ACQ fluorescent probe composition, CMC measurement method, dirt cleaning concentration determination method, detergent dispensing control method and system

Abstract

The present invention relates to a probe solution used for directly measuring the cmc concentration of a surfactant, comprising an ACQ fluorescent probe composition containing a probe molecule and an auxiliary agent, wherein the probe molecule is a fluorescent molecule having aggregation-induced quenching (ACQ) properties, the auxiliary agent contains one or more non-volatile organic solvents, the boiling point of the organic solvent is 100°C or higher, and the distance between the Hansen solubility parameter of the probe molecule and the organic solvent, i.e., the HSP distance Ra, is 17 (MPa). 1 / 2 The present invention provides an ACQ fluorescent probe composition characterized by the following. The present invention further provides a CMC measurement method, a dirt cleaning concentration determination method, a detergent dispensing control method, and a detergent dispensing control system using the ACQ fluorescent probe composition.

Description

[Technical Field]

[0001] The present invention relates to an ACQ fluorescent probe composition, a CMC measurement method using the ACQ fluorescent probe composition, a dirt cleaning concentration determination method, a detergent dispensing control method, and a system. [Background technology]

[0002] Detergents generally consist of surfactants, builders, and additives. Conventional automatic washing machines primarily add detergent based on the weight of the fabric being loaded, but the amount of detergent added varies considerably depending on the washing machine manufacturer, resulting in insufficient versatility and flexibility for different detergents and washing scenarios.

[0003] The inventors have found through their research that when the surfactant concentration in the wash water reaches the critical micelle concentration (CMC), the washing effect reaches an equilibrium point where cost-effectiveness is optimal. Therefore, it is desirable to monitor whether the surfactant concentration in the wash water has reached CMC and use this as a criterion for deciding whether to automatically dispense detergent.

[0004] Furthermore, the detergent concentration required for cleaning varies depending on the type of stain on the clothing, and this concentration may be equal to or greater than the critical micelle concentration (CMC) mentioned above. Therefore, different threshold concentrations may be determined for each of the three types of stains: oil stains, pigment stains, and invisible stains. If the detergent concentration in the wash water is measured to have already reached or exceeded the threshold concentration, it can be predicted that the stains can be cleaned. Therefore, it is desirable to monitor whether the surfactant concentration in the wash water has reached the threshold concentration and use this as a criterion for deciding whether to automatically dispense detergent.

[0005] In short, there are two methods for determining the criteria for automatic detergent dispensing control: 1. Using CMC (Common Cleaning Concentration) as the criterion for the highest cost-effectiveness, where the cleaning efficiency is highest at that concentration. 2. Using the dirt cleaning threshold concentration as the criterion for dirt cleaning degree, where the cleaning effect is best at that concentration. Generally, the dirt cleaning threshold concentration is above CMC.

[0006] Conventional methods for measuring the CMC of surfactants include the surface tension method, conductivity method, and fluorescence probe method. However, the surface tension method requires a series of complex operations, the conductivity method cannot measure nonionic surfactants and surfactants with low conductivity, and the fluorescence probe method suffers from low probe sensitivity and accuracy. For example, the fluorescence probe method generally uses pyrene as a probe, and the CMC is determined by measuring the intensity and ratio of the fluorescence peaks of the first and third emission peaks (373 nm and 384 nm) of pyrene. However, when pyrene is used as a probe for online CMC measurement, the peak position may shift, causing the selected 373 nm and 384 nm to no longer be inflection points of the peak, resulting in insufficient detection sensitivity. Therefore, it is necessary to search for a probe molecule with more appropriate fluorescence characteristics. In addition, conventional spectrofluorometers have the problem of being difficult to miniaturize and being expensive.

[0007] Fluorescent probe molecules are broadly classified into AIE molecules, which utilize the aggregation-induced luminescence (AIE) method, and ACQ molecules, which utilize the aggregation-induced quenching (ACQ) method. We have previously succeeded in developing an AIE fluorescent probe composition containing an AIE molecule and an auxiliary agent (Patent Document 1). However, compared to AIE molecules, ACQ molecules have a wider range of types and origins, and most ACQ molecules have efficient manufacturing methods and commercially available products. Furthermore, compared to AIE molecules, ACQ molecules have a lower probe cost when equivalent detection accuracy is guaranteed, making them more cost-effective in applications. Therefore, it is expected that developing an inexpensive, simple, and easy-to-use ACQ fluorescent probe composition will allow for its use in various scenarios, such as CMC monitoring of laundry water, and a wide range of applications are anticipated.

[0008] A conventional problem is that ACQ probe molecules used to measure cmc are mostly poorly water-soluble substances. To dissolve these hydrophobic substances, it is common to dissolve them in organic solvents such as tetrahydrofuran or ethanol. However, in this field, the presence of these organic solvents is thought to cause deviations in the cmc measurement results. Therefore, to avoid these problems, it is necessary to limit the amount of organic solvent used to a very small amount (Non-Patent Document 1), or to completely evaporate the volatile organic solvent before measurement or wait until it volatilizes naturally (Non-Patent Documents 2, 3). Because these organic solvents are highly volatile, it is difficult to store or keep the ACQ probe solution for a long time in actual use environments, or treatment is required before use. This makes the operation of the cmc measurement process complicated, reduces the accuracy of sample collection for measurement, and makes it inconvenient to use. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] CN116554861A [Non-patent literature]

[0010] [Non-Patent Document 1] Role of Curcumin on The Determination of The Critical Micellar Concentration by Absorbance,Fluorescence and Fluorescence Anisotropy Techniques,J Photochem. Photobiol.,B,2012,115(3),9-15. [Non-Patent Document 2] Measurement of critical micelle concentration of CTAB by pyrene fluorescence probe spectroscopy, Petrochemical Technology and Applications, 2007, 25(1), 48-50. [Non-Patent Document 3] Fluorescence Emission of Pyrene in Surfactant Solution,Advance in Colloid and Interface Science,215(2015),1-12. [Overview of the project] [Problems that the invention aims to solve]

[0011] The present invention has been made in view of the above circumstances and aims to provide an ACQ fluorescent probe composition that is inexpensive, simple, and easy to use, can be stored for a long time in the form of a stable solution, and can be used directly to measure the cmc concentration of a surfactant solution. The present invention also provides a method for measuring the cmc of a surfactant solution using the ACQ fluorescent probe composition, a method for determining the dirt cleaning concentration, and a method for controlling the amount of detergent dispensed. [Means for solving the problem]

[0012] The inventors of this invention have diligently investigated the above-mentioned problems and have found the following: By utilizing a specific combination of ACQ probe molecules and auxiliary agents, the ACQ molecules can be well dissolved in the auxiliary agent to form a stable probe solution that can be stored for a long time, which can then be directly used to measure the cmc of a surfactant solution. Furthermore, the influence of the auxiliary agent on the cmc measurement results is limited to an acceptable range, allowing for accurate measurement results, thus effectively solving the above-mentioned problems.

[0013] The present invention relates to a probe solution used for directly measuring the cmc concentration of a surfactant, comprising an ACQ fluorescent probe composition containing a probe molecule and an auxiliary agent, wherein the probe molecule is a fluorescent molecule having aggregation-induced quenching (ACQ) properties, the auxiliary agent contains one or more non-volatile organic solvents, the boiling point of the organic solvent is 100°C or higher, and the distance between the Hansen solubility parameter of the probe molecule and the organic solvent, i.e., the HSP distance Ra, is 17 (MPa). 1 / 2 The present invention provides an ACQ fluorescent probe composition characterized by the following:

[0014] Preferably, the Hansen solubility parameter (HSP) δ of the probe molecule is 15 (MPa). 1 / 2 ~35 (MPa) 1 / 2 That is the case.

[0015] Preferably, the solubility category of the probe molecule in the auxiliary agent is soluble or higher.

[0016] Preferably, the difference Δδ of the Hansen solubility parameter between the auxiliary agent and the probe molecule is -3 (MPa). 1 / 2 ~+12 (MPa) 1 / 2 That is the case.

[0017] Preferably, the viscosity of the auxiliary agent is 30 mPa·s or less.

[0018] Preferably, the auxiliary agent is soluble in water and has a density of 0.9 g / cm³. 3 ~1.2g / cm 3 That is the case.

[0019] Preferably, the flash point of the auxiliary agent is 60°C or higher.

[0020] Preferably, the probe molecule is an ACQ molecule whose emission method is based on a change in fluorescence intensity or a change in characteristic wavelength, and includes an ACQ molecule whose characteristic wavelength has a blueshift characteristic, an ACQ molecule whose characteristic wavelength has a redshift characteristic, and an ACQ molecule whose characteristic wavelength does not change.

[0021] Preferably, the probe molecule is one or more ACQ molecules selected from curcumin (CUR), Nile red (NR), coumarin (C480), rhodamine B (RhB), N-phenyl-1-naphthylamine (NPN), and pyrene (PYR).

[0022] Preferably, the auxiliary agent includes one or more organic solvents selected from n-butanol, ethylene glycol, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide (DMF), diethylene glycol monoethyl ether (DGME), ethyl glycolate, polyethylene glycol 200 (PEG200), 1,3-butanediol, and 1,5-pentanediol.

[0023] Preferably, the probe molecule is at least one ACQ molecule selected from curcumin (CUR), Nile red (NR), and coumarin (C480), and the auxiliary agent includes at least one organic solvent selected from N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), polyethylene glycol 200 (PEG200), and diethylene glycol monoethyl ether (DGME).

[0024] The present invention further provides a method for measuring the CMC of the following surfactant solutions. A solution preparation step for preparing a series of surfactant solutions of different concentrations, A probe addition step involves adding a fixed amount of probe solution to each of the aforementioned surfactant solutions, A detection step involves detecting the fluorescence response value of each surfactant solution using a detection means, The following steps are included in this order: creating a fluorescence response value-concentration curve diagram having at least a first plateau region and an upward region based on the results obtained in the detection step, and determining the concentration corresponding to the inflection point where the fluorescence response value changes from the first plateau region to the upward region as the cmc of the surfactant solution; A method for measuring the cmc of a surfactant solution, characterized in that the probe solution is the above-described ACQ fluorescent probe composition of the present invention.

[0025] Preferably, in the determination step, the concentration corresponding to the intersection of the fitting line of the first plateau region and the fitting line of the rising region in the fluorescence response value-concentration curve diagram is determined as the cmc of the surfactant solution.

[0026] Preferably, the amount of solvent added to the probe solution per 10 mL of the surfactant solution does not exceed 400 μL, and the probe operating concentration of the probe molecule does not exceed 10 μg / mL.

[0027] Preferably, the surfactant includes at least one of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0028] Preferably, the surfactant solution further contains a fluorescent whitening agent.

[0029] The present invention further provides the following method for determining the concentration of dirt being removed during cleaning. A solution preparation step involves adding a predetermined amount of detergent to a washing machine containing a predetermined amount of water and clothes, stirring to mix uniformly, and then obtaining wash water. A sample collection step involves taking a sample from the aforementioned wash water and adding a small amount of probe solution to obtain the wash water to be measured. A detection step of detecting the fluorescence response value S of the washing water to be measured using a detection means, A determination step in which, based on whether the detected fluorescence response value S has reached or exceeds a preset washing response threshold S0, it is determined whether the detergent concentration of the measured washing water is a dirt-cleaning concentration, and if it has not reached the preset washing response threshold S0, the determination result is "no", and if it has already reached or exceeded the preset washing response threshold S0, the determination result is "yes", The control step includes controlling the subsequent addition of the detergent in the solution preparation step based on the determination result of the determination step, and if the determination result is "no", returning to the solution preparation step and continuing to add a second predetermined amount of detergent, then performing the subsequent sample collection step, detection step and determination step, and if the determination result is "yes", stopping the addition of the detergent and outputting the determination result. A method for determining the concentration of dirt removal, characterized in that the probe solution is the above-described ACQ fluorescent probe composition of the present invention.

[0030] Preferably, the cleaning response threshold S0 is a fluorescence response value corresponding to the critical micelle concentration cmc of the washing water, or a fluorescence response value corresponding to the stain cleaning threshold concentration C t and is the stain cleaning threshold concentration C t is the minimum concentration required to clean clothes with different types of stains, and is determined by the following formula 3 C t = cmc × (1 + a) (Formula 3) In Formula 3, cmc is the critical micelle concentration of the washing water, a is a cleaning coefficient, and the range is 0 ≦ a ≦ 10. Corresponding to different types and degrees of stains, a takes different values

[0031] Preferably, the cleaning response threshold S0 is determined by the following Formula 4 or Formula 5 S0 = β × S max (Formula 4) S0 = S blank + β × (S max - S blank (Formula 5) Here, S max is the maximum fluorescence intensity or maximum voltage response value of the washing water, or the second plateau value in the fluorescence response value-concentration curve diagram of the washing water, and S blank is the background fluorescence intensity or minimum voltage response value of the washing water, or the first plateau value in the fluorescence response value-concentration curve diagram of the washing water. β is a threshold percentage, with the unit of 100%, and the range is 0 < β < 1. Corresponding to different types and degrees of stains, β takes different values

[0032] The present invention further provides the following detergent input control method In a washing facility, a solution preparation step of obtaining washing water or a detergent solution by introducing a first predetermined amount of detergent into an inner tub based on the weight of the laundry and the water supply amount, and mixing and stirring the detergent with the water in the inner tub A sample collection step of collecting a predetermined amount of the washing water or detergent solution from the inner tub as a sample The extraction step involves taking out a small amount of probe solution and adding it to the sample, A mixing step of mixing the sample and the probe solution to obtain the liquid to be measured, A detection step which involves detecting the fluorescence response value of the liquid to be measured and outputting a detection signal S, Upon receiving the detection signal S, and based on whether the detection signal S has reached or exceeds a preset response threshold S0, the detergent concentration of the liquid to be measured is determined to be either the critical micelle concentration cmc or the preset washing threshold concentration C. t A step of determining whether the washing threshold concentration C has reached the target, t This involves a determination step of whether the critical micelle concentration (cmc) is equal to or greater than the above-mentioned critical micelle concentration (cmc), The control step includes controlling the subsequent addition of the detergent based on the determination result of the determination step, and if the determination result is that the critical micelle concentration or a preset cleaning threshold concentration has not been reached, returning to the solution preparation step and continuing to add a second predetermined amount of the detergent to the inner tank, and stopping the addition of the detergent if the determination result has already reached the critical micelle concentration or a preset cleaning threshold concentration. A detergent dispensing control method characterized in that the probe solution is the above-described ACQ fluorescent probe composition of the present invention.

