WO2020113616A1 - 一种含有水性非离子聚氨酯分散体的组合物及其制备方法 - Google Patents

一种含有水性非离子聚氨酯分散体的组合物及其制备方法 Download PDF

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Publication number
WO2020113616A1
WO2020113616A1 PCT/CN2018/120265 CN2018120265W WO2020113616A1 WO 2020113616 A1 WO2020113616 A1 WO 2020113616A1 CN 2018120265 W CN2018120265 W CN 2018120265W WO 2020113616 A1 WO2020113616 A1 WO 2020113616A1
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weight
glycol
hair
polyurethane dispersion
diisocyanate
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English (en)
French (fr)
Inventor
李棒棒
周操
许诺
贾海东
张洁
曲鹏飞
孙家宽
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Wanhua Chemical Group Co Ltd
Shanghai Wanhua Keju Chemical Technology Development Co Ltd
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Wanhua Chemical Group Co Ltd
Shanghai Wanhua Keju Chemical Technology Development Co Ltd
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Priority to EP18941986.4A priority Critical patent/EP3892258B1/en
Priority to US17/278,171 priority patent/US12251463B2/en
Publication of WO2020113616A1 publication Critical patent/WO2020113616A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/044—Suspensions
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • 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
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5422—Polymers characterized by specific structures/properties characterized by the charge nonionic

Definitions

  • the invention belongs to the field of cleaning and care, and relates to a composition containing water-based nonionic polyurethane.
  • the hair is mainly composed of the epidermis, cortex, and medulla from the outside to the inside.
  • the epidermis is made up of many small scales (ie, hairy scales) that overlap. It is a protective layer. If the scales on the hair are neatly arranged, it will refract more light and the hair will look bright and moving; if the scales are scratched or damaged, the hair will easily break and appear frizzy. After the hair is dyed and scalded, the moisture content of the hair scales will decrease sharply, which will cause the hair scales to curl up, which will reduce the combability and luster of the hair. It is also the main reason for the "stickiness" and fragility of the damaged hair.
  • patent document CN105188851A uses a shampoo containing siloxane grafted cassava powder to provide the effect of hair volume gain.
  • the use of siloxane-grafted cassava powder particles achieves smoothness without Sacrificing the volume, and then obtaining the effect of lifting the hair root through the combination of conditioning agents, the essence of this patent document is to use silicone conditioning to improve the astringency after adding the particles.
  • silicone conditioning to improve the astringency after adding the particles.
  • the silicon compounds in the shampoo can make the hair smooth, but because these silicon-containing compounds are insoluble in water and the structure is very stable and difficult to biodegrade, the silicon wrapped in the hair and scalp is not easy to clean. Long-term use will cause a certain burden on the hair and the environment.
  • Patent document CN102020774A discloses a water-permeable and waterproof PU water-based resin used for fabric coating. It is mentioned that the use of sulfonate can greatly improve the hydrophilicity of PUD to obtain a good moisture retention effect.
  • One use is to In personal care products such as cosmetics and shampoos; however, the water absorption and moisturizing effect of PUD mentioned in this patent document does not provide a fullness effect in shampoos, but instead reduces the fullness of hair through water absorption and moisturization effects.
  • the technical problem to be solved by the present invention is to provide a composition based on nonionic polyurethane, which can achieve the effect of dry hair, smoothness and fullness at the same time by adding an aqueous nonionic polyurethane dispersion.
  • the present invention provides a composition comprising an aqueous nonionic polyurethane dispersion, including the following ingredients:
  • conditioning agent 0.01 to 5 parts by weight of conditioning agent; preferably 0.1 to 2 parts by weight;
  • the aqueous nonionic polyurethane dispersion is a product including the following components obtained by a reaction, preferably, the reaction is a normal reaction at 70 to 80° C. under normal pressure:
  • S1 at least one diisocyanate, the amount of which is added is 5-25wt%, preferably 9-13wt%;
  • Macromolecular polyol its number average molecular weight is 500-3000g/mol, preferably the number average molecular weight is about 1000-2000g/mol, and its added amount is 1-25wt%, preferably 4-15wt%;
  • S3 at least one monohydric alcohol and/or dihydric alcohol whose main chain and/or side chain contains polyoxyethylene segments, has a number average molecular weight of about 500-3000 g/mol, and its added amount is 1-20 wt%, preferably 7 -10wt%;
  • At least one diol small molecule chain extender containing active hydrogen having a molecular weight of 60-400 g/mol, and its added amount is 0.1-10 wt%, preferably 1-5% by weight;
  • At least one diamine small molecule chain extender containing active hydrogen having a molecular weight of 59-200 g/mol, and its added amount is 0.01-5 wt%, preferably 0.04-0.7 wt%;
  • S6 low boiling point organic solvent, the amount of addition is 0.2-2 times the total weight of S1-S5, preferably 0.5-1.5 times;
  • the added amount of each component is the content of the total weight of the reaction system, wherein the total weight of the reaction system is the sum of the weights of S1-S5 and S7 and S8, which is 100 wt%.
  • S6 is a solvent and is removed in the final system.
  • the component (a) aqueous nonionic polyurethane dispersion is an aqueous nonionic polyurethane dispersion with a solid content of 20-50% by weight, and the particle size of the aqueous nonionic polyurethane dispersion is 10 nm to 100 nm, preferably 10 nm to 60 nm.
