Washing apparatus, method and system for dispensing control of a washing agent for a washing apparatus

Abstract

The present application discloses a washing equipment, a detergent dispensing control method and system, which collects a predetermined amount of washing water as a sample from a sink; adds a predetermined amount of probe solution to the sample, the probe solution comprising a fluorescent probe composition comprising a probe and an auxiliary agent, the probe being an aggregation-induced emission (AIE) molecule; detects the detergent concentration of the sample added with the probe solution and outputs a detection signal; determines whether the detected detergent concentration reaches a critical micelle concentration (cmc), and based on the determination result, controls the subsequent dispensing of the detergent. The present application determines that the cmc in the washing water is the best point for washing and decontamination efficiency or the highest point for cost performance. When a hydrophobic AIE molecule is used, a non-volatile auxiliary agent is used. A low-sensitivity detection device with a specific detection wavelength is used, which eliminates the interference of fluorescent whitening agents and realizes simple, fast and efficient detection and determination of the cmc of the washing water in the washing equipment application scenario.

Description

Technical Field

[0001] This invention relates to the field of surfactant concentration detection technology in aquatic environments, and more particularly to a washing device for detecting the critical micelle concentration of detergents containing surfactants in washing water, and a method and system for controlling the addition of detergents to the washing device. Background Technology

[0002] Currently, many laundry appliances on the market have an automatic detergent dispensing function, eliminating the hassle of manual detergent addition for users. Some of these appliances can also detect the water quality parameters of the washing water (the detergent solution) during the washing process and calculate the detergent dosage based on the test results.

[0003] In the existing technology, the main technologies for detecting water quality parameters of washing water include conductivity or resistivity detection technology, turbidity detection and suspended solids detection technology, combined conductivity and turbidity value detection technology, fluorescent agent concentration detection technology, and surfactant or detergent concentration detection technology.

[0004] In the prior art related to surfactant or detergent concentration detection technology, patent document CN106758005 discloses a method, system, and washing machine for automatically detecting detergent concentration in a washing machine. The method includes: after the washing machine automatically fills with water, adding a predetermined amount of detergent according to the water volume; after the detergent and water are mixed evenly, activating a spectrometer installed inside the washing machine to collect spectral data of the washing water in the washing tub and generating a corresponding spectral image; analyzing the spectral image to obtain the concentration of surfactant in the washing water; pre-setting a first concentration value, and calculating the amount of detergent to be added based on the concentration, the predetermined amount of detergent added, and the predetermined first concentration value, and adding the corresponding amount of detergent to the washing tub. By installing a spectrometer on the washing machine, the concentration of surfactant in the washing water can be detected, thereby determining whether the amount of detergent used is appropriate based on the surfactant concentration. Specifically, analyzing the spectral image to obtain the surfactant concentration in the washing water includes: after acquiring the spectral image, performing pattern recognition and signal-to-noise separation processing on the spectral image to obtain the spectral data corresponding to the spectral image; comparing the spectral data with a standard spectrum to obtain the concentration of surfactant in the washing water. Wherein, the concentration is a volume percentage concentration, and the concentration = solute volume (ml) / (solute volume (ml) + solvent volume (ml)) 100%, meaning the concentration of the surfactant in the washing water = surfactant volume / (surfactant volume + water volume corresponding to the current washing mode).

[0005] Furthermore, CN106758005 further discloses a method for determining the concentration of surfactants in wash water by detecting the absorption spectra of hydrocarbon chains in a spectral image. After acquiring the spectral image, the washing machine compresses the spectral data contained in the spectral image using a spectral data compression module and uploads it to the server via a network interface using a wireless / wired network connection. The server, after acquiring the spectral image, decompresses it and performs pattern recognition and signal-to-noise separation processing to obtain the corresponding spectral data. The processed spectral data is then transmitted to the spectral analysis module. The server pre-establishes a database to store standard spectra. The spectral analysis module compares the spectral data with the standard spectra to determine the molecules contained in the wash water and the absorbance of each molecule, thus obtaining the absorbance of hydrocarbon chains in the wash water. Based on the Lambert-Beer absorption law, the concentration of hydrocarbon chains in the wash water is obtained using the linear relationship between the absorbance of molecules and their concentration, thereby determining the concentration of surfactants in the wash water. After obtaining the concentration of surfactants in the wash water, the server transmits it back to the washing machine via the network interface.

[0006] Therefore, the system and washing machine disclosed in CN106758005 have the following shortcomings: (1) The detected concentration is the volume percentage concentration of surfactant in the washing water, which is not the point of optimal cleaning efficiency or the point of highest cost performance, and cannot achieve the ideal washing effect. (2) The detection sensitivity of the fluorescence spectroscopy method is low, requiring the configuration of a high-sensitivity spectrometer, as well as a remote server, resulting in high system cost. (3) The concentration of surfactant in the washing water needs to be detected after each rinse but before draining, requiring data transmission via wireless / wired network connection and data processing by the server, making the operation process relatively complicated.

[0007] Patent document CN103411961 discloses a sensitive fluorescent luminescence probe method for determining the critical micelle concentration (CMC) of surfactants. This method utilizes a pentasubstituted tetrahydropyrimidine compound with aggregation-induced emission (AIE) properties as a fluorescent probe. This type of compound exhibits no fluorescence in micelles but emits strong fluorescence in solution, making it an ideal CMC fluorescent luminescence probe (Type II fluorescent probe). Therefore, the change in the compound's fluorescence signal in solution indicates the micelle disassembly process, thereby determining the CMC. Specifically, the process of micelle disassembly is indicated by the abrupt change in fluorescence intensity from no fluorescence (the probe is completely contained within the micelles) to the strongest fluorescence (the micelles are completely converted into monomers, and the probe is completely released into the solution). This process is the fluorescence luminescence process, which is highly sensitive. The point of strongest fluorescence abrupt change is the CMC. The method further discloses the preparation of a stock solution by dissolving the aggregation-induced emission organic compound in a solvent, preferably one or more of methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, and water.

[0008] Because the method for determining the critical micelle concentration of surfactant disclosed in CN103411961 uses a pentasubstituted tetrahydropyrimidine compound as a type II fluorescent probe, it requires first preparing a high-concentration aggregation-induced emission (AIE) organic compound (fluorescent probe) stock solution, then using a diluent containing a certain amount of surfactant to obtain a non-fluorescent solution (the fluorescent probe is completely contained within the micelles and cannot emit fluorescence), and then gradually adding a diluent (such as water, salt solution, or buffer solution) to obtain a detection solution (so that the fluorescent probe is released from the micelles into the dilute solution, thus emitting fluorescence), and then determining the critical micelle concentration of the surfactant in the detection solution by fluorescence detection. Therefore, the method disclosed in CN103411961 is not applicable to washing equipment that requires gradually adding detergent to achieve a target concentration. Furthermore, the solvent type in the aggregation-induced emission (AIE) organic compound (fluorescent probe) stock solution disclosed in CN103411961 has almost no effect on the AIE performance of the pentasubstituted tetrahydropyrimidine compound.

[0009] Non-patent literature (“Detection of the critical micelle concentration of cationic and anionic surfactants based on aggregation-induced emission property of hexaphenylsilole derivatives” TANG Li et al., Sci China Ser B-Chem, Jun. 2009, vol. 52, no. 6, 755-759) discloses a method of first dissolving hydrophobic AIE molecules in a volatile organic solvent, then adding them to a surfactant solution, and mixing them using ultrasound. The AIE properties are then observed after the readily soluble organic solvent has completely evaporated. However, because this method includes an ultrasonic mixing step and uses a volatile organic solvent, it is not suitable for applications involving washing equipment.

[0010] Therefore, there is a need for methods and equipment suitable for washing equipment applications, with relatively simple processing procedures, low equipment (system) costs, high accuracy in detecting detergent concentration in washing water, and good accuracy in controlling detergent dosing. Summary of the Invention

[0011] In view of the above, the purpose of this invention is to provide a washing device, a detergent dosing control method and system for the washing device, which realizes a simple, rapid and efficient detection and determination of the critical micelle concentration of detergent in the washing water with a relatively simple processing procedure and low equipment (system) cost in the use scenario of the washing device, thereby improving the accuracy of detergent dosing control.

[0012] According to a first aspect of the present invention, a washing apparatus is provided, comprising a storage device for storing detergent; and a dispensing device for dispensing a first predetermined amount of the detergent into a water tank of the washing apparatus according to the weight of the laundry placed in the washing apparatus or the water intake of the washing apparatus or a predetermined water intake, so as to mix and stir with the water in the water tank after the washing apparatus has been filled with water to obtain washing water, wherein the detergent contains a surfactant, characterized in that the washing apparatus further comprises:

[0013] A storage device for storing a probe solution, wherein the probe solution comprises an AIE fluorescent probe composition comprising a probe compound and an auxiliary agent, the probe compound being a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent being a non-volatile organic solvent represented by the following general formula (1).

[0014] R n-X (1)

[0015] Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups.

[0016] The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive.

