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WO2012167545A1 - 洗涤用固体颗粒及其洗涤方法 - Google Patents

洗涤用固体颗粒及其洗涤方法 Download PDF

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Publication number
WO2012167545A1
WO2012167545A1 PCT/CN2011/082078 CN2011082078W WO2012167545A1 WO 2012167545 A1 WO2012167545 A1 WO 2012167545A1 CN 2011082078 W CN2011082078 W CN 2011082078W WO 2012167545 A1 WO2012167545 A1 WO 2012167545A1
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WIPO (PCT)
Prior art keywords
solid particles
washing
solid
granule
particles
Prior art date
Application number
PCT/CN2011/082078
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English (en)
French (fr)
Inventor
何政保
劳春峰
Original Assignee
海尔集团公司
海尔集团技术研发中心
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.)
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Publication date
Application filed by 海尔集团公司, 海尔集团技术研发中心 filed Critical 海尔集团公司
Priority to EP11867312.8A priority Critical patent/EP2719807A4/en
Priority to JP2014513882A priority patent/JP6020853B2/ja
Priority to US14/124,281 priority patent/US9315766B2/en
Publication of WO2012167545A1 publication Critical patent/WO2012167545A1/zh

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
    • D06F35/005—Methods for washing, rinsing or spin-drying
    • D06F35/006—Methods for washing, rinsing or spin-drying for washing or rinsing only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • This invention relates to the field of washing technology, and more particularly to a solid particle for use in a washing process, and a method of washing a laundry with solid particles. Background technique
  • the washing medium used in the washing process is as follows: 1. Using water as the washing medium; 2. Using organic solvent as the medium, the method is suitable for removing hydrophobic stains; 3. Using air, such as washing with liquid C02; Plastic particles, such as the Chinese patent CN 101466482A, published June 24, 2009, discloses a new cleaning method which uses plastic nylon particles as a washing medium, using polar groups on the surface of the nylon, such as -0H, Adsorbs the stains on the clothes to achieve the decontamination effect.
  • the above washing medium also has the following defects in the washing process: 1. Water is used as the washing medium, and the water consumption is very large; 2. The organic solvent is used as the medium, the organic solvent itself is highly toxic, and the distillation method is adopted. The safety factor for recovering the medium is low; 3. The air and air require a good air tightness of the system, and the liquefaction of the gas requires high pressure, the safety factor is low and the process is complicated; 4. Plastic particles, The method is a newly developed new washing method. Compared with water as a washing medium, the method is easy to remove hydrophobic stains. Compared with organic solvents and liquid air as a medium, the method has little environmental pollution and is convenient to operate, but nylon particles. The ability to adsorb dirt is limited, and the ability to remove a large amount of stains is also limited. Second, there is a clear cross-color effect in the process of washing clothes, and there is no way to completely remove the stains. Summary of the invention
  • the present invention provides a solid particle for washing.
  • the surface of a contaminant is washed by the solid particles of the present invention, the surface of the particle has a large amount of openness.
  • the cell has a strong adsorption capacity and a high surface activity, and the contaminant is easily removed from the surface of the object to be washed.
  • the present invention also provides a method of washing with solid particles.
  • the technical solution adopted by the present invention to solve the technical problems thereof is: a solid particle for washing, the solid particle being a polymer solid particle, characterized in that: the surface of the particle is distributed with open cells.
  • the surface of the polymer solid particles is not smooth enough to bind the contaminants, the washing effect is not satisfactory, and the color is easy to cross. And the surface is densely covered with a large number of dispensing cells.
  • the polymer solid particles are washed in place of the original polymer particles by utilizing a large number of open cells on the surface of the particles to adsorb and remove contaminants. The smaller the diameter of the cell, the better the effect of adsorbing and removing contaminants.
  • the adsorption capacity of the cell material will have a qualitative leap, because the material cell at this time
  • the specific surface area will be very large and the surface energy will be very large, so the ability to adsorb and remove contaminants will multiply. Therefore, the use of polymer solid particles having open cells on the surface can achieve a good washing effect and can effectively prevent cross-coloring.
  • the surface layer of the solid particles is a cell layer, and the inside of the particles is a solid structure.
  • the solid particles are internally distributed with open cells.
  • the solid particles have a solid structure inside.
  • the solid particles have a cell diameter of from 10 nm to 100 ⁇ m.
  • the solid particles have a cell density of from 10 3 /cm 3 to 10 12 /cm 3 .
  • the density of the solid particles is preferably 0. 3g / cm 3 ⁇ l g / cm 3.
  • the shape of the solid particles is spherical, or cubic, or cylindrical, or olive-shaped, or crescent-shaped.
  • the solid particles have an average particle diameter of from 1 mm to 10 mm.
  • the polymer in the solid particles comprises PP, or PE, or PS, or PVC, or EVA, or PA, or PET, or a mixture of one or more of the above materials. .