[0033] Preferably, the control step further includes a count limit step, in which a count threshold indicating the maximum number of times detergent can be added is set in advance, and even if the determination result of the determination step has not yet reached the critical micelle concentration or the preset cleaning threshold concentration after adding the detergent once or more times, if the number of times the detergent has been added has already reached the count threshold, the addition of detergent in the solution preparation step is stopped.

[0034] The present invention further provides the following detergent dispensing control system. A detergent dispensing control system used to automatically control the amount of detergent dispensed into a washing machine, wherein the washing machine includes an inner tub used to hold laundry and water, a storage device used to store detergent, and a dispensing device used to dispense a first predetermined amount of the detergent into the inner tub and mix and agitate it with the water in the inner tub to obtain washing water or a detergent solution. The detergent dispensing control system is A liquid storage device used for storing probe solutions, A sample collection device used to collect a predetermined amount of the wash water or detergent solution as a sample from the inner tub, A liquid extraction device used to take a small amount of probe solution from the liquid storage device and add it to the sample, A mixing device used to obtain a liquid to be measured by mixing the aforementioned sample with the aforementioned probe solution, A detection device used to detect the fluorescence response value of the liquid to be measured and to output a detection signal S, Upon receiving the detection signal S, and based on whether the detection signal S has reached or exceeds a preset response threshold S0, the detergent concentration of the liquid to be measured is determined to be either the critical micelle concentration cmc or the preset washing threshold concentration C. t A determination device used to determine whether the washing threshold concentration C has reached the target, wherein t This includes a device for determining whether the critical micelle concentration (cmc) is equal to or greater than the aforementioned critical micelle concentration (cmc), A CMC determination device is used to determine the critical micelle concentration of the detergent solution when there is no laundry in the inner tub, by using the dispensing device to dispense a predetermined amount of the detergent into the inner tub in several portions, and by repeatedly performing multiple sets of measurements using the liquid storage device, the sample collection device, the liquid extraction device, the mixing device and the detection device, and based on multiple detection data corresponding to different detergent concentrations output by the detection device. The control device is used to control the subsequent dispensing of the detergent by the dispensing device of the washing equipment based on the determination result of the determination device, The determination result of the aforementioned determination device is the critical micelle concentration cmc or the preset washing threshold concentration C. t If the critical micelle concentration (cmc) has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of the detergent into the inner tub of the washing equipment, and the determination result of the determination device is that the critical micelle concentration (cmc) or the preset washing threshold concentration (C) has already been reached. t If the level reaches or exceeds a certain point, the control device controls the dispensing device to stop dispensing the detergent. The detergent dispensing control system is characterized in that the probe solution is the above-described ACQ fluorescent probe composition of the present invention.

[0035] Preferably, the cleaning response threshold S0 is the fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or the dirt cleaning threshold concentration C t This is the corresponding fluorescence response value, The critical micelle concentration (CMC) is the critical micelle concentration of the detergent solution measured in advance, or the critical micelle concentration of the detergent solution or wash water determined by online measurement using the CMC determination device. The aforementioned washing threshold concentration C t The following formula 3 is used to calculate the result: C t =cmc×(1+a)(Formula 3) Here, a is the cleaning coefficient, with a range of 0 ≤ a ≤ 10, and a is set to a different value corresponding to different types and degrees of dirt. Alternatively, the cleaning response threshold S0 is determined by the following equation 4 or equation 5: S0 = β × S max (Formula 4) S0=S blank +β×(S max -S blank )(Formula 5) Here, S max is the maximum fluorescence intensity or maximum voltage response value of the wash water, or the second plateau value in the fluorescence response value-concentration curve diagram of the wash water, and S blankβ is the background fluorescence intensity or minimum voltage response value of the wash water, or the first plateau value in the fluorescence response value-concentration curve of the wash water, where β is a threshold percentage with a unit of 100%, a range of 0 < β < 1, and β is set to different values ​​corresponding to different types and degrees of soiling.

[0036] Preferably, the control device is further configured with a count threshold indicating the maximum number of times detergent can be dispensed. If, after the dispensing device dispenses detergent once or more times, the determination result of the judgment device indicates that the critical micelle concentration or the preset washing threshold concentration has not been reached, but the number of times the detergent has been dispensed has already reached the count threshold, the control device controls the dispensing device to stop dispensing the detergent. [Effects of the Invention]

[0037] The ACQ fluorescent probe composition of the present invention employs a specific combination of ACQ probe molecules and auxiliary agents. This allows for the dissolution of ACQ molecules with the auxiliary agent to form a stable probe solution, enabling long-term storage, good operability during measurement, and accurate measurement of CMC within an appropriate concentration range. As a result, an inexpensive and easy-to-use ACQ fluorescent probe composition is available, which is expected to have applications in a wide range of fields, including laundry, detergents, and washing machines.

[0038] By using the above ACQ fluorescent probe composition, a more convenient and accurate CMC measurement method can be provided. Furthermore, a stain cleaning concentration determination method that determines online whether clothes with different types of stains can be cleaned, a detergent dispensing control method and a detergent dispensing control system that automatically control the amount of detergent dispensed into the laundry equipment based on cost-effectiveness or cleaning effect can be provided. [Brief explanation of the drawing]

[0039] [Figure 1]Figure 1 shows the fluorescence spectrum results measured using a spectrofluorometer for ACQ fluorescent probe composition (CUR-DGME) according to Example 1 of the present invention in different concentrations of "Zhizun Biotechnology (whitening type)" detergent solution (abbreviated as ZZLB). [Figure 2] Figure 2 shows a fluorescence response value-detergent concentration curve diagram created by selecting the peak height data of the fluorescence intensity at the maximum emission wavelength Em=495nm as the fluorescence response value for the ACQ fluorescent probe composition (CUR-DGME) according to Example 1 of the present invention, and the cmc value or cmc range is determined using the intersection method of fitting lines. [Figure 3] Figure 3 shows a fluorescence response value-detergent concentration curve diagram created using a fluorescence photoelectric detector (abbreviated as CD detector) to obtain voltage values ​​as fluorescence response values ​​in laundry water of different concentrations of "Zhizun Biotechnology (whitening type)" for the ACQ fluorescent probe composition (NR-NMP) according to Example 2 of the present invention, and the cmc value or cmc range is determined using the inflection point method. [Figure 4] Figure 4 shows the fluorescence response value-detergent concentration curves obtained when measuring the cmc of "Zhizun Biotechnology (Whitening Type)" detergent solution (abbreviated as ZZLB) using various ACQ fluorescent probe compositions in Example 3 of the present invention, (A) is a CUR probe composition, with auxiliary agents being BUT, EG, NMP, and PEG200 (indicated as PEG in the figure), respectively, and (B) is an NR probe composition, with auxiliary agents being BUT, NMP, and PEG200, respectively. [Figure 5] Figure 5 shows the curve diagram when measuring the cmc of various detergent solutions of different brands using the surface tension method in Example 4 of the present invention. [Figure 6] Figure 6 shows the fluorescence response value-detergent concentration curve when measuring the cmc of various detergent solutions of different brands using two types of ACQ fluorescent probe compositions of the present invention in Example 4 of the present invention, where (A) is the CUR probe composition and (B) is the NR probe composition. [Figure 7]Figure 7 shows the fluorescence response value-detergent concentration curve diagrams when testing the cmc of detergent solution or wash water in different scenarios using two types of ACQ fluorescent probe compositions in Example 5 of the present invention, where (A) is the CUR probe composition and (B) is the NR probe composition. [Figure 8] Figure 8 shows the fluorescence response value-detergent concentration curve when testing the cmc of other types of products containing surfactant components (fabric softener, oxygen bleach, disinfectant) using two ACQ fluorescent probe compositions in Example 6 of the present invention, where (A) is the CUR probe composition and (B) is the NR probe composition. [Modes for carrying out the invention]

[0040] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited to the following embodiments and may be modified as appropriate without departing from the objective of the present invention.

[0041] In this specification, a numerical range indicated using "~" refers to a range that includes the numbers on either side of "~" as the lower and upper limits, respectively. Unless otherwise specified, the upper and lower limits of each preferred range may be combined with each other.

[0042] In this specification, "surfactant solution" refers to an aqueous solution containing a surfactant. When a surfactant is used to wash clothes or articles (abbreviated as clothes or laundry), the surfactant is referred to as "detergent," and the aqueous solution of the surfactant is referred to as "detergent solution" or "laundry water." Specifically, an aqueous solution prepared and diluted directly from detergent and water is called a "detergent solution," which includes an aqueous solution obtained by adding detergent and water to an industrial water washing machine or a household washing machine using the inner tub as a container, without adding any load of clothes or fabrics. On the other hand, a detergent solution obtained by placing clothes or fabrics in an industrial water washing machine or a household washing machine, adding detergent and water, and mixing the detergent and water in the inner tub is called "laundry water." Furthermore, regarding surfactant concentration, when various surfactant components are present in a surfactant solution, unless otherwise specified, it refers to the total concentration of the various surfactant components present in the surfactant solution.

[0043] In this specification, "fluorescence response value" refers to the FL fluorescence intensity (au) when measured using a spectrofluorometer, and to the response voltage value (V) when measured using a fluorescence photoelectric detector (abbreviated as CD detector).

[0044] Furthermore, in this specification, the units for Hansen solubility parameter (HSP) values ​​(δd, δp, δh) and HSP distance Ra are all (MPa). 1 / 2 However, for the sake of simplifying the description, the units for Ra and HSP values ​​may be omitted, and only numerical values ​​may be shown.

[0045] (ACQ fluorescent probe composition) The ACQ fluorescent probe composition of the present invention is a probe solution used for directly measuring the cmc concentration of a surfactant, comprising a probe molecule and an auxiliary agent, wherein the probe molecule is a fluorescent molecule having aggregation-induced quenching (ACQ) properties, the auxiliary agent comprises one or more non-volatile organic solvents, the boiling point of the organic solvent is 100°C or higher, and the distance Ra between the Hansen solubility parameter of the probe molecule and the organic solvent is 17 (MPa). 1 / 2 The following characteristics apply:

[0046] In this invention, "direct measurement" means that the ACQ fluorescent probe composition of the present invention may be added directly to the solution to be measured in the probe solution state without any pretreatment (for example, waiting for the organic solvent to evaporate after adding it to the solution to be measured), and then cmc measurement may be performed.

[0047] In this invention, "non-volatility" refers to the property of an organic solvent that its volume does not change after being stored for a long period of time at room temperature and pressure. Generally, the higher the boiling point of an organic solvent, the lower its volatility. Therefore, in this invention, the boiling point of the organic solvent contained in the auxiliary agent is specified to be 100°C or higher, thereby providing non-volatility. When the organic solvent satisfies the requirement of non-volatility, the probe solution formed by dissolving the probe of this invention in the auxiliary agent is considered a stable solution and can be considered to be able to be stored for a long period of time.

[0048] In this invention, the magnitude of molecular polarity and intermolecular forces of the ACQ probe molecule are determined using the Hansen solubility parameter (HSP). In the following description, the Hansen solubility parameter may be appropriately referred to as "HSP". In order to form a stable probe solution in an aqueous surfactant solution and to exhibit a clear aggregation-induced quenching (ACQ) phenomenon at an appropriate cmc concentration, the Hansen solubility parameter δ of the ACQ probe molecule of this invention is preferably 15 (MPa). 1 / 2 ~35 (MPa) 1 / 2 More preferably 20 (MPa) 1 / 2 ~25 (MPa) 1 / 2 It is set to [value]. In this specification, the units of the Hansen solubility parameter may be omitted, that is, the Hansen solubility parameter δ is preferably 15 to 35, and more preferably 20 to 25.

[0049] Furthermore, the solubility of ACQ probe molecules in organic solvents can be predicted using the Hansen solubility parameter (HSP) distance Ra. Generally, if the absolute value of the HSP distance Ra between the ACQ probe molecule and the organic solvent is 17 or less, it can be considered that the ACQ probe molecule is sufficiently soluble in the organic solvent and can form a relatively stable probe solution.

[0050] The auxiliary agent of the present invention may use only one organic solvent that meets the above requirements, or a combination of multiple organic solvents. Furthermore, in addition to the non-volatile organic solvent as an essential component, the auxiliary agent may optionally contain a small amount of a volatile organic solvent or an inorganic solvent (e.g., water) as an optional component, as long as it does not affect the solubility of the probe or the accuracy of the CMC measurement results. In other words, in the present invention, the auxiliary agent may be only one organic solvent, a mixed solvent of multiple organic solvents, or a mixed solvent of an organic solvent and an inorganic solvent.

[0051] The non-volatile organic solvent contained in the auxiliary agent is not particularly limited in content, and as an essential component, its content is greater than 0%, may be 10% by volume or more, preferably 30% by volume or more, more preferably 50% by volume or more, even more preferably 70% by volume or more, even more preferably 90% by volume or more, and most preferably 100% by volume.

[0052] In order to form a stable and clear probe solution and to ensure a sufficient probe mother liquor concentration, the ACQ probe molecules of the present invention need to have good solubility in organic solvents used as auxiliary agents.

[0053] Even if the ACQ probe molecule is soluble in an auxiliary agent, CMC measurement may still be possible, and therefore, it may not be possible to accurately qualitatively determine solubility using the usual quantitative description. Furthermore, considering compatibility with different probe molecules, this invention qualitatively classifies the solubility of ACQ probe molecules using the concept of solubility categories.

[0054] According to the reference standards for solubility classifications listed in Table 1 below, the solubility classification of the ACQ probe molecule of the present invention in an auxiliary agent is "soluble" or higher, preferably "slightly soluble" or higher, and more preferably "easily soluble". In other words, the solubility of the ACQ probe molecule in an auxiliary agent is 0.1 mg / mL or higher (0.01% or higher), preferably 1 mg / mL or higher (0.1% or higher), and more preferably 10 mg / mL or higher (1% or higher).