[0017] The boiling point of the additive is greater than 70°C;

[0018] A sampling device for collecting a predetermined amount of the washing water from the water tank as a sample;

[0019] The addition device takes a predetermined amount of probe solution from the storage device and adds it to the sample in the sampling device;

[0020] The detection device is used to detect the detergent concentration of the sample in which the probe solution of the sampling device has been added in a predetermined amount, and to output a detection signal with corresponding fluorescence intensity.

[0021] A judging device is used to receive the detection signal of the fluorescence intensity and, based on the change in the difference between the detection signals of the fluorescence intensity, determine whether the concentration of the detergent in the sample has reached the critical micelle concentration; and

[0022] A control device is used to control the subsequent dispensing of detergent by the dispensing device according to the judgment result of the judgment device. If the judgment result of the judgment device is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of detergent into the water tank of the washing equipment. If the judgment result of the judgment device is that the critical micelle concentration has been reached, the control device controls the dispensing device to stop dispensing detergent.

[0023] According to a second aspect of the present invention, a method for controlling the dispensing of detergent for the above-described washing apparatus is provided, characterized in that the dispensing control method comprises:

[0024] Solution preparation step: Using the dispensing device of the washing equipment, a first predetermined amount of detergent is added to the water tank of the washing equipment according to the weight of the laundry or the amount of water or a predetermined amount of water to be added, so as to mix and stir with the water in the water tank after the washing equipment is filled with water to obtain washing water;

[0025] Sampling steps: Collect a predetermined amount of the washing water from the tank as a sample using the sampling device of the washing equipment;

[0026] Addition step: A predetermined amount of probe solution is added to the sample through the storage device and addition device of the washing equipment, wherein the probe solution contains an AIE fluorescent probe composition, the AIE fluorescent probe composition contains a probe and an auxiliary agent, the probe is a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent is a non-volatile organic solvent represented by the following general formula (1).

[0027] R n -X (1)

[0028] Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups.

[0029] The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive.

[0030] The boiling point of the additive is greater than 70°C;

[0031] Detection steps: The detection device of the washing equipment detects the detergent concentration of the sample with the added predetermined amount of the probe solution, and outputs a detection signal with corresponding fluorescence intensity;

[0032] Judgment and control steps: The judgment device of the washing equipment determines whether the detergent concentration of the sample has reached the critical micelle concentration based on the difference between the detection signals of fluorescence intensity. The control device of the washing equipment controls the subsequent addition of detergent by the dispensing device based on the judgment result of the judgment step.

[0033] According to a third aspect of the present invention, a detergent dispensing control system for a washing apparatus is provided, wherein the washing apparatus includes a storage device for storing the detergent; and a dispensing device that dispenses a first predetermined amount of the detergent into a water tank of the washing apparatus according to the weight of the laundry placed in the washing apparatus or the water intake of the washing apparatus or a predetermined water intake, so as to mix and stir with the water in the water tank after the washing apparatus has been filled with water to obtain washing water, wherein the detergent contains a surfactant, characterized in that the dispensing control system includes:

[0034] A storage device for storing a probe solution, wherein the probe solution contains an AIE fluorescent probe composition comprising a probe and an auxiliary agent, the probe being a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent being a non-volatile organic solvent represented by the following general formula (1).

[0035] R n -X (1)

[0036] Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups.

[0037] The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive.

[0038] The boiling point of the additive is greater than 70°C;

[0039] A sampling device for collecting a predetermined amount of the washing water from the water tank as a sample;

[0040] An addition device is used to take a predetermined amount of probe solution from the storage device and add it to the sample in the sampling device;

[0041] The detection device is used to detect the detergent concentration of the sample in which the probe solution of the sampling device has been added in a predetermined amount, and to output a detection signal with corresponding fluorescence intensity.

[0042] A judging device is used to receive the detection signal of the fluorescence intensity and, based on the change in the difference between the detection signals of the fluorescence intensity, determine whether the detergent concentration of the sample has reached the critical micelle concentration; and

[0043] A control device is used to control the subsequent dispensing of detergent by the dispensing device according to the judgment result of the judgment device. If the judgment result of the judgment device is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of detergent into the water tank of the washing equipment. If the judgment result of the judgment device is that the critical micelle concentration has been reached, the control device controls the dispensing device to stop dispensing detergent.

[0044] In a preferred embodiment, the probe compound is a hydrophobic AIE molecule comprising a compound represented by any one of the following chemical formulas 1 to 12 as its basic framework:

[0045]

[0046]

[0047]

[0048]

[0049] In a preferred embodiment, the hydrophobic AIE molecule is any one of unsubstituted tetraphenylethylene (TPE) represented by Formula 1, unsubstituted stilbeneylanthracene (DSA) represented by Formula 2, unsubstituted hexaphenylsilanecyclopentadiene (HPS) represented by Formula 7, and unsubstituted benzo[a]perylene (BP) represented by Formula 10.

[0050] In a preferred embodiment, in the general formula (1), R is an unsubstituted straight-chain or branched alkyl group having 3 to 6 carbon atoms, and X is selected from hydroxyl or amino groups.

[0051] In a preferred embodiment, the adjuvant is selected from one or more of n-propanol, isopropanol, tert-butanol, n-butanol, n-butylamine, and pentylamine.

[0052] In a preferred embodiment, the adjuvant has an amphiphilic structure, having a hydrophilic region composed of the polar group and a hydrophobic region composed of the alkyl group in the molecule, and the probe compound has a higher solubility in the adjuvant than in water.

[0053] In a preferred embodiment, the auxiliary agent is an alkyl alcohol having 3 to 6 carbon atoms. The probe solution is prepared by dissolving the probe compound in acetone beforehand, allowing it to evaporate and dry, and finally adding the alkyl alcohol to obtain the AIE fluorescent probe composition.

[0054] In a preferred embodiment, the concentration of the probe compound in the AIE fluorescent probe composition is 500~2000µmol / L, and the concentration of the probe compound in the detergent solution is 1~1000µmol / L.

[0055] In a preferred embodiment, the content of the auxiliary agent relative to the probe composition is 70% to 99% by mass, and the content of the probe compound relative to the probe composition is 1% to 30% by mass.

[0056] In a preferred embodiment, the detection device is a fluorescence sensor with an excitation wavelength range of 275-375nm and an emission wavelength range of 350-750nm. The fluorescence intensity is output by detecting the change in the peak intensity of the fluorescence emission peak of the washing water in the wavelength range of 350-370nm or 720-740nm.

[0057] In a preferred embodiment, the determining device determines whether the detergent concentration has reached the critical micelle concentration by performing the following processing steps:

[0058] Judgment Step 1: When the first predetermined amount of detergent is added to the water tank of the washing equipment by the dispensing device, the sampling device collects the predetermined amount of washing water from the water tank as a sample, and the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives the first detection signal of fluorescence intensity output by the detection device.

[0059] Judgment Step Two: The dispensing device adds a second predetermined amount of detergent to the water tank of the washing equipment. The adding device discharges the previously collected washing water as a sample and collects the predetermined amount of washing water from the water tank again as a sample. After the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives a second detection signal of fluorescence intensity output by the detection device. The first predetermined amount and the second predetermined amount may be the same or different.

[0060] Judgment Step 3: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the second detection signal and the first detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the second addition operation is equal to or less than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration.

[0061] Judgment Step 4: If the difference is greater than 0, it means that the fluorescence intensity detected for the second addition operation is greater than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has not reached the critical micelle concentration, and repeats the above judgment step 2. The judgment device receives the third detection signal of fluorescence intensity output by the detection device.

[0062] Step 5: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it indicates that the fluorescence intensity detected for the third addition operation is equal to or less than the fluorescence intensity detected for the second addition operation. Therefore, the judgment device determines that the detergent concentration has reached the critical micelle concentration.

[0063] Judgment and control step six: If the difference is greater than 0, repeat judgment steps four and five.

[0064] In a preferred embodiment, the determination and control step includes the following processing steps:

[0065] Judgment and Control Step 1: The judgment device of the washing equipment determines whether the detergent concentration of the sample has reached the critical micelle concentration based on the difference between the detected fluorescence intensity signals. If the judgment result is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue the solution preparation step to add a second predetermined amount of detergent to the water tank of the washing equipment, and repeats the sampling step, the addition step, the detection step, and the judgment step to continue to detect and judge whether the detergent concentration of the probe solution sample has reached the critical micelle concentration. In the solution preparation step, after each addition of detergent by the dispensing device, in the sampling step, the sampling device empties the previously collected sample and re-collects a predetermined amount of washing water as a sample.

[0066] Judgment and control step two: If the judgment result is that the critical micelle concentration has been reached, the dispensing device is controlled by the control device to stop dispensing detergent.

[0067] In a preferred embodiment, the determination and control step includes the following processing steps:

[0068] Judgment and control step one: When the first predetermined amount of detergent is added to the water tank of the washing equipment by the dispensing device, the sampling device collects the predetermined amount of washing water from the water tank as a sample, and the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives the first detection signal of fluorescence intensity output by the detection device.