  • the solid particles contain an inorganic powder.
  • the pellet according to claim 13, wherein the magnetic material is an alloy containing one, or two, or three of iron, cobalt, and nickel.
  • the granule according to claim 14 wherein the magnetic material is iron or an iron alloy.
  • a method of washing with solid particles comprising: a step of washing the laundry to be washed with the solid particles; a step of separating the laundry to be separated from the solid particles; a step of washing the laundry; and drying the laundry A step of.
  • Washing the laundry with the above method can completely remove the contaminants and is convenient to use.
  • the neutral particles are also washed with a neutral nonionic surfactant in the step of washing the laundry.
  • the mass ratio of the mass to be washed and the solid particles is 1: 0. 5 ⁇ 1 : 5; Further preferably, the mass ratio is 1: 1 to 1: 3 .
  • the step of separating the object to be washed from the solid particles is carried out in a magnetic field.
  • the invention has the beneficial effects that after the polymer solid particles having a large number of open cells on the surface are used as the washing medium, the decontamination ability and the effect of preventing the cross color are remarkably enhanced, and the surface cell structure can also be Saving the use of materials, protecting the environment, and saving costs, using the method described in the present invention is simple and convenient.
  • Fig. 1 is a schematic view showing the outer surface of a polymer solid particle according to an embodiment of the present invention.
  • Figure 2 is a cross-sectional view of the polymer solid particles of the first embodiment.
  • Figure 3 is a cross-sectional view of the polymer solid particles of the second embodiment.
  • Figure 4 is a cross-sectional view of the polymer solid particles of the third embodiment.
  • Fig. 5 is a schematic view of a washing machine used in the fourth embodiment.
  • the inside of the solid particle 1 is a solid structure, that is, the inside of the particle is a solid inside the particle.
  • the surface layer of the particle is a cell layer
  • the cell layer contains a large number of open cells 2
  • the cell is surrounded by a cell wall 3
  • the surface of the polymer solid particles is not smooth enough to bind the contaminants, the washing effect is not satisfactory, and the color is easy to cross.
  • the use of polymer solid particles with a large number of open cells on the surface instead of the original polymer particles for washing utilizes a large number of open cells on the surface of the particles to adsorb and remove contaminants.
  • the open cell is that the inside of the cell can communicate with the outside. The smaller the diameter of the cell, the better the effect of adsorbing and removing contaminants.
  • the cell material is The adsorption capacity will have a qualitative leap, because the specific surface area of the material cells will be very large and the surface energy will be very large, so the ability to adsorb and remove pollutants will multiply. Therefore, the use of polymer solid particles with open cells on the surface can achieve a good washing effect, and Effectively prevent cross color. In addition, the presence of cells can save material use, protect the environment, and save costs. Further, the surface layer of the solid particles is a cell layer, and the inside of the particles is a solid structure.
  • the volume occupied by the cell surface layer is 0.01%-20% of the entire solid particle volume, so that the particles can be adsorbed on the surface or surface layer of the particle during the washing without entering the center of the particle. It is easy to clean the particles and make the particles easy to reuse.
  • the solid particles suitable for washing application have an opening ratio of 50% to 100%; the solid particles have a cell diameter of 10 nm to 100 ⁇ m; and the solid particles have a cell density of 10 3 /cm 3 to 10 12 /cm 3 ;
  • the solid particles have a density of 0.3 g /cm 3 to 1 g / C m 3 ; the shape of the solid particles is spherical, or cubic, or cylindrical, or olive-shaped, or crescent; the average particle diameter of the solid particles is lmm ⁇ 10mm.
  • Common polymeric materials with cells on the surface are relatively soft and elastic.
  • the surface of the polymer particles also has such a foamed structure, during the washing process and the surface of the fabric. Contact is more similar to human handcuffs.
  • the cells in the surface of the polymer particles communicate with one another to provide conditions for contaminants to enter and exit and adsorb contaminants. Further, the cell walls 3 on the surface of the polymer particles can reduce the adhesion of the contaminants to the fabric as in the case of a toothbrush in contact with the fabric.
  • the polymer solid particles may be selected from PP, or PE, or PS, or PVC, or EVA, or PA, or PET; or a mixture of one or more of the above materials may be selected.
  • an inorganic powder is added to the polymer.
  • the dense powder should also be more uniform and fine.
  • an inorganic powder such as talc powder, calcium carbonate or the like to the polymer solid particles, and it is more preferable to add the inorganic nano powder, and the powder mainly functions to form a cell or a nucleating agent.
  • a powder containing silver ions may be added, and the polymer solid particles will have a bactericidal function.
  • the polymer solid particles are prepared by uniformly mixing the polymer with the powder and extruding the granules, then immersing the granules in an organic solvent xylene for 8 to 48 hours for swelling, and then soaking the granules in a strong acidic solution. 0. 1 to 10 hours to dissolve the powder in the particles, so that the powder on the surface layer of the particles dissolves the cells, leaving a cell layer on the surface, and the inside is a solid structure.