[0055] Taking the curcumin (CUR) molecule as an example, if its solubility in a particular solvent at room temperature is 0.1 mg / mL or higher (i.e., 0.01% or higher), it may be determined that its solubility in that particular solvent is "soluble" or higher. The CUR molecule may then be used as a probe to form the ACQ fluorescent probe composition of the present invention with that particular solvent. In practice, in the present invention, when CUR is prepared as a probe solution with a concentration of 1.0 mg / mL, appropriate fluorescence characteristics are observed, and CMC measurement can be performed. [Table 1]

[0056] In the fluorescent probe composition of the present invention, the ACQ probe molecules are dissolved in an auxiliary agent, and since the auxiliary agent contains a non-volatile organic solvent with a boiling point of 100°C or higher, a stable and homogenized probe solution can be formed, making it convenient for long-term storage, and no volume reduction or concentration change occurs even when stored for a long time. Furthermore, the fluorescent probe composition can be transferred and extracted just before use and used directly for measuring the CMC concentration of surfactants without volatilizing the solvent, thus shortening the operation time. In addition, if the ACQ molecules are added directly without dissolving them in an organic solvent, the amount of probe added will be inaccurate, the mixing will be non-uniform, and the accuracy of the CMC measurement results will be affected. Since the fluorescent probe composition of the present invention exists in the form of a solution, accurate measurement, transfer, and sample injection can be performed using a sample collection means (e.g., peristaltic pump, suitable pipeline), making it easier to handle.

[0057] Practical applications of the ACQ fluorescent probe composition of the present invention include using the ACQ fluorescent probe composition as a probe solution for measuring the cmc of surfactant solutions, or determining whether different types of stains on clothing can be cleaned. This provides appropriate criteria for controlling the amount of detergent dispensed into laundry equipment.

[0058] The various components contained in the ACQ fluorescent probe composition of the present invention will be described in detail below.

[0059] "ACQ molecule" The probe molecule of the present invention is a fluorescent molecule having ACQ properties.

[0060] Aggregation-caused quenching (ACQ) is a phenomenon that occurs in ACQ fluorescent molecules. Specifically, while fluorescent molecules emit light in dilute solutions, their fluorescence intensity significantly decreases or disappears when they aggregate or become solid. Common ACQ molecules include curcumin, fluorescein, rhodamine, Nile red, pyrene, and perylene. These molecules generally have a planar conjugated system and are relatively rigid. In good solvents and low-concentration solutions, the fluorescent molecules exist as independent molecules, but can emit strong fluorescence when excited by specific light. However, in poor solvents or when the concentration increases to a certain level and aggregation occurs, the intermolecular π-π interactions increase. At this point, most of the excitation energy is converted into non-radiative transitions (such as molecular thermal motion) and released, resulting in a decrease or disappearance of fluorescence.

[0061] ACQ molecules exhibit completely different fluorescence properties, such as fluorescence intensity (none / weak / strong) and characteristic wavelength (blue shift / no change / red shift in the spectrum), depending on their aggregation or dispersion state in solution and micelles. These properties allow them to be used as probes for measuring the CMC of surfactant solutions.

[0062] In this invention, hydrophobic ACQ molecules can be used for measuring CMC. These ACQ molecules are dissolved in a suitable organic solvent as a probe to form a probe solution, i.e., an ACQ fluorescent probe composition. When such a probe solution is added to water or an aqueous solution of a low concentration of surfactant, the ACQ molecules exist in aggregated form due to their hydrophobicity, and at this time there is no fluorescence or only weak fluorescence. However, when the surfactant reaches the CMC concentration and micelles are formed, the hydrophobic core of the micelles acts as a good solvent for the ACQ fluorescent molecules, promoting their dissolution. The ACQ molecules then dissolve in the micelles in the form of single molecules and emit strong, characteristic fluorescence. As a result, clear ACQ properties are observed within an appropriate concentration range.

[0063] Furthermore, partially hydrophilic or partially hydrophilic ACQ molecules can also be used for CMC measurement. For example, rhodamine B is a hydrophilic ACQ molecule that can completely dissolve in water and form a homogenized, stable solution. In aqueous solutions, low concentrations of rhodamine B disperse and emit strong fluorescence, but at very high concentrations, it aggregates and loses fluorescence. This matches the ACQ characteristic that it dissolves and disperses and emits fluorescence at low concentrations and in good solvents, but quenches in an aggregated state. The inventors speculate on the mechanism as follows: Due to its hydrophilic-hydrophobic amphiphilic structure, rhodamine B can be inserted into the fence layer of surfactant micelles and participate in micelle formation. The hydrophilic end is located in the hydrophilic surface layer of the micelle, and the hydrophobic end is held in the fence layer. An increase in local concentration causes an increase in fluorescence intensity or a shift in fluorescence wavelength, resulting in different fluorescence characteristics in systems with and without micelles. However, considering its structural characteristics and pH test results, the accuracy of the measurement results when using rhodamine B as a probe may be significantly affected by the pH of the solution.

[0064] As described above, the luminescence mechanism of the ACQ probe molecule usable in the present invention may be due to a change in fluorescence intensity accompanying the solubilization of the hydrophobic core, or it may be due to a characteristic redshift / blueshift of the emission wavelength that occurs when the amphiphilic structure of the molecule enters the fence layer or micelle. In other words, the luminescence method of the ACQ probe molecule of the present invention is due to a change in fluorescence intensity or a change in characteristic wavelength, but is not limited to these. Of these, the change in fluorescence intensity may be from no fluorescence to fluorescence or from weak to strong fluorescence, and the change in characteristic wavelength includes a change in wavelength redshift or blueshift.

[0065] In other words, the ACQ probe molecules of the present invention include ACQ molecules having a blueshift characteristic wavelength, ACQ molecules having a redshift characteristic wavelength, and ACQ molecules having a characteristic wavelength that does not change. Specific examples include pyrene, Nile Red, curcumin, coumarin, sodium 8-anilino-1-naphthalenesulfonate, N-phenyl-1-naphthylamine, rhodamine B, dancylcloride, 6-propionyl-2-(dimethylamino)naphthalene, neutral Red, fluorescein, anthracene, and lycopene. Preferably, the ACQ molecules are Nile Red, curcumin, coumarin, N-phenyl-1-naphthylamine, rhodamine B, pyrene, etc. More preferably, the ACQ molecules have a characteristic wavelength that does not change or has a blueshift characteristic, such as curcumin, Nile Red, and coumarin.

[0066] The inventors first conducted a preliminary screening of several common fluorescent probe molecules, including the following substances, based on the requirements for the availability and low toxicity of the fluorescent reagents: PYR (Pyrene): A molecule with fluorescent properties, always used in the study of biomarkers and fluorescent probes. NR (Nile Red): A common lipophilic fluorescent dye, always used for staining and labeling lipid substances such as lipids. CUR (Curcumin): A versatile natural fluorescent probe and drug molecule. C480 (Coumarin): A common (heavy) metal detection fluorescent probe. ANS (8-anilino-1-naphthalenesulfonate sodium): A fluorescent probe widely used in the study of changes in protein structure and three-dimensional structure. NPN (N-phenyl-1-naphthylamine): A common fluorescent dye with applications in a wide range of fields, including biomedicine, materials science, and chemical analysis. RhB (Rhodamine B): A common cell fluorescent dye for laboratory use.

[0067] The chemical structures of these fluorescent molecules are shown below. [ka]

[0068] To determine whether these fluorescent probe molecules could form a stable probe solution, the inventors dissolved these probe molecules in N-methylpyrrolidone (NMP). As a result, all of them formed a clear solution and emitted fluorescence of various colors in solution.

[0069] Using the probe solution prepared as described above, a series of detergent solutions prepared at various concentrations (including a directly prepared "Supreme Cleaning" (i.e., Supreme Biotechnology (cleaning type)) solution and "Supreme Whitening" (i.e., Supreme Biotechnology (whitening type)) laundry water containing a fluorescent whitening agent) were tested. Specifically, an appropriate wavelength was selected based on the spectrofluorometer measurement results to create a fluorescence response value-concentration curve plot with detergent concentration on the x-axis and fluorescence intensity on the y-axis. The transition interval where the curve shifts from a plateau to an upward region was determined visually, corresponding to the range of CMC measurements. The results are shown in Table 2 below.

[0070] The meanings of the abbreviations in Table 2 are as follows: PYR is pyrene, ANS is sodium 8-anilino-1-naphthalenesulfonate, NPN is N-phenyl-1-naphthylamine, and C480 is coumarin 480 (density 1.3 g / cm³). 3 ) is CUR stands for curcumin, and NR stands for Nile Red. " / " indicates not measured. The meaning of the "Overall Evaluation" column in the table is as follows: × means not measurable, △ means usable but with large errors or susceptibility to interference, ○ means favorable, and ◎ means even more favorable.

[0071] Furthermore, Table 2 summarizes the spectral parameters of various probes, the numerical values ​​of the solubility parameter δ, the changes in characteristic wavelength, and the comparative results of CMC measured based on the surface tension method. [Table 2]

[0072] As shown in Table 2, the characteristic wavelength of the fluorescent probe molecule may change near the CMC of the surfactant, and Δλ = λ(surfactant concentration ≥ CMC) - λ(surfactant concentration<cmc)であり、△λ> If Δλ is 0, it is redshift (i.e., the wavelength increases); if Δλ < 0, it is blueshift (i.e., the wavelength decreases); and if Δλ = 0, the wavelength remains unchanged.

[0073] As is clear from the results in Table 2, in probe composition systems where the auxiliary agent is NMP, the fluorescence response value of the water-soluble ANS probe and the detergent concentration show an almost linear relationship, and there is no clear inflection point, making it difficult to measure cmc. PYR and NPN can measure cmc as probes in the directly prepared "Supreme Cleaning" solution, and the deviation of the measurement results is small, but PYR shows a large deviation in the measurement results in the "Supreme Whitening" wash water actually used due to the influence of various factors. NPN is greatly affected by the fluorescent whitening agent when measured in the "Supreme Whitening" wash water, making it impossible to measure cmc. The overall evaluation results show that the four fluorescent molecules C480, CUR, NR, and RhB are suitable for measuring the cmc concentration of surfactant solutions or wash water actually used in systems where the auxiliary agent is NMP, and are preferred ACQ molecules.

[0074] Furthermore, as can be seen from Table 2, the measurement results for RhB and C480 show a slightly larger deviation, and the more preferred ACQ molecules in this invention are curcumin (CUR) and Nile Red (NR). The range of cmc values ​​measured for the directly prepared "Supreme Cleaning" solution (without fluorescent whitening agents) can be verified against each other and are consistent with the results measured by the surface tension method (0.066 g / L), indicating high accuracy. In addition, in the "Supreme Whitening" laundry water containing fluorescent whitening agents that is actually used, the range of cmc values ​​measured for both is consistent with the results measured by the surface tension method (0.3 g / L), and neither is interfered with by the fluorescent whitening agent (CBS or FB-33) contained therein. The inventors speculate that the reason for this is as follows. The fluorescent whitening agent 33# (FB-33) has an Ex / Em of 370 / 430 nm, and 4,4'-bis(2-sulfonatostyryl)biphenyl disodium (CBS) has an Ex / Em of 340 / 425 nm. The emission peak of NR is 638 nm, which is outside the emission peak range of the fluorescent whitening agent, so NR is not affected. The emission wavelength of CUR is within the fluorescence emission peak range of the fluorescent whitening agent, but the response of the fluorescent whitening agent at its excitation wavelength of 430 nm is not clear. In other words, the fluorescent whitening agent does not emit fluorescence at this excitation wavelength, so interference from the fluorescent whitening agent can be avoided.

[0075] In this invention, the magnitude of molecular polarity and intermolecular forces of ACQ probe molecules are determined using the Hansen solubility parameter (HSP) δ. As can be seen from the data in Table 2, the solubility parameter δ of ACQ probe molecules that can form a stable probe solution is in the range of approximately 15 to 35. Therefore, the Hansen solubility parameter δ of ACQ probe molecules is preferably in the range of 15 to 35, and more preferably in the range of 20 to 25 from the viewpoint of accuracy of cmc measurement.

[0076] The above screening results represent only one example of the ACQ fluorescent probe compositions of the present invention. Different ACQ fluorescent probe compositions may exhibit different fluorescence and ACQ properties depending on the organic solvent used as an auxiliary agent. Therefore, the ACQ fluorescent molecules used in the present invention are not limited to RhB, C480, CUR, and NR, nor are the auxiliary agents limited to NMP. Appropriate combinations of ACQ fluorescent molecules and auxiliary agents may be screened according to specific application scenarios and needs.

[0077] "Auxiliary agent" The auxiliary agent in the ACQ fluorescent probe composition of the present invention comprises one or more non-volatile organic solvents, the type of which is determined mainly by its own volatility, the solubility of the ACQ molecule in the organic solvent, and its fluorescence properties.

[0078] In this invention, when the auxiliary agent contains only one type of organic solvent, the properties of the auxiliary agent (viscosity, density, flash point, etc.) refer to the properties of that organic solvent. When the auxiliary agent is a mixed solvent of multiple types of organic solvents or a mixed solvent of an organic solvent and an inorganic solvent, the properties of the auxiliary agent refer to the properties of that mixed solvent.

[0079] In conventional techniques, to measure cmc using ACQ molecules as a probe, ACQ molecules are generally dissolved in a volatile organic solvent such as methanol, ethanol, benzene, tetrahydrofuran, or dioxane beforehand, and then the organic solvent is removed before measurement. However, these organic solvents are colorless liquids with high volatility and low boiling and flash points. When preparing the probe solution of the present invention using these solvents, it is difficult to store the mother liquor for a long time after preparation, and the volume of the solution and the probe concentration tend to change.