[0069] Judgment and control step two: The dispensing device adds a second predetermined amount of detergent to the water tank of the washing equipment. The adding device discharges the previously collected washing water as a sample and collects the predetermined amount of washing water from the water tank again as a sample. After the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives a second detection signal of fluorescence intensity output by the detection device. The first predetermined amount and the second predetermined amount may be the same or different.

[0070] Judgment and control step three: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the second detection signal and the first detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the second addition operation is equal to or less than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration, and the control device controls the dispensing device to stop dispensing detergent.

[0071] Judgment and control step four: If the difference is greater than 0, it means that the fluorescence intensity detected for the second addition operation is greater than the fluorescence intensity detected for the first addition operation. Then the judgment device judges that the detergent concentration has not reached the critical micelle concentration, and repeats the above judgment and control step two. The judgment device receives the third detection signal of fluorescence intensity output by the detection device.

[0072] Judgment and Control Step 5: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it indicates that the fluorescence intensity detected for the third addition operation is equal to or less than the fluorescence intensity detected for the second addition operation. Therefore, the judgment device determines that the detergent concentration has reached the critical micelle concentration, and the control device controls the dispensing device to stop dispensing detergent.

[0073] Judgment and control step six: If the difference is greater than 0, repeat judgment and control steps four and five.

[0074] In a preferred embodiment, if the difference is 0 or becomes negative, and the detected fluorescence intensity undergoes a sudden change from zero to the strongest, with a sudden change point corresponding to the strongest fluorescence intensity, then the judgment device (the judgment step) determines that the detergent concentration has reached the critical micelle concentration.

[0075] Compared with the prior art, the washing equipment, detergent dosing control method and system disclosed in this invention make the following inventive contributions and achieve the following beneficial technical effects:

[0076] (1) In the existing washing equipment, the volume percentage solubility of surfactant in the washing water is used as a reference index point for complete or basic cleaning. In this invention, through the inventor's preliminary research, the invention has been developed and verified in terms of principle feasibility and feasibility in the application scenario. It has been determined that the critical micelle concentration of detergent in the washing water is the point with the best washing and decontamination efficiency or the highest cost performance. Based on the detection of the critical micelle concentration of detergent in the washing water, the accuracy of detergent dosing control has been improved and the ideal washing effect has been achieved.

[0077] (2) In existing methods for determining the critical micelle concentration of surfactants (e.g., CN103411961), volatile organic solvents are used as additives, making them unsuitable for use in washing equipment applications. In this invention, through in-depth research, the inventors discovered that some hydrophobic AIE molecules can dissolve in organic solvents with specific structures to form stable solutions. These solutions can carry the hydrophobic AIE molecules into the internal cavities of the surfactant micelles without waiting for the organic solvent to evaporate, exhibiting significant AIE characteristics within a suitable concentration range. Therefore, when using hydrophobic AIE probe molecules in the AIE fluorescent probe composition, a non-volatile organic solvent is used as an additive, enabling direct determination of the critical micelle concentration of detergent solutions containing surfactants. This allows for the detection of the critical micelle concentration of detergents in washing water within the application scenarios of washing equipment.

[0078] (3) In existing washing equipment (e.g., CN106758005), a high-sensitivity spectrometer and a remote server are required, resulting in high system costs and complex processing. After determining the feasibility of detecting the critical micelle concentration of detergent in washing water under the application scenario of the washing equipment, this invention utilizes the unique properties of AIE fluorescent probes in solutions containing surfactants due to their aggregation-induced emission characteristics. By using a detection device with relatively low sensitivity (e.g., a fluorescence sensor), the detection wavelength is specifically set, and the interference of fluorescent whitening agents in the washing water is eliminated. This enables a simple, rapid, and efficient detection and determination of the critical micelle concentration of detergent in washing water. The processing is relatively simple, and the equipment (system) cost is low. Attached Figure Description

[0079] Figure 1 This is a schematic diagram illustrating the correlation between the detergency of washing water and the critical micelle concentration (cmc) of the detergent in the washing water.

[0080] Figure 2A This is a schematic diagram illustrating the determination of the critical micelle concentration of a directly prepared detergent solution using the surface tension method.

[0081] Figure 2B This is a schematic diagram illustrating the use of the surface tension method to detect the critical micelle concentration of a washing solution in a washing machine (drum washing machine);

[0082] Figure 2C This is a schematic diagram illustrating the use of aggregation-induced emission (AIE) probe method to detect the critical micelle concentration of a washing solution in a washing machine (drum washing machine);

[0083] Figures 3A-3DThis is a schematic diagram illustrating the detection of the critical micelle concentration of a directly prepared detergent solution within a specific wavelength range using the AIE fluorescent probe testing method.

[0084] Figure 4 This is a structural block diagram of a washing device according to a first embodiment of the present invention;

[0085] Figure 5 This is a structural block diagram of a detergent dispensing control system for a washing device according to a third embodiment of the present invention;

[0086] Figure 6 This is a flowchart of a detergent dispensing control method for a washing equipment according to a fourth embodiment of the present invention;

[0087] Figure 7 This is a flowchart of a detergent dosing control method for a washing device according to a fifth embodiment of the present invention. Detailed Implementation

[0088] To make the technical problems solved by this invention, the technical solutions adopted, and the technical effects achieved clearer, the technical solutions of this invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only for explaining this invention and not for limiting it. Furthermore, it should be noted that, for ease of description, only the parts related to this invention are shown in the accompanying drawings, not all of them.

[0089] In this specification, the numerical range represented by “~” refers to the range in which the values ​​before and after “~” are respectively the minimum and maximum values.

[0090] In this specification, the critical micelle concentration of a detergent solution containing surfactants, unless otherwise specified, refers to the total amount of the various surfactant components present in the detergent solution containing surfactants.

[0091] Figure 1 The graph shows the correlation between the detergency of detergent and the critical micelle concentration (cmc) of detergent in the wash water. The vertical axis represents detergency (UV0, excluding the effect of fluorescent whitening agents on detergency), and the horizontal axis represents the detergent concentration in the wash water (unit: g / L). When washing a 1.5 kg load of pure cotton in a washing machine (e.g., a drum washing machine), as the detergent concentration in the wash water increases, both detergency and surfactant adsorption gradually increase and then plateau. After the detergent concentration in the wash water reaches the cmc, the rate of increase in detergency decreases. Figure 1The first inflection point A of the slope of the medium curve CD indicates the highest detergency. After the surfactant becomes saturated on the fabric, the detergency tends to level off. Figure 1 The second inflection point B of the slope of the middle curve CD). The detergency of detergent is closely related to whether the detergent concentration in the wash water reaches CMC: after reaching CMC, the detergency of oil stains (SUM oil stains, Figure 1 The detergency of medium curve D) and sebum stains (SUM sebum, Figure 1 The medium curve (E) basically reaches a plateau; the detergency of protein stains (SUM protein, Figure 1 The medium curve (C) shows that as the detergent concentration in the washing water continues to increase, the rate of increase decreases until the adsorption of surfactant on the fabric reaches saturation and then plateaus. Therefore, detecting whether the detergent concentration in the washing water reaches CMC can be an effective method to determine whether more detergent needs to be added.

[0092] Figure 2A and 2B A graph showing the critical micelle concentration (cmc) of a detergent solution determined using the surface tension method is presented. Among them, Figure 2A This is a graph showing the change in surface tension of a detergent solution (Blue Moon Supreme Laundry Detergent - Deep Clean, or Supreme Clean for short) as a function of detergent concentration. Figure 2A The vertical axis represents the surface tension of the detergent solution (unit: mN / m), and the horizontal axis represents the detergent concentration (unit: mg / L). The inventors measured the CMC concentration range (100 mg / L~200 mg / L) of the directly prepared detergent solution using the aggregation-induced emission (AIE) probe method, corresponding to the maximum observed fluorescence intensity (not shown). This CMC concentration range is related to... Figure 2A The inventors have provided CMC measurement results using the surface tension method (using a K100C surface tension meter). ≈ The results (100 mg / L) are basically the same, indicating that the AIE fluorescent probe test method is effective and feasible for detecting CMC in directly prepared detergent solutions.

[0093] Figure 2B This is a graph showing the interfacial tension of a detergent solution (Blue Moon Supreme Laundry Detergent - Deep Clean, or Supreme Clean for short) as a function of detergent concentration in a washing machine (drum washing machine) application scenario. Figure 2B The vertical axis represents the interfacial tension of the washing solution (unit: mN / m), and the horizontal axis represents the concentration of the detergent (unit: g / L). According to... Figure 2B The curves shown indicate that, in the context of a washing machine (drum washing machine), the apparent CMC of the washing solution was detected using the surface tension method. ≈ 0.7 g / L.

