优选选自月桂醇聚醚硫酸酯钠、烷基氨氧化物、烷基甜菜碱、烷基氨基丙基甜菜碱、烷基磺基甜菜碱、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基糖苷、酰基牛磺酸盐和酰基谷氨酸盐中的一种或两种以上的组合；其中优选上述表面活性剂中所述的烷基和酰基分别具有8-19个碳原子；更优选所述其他表面活性剂选自月桂醇聚醚硫酸酯钠和/或椰油酰胺基丙基甜菜碱。
  13. 一种毛发清洁组合物，其特征在于，其中含有权利要求12所述的表面活性剂组合物；优选所述毛发清洁组合物中还含有调理剂、增稠剂、去屑剂中的一种或至少两种；
    优选的，所述毛发清洁组合物中含有如下质量百分比的各组分：所述含硅改性水性聚氨酯分散体1-20％，所述其他表面活性剂14-20％，调理剂0.1-1％，增稠剂0.1-3％，去屑剂0.1-3％，防腐剂0.3-0.5％，香精0-3％，水33.5-92.45％；
    所述调理剂优选选自聚季铵盐、瓜儿胶、季铵化蛋白中的一种或至少两种的组合，更优选聚季铵盐；
    所述增稠剂优选选自氯化钠、椰油酰胺MIPA、PEG-150二硬脂酸酯、氯化铵，羟乙基纤维素、羟丙基甲基纤维素、聚丙烯酸、聚丙烯酸酯、聚氨酯和数均分子量6000-10000g/mol的聚氧化乙烯(中的一种或至少两种的组合，更优选氯化钠；
    所述去屑剂优选选自甘宝素、ZPT、OCT和DP-300中的一种或至少两种的组合，更优选ZPT。
  14. 一种应用，其特征在于，使用权利要求13所述的毛发清洁组合物清洁或护理毛发。
PCT/CN2018/109674 2018-09-30 2018-10-10 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用 WO2020062327A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811155999.1 2018-09-30
CN201811155999.1A CN110964168B (zh) 2018-09-30 2018-09-30 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用

Publications (1)

Publication Number Publication Date
WO2020062327A1 true WO2020062327A1 (zh) 2020-04-02

Family

ID=69951017

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/109674 WO2020062327A1 (zh) 2018-09-30 2018-10-10 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用

Country Status (2)

Country Link
CN (1) CN110964168B (zh)
WO (1) WO2020062327A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605610A (zh) * 2022-04-20 2022-06-10 江苏恒力化纤股份有限公司 一种含硅网络结构架桥接枝聚氨酯及其制备方法和应用

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111349210A (zh) * 2020-05-07 2020-06-30 邦弗特新材料股份有限公司 一种高强度非离子水性聚氨酯乳液及其制备方法
CN115089513A (zh) * 2020-11-26 2022-09-23 徐美铃 一种山茶籽油提取物滋润保湿面霜
CN114805783B (zh) * 2021-01-18 2023-05-26 万华化学集团股份有限公司 一种亲水扩链剂的制备方法及扩链剂在水性聚氨酯中的应用
CN114130320B (zh) * 2021-10-24 2024-04-16 武汉中科先进材料科技有限公司 电子墨水微胶囊、电子墨水及制备方法和柔性显示屏
CN114872388B (zh) * 2022-04-30 2023-09-22 维尔特新材料科技(无锡)有限公司 一种低VOCs释放的玻镁板复合地板及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1487962A (zh) * 2001-01-26 2004-04-07 3M 用于化妆品应用的甲硅烷基化聚氨酯-脲组合物
WO2012096124A1 (ja) * 2011-01-13 2012-07-19 住友精化株式会社 水溶性ポリアルキレンオキシド変性物
CN106432670A (zh) * 2016-09-16 2017-02-22 淄博鲁瑞精细化工有限公司 有机硅改性聚氨酯共聚物织物柔软剂的制备方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2708199B1 (fr) * 1993-07-28 1995-09-01 Oreal Nouvelles compositions cosmétiques et utilisations.
GB9405592D0 (en) * 1994-03-22 1994-05-11 Zeneca Ltd Process
CA2232588A1 (en) * 1995-09-26 1997-04-03 Ameron International Corporation Polysiloxane polyurethane compositions
FR2798852B1 (fr) * 1999-09-29 2003-05-30 Oreal Composition de lavage des matieres keratiniques, a base d'un agent tensio-actif detergent, d'une silicone fonctionnalisee et d'un terpolymere acrylique
US6613314B1 (en) * 2000-07-27 2003-09-02 L'oreal Reshapable hair styling composition comprising polyurethane dispersions
US6433073B1 (en) * 2000-07-27 2002-08-13 3M Innovative Properties Company Polyurethane dispersion in alcohol-water system
GB0101736D0 (en) * 2001-01-23 2001-03-07 Unilever Plc Cosmetic composition
US20050209428A1 (en) * 2002-06-19 2005-09-22 Krishnan Tamareselvy Breathable polyurethanes, blends, and articles
US8591923B2 (en) * 2005-12-16 2013-11-26 L'oreal Cosmetic compositon comprising a (thio)urethane/(thio)urea copolymer capable of forming at least 3 hydrogen bonds, and a method of cosmetic treatment
EP2039347A4 (en) * 2006-07-03 2013-08-21 Shiseido Co Ltd COSMETIC PREPARATION FOR HAIR
EP2178948B1 (de) * 2007-08-14 2017-04-05 Momentive Performance Materials GmbH Neue polyharnstoff- und/oder polyurethan-polyorganosiloxan-verbindungen
US20110027211A1 (en) * 2008-03-26 2011-02-03 Bayer Materialscience Ag Hair styling composition
CN101514242B (zh) * 2009-01-06 2011-08-10 华东理工大学 一种含聚二甲基硅氧烷的聚己内酯型聚氨酯的制备方法
CN102206921B (zh) * 2011-01-21 2012-10-24 北京服装学院 一种聚醚嵌段氨基硅油柔软整理剂及其制备方法和应用
FR3006183B1 (fr) * 2013-06-03 2015-07-31 Oreal Composition cosmetique comprenant des polymeres associatifs non io-niques et des tensioactifs non ioniques, et procede de traitement cosmetique
DE102013106906A1 (de) * 2013-07-01 2015-01-08 Evonik Industries Ag Siloxan-Polymere mit zentralem Polysiloxan-Polymerblock mit terminalen organofunktionellen Resten umfassend Harnstoff- und/oder Carbamat-Gruppen sowie Aminosäure-Reste
CN105482439A (zh) * 2016-01-07 2016-04-13 华南理工大学 一种硅油改性聚氨酯手感剂及其制备方法与应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1487962A (zh) * 2001-01-26 2004-04-07 3M 用于化妆品应用的甲硅烷基化聚氨酯-脲组合物
WO2012096124A1 (ja) * 2011-01-13 2012-07-19 住友精化株式会社 水溶性ポリアルキレンオキシド変性物
CN106432670A (zh) * 2016-09-16 2017-02-22 淄博鲁瑞精细化工有限公司 有机硅改性聚氨酯共聚物织物柔软剂的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605610A (zh) * 2022-04-20 2022-06-10 江苏恒力化纤股份有限公司 一种含硅网络结构架桥接枝聚氨酯及其制备方法和应用
CN114605610B (zh) * 2022-04-20 2023-08-01 江苏恒力化纤股份有限公司 一种含硅网络结构架桥接枝聚氨酯及其制备方法和应用