  • the diisocyanate in component S1 is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate It is preferably one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
  • the macromolecular polyol described in component S2 is polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polycarbonate glycol ⁇ Polyethylene adipate glycol, poly 1,4-butanediol adipate glycol, neopentyl adipate glycol, poly adipate 1,6- One or more of hexanediol ester glycol and poly neopentyl adipate 1,6-hexanediol ester glycol, preferably polypropylene glycol.
  • the monohydric alcohol and/or dihydric alcohol containing a polyoxyethylene segment in the main chain and/or the side chain described in component S3 is preferably Tego Chemie’s D-3403, one or more of YmerTM N120 of Perstrop Corporation and MPEG1200 of Korea Lotte Corporation. More preferred S3 components include YmerTM N120 of Perstrop Corporation and/or MPEG1200 of Korea Lotte Corporation.
  • the diol small molecule chain extender containing active hydrogen described in component S4 is 1,3-propanediol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1 One or more of 6,6-hexanediol and 1,4-cyclohexanedimethanol, preferably 1,4-cyclohexanedimethanol.
  • the active hydrogen containing diamine small molecule chain extender in component S5 is ethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophor One or more of ketone diamine, 4,4-diphenylmethane diamine and diethanolamine, preferably one or two of ethylene diamine and isophorone diamine.
  • the low-boiling organic solvent described in component S6 includes but is not limited to acetone and/or methyl ethyl ketone, preferably acetone is used.
  • the catalyst described in component S8 includes, but is not limited to, dibutyltin dilaurate or organic bismuth 8108 from a leading US company.
  • the molar ratio R of diisocyanate and polyol is 1.85-4.5.
  • the polyethylene oxide segment content accounts for more than 20% of the weight of the solid content of the aqueous non-ionic polyurethane, and is at the end or side group of the molecular chain.
  • the detersive surfactant described in (b) is selected from sodium laureth sulfate, alkyl ammonium oxide, alkyl betaine, cocamidopropyl betaine, cocoyl amphoteric Disodium diacetate, alkyl sulfobetaine, alkyl glycinate, alkyl carboxyglycinate, alkylaminopropyl hydroxy, acyl taurine and acyl glutamate, sodium lauryl sulfate, Sodium dodecyl polyether sulfate, C12-16 alkyl glucoside, sodium lauroyl glutamate or mixtures thereof, wherein the alkyl group and acyl group have 8-19 carbon atoms.
  • Preference is given to sodium laureth sulfate, cocamidopropyl betaine, sodium lauryl sulfate, C12-16 alkyl glucoside, sodium lauroyl glutamate or mixtures thereof.
  • the conditioning agent described in (c) is selected from polyquaterniums, quaternized proteins, cationic guar gums, water-soluble silicone oils, or mixtures thereof. Preference is given to guar hydroxypropyltrimethylammonium chloride, polyquaternium-10, polydimethylsiloxane or mixtures thereof.
  • the aqueous carrier described in (d) includes water and sodium chloride, thickener, pH adjuster, anti-dandruff agent, essence, emulsifier, chelating agent, opacifier, preservative, pearlescent agent One or a mixture of several;
  • the aqueous carrier contains one or more of the following:
  • sunscreen agent 0-1% by weight of sunscreen agent
  • the thickener is selected from sodium chloride, linoleamide MIPA, PEG-150 distearate, ammonium chloride, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyacrylic acid, poly Acrylate, polyurethane or high molecular weight polyethylene oxide, preferably sodium chloride.
  • the anti-dandruff agent is selected from the group consisting of glyphosate, zinc pyrithione, piroctone ethanolamine salt or triclosan, preferably piroctone ethanolamine salt.
  • the preservative is selected from carson, paraben, sodium benzoate, salicylic acid, DMDM hydantoin, or phenoxyethanol, preferably sodium benzoate.
  • the fragrance is selected from synthetic or natural fragrances, preferably natural fragrances.
  • the composition is used as a shampoo.
  • a method for preparing the composition which includes: stirring and mixing the components in a uniform ratio to a uniform state; preferably, heating, cooling, vacuum, etc. can be used.
  • the design of the invention by the particle size of the aqueous nonionic polyurethane dispersion, the molar ratio (R) of the isocyanate and polyol in the final product and the content of the polyethylene oxide segment makes the film forming elasticity good, high gloss and good toughness , Moderate hardness, non-sticky feel.
  • the weight of the polyethylene oxide segment accounts for more than 20% of the solid content in the aqueous nonionic polyurethane dispersion and is at the end or side group of the molecular chain, which can make the polyurethane microspheres well dispersed in water, so that the polyurethane can A non-sticky protective film is formed on the hair surface.
  • the non-ionic hydrophilic segment makes the aqueous non-ionic polyurethane not only compatible with non-ionic surfactants, thickeners and silicone oils, but also compared to anionic polyurethanes, it is suitable for various commonly used anionic and zwitterionic surfaces. Active agents, cationic conditioning agents, sodium chloride, hydrolyzed protein nutrients and alkali swelling and thickening systems are compatible and compatible, and the system has better stability.
  • Non-ionic polyurethane forms a film on the hair, which can play a role in shielding part of the charge, reducing the phenomenon of hair curling up due to static electricity, and easier to care for.
  • the nonionic polyurethane dispersion with a particle size of 10nm-100nm, especially 10-60nm is added to the shampoo formulation, it does not change the refractive index of the shampoo, and has no effect on the dissolving ability of the surfactant, so that the formulation is still Can maintain transparency, thereby greatly improving consumer acceptance. Due to the dyeing process or long-term exposure to ultraviolet light, the hair scales on the hair are easily dehydrated and the hair scales are lifted, which leads to the formation of voids in the hair scales, which reduces the smoothness of the hair. Causes hair to collapse and reduce hair volume.