[0094] Figure 2C This diagram illustrates the use of aggregation-induced emission (AIE) probes to detect the critical micelle concentration of a Supreme Clean detergent solution in a washing equipment (e.g., a drum washing machine) environment. Specifically, it shows a curve of the detection signal (voltage value) output by the fluorescence sensor detecting the washing solution as a function of detergent concentration. Figure 2C The vertical axis represents voltage (unit: V), and the horizontal axis represents detergent concentration (unit: g / L). A fluorescence sensor is used to detect the fluorescence intensity of the wash water solution; the detection signal (voltage value) output by the fluorescence sensor is directly proportional to the fluorescence intensity of the wash water. For example... Figure 2C As shown, the detection results of the AIE fluorescent probe detection method indicate that the concentration of CMC is 0.62 g / L, which is consistent with the concentration corresponding to the maximum fluorescence intensity observed by the naked eye, and is also consistent with the concentration obtained using... Figure 2B The results shown are obtained using the surface tension method. ≈ The 0.7 g / L solution showed good compatibility. The slight difference between the two solutions was due to the fact that the washing solution used for actual machine washing contained a large amount of clothing, which adsorbed the detergent to some extent, thus increasing the apparent CMC concentration. Figure 2B and Figure 2C The test results show that the AIE fluorescent probe test method is also effective and feasible for detecting the CMC of the washing solution under actual machine washing conditions in the context of washing equipment (drum washing machine).

[0095] Figures 3A-3D A graph showing the critical micelle concentration (cmc) of detergent in wash water within a specific wavelength range is presented using the AIE fluorescent probe assay. Figures 3A-3B The vertical axis represents fluorescence intensity (unit: AU), and the horizontal axis represents wavelength (unit: nm). Figures 3A-3B The values ​​in g / L at the top right of the figure represent different concentrations of detergent used in the detection. The curves in the figure are fluorescence intensity curves detected under 365 nm ultraviolet light excitation for different concentrations of detergent in the wash water. Figure 3C-3D The vertical axis represents fluorescence intensity (unit: AU), and the horizontal axis represents concentration (unit: g / L). Figure 3C-3D Curve A in the upper middle section represents the fluorescence intensity at an emission wavelength of 361 nm, and curve B in the lower section represents the visible fluorescence intensity at an emission wavelength of 729 nm. Figure 3C The detergent used is Blue Moon Supreme Clean detergent. Figure 3DThe detergent used was Blue Moon Supreme Brightening Detergent. The inventors used an AIE (specifically HPS) fluorescent probe testing method to detect the CMC of a washing solution directly prepared with the detergent (e.g., Blue Moon Supreme Clean and Supreme Brightening Detergent). Figures 3A-3B As shown, under 365nm ultraviolet light excitation, the fluorescence intensity curves of HPS corresponding to various concentration values ​​mainly have two fluorescence intensity emission peaks: a sharp and intense fluorescence peak in the 350-370 nm range and a relatively weak and broad fluorescence peak in the 720-740 nm range. These peaks do not coincide with the emission peaks of the fluorescent whitening agent CBS contained in detergents (such as Blue Moon's Supreme Brightening Detergent) (i.e., they avoid the 400-550 nm wavelength range where the emission peak of the fluorescent whitening agent CBS appears). By observing the changes in the peak intensity of the fluorescence emission peaks in the 350-370 nm or 720-740 nm wavelength range, the CMC of the detergent can be determined, while eliminating the interference of the fluorescent whitening agent in the detergent aqueous solution. Moreover, as... Figure 3C-3D As shown, the fluorescence intensity at an emission wavelength of 361 nm for each concentration value basically matches the visible fluorescence intensity at an emission wavelength of 729 nm. Furthermore, the detergent concentration in the washing water at 0.1 g / L exhibits a relatively high overall fluorescence intensity, corresponding to the maximum visible fluorescence intensity. Based on this and through multiple experimental verifications, the inventors discovered that by using a fluorescence detection device (e.g., a fluorescence sensor) with an excitation wavelength range of 275-375 nm and an emission wavelength range of 350-750 nm, the CMC of the detergent can be effectively detected by detecting changes in the peak intensity of the fluorescence emission peak in the 350-370 nm or 720-740 nm wavelength range of the washing water, while eliminating interference from fluorescent whitening agents in the detergent aqueous solution.

[0096] Figure 4 A washing device 100 according to a first embodiment of the present invention is shown. In this embodiment, the washing device 100 is a drum washing machine. Of course, in different application scenarios than this embodiment, the washing device 100 can also be any of various types of washing machines such as industrial washer-extractors and wet washing machines.

[0097] The washing equipment 100 includes a water tank 101, a storage device 102, a dispensing device 103, a liquid storage device 104, a sampling device 105, an adding device 106, a detection device 107, a judgment device 108, and a control device 109.

[0098] Storage device 102 is used to store detergent (such as Blue Moon Supreme Clean or Supreme Brightening Detergent), which contains surfactants.

[0099] In this embodiment, the surfactant is an anionic surfactant.

[0100] Of course, in application scenarios different from this embodiment, the detergent may contain at least one of anionic surfactants, nonionic surfactants, cationic surfactants, and amphiphilic surfactants, depending on specific needs. More preferably, the surfactant contains at least anionic surfactants and / or nonionic surfactants.

[0101] The anionic surfactant can be any one of carboxylate, sulfonate, sulfate, or phosphate surfactants. The nonionic surfactant can be any one of alkyl glucoside, alkyl alcohol ether glucoside, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, or fatty acid alkanolamide surfactants.

[0102] In addition, the surfactant may also contain a fluorescent whitening agent.

[0103] The dispensing device 103 is used to dispense detergent stored in the storage device 102 into the water tank 101 of the washing equipment 100 according to the weight of the laundry or the water intake of the washing equipment 100 or a predetermined water intake, so as to mix and stir with the water in the water tank 101 after the washing equipment 100 is filled with water to obtain washing water.

[0104] In this embodiment, a first predetermined amount of detergent is added to the water tank 101 of the washing equipment 100 according to the weight of the laundry. For example, if 1.5 kg of laundry is put in, 8 g (the first predetermined amount) of detergent is added to the water tank 101 of the washing equipment 100.

[0105] Of course, in application scenarios different from this embodiment, depending on specific needs, the dispensing device 103 can dispense different first predetermined amounts of detergent into the water tank 101 of the washing equipment 100 according to the water inlet volume or predetermined water inlet volume of the washing equipment 100.

[0106] The storage device 104 is used to store a probe solution containing an AIE fluorescent probe composition, which includes a probe compound and an auxiliary agent, wherein the probe compound is an aggregation-induced emission AIE molecule.

[0107] In this embodiment, the additive is a non-volatile organic solvent represented by the following formula (1).

[0108] R n -X (1)

[0109] Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, and n is an integer of 1 or 2. When n is 2, the two Rs can be the same or different.

[0110] X is a polar group selected from hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups.

[0111] In this embodiment, n is 1, meaning that the hydrophilic region composed of polar groups is located at the end of the alkyl molecular chain. The polar group X is selected from hydroxyl groups.

[0112] As can be seen from the structure of the above general formula (1), the auxiliaries of the present invention not only have hydrocarbon molecular chains of a certain length in the molecule, but also have polar groups at the ends of the molecular chains, thereby forming an amphiphilic structure that has both hydrophilic and hydrophobic regions in the molecule.

[0113] In this embodiment, the AIE molecule is an unsubstituted hydrophobic AIE molecule, such as hexaphenylthiophene (i.e., hexaphenylsilanecyclopentadiene, HPS), which is soluble or slightly soluble in the additive, higher than its solubility in water. Thus, when the probe composition is added to a detergent solution containing a surfactant, the probe compound tends to dissolve and be stably dispersed in the organic solvent that is the additive.

[0114] Of course, in application scenarios different from this embodiment, the AIE molecule can be a hydrophobic AIE molecule with a basic framework represented by any one of the following chemical formulas 1 to 12:

[0115]

[0116]

[0117]

[0118]

[0119] The hydrophobic AIE molecules used in this invention include unsubstituted AIE molecules such as tetraphenylethylene (TPE) represented by Formula 1, hexaphenylsilole (HPS) represented by Formula 7, distyrenylanthracene (DSA) represented by Formula 2, and 1,12-benzeneperylene (BP) represented by Formula 10. These can also be derivatives, polymers, or metal complexes containing the basic framework structure of these AIE molecules, but all exhibit hydrophobicity in aqueous solutions. In this invention, "hydrophobicity" refers to the property of being insoluble in water.

[0120] Of course, in application scenarios different from this embodiment, the AIE molecule can also be a hydrophilic AIE molecule.

[0121] In this invention, in the above general formula (1), R is an unsubstituted straight-chain or branched alkyl group with 3 to 6 carbon atoms, and X is selected from hydroxyl or amino groups.

[0122] In this invention, the boiling point of the additive is preferably greater than 70°C, more preferably 70~155°C, and even more preferably 75~150°C.

[0123] In this embodiment, the auxiliary agent is an alkyl alcohol with 3 to 6 carbon atoms. The preparation method of the probe solution is as follows: the probe compound is first dissolved in acetone, then allowed to evaporate and dry, and finally the alkyl alcohol is added to obtain the AIE fluorescent probe composition.

[0124] Of course, in application scenarios different from this embodiment, the additive may be a combination of organic alcohols or organic amines with 3 to 5 carbon atoms, preferably one or more of n-propanol, isopropanol, tert-butanol, n-butanol, n-propylamine, n-butylamine, and pentylamine. The additive may be a single one or a mixture of two or more of them.

