WO2023202443A1 - 一种整理液组合物及其应用 - Google Patents

一种整理液组合物及其应用 Download PDF

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Publication number
WO2023202443A1
WO2023202443A1 PCT/CN2023/087806 CN2023087806W WO2023202443A1 WO 2023202443 A1 WO2023202443 A1 WO 2023202443A1 CN 2023087806 W CN2023087806 W CN 2023087806W WO 2023202443 A1 WO2023202443 A1 WO 2023202443A1
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WO
WIPO (PCT)
Prior art keywords
hyaluronic acid
salt
liquid composition
finishing liquid
finishing
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Application number
PCT/CN2023/087806
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English (en)
French (fr)
Inventor
刘喆
杨娟
Original Assignee
华熙生物科技股份有限公司
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Publication of WO2023202443A1 publication Critical patent/WO2023202443A1/zh

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47KSANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00Body-drying implements; Toilet paper; Holders therefor
    • A47K10/16Paper towels; Toilet paper; Holders therefor
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002Tissue paper; Absorbent paper

Definitions

  • the present application relates to the technical field of paper product preparation, and in particular to a finishing liquid composition and its application.
  • HA Sodium hyaluronate
  • hyaluronic acid also known as hyaluronic acid, or hyaluronic acid
  • hyaluronic acid a natural moisturizing ingredient that has been widely used in pharmaceuticals and personal health consumer products.
  • hyaluronic acid tissues have appeared in the consumer goods market, with the intention of adding HA to improve the skin care properties of the tissues.
  • HA can form strong hydrogen bonds with the cellulose of the tissue. Therefore, during the friction between the tissue and the skin, HA is difficult to migrate from the surface of the tissue to the surface of the skin, making it difficult to achieve the skin care effect of HA.
  • oil and HA can be combined and coated on paper towels.
  • the water repellency of oil can block the strong hydrogen bonding between HA and cellulose.
  • the addition of oil will affect the absorbency of paper towels.
  • the present application provides a finishing liquid composition and its application.
  • the finishing liquid composition contains grease, and the particle size D50 of the grease is controlled within 300-1300nm, and is coated on a paper towel base. When used on the paper, it ensures the mobility of hyaluronic acid without affecting the water absorption performance of the paper towel.
  • a finishing liquid composition which contains oil and fat, and the particle size D 50 of the oil and fat is 300-1300 nm.
  • finishing liquid composition according to item 1 wherein the grease is 3-20%, preferably 3-8%, in terms of mass percentage in the finishing liquid composition.
  • finishing liquid composition according to item 1 or 2 wherein the finishing liquid composition further contains hyaluronic acid or a salt thereof, preferably in terms of mass percentage in the finishing liquid composition.
  • the hyaluronic acid or its salt is 0.01-0.5%, preferably 0.1-0.2%.
  • the finishing liquid composition according to any one of items 1 to 3, wherein the finishing liquid composition It also contains an emulsifier.
  • the emulsifier is a nonionic or anionic surfactant.
  • the nonionic surfactant is selected from Tween-20, Tween-80, and cetearyl alcohol polyether. -6. One or more of cetearyl alcohol polyether-25, cetearyl olive acid ester and sorbitan olive acid ester.
  • the anionic surfactant is selected from hard One or more of sodium fatty acid glutamate, sodium laurate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium oleate.
  • finishing liquid composition according to any one of items 1 to 4, wherein the finishing liquid composition further contains a polyol.
  • the cross-linked hyaluronic acid or a salt thereof is either a combination of a first hyaluronic acid or a salt thereof and a second hyaluronic acid or a salt thereof or a first hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof
  • the combination is either a combination of a second hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof or a first hyaluronic acid or a salt thereof, a second hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a combination of its salts.
  • a paper towel comprising:
  • the finishing fluid composition described in the present application contains grease, and the particle size D 50 of the grease is 300-1300 nm.
  • the finishing fluid composition is applied to paper towels. , while ensuring the mobility of HA without affecting the water absorption performance of the paper towel.
  • Figure 1 is a flow chart for coating.
  • Figure 2 is a flow chart for measuring HA in imitation leather.
  • Figure 2A is a schematic diagram of fixing paper towels on a square weight block
  • Figure 2B is a schematic diagram of the friction migration test method.
  • 1-paper towel base material 2-first guide roller, 3-second guide roller, 4-third guide roller, 5-fourth guide roller, 6-squeeze roller, 7-transfer roller, 8-impregnation Roller, 9-trough, 10-fifth guide roller, 11-paper towel after coating
  • the present application provides a finishing liquid composition, which contains grease, and the particle size D 50 of the grease is 300-1300 nm.
  • the particle size D 50 of the grease can be 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, etc.
  • the grease is a grease containing hydrocarbons, that is, the grease can be a pure hydrocarbon grease, such as mineral oil, petrolatum, squalane, etc., or it can be a grease containing a part of hydrocarbons, such as beeswax, etc.
  • the carbon number of the grease is 20-50.
  • finishing liquid composition described in the present application when coated on the paper towel base material, ensures the migration of hyaluronic acid without affecting the migration performance of the paper towel.
  • the particle size D 50 of the oil can be measured using conventional methods in the art. For example, it can be measured using conventional particle size testing methods, such as Brownian motion of nanoparticles in a colloidal system. Establish a relevant function model, calculate the diffusion coefficient, and then calculate the particle size distribution of the particles. For example, calculate the equivalent particle size distribution of the particles through the Einstein-Stokes equation. For example, dilute the sample and put it into the particles. Test in a size analyzer to obtain the particle size distribution density curve, and integrate the distribution density curve to obtain the particle size D50. More specifically, take 1g of the sample to be tested, dilute it 1000 times with pure water, and then take 1.8 to 3ml of the diluted The sample is placed in a quartz glass sample cell.