  • polyurethane particles can more easily fill the voids of damaged hair, which not only improves the gloss of the hair, but also makes it easier for polyurethane to form a film on the hair, increase the volume of the hair, achieve a strong hair root, and increase the hair.
  • the spacing between them brings a sense of abundance to the air.
  • Non-ionic polyurethane with small particle size enters the cavity of the hair, fits the damaged scales to fill the cavity, blocks dirt, reduces the difficulty of combing, and the non-ionic hydrogen bond with water molecules can maintain the moisture in the hair,
  • the special design makes the polyurethane not sticky after the film is formed outside the hair scales, and ultimately improves the smoothness of the hair.
  • the composition of the present invention has the advantages of dry and non-sticky film formation, high gloss, good toughness and good elasticity.
  • the non-ionic hydrogen-hydrogen bonding effect with keratin in the hairline is easy to attach to the damaged hair scales
  • non-ionic polyurethane can also easily form a film on the hair, increase the volume of the hair, and after use, achieve a strong hair root, increase the spacing between the hairline, and thereby bring a feeling of a sense of fullness of air, Can improve the shortcomings of soft and collapsed hair.
  • the content ratio of isocyanate and polyol is moderate, so that the composition has a suitable glass transition temperature, and the non-ionic polyurethane is neither sticky (improving the smoothness of the hair) after forming a film on the hair surface, but also not too hard ( The hair can not be hard-set, to achieve a natural feeling of fullness), can make the hair naturally strong, and can also extend the duration of the hair's fullness.
  • YmerTM N120 polyethylene oxide ether glycol, hydroxyl value 110mgKOH/g, number average molecular weight ⁇ 1000g/mol, functionality 2; Swedish perstorp company
  • CMA-654 (Poly(neopentyl glycol adipate glycol glycol, hydroxyl value 74.8mgKOH/g, number average molecular weight ⁇ 1500g/mol, functionality 2), Yantai BGI);
  • NPG neopentyl glycol, Wanhua Chemical Group Co., Ltd.
  • EDA ethylenediamine, German BASF company
  • PPG1000 polypropylene glycol, Shandong Bluestar Co., Ltd.
  • IPDA isophorone diamine, Wanhua Chemical Group Co., Ltd.
  • C12-16 alkyl glucoside nonionic surfactant, Zhongqing Daily Chemical Technology Co., Ltd.
  • Guar hydroxypropyltrimethylammonium chloride (cationic guar conditioning agent, Guangzhou Tianci New Material);
  • Polyquaternium-10 (polyquaternary conditioning agent, Guangzhou Tianci New Material);
  • Polydimethylsiloxane (water-soluble silicone oil, Guangzhou Tianci New Material);
  • Polyacrylic acid polymer (thickener, Lubrizol);
  • Citric acid pH regulator, Guangzhou Huazhiwang Chemical Co., Ltd.
  • Ammonium dodecyl sulfate emulsifier, Henan Botel Chemical Products Co., Ltd.;
  • Disodium EDTA (chelating agent, AkzoNobel, USA);
  • Styrene/acrylate copolymer (sunscreen, Dow Chemical);
  • Phenoxyethanol (preservative, Dow Chemical);
  • Ethylene glycol distearate and fatty alcohol ether sodium sulfate pearlized pulp, Jining Baiyi Chemical Co., Ltd.
  • TCW2890404 (Flavour, Lihua Flavor Co., Ltd.).
  • Non-ionic polyurethane dispersion-1 is a non-ionic polyurethane dispersion-1:
  • Non-ionic polyurethane dispersion-2 is a non-ionic polyurethane dispersion-2:
  • Non-ionic polyurethane dispersion-3 is a non-ionic polyurethane dispersion-3:
  • the formula is shown in the following table (parts by weight), and its preparation method includes the following steps: mix the ingredients in proportion, add each component in turn at room temperature under 1500r/min stirring, and adjust the PH value to 5-6, stirring for 15-30 minutes Until completely dispersed.
  • the test composition abundance index can be expressed as:
  • Hair bundle smoothness test take 15wt% sodium laureth sulfate ether solution to wash the two groups of unused hair bundles, use the above MTT175 hair tester to obtain the combing work as the initial combing work, and record as W initial1 , W initial2 ; use the test shampoo diluted 20 times (including polymer) and blank shampoo (without any conditioning agent) to clean the above tresses, obtain the test combing work and blank combing work through the above test steps and record as W test and W blank .
  • the dry hair combing smoothness index can be recorded as:
  • Fullness test recruit 10 women with fine and soft hair, use them for 2 weeks, wash your hair every two days, and then evaluate the score (1-5 points). The soft hair without a fullness effect is 1 and the hair fullness is 5 .
  • Dandruff 10 women with soft hair were collected. After 2 weeks of use, the hair was washed every two days for scoring and evaluation (1-5 scale). The dandruff was severely 1 and almost no dandruff was produced.
  • the shampoo appearance transparency was rated (1-5 points). The worst acceptance degree of shampoo appearance transparency was 1, and the highest acceptance degree of shampoo appearance transparency was 5.
  • Example 1 Example 2 and Example 3 have outstanding abundance in hair styling and consumer evaluation, and also have good smoothness and appearance, and are not prone to dandruff.