[0125] Furthermore, not only alcohols, but any organic solvent that has an alkyl molecular chain of a certain length in the molecule and has polar groups at the end or middle of the molecular chain, thereby forming an amphiphilic structure in the molecule that has both a hydrophilic region composed of polar groups and a hydrophobic region composed of alkyl groups, can be used as an auxiliary agent of the present invention.

[0126] In the AIE fluorescent probe composition of the present invention, the auxiliary agent not only acts as a solvent for the hydrophobic AIE molecules, but also, due to its amphiphilic structural characteristics of hydrophilic polar groups and hydrophobic alkyl chains, facilitates the entry of hydrophobic AIE molecules into the palisade layer of surfactant micelles, thus exhibiting a solubilizing effect within the micelles and demonstrating significant AIE properties within a suitable concentration range. Using the composition of this embodiment, which contains hydrophobic AIE molecules and a specific, non-volatile organic solvent with a boiling point above 70°C as an auxiliary agent, it can be directly used in the form of a stable solution to determine the CMC of wash water in washing equipment applications.

[0127] In the AIE fluorescent probe composition of the present invention, in addition to the hydrophobic AIE molecule as the probe compound and the specific organic solvent as an adjuvant, other components may be included, such as stabilizers, preservatives, and other additives, without affecting the AIE effect. When other components are included, the total content of these other components is preferably less than 5% by mass, more preferably less than 1% by mass, relative to the total amount of the AIE probe composition.

[0128] In this invention, the AIE fluorescent probe composition may also contain only an auxiliary agent and a probe compound. The proportion of the auxiliary agent relative to the AIE probe composition is not particularly limited, but is preferably 40% to 90% by mass, more preferably 50% to 80% by mass; the proportion of the probe compound relative to the AIE probe composition is not particularly limited, but is preferably 10% to 60% by mass, more preferably 20% to 50% by mass.

[0129] From the perspectives of solubility, storage stability, and AIE luminescence intensity, the concentration of the hydrophobic AIE molecule as the probe compound in the AIE fluorescent probe composition of the present invention is preferably 500-2000 µmol / L, more preferably 600-1500 µmol / L. When the AIE fluorescent probe composition is added to washing water, the concentration of the probe compound in the washing water is preferably 1-1000 µmol / L, more preferably 10-500 µmol / L.

[0130] The sampling device 105 is used to collect a predetermined amount of washing water from the water tank 101 as a sample.

[0131] In this embodiment, the sampling device 105 collects 50 ml (the predetermined amount) of washing water as a sample each time.

[0132] Of course, in application scenarios different from this embodiment, the sampling device 105 can collect different predetermined amounts of washing water as samples according to specific needs.

[0133] The adding device 106 is used to take a predetermined amount of probe solution from the storage device 104 and add it to the sample in the sampling device 105.

[0134] In this embodiment, the adding device 106 adds 1 ml (the predetermined amount) of probe solution to the sample in the sampling device 105 each time.

[0135] Of course, in application scenarios different from this embodiment, depending on specific needs, the adding device 106 can add different predetermined amounts of probe solution to the sampling device 105 each time.

[0136] The detection device 107 is used to detect the detergent concentration of a sample in which a predetermined amount of probe solution has been added in the sampling device 105, and outputs a detection signal.

[0137] In this embodiment, the detection device 107 is a fluorescence sensor with an excitation wavelength of 365nm and an emission wavelength of 729nm. It outputs a fluorescence intensity detection signal (corresponding to a voltage signal of fluorescence intensity at the specific wavelength) by detecting the change in the peak intensity of the fluorescence emission peak of the washing water in the wavelength range of 350-370nm or 720-740nm.

[0138] Of course, in application scenarios different from this embodiment, depending on specific needs, the excitation wavelength of the fluorescence sensor can be any value in the range of 275-375nm and the emission wavelength can be any value in the range of 350-750nm.

[0139] The judgment device 108 is used to receive the detection signal and determine whether the detergent concentration of the detected sample reaches cmc.

[0140] In this embodiment, the judging device 108 determines whether the detergent concentration has reached cmc by judging whether the peak intensity of the fluorescence emission peak in the fluorescence intensity detection signal output by the detection device (fluorescence sensor) 107 has reached the maximum value.

[0141] The control device 109 is used to control the subsequent dispensing of detergent by the dispensing device 103 based on the judgment result of the judgment device 108.

[0142] In this embodiment, the dispensing device 103 initially dispenses a first predetermined amount (8g in this embodiment) of detergent into the water tank 101 of the washing equipment 100. The sampling device 105 collects 50ml of the washing water from the water tank 101 as a sample. The adding device 106 adds 1ml of probe solution to the sample. The judging device 108 determines whether the detergent concentration has reached CMC based on the fluorescence intensity detection signal output by the detection device (fluorescence sensor) 107. If the detergent concentration has not reached CMC, the control device 109 controls the dispensing device 103 to add a second predetermined amount (4g in this embodiment) of detergent into the water tank 101 of the washing equipment 100 (i.e., a total of 12g of detergent is dispensed). The sampling device 105 discharges the previously collected washing water as a sample, collects another 50ml of washing water from the water tank 101 as a sample, and the adding device 106 adds 1ml of probe solution to the sample. The judging device 108 again determines whether the detergent concentration has reached CMC based on the fluorescence intensity detection signal output by the detection device (fluorescence sensor) 107. The system detects the detergent concentration and determines whether it has reached the required concentration (cmc). If the concentration has not reached cmc, the control device 109 controls the dispensing device 103 to add a second predetermined amount (4g in this embodiment) of detergent to the water tank 101 of the washing equipment 100 (i.e., a total of 16g ​​of detergent is added in three batches). The sampling device 105, the adding device 106, the detection device (fluorescent sensor) 107, and the judgment device 108 repeat these steps until the judgment device 108 determines that the detergent concentration in the sample has reached cmc. If the judgment device 108 determines that cmc has been reached, the control device 109 controls the dispensing device 103 to stop adding detergent.

[0143] In this embodiment, the control device 109 is set with a threshold (e.g., 3 times) representing the maximum number of times detergent can be dispensed. If, after dispensing detergent 3 times, although the judgment result of the judgment device 108 is still that CMC has not been reached, but the number of times the dispensing device 103 dispenses detergent has reached the threshold, the control device 109 controls the dispensing device 103 to stop dispensing detergent.

[0144] Of course, in application scenarios different from this embodiment, depending on specific needs, the control device 109 may not be set with a threshold indicating the maximum number of times detergent can be added and may not perform corresponding control operations.

[0145] According to a second embodiment of the present invention (not shown), another washing device is provided, the structure of which is similar to... Figure 4The washing equipment 100 shown is basically the same, and the surfactants, probe solutions, probe compositions, probe compounds, additives, and various parameter indicators involved in the second embodiment are the same as those in the first embodiment. The difference between the second embodiment and the first embodiment is that the judgment device 108 in the washing equipment in the second embodiment determines whether the detergent concentration has reached cmc based on the change in the difference between the detection signals of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0146] Specifically, in the second embodiment, the storage device 102, the dispensing device 103, the liquid storage device 104, the sampling device 105, the adding device 106, the detection device 107, the judgment device 108, and the control device 109 cooperate to perform the following processing steps:

[0147] Step 1: The first predetermined amount (8g in this embodiment) of detergent is first added to the water tank 101 of the washing equipment 100 by the dispensing device 103. The sampling device 105 collects 50ml of washing water from the water tank 101 as a sample. After the adding device 106 adds 1ml of probe solution to the sample, the judging device 108 receives the first detection signal of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0148] Step 2: Add a second predetermined amount (4g in this embodiment) of detergent to the water tank 101 of the washing equipment 100 through the dispensing device 103 (i.e., a total of 12g of detergent is added twice). The sampling device 105 discharges the previously collected washing water as a sample and collects 50ml of washing water from the water tank 101 again as a sample. After the adding device 106 adds 1ml of probe solution to the sample, the judging device 108 receives the second detection signal of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0149] Step 3: The judging device 108 determines whether the detergent concentration in the washing water has reached cmc based on the difference between the second detection signal and the first detection signal (i.e., the difference between the fluorescence intensities of the two detections). If the difference is 0 or becomes negative, it indicates that the fluorescence intensity of the washing water detected for the second addition operation is equal to or less than the fluorescence intensity of the washing water detected for the first addition operation, and the judging device 108 determines that the detergent concentration has reached cmc.

[0150] Step 4: If the difference is greater than 0, it means that the fluorescence intensity of the washing water detected for the second addition operation is greater than the fluorescence intensity of the washing water detected for the first addition operation. Then, the judgment device 108 determines that the detergent concentration in the washing water has not reached CMC. The control device 109 controls the dispensing device 103, the sampling device 105, and the adding device 106 to repeat the above step 2. The dispensing device 103 adds a second predetermined amount (i.e., a total of 16g ​​of detergent is added in three additions) of detergent into the water tank 101 of the washing equipment 100. The judgment device 108 receives the third detection signal of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0151] Step 5: The judging device 108 determines whether the detergent concentration in the washing water has reached cmc based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it indicates that the fluorescence intensity of the washing water detected for the third addition operation is equal to or less than the fluorescence intensity of the washing water detected for the second addition operation. In this case, the judging device 108 determines that the detergent concentration in the washing water has reached cmc.