  • conventional particle size testing methods such as Brownian motion of nanoparticles in a colloidal system.
  • the test temperature was set to 25°C, and the particle size distribution curve was measured.
  • the particle size distribution density curve is integrated between the particle size 0 nm and T nm. When the integral value reaches 49.9% ⁇ 50.1%, T nm is recorded as D50.
  • the particle size D50 of the oil is the particle size measured after emulsification.
  • This application does not impose any restrictions on the emulsification method. It can be selected according to needs. For example, emulsifier and oil are added to water for high-pressure homogenization. The particle size of the oil is controlled to be in the range of 300-1300nm, and then polyols and hyaluronic acid are added. Acid or its salt is mixed to obtain a finishing fluid composition.
  • emulsifier and grease are added to water, heated to 60-70°C for high-pressure homogenization, and the particle size of the grease is controlled to be in the range of 300-1300nm, and then polyols and transparent Hydronic acid or its salt is mixed to obtain a finishing liquid composition.
  • the grease is 3-20%, preferably 3-8%, in terms of mass percentage in the finishing liquid composition.
  • the grease in terms of mass percentage in the finishing liquid composition, can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% , 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.
  • the finishing fluid composition further includes hyaluronic acid or a salt thereof.
  • the hyaluronic acid or a salt thereof is 0.01-0.5 in terms of mass percentage in the finishing fluid composition. %, preferably 0.1-0.2%.
  • the salt of hyaluronic acid is a metal salt of hyaluronic acid.
  • the salt may be a sodium salt of hyaluronic acid, a magnesium salt of hyaluronic acid, a zinc salt of hyaluronic acid, a calcium salt of hyaluronic acid, etc.
  • a sodium salt of hyaluronic acid may be used.
  • the content of hyaluronic acid or its salt in the finishing liquid composition may be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc.
  • the hyaluronic acid or salt thereof is cross-linked hyaluronic acid or salt thereof.
  • the cross-linked hyaluronic acid or its salt refers to a derivative of hyaluronic acid or its salt after chemical modification. After modification by a cross-linking agent, linear hyaluronic acid molecules are connected into a spatial network structure. .
  • the hyaluronic acid or salt thereof has a molecular weight of 1000-300 W Da.
  • the hyaluronic acid or a salt thereof is a first hyaluronic acid or a salt thereof or a second hyaluronic acid or a salt thereof.
  • Hyaluronic acid or its salt preferably, the molecular weight of the first hyaluronic acid or its salt is 1w-5w Da; the molecular weight of the second hyaluronic acid or its salt is 50w-100w Da.
  • the hyaluronic acid or a salt thereof is a first hyaluronic acid or a salt thereof or a second hyaluronic acid or a salt thereof or a cross-linked hyaluronic acid or a salt thereof or a first hyaluronic acid
  • the combination of an acid or a salt thereof and a second hyaluronic acid or a salt thereof is either a combination of a first hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof or a second hyaluronic acid or a salt thereof and a cross-link
  • the combination of hyaluronic acid or a salt thereof is either a combination of a first hyaluronic acid or a salt thereof, a second hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof.
  • the mass ratio of the first hyaluronic acid or its salt and the second hyaluronic acid or its salt is 1:0.1-10;
  • the mass ratio of the second hyaluronic acid or its salt and the cross-linked hyaluronic acid or its salt may be 1:0.1-10 ;
  • the mass ratio of the first hyaluronic acid or its salt and the cross-linked hyaluronic acid or its salt may be 1:0.01-1 .
  • the mass ratio of the first hyaluronic acid or its salt, the second hyaluronic acid or its salt and the cross-linked hyaluronic acid or its salt may be 1:1:1 or 1:1:0.5 or 1:1:0.1.
  • the composition further includes an emulsifier.
  • the emulsifier is a nonionic or anionic surfactant.
  • the nonionic surfactant is selected from Tween-20, Tween -80, one or more of cetearyl ether-6, cetearyl ether-25, cetearyl olivate and sorbitan olive ester, preferably , the anionic surfactant is selected from one or two or more types of sodium laurate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate and sodium oleate.
  • the content of the emulsifier in the finishing liquid composition can be routinely selected according to needs.
  • the content of the emulsifier in the finishing liquid composition can be 0.5-10%.
  • the finishing fluid composition further includes a polyol.
  • a polyol This application does not impose any restrictions on the type of polyol, which can be selected according to needs.
  • the polyol can be glycerin, ethylene glycol, butylene glycol, etc.
  • This application does not impose any restrictions on the content of polyol in the finishing liquid composition, and it can be based on Select according to needs, for example, the content of polyol in the finishing liquid composition can be 0.1-80%.
  • the finishing fluid composition further includes a water-soluble active ingredient.
  • the water-soluble active ingredient is selected from the group consisting of ectoine, ergothioneine, ⁇ -aminobutyric acid, amino acids and proteins. One or more than two types.
  • the preparation method of the finishing fluid composition can be conventionally selected according to needs.
  • it can be prepared using a high-pressure homogenization method, such as mixing emulsifier, grease and water. Homogenize, control the emulsified particle size D 50 of the oil and fat, then add hyaluronic acid or its salt and glycerol and mix to obtain it.
  • a high-pressure homogenization method such as mixing emulsifier, grease and water. Homogenize, control the emulsified particle size D 50 of the oil and fat, then add hyaluronic acid or its salt and glycerol and mix to obtain it.
  • the emulsifier, oil and water are mixed and then added at 60-70°C for high-pressure homogenization.
  • the finishing liquid composition includes oil and fat, and the particle size D 50 of the oil and fat is 300-1300 nm.
  • the grease is 3-20%, preferably 3-8%, in terms of mass percentage in the finishing liquid composition.
  • the finishing fluid composition further includes hyaluronic acid or a salt thereof.