  • the washing method adopted in this embodiment is achieved by the following scheme: Before washing, the polymer solid particles 1 are stored in a storage tank of the washing machine, the washing aid can be quantitatively added by an automatic adding device, and the addition of a small amount of water can be passed through the flow rate.
  • the meter device controls the amount of water added.
  • the process of washing the laundry with the polymer particles comprises opening the discharge valve, placing the polymer solid particles in the storage tank into the drum, and simultaneously infiltrating the clothes through the pipeline through the automatic soap adding device and the water quantitative adding device. , washing time is 10-60 minutes, washing temperature is maintained at 50-70 degrees, steam heating can be used, the mass ratio of clothes to solid particles is 1: 0. 5 ⁇ 1: 5, the preferred mass ratio is 1: 1 ⁇ 1 : 3.
  • the drying speed and time can be referred to the first drying condition, and the second and third rinsing can be performed according to the degree of dirty clothes. After the rinsing, the clothes are dried, and the separation of the granules and the clothes is carried out.
  • the centrifugal separation method is adopted to rotate the inner cylinder at a high speed, the rotation speed can be 150-800 rpm, the feed port is opened, and the polymer solid particles 1 are centrifuged at high speed. Under the action, the feed port enters the storage bin to realize the recovery of the particles for the next use.
  • the rinsing function of the granules open the discharge valve port, put the particles into the drum, add a small amount of water for rinsing, rinse time 10-40 minutes, dry after rinsing, dry at 100-800 rpm, dry After the feed valve is opened, the recovery of the particles is achieved by a high-speed rotary centrifugation method.
  • the polymer solid particles also use a neutral nonionic surfactant in the process of washing the laundry, so that the washing effect is better and the pollutants are more easily removed.
  • the laundry is washed by the polymer solid particles of the embodiment, and the polymer solid particles are densely covered with a large number of open cells, and have strong ability to adsorb and remove contaminants, and wash hydrophilic and hydrophobic pollutants.
  • the results are ideal and avoid cross-color.
  • the porous surface of the polymer layer can save material usage, protect the environment, and save costs compared with ordinary polymerization.
  • the surface structure of the washing polymer solid described in this embodiment is shown in Fig. 1, and its cross-sectional view is shown in Fig. 3. Since the polymer solid particles adsorb the contaminants, the contaminants will enter the interior of the open cells on the surface of the particles, and may further enter the deep cells from the cells in the surface layer. Thus, the particles need to be washed when the solid particles are repeatedly used. If the particles penetrate deep into the particles, it is difficult to remove them, so that the polymer solid has only open cells on the surface, and there is no open bubble inside. The pores, that is, the inside of the particles, are solid structures. Such polymer solid particles adhere to the surface of the particles only after washing the particles, and are easily removed, and the particles are easily reused.
  • the granules only have open vesicles on the surface of the granules.
  • the granules have an open blister on the surface. hole.
  • the surface structure of the washing polymer solid described in this embodiment is shown in Fig. 1, and its cross-sectional view is shown in Fig. 4.
  • the polymer solid particles can be prepared by physical foaming or chemical foaming, adding a foaming agent to the polymer melt, and controlling foaming.
  • the amount of the agent added and the foaming temperature and time give cells of different sizes and shapes.
  • a large number of cells are formed on the surface and inside of the polymer solid particles, which can save materials.
  • the solid particles 1 in the present embodiment contain a magnetic material having a mass fraction of 5% to 10%.
  • polymer solid particles to wash the laundry requires separation of the polymer particles from the laundry, but the separation of the polymer particles from the laundry is undesirable due to the presence of surfactants and water, especially in automated cleaning equipment such as washing machines. Although manual separation can be used, the washing efficiency will be significantly reduced.
  • a magnetic material capable of being attracted by a magnetic field is added to the polymer solid particles, the magnetic particles can be separated from the laundry in the inner cylinder of the washing machine and fixed on the surface of the magnetic field, and the particles are separated from the clothes. Re-in combination with the granules can improve the separation efficiency of the granules from the laundry.
  • the magnetic material or the material capable of being attracted by the magnetic field is one of iron, cobalt, and nickel, or an alloy containing one, or two, or three of iron, cobalt, and nickel. In order to reduce the cost, it is also possible to ensure that the laundry is easily separated from the particles.
  • the magnetic material is preferably iron or iron alloy.
  • the particle size of the particles is 0. 01mm ⁇ 2mm.
  • the average particle diameter of the solid particles for washing is from 1 mm to 5 mm.
  • the solid particles for washing have an average particle diameter of from 1 mm to 3 mm.
  • the magnetic properties of the particles disappear after the magnetic field disappears, and the mass fraction of the magnetic materials in the solid particles for washing is 5% to 10%. Choose 5%, 6%, 7%, 8%, 9%, 10%.