[0080] The inventors, by studying and screening the physical properties of a series of organic solvents using curcumin (CUR) as a specific probe molecule, have identified certain organic solvents that can be used as auxiliary agents for the ACQ molecule. These organic solvents have sufficient solubility for the ACQ molecule, are not highly volatile, and can cause curcumin (CUR) to exhibit clear ACQ properties within an appropriate concentration range of a specific surfactant solution.

[0081] The parameters of the series of organic solvents investigated by the inventors, including volatility, water solubility, density, viscosity, and probe solubility, are shown in Table 3. [Table 3]

[0082] In order to form a stable probe solution that can be stored for a long period of time, the auxiliary agent in the ACQ fluorescent probe composition of the present invention must contain one or more non-volatile organic solvents.

[0083] In this invention, the volatility of organic solvents is evaluated using their boiling point. Generally, the lower the boiling point of an organic solvent, the higher its volatility. As can be seen from Table 3, volatile organic solvents commonly used in this field (such as acetone) have low boiling points and are very volatile, making them unsuitable as auxiliary agents for the stable probe solution of this invention.

[0084] As a suitable auxiliary agent, the boiling point of the non-volatile organic solvent of the present invention is specified to be 100°C or higher, preferably 120°C or higher, and more preferably 150°C or higher.

[0085] Furthermore, in order to form a uniform and clear solution and to have a sufficient probe concentration, the ACQ probe molecule of the present invention must have good solubility in organic solvents used as auxiliary agents. Preferably, the solubility of the probe is at least soluble; that is, the solubility of the probe molecule in organic solvents is preferably 0.1 mg / mL (0.01%) or higher.

[0086] When screening for appropriate organic solvents for selected probe molecules, it is difficult to perform solubility tests for each of the many available solvents. If the solubility of probes in solvents can be evaluated and predicted in advance, the time and cost required for screening auxiliary agents can be significantly reduced.

[0087] In this invention, in order to establish an internal relationship between the microstructure and macrosolubility of probe molecules, the solubility of ACQ molecules in organic solvents is evaluated and predicted using Hansen solubility parameter theory (HSP theory).

[0088] There are many methods for calculating solubility parameters, but HSP theory classifies the surface energies of the solute and solvent using three energy terms. These three energy terms are dispersion δd, polarity δp, and hydrogen bonding δh, and their units are MPa. 1 / 2 According to HSP theory, when the HSP values ​​of a solute are (δd1, δp1, δh1) and the HSP values ​​of a solvent are (δd2, δp2, δh2), the distance Ra of the Hansen solubility parameters between these solutes and solvents (abbreviated as HSP distance Ra) can be expressed by the following equation 1. Ra 2 =4(δd1-δd2) 2 +(δp1-δp2) 2 +(δh1-δh2) 2 (Formula 1)

[0089] The smaller the HSP distance Ra, the more easily the solute dissolves in the solvent. In a probe-organic solvent system, the organic solvent is the dispersion medium, and the probe molecule, as the solute, is the dispersed phase. Generally, a dispersed state is obtained when Ra ≤ 20, a moderately dispersed state when Ra ≤ 15, a highly dispersed state when Ra ≤ 10, and a very highly dispersed state when Ra ≤ 5. By comparing the Ra values ​​between the solute and different solvents, it is possible to find a solvent with similar interaction forces with the solute and obtain high solubility.

[0090] The inventors have investigated the literature-listed or calculated values ​​of solubility parameters for various organic solvents, or mixed solvents of organic solvents and inorganic solvents, using a probe molecule, namely curcumin (CUR), as an example of a solute, as well as the results of actual measurements of solubility classifications. The results are shown in Table 4-1 below. [Table 4-1] TIFF2026509034000007.tif158170

[0091] As can be seen from Table 4-1, with the exception of a very small number of nonpolar organic solvents (e.g., cyclohexane, toluene), the HSP distance Ra value is in close relation to the measured solubility category. Among these, most organic solvents or mixed solvents with an HSP distance Ra value of 17 or less have good solubility for the ACQ probe molecule (CUR), and their solubility category is soluble or better. When the Ra value is 15 or less, preferably 12 or less, the solubility of the ACQ probe molecule in the solvent predicted by the HSP distance Ra value is in closer agreement with the measured solubility category results.

[0092] Therefore, in the present invention, in order to obtain good probe solubility, the value of the HSP distance Ra between the ACQ probe molecule and the organic solvent or mixed solvent that acts as an auxiliary agent is set to 17 or less, preferably 15 or less, and more preferably 12 or less.

[0093] However, predicting solubility based solely on the HSP distance Ra can lead to certain errors. For example, the HSP distance Ra between acetonitrile and the probe molecule (16.858) is much larger than the HSP distance Ra between n-octanol and the probe molecule (3.753). However, experimental results show that acetonitrile is actually more soluble in the probe molecule than n-octanol. The reason for this is still unknown, but it is thought to be due to intermolecular forces (e.g., hydrogen bonding), polarity, or the influence of the molecular's three-dimensional structure on solubility. Therefore, we further modify the prediction results by introducing the difference Δδ of the Hansen solubility parameter δ.

[0094] According to the solubility parameter theory proposed by Hildebrand, the total δ value (abbreviated as δ) of the solubility parameter is the vector sum of three components: dispersion δd, polarity δp, and hydrogen bonding δh (see Equation 2 below). When the difference in total δ between the solute and the solution, i.e., the δ difference (Δδ), is smaller than a certain value, the solution is relatively stable, and this is the so-called mismatch theory. δ 2 =δd 2 +δp 2 +δh 2 (Formula 2)

[0095] As can be seen from Table 4-1, the total δ value of the ACQ probe molecule, CUR, is 22.579, and the total δ values ​​of most organic solvents or mixed solvents that have good solubility for CUR molecules (solubility category is soluble or higher) are in the range of 19 to 34.

[0096] Therefore, in the present invention, from the viewpoint of compatibility between the solute and the solvent, the δ difference between the total δ of the organic solvent or mixed solvent that serves as an auxiliary agent and the total δ of the ACQ probe molecules (i.e., Δδ = total δ of the auxiliary agent - total δ of the ACQ probe molecules) is preferably in the range of -3 to +12, more preferably in the range of -2.5 to +10, even more preferably in the range of -2 to +4, and even more preferably in the range of -2.0 to +2.5. Furthermore, from the viewpoint of making the formed probe solution more stable, the absolute value of the δ difference is preferably 2 or less, and more preferably 1 or less.

[0097] As can be seen from Table 4-1, firstly, acetone, acetonitrile, and ethanol should be excluded due to the requirement that the organic solvent be non-volatile (see Table 3). Next, organic solvents or mixed solvents that simultaneously satisfy the requirements that the HSP distance Ra of the organic solvent is 17 or less and the δ difference is -3 to +12 include dibutyl phthalate, n-octanol, polyethylene glycol 200 (PEG200), diethylene glycol ethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, ethyl glycolate, dimethylformamide (DMF), dimethyl sulfoxide, 1,5-pentanediol, 1,3-butanediol (1,3-BDO), ethylene glycol, and mixed solvents of these organic solvents (e.g., DGME, 1,3-BDO, NMP) in specific proportions with water. These solvents have good solubility and compatibility with the ACQ probe molecules of the present invention and can therefore be used as auxiliary agents of the present invention.

[0098] Furthermore, preferred auxiliary agents of the present invention include solvents that simultaneously satisfy the requirements of having an HSP distance Ra of 15 or less, a δ difference of -2.5 to +10, and non-volatility, such as dibutyl phthalate, n-octanol, polyethylene glycol 200 (PEG200), diethylene glycol ethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, ethyl glycolate, dimethylformamide (DMF), dimethyl sulfoxide, 1,5-pentanediol, 1,3-butanediol (1,3-BDO), and the following: These are mixed solvents with specific mixing ratios of organic solvents and water (for example, a mixed solvent of DGME and water (9:1), a mixed solvent of DGME and water (7:3), a mixed solvent of 1,3-BDO and water (8:2), etc.). More preferred additives of the present invention are solvents that simultaneously satisfy the conditions that the HSP distance Ra of the organic solvent is 12 or less and the δ difference is in the range of -2.0 to +2.5, such as diethylene glycol ethyl ether (DGME), ethylene glycol monophenyl ether, N-ethylpyrrolidone (NEP), N-methylpyrrolidone (NMP), n-butanol, a mixed solvent of DGME and water (9:1), and dimethylformamide (DMF).

[0099] The range of organic solvent types selected by the method described above closely matches the range of organic solvent types that the inventors later screened in a large number of experiments. Therefore, in this invention, it is possible to predict and screen appropriate combinations of ACQ probe molecules and auxiliary agents by utilizing the boiling point of the organic solvent and the solubility parameter δ of the probe molecule and the organic solvent.

[0100] In other words, when determining the combination of probe and auxiliary agent in the ACQ fluorescent probe composition of the present invention, first, considering the volatility of the auxiliary agent itself, many organic solvents may be selected as candidate auxiliary agents by referring to the boiling point of the solvent. Next, by prior investigation or calculation of the solubility parameters of the selected probe molecule and candidate organic solvents, the solubility and compatibility of the probe molecule with various auxiliary agents can be accurately predicted. This greatly improves the efficiency of auxiliary agent screening and reduces costs, which has significant guiding importance for the preparation of the ACQ fluorescent probe composition of the present invention.

[0101] Generally, the components of the HSP value (δd, δp, δh) for most small molecules can be found in the literature, but for polymers, calculation is generally required. The values ​​of δd, δp, and δh for different substances can be found in the Hansen Solubility Parameters: A User's Handbook and the appendix on properties of polymers, or they can be calculated using the functional group contribution method. However, since intermolecular interactions are not considered in this calculation, the δh value may be low.

[0102] When preparing the ACQ fluorescent probe composition of the present invention, the organic solvent in the auxiliary agent must not only be non-volatile and have good solubility with respect to the probe, but other properties of the auxiliary agent (e.g., viscosity, water solubility, density, flash point, etc.) must also be considered.

[0103] From the viewpoint of ensuring that the prepared probe solution is easily dispersed and homogeneous, and that it is easy to collect a sample and accurately measure it, the viscosity of the organic solvent used as an auxiliary agent is preferably 30 mPa·s or less, more preferably 25 mPa·s or less, and even more preferably 10 mPa·s or less.

[0104] For highly viscous organic solvents, viscosity can be reduced by combining multiple solvents to form a mixed solvent. For example, 1,3-butanediol (1,3-BDO) has a viscosity of 130 mPa·s, but its viscosity can be significantly reduced by preparing a mixed solvent by adding low-viscosity solvents such as NMP, DGME, or water in a certain ratio.

[0105] To ensure a stable solution system is formed, the organic solvent is preferably soluble in water. In this invention, "soluble in water" means that the organic solvent has a certain degree of solubility in water, and specifically, it may be slightly soluble, soluble, or readily soluble in water (see Table 3).

[0106] Furthermore, to ensure that the probe solution is uniformly dispersed in the surfactant solution when measuring CMC, the density of the organic solvent in the auxiliary agent is 0.9 g / cm³. 3 ~1.2g / cm 3 This is preferable, as it facilitates uniform diffusion of the probe solution in water. When the density difference between the organic solvent and water is large, diffusion tends to be non-uniform. Since the probe solution is generally added from above the liquid being measured, the density of the organic solvent may be slightly higher than that of water, but preferably it is 1.2 g / cm³. 3 The following is limited: Density of 0.9 g / cm³ 3 Lower values ​​are unfavorable for the diffusion of probe molecules in aqueous solutions because they tend to suspend more easily in the upper part of the solution.

[0107] The density of the mixed solvent may be adjusted by using a combination of multiple solvents. For example, the density of n-butanol is only 0.811 g / cm³. 3 However, by mixing it with a solvent with a high density, such as ethylene glycol or NMP, a mixed solvent with an appropriate density can be obtained.

[0108] Furthermore, from a safety standpoint, the auxiliary agent of the present invention is preferably a low-toxicity, mildly toxic, or non-toxic organic solvent with a flash point of 60°C or higher, preferably 70°C or higher, and more preferably 75°C or higher.

[0109] Similarly, the flash point of a mixed solvent may be adjusted by using a combination of multiple solvents. For example, n-butanol has good solubility in the probe (CUR) (it is somewhat easily soluble), but its flash point is low at only 37°C, while ethylene glycol has somewhat poor solubility in the probe (CUR), but its flash point is 110°C. By mixing a small amount of n-butanol with ethylene glycol (for example, 99.5% ethylene glycol - 0.5% n-butanol (v / v)), a good balance can be achieved between solubility and flash point characteristics.

[0110] As is evident from a comprehensive consideration of the various characteristic parameters of organic solvents, the auxiliary agent of the present invention is preferably one or more selected from n-butanol, ethylene glycol, NMP, NEP, DMF, DGME, ethyl glycolate, polyethylene glycol 200, 1,3-butanediol, and 1,5-pentanediol, more preferably one or more selected from n-butanol, ethylene glycol, NMP, NEP, DGME, and polyethylene glycol 200, and even more preferably NMP, NEP, DGME, or polyethylene glycol 200.

[0111] Furthermore, when the type of ACQ molecule changes, the preferred range of the corresponding auxiliary agent may also change accordingly, which, as mentioned above, is mainly determined by the degree of compatibility of the solubility parameters of both.

[0112] For example, when pyrene or rhodamine B is used as a solute, its solubility in various solvents can be evaluated and predicted using the solubility parameters in Tables 4-2 and 4-3 below. [Table 4-2] [Table 4-3]

[0113] According to Table 4-3, rhodamine B has an HSP distance Ra of 23.968 with water, yet it is "soluble" in water. The inventors speculate on the reason for this as follows: Rhodamine B itself is an ionic form of a quaternary ammonium salt, and the tertiary amine group contained therein can be protonated in aqueous solution to form hydrogen bonds, meaning there is a strong intermolecular interaction force between rhodamine B and water. However, when calculating using HSP parameters, such a strong interaction force cannot be taken into account, so the calculation results do not perfectly match the actual test results.