  • the hyaluronic acid or a salt thereof is 0.01-0.5 in terms of mass percentage in the finishing fluid composition. %, preferably 0.1-0.2%.
  • the finishing fluid composition further includes an emulsifier.
  • the emulsifier is a nonionic or anionic surfactant.
  • the nonionic surfactant is selected from Tween-20, One or more of Tween-80, Cetearyl-6, Cetearyl-25, Cetearyl Olivate and Sorbitan Olivate,
  • the anionic surfactant is selected from one or more of sodium stearoyl glutamate, sodium laurate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate and sodium oleate.
  • the finishing fluid composition further includes a polyol.
  • the hyaluronic acid or a salt thereof is a first hyaluronic acid or a salt thereof or a second hyaluronic acid or a salt thereof or a cross-linked hyaluronic acid or a salt thereof or a first hyaluronic acid
  • the combination of an acid or a salt thereof and a second hyaluronic acid or a salt thereof is either a combination of a first hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof or a second hyaluronic acid or a salt thereof and a cross-link
  • the combination of hyaluronic acid or a salt thereof is either a combination of a first hyaluronic acid or a salt thereof, a second hyaluronic acid or a salt thereof and a cross-linked hyaluronic acid or a salt thereof.
  • the hyaluronic acid or salt thereof has a molecular weight of 1000-300 W Da. In some embodiments, the molecular weight of the first hyaluronic acid or its salt is 1w-5w Da; the molecular weight of the second hyaluronic acid or its salt is 50w-100w Da. In some embodiments, the carbon number of the grease is 20-50.
  • This application provides the use of the above-mentioned finishing liquid composition in paper products.
  • the present application provides a paper towel, which includes a base material and the above-mentioned finishing liquid composition.
  • the ideal microstructure after grease coating should be that the grease spreads evenly on the fiber surface without entering the internal pores of the fiber or adhering to the gaps between fibers.
  • the inventor of the present application creatively discovered that when the particle size D50 of the oil in the finishing fluid composition is controlled within the range of 300-1300 nm, the mobility of hyaluronic acid can be ensured, that is, the mobility is above 5%, without affecting the paper towels. absorption properties.
  • the content of grease in paper towels can be measured using conventional methods in the field, such as using the method for measuring the oil content of chemical fibers, such as using the national standard measurement method GB/T 6504, such as Organic solvents such as isopropyl alcohol or acetone are used to extract the grease on paper towels, and then the extract is measured using liquid chromatography coupled with mass spectrometry.
  • GB/T 6504 such as Organic solvents such as isopropyl alcohol or acetone are used to extract the grease on paper towels, and then the extract is measured using liquid chromatography coupled with mass spectrometry.
  • the water-soluble active ingredients can increase the skin care properties of the tissue.
  • the hyaluronic acid or salt thereof has a mobility ⁇ 5%.
  • the migration rate refers to the efficiency of HA migration to imitation leather during the friction test. Its calculation formula is as follows:
  • Migration rate the amount of HA on the imitation leather after rubbing/the HA content of the paper towel on the contact surface of the cube before rubbing.
  • the base material refers to the paper towel base material, which can be any commercially available base material.
  • Zhongshunjie can be used Soft tissue base.
  • the tissue base material contains cellulosic fibers.
  • the composition is coated on a paper towel. Since the composition contains a grease composition with a carbon number of 20-50, it ensures the mobility of hyaluronic acid without affecting the water absorption performance of the paper towel.
  • the roller coating method can be used for coating.
  • the finishing liquid a composition of grease with a carbon number of 20-50
  • the material trough has a heating function to control the temperature of the finishing liquid at 60 to 80°C.
  • the dipping roller is partially immersed in the finishing liquid in the material trough, and rotates clockwise to bring up the finishing liquid;
  • the transfer roller rotates counterclockwise, and through contact with the dipping roller, the finishing liquid is evenly spread on the surface of the transfer roller; the paper towel base material passes between the squeeze roller and the transfer roller, where the transfer roller rotates counterclockwise, and the squeeze roller The hour hand rotates to evenly apply the finishing liquid on the surface of the paper towel.
  • the coating amount used is 35% or 36%, and its calculation formula is W2- W1/W1*100%.
  • W1 is the original mass of the paper towel base material
  • W2 is the total water content of the paper towel after coating.
  • the finishing fluid composition described in this application controls the particle size D50 of the grease in the range of 300-1300nm.
  • it When it is coated on the paper towel base material, it can be spread evenly on the fiber surface without entering the interior of the fiber. channel, thereby ensuring the mobility of hyaluronic acid without affecting the water absorption performance of the paper towel.
  • the finishing liquid composition is coated on the paper towel base material, which ensures the mobility of hyaluronic acid without affecting the water absorption performance of the paper towel.
  • Wicking rate can be used to determine the absorption performance of paper towels, for example, the method described by EDANA (European Disposables And Nonwovens Association) can be used for measurement.
  • EDANA European Disposables And Nonwovens Association
  • the Wicking rate of paper towels is used to characterize the water absorption performance of paper towels. The larger the value, the better the water absorption performance.
  • the Wicking rate of paper towels coated with the finishing liquid composition described in this application is above 30 mm, preferably 31-46mm, indicating that the finishing liquid composition described in the present application has good performance when coated on the paper towel base material. It can ensure the mobility of hyaluronic acid without affecting the absorption performance of the paper towel.
  • % means wt%, that is, weight percentage. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional reagent products that are commercially available.
  • the sources of raw materials described in the examples and comparative examples are shown in Table 1.
  • the sample pool into the sample tank of the particle size meter (DLS nanoparticle size measuring instrument, NanoBrook series of Brookhaven Instruments, USA) and conduct the test.
  • the test temperature was set to 25°C, and the particle size distribution curve was measured.
  • the particle size distribution density curve is integrated between the particle size 0 nm and Tnm. When the integral value reaches 49.9% ⁇ 50.1%, T nm is recorded as D50.