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Abstract

提供一种包含水性非离子聚氨酯的组合物，包括(a)0.1～30重量份的水性非离子聚氨酯分散体；(b)10～30重量份的去污表面活性剂；(c)0.01～5重量份的调理剂；(d)含水载体至100重量份。本发明的组合物用作洗发剂，能够使得头发自然强韧，也能延长头发的丰盈持续时间。

Description

一种含有水性非离子聚氨酯分散体的组合物及其制备方法 技术领域
本发明属于清洁洗护领域，涉及一种含有水性非离子聚氨酯的组合物。
背景技术
随着生活水平的不断提高，人们对于个人清洁产品不断提出新的需求。目前脱发、少发及发质受损已经成为头发护理领域被关注的首要问题，通过使用洗发水来解决这些难题成为最简单有效的实施办法。
头发从外到内主要由表皮层、皮质层、髓质层组成。表皮层是由许多细小的鳞片(即，毛鳞片)重叠而成。它是一种保护层。如果发丝上的毛鳞片排列整齐，就会折射更多的光线，头发将显得亮丽动人；如果毛鳞片被刮伤或者受损，头发会容易断裂并且显得毛躁无光泽。头发经过染烫后毛鳞片含水量会急剧降低，使毛鳞片翘起，使头发的梳理性和光泽降低，也是导致受损发质出现“粘滞”和脆弱易断的主要原因。现有的市售使头发丰盈的洗发剂很多都通过打开毛鳞片来提升头发的体积，但通过该种方法来改善头发软塌往往会使头发更加干涩不易打理，同时头发毛鳞片打开后光线无规反射也会降低头发光泽。
为解决上述问题，专利文献CN105188851A采用了一种含硅氧烷接枝木薯粉的洗发剂来提供头发体积增益的效果，利用硅氧烷接枝的木薯粉颗粒在达到顺滑的同时而不牺牲体积，再通过调理剂的组合获得发根提拉的效果，本质上该专利文献是利用硅氧烷的调理性改善了颗粒加入后的发涩感。然而，洗发水中的硅化合物虽然能让头发顺滑，但是由于这些含硅化合物不溶于水和结构十分稳定、难以被生物降解的特性，包裹在头发和头皮上的硅不容易被清洗干净，长期使用会对头发和环境造成一定负担。因此，从环保和健康的角度上已有专家建议应减少硅油在化妆品中的使用。而且硅氧烷的引入会使得体系必须引入硅油乳化体系，使得洗发水很难做到透明。中国专利文献CN107126378A公开了“一种表面活性剂组合物及由其制成的清洁剂的使用”，其中主要使用了一种阴离子水性聚氨酯，起到定型的效果，但是无法达到丰盈和顺滑的功效。由于该清洁剂无法做成透明，极大地限制了消费者的接受度，并且在添加阳离子调理剂的体系中大量引入阴离子树脂对体系的稳定性会有很大影响。专利文献CN102020774A公开了一种透湿防水PU水性树脂用于织物涂层，提到了采用磺酸盐可以使PUD大幅度提高亲水性，以得到很好的含水保湿效果，一个用途是可以用于化妆品、洗发等个人护理品中；但是该专利文献所提到的PUD的吸水保湿作用并不能在洗发剂中提供丰盈的效果，通过吸水保湿作用反而降低了头 发的丰盈度。
发明内容
本发明所要解决的技术问题在于，提供一种基于非离子聚氨酯的组合物，通过加入水性非离子聚氨酯分散体可同时达到干发爽滑和丰盈的效果。
第一个方面，本发明提供一种包含水性非离子聚氨酯分散体的组合物，包括以下成分：
(a)0.1～30重量份的水性非离子聚氨酯分散体；优选5～25重量份；
(b)10～30重量份的去污表面活性剂；优选15～25重量份；
(c)0.01～5重量份的调理剂；优选0.1～2重量份；
(d)含水载体至100重量份；其中，
(a)所述的水性非离子聚氨酯分散体为包括以下组分通过反应得到的产物，优选地，所述反应为70～80℃、常压下的常规反应：
S1：至少一种二异氰酸酯，其加入量为5-25wt％，优选9-13wt％；
S2：大分子多元醇，其数均分子量为500-3000g/mol，优选数均分子量约1000-2000g/mol，其加入量为1-25wt％，优选4-15wt％；
S3：至少一种主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇，具有约500-3000g/mol的数均分子量，其加入量为1-20wt％，优选7-10wt％；
S4：至少一种含有活泼氢的二元醇小分子扩链剂，具有60-400g/mol的分子量，其加入量为0.1-10wt％，优选1-5wt％；
S5：至少一种含有活泼氢的二元胺小分子扩链剂，具有59-200g/mol的分子量，其加入量为0.01-5wt％，优选0.04-0.7wt％；
S6：低沸点有机溶剂，其加入量为S1-S5重量总和的0.2-2倍，优选0.5-1.5倍；
S7：蒸馏水，其加入量为20-80wt％，优选57-70wt％；
S8：催化剂，其加入量为S1-S5重量总和的100-300ppm。
各组分的加入量为占反应体系总重量的含量，其中，反应体系总重量是S1-S5以及S7和S8的重量总和，为100wt％。S6为溶剂，在最后的体系中被除去。
优选地，本发明组合物中，所述成分(a)水性非离子聚氨酯分散体是固含为20wt％～50wt％的水性非离子聚氨酯分散体，所述水性非离子聚氨酯分散体的粒径为10nm～100nm，优选10nm～60nm。
优选地，组分S1中所述的二异氰酸酯为甲苯二异氰酸酯、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 酯中的一种或多种，优选为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多种。