  • the mass fraction of the polymer material is 50% to 95%, specifically 50%, 60%, 70%, 80%, 90%, 95%.
  • the solid particles for washing in this embodiment were prepared by uniformly mixing 7 parts by weight of iron particles with 93 parts by weight of PA, followed by extrusion by an extruder, and then passing through a granulator to obtain solid particles.
  • the solid particles are immersed in a strongly acidic solution such as a hydrochloric acid solution for 30 minutes, so that the magnetic material particles on the surface of the particles are dissolved to leave cells, and finally dried.
  • the solid particles are prepared, as shown in Figure 1, Figure 2.
  • the washing machine includes a washing machine casing 11, an outer cylinder 12 disposed inside the casing, and an inner cylinder 13 disposed inside the outer cylinder.
  • the outer surface of the inner cylinder 13 is provided with a solid particle capable of pushing the solid particles along the bottom of the outer cylinder a scraper 14 that moves upward, and has an inner cylinder 12
  • the magnetic field is generated by the electromagnet 15.
  • the electromagnet will generate a magnetic field, that is, the step of separating the object to be washed from the solid particles in the first embodiment is performed in a magnetic field.
  • the magnetic field inside the outer cylinder can attract the washing particles in the outer cylinder of the washing machine to a position corresponding to the magnetic pole of the electromagnet in the outer cylinder, and the magnetic field can be generated by the electromagnet. Remove the magnetic field at any time when no magnetic field is needed.
  • the separation time is reduced by 50% to 80% compared to ordinary polymer solid particles, and the color separation can be well avoided. Therefore, it is easy to separate the granules from the clothes after washing the laundry with the solid particles for washing, and to improve the washing efficiency.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种洗涤用固体颗粒及其洗涤方法，固体颗粒为聚合物固体颗粒（1），其特征是：颗粒表面分布有开放性泡孔（2）。一种应用该颗粒洗涤的方法，包括将待洗物与固体颗粒分离的步骤，漂洗待洗物的步骤，甩干待洗物的步骤。

Description

洗涤用固体颗粒及其洗涤方法 技术领域
本发明涉及洗涤技术领域， 特别是一种在洗涤过程中使用的固体颗粒， 还包括 一种用固体颗粒洗涤待洗物的方法。 背景技术
洗涤过程中采用的洗涤介质有以下几种： 1、 采用水作为洗涤介质； 2、 采用有 机溶剂作介质， 该方式适用于清除疏水性污渍； 3、 采用空气， 如采用液态 C02洗； 4、 塑料粒子， 如中国专利 CN 101466482A, 公开日期 2009年 6月 24日， 公开了一 种新的清洗方法， 该方法采用塑料尼龙粒子作为洗涤介质， 利用尼龙表面的极性基 团， 如 -0H， 吸附衣服上的污渍， 进而实现去污的效果。
但是采用上述洗涤介质在洗涤的过程中也存在下述缺陷： 1、 采用水作为洗涤介 质， 水消耗量非常大； 2、 采用有机溶剂作介质、 有机溶剂本身有剧毒， 而且采用蒸 馏的方法对介质进行回收的安全系数较低； 3、 采用空气、 空气需要体系有好的气密 性， 同时对气体进行液化需要很高的压力， 安全系数较低且工艺较复杂； 4、 塑料粒 子、 该方法是最新研发出的新的洗涤方法， 相对于水作为洗涤介质， 该方法容易清 除疏水性污渍， 相对于有机溶剂和液态空气作为介质， 该方法对环境污染小而且操 作方便， 但是尼龙粒子的吸附污垢能力有限， 去除大量污渍的能力也有限， 二是洗 涤衣服的过程中存在明显串色效果， 污渍没有办法彻底去除干净。 发明内容
为了克服塑料颗粒作为洗涤介质其吸附能力有限容易串色的缺点， 本发明提供 了一种洗涤用固体颗粒， 使用本发明所述的固体颗粒洗涤污染物表面时， 由于颗粒 表面有大量的开放性泡孔， 所以吸附能力强， 而且表面活性高， 容易将污染物从待 洗物表面彻底清除干净， 本发明还提供了一种使用固体颗粒洗涤的方法。
本发明解决其技术问题所采用的技术方案是： 一种洗涤用固体颗粒， 固体颗粒 为聚合物固体颗粒， 其特征是： 颗粒表面分布有开放性泡孔。
原有的聚合物固体颗粒洗涤衣物时， 由于聚合物固体颗粒表面光滑与污染物的 结合力不够， 洗涤效果不理想， 还容易串色。 而采用表面密布有大量发放性泡孔的 聚合物固体颗粒替代原有的聚合物颗粒进行洗涤是利用了颗粒表面有大量开放式的 泡孔能够将污染物进行吸附进而除去。 泡孔的直径越小， 吸附和清除污染物的效果 会越好， 如果泡孔的直径进一步减小到 lOOnm 以下时， 泡孔材料的吸附能力将会有 质的飞跃， 因为此时材料泡孔的比表面积将非常大， 表面能也非常大， 所以吸附和 清除污染物的能力将成倍增长。 所以采用表面具有开放性泡孔的聚合物固体颗粒能 够获得很好的洗涤效果， 还可以有效防止串色。
优选所述固体颗粒的表层为泡孔层， 颗粒的内部为实心结构。
优选所述固体颗粒的内部分布有开放性泡孔.