Also Published As

Publication number Publication date
CN110964168A (zh) 2020-04-07
CN110964168B (zh) 2021-09-07

Similar Documents

Publication Publication Date Title
WO2020062327A1 (zh) 非离子型含硅水性聚氨酯分散体及其制备和在毛发清洁中的应用
DE60112948T2 (de) Polyurethandispersion in alkohol-wasser-system
TWI468181B (zh) 以聚碳酸酯多元醇類為主且適用於個人保養產品之聚胺基甲酸酯分散液
EP1035144B1 (de) Wasserlösliche oder wasserdispergierbare polymere Salze
US20040001798A1 (en) Self-adhesive cationic or amphoteric polyurethanes
FR2743297A1 (fr) Composition cosmetiques a base de polycondensats ionisables multisequences polysiloxane/polyurethane et/ou polyuree en solution et utilisation
WO2014074299A1 (en) Silicon-containing zwitterionic linear copolymer composition
EP2688929B1 (de) Polyurethanharnstoff-mischung für die haarkosmetik
JP4104790B2 (ja) 化粧料
JP2003508560A (ja) ウレタン及び／または尿素官能基を含有するオリゴマー及びポリマーに基づく化粧品
EP3892258A1 (en) Composition containing water-soluble non-ionic polyurethane dispersion, and preparation method therefor
CN109923141B (zh) 包含聚氨酯-聚有机硅氧烷共聚物的个人护理组合物
EP1410782B1 (en) Cosmetic composition comprising an amphiphilic urethane resin
TW201000148A (en) Cosmetic compositions for application to the skin
EP3020454A1 (de) Polyurethanharnstoffe für Haarstyling-Zusammensetzungen
CN109419643B (zh) 含水性聚氨酯分散体的洗发剂组合物及该分散体的用途
JP4165675B2 (ja) 化粧品用樹脂組成物およびその製法、それを用いた化粧品
KR101961487B1 (ko) 고기능성 실리콘 에멀젼 조성물 및 제조 방법
JP2015052105A (ja) 化粧料用ウレタン−（メタ）アクリル複合樹脂水性分散液
US11964032B2 (en) Aqueous polyurethane functional mask substrate and application thereof
JP2021514978A (ja) ヘアスタイルの耐性を改善するための化粧品組成物
CN113440436B (zh) 一种含有非离子型含硅改性水性聚氨酯分散体的bb霜
CN106999368A (zh) 涂布有锌盐的聚氨基甲酸酯微米粒子和制备其的方法
KR20200070242A (ko) 미용 조성물 및 이를 포함하는 세정 및 관리 제품
CN112778498B (zh) 一种水性改性聚氨酯分散体及其用途与其制备的头发调理剂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18935686

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18935686

Country of ref document: EP

Kind code of ref document: A1