  • the finishing liquid composition obtained in Example 1 is placed in the trough 9, and the dipping roller 8 is partially immersed in the finishing liquid in the trough 9 to maintain the temperature at 60-80°C. rotation, bringing up the finishing liquid, the transfer roller 7 rotates counterclockwise, and through contact with the dipping roller 8, the finishing liquid
  • the liquid is evenly spread on the surface of the transfer roller 7, and the paper towel base material 1 is contacted by the first guide roller 2, the second guide roller 3 and the squeeze roller 6, thereby coating the finishing liquid on the paper towel base material, and the coating amount is 30 %
  • the calculation formula for the coating amount is: W2–W1/W1*100%, where W1 is the original mass of the paper towel base material, W2 is the total water content of the paper towel after coating, and the number of the obtained paper towel is Nap1- Nap16, the content of each component is shown in Table 3.
  • the measurement method of HA is measured according to the method disclosed in CN109298112A;
  • the measurement method of grease follows the national standard measurement method GB/T 6504 for the oil content of chemical fibers.
  • the operation of fibers is changed to the operation of paper towels: organic solvents, such as isopropyl alcohol or acetone, can be used first. Extract hydrophobic substances from paper towels, and then measure the extract using liquid chromatography coupled with mass spectrometry;
  • emulsifier and glycerol can be measured according to conventional methods in the art.
  • Migration rate Amount of HA in imitation leather after friction test/Amount of HA on the contact area of the cube before friction test
  • the detection method of HA content in imitation leather is as follows:
  • Mr is the weighed sample amount of the reference substance (mg); Z is the content of the reference substance; h% is the weight loss on drying of the reference substance; Vr is the volume of the reference substance solution (mL); Ar is the control The peak area of product solution; M imitation leather is the quality of imitation leather.

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  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

本申请公开了一种整理液组合物及其应用,所述整理液组合物包含油脂,所述油脂的粒径D50为300-1300nm,将所述整理液组合物涂布在纸巾基材中,在保证HA迁移性的情况下,又不影响纸巾的吸水性能。

Description

一种整理液组合物及其应用 技术领域
本申请涉及纸品制备技术领域,尤其涉及一种整理液组合物及其应用。
背景技术
透明质酸钠(HA,又称玻尿酸,或透明质酸)是一种天然保湿成分,已被广泛应用于药品和个人健康消费品中。近年来,消费品市场又出现了玻尿酸纸巾,意在添加HA,提升纸巾的护肤性。