优选所述固体颗粒的内部有实心结构。
优选所述固体颗粒的泡孔直径为 10nm〜100um。
优选所述固体颗粒的泡孔密度为 103个 /cm3〜1012个 /cm3。
优选所述固体颗粒的密度为 0. 3g/cm3〜lg/cm3。
优选所述固体颗粒的形状为球形、 或立方体、 或圆柱形、 或橄榄形、 或月牙形。 优选所述固体颗粒的平均粒径在 lmm〜10mm。
优选所述固体颗粒中的聚合物包括 PP、 或 PE、 或 PS、 或 PVC、 或 EVA、 或 PA、 或 PET、 或者选择上述一种或多种材料的混合物。。
优选所述固体颗粒中含有无机粉体。
优选根据权利要求 1-4 中任何一项所述的颗粒， 其特征是： 所述固体颗粒含有 质量分数 5%〜10%的磁性材料。
优选根据权利要求 12所述的颗粒， 其特征是： 所述磁性材料为铁、 钴、 镍中的 一种。
优选根据权利要求 13所述的颗粒， 其特征是： 所述磁性材料为含有铁、 钴、 镍 中的一种、 或两种、 或三种的合金。
优选根据权利要求 14所述的颗粒， 其特征是： 所述磁性材料为铁、 或铁合金。 优选根据权利要求 15所述的颗粒， 其特征是： 所述磁性材料为颗粒状， 颗粒的 粒径为 0. Olira！〜 2mm。
一种用固体颗粒洗涤的方法， 其特征是： 包括用所述的固体颗粒洗涤待洗物的 步骤； 将待洗物与固体颗粒分离的步骤； 漂洗待洗物的步骤； 甩干待洗物的步骤。
采用上述方法洗涤待洗物能够彻底清除污染物， 方便使用。
优选所述固体颗粒洗涤待洗物的步骤中还使用了中性非离子表面活性剂。
优选所述固体颗粒洗涤待洗物的步骤中待洗物与固体颗粒的质量比为 1 : 0. 5〜 1 : 5； 进一步优选质量比为 1 : 1〜1 : 3。
优选所述将待洗物与固体颗粒分离的步骤在磁场中进行。
本发明的有益效果是， 用表面具有大量开放性泡孔的聚合物固体颗粒代替普通 的聚合物颗粒作为洗涤介质后， 去污能力和防止串色的效果显著增强， 而且表层泡 孔结构还可以节约材料的使用， 保护环境， 节约成本， 使用本发明所述的方法简单 方便。 附图说明
下面结合附图对本发明实施例所述的聚合物固体颗粒的结构进行具体说明。 图 1是本发明实施例所述的聚合物固体颗粒的外表面示意图。
图 2是第一种实施例的聚合物固体颗粒的剖视图。
图 3是第二种实施例的聚合物固体颗粒的剖视图。
图 4是第三种实施例的聚合物固体颗粒的剖视图。
图 5是第四种实施例中使用的洗衣机的示意图。
其中 1.聚合物固体颗粒， 2. 泡孔， 3.泡孔壁， 5.颗粒内部实心， 6.泡孔间通 道， 11.箱体， 12. 外筒， 13.内筒， 14.刮板， 15.电磁铁。 具体实施方式
实施例一
图 1为本实施例所述聚合物固体颗粒 1， 颗粒的表面分布有大量开放性的泡孔 2 和泡孔间通道 6， 固体颗粒 1的内部为实心结构， 即颗粒的内部为颗粒内部实心 5， 颗粒的表层为泡孔层，泡孔层中含有大量的开放性的泡孔 2，泡孔的周围是泡孔壁 3， 泡孔与泡孔之间有通道 6连接， 见图 2。
原有的聚合物固体颗粒洗涤衣物时， 由于聚合物固体颗粒表面光滑与污染物的 结合力不够， 洗涤效果不理想， 还容易串色。 而采用表面密布有大量开放性泡孔的 聚合物固体颗粒替代原有的聚合物颗粒进行洗涤是利用了颗粒表面有大量开放式的 泡孔， 能够将污染物进行吸附进而除去。 开放性泡孔就是泡孔的内部能够与外界相 连通， 泡孔的直径越小， 吸附和清除污染物的效果会越好， 如果泡孔的直径进一步 减小到 lOOnm 以下时， 泡孔材料的吸附能力将会有质的飞跃， 因为此时材料泡孔的 比表面积将非常大， 表面能也非常大， 所以吸附和清除污染物的能力将成倍增长。 所以采用表面具有开放性泡孔的聚合物固体颗粒能够获得很好的洗涤效果， 还可以 有效防止串色。 另外， 由于泡孔的存在可以节约材料的使用， 保护环境， 节约成本。 另外所述固体颗粒的表层为泡孔层， 颗粒的内部为实心结构。 颗粒表面泡孔层 所占的体积为整个固体颗粒体积的 0. 01%-20%，这样颗粒在洗涤的过程中污染物可被 吸附在颗粒的表面或表层而不会进入颗粒的中心部。 方便清洗颗粒， 使颗粒容易被 重新使用。