[0114] Although it differs from the AIE fluorescent probe compositions we have studied so far, when determining the specific combination of fluorescent molecules and auxiliary agents in the ACQ fluorescent probe composition of the present invention, the AIE fluorescent probe composition emphasizes the hydrophilic-hydrophobic amphiphilic molecular structure of the auxiliary agent, while the present invention places greater emphasis on the differences in properties such as solubility, dispersibility, and molecular polarity between the auxiliary agent and the ACQ molecule. The reason for this is thought to be as follows: AIE molecules are mostly nonpolar large molecular structures, and auxiliary agents have a hydrophilic-hydrophobic amphiphilic structure. Therefore, a hydrophilic layer is formed by adsorption to the surface of the AIE molecule by the hydrophobic part, which is advantageous for the stable dispersion of AIE molecules in aqueous systems. Consequently, in low-concentration surfactant solutions, AIE molecules exist in a dispersed state and do not emit light. However, when micelles are formed above the CMC concentration, the auxiliary agent enters the fence layer of the micelle according to the AIE molecule, aggregates, and emits light. In contrast, in the fluorescent probe composition of the present invention, the auxiliary agent has high solubility in water, so the dissolution of the auxiliary agent and ACQ molecules is in a competitive relationship between hydrophilic and hydrophobic systems. When the ACQ fluorescent probe composition is added to a surfactant solution or laundry water, the diffusion rate of the auxiliary agent is significantly faster than that of the ACQ probe molecules, and the auxiliary agent dissolves in water first, but the probe tends to aggregate in water due to its hydrophobicity. Because the auxiliary agent molecules affect the solubility and stability of the ACQ probe molecules in water only at a certain level, in low-concentration surfactant solutions, the ACQ probe molecules exist in an aggregated state and do not emit light. When the surfactant concentration exceeds cmc and micelles are formed, the auxiliary agent cannot enter the micelles according to the ACQ molecules, and the ACQ molecules enter the inside of the micelles in monomer form and emit light.

[0115] "Other ingredients" In addition to the ACQ molecule, which is the probe, and the auxiliary agent, the ACQ fluorescent probe composition of the present invention may also contain other components, such as stabilizers and preservatives, provided that they do not affect the ACQ effect.

[0116] If other components are present, the total content of the other components is preferably less than 5% by mass, and more preferably less than 1% by mass, relative to the total amount of the ACQ probe composition.

[0117] "ACQ Fluorescent Probe Composition" The ACQ fluorescent probe composition of the present invention comprises an ACQ molecule as a probe and an auxiliary agent, the auxiliary agent of which contains one or more non-volatile organic solvents.

[0118] The fluorescence emission spectrum of ACQ molecules is one of their inherent characteristics, related to the fluorescent groups they possess. However, the characteristics of this fluorescence emission (excitation / emission wavelength, fluorescence intensity, etc.) vary depending on the environment in which the molecule is located. Therefore, further investigation is needed into the fluorescence characteristics and measurability of specific combinations of ACQ molecules and auxiliary agents in actual measurement environments.

[0119] Based on the results of screening CUR and NR as specific probe compounds using the method described above, the inventors studied the solubility and fluorescence properties of these two probe molecules in various solvents. They also investigated the possibility of actually using an ACQ fluorescent probe composition containing the probes and auxiliary agents as a probe solution to measure the cmc of surfactant solutions. The results are shown in Table 5. [Table 5] TIFF2026509034000011.tif225170

[0120] In Table 5, "UV irradiation results" refers to the fluorescence emission observed when the target probe molecule (e.g., 1 mg / mL CUR or 1 mM NR) is dissolved in the corresponding solvent, and the clear mother liquor or supernatant of the mother liquor is collected and irradiated with a UV lamp. Since no surfactants are present, these results can, from a macroscopic perspective, reflect 1) the solubility of the probe, 2) the homogeneity / dispersibility of the probe, 3) whether there is an interaction between the probe and the solvent, and 4) the change in the wavelength of the probe's fluorescence emission peak.

[0121] Generally, probe molecules can emit strong fluorescence only if they have a certain degree of solubility in the auxiliary agent, good homogeneity / dispersibility, and little to no interaction with the solvent. The change in fluorescence color reflects the wavelength shift at the maximum emission intensity of the corresponding probe.

[0122] Therefore, the "UV irradiation results" in Table 5 provide a supplementary explanation of the probe's dispersibility in the solvent from a macroscopic perspective. For example, the probe molecules CUR and NR emit strong fluorescence in good solvents but are non-fluorescent or emit weak fluorescence in poor solvents. It also reflects the interaction between the solvent and the probe. For instance, the benzene ring structure of ethylene glycol monophenyl ether may cause phenomena such as aggregation quenching of the probe molecules CUR and NR, resulting in a significant decrease in fluorescence intensity.

[0123] Furthermore, the results in the "CMC Measurement" column in Table 5 indicate the possibility of using the composition (probe solution) containing the probe molecule and solvent for actual CMC measurement. Specifically, the corresponding probe-solvent composition is added to surfactant solutions of different concentrations, and the fluorescence is measured on the homogeneously dispersed probe-solvent-surfactant aqueous solution mixture to determine whether there is a difference in fluorescence, thereby determining whether CMC measurement can be achieved.

[0124] As can be seen from the results in Table 5, when using n-butanol, n-octanol, dibutyl phthalate, NMP, polyethylene glycol 200, DGME, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol as solvents, both CUR and NR emit strong or weak fluorescence in the solvent, clearly indicating that the probe molecules have a certain degree of solubility and dispersibility in the above solvents. On the other hand, when using ethylene glycol as the solvent, CUR partially dissolves but the fluorescence intensity is weak, and the solubility or dispersibility of NR is poor, indicating that it is poorly soluble and hardly emits any fluorescence visible to the naked eye.

[0125] Furthermore, while ethylene glycol monophenyl ether satisfies the requirement of being a low-volatility organic solvent with good probe solubility, when probe molecules dissolve in ethylene glycol monophenyl ether, they emit only very weak fluorescence. This is thought to be because the benzene ring structure of the solvent molecule itself creates an interaction force with the probe molecule, reducing the probe molecule's ability to convert excitation light into fluorescence, thus resulting in only very weak fluorescence being generated in that solvent.

[0126] Furthermore, CMC measurement tests were performed on the same detergent ("Zhizun Biotechnology" laundry solution) using various single or mixed solvents listed in Table 5. As is clear from the results, in all cases, the probe compositions prepared with the three solvents n-octanol, dibutyl phthalate, and ethylene glycol monophenyl ether underwent oil-water separation of the laundry aqueous solution and the probe solution during the test process, and the probes tended to dissolve more in the organic solvent layer than in the aqueous phase. When ethylene glycol monophenyl ether is used as an auxiliary agent, CMC measurement of the detergent can be achieved even if separation occurs because ethylene glycol monophenyl ether is partially soluble in water. However, since n-octanol and dibutyl phthalate are insoluble in water (see Table 3), clear oil-water separation occurred after adding the prepared probe solutions to the surfactant solution. Because n-octanol has a low density, the probe composition was in the upper layer, and because dibutyl phthalate has a high density, the probe composition was in the lower layer. As a result of oil-water separation, a homogeneously dispersed solution could not be obtained, and since there was no clear difference in fluorescence between the aqueous and organic phases of surfactant solutions of different concentrations, CMC could not be measured. This indicates that the water solubility of the auxiliary agent also significantly affects the measurement results of the probe composition.

[0127] Furthermore, as can be seen from the measurement results in Table 5, when CUR and NR are used as probes and n-butanol, ethylene glycol, NMP, polyethylene glycol 200, DGME, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol are used as auxiliary agents, adding the probe solution to an aqueous solution of a surfactant produces a detectable change in the fluorescence signal in all cases. In other words, any of the above organic solvents can be used alone as an auxiliary agent to monitor CMC relatively accurately.

[0128] In addition to properties such as the non-volatility of organic solvents, probe solubility, water solubility, and CMC-monitored fluorescence characteristics, other physical and chemical properties of the probe solution, such as viscosity, density, flash point, and safety, must be comprehensively considered.

[0129] For example, ethylene glycol, 1,3-butanediol, and 1,5-pentanediol have properties such as low volatility and good water solubility, but their high viscosity and low fluidity are unfavorable for the dissolution, addition, and diffusion of probes. Due to the low density of n-butanol, when a probe-butanol composition is added to a laundry aqueous solution, diffusion is poor or slow, resulting in a non-uniform distribution of the probe in the solution. Ethyl glycolate satisfies the requirements of low volatility of the organic solvent and probe solubility, and the probe solution emits strong fluorescence, but its low flash point (62°C) means that there are many considerations regarding the storage and safety of the probe composition.

[0130] Considering a comprehensive set of parameters, including the physical and chemical properties of each solvent and the solubility of the probe, NMP, NEP, polyethylene glycol 200 (PEG200), and DGME are the preferred solvents obtained through screening. They can be used to directly dissolve the probe molecule and allow for accurate monitoring of the CMC.

[0131] Furthermore, when using Nile Red (NR) as the ACQ molecule, the inventors have obtained similar screening results regarding the preferred type of auxiliary agent.

[0132] Specifically, the most preferred probe + additive combinations for the ACQ fluorescent probe composition of the present invention are CUR+NMP, CUR+DGME, CUR+NEP, CUR+PEG200, NR+NMP, NR+DGME, NR+NEP, and NR+PEG200.

[0133] Furthermore, for single solvents that have defects in certain properties, such as n-butanol, ethylene glycol, ethyl glycolate, 1,3-butanediol, and 1,5-pentanediol, these defects can be resolved by mixing them with solvents that have different properties. For example, organic solvents with high viscosity, such as ethylene glycol, butanediol, and pentanediol, may be mixed in a certain ratio with a solvent that has good probe solubility and low viscosity, such as n-butanol or DGME. For organic solvents with low density, such as butanol, mixing them with a solvent with high density, such as ethylene glycol or NMP, can yield a mixed solvent with an appropriate density, thereby accelerating the diffusion rate of the probe in the aqueous solution used for washing.

[0134] Similarly, the preferred solvents described above may be further mixed with other different types of solvents in different ratios to improve the various physical and chemical properties, safety, stability, cost, and other usability characteristics of the solvent in the probe composition.

[0135] In other words, according to the research results of the present invention, a preferred combination of probe molecule and auxiliary agent can be obtained directly or by appropriately adjusting it, based on the various properties inherent in the probe molecule and the organic solvent itself.

[0136] Furthermore, the inventors have found that the amount of organic solvent added to the probe solution, mainly the amount of organic solvent in the probe solution, has a certain effect on the CMC measurement results. From the viewpoint of reducing the amount of organic solvent used in the probe solution and mitigating its effect on the CMC measurement results, it is preferable to reduce the amount of organic solvent added to the surfactant solution. In addition, in order to ensure good fluorescence sensitivity and ease of detection, it is necessary to ensure a certain amount of additive in the surfactant solution so that the probe solution reaches a sufficient probe operating concentration.

[0137] As shown in Table 6, the inventors investigated the effect of different solvent addition amounts on the CMC test results in the probe solution (CUR-NMP). Here, the test solution was "Zhizun Biotechnology (whitening type)" detergent solution (ZZLB), and a customized fluorescence photoelectric detector (CD detector) was used.

[0138] Furthermore, since a single organic solvent composition system of CUR-NMP is used, the amount of solvent added in Table 6 may be considered the same as the amount added in the probe solution. To determine the cmc value, the fitting linear intersection method is used. That is, based on the measurement results of the spectrofluorometer, an appropriate wavelength within the corresponding fluorescence emission peak range is selected, a fluorescence response value-concentration curve is created with detergent concentration on the x-axis and fluorescence intensity on the y-axis, and linear regression fitting is performed on the plateau region and rising region of the curve, respectively, to find the intersection of the two fitting lines, and the surfactant concentration on the x-axis corresponding to that intersection is the cmc concentration (measured value). [Table 6]

[0139] The CMC equivalent values ​​in Table 6 are the actual CMC concentrations estimated after considering the dilution effect of the solvent on the surfactant. Specifically, the CMC equivalent concentration = CMC measured concentration / (1 + volume of added solvent / volume of sample), where the volume of added solvent corresponds to the volume of the added probe solution, and the volume of the sample is the volume of the surfactant solution being measured.

[0140] Since the probe solution is formed by dissolving probe molecules in a solvent, the amount of solvent added can be considered approximately the amount of probe solution added. When the amount of probe solution added is small, the CMC equivalent value in the table is the same as the actual CMC measurement value. However, when the amount of probe solution added is very large, the solvent in that solution is clearly diluted relative to the surfactant concentration of the original solution being measured, so conversion processing of the original data as a measurement result is necessary. For example, when the amount of probe solution added is 5000 μL, the CMC equivalent value is 3.341 = 5.012 / (1 + 5 mL / 10 mL). In other words, the CMC equivalent concentration takes into account the change in solution volume and the dilution of the surfactant concentration caused by the addition of the probe solution. When the amount of probe solution added is small, the dilution effect can be ignored.

[0141] As shown in Table 6, when using a probe solution in which the probe-auxiliary agent is CUR-NMP, the amount of solvent added to the solution under test in 10 mL of surfactant solution is preferably not more than 1000 μL (i.e., not more than 10%), and more preferably not more than 400 μL (i.e., not more than 4%). In this case, the range of CMC measurements in the table is relatively stable and close to the CMC measurements obtained using a spectrofluorometer (0.100 g / L) and the CMC values ​​obtained by the surface tension method (0.067 g / L). Similar results can be obtained with different solvent addition amounts when using other organic solvents.

[0142] Therefore, in the present invention, in order to reduce the influence of organic solvents in the auxiliary agent on the CMC measurement results, the amount of probe solution (also called probe mother liquor) added to the solution under test is kept low, and its preferred range may be set by referring to the preferred range of solvent addition. That is, for 10 mL of surfactant solution, the upper limit of the amount of probe mother liquor added is preferably 1000 μL or less, and more preferably 400 μL or less. The lower limit of the amount of probe mother liquor added is determined based on the sensitivity of the probe and the concentration of the probe in the probe mother liquor, for example, 1 μL or more, preferably 10 μL or more, and more preferably 20 μL or more, and the lower limit of the amount of probe mother liquor added may be appropriately lowered when the probe concentration is high. When a mixed solvent is used, the amount of probe mother liquor added may be applied after being converted based on the proportion of the mixed solvent, and it satisfies the preferred range of organic solvents, that is, solvent addition amount = proportion of organic solvent in probe mother liquor × amount of probe mother liquor added.