优选地，组分S2中所述的大分子多元醇为聚乙二醇、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多种，优选聚丙二醇。
优选地，组分S3中所述的主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇优选为Tego Chemie公司的
Figure PCTCN2018120265-appb-000001
D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG1200中的一种或多种，更优选的S3组分包括Perstrop公司的YmerTM N120和/或韩国乐天公司的MPEG1200。
优选地，组分S4中所述的含有活泼氢的二元醇小分子扩链剂为1,3-丙二醇、1,4-丁二醇、一缩二乙二醇、新戊二醇、1,6-己二醇、1,4-环己烷二甲醇中的一种或多种，优选1,4-环己烷二甲醇。
优选地，组分S5中所述的含有活泼氢的二元胺小分子扩链剂为乙二胺、六亚甲基二胺、五亚甲基二胺、二亚乙基三胺、异佛尔酮二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或多种，优选乙二胺和异佛尔酮二胺中的一种或两种。
优选地，组分S6中所述的低沸点有机溶剂包括但不限于丙酮和/或丁酮，优选使用丙酮。
优选地，组分S8中所述的催化剂包括但不限于二丁基二月桂酸锡或美国领先公司的有机铋8108。
优选地，所述水性非离子聚氨酯分散体中，二异氰酸酯和多元醇的摩尔比R为1.85-4.5。
优选地，所述水性非离子聚氨酯分散体中，聚氧化乙烯链段含量占水性非离子聚氨酯固体份重量的20％以上，且在分子链的末端或者侧基上。
本发明组合物中，(b)所述的去污表面活性剂选自月桂醇聚醚硫酸酯钠、烷基氨氧化物、烷基甜菜碱、椰油酰胺丙基甜菜碱、椰油酰两性基二乙酸二钠、烷基磺基甜菜碱、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基氨基丙基羟基、酰基牛磺酸盐和酰基谷氨酸盐、十二烷基硫酸钠、十二烷基聚醚硫酸酯钠、C12-16烷基葡糖苷、月桂酰谷氨酸钠或它们的混合物，其中烷基和酰基具有8-19个碳原子。优选月桂醇聚醚硫酸酯钠、椰油酰胺丙基甜菜碱、十二烷基硫酸钠、C12-16烷基葡糖苷、月桂酰谷氨酸钠或它们的混合物。
本发明组合物中，(c)所述的调理剂选自聚季铵盐、季铵化蛋白、阳离子 瓜尔胶类、水溶性硅油或它们的混合物。优选瓜尔胶羟丙基三甲基氯化铵、聚季铵盐-10、聚二甲基硅氧烷或它们的混合物。
本发明的组合物中，(d)所述的含水载体包括水以及氯化钠、增稠剂、pH调节剂、去屑剂、香精、乳化剂、螯合剂、遮光剂、防腐剂、珠光剂的一种或几种的混合物；
优选地，所述含水载体中包含以下一种或多种：
0-2％重量份的氯化钠；
0-3％重量份的增稠剂；
0-1％重量份的PH调节剂；
0-3％重量份的去屑剂；
0-3％重量份的香精；
0-3％重量份的乳化剂；
0-0.5％重量份的螯合剂；
0-1％重量份的遮光剂；
0-1％重量份的防腐剂；
0-1％重量份的珠光剂。
进一步地，所述增稠剂选自氯化钠、耶油酰胺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、聚氨酯或高分子量的聚氧化乙烯，优选氯化钠。
所述去屑剂选自甘宝素、吡硫鎓锌、吡罗克酮乙醇胺盐或三氯生，优选吡罗克酮乙醇胺盐。
所述防腐剂选自卡松、尼泊金酯、苯甲酸钠、水杨酸、DMDM乙内酰脲或苯氧乙醇，选优苯甲酸钠。
所述香精选自人工合成或天然香精，优选天然香精。
优选地，所述组合物用作洗发剂。
第二个方面，提供所述组合物的制备方法，包括：将各组分按照配比搅拌混合至均一状态；优选地，可使用加热、冷却、真空等方式。
本发明通过对水性非离子聚氨酯分散体的粒径、终产物中异氰酸酯和多元醇的摩尔比(R)以及聚氧化乙烯链段的含量的设计，使得成膜弹性佳、光泽度高、韧性好、硬度适中、手感不黏腻。其中，聚氧化乙烯链段重量占水性非离子聚氨酯分散体中固体份的20％以上且在分子链的末端或者侧基上，可以使得聚氨酯微球很好地分散在水中，使得聚氨酯在能在头发表面形成一层不黏腻的保护膜。非离子的亲水链段使得该水性非离子聚氨酯不仅对非离子表面活性剂、增稠剂、硅油的兼容性良好，而且相比于阴离子型聚氨酯，它对于各种常 用的阴离子和两性离子表面活性剂、阳离子调理剂、氯化钠、水解蛋白质类营养成分及碱溶胀增稠体系兼容及配伍性更好，体系具有更好的稳定性，加入至其它成分中，不仅能保证洗发剂透明的外观，而且使用后非离子基团与头发的角蛋白形成氢键，有利于附着在发丝上成膜，实现强韧发根，增加头发体积，带来空气感丰盈的感觉。市售洗发水中一般添加阳离子调理剂来提升头发的顺滑效果，加入阴离子聚氨酯的洗发水由于阳离子的调理剂的静电作用，使得阳离子调理剂的沉积效果会大大降低，进而影响使用后头发的调理性。而非离子聚氨酯在头发上成膜，能够起到屏蔽部分电荷的作用，减少头发由于静电作用而使碎发翘起的现象，更易打理。