[0152] Step Six: If the difference is greater than 0, repeat Steps Four and Five above.

[0153] Figure 5 A detergent dispensing control system 200 for a washing apparatus according to a third embodiment of the present invention is shown, wherein the washing apparatus includes a water tank 201, a storage device 202, and a dispensing device 203. The dispensing control system 200 includes a liquid storage device 204, a sampling device 205, an adding device 206, a detection device 207, a judgment device 208, and a control device 209.

[0154] The water tank 201, storage device 202 and dispensing device 203 in this washing device are the same as the water tank 101, storage device 102 and dispensing device 103 in the washing device 100 of the first embodiment shown in FIG3, and will not be described again here.

[0155] The liquid storage device 204, sampling device 205, adding device 206, detection device 207 and control device 209 in the dispensing control system 200 are the same as the liquid storage device 104, sampling device 105, adding device 106, detection device 107 and control device 109 in the washing equipment 100 of the first embodiment shown in FIG3, and will not be described again here.

[0156] The judgment device 208 in the dispensing control system 200 is the same as the judgment device 108 in the washing equipment of the first or second embodiment described above, and will not be repeated here.

[0157] Furthermore, the surfactants, probe solutions, probe compositions, probe compounds, auxiliaries, and various parameter indicators involved in the third embodiment of the present invention are the same as those in the first embodiment.

[0158] Figure 6 A flowchart of a detergent dosing control method 300 for a washing device according to a fourth embodiment of the present invention is shown. The washing device is the washing device 100 described in the first embodiment above, and the surfactants, probe solutions, probe compositions, probe compounds, additives, and various parameter indicators involved in the fourth embodiment are the same as those in the first embodiment. The dosing control method 300 includes the following processing steps:

[0159] Solution preparation step 301: Using the dispensing device 103, a first predetermined amount of detergent from the storage device 102 is dispensed into the water tank 101 of the washing equipment 100 according to the weight of the laundry, the amount of water entering the tank, or a predetermined amount of water entering the tank, so as to mix and stir with the water in the water tank 101 after the washing equipment 100 has been filled with water to obtain washing water.

[0160] In this embodiment, a first predetermined amount of detergent is added to the water tank of the washing equipment 100 according to the weight of the laundry. For example, if 1.5 kg of laundry is placed in the tank, 8 g (the first predetermined amount) of detergent is added to the water tank 101 of the washing equipment 100.

[0161] Of course, in application scenarios different from this embodiment, depending on specific needs, the dispensing device 103 can dispense different first predetermined amounts of detergent into the water tank 101 of the washing equipment 100 according to the water inlet volume or predetermined water inlet volume of the washing equipment 100.

[0162] Sampling step 302: Collect a predetermined amount of washing water from the water tank 101 as a sample using the sampling device 105.

[0163] In this embodiment, the sampling device 105 collects 50 ml (the predetermined amount) of washing water as a sample each time.

[0164] Of course, in application scenarios different from this embodiment, the sampling device 105 may collect different predetermined amounts of washing water as samples each time, depending on specific needs.

[0165] Step 303: Add a predetermined amount of probe solution to the sample through the storage device 104 and the addition device 106.

[0166] In this embodiment, the adding device 106 draws 1 ml (the predetermined amount) of probe solution from the storage device 104 each time and adds it to the sample in the sampling device 105.

[0167] Of course, in application scenarios different from this embodiment, depending on specific needs, the adding device 106 can add different predetermined amounts of probe solution to the sample in the sampling device 105.

[0168] Detection step 304: The concentration of detergent in the sample containing the predetermined amount of probe solution is detected by the detection device 107, and a detection signal is output.

[0169] In this embodiment, the detection device 107 is a fluorescence sensor with an excitation wavelength of 365nm and an emission wavelength of 729nm. It outputs a fluorescence intensity detection signal by detecting the change in the peak intensity of the fluorescence emission peak in the wavelength range of 350-370nm or 720-740nm.

[0170] Of course, in application scenarios different from this embodiment, depending on specific needs, the excitation wavelength of the fluorescence sensor can be any value in the range of 275-375nm and the emission wavelength can be any value in the range of 350-750nm.

[0171] Judgment and control step 305: The judgment device 108 determines whether the detergent concentration of the detected sample reaches cmc based on the detection signal, and the control device 109 controls the subsequent addition of detergent by the dispensing device 103 based on the judgment result.

[0172] In this embodiment, the judging device 108 determines whether the detergent concentration has reached the critical micelle concentration (cmc) by judging whether the fluorescence emission peak intensity in the fluorescence intensity detection signal output by the detection device (fluorescence sensor) 107 has reached the maximum value.

[0173] In this embodiment, the judgment and control step 305 includes the following processing steps:

[0174] Judgment and control step one: If the judgment result of the judgment device 108 is that CMC has not been reached (corresponding to...) Figure 6 If the indicator shows "No", then the control device 105 controls the dispensing device 103 to continue executing the liquid preparation step 301 to add a second predetermined amount (4g in this embodiment) of detergent to the water tank 101 of the washing equipment 100 (i.e., a total of 12g of detergent is added twice). The sampling step 302, the adding step 303, the detection step 304, and the judgment and control step 305 are repeatedly executed to continue detecting and judging whether the detergent concentration in the sample reaches CMC. In the liquid preparation step 301, after each addition of detergent by the dispensing device 103, in the sampling step 302, the sampling device 104 clears the previously collected sample and re-collects a predetermined amount of washing water as a sample.

[0175] Judgment and control step two: If the judgment result of the judgment device 108 is that CMC (corresponding to...) is achieved... Figure 6 If the indicator shows "Yes", then the dispensing device 103 will stop dispensing detergent via the control device 105.

[0176] Figure 7 A detergent dispensing control method 300' for a washing apparatus according to a fifth embodiment of the present invention is shown, wherein the washing apparatus is the washing apparatus described in the second embodiment above. This dispensing control method 300' is substantially the same as the dispensing control method 300 of the fourth embodiment, the difference being that: Figure 7 As shown, the judgment and control step 305 in the dosing control method 300' determines whether the detergent concentration in the sample reaches cmc through the following processing steps:

[0177] Step 3051: The dispensing device 103 dispenses a first predetermined amount (8g in this embodiment) of detergent into the water tank 101 of the washing equipment 100 for the first time. The sampling device 105 collects a predetermined amount (50ml in this embodiment) of washing water from the water tank 101 as a sample. After the adding device 106 adds a predetermined amount (1ml in this embodiment) of probe solution to the sample for the first time, the judging device 108 receives the first detection signal of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0178] Step 3052: Add a second predetermined amount (4g in this embodiment) of detergent to the water tank 101 of the washing equipment 100 through the dispensing device 103 (i.e., a total of 12g of detergent is added twice). The sampling device 105 discharges the previously collected washing water as a sample and collects a predetermined amount (50ml in this embodiment) of washing water from the water tank as a sample again. After the adding device 106 adds a predetermined amount (1ml in this embodiment) of probe solution to the sample for the second time, the judging device 108 receives the second detection signal of fluorescence intensity output by the detection device (fluorescence sensor) 107.

[0179] Step 3053: The judging device 108 determines whether the detergent concentration in the sample reaches CMC based on the difference between the second detection signal and the first detection signal. If the difference is greater than 0, it indicates that the fluorescence intensity of the washing water detected for the second addition operation is greater than the fluorescence intensity of the washing water detected for the first addition operation. Therefore, the judging device 108 determines that the detergent concentration in the sample has not reached CMC (corresponding to...). Figure 7If the indicator shows "No", the control device 109 controls the dispensing device 102 to continue executing the solution preparation step 301 to add a second predetermined amount of detergent to the water tank of the washing equipment, and repeats the sampling step 302, the addition step 303, the detection step 304, and the judgment and control step 305 to continue to detect and judge whether the detergent concentration of the probe solution sample has reached the critical micelle concentration; if the difference is 0 or becomes negative, it means that the fluorescence intensity of the washing water in the sample detected for the second addition operation is equal to or less than the fluorescence intensity of the washing water in the sample detected for the first addition operation, then the judgment device 108 judges that the detergent concentration of the washing water has reached CMC (corresponding to Figure 7 The indicator "Yes" is shown in the figure, and the dispensing device 102 is stopped from dispensing detergent by the control device 109.