适合作为洗涤应用的固体颗粒的开孔率为 50%〜100%； 固体颗粒的泡孔直径为 10nm〜100um; 固体颗粒的泡孔密度为 103个 /cm3〜1012个 /cm3; 固体颗粒的密度为 0. 3g/cm3〜l g/Cm3 ; 固体颗粒的形状为球形、 或立方体、 或圆柱形、 或橄榄形、 或 月牙形； 固体颗粒的平均粒径在 lmm〜10mm。
常见的表面带有泡孔的聚合物材料， 例如在建筑保温中使用的发泡聚苯颗粒比 较柔软、 有弹性， 聚合物颗粒的表层也有这样的发泡结构， 在洗涤的过程中与织物 表面接触更近似于人手揉搓。 聚合物颗粒表层的泡孔相互连通为污染物进出和吸附 污染物提供了条件。 另外聚合物颗粒表面的泡孔壁 3在与织物接触时类似牙刷一样 可以减小污染物与织物的结合力。
制作所述聚合物固体颗粒可以选择 PP、 或 PE、 或 PS、 或 PVC、 或 EVA、 或 PA、 或 PET; 或者选择上述一种或多种材料的混合物。为了产生聚合物固体颗粒表层的泡 孔和调节颗粒的密度， 在聚合物中添加无机粉体。 为了使泡孔更加均匀细密， 密粉 体也应该更加均匀和细小。 在聚合物固体颗粒中添加无机粉体， 如滑石粉、 碳酸钙 等， 添加无机纳米粉体更好， 粉体主要起形成泡孔或成核剂的作用。 另外还可以加 入含有银离子的粉体， 则聚合物固体颗粒将具有杀菌功能。
聚合物固体颗粒的制备方法是首先将聚合物与粉体均匀混合挤出造粒， 然后将 颗粒放在有机溶剂二甲苯中浸泡 8到 48小时进行溶涨， 再将颗粒在强酸性溶液中浸 泡 0. 1到 10小时溶解颗粒中的粉体， 这样颗粒表层的粉体溶解后就留下了泡孔， 形 成了表面的泡孔层， 内部为实心结构。
本实施例采用的洗涤方法是通过以下方案实现的： 洗涤前， 聚合物固体颗粒 1 是储存在洗衣机一储料箱中， 洗涤助剂可通过自动添加装置定量添加， 少量水的添 加可通过流量计装置控制水的添加量。聚合物颗粒洗涤衣物的过程包括打开出料阀， 将储料箱中的聚合物固体颗粒放入滚筒内， 同时通过皂液自动添加装置以及水量定 量添加装置通过管道进入到滚筒内， 把衣服浸润， 洗涤时间在 10-60分钟， 洗涤温 度保持在 50-70度， 可采用蒸汽加热方式， 衣物与固体颗粒的质量比为 1 : 0. 5〜1 : 5， 优选质量比为 1 : 1〜1 : 3。 洗涤完后， 是将聚合物颗粒与衣物分离的步骤， 包括中高 速甩干衣服及颗粒， 将脏水甩出， 甩干速度在 150-1000转 /分， 甩干时间 5-10分钟 即可； 甩干后进行漂洗步骤， 按设定的用水量进水， 进行漂洗， 漂洗时间在 5-20分 钟， 漂洗完毕后进行甩干步骤， 甩干速度及时间可参考第一次甩干条件， 根据衣服 脏的程度， 可进行第二次、 第三次漂洗。 漂洗结束后甩干衣服， 进行颗粒与衣服的 分离环节， 采用离心分离方式， 中高速转动内筒， 转速可在 150-800转 /分钟， 打开 进料口， 聚合物固体颗粒 1 在高速离心的作用下， 经进料口进入到储料箱中， 实现 颗粒的回收， 以备下次的使用。 颗粒的漂洗功能， 打开出料阀口， 将粒子进入到滚 筒内， 添加少量水进行漂洗， 漂洗时间 10-40分钟， 漂洗完毕后甩干， 甩干速度在 100-800转 /分钟， 甩干后打开进料阀， 通过高速转动离心方法实现颗粒的回收。 聚 合物固体颗粒在洗涤待洗物的过程中还使用了中性非离子表面活性剂， 这样洗涤效 果更好， 更容易去除污染物。
采用本实施例所述的聚合物固体颗粒洗涤衣物， 由于聚合物固体颗粒表面密布 有大量的开放性泡孔而具有很强的吸附和清除污染物的能力， 洗涤亲水性和疏水性 污染物的效果都很理想， 还避免了串色。 另外， 聚合物表面为多孔层与普通的聚合 相比可以节约材料的使用， 保护环境， 节约成本。