粒径在10nm～100nm、特别是10-60nm的非离子聚氨酯分散体加入至洗发剂配方当中后，不改变洗发剂的折光度，而且对表面活性剂的溶解能力无影响，使配方仍能保持透明，从而极大地提升消费者的接纳程度。由于染烫过程或长期暴露在紫外线环境中，头发上的毛鳞片容易缺水而使毛鳞片翘起，进而导致毛鳞片缺损形成空洞，降低头发顺滑性，长期得不到有效的改善还会造成头发垮塌和发量减少。该粒径范围内聚氨酯颗粒能更容易填充在受损头发的空洞，不仅能使头发光泽提升，而且使得聚氨酯更容易在头发上成膜，增加头发体积，实现强韧发根，增加了发丝之间的间距，进而带来空气感丰盈的感觉。粒径小的非离子聚氨酯进入头发的空洞中，贴合受损的毛鳞片填补空洞，阻隔污垢，减少梳理的难度，而且非离子与水分子的氢键结合，能保持发丝中的水分，进而修复受损发质，特殊的设计使得聚氨酯在毛鳞片外成膜后不黏腻，最终提升头发的顺滑效果。
本发明的组合物具有成膜干爽不黏腻、光泽度高、韧性好、弹性佳的优点，非离子与发丝中的角蛋白产氢氢键作用，容易在头发受损的毛鳞片上附着，填补发丝的空洞；非离子聚氨酯也很容易在头发上成膜，增加头发体积，而且使用后实现强韧发根，增加了发丝之间的间距，进而带来空气感丰盈的感觉，可以改善头发细软垮塌的缺点。本发明组合物中，异氰酸酯与多元醇含量比例适中，使得组合物具有合适的玻璃化温度，非离子聚氨酯在头发表面成膜后既不黏腻(提升头发的顺滑感觉)，也不过硬(头发能够不至于硬定型，达到自然丰盈的感觉)，能够使得头发自然强韧，也能延长头发的丰盈持续时间。
实施例
实施例及对比例中使用的原料：
Figure PCTCN2018120265-appb-000002
(异佛尔酮二异氰酸酯，NCO含量(NCO基团质量/分子总质量)约为37.8％，万华化学集团股份有限公司)；
Figure PCTCN2018120265-appb-000003
(二环己基甲烷二异氰酸酯，NCO含量约为32.0％，万华化学集团股份有限公司)；
YmerTM N120(聚环氧乙烷醚二醇，羟值110mgKOH/g，数均分子量≈1000g/mol，官能度为2，瑞典perstorp公司)；
CMA-654：(聚己二酸新戊二醇己二醇酯二元醇，羟值74.8mgKOH/g，数均分子量≈1500g/mol，官能度为2，烟台华大化学)；
Figure PCTCN2018120265-appb-000004
(六亚甲基二异氰酸酯，NCO含量约为50.0％，万华化学集团股份有限公司)；
Figure PCTCN2018120265-appb-000005
(2-(2-氨基乙基)氨基乙磺酸钠，固含量51±2％水溶液，胺值260±20mgKOH/g，德国EVONIK公司)；
CHDM(1,4-环己烷二甲醇，凯凌化工有限公司)；
NPG(新戊二醇，万华化学集团股份有限公司)；
EDA(乙二胺，德国BASF公司)；
8108：有机铋催化剂(美国领先公司)；
PPG1000(聚丙二醇，山东蓝星有限公司)；
IPDA(异佛尔酮二胺，万华化学集团股份有限公司)；
月桂醇聚醚硫酸酯钠(阴离子表面活性剂，山东佰仟化工有限公司)；
C12-16烷基葡糖苷(非离子表面活性剂，中轻日化科技有限公司)；
月桂酰谷氨酸钠(两性表面活性剂，明德生物科技有限公司)；
瓜尔胶羟丙基三甲基氯化铵(阳离子瓜尔胶调理剂，广州天赐新材料)；
聚季铵盐-10(聚季铵盐调理剂，广州天赐新材料)；
聚二甲基硅氧烷(水溶性硅油，广州天赐新材料)；
聚丙烯酸聚合物(增稠剂，路博润)；
柠檬酸(pH调节剂，广州花之王化工有限公司)；
吡硫翁锌(去屑剂，济宁佰一化工有限公司)；
吡罗克酮乙醇胺盐(去屑剂，山东佰仟化工有限公司)；
十二烷基硫酸铵(乳化剂，河南博特尔化工产品有限公司；
EDTA二钠(螯合剂，美国阿克苏诺贝尔)；
苯乙烯/丙烯酸酯共聚物(遮光剂，陶氏化学)；
苯氧乙醇(防腐剂，陶氏化学)；
乙二醇双硬脂酸酯和脂肪醇醚硫酸钠(珠光浆，济宁佰一化工有限公司)；
TCW2890404(香精，丽华香精有限公司)。
阴离子聚氨酯：
在四口烧瓶内加入80g CMA-654(烟台华大化学)、2.5g新戊二醇，70℃条件下混合搅拌10min，降温至50℃加入19g
Figure PCTCN2018120265-appb-000006
反应，测试该反应约NCO％＝2.95wt％时，使得预聚物冷却到40℃，溶解在150g丙酮溶剂中，混合15min后，加入0.7g乙二胺和5g
Figure PCTCN2018120265-appb-000007
在15g去离子水形成的溶液，45℃条件下继续反应30min后，在剪切分散条件下加入210g水，然后减压蒸馏脱除丙酮得到固含量约31wt％聚氨酯分散体，粒径为50nm。(R＝2.12，无氧化乙烯链段)
非离子聚氨酯分散体-1：
将87克
Figure PCTCN2018120265-appb-000008
(S1)，31克PPG1000(S2)，29克CHDM(S4)，65克YmerTM N120(S3)，0.0424克8108(S8)，21.2克丙酮(S6)加入到带有温度计和搅拌杆的四口烧瓶中，加热到70度反应至NCO达到3.0％(理论NCO值为3.39％)，降温至40度，加入212克丙酮(S6)，然后在高速搅拌(1200-1500r/min)下加入487克蒸馏水(S7)，分散结束之后加入4.2克EDA(S5)和17克蒸馏水(S7)的混合物，继续搅拌5min，脱去丙酮，得到粒径为26nm、固含为30wt％的非离子聚氨酯分散体-1。R＝4.08，聚氧化乙烯链段占固体份重量的30％。
非离子聚氨酯分散体-2：