[0180] In summary, this invention provides a washing device, a method and system for controlling the dosing of detergent in the washing device, and determines the critical micelle concentration of detergent in the washing water as the point of optimal washing and detergency or the point of highest cost-effectiveness. By detecting the critical micelle concentration of the washing water, the accuracy of detergent dosing control is improved, and ideal washing results can be achieved. Furthermore, by utilizing the unique properties of AIE fluorescent probes in detergent solutions containing surfactants due to their aggregation-induced emission characteristics, and by using a relatively low-sensitivity detection device (e.g., a fluorescence sensor) and specifically setting the detection wavelength, fluorescent whitening agents in the washing water are eliminated. This method eliminates interference, enabling simple, rapid, and efficient detection and determination of the critical micelle concentration in washing water. It improves the accuracy of detergent concentration detection in washing water, and the process is relatively simple with low equipment (system) costs. Furthermore, by using hydrophobic AIE molecules and employing non-volatile organic solvents as additives, a stable dispersion structure is formed in aggregates such as micelles in detergent solutions containing surfactants. After adding detergent to the probe solution, the critical micelle concentration can be accurately determined without the need for additive evaporation, further enhancing its applicability for detecting the critical micelle concentration of washing water in washing equipment applications.

[0181] Those skilled in the art will recognize that, although numerous exemplary embodiments of the invention have been shown and described in detail herein, many other variations or modifications conforming to the principles of the invention can be directly determined or derived from the disclosure of the invention without departing from its spirit and scope. Therefore, the scope of the invention should be understood and construed as covering all such other variations or modifications.

Claims

1. A washing apparatus, comprising a storage device for storing detergent; and a dispensing device for dispensing a first predetermined amount of the detergent into a water tank of the washing apparatus according to the weight of the laundry placed in the washing apparatus or the water intake of the washing apparatus or a predetermined water intake, so as to mix and stir with the water in the water tank after the washing apparatus has been filled with water to obtain washing water, wherein the detergent contains a surfactant, characterized in that... The washing equipment also includes: A storage device for storing a probe solution, wherein the probe solution comprises an AIE fluorescent probe composition, the AIE fluorescent probe composition comprising a probe compound and an auxiliary agent, the probe compound being a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent being a non-volatile organic solvent represented by the following general formula (1). R n -X (1) Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups. The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive. The boiling point of the additive is greater than 70°C; A sampling device for collecting a predetermined amount of the washing water from the water tank as a sample; An adding device is used to take a predetermined amount of probe solution from the storage device and add it to the sample in the sampling device; The detection device is used to detect the detergent concentration of the sample in which the predetermined amount of the probe solution has been added to the sampling device, and to output a detection signal with corresponding fluorescence intensity. A judging device is configured to receive the detection signal of the fluorescence intensity and, based on the change in the difference between the detection signals of the fluorescence intensity, determine whether the detergent concentration of the detected sample has reached the critical micelle concentration; and A control device is configured to control the subsequent dispensing of detergent by the dispensing device based on the judgment result of the judgment device, wherein if the judgment result of the judgment device is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of detergent into the water tank of the washing equipment; if the judgment result of the judgment device is that the critical micelle concentration has been reached, the control device controls the dispensing device to stop dispensing detergent.

2. The washing equipment according to claim 1, characterized in that, The surfactant comprises at least anionic surfactants and / or nonionic surfactants.

3. The washing equipment according to claim 1 or 2, characterized in that, The probe compound is a hydrophobic AIE molecule comprising a compound represented by any one of the following chemical formulas 1 to 12 as its basic framework: 。 4. The washing equipment according to claim 3, characterized in that, The hydrophobic AIE molecule is any one of the following: unsubstituted tetraphenylethylene represented by chemical formula 1, unsubstituted stilbeneylanthracene represented by chemical formula 2, unsubstituted hexaphenylsilanecyclopentadiene represented by chemical formula 7, and unsubstituted benzo[a]perylene represented by chemical formula 10.

5. The washing equipment according to claim 1 or 2, characterized in that, In the general formula (1), R is an unsubstituted straight-chain or branched alkyl group with 3 to 6 carbon atoms, and X is selected from hydroxyl or amino groups.

6. The washing equipment according to claim 1 or 2, characterized in that, The auxiliary agent is selected from one or more of n-propanol, isopropanol, tert-butanol, n-butanol, n-butylamine, and pentylamine.

7. The washing equipment according to claim 1 or 2, characterized in that, The adjuvant has an amphiphilic structure, having a hydrophilic region composed of the polar group and a hydrophobic region composed of the alkyl group in the molecule, and the probe compound has a higher solubility in the adjuvant than in water.

8. The washing equipment according to claim 1 or 2, characterized in that, The auxiliary agent is an alkyl alcohol with 3 to 6 carbon atoms. The preparation method of the probe solution is as follows: the probe compound is pre-dissolved in acetone, then allowed to evaporate and dry, and finally the alkyl alcohol is added to obtain the AIE fluorescent probe composition.

9. The washing equipment according to claim 1 or 2, characterized in that, The concentration of the probe compound in the AIE fluorescent probe composition is 500~2000µmol / L, and the concentration of the probe compound in the detergent solution is 1~1000µmol / L.

10. The washing apparatus according to claim 1 or 2, characterized in that, The content ratio of the auxiliary agent to the AIE fluorescent probe composition is 70% to 99% by mass, and the content ratio of the probe compound to the AIE fluorescent probe composition is 1% to 30% by mass.

11. The washing equipment according to claim 1 or 2, characterized in that, The detection device is a fluorescence sensor with an excitation wavelength range of 275-375nm and an emission wavelength range of 350-750nm. It outputs a fluorescence intensity detection signal by detecting the change in the fluorescence emission peak intensity of the washing water in the wavelength range of 350-370nm or 720-740nm.

12. The washing equipment according to claim 1, characterized in that, The determining device determines whether the detergent concentration has reached the critical micelle concentration by performing the following processing steps: Judgment Step 1: When the dispensing device first dispenses a predetermined amount of detergent into the water tank of the washing equipment, the sampling device collects the predetermined amount of washing water from the water tank as a sample, and the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives the first detection signal of fluorescence intensity output by the detection device. Judgment Step Two: The dispensing device adds a second predetermined amount of detergent to the water tank of the washing equipment. The adding device discharges the previously collected washing water as a sample and collects the predetermined amount of washing water from the water tank again as a sample. After the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives a second detection signal of fluorescence intensity output by the detection device. The first predetermined amount and the second predetermined amount may be the same or different. Judgment Step 3: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the second detection signal and the first detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the second addition operation is equal to or less than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration. Judgment Step 4: If the difference is greater than 0, it means that the fluorescence intensity detected for the second addition operation is greater than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has not reached the critical micelle concentration, and repeats the above judgment step 2. The judgment device receives the third detection signal of fluorescence intensity output by the detection device. Judgment Step 5: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the third addition operation is equal to or less than the fluorescence intensity detected for the second addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration. as well as Judgment step six: If the difference is greater than 0, then repeat steps four and five.

13. The washing equipment according to claim 12, characterized in that, If the difference is 0 or becomes negative, and the detected fluorescence intensity undergoes a sudden change from zero to the strongest, with a sudden change point corresponding to the strongest fluorescence intensity, then the judgment device determines that the detergent concentration has reached the critical micelle concentration.

14. The washing equipment according to claim 1 or 2, characterized in that, The control device is also configured to set a threshold representing the maximum number of times the detergent is dispensed in each wash. If, after the detergent is dispensed several times by the dispensing device, the detection device determines that the critical micelle concentration has not been reached, but the number of dispensing times has reached the threshold, then the control device controls the dispensing device to stop dispensing the detergent.

15. A method for controlling the dosing of detergent in a washing device, wherein the washing device is the washing device according to any one of claims 1-14, characterized in that, The delivery control method includes: Solution preparation step: Using the dispensing device of the washing equipment, a first predetermined amount of detergent is added to the water tank of the washing equipment according to the weight of the laundry or the amount of water or a predetermined amount of water to mix and stir with the water in the water tank after the washing equipment is filled with water to obtain washing water; Sampling steps: Collect a predetermined amount of the washing water from the water tank as a sample using the sampling device of the washing equipment; Addition step: A predetermined amount of probe solution is added to the sample through the storage device and the addition device of the washing equipment, wherein the probe solution contains an AIE fluorescent probe composition, the AIE fluorescent probe composition contains a probe compound and an auxiliary agent, the probe compound is a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent is a non-volatile organic solvent represented by the following general formula (1). R n -X (1) Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups. The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive. The boiling point of the additive is greater than 70°C; Detection steps: The detergent concentration of the sample containing the predetermined amount of the probe solution is detected by the detection device of the washing equipment, and a detection signal with corresponding fluorescence intensity is output; Judgment and control steps: The judgment device of the washing equipment determines whether the detergent concentration of the detected sample has reached the critical micelle concentration based on the difference between the detection signals of the fluorescence intensity. The control device of the washing equipment controls the subsequent addition of detergent by the dispensing device based on the judgment result of the judgment step.