然而,由于HA分子存在大量的羟基和羧基,HA可与纸巾的纤维素形成强烈的氢键。因此,在纸巾与皮肤摩擦过程中,HA难以从纸巾表面迁移到皮肤表面,从而也就很难实现HA的护肤效果。
为了提升HA在纸巾与皮肤摩擦过程中的迁移性,可以将油脂与HA组合,将其涂布在纸巾上,通过油脂的拒水性,阻断HA与纤维素之间的强氢键作用。但是,油脂的添加会影响纸巾的吸水性。
发明内容
为了解决上述问题,本申请提供了一种整理液组合物及其应用,所述整理液组合物中含有油脂,并且使油脂的粒径D50控制在300-1300nm内,将其涂布上纸巾基材上时,其在保证透明质酸迁移率的情况下,又不影响纸巾的吸水性能。
本申请具体技术方案如下:
1.一种整理液组合物,其包含油脂,所述油脂的粒径D50为300-1300nm。
2.根据项1所述的整理液组合物,其中,以在整理液组合物中所占的质量百分比计,所述油脂为3-20%,优选为3-8%。
3.根据项1或2所述的整理液组合物,其中,所述整理液组合物还包含透明质酸或其盐,优选的,以在整理液组合物中所占的质量百分比计,所述透明质酸或其盐为0.01-0.5%,优选为0.1-0.2%。
4.根据项1-3中任一项所述的整理液组合物,其中,所述整理液组合物 还包含乳化剂,优选的,所述乳化剂为非离子或阴离子表面活性剂,优选的,所述非离子表面活性剂选自吐温-20、吐温-80、鲸蜡硬脂醇聚醚-6、鲸蜡硬脂醇聚醚-25、鲸蜡硬脂醇橄榄油酸酯和山梨坦橄榄油酸酯中的一种或两种以上,优选的,所述阴离子表面活性剂选自硬脂酰谷氨酸钠、月桂酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠和油酸钠中的一种或两种以上。
5.根据项1-4中任一项所述的整理液组合物,其中,所述整理液组合物还包含多元醇。
6.根据项3-5中任一项所述的整理液组合物,其中,所述透明质酸或其盐为第一透明质酸或其盐或者为第二透明质酸或其盐或者为交联的透明质酸或其盐或者为第一透明质酸或其盐和第二透明质酸或其盐的组合或者为第一透明质酸或其盐和交联的透明质酸或其盐的组合或者为第二透明质酸或其盐和交联的透明质酸或其盐的组合或者为第一透明质酸或其盐、第二透明质酸或其盐和交联的透明质酸或其盐的组合。
7.根据项1-6中任一项所述的整理液组合物,其中,所述油脂的碳原子数为20-50。
8.项1-7中任一项所述的整理液组合物在纸品中的用途。
9.一种纸巾,其包括:
基材;以及
涂覆在基材表面上项1-7中任一项所述的整理液组合物。
发明的效果
本申请所述的整理液组合物,其包含油脂,所述油脂的粒径D50为300-1300nm,通过将油脂的粒径控制在上述范围内,将所述的整理液组合物应用在纸巾中,在保证HA迁移性的情况下,又不影响纸巾的吸水性能。
附图说明
图1是进行涂布的流程图。
图2是测定仿皮中HA的流程图,其中,图2A是将纸巾固定于正方体重块上的示意图,图2B是摩擦迁移测试方法的示意图。
其中,1-纸巾基材,2-第一导辊,3-第二导辊,4-第三导辊,5-第四导辊,6-挤压辊,7-转移辊,8-浸渍辊,9-料槽,10-第五导辊,11-涂布后纸巾
具体实施方式
下面对本申请做以详细说明。虽然显示了本申请的具体实施例,然而应当理解,可以以各种形式实现本申请而不应被这里阐述的实施例所限制。相反,提供这些实施例是为了能够更透彻地理解本申请,并且能够将本申请的范围完整的传达给本领域的技术人员。
需要说明的是,在说明书及权利要求当中使用了某些词汇来指称特定组件。本领域技术人员应可以理解,技术人员可能会用不同名词来称呼同一个组件。本说明书及权利要求并不以名词的差异作为区分组件的方式,而是以组件在功能上的差异作为区分的准则。如在通篇说明书及权利要求当中所提及的“包含”或“包括”为开放式用语,故应解释成“包含但不限定于”。说明书后续描述为实施本申请的较佳实施方式,然而所述描述乃以说明书的一般原则为目的,并非用以限定本申请的范围。本申请的保护范围当视所附权利要求所界定者为准。
本申请提供了一种整理液组合物,其包含油脂,所述油脂的粒径D50为300-1300nm。
油脂的粒径D50可以为300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm、1100nm、1200nm、1300nm等。
所述油脂为含有烃类的油脂,即所述油脂可以是纯烃类的油脂,例如矿物油、矿脂、角鲨烷等,也可以是含有一部分烃类的油脂,例如可以为蜂蜡等,所述油脂的碳原子数为20-50。
本申请所述的整理液组合物,在涂布在纸巾基材上,在保证透明质酸迁移性的基础上,又不影响纸巾的迁移性能。
在一些实施方式中,对于油脂的粒径D50,其可以采用本领域常规的方法进行测定,例如可以采用常规的测试粒径的方法进行测定,例如通过对胶体体系中的纳米颗粒的布朗运动建立相关的函数模型,并计算扩散系数,再计算出颗粒的粒径分布,例如通过爱因斯坦-斯托克斯方程计算出颗粒的等效粒径分布,例如将样本进行稀释,放入粒径仪中进行测试得到粒径分布密度曲线,并对分布密度曲线进行积分得到粒径D50,更具体地,将取1g待测样品,用纯净水稀释1000倍,然后取1.8~3ml稀释后的样品置于石英玻璃样品池中。
将样品池放入粒径仪的样品槽内,进行测试。测试温度设定为25℃,测得粒径分布曲线。
在粒径0nm到T nm之间,对粒径分布密度曲线进行积分。当积分数值达到49.9%~50.1%时,T nm记录为D50。
在本申请中,所述油脂的粒径D50是通过乳化后所测得的粒径。对于乳化方法,本申请不作任何限制,其可以根据需要进行选择,例如将乳化剂和油脂加入水中进行高压均质,控制油脂的粒径在300-1300nm的范围内,接着再加入多元醇和透明质酸或其盐进行混合得到整理液组合物,例如将乳化剂和油脂加入水中,加热至60-70℃进行高压均质,控制油脂的粒径在300-1300nm的范围内,再加入多元醇和透明质酸或其盐进行混合得到整理液组合物。
在一些实施方式中,以在整理液组合物中所占的质量百分比计,所述油脂为3-20%,优选为3-8%。