实施例二
本实施例中所述的洗涤用聚合物固体的表面结构见图 1， 其剖视图见图 3。 由于 聚合物固体颗粒吸附污染物后， 污染物会进入颗粒表面的开放性泡孔的内部， 还有 可能从表层的泡孔进一步向深层泡孔进入。 这样在重复使用所述固体颗粒时需要对 颗粒进行洗涤， 如果污染物渗入颗粒较深， 则清除起来很困难， 所以要使聚合物固 体只在表面有开放性泡孔， 而内部没有开放性泡孔， 即颗粒的内部为实心结构。 这 样聚合物固体颗粒在洗涤完待洗物后污染物只附着在颗粒的表面， 很容易被清除， 颗粒也容易被重复利用。
要获得只有表面带有开放性泡孔的聚合物固体颗粒， 可以通过控制颗粒在溶胀 后与强酸性溶液的浸泡时间， 时间在 0. 1到 0. 5小时， 这样颗粒只有表面含有开放 性泡孔。
实施例三
本实施例中所述的洗涤用聚合物固体的表面结构见图 1， 其剖视图见图 4。 聚合 物颗粒的表面和内部均有大量的开放性泡孔， 聚合物固体颗粒的制作方法可以采用 物理发泡或化学发泡的方法， 在聚合物熔体中添加发泡剂， 通过控制发泡剂的添加 量和发泡温度和时间得到不同大小和形态的泡孔。 本实施例中， 聚合物固体颗粒的表面和内部均有大量的泡孔， 可以节约材料。 实施例四
本实施例是对上述三个实施例的一种改进， 为了在洗涤后方便衣物与颗粒分离， 本实施例中的固体颗粒 1含有质量分数 5%〜10%的磁性材料，。
使用聚合物固体颗粒洗涤衣物后需要将聚合物颗粒与衣物分离， 但是由于表面 活性剂和水的存在聚合物颗粒与衣物的分离效果并不理想， 尤其是在如洗衣机这样 的自动化清洗设备中。 虽然可以采用手动分离的方式， 但是洗涤效率将明显降低。 当在聚合物固体颗粒中加入能够被磁场吸引的磁性材料后， 可以在洗衣机的内筒中 增加磁场的方式使聚合物颗粒与衣物分离并被固定在磁场的表面， 还避免了颗粒与 衣服分离后重新与颗粒相结合， 可以提高颗粒与衣物的分离效率。 为了避免颗粒表 面的磁性材料因生锈而污染待洗物， 需要去除固体颗粒表面的磁性材料颗粒， 从而 固体颗粒的表面会分布有的开放性泡孔。
磁性材料或能够被磁场吸引的材料为铁、 钴、 镍中的一种， 或为含有铁、 钴、 镍中的一种、 或两种、 或三种的合金。 为了降低成本， 同时也能够保证容易使衣物 与颗粒分离磁性材料优选铁、 或铁合金。
为了便于加工生产该洗涤用固体颗粒， 所述磁性材料为颗粒状， 颗粒的粒径为 0. 01mm〜2mm。 同时为了保证颗粒的性能均匀， 优选所述磁性材料的粒径为 0. lmm〜 为了获得良好的洗涤效果， 洗涤用固体颗粒的平均粒径在 lmm〜5mm。 所述洗涤 用固体颗粒的平均粒径在 lmm〜3mm。
为了使所述固体颗粒容易与衣物分离以及分离后的颗粒便于回收， 最好在磁场 消失后颗粒的磁性也随之消失， 洗涤用固体颗粒中磁性材料的质量分数为 5%〜10%， 可以选择 5%、 6%、 7%、 8%、 9%、 10%。 聚合物材料的质量分数为 50%〜95%， 具体是 50%、 60%、 70%、 80%、 90%、 95%。
本实施例中洗涤用固体颗粒的制备方法是将 7份重量的铁颗粒与 93份重量的 PA 均匀混合、 然后挤出机挤出、 再通过造粒机获得固体颗粒。 将固体颗粒在强酸性溶 液如盐酸溶液中浸泡 30分钟， 这样颗粒表面的磁性材料颗粒溶解后就留下了泡孔， 最后晾干。 固体颗粒制备完毕， 如图 1、 图 2。
结合图 4对介绍本实施例中的洗涤方法。 为了方便分离颗粒与衣物， 洗衣机包 括洗衣机箱体 11、 设置在箱体内部的外筒 12、 设置在外筒内部的内筒 13， 内筒 13 的外表面设置有能够推动固体颗粒沿着外筒底部向上移动的刮板 14，外筒 12内部有 磁场， 所述磁场由电磁铁 15产生， 当需要使固体颗粒与衣服分离时， 电磁铁将产生 磁场， 即实施例一中所述将待洗物与固体颗粒分离的步骤在磁场中进行。