将90克
Figure PCTCN2018120265-appb-000009
(S1)，102克PPG1000(S2)，21克CHDM(S4)，60克YmerTMN120(S3)，0.05克8108(S8)，27.3克丙酮(S6)加入到带有温度计和搅拌杆的四口烧瓶中，加热到70度反应至NCO达到2.3％(理论NCO值为2.70％)，降温至35度，加入273克丙酮(S6)，然后在高速搅拌(1200-1500r/min)下加入538克水(S7)，分散结束之后加入4克EDA(S5)和16克水(S7)的混合物，继续搅拌5min，脱去丙酮，得到粒径为36nm，固含为30％的非离子聚氨酯分散体-2。R＝2.50，聚氧化乙烯链段占固体份重量的21.6％。
非离子聚氨酯分散体-3：
将63克
Figure PCTCN2018120265-appb-000010
(S1)，102克PPG1000(S2)，9克CHDM(S4)，50克YmerTMN120(S3)，0.04克8108(S8)，22.4克丙酮(S6)加入到带有温度计和搅拌杆的四口烧瓶中，加热到70度反应至NCO达到2.1％(理论NCO值为2.33％)，降温至35度，加入224克丙酮(S6)，然后在高速搅拌(1200-1500r/min)下加入442克水(S7)，分散结束之后加入3克EDA(S5)和12克水(S7)的混合物，继续搅拌5min，脱去丙酮，得到粒径为20nm，固含为30％的非离子聚氨酯分散体-3。R＝1.87，聚氧化乙烯链段占固体份重量的22.0％。
实施例1
配方如下表所示(重量份)，其制备方法包括以下步骤：按照比例配比成分，室温下1500r/min搅拌下依次加入各组分，并调整PH值至5-6，搅拌15-30分钟至完全分散即可。
Figure PCTCN2018120265-appb-000011
Figure PCTCN2018120265-appb-000012
测试方法
A.体外发束测试
取15wt％月桂醇聚醚硫酸酯钠溶液清洗未使用过的头发。待干燥后使用DIA STRON MTT175头发测试仪测试测试头发束在1cm孔拉动15cm时的压缩功作为最初拉力功并记录为W initial；取0.6g测试上述实施例和对比例的组合物清洗上述发束，并采用MTT175头发测试仪重复上述测试步骤获得拉力功并记录为W test。测试拉力功和最初拉力功的差值记录为W treatment＝W test–W initial；市售某品牌透明丰盈洗发水测试拉力功和最初拉力功的差值作为顶部对照(W topcontrol)，空白洗发水(无聚合物)测试拉力功和最初拉力功的差值作为底部对照(W bottomcontrol)。测试组合物丰盈指数可以表示为:
Figure PCTCN2018120265-appb-000013
发束顺滑度测试：取15wt％月桂醇聚醚硫酸酯钠溶液清洗两组未使用过的发束，使用上述MTT175头发测试仪获得梳理功作为最初梳理功，并分别记录为W initial1、W initial2；采用稀释二十倍的测试洗发水(包含聚合物)和空白洗发水(无任何调理剂)清洗上述发束，通过上述测试步骤获得测试梳理功和空白梳理功并分别记录为W test和W blank。干发梳理顺滑指数可以记录为：
顺滑指数＝(W blank/W initial2-W test/W initial1)*100％。
B.消费者测试感官评估实验
丰盈度测试：征集10位发质细软的女性，使用2周，每两天洗一次头发后进行打分评价(1-5分制)，头发软榻无丰盈效果为1，头发丰盈度好为5。
顺滑度测试：征集10个发质细软的女性，使用2周，每两天洗一次头发后进行打分评价(1-5分制)，干发后缠结现象严重、难梳理、阻力非常大为1，无缠结、极易梳理、几乎无阻力为5。
头屑：征集10个发质细软的女性，使用2周，每两天洗一次头发后进行打 分评价(1-5分制)，头屑现象严重为1，几乎无头屑产生为5。
洗发水外观：对洗发水外观透明度进行打分评价(1-5分制)，洗发水外观透明接受程度最差为1，洗发水外观透明度接受程度最高为5。
评价结果
Figure PCTCN2018120265-appb-000014
由评价结果可以看出，实施例1，实施例2及实施例3在发束及消费者评价均具有比较突出的丰盈度，也具有很好的顺滑度、外观，不易起头屑。

Claims (10)

  1. 一种包含水性非离子聚氨酯分散体的组合物，包括以下成分：
    (a)0.1～30重量份的水性非离子聚氨酯分散体；优选5～25重量份；
    (b)10～30重量份的去污表面活性剂；优选15～25重量份；
    (c)0.01～5重量份的调理剂；优选0.1～2重量份；
    (d)含水载体至100重量份。
  2. 根据权利要求1所述的组合物，其中，所述的(a)水性非离子聚氨酯分散体是固含为20wt％～50wt％的水性非离子聚氨酯分散体，所述水性非离子聚氨酯分散体的粒径为10nm～100nm，优选10nm～60nm。
  3. 根据权利要求1或2所述的组合物，其中，所述(a)水性非离子聚氨酯分散体为包括以下组分通过反应得到的产物：
    S1：至少一种二异氰酸酯，其加入量为5-25wt％，优选9-13wt％；
    S2：大分子多元醇，其数均分子量为500-3000g/mol，优选数均分子量1000-2000g/mol，其加入量为1-25wt％，优选4-15wt％；