例如,以在整理液组合物中所占的质量百分比计,所述油脂可以为3%、4%、5%、6%、7%、8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%等。
在一些实施方式中,所述整理液组合物还包含透明质酸或其盐,优选的,以在整理液组合物中所占的质量百分比计,所述透明质酸或其盐为0.01-0.5%,优选为0.1-0.2%。
在本申请中,对于透明质酸的盐,其为透明质酸的金属盐,对于具体的金属盐,本申请不作任何限制,其可以根据本领域的需要进行常规选择,例如透明质酸的金属盐可以为透明质酸的钠盐、透明质酸的镁盐、透明质酸的锌盐或透明质酸的钙盐等,优选可以使用透明质酸的钠盐。
透明质酸或其盐在整理液组合物中的含量可以为0.01%、0.05%、0.1%、0.2%、0.3%、0.4%、0.5%等。
在一些实施方式中,所述透明质酸或其盐为交联的透明质酸或其盐。
所述交联的透明质酸或其盐指的是透明质酸或其盐在化学修饰以后构成的一种衍生物,通过交联剂进行修饰后将线性的透明质酸分子连接成空间网络结构。
在一些实施方式中,所述透明质酸或其盐的分子量为1000-300W Da。在一些实施方式中,所述透明质酸或其盐为第一透明质酸或其盐或者为第二 透明质酸或其盐,优选的,所述第一透明质酸或其盐的分子量为1w-5w Da;所述第二透明质酸或其盐的分子量,其为50w-100w Da。
在一些实施方式中,所述透明质酸或其盐为第一透明质酸或其盐或者为第二透明质酸或其盐或者为交联的透明质酸或其盐或者为第一透明质酸或其盐和第二透明质酸或其盐的组合或者为第一透明质酸或其盐和交联的透明质酸或其盐的组合或者为第二透明质酸或其盐和交联的透明质酸或其盐的组合或者为第一透明质酸或其盐、第二透明质酸或其盐和交联的透明质酸或其盐的组合。
对于上述组合的质量比,本申请不作任何限制,其可以根据需要进行常规选择,例如,第一透明质酸或其盐和第二透明质酸或其盐的质量比(m第一 透明质酸或其盐:m第二透明质酸或其盐)为1:0.1-10;
第二透明质酸或其盐和交联的透明质酸或其盐的质量比(m第二透明质酸或其 :m交联的透明质酸或其盐)可以为1:0.1-10;
第一透明质酸或其盐和交联的透明质酸或其盐的质量比(m第一透明质酸或其 :m交联的透明质酸或其盐)可以为1:0.01-1。
优选的,第一透明质酸或其盐、第二透明质酸或其盐和交联的透明质酸或其盐的质量比(m第一透明质酸或其盐:m第二透明质酸或其盐:m交联的透明质酸或其盐)可以为1:1:1或1:1:0.5或1:1:0.1。
在一些实施方式中,所述组合物还包含乳化剂,优选的,所述乳化剂为非离子或阴离子表面活性剂,优选的,所述非离子表面活性剂选自吐温-20、吐温-80、鲸蜡硬脂醇聚醚-6、鲸蜡硬脂醇聚醚-25、鲸蜡硬脂醇橄榄油酸酯和山梨坦橄榄油酸酯中的一种或两种以上,优选的,所述阴离子表面活性剂选自月桂酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠和油酸钠中的一种或两种以上。
在本申请中,对于乳化剂在整理液组合物中的含量,本申请不作任何限制,其可以根据需要进行常规选择,例如,乳化剂在整理液组合物中的含量可以为0.5-10%。
在一些实施方式中,所述整理液组合物还包含多元醇。对于多元醇的类型,本申请不作任何限制,其可以根据需要进行选择,例如多元醇可以为甘油、乙二醇、丁二醇等。
对于多元醇在整理液组合物中的含量,本申请不作任何限制,其可以根 据需要进行选择,例如,多元醇在整理液组合物中的含量可以为0.1-80%。
在一些实施方式中,所述整理液组合物还包含水溶性活性成分,优选的,所述水溶性活性成分选自依克多因、麦角硫因、γ-氨基丁酸、氨基酸和蛋白质中的一种或两种以上。
对于水溶性活性成分在整理液组合物中的含量,本申请不作任何限制,其可以根据需要进行选择。
在本申请中,对于整理液组合物的制备方法,本申请不作任何限制,其可以根据需要进行常规选择,例如,可以采用高压均质的方法进行制备,例如将乳化剂、油脂与水进行混合均质,控制油脂的乳化粒径D50,接着加入透明质酸或其盐和甘油进行混合得到,优选将乳化剂、油脂与水进行混合后加入60-70℃进行高压均质。
在一些实施方式中,所述整理液组合物包含油脂,所述油脂的粒径D50为300-1300nm。在一些实施方式中,以在整理液组合物中所占的质量百分比计,所述油脂为3-20%,优选为3-8%。在一些实施方式中,所述整理液组合物还包含透明质酸或其盐,优选的,以在整理液组合物中所占的质量百分比计,所述透明质酸或其盐为0.01-0.5%,优选为0.1-0.2%。在一些实施方式中,所述整理液组合物还包含乳化剂,优选的,所述乳化剂为非离子或阴离子表面活性剂,优选的,所述非离子表面活性剂选自吐温-20、吐温-80、鲸蜡硬脂醇聚醚-6、鲸蜡硬脂醇聚醚-25、鲸蜡硬脂醇橄榄油酸酯和山梨坦橄榄油酸酯中的一种或两种以上,优选的,所述阴离子表面活性剂选自硬脂酰谷氨酸钠、月桂酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠和油酸钠中的一种或两种以上。在一些实施方式中,所述整理液组合物还包含多元醇。在一些实施方式中,所述透明质酸或其盐为第一透明质酸或其盐或者为第二透明质酸或其盐或者为交联的透明质酸或其盐或者为第一透明质酸或其盐和第二透明质酸或其盐的组合或者为第一透明质酸或其盐和交联的透明质酸或其盐的组合或者为第二透明质酸或其盐和交联的透明质酸或其盐的组合或者为第一透明质酸或其盐、第二透明质酸或其盐和交联的透明质酸或其盐的组合。在一些实施方式中,所述透明质酸或其盐的分子量为1000-300W Da。在一些实施方式中,所述第一透明质酸或其盐的分子量为1w-5w D a;所述第二透明质酸或其盐的分子量,其为50w-100w Da。在一些实施方式中,所述油脂的碳原子数为20-50。
本申请提供了上述所述的整理液组合物在纸品中的用途。
本申请提供了一种纸巾,其包含基材以及上述所述的整理液组合物。
对于纸巾的吸水性能,从原理上进行推测由两方面因素贡献的:
(1)纸巾纤维内孔道的毛细现象;
(2)纸巾纤维间空隙的毛细现象。
在纸巾上涂布油脂,如果可以不影响这两个因素,则不会对纸巾的吸水能力造成负面影响。因此,油脂涂布后的理想微观结构应该是,油脂均匀地铺展在纤维表面,不进入纤维内部孔道,也不黏连纤维间的空隙。
本申请的发明人创造性地发现,当整理液组合物的油脂的粒径D50控制在300-1300nm的范围内,能够保证透明质酸的迁移性,即迁移率在5%以上,又不影响纸巾的吸收性能。
在本申请中,对于油脂在纸巾中的含量,可以采用本领域常规的方法进行测量,例如采用化学纤维含油率的测定方法进行测量,例如采用国标测量方法GB/T 6504的方法进行测定,例如采用有机溶剂比如异丙醇或丙酮,对纸巾上的油脂进行萃取,接着对萃取液进行液相色谱与质谱联用的方法进行测量。
对于透明质酸或其盐在纸巾中的含量测定,本申请不作任何限制,其可以根据需要进行常规选择,例如,可以采用CN109298112A公开的方法进行测定。
对于乳化剂在纸巾中的含量的测定方法,本申请不作任何限制,其可以根据本领域常规的方法进行测定。
对于甘油在纸巾中的含量测定方法,本申请不作任何限制,其可以根据本领域常规的方法进行测定。
所述水溶性活性成分可以增加纸巾的护肤性能。
对于水溶性活性成分在纸巾中的含量的测定方法,本申请不作任何限制,其可以采用本领域常规的方法进行测定。
在一些实施方式中,所述透明质酸或其盐的迁移率≥5%。
所述迁移率指的是在摩擦测试过程中,HA迁移到仿皮上的效率,其计算公式如下:
迁移率=摩擦后仿皮上的HA量/摩擦前正方体接触面上纸巾的HA含量。
所述基材指的纸巾基材,可以是任何市售的基材,例如可以使用中顺洁 柔的纸巾基材。
在一些实施方式中,所述纸巾基材中含有纤维素纤维。
本申请将组合物涂布在纸巾上,由于组合物中含有碳原子数为20-50的油脂的组合物,其在保证透明质酸迁移性的基础上,又不影响纸巾的吸水性能。
对于涂布方法,本申请不作任何限制,本领域技术人员可以根据需要进行选择,例如,可以采用辊涂的方法进行涂布,例如将整理液(碳原子数为20-50的油脂的组合物)置于料槽中,其中料槽具有加热功能,将整理液温度控制在60~80℃,浸渍辊部分浸渍在料槽的整理液中,通过顺时针旋转,将整理液带起;
转移辊逆时针旋转,并且通过与浸渍辊的接触,将整理液均匀地铺展于转移辊的表面;纸巾基材从挤压辊与转移辊中间通过,其中转移辊逆时针旋转,挤压辊顺时针旋转,从而将整理液均匀地涂布在纸巾表面。
对于涂布在纸巾中的涂布量,本申请不作任何限制,本领域技术人员可以根据需要进行选择,在本申请中,使用的涂布量为35%或36%,其计算公式为W2–W1/W1*100%。其中,W1为纸巾基材的原始质量,W2为涂布后纸巾的含水总质量。
本申请所述的整理液组合物通过将油脂的粒径D50控制在300-1300nm的范围内,当将其涂布在纸巾基材上时,其能均匀地铺展在纤维表面,不进入纤维内部通道,从而保证透明质酸迁移性的基础上又不影响纸巾的吸水性能。
本申请将整理液组合物涂布在纸巾基材上,其在保证透明质酸迁移性的基础上,又不影响纸巾的吸水性能。
对于纸巾的吸水性能的测定方法,本申请不作任何限制,例如可以采用Wicking rate来确定纸巾的吸收性能,例如采用EDANA(European Disposables And Nonwovens Association)所述的方法进行测定。
在本申请中,采用纸巾的Wicking rate表征纸巾的吸水性能,数值越大,表明吸水性能较好,采用本申请所述的整理液组合物涂布的纸巾,其Wicking rate在30mm以上,优选为31-46mm,表明本申请所述的整理液组合物涂布在纸巾基材上,具有较好的性能,其既能保证透明质酸的迁移率,又不影响纸巾的吸收性能。
实施例
本申请对试验中所用到的材料以及试验方法进行一般性和/或具体的描述,在下面的实施例中,如果无其他特别的说明,%表示wt%,即重量百分数。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品,其中,实施例和对比例中所述的原料来源如表1所示。
表1原料来源
实施例1
将乳化剂和油脂加入到水中,加热至60-70℃,接着进行高压均质,通过调节压力和均质时间,将油脂的粒径D50控制为表2中所述的粒径,然后加入甘油和透明质酸钠混合均匀后得到整理液组合物,其中,各种组分的含量如表2所示,油脂的粒径D50的测试原理为通过对胶体体系中的纳米颗粒的布朗运动建立相关函数模型,计算出其运动的扩散系数,再通过爱因斯坦-斯托克斯方程计算出颗粒的等效粒径分布,其具体测试方法如下:
取1g所述的整理液组合物,用纯净水稀释1000倍,然后取1.8~3ml稀释后的样品置于石英玻璃样品池中。
将样品池放入粒径仪(DLS纳米粒度测量仪,美国布鲁克海文仪器公司NanoBrook系列)的样品槽内,进行测试。测试温度设定为25℃,测得粒径分布曲线。
在粒径0nm到Tnm之间,对粒径分布密度曲线进行积分。当积分数值达到49.9%~50.1%时,T nm记录为D50。
表2各种组分的含量表

实施例2纸巾的制备
如图1所示,将实施例1所得到的整理液组合物放在料槽9中,浸渍辊8部分浸渍在料槽9的整理液中使其温度保持在60-80℃,通过顺时针旋转,将整理液带起,转移辊7逆时针旋转,并且通过与浸渍辊8的接触,将整理 液均匀地铺展于转移辊7的表面,纸巾基材1通过第一导辊2、第二导辊3和挤压辊6接触,从而在纸巾基材上涂布整理液,涂布量为30%,涂布量的计算公式为:W2–W1/W1*100%,其中,W1为纸巾基材的原始质量,W2为涂布后纸巾的含水总质量,所得到的纸巾的编号为Nap1-Nap16,各个组分的含量如表3所示。
其中,HA的测定方法按照CN109298112A公开的方法进行测定;
油脂的测定方法按照化学纤维含油率的国标测量方法GB/T 6504,但在此方法中,将对纤维的操作,变成对纸巾的操作:可先用有机溶剂,比如异丙醇或丙酮,对纸巾上疏水性物质进行萃取,再对萃取液进行液相色谱与质谱联用的方法进行测量;