16. The delivery control method according to claim 15, characterized in that, The judgment and control steps include the following processing steps: Judgment and Control Step 1: Using the judgment device of the washing equipment, based on the change in the difference between the detected fluorescence intensity signals, it is determined whether the detergent concentration of the sample has reached the critical micelle concentration. If the judgment result is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue executing the solution preparation step to add a second predetermined amount of detergent to the water tank of the washing equipment, and repeats the sampling step, the adding step, the detection step, and the judgment step to continue detecting and judging whether the detergent concentration of the probe solution sample has reached the critical micelle concentration. In the solution preparation step, after each addition of detergent by the dispensing device, in the sampling step, the sampling device clears the previously collected sample and re-collects the predetermined amount of washing water as a sample; and Judgment and control step two: If the judgment result is that the critical micelle concentration has been reached, the dispensing device is controlled by the control device to stop dispensing detergent.

17. The delivery control method according to claim 15 or 16, characterized in that, The judgment and control steps include the following processing steps: Judgment and control step one: When the dispensing device first dispenses a first predetermined amount of detergent into the water tank of the washing equipment, the sampling device collects the predetermined amount of washing water from the water tank as a sample, and the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives the first detection signal of fluorescence intensity output by the detection device. Judgment and control step two: The dispensing device adds a second predetermined amount of detergent to the water tank of the washing equipment. The adding device discharges the previously collected washing water as a sample and collects the predetermined amount of washing water from the water tank again as a sample. After the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives a second detection signal of fluorescence intensity output by the detection device. The first predetermined amount and the second predetermined amount may be the same or different. Judgment and Control Step 3: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the second detection signal and the first detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the second addition operation is equal to or less than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration, and the control device controls the dispensing device to stop dispensing detergent. Judgment and control step four: If the difference is greater than 0, it means that the fluorescence intensity detected for the second addition operation is greater than the fluorescence intensity detected for the first addition operation. Then the judgment device judges that the detergent concentration has not reached the critical micelle concentration, and repeats the above judgment and control step two. The judgment device receives the third detection signal of fluorescence intensity output by the detection device. Judgment and Control Step 5: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the third addition operation is equal to or less than the fluorescence intensity detected for the second addition operation. Then, the judgment device determines that the detergent concentration has reached the critical micelle concentration, and the control device controls the dispensing device to stop dispensing detergent. as well as Judgment and control step six: If the difference is greater than 0, then repeat judgment and control steps four and five.

18. A detergent dispensing control system for a washing apparatus, wherein the washing apparatus includes a storage device for storing the detergent; The detergent dispensing device dispenses a first predetermined amount of detergent into the water tank of the washing equipment according to the weight of the laundry placed in the washing equipment or the water intake of the washing equipment or a predetermined water intake, so as to mix and stir with the water in the water tank after the washing equipment has been filled with water to obtain washing water, wherein the detergent contains a surfactant, characterized in that... The delivery control system includes: A storage device for storing a probe solution, wherein the probe solution comprises an AIE fluorescent probe composition, the AIE fluorescent probe composition comprising a probe compound and an auxiliary agent, the probe compound being a hydrophobic aggregation-induced emission AIE molecule, and the auxiliary agent being a non-volatile organic solvent represented by the following general formula (1). R n -X (1) Wherein, R is a substituted or unsubstituted straight-chain or branched alkyl group with 3 to 10 carbon atoms, n is an integer of 1 or 2, when n is 2, the two Rs can be the same or different, and X is a polar group selected from any one of hydroxyl, amino, cyano, halogen, amide, carbonyl, aldehyde, ester, and ether groups. The hydrophobic aggregation-induced emission (AIE) molecules are dissolved in the additive. The boiling point of the additive is greater than 70°C; A sampling device for collecting a predetermined amount of the washing water from the water tank as a sample; An adding device is used to take a predetermined amount of probe solution from the storage device and add it to the sample in the sampling device; The detection device is used to detect the detergent concentration of the sample in which the predetermined amount of the probe solution has been added to the sampling device, and to output a detection signal with corresponding fluorescence intensity. A judging device is configured to receive the detection signal of the fluorescence intensity and, based on the change in the difference between the detection signals of the fluorescence intensity, determine whether the detergent concentration of the detected sample has reached the critical micelle concentration; and A control device is configured to control the subsequent dispensing of detergent by the dispensing device based on the judgment result of the judgment device, wherein if the judgment result of the judgment device is that the critical micelle concentration has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of detergent into the water tank of the washing equipment; if the judgment result of the judgment device is that the critical micelle concentration has been reached, the control device controls the dispensing device to stop dispensing detergent.

19. The delivery control system according to claim 18, characterized in that, The surfactant comprises at least anionic surfactants and / or nonionic surfactants.

20. The delivery control system according to claim 18 or 19, characterized in that, The probe compound is a hydrophobic AIE molecule comprising a compound represented by any one of the following chemical formulas 1 to 12 as its basic framework: 。 21. The delivery control system according to claim 20, characterized in that, The hydrophobic AIE molecule is any one of the following: unsubstituted tetraphenylethylene represented by chemical formula 1, unsubstituted stilbeneylanthracene represented by chemical formula 2, unsubstituted hexaphenylsilanecyclopentadiene represented by chemical formula 7, and unsubstituted benzo[a]perylene represented by chemical formula 10.

22. The delivery control system according to claim 18 or 19, characterized in that, In the general formula (1), R is an unsubstituted straight-chain or branched alkyl group with 3 to 6 carbon atoms, and X is selected from hydroxyl or amino groups.

23. The delivery control system according to claim 18 or 19, characterized in that, The auxiliary agent is selected from one or more of n-propanol, isopropanol, tert-butanol, n-butanol, n-butylamine, and pentylamine.

24. The delivery control system according to claim 18 or 19, characterized in that, The adjuvant has an amphiphilic structure, having a hydrophilic region composed of the polar group and a hydrophobic region composed of the alkyl group in the molecule, and the probe compound has a higher solubility in the adjuvant than in water.

25. The delivery control system according to claim 18 or 19, characterized in that, The auxiliary agent is an alkyl alcohol with 3 to 6 carbon atoms. The preparation method of the probe solution is as follows: the probe compound is pre-dissolved in acetone, then allowed to evaporate and dry, and finally the alkyl alcohol is added to obtain the AIE fluorescent probe composition.

26. The delivery control system according to claim 18 or 19, characterized in that, The concentration of the probe compound in the AIE fluorescent probe composition is 500~2000µmol / L, and the concentration of the probe compound in the detergent solution is 1~1000µmol / L.

27. The delivery control system according to claim 18 or 19, characterized in that, The content ratio of the auxiliary agent to the AIE probe composition is 70% to 99% by mass, and the content ratio of the probe compound to the AIE probe composition is 1% to 30% by mass.

28. The delivery control system according to claim 18 or 19, characterized in that, The detection device is a fluorescence sensor with an excitation wavelength range of 275-375nm and an emission wavelength range of 350-750nm. It outputs a fluorescence intensity detection signal by detecting the change in the fluorescence emission peak intensity of the washing water in the wavelength range of 350-370nm or 720-740nm.

29. The delivery control system according to claim 18, characterized in that, The determining device determines whether the detergent concentration has reached the critical micelle concentration by performing the following processing steps: Judgment Step 1: When the dispensing device first dispenses a first predetermined amount of detergent into the water tank of the dispensing control system, the sampling device collects the predetermined amount of washing water from the water tank as a sample, and the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives the first detection signal of fluorescence intensity output by the detection device. Judgment Step Two: The dispensing device adds a second predetermined amount of detergent to the water tank of the dispensing control system. The adding device discharges the previously collected washing water used as a sample and collects the predetermined amount of washing water from the water tank again as a sample. After the adding device adds the predetermined amount of probe solution to the sample, the judgment device receives a second detection signal of fluorescence intensity output by the detection device. The first predetermined amount and the second predetermined amount may be the same or different. Judgment Step 3: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the second detection signal and the first detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the second addition operation is equal to or less than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration. Judgment Step 4: If the difference is greater than 0, it means that the fluorescence intensity detected for the second addition operation is greater than the fluorescence intensity detected for the first addition operation. Then the judgment device determines that the detergent concentration has not reached the critical micelle concentration, and repeats the above judgment step 2. The judgment device receives the third detection signal of fluorescence intensity output by the detection device. Judgment Step 5: The judgment device determines whether the detergent concentration has reached the critical micelle concentration based on the difference between the third detection signal and the second detection signal. If the difference is 0 or becomes negative, it means that the fluorescence intensity detected for the third addition operation is equal to or less than the fluorescence intensity detected for the second addition operation. Then the judgment device determines that the detergent concentration has reached the critical micelle concentration. as well as Judgment step six: If the difference is greater than 0, then repeat judgment steps four and five.

30. The delivery control system according to claim 29, characterized in that, If the difference is 0 or becomes negative, and the detected fluorescence intensity undergoes a sudden change from zero to the strongest, with a sudden change point corresponding to the strongest fluorescence intensity, then the judgment device determines that the detergent concentration has reached the critical micelle concentration.

31. The delivery control system according to claim 18 or 19, characterized in that, The control device is also configured to set a threshold representing the maximum number of times the detergent is dispensed in each wash. If, after the detergent is dispensed several times by the dispensing device, the detection device determines that the critical micelle concentration has not been reached, but the number of dispensing times has reached the threshold, then the control device controls the dispensing device to stop dispensing the detergent.

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