[0143] In this case, the CMC measurement results obtained using the customized miniaturized fluorescence photoelectric detector (CD detector) shown in Table 6 are in the range of 0.084 g / L to 0.107 g / L, which is close to the measured value (0.100 g / L) obtained using the spectrofluorometer in the example below. Here, the customized miniaturized detector is a fluorescence response value detector under a specific single wavelength, while the spectrofluorometer can scan the entire wavelength range of the fluorescence spectrum. Both are fluorescence detection instruments, but the former is smaller in volume, easier to operate, and has a faster detection speed, while the latter provides more spectral information and higher accuracy. Both can be used for various tests by adjusting the spectral parameters according to the corresponding fluorescence probe.

[0144] Furthermore, as can be seen from Table 6, the CMC test value measured by fluorescence spectroscopy using a CD detector or spectrofluorometer is slightly higher than the value measured by surface tension spectroscopy (0.067 g / L). The inventor speculates on the reason for this as follows: When the surfactant is adsorbed at the gas-liquid interface and becomes saturated, aggregates begin to form in the solution. The CMC measured by surface tension spectroscopy corresponds to the concentration when aggregates have just formed, while the CMC measured by fluorescence spectroscopy corresponds to the concentration when a large number of aggregates have formed in the solution and fluorescent molecules present in micelles in the form of single molecules are emitted. When micelles begin to form, the number of probe molecules may be greater than the number of micelles, so each micelle may contain one or more probe molecules. Therefore, the CMC result measured by fluorescence spectroscopy will be slightly higher than the CMC result measured by surface tension spectroscopy.

[0145] When the amount of NMP added is higher than the above range (1000 μL), the cmc measurement result is clearly higher, and the inventors speculate on the mechanism as follows: NMP is a short-chain hydrophilic molecule, and in the process of micelle formation, the hydrophilicity of NMP affects the hydrophobic interactions between surfactant molecules, and further affects micelle formation. When the NMP concentration is low, the effect on the cmc measurement result is small, but when the NMP concentration increases and exceeds a certain value, the degree to which it reduces hydrophobic interactions increases significantly, and the cmc value increases further.

[0146] Based on the above inference, the inventors also used the surface tension method to observe the change in the cmc value of CUR-NMP at different amounts of NMP solvent (without the probe) added to the probe solution. As shown in Table 7, when the amount of NMP added was less than 10%, the measured cmc value was affected to some extent, but the effect was small, and when it was less than 4%, the measured cmc value was hardly affected. This result is in close agreement with the measurement results of the fluorescence spectroscopy method and is in line with the inference. [Table 7]

[0147] Furthermore, the inventors have found the following: The probe operating concentration in the liquid being measured also has some influence on the CMC measurement results. In this specification, the probe mother liquor concentration refers to the concentration of the probe in the probe solution, while the probe operating concentration refers to the probe concentration after the probe mother liquor containing the probe has been added to an aqueous surfactant solution or wash water.

[0148] The inventors conducted experiments on the effect of probe operating concentration on cmc measurement results, using a CUR-DGME probe composition as an example, and the results are shown in Table 8. [Table 8]

[0149] As shown in Table 8, the probe operating concentration is closely related to the measured CMC concentration. When the probe operating concentration in the solution under test is lower than 10 μg / mL, the difference between the CMC measurement and the value measured by the surface tension method is small. However, as the probe operating concentration increases, a large deviation occurs in the CMC measurement results when the CUR operating concentration exceeds 20 μg / mL. The reason for this is thought to be as follows: When the probe concentration is very high, fluorescence quenching due to probe aggregation occurs at the inflection point of the curve diagram corresponding to the formation of micelles, and the second plateau region after the rising region is not observed within the original concentration range. As a result, the CMC measurement result becomes significantly larger.

[0150] The inventors speculate on the mechanism as follows: CUR is a hydrophobic ACQ molecule and emits fluorescence only when dissolved in a good solvent. At low CUR operating concentrations, CUR enters micelles as single molecules, dissolves, and emits fluorescence. However, as the CUR operating concentration increases, the proportion of CUR entering micelles as single molecules decreases, while the proportion entering micelles as aggregated CUR molecules increases. Therefore, fluorescence is not evident at the cmc concentration. Fluorescence becomes detectable only when the number of micelle molecules increases further, promoting the entry of more CUR molecules into micelles in single-molecule form. Consequently, if the CUR operating concentration is too high, the measured cmc value increases.

[0151] As can be seen from a comparison of the measurement results of the surface tension method and the fluorescence spectroscopy method, the probe operating concentration used for the target liquid to be measured, which is the detergent solution or laundry water, may be 0.04 μg / mL or higher, but not exceeding 20 μg / mL, and preferably not exceeding 10 μg / mL. Therefore, the range of the probe operating concentration is preferably 0.04 μg / mL to 10 μg / mL, more preferably 0.4 μg / mL to 6 μg / mL, and particularly preferably 0.8 μg / mL to 4 μg / mL.

[0152] The ACQ fluorescent probe composition of the present invention can be stored for a long time as a stable probe solution, and after adding the sample to be measured, the cmc can be accurately measured without the solvent volatilizing. This eliminates the step of waiting for the organic solvent to volatilize, greatly improving ease of use in real-world scenarios and meeting the actual needs for ACQ fluorescent probes in application fields such as the measurement of the cmc of surfactant solutions.

[0153] (Method for measuring CMC of surfactant solutions) When using the ACQ fluorescent probe composition of the present invention, it can be directly used in the form of a stable solution to measure the cmc concentration of a surfactant solution.

[0154] The method for measuring the CMC of a surfactant solution according to the present invention is characterized by the following: A solution preparation step for preparing a series of surfactant solutions of different concentrations, A probe addition step involves adding a fixed amount of probe solution to each of the aforementioned surfactant solutions, A detection step involves detecting the fluorescence response value of each surfactant solution using a detection means, The determination step includes creating a fluorescence response value-concentration curve diagram having at least a first plateau region and an upward region based on the results obtained in the detection step, and determining the concentration corresponding to the inflection point where the fluorescence response value changes from the first plateau region to the upward region as the cmc of the surfactant solution. The probe solution is the ACQ fluorescent probe composition of the present invention.

[0155] In a fluorescence response value-concentration curve diagram with the concentration obtained in the determination step on the x-axis and fluorescence intensity or voltage value on the y-axis, detergent solutions to which the ACQ fluorescent probe composition of the present invention has been added typically do not emit fluorescence or the fluorescence intensity is very weak in the low concentration range, and are maintained in a stable plateau region (also called the first plateau region). This indicates that the ACQ probe molecules are aggregated with each other in the aqueous system and therefore do not emit fluorescence or emit weak fluorescence. As the detergent concentration increases to a certain value (cmc), the fluorescence intensity clearly begins to increase. At this point, micelles of the detergent begin to form, and the ACQ probe molecules are transferred from the aqueous solution to the hydrophobic core of the micelles. Because it is a good solvent environment, the probe molecules can exist individually, thereby emitting fluorescence. As the number of micelles increases, the fluorescence intensity of the probe also increases continuously, and the fluorescence curve rises rapidly. When all the fluorescent probe molecules exist in the form of single molecules in micelles or surfactant aggregates, the fluorescence intensity returns to a stable state (second plateau region).

[0156] In the fluorescence response value-concentration curve diagram, a second plateau region located after the rising region is not always present, and this is related to the relative relationship between the number of fluorescent probe molecules and the number of micelles. However, the plateau region located before the rising region (first plateau region) and the concentration corresponding to the inflection point of the rising region are always the concentration at the very beginning of micelle formation (i.e., cmc). Therefore, if the inflection point where the above-mentioned fluorescence response value (e.g., fluorescence intensity or voltage value) changes from a plateau region to a rising region can be detected by the detector and transmitted to the determination means, the concentration corresponding to the inflection point can be determined by the determination means as a cmc measurement value.

[0157] The inflection point in the change in fluorescence response value may be determined by the fitting line intersection method or the inflection point determination method. The fitting line intersection method involves finding the intersection point of the fitting line in the plateau region and the fitting line in the rising region in the obtained fluorescence response value-concentration curve diagram, and setting the concentration of the detergent solution corresponding to that intersection point as cmc (see Figure 2). The inflection point determination method involves judging the trend of the change in fluorescence intensity at two data points before and after in the obtained fluorescence response value-concentration curve diagram, directly determining the inflection point based on the phenomenon that the change in fluorescence intensity at the later data point is clearly greater than the change in fluorescence intensity at the earlier data point, and setting the concentration of the detergent solution corresponding to that inflection point as cmc (see Figure 3).

[0158] While determining CMC using the inflection point method is relatively easy, the accuracy of CMC measurement depends on the set interval of the measurement concentration. When the concentration interval is very large (few data points for measurement concentration), accuracy decreases and errors become large. On the other hand, the fitting line intersection method creates a fitting line by combining multiple sets of data and finds the intersection point, resulting in higher stability and accuracy of CMC measurement. Therefore, it is preferable to determine CMC using the fitting line intersection method.

[0159] The surfactant solution of the present invention contains at least one of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. More preferably, the surfactant contains at least anionic surfactant and / or nonionic surfactant.

[0160] Examples of anionic surfactants include alkyl carboxylate type, alkyl sulfate type, alkyl sulfonate type, alkyl ether sulfate ester type, and phosphate type surfactants.

[0161] Examples of nonionic surfactants include alkyl glucosides, alkyl alcohol ether glucosides, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, alkylamine oxides, alkylamidopropylamine oxides, and fatty acid alkanolamides.

[0162] The above-mentioned surfactants may be used individually or in combination of two or more. Furthermore, the surfactant solution may also contain fluorescent whitening agents or the like.

[0163] Furthermore, the detection means used in this invention include a conventional spectrofluorometer and a fluorescence photoelectric detector (abbreviated as CD detector) customized for the spectral characteristics of a specific ACQ molecule. The excitation wavelength of the spectrofluorometer may be set to any wavelength within the fluorescence excitation peak wavelength range corresponding to the probe molecule, and the emission wavelength may be selected to any wavelength within the fluorescence emission peak wavelength range. Based on the fluorescence intensity or the fluorescence voltage response curve, measurement of detergent cmc can be achieved.

[0164] Customized fluorescence photoelectric detectors and conventional spectrofluorometers differ in terms of cost, accuracy, size, speed, and modularity. Spectrofluorometers offer high accuracy and the ability to distinguish between red and blue shifts, but they are expensive, large, and have limited applicability. On the other hand, customized detectors can detect only the target wavelength and cannot distinguish between red and blue shifts, but they are smaller in volume, have a faster detection speed, are modular, and offer greater applicability.

[0165] In this specification, when measuring using a spectrofluorometer, "fluorescence response value" in the fluorescence response value-concentration curve diagram refers to fluorescence intensity, and when measuring using a CD detector, "fluorescence response value" refers to voltage value.

[0166] The fluorescence photoelectric detector used in this invention is one of the following: 1) The light source includes an excitation filter (430 nm), a dichroic mirror, and an emission filter (495 nm). The light source has a peak wavelength of 430 nm, a bandwidth of 420 nm to 440 nm, an operating current of 0.02 A, an operating voltage of 5 V, and the detector's compatible wavelength range includes at least 480 nm to 510 nm. 2) The light source includes an excitation filter (550 nm), a dichroic mirror, and an emission filter (638 nm), with a peak wavelength of 550 nm, a bandwidth of 540 nm to 560 nm, an operating current of 0.02 A, an operating voltage of 5 V, and a detector capable of handling wavelengths including at least 620 nm to 650 nm.

[0167] The above-mentioned fluorescence photoelectric detectors are customized for the fluorescence spectral characteristics of the ACQ probe molecules of the present invention, and specifically correspond to two types of ACQ molecules, CUR and NR. Test results show that both types of CD detectors have good responsiveness and sensitivity.

[0168] Furthermore, in this invention, steps such as preparing the probe composition, preparing the detergent solution to be measured and the wash water, adding the probe, detecting fluorescence, and determining the CMC value may all be realized by high-precision measuring equipment (sensor, peristaltic pump, solenoid valve) and automatic control.

[0169] For example, the probe composition mother liquor can be prepared in advance using an electronic balance and a volumetric flask, or the probe can be quantitatively measured using a pressure sensor, and then the solvent can be pumped with a peristaltic pump to prepare a probe composition mother liquor of 0.001 mg / mL to 100 mg / mL. Different concentrations of the detergent solution / wash water to be measured can be prepared by pumping different amounts of detergent and water using a peristaltic pump. The predetermined amounts of the detergent solution / wash water to be measured and the probe composition mother liquor can be transferred and mixed using a peristaltic pump, and the amount of organic solvent added to the wash water to be measured can be controlled so as not to exceed 10%, and the probe operating concentration can be controlled so as not to exceed 20 μM. A photoelectric sensor can be used to detect changes in the fluorescence response value, and automatic judgment and measurement control can be performed based on the response value result, and finally the CMC value measurement result of the detergent can be output.

[0170] Furthermore, improvements may be made to enhance the convenience of the qualitative determination of CMC. For example, when the CMC measurement method of the present invention is used to qualitatively determine whether the detergent in the liquid being measured has already reached the CMC value, a threshold corresponding to the CMC value (the threshold concentration being equal to or greater than the CMC value concentration) can be set based on the measured data. If the measurement result is lower than the threshold, it is determined that the CMC value has not been reached, and if the measurement result is equal to or greater than the threshold, it is determined that the CMC value has already been reached or exceeded. When used in the laundry field, the threshold may be set based on the purpose of washing, the level of a predetermined detergent concentration, a specific washing scenario, etc.

[0171] (Method for determining the concentration of dirt removal) In the field of laundry, the criteria for setting the amount of detergent to be used are related not only to the cost-effectiveness of the detergent, i.e., the cleaning efficiency, but also to the degree of stain removal, i.e., the cleaning effect. According to numerous studies by the inventors, the required detergent concentration differs depending on the type of stain to be cleaned, and in this specification, the minimum concentration required to clean clothes with different types of stains is called the "stain removal threshold concentration C t " is called ("wash threshold concentration C t " or "Threshold concentration C t The fluorescence response value corresponding to the threshold concentration is called the "dirt cleaning response threshold S0" (sometimes abbreviated as "cleaning response threshold S0" or "response threshold S0"). Generally, the dirt cleaning threshold concentration C t This is above the critical micelle concentration (cmc) of the wash water.

[0172] Based on the principles of laundry, stains are generally classified into three types: oil stains, pigment stains, and invisible stains. Oil stains include, but are not limited to, stains primarily composed of animal or vegetable oils or mineral oils, such as collar stains, food-derived oil stains, and cosmetic-derived oil stains. Pigment stains include, but are not limited to, various colored stains, such as blood stains, fruit-derived stains, yellowing due to deterioration, pigment stains, and dye stains. Invisible stains include stains that are difficult to see, such as milk stains, saliva stains, and stains from porridge, and generally consist of protein-derived stains and starch-derived stains.

[0173] In this invention, different stain cleaning threshold concentrations C are used for three types of stains: oil stains, pigment stains, and invisible stains. t It is also possible to set this, and in actual washing by a washing machine, if it is detected that the concentration of detergent put into the wash water has already reached or exceeded the above-mentioned dirt cleaning threshold concentration, it may be considered that the wash water at that concentration can clean dirty clothes, and the detergent concentration at this time may be determined to be the "dirt cleaning concentration".

[0174] Therefore, in the stain cleaning concentration determination method of the present invention, it is possible to determine whether the measured concentration of the wash water can clean clothes based on whether it has reached or exceeds a preset cleaning threshold concentration corresponding to different types of stains. Here, the preset cleaning threshold concentration is CMC or higher.

[0175] The present invention's method for determining the concentration of dirt in cleaning is: A solution preparation step involves adding a predetermined amount of detergent to a washing machine containing a predetermined amount of water and clothes, stirring to mix uniformly, and then obtaining wash water. A sample collection step involves taking a sample from the aforementioned wash water and adding a small amount of probe solution to obtain the wash water to be measured. A detection step of detecting the fluorescence response value S of the washing water to be measured using a detection means, A determination step in which, based on whether the detected fluorescence response value S has reached or exceeds a preset washing response threshold S0, it is determined whether the detergent concentration of the measured washing water is a dirt-cleaning concentration, and if it has not reached the preset washing response threshold S0, the determination result is "no", and if it has already reached or exceeded the preset washing response threshold S0, the determination result is "yes", A control step that controls the number of times the detergent is added in the solution preparation step based on the determination result of the determination step, comprising: if the determination result is "no", continuing to add a second predetermined amount of detergent in the solution preparation step, then performing the subsequent sample collection step, detection step and determination step, and if the determination result is "yes", stopping the addition of the detergent, outputting the determination result, or starting the washing equipment to continue washing.

[0176] Here, the probe solution may be the ACQ fluorescent probe composition of the present invention.

[0177] The wash response threshold S0 set in the above determination step may be a fluorescence response value corresponding to the cmc of the wash water, and the wash threshold concentration C of the wash water may be tThe corresponding fluorescence response value may also be used.

[0178] The CMC of the washing water may be measured in advance using the CMC measurement method of the present invention. Alternatively, the stain cleaning concentration determination method of the present invention may be used to repeat the steps from the solution preparation step to the measurement step multiple times, create a fluorescence response value-concentration curve diagram based on the results obtained in the detection step, and determine the concentration corresponding to the inflection point where the fluorescence response value changes as the CMC.

[0179] Dirt cleaning threshold concentration C t This can also be determined by the effectiveness of actual washing in a washing machine; that is, by actually washing soiled clothes in a washing machine using wash water of a series of detergent concentrations, the minimum concentration at which a good cleaning effect is confirmed is determined as the dirt cleaning threshold concentration. Alternatively, after measuring the cmc of the detergent solution, the dirt cleaning threshold concentration C can be determined. t You may set this to a fixed value equal to or greater than the CMC concentration.

[0180] In this invention, a fluorescence response value-concentration curve diagram is created based on the detection results of the detection step, and this curve diagram generally includes two plateau regions and an upward region between them. Considering the washing effect and the cost-effectiveness of the detergent, the stain removal threshold concentration C t It is preferable to set the washing threshold concentration C within the range of the rising region of the curve diagram, that is, between the inflection point between the two plateau regions and the rising region, select any value as needed. t It is preferable to set this.

[0181] Dirt cleaning threshold concentration C tIn the settings, considering the purpose of washing, settings may be made for each load / dirt (garment load, type of dirt, amount of dirt, etc.) and each scene (household washing machine, industrial water washing machine, etc.) according to the needs of different scenes. When used in a detergent dispensing control method for washing equipment, the amount of detergent required to be added during the washing process is related to the load of the fabric being washed, the type and degree of dirt, etc. When the load on the washing equipment is high and the dirt is heavy and complex, a high threshold may be set to improve the washing rate of the clothes (for example, the fluorescence response threshold of the fluorescence photoelectric detector may be set to 0.22, and the corresponding detergent washing threshold concentration is approximately 0.45 g / L). Conversely, when the load on the washing equipment is low and the dirt is light and simple, a normal threshold may be set (the fluorescence response threshold of the fluorescence photoelectric detector may be set to 0.15, and the corresponding washing threshold concentration is approximately 0.35 g / L). This ensures the washing effect while saving on detergent usage, thereby maximizing the cost-effectiveness of detergent addition.

[0182] Considering that the CMC value of various detergents changes in different scenarios and is not a constant value, the dirt removal threshold concentration C t The cleaning threshold concentration C may be determined by cmc and the cleaning coefficient a (a coefficient without units), that is, the dirt cleaning threshold concentration C t The following equation 3 is used to determine this: C t =cmc×(1+a)(Formula 3) In Equation 3, cmc is the measured cmc of the wash water, and a is the washing coefficient, with a range of 0 ≤ a ≤ 10, preferably 0.1 ≤ a ≤ 5, and more preferably 0.15 ≤ a ≤ 3.5. Different values ​​of a are used depending on the type and degree of soiling.

[0183] Furthermore, the wash response threshold S0, which is set in advance in the above determination step, is the maximum fluorescence intensity response value (S max ) Percentage or fluorescence increment (S max -S blankThe threshold may be set by a percentage of the set percentage or incremental percentage response value, where the detergent concentration corresponding to the set percentage or incremental percentage response value is still greater than or equal to the CMC concentration. In this specification, the percentage of the maximum fluorescence intensity response value or the percentage of the fluorescence increment is called the threshold percentage β, and its unit is 100%.

[0184] For example, in industrial and household scenarios, the cleaning rate of common oil stains, pigment stains, and invisible dirt, as well as the relationship between detergent usage and the measured value (voltage value) of a customized fluorescence photoelectric detector, can be measured. The threshold percentage (β) can be arbitrarily set within the range of 0 < β < 1 (i.e., in the range of 0% to 100%, but excluding the endpoint value). In industrial laundry scenarios, considering that there are many pre-treatment steps before washing, such as detergent application and immersion of pigment stains, β can be set lower, for example, to 0.35, that is, the cleaning response threshold S0 can be set to 0.35 × S max It is also possible to set it as follows: In household laundry scenarios, there is generally no pretreatment or the treatment method is relatively simple, and household washing machines have less mechanical force than industrial washing machines. In other words, household scenarios require a higher detergent concentration than industrial scenarios to achieve the same washing effect, so β ​​may be set higher, for example to 0.55, that is, the washing response threshold S0 can be set to 0.55 × S max Alternatively, the increment of the cleaning response threshold S0 can be set to 0.2 × (S) in industrial scenarios. max -S blank Set to ) and in home use scenes 0.4×(S max -S blank You can also set it to ).

[0185] In other words, the washing response threshold S0 is determined by equation 4 or equation 5 below, S0 = β × S max (Formula 4) S0=S blank +β×(S max -S blank )(Formula 5) Here, S maxS is the maximum fluorescence intensity or maximum voltage response value of the wash water, or the second plateau value in the fluorescence response value-concentration curve diagram. blank β is the background fluorescence intensity or minimum voltage response value of the wash water, or the first plateau value in the fluorescence response value-concentration curve diagram, where β is a threshold percentage with a unit of 100% and a range of 0 < β < 1. Depending on the different types of dirt, the degree of soiling, and different application scenes of washing, β will have different values, preferably 0.1 ≤ β ≤ 0.9, and more preferably 0.2 ≤ β ≤ 0.8.

[0186] In the stain removal concentration determination method of the present invention, the amount of detergent to be added may be set as needed, according to the "first predetermined amount" and "second predetermined amount" described above. Furthermore, there are no specific provisions regarding the amount of water, the amount of laundry, the amount of laundry water sample taken, and the amount of probe solution added, and these may be set appropriately based on the needs of the actual usage scenario and the preferred range of probe operating concentration.

[0187] The ACQ fluorescent probe composition of the present invention is particularly suitable for determining whether clothes are being cleaned by comparing the relationship between the real-time concentration of detergent and the dirt cleaning threshold concentration. The reason for this is as follows: As can be seen by comparing the differences in fluorescence response value-concentration curves of ACQ probes and AIE probes, in the curve obtained using the ACQ fluorescent probe composition, the first inflection point where the plateau region becomes an upward region is cmc, and beyond cmc, the fluorescence response gradually increases until it reaches the second plateau region, making it very suitable for monitoring concentrations greater than cmc (see Figure 2). In contrast, in the fluorescence response value-concentration curve obtained using an AIE fluorescent probe composition (e.g., HPS), only the highest point of the curve corresponds to cmc, and the vertical coordinate values ​​(fluorescence intensity or voltage) below the highest point may correspond to two concentration values ​​on the horizontal axis, making it impossible to accurately monitor concentrations greater than cmc. Furthermore, in the curve obtained using the ACQ fluorescent probe composition, there is a relatively gradual change interval between the plateau regions, which is advantageous for adjusting the set value of the dirt cleaning threshold concentration.

[0188] Since the curve obtained using the ACQ probe molecule is suitable for determining the dirt cleaning concentration and adjusting the dirt cleaning threshold concentration, the ACQ fluorescent probe composition of the present invention is more advantageous than the AIE fluorescent probe composition in terms of controlling the automatic dispensing of detergent by setting and adjusting the dirt cleaning threshold concentration.

[0189] (Detergent dispensing control method) One practical application area of ​​the ACQ fluorescent probe composition of the present invention is its use in controlling detergent dispensing in automatic washing machines.

[0190] In the detergent dispensing control of an automatic washing machine, the amount of detergent required during the washing process is related to the amount of water, the load of the fabric being washed, and the type and degree of soiling. The present invention allows for the automatic determination of the required amount of detergent by adding detergent in multiple quantitative dispensing methods and measuring whether the surfactant concentration of the washing solution is greater than the CMC or greater than the washing threshold concentration.

[0191] The present invention can provide the following detergent dispensing control method. In a washing machine, a solution preparation step is performed in which a first predetermined amount of the detergent is put into the inner tub based on the weight of the laundry and the amount of water supplied, and the detergent is mixed with the water in the inner tub and stirred to obtain washing water or a detergent solution. A sample collection step of taking a predetermined amount of the wash water or detergent solution as a sample from the inner tub, The extraction step involves taking out a small amount of probe solution and adding it to the sample, A mixing step of mixing the sample and the probe solution to obtain the liquid to be measured, A detection step which involves detecting the fluorescence response value of the liquid to be measured and outputting a detection signal S, A step of receiving the detection signal S and determining whether the detergent concentration of the liquid to be measured has reached a critical micelle concentration or a preset washing threshold concentration based on whether the detection signal S has reached or exceeds a preset response threshold S0, wherein the step of determining whether the washing threshold concentration is equal to or greater than the critical micelle concentration, The control step includes controlling the subsequent addition of the detergent based on the determination result of the determination step, and if the determination result is that the critical micelle concentration or a preset cleaning threshold concentration has not been reached, the solution preparation step continues to add a second predetermined amount of the detergent to the inner tank, and if the determination result is that the critical micelle concentration or a preset cleaning threshold concentration has already been reached, the addition of the detergent is stopped. The detergent dispensing control method is characterized in that the probe solution may be the ACQ fluorescent probe composition of the present invention.

[0192] In order to determine the detergent dispensing control, it is necessary to output the fluorescence intensity F of the wash water detected by the fluorescence detector in the detection step as a detection signal S. The detection signal S is a voltage signal corresponding to the fluorescence intensity F of the wash water at a specific wavelength, and this detection signal S is output to the following determination step and control step.

[0193] A series of solutions to be measured, including detergents whose concentration gradually increases in multiple sample cells or a single sample cell, may be prepared in advance, or a sample of wash water may be taken directly from the inner tub of the washing machine in real time while the machine is operating and washing is being performed and added to the sample cell. The detection signal corresponding to the inflection point where the plateau region of the detected curve changes to an upward region may be set as the response threshold S0 corresponding to the critical micelle concentration cmc, or, depending on the situation, a specific dirt cleaning threshold concentration C may be set in the plateau region of the curve. t Select the relevant dirt cleaning threshold concentration C t The detection signal corresponding to the cleaning threshold concentration C t Corresponding response threshold S0(S t It may also be set to (sometimes called) the dirt cleaning threshold concentration C. t This is equal to or greater than the critical micelle concentration (cmc).

[0194] Next, in the above determination step, if the detected signal S is equal to or higher than the preset response threshold S0, the determination result is yes (detergent concentration C is already cmc or washing threshold concentration C thas reached), and at this time, stop continuously adding the detergent. When the detection signal S is lower than the preset response threshold S0, the judgment result is no (the detergent concentration C has not reached the cmc or the cleaning threshold concentration C t has not reached), return to the solution preparation step, and continue to add the detergent.

[0195] The cmc concentration of the washing water actually used in the washing equipment is affected by various factors (such as the type of fabric, quantity, amount of dirt, water temperature, etc.). Analyzing with the data of Gibbs free energy, the surfactant is first adsorbed on the gas-liquid, liquid-liquid and solid-liquid interfaces (fabric, dirt), and then aggregates (such as micelles) are formed in the solution. In actual washing by a washing machine, the surfactant in the washing water is adsorbed on the gas-liquid, solid-liquid, and liquid-liquid interfaces before forming micelles in the washing water, and thereby part of the surfactant is consumed. It is understandable that the cmc of the washing water is greater than the cmc of the detergent solution. Based on exactly this principle of action, we online monitor whether the detergent concentration in the washing water has reached the cmc or the cleaning threshold concentration, and use this as the judgment criterion for automatic detergent input.

[0196] For the washing water of actual washing by a washing machine, similarly, set the detection signal S corresponding to the value of the inflection point where the plateau region of the detected curve changes to the rising region as the critical micelle concentration value S0, and set the detection signal S corresponding to the case when it is determined that the dirt can be washed as the washing response threshold S t It may also be set. The surfactant concentration (washing threshold concentration C t ) corresponding to the washing response threshold S t is generally greater than the critical micelle concentration cmc.

[0197] During actual washing by a washing machine, the washing response threshold S t may be set in advance. First, add a certain amount of detergent, monitor whether the fluorescence response value of the washing water has reached the washing response threshold S t , if it has not reached, continue to add detergent, and continue to monitor whether the fluorescence response value of the washing water has reached the washing response threshold S t , and whether the washing response threshold S tIf it has reached or exceeded that level, no more detergent is added.

[0198] Also, when washing with an actual washing machine, in order to avoid excessive addition of detergent due to a malfunction of the detector, a maximum number of additions may be set.

[0199] Therefore, preferably, the control step further includes a count limit step. That is, a count threshold indicating the maximum number of times of detergent input is set in advance. After the detergent has been input one or more times, if the determination result has not reached the critical micelle concentration or the preset washing threshold concentration, but the number of times of detergent input has already reached the count threshold, continue to input detergent in the solution preparation step is stopped.

[0200] Specifically, the detergent input control of the present invention may be performed in the following two ways.

[0201] (Method 1) Determine by online monitoring whether the concentration of the washing water is above the cmc. In an industrial washing machine, when the concentration of the "Supreme Biotechnology" washing liquid reaches the cmc, the overall detergency has reached or is close to the detergency platform. As can be seen from Table 9, the cmc concentration of the "Supreme" washing water for washing with an actual washing machine reaches at least 0.3 (±0.01) g / L, which is significantly higher than the cmc of the directly prepared detergent solution. Therefore, in washing with an actual washing machine, once the washing liquid is input in equal amounts in multiple times, preferably, the concentration of the washing water corresponding to the second-to-last addition is consistent with the cmc.

Table 9

[0203] Load a fabric with 5 kg of simple dirt into an industrial washing machine. At this time, for the fluorescence response threshold corresponding to the dirt washing threshold concentration C t it may be 0.15. In the actual washing scene shown in Table 10, preferably, the number of times of detergent input is 1. At this time, the dirt is washed and both the amount of detergent used and the amount of water used are small. When the input is completed, the fluorescence response value is 0.161 V, the detergent concentration is 0.41 g / L, which exceeds the cmc measurement value of 0.3 g / L during washing by an actual washing machine by 37% (that is, the washing coefficient a = 0.37) (see Table 10).

Table 10

[0204] (Detergent input control system) The present invention also provides the following detergent input control system. A detergent input control system used to automatically control the amount of detergent input into washing equipment. The washing equipment includes an inner tub used to hold the laundry to be washed and water, a storage device used to store the detergent, and an input device used to input a first predetermined amount of the detergent into the inner tub, mix it with the water in the inner tub, and stir to obtain washing water or a detergent solution. The detergent input control system includes a liquid storage device used to store a probe solution, a sample collection device used to collect a predetermined amount of the washing water or detergent solution from the inner tub as a sample, a liquid extraction device used to take out a small amount of the probe solution from the liquid storage device and add it to the sample, a mixing device used to mix the sample and the probe solution to obtain a measured liquid, a detection device used to detect the fluorescence response value of the measured liquid and output a detection signal S, Receives the detection signal S, and based on whether the detection signal S has reached or exceeded a preset response threshold S0, determines whether the detergent concentration of the measured liquid has reached the critical micelle concentration cmc or a preset cleaning threshold concentration C t A determination device used to determine whether the cleaning threshold concentration C t is equal to or greater than the critical micelle concentration cmc, and When there is no laundry in the inner tub, a predetermined amount of the detergent is divided into several portions and introduced into the inner tub using the introduction device, and a plurality of sets of measurements are repeatedly performed using the liquid storage device, the sample collection device, the liquid extraction device, the mixing device, and the detection device. Based on a plurality of detection data corresponding to different detergent concentrations output by the detection device, a cmc determination device used to determine the critical micelle concentration of the detergent solution A control device used to control subsequent introduction of the detergent by the introduction device of the washing equipment based on the determination result of the determination device, and When the determination result of the determination device is that the critical micelle concentration cmc or the preset cleaning threshold concentration C t has not been reached, the control device controls the introduction device to continue introducing a second predetermined amount of the detergent into the inner tub of the washing equipment. When the determination result of the determination device is that the critical micelle concentration cmc or the preset cleaning threshold concentration C t has been reached or exceeded, the control device controls the introduction device to stop introducing the detergent, The detergent input control system is characterized in that the probe solution may adopt the ACQ fluorescent probe composition of the present invention.

[0205] In an embodiment of the detergent input control system of the present invention, the control device may control subsequent introduction of the detergent by the introduction device of the washing equipment based on the determination result of the determination device.

[0206] Here, the cleaning response threshold S0 is the fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or the fluorescence response value corresponding to the dirt cleaning threshold concentration C t is.

[0207] The critical micelle concentration (CMC) is the critical micelle concentration of the detergent solution measured in advance, or the critical micelle concentration of the detergent solution or wash water determined by online measurement using the CMC determination device, and the washing threshold concentration (C) is C. t The following formula 3 is used to calculate the result: C t =cmc×(1+a)(Formula 3) Here, a is the cleaning coefficient, with a range of 0 ≤ a ≤ 10, and a has different values ​​corresponding to different types and degrees of dirt.

[0208] Alternatively, the washing response threshold S0 is determined by the following equation 4 or equation 5: S0 = β × S max (Formula 4) S0=S blank +β×(S max -S blank )(Formula 5) Here, S max is the maximum fluorescence intensity or maximum voltage response value of the wash water, or the second plateau value in the fluorescence response value-concentration curve diagram of the wash water, and S blank β is the background fluorescence intensity or minimum voltage response value of the wash water, or the first plateau value in the fluorescence response value-concentration curve diagram of the wash water, where β is a threshold percentage with a unit of 100%, a range of 0 < β < 1, and β is set to different values ​​corresponding to different types and degrees of soiling.

[0209] Preferably, the control device is further configured with a threshold number indicating the maximum number of times detergent can be dispensed. If, after the dispensing device dispenses detergent once or more times, the determination result does not reach the critical micelle concentration or the preset washing threshold concentration, but the number of times the detergent has been dispensed has already reached the preset threshold number, the control device controls the dispensing device to stop dispensing the detergent.

[0210] (Examples) The present invention will be described in more detail below with reference to examples, however, the present invention is not limited to the following examples unless it deviates from the spirit of the invention.

[0211] (Example 1) The cmc value of the "Supreme Biotechnology (Whitening Type)" detergent solution was detected using the CUR-DGME probe composition.

[0212] <1>Preparation of the CUR-DGME Fluorescent Probe Composition The CUR probe was accurately weighed and placed in a clean beaker. DGME was added, and the solution was transferred to a volumetric flask for constant volume. Finally, the mother liquor concentration of the CUR-DGME probe composition was 1 mg / mL.

[0213] <2>Preparation of the Detergent Solution to Be Measured A series of concentrations of detergent solutions were prepared using the "Supreme Biotechnology (Whitening Type)" detergent (batch number AHA20260206, manufactured by Blue Moon Co., abbreviated as ZZLB) by weighing or gradient dilution. The concentrations were 0.02 g / L, 0.05 g / L, 0.1 g / L, 0.2 g / L, 0.5 g / L, 1 g / L, 2 g / L, 10 g / L, and 20 g / L.

[0214] <3>Addition and Treatment of the Probe Composition Using a pipette, 40 μL of the CUR-DGME probe composition was accurately transferred to 10 mL of the detergent solution to be measured. As a result, the probe working concentration in the detergent solution to be measured was 4 μg / mL (a slight volume change was ignored).

[0215] <4>Detection of Fluorescence Intensity The spectral parameters of the spectrofluorometer were set as excitation wavelength Ex = 430 nm, slit width 5 nm, scan speed 1200 nm / min, and emission wavelength scan range 440 nm - 700 nm. 2 mL of the detergent solution to be measured containing the uniformly mixed probe was accurately transferred to a cuvette for fluorescence measurement, and the fluorescence emission status of the detergent concentration solutions at different concentrations was measured using a spectrofluorometer. The scan results are shown in Figure 1.

[0216] <5>Measurement of the cmc Value Referring to the results in Figure 1, the peak height data at the maximum emission wavelength Em = 495 nm was selected as the fluorescence response value of the target detergent solution. A graph was then created using this fluorescence response value against the detergent concentration, and the results are shown in Figure 2. From the fluorescence response value (fluorescence intensity)-detergent concentration curve in Figure 2, fitting lines for the plateau region and the curve of the rising region were obtained, respectively. The coordinates of the concentration corresponding to the intersection of the fitting lines were the cmc values ​​of the detergent.

[0217] As can be seen from Figure 2, the CMC of the directly prepared "Zhizun Biotechnology (whitening type)" detergent solution was approximately 0.1 g / L.

[0218] (Example 2) The CMC value of the "Zhizun Biotechnology (Whitening Type)" wash water is detected using the NR-NMP composition.

[0219] <1> Preparation of NR-NMP fluorescent probe compositions The NR probe was accurately measured and placed in a clean beaker, dissolved directly with NMP, and the solution was transferred to a volumetric flask and brought to a final volume. The final mother liquor concentration of the NR-NMP probe composition was 1 mM.

[0220] <2> Preparation of the measured wash water The parameters for preparing the "Zhizun Biotechnology (Whitening Type)" laundry water were as follows: "Zhizun Biotechnology (Whitening Type)" detergent (batch number AHA20260206), 12 types of soiled cloths (carbon black, clay, egg white, whole egg, blood stains, sebum, vegetable oil, lipstick, beef tallow, rice starch, etc.), and a 2.5 kg load of clothing. The water quality was 250 ppm hard water, the washing equipment was a drum-type washing machine, and the pre-fill water volume was 13 L.

[0221] Using the same soiled cloth, garment load, water quality, and laundry equipment, different amounts of "Zhizun Biotechnology (Whitening Type)" detergent were added to prepare measured wash water with different detergent concentrations. The converted concentrations were 0.025 g / L, 0.075 g / L, 0.15 g / L, 0.3 g / L, 0.6 g / L, 0.9 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, and 2.4 g / L.

[0222] <3> Addition and processing of probe composition Using a pipette, 20 μL of NR-NMP probe mother liquor was accurately transferred to 10 mL of the laundry water being tested, resulting in a probe operating concentration of 2 μM in the laundry water (slight volume changes were ignored).

[0223] <4> Detection of fluorescence intensity Ten mL of the laundry water containing the probe was transferred to a glass sample bottle, and the fluorescence response values ​​(voltage values) of the laundry water under different detergent concentrations were measured using a customized fluorescence photoelectric detector (including an excitation filter (550 nm), a dichroic mirror, and an emission filter (638 nm), with a light source having a peak wavelength of 550 nm, a bandwidth of 540 nm to 560 nm, an operating current of 0.02 A, and an operating voltage of 5 V).

[0224] <5> Measurement of Parallelc Value Based on the results from a customized fluorescence photoelectric detector, a graph was created using the fluorescence response values ​​against the laundry water concentration, and the results are shown in Figure 3. From the fluorescence response value (voltage value)-detergent concentration curve in Figure 3, it can be directly determined that the inflection points of the curve correspond to the cmc value of the detergent.

[0225] As can be seen from Figure 3, the CMC value of the "Zhizun Biotechnology (Whitening Type)" laundry water was approximately 0.3 g / L.

[0226] (Example 3) Referring to Example 1 or Example 2, the tested "Zhizun Biotechnology (Whitening Type)" detergent solution was prepared, and the probe and auxiliary agent types in the fluorescent probe composition were adjusted. Here, the probes were CUR and NR, and the auxiliary agents included BUT, EG, NMP, and PEG200. Detection was performed using a customized CD detector, and the resulting fluorescence response (voltage value)-detergent concentration curve is shown in Figure 4. Note that the detection signal for NR-EG was weak, so the result is not shown in Figure 4(B).

[0227] As can be seen from Figure 4, by using various combinations of probe and auxiliary agents in the fluorescent probe composition of the present invention, the cmc value of the detergent solution can be measured using either the fitting linear intersection method or the inflection point determination method, based on the change curve of the characteristic emission peak in the obtained fluorescence response value (voltage value)-detergent concentration curve. Among these, when NMP and PEG200 are used as auxiliary agents, the agreement of the obtained curves is better, indicating that they have less influence on the cmc measurement results and are therefore more preferable auxiliary agents of the present invention.

[0228] (Example 4) The detergents being tested were changed to commercially available detergent solutions from other brands such as GB, LYL, AM, CN, WLS, LBJH, SGY, and TZ. See Table 11 for the meaning of the abbreviations for each detergent.

[0229] Except for changing the type of detergent to the detergents shown in Table 11, the measurements were carried out in the same manner as in Example 1 or Example 2, and the measurement results are shown in Table 11 below. [Table 11]

[0230] Figure 5 shows the curves obtained when measuring the CMC of various detergent solutions of different brands mentioned above using the surface tension method.

[0231] Figure 6 shows fluorescence response-detergent concentration curves when measuring the cmc of various detergent solutions of different brands using a spectrofluorometer, with (A) the CUR probe composition and (B) the NR probe composition.

[0