乳化剂和甘油的含量可以按照本领域常规的方法进行测量。
表3纸巾中不同组分的含量表
实验例1透明质酸的迁移率的测定
实验材料:尺寸为5cm×12cm的硅胶仿皮、质量为300g尺寸为5cm×5cm正方体方块、量程为5N的拉力计以及皮筋。
操作方法:
1)用去离子水清洗仿皮表面后,室温晾干表面水分;
2)使用分析天平,精确记录仿皮的质量;
3)使用喷雾器,在仿皮表面均匀喷0.1g去离子水;
4)用酒精将实验桌面擦干净,将5cm×12cm的硅胶仿皮固定于光滑的水平桌面上;
5)将编号为Nap1-Nap16的纸巾固定于正方体重块一面,并将固定有纸巾的那一面置于仿皮正上方,正方体重块重心与仿皮一端竖直方向对齐,重物的边与仿皮边缘对齐,如图2A和图2B所示;
6)使用拉力计水平匀速拖动重块,直到拖动重块重心至仿皮末端结束,如此重复5次;
7)将仿皮剪成小碎块,置于窄口玻璃瓶中,检测仿皮中HA的含量;
8)计算HA从纸巾到仿皮中的迁移率,其结果如表4所示,其中,迁移率的计算公式为:
迁移率=摩擦测试后仿皮中HA量/摩擦测试前正方体接触面积上纸巾的
HA含量
仿皮中HA含量检测方法如下:
(1)试剂以及材料:
磷酸二氢钠(国药基团化学试剂有限公司)、磷酸氢二钠(国药基团化学试剂有限公司)、磷酸(国药基团化学试剂有限公司)、透明质酸对照品(华熙生物科技股份有限公司)和透明质酸酶(华熙生物科技股份有限公司)
(2)色谱条件
色谱柱:MCI GEL CK08EH色谱柱(8×300mm,9μm),流动相:1%磷酸;流速:0.6ml/min;进样量:20μL;柱温:40℃;检测波长:232nm
(3)溶液配制
A)酶解缓冲液:
称取磷酸二氢钠(NaH2PO4·2H2O)27.4g、磷酸氢二钠(Na2HPO4·12H2O) 8.8g置1000mL容量瓶中,加水稀释至刻度,摇匀,得0.2mol/L NaH2PO4-Na2HPO4缓冲液,将该缓冲液稀释40倍后得到酶解缓冲液(5mM/L NaH2PO4-Na2HPO4缓冲液,pH6.0)
B)对照溶液:
精密称取透明质酸钠对照品约50mg于50mL容量瓶中,酶解缓冲液溶解并定容至刻度,混匀。取上述溶液0.5mL置于10mL容量瓶中,加入5mL酶解缓冲液和0.5mL透明质酸酶,混匀,密封,42℃酶解2h,煮沸2min使酶失活,酶解缓冲液定容至刻度,0.22μm滤膜过滤,即得对照品溶液。
C)固体供试品:
称取仿皮15-18g,置于窄口玻璃瓶中,精确记录仿皮质量,加入酶解缓冲液,缓冲液体积以能浸没仿皮为准,加入0.5mL透明质酸酶,混匀、密封,42℃酶解2h,煮沸2min使酶失活,酶解缓冲液定容至刻度,0.22μm滤膜过滤,即得供试品溶液,平行制备两份。
D)测定:
分别取对照品溶液和供试品溶液20μL进样,记录色谱图,按下式计算仿皮中HA的含量(μg/g)
式中:As为供试品溶液峰面积,Mr为对照品称样量(mg);Z为对照品含量;h%为对照品干燥失重;Vr为对照品溶液体积(mL);Ar为对照品溶液峰面积;M仿皮为仿皮的质量。
表4 HA的迁移率

实验例2吸水性能的测定
其采取的是Wicking Rate方法,即采用EDANA(European Disposables And Nonwovens Association)10.4-02中的Liquid Wicking Rate方法,其中Wicking时间设定100秒,其结果如表5所示。
表5 Wicking Rate
以上所述,仅是本申请的较佳实施例而已,并非是对本申请作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本申请技术方案内容,依据本申请的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本申请技术方案的保护范围。

Claims (9)

  1. 一种整理液组合物,其包含油脂,所述油脂的粒径D50为300-1300nm。
  2. 根据权利要求1所述的整理液组合物,其中,以在整理液组合物中所占的质量百分比计,所述油脂为3-20%,优选为3-8%。
  3. 根据权利要求1或2所述的整理液组合物,其中,所述整理液组合物还包含透明质酸或其盐,优选的,以在整理液组合物中所占的质量百分比计,所述透明质酸或其盐为0.01-0.5%,优选为0.1-0.2%。
  4. 根据权利要求1-3中任一项所述的整理液组合物,其中,所述整理液组合物还包含乳化剂,优选的,所述乳化剂为非离子或阴离子表面活性剂,优选的,所述非离子表面活性剂选自吐温-20、吐温-80、鲸蜡硬脂醇聚醚-6、鲸蜡硬脂醇聚醚-25、鲸蜡硬脂醇橄榄油酸酯和山梨坦橄榄油酸酯中的一种或两种以上,优选的,所述阴离子表面活性剂选自硬脂酰谷氨酸钠、月桂酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠和油酸钠中的一种或两种以上。
  5. 根据权利要求1-4中任一项所述的整理液组合物,其中,所述整理液组合物还包含多元醇。
  6. 根据权利要求3-5中任一项所述的整理液组合物,其中,所述透明质酸或其盐为第一透明质酸或其盐或者为第二透明质酸或其盐或者为交联的透明质酸或其盐或者为第一透明质酸或其盐和第二透明质酸或其盐的组合或者为第一透明质酸或其盐和交联的透明质酸或其盐的组合或者为第二透明质酸或其盐和交联的透明质酸或其盐的组合或者为第一透明质酸或其盐、第二透明质酸或其盐和交联的透明质酸或其盐的组合。
  7. 根据权利要求1-6中任一项所述的整理液组合物,其中,所述油脂的碳原子数为20-50。
  8. 权利要求1-7中任一项所述的整理液组合物在纸品中的用途。
  9. 一种纸巾,其包括:
    基材;以及
    涂覆在基材表面上权利要求1-7中任一项所述的整理液组合物。
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