    S3：至少一种主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇，具有500-3000g/mol的数均分子量，其加入量为1-20wt％，优选7-10wt％；
    S4：至少一种含有活泼氢的二元醇小分子扩链剂，具有60-400g/mol的分子量，其加入量为0.1-10wt％，优选1-5wt％；
    S5：至少一种含有活泼氢的二元胺小分子扩链剂，具有59-200g/mol的分子量，其加入量为0.01-5wt％，优选0.04-0.7wt％；
    S6：低沸点有机溶剂，其加入量为S1-S5重量总和的0.2-2倍，优选0.5-1.5倍；
    S7：蒸馏水，其加入量为20-80wt％，优选57-70wt％；
    S8：催化剂，其加入量为S1-S5重量总和的100-300ppm；
    各组分的加入量为占反应体系总重量的含量，其中，反应体系总重量是S1-S5以及S7和S8的重量总和，为100wt％；
    优选地，组分S1中所述的二异氰酸酯为甲苯二异氰酸酯、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多种；
    优选地，组分S2中所述的大分子多元醇为聚乙二醇、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 一种或多种；
    优选地，组分S3中所述的主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇优选为Tego Chemie公司的
    Figure PCTCN2018120265-appb-100001
    D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG1200中的一种或多种；
    优选地，组分S4中所述的含有活泼氢的二元醇小分子扩链剂为1,3-丙二醇、1,4-丁二醇、一缩二乙二醇、新戊二醇、1,6-己二醇、1,4-环己烷二甲醇中的一种或多种；
    优选地，组分S5中所述的含有活泼氢的二元胺小分子扩链剂为乙二胺、六亚甲基二胺、五亚甲基二胺、二亚乙基三胺、异佛尔酮二胺、4,4-二苯基甲烷二胺和二乙醇胺中的一种或多种；
    优选地，组分S6中所述的低沸点有机溶剂包括丙酮和/或丁酮；
    优选地，组分S8中所述的催化剂包括二丁基二月桂酸锡或美国领先公司的有机铋8108。
  4. 根据权利要求3所述的组合物，其中，所述水性非离子聚氨酯分散体中，二异氰酸酯和多元醇的摩尔比R为1.85-4.5；优选地，所述水性非离子聚氨酯分散体中，聚氧化乙烯链段含量占水性非离子聚氨酯固体份重量的20％以上，且在分子链的末端或者侧基上。
  5. 根据权利要求1～4任一项所述的组合物，其中，(b)所述的去污表面活性剂选自月桂醇聚醚硫酸酯钠、烷基氨氧化物、烷基甜菜碱、椰油酰胺丙基甜菜碱、椰油酰两性基二乙酸二钠、烷基磺基甜菜碱、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基氨基丙基羟基、酰基牛磺酸盐和酰基谷氨酸盐、十二烷基硫酸钠、十二烷基聚醚硫酸酯钠、C12-16烷基葡糖苷、月桂酰谷氨酸钠或它们的混合物，其中烷基和酰基具有8-19个碳原子。
  6. 根据权利要求1～4任一项所述的组合物，其中，(c)所述的调理剂选自聚季铵盐、季铵化蛋白、阳离子瓜尔胶类、水溶性硅油或它们的混合物；优选地，所述调理剂为瓜尔胶羟丙基三甲基氯化铵、聚季铵盐-10、聚二甲基硅氧烷或它们的混合物。
  7. 根据权利要求1～4任一项所述的组合物，其中，(d)所述的含水载体包括水以及氯化钠、增稠剂、pH调节剂、去屑剂、香精、乳化剂、螯合剂、遮光剂、防腐剂、珠光剂的一种或几种的混合物；优选地，所述含水载体中包含以下一种或多种：
    0-2％重量份的氯化钠；
    0-3％重量份的增稠剂；
    0-1％重量份的PH调节剂；
    0-3％重量份的去屑剂；
    0-3％重量份的香精；
    0-3％重量份的乳化剂；
    0-0.5％重量份的螯合剂；
    0-1％重量份的遮光剂；
    0-1％重量份的防腐剂；
    0-1％重量份的珠光剂。
  8. 根据权利要求7所述的组合物，其中，
    所述增稠剂选自氯化钠、耶油酰胺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、聚氨酯或高分子量的聚氧化乙烯；
    所述去屑剂选自甘宝素、吡硫鎓锌、吡罗克酮乙醇胺盐或三氯生；
    所述防腐剂选自卡松、尼泊金酯、苯甲酸钠、水杨酸、DMDM乙内酰脲或苯氧乙醇；
    所述香精选自人工合成或天然香精。
  9. 根据权利要求1～8任一项所述的组合物，其中，所述组合物用作洗发剂。
  10. 权利要求1～8任一项所述的组合物的制备方法，包括，各成分按照配比搅拌混合至均一状态。
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CN109394571B (zh) 2020-07-24
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