当在聚合物颗粒中加入能够被磁场吸引的磁性材料后， 外筒内部的磁场能够将 洗衣机外筒中的洗涤颗粒吸引到外筒中与电磁铁的磁极相对应的位置， 而且磁场由 电磁铁产生可以在不需要磁场的时候随时去掉磁场的作用。
与普通的聚合物固体颗粒相比分离的时间縮短了 50%〜80%， 而且可以很好的避 免串色。 所以使用洗涤用固体颗粒洗涤衣物后可以很容易使颗粒与衣服分离， 并提 高洗涤效率。

Claims

权 利 要 求 书
1. 一种洗涤用固体颗粒， 固体颗粒为聚合物固体颗粒， 其特征是： 颗粒表面分 布有开放性泡孔。
2. 根据权利要求 1所述的颗粒， 其特征是： 所述固体颗粒的表层为泡孔层， 颗 粒的内部为实心结构。
3. 根据权利要求 1所述的颗粒， 其特征是： 所述固体颗粒的内部分布有开放性 泡孔。
4. 根据权利要求 1所述的颗粒， 其特征是： 所述固体颗粒的内部有实心结构。
5. 根据权利要求 1-4中任何一项所述的颗粒， 其特征是： 所述固体颗粒的泡孔 直径为 10nm〜100um。
6. 根据权利要求 1-4中任何一项所述的颗粒， 其特征是： 所述固体颗粒的泡孔 密度为 103个 /cm3〜1012个 /cm3。
7. 根据权利要求 1-4中任何一项所述的颗粒， 其特征是： 所述固体颗粒的密度 为 0. 3g/cm3〜lg/cm3。
8. 根据权利要求 1-4中任何一项所述的颗粒， 其特征是： 所述固体颗粒的形状 为球形、 或立方体、 或圆柱形、 或橄榄形、 或月牙形。
9. 根据权利要求 1-4中任何一项所述的颗粒， 其特征是： 所述固体颗粒的平均 粒径在 lira！〜 10mm。
10. 根据权利要求 1-4 中任何一项所述的颗粒， 其特征是： 所述固体颗粒中的 聚合物包括 PP、 或 PE、 或 PS、 或 PVC、 或 EVA、 或 PA、 或 PET、 或者选择上述一种 或多种材料的混合物。
11. 根据权利要求 1-4 中任何一项所述的颗粒， 其特征是： 所述固体颗粒中含 有无机粉体。
12. 根据权利要求 1-4 中任何一项所述的颗粒， 其特征是： 所述固体颗粒含有 质量分数 5%〜10%的磁性材料。
13. 根据权利要求 12所述的颗粒， 其特征是： 所述磁性材料为铁、 钴、 镍中的 一种。
14. 根据权利要求 13所述的颗粒， 其特征是： 所述磁性材料为含有铁、 钴、 镍 中的一种、 或两种、 或三种的合金。
15. 根据权利要求 14所述的颗粒， 其特征是： 所述磁性材料为铁、 或铁合金。
16. 根据权利要求 15所述的颗粒， 其特征是： 所述磁性材料为颗粒状， 颗粒的 粒径为 0. Olira！〜 2mm。
17.—种用固体颗粒洗涤的方法， 其特征是： 包括：
用权力要求 1-16中任何一项所述的固体颗粒洗涤待洗物的步骤；
将待洗物与固体颗粒分离的步骤；
漂洗待洗物的步骤；
甩干待洗物的步骤。
18. 根据权利要求 17所述的方法， 其特征是： 所述固体颗粒洗涤待洗物的步骤 中还使用了中性非离子表面活性剂。
19. 根据权利要求 17所述的方法， 其特征是： 所述固体颗粒洗涤待洗物的步骤 中待洗物与固体颗粒的质量比为 1:0.5〜1:5。
20. 根据权利要求 19所述的方法， 其特征是： 所述固体颗粒洗涤待洗物的步骤 中待洗物与固体颗粒的质量比为 1:1〜1:3。
21. 根据权利要求 17所述的方法， 其特征是： 所述将待洗物与固体颗粒分离的 步骤在磁场中进行。
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US20140096328A1 (en) 2014-04-10
US9315766B2 (en) 2016-04-19
CN102817208A (zh) 2012-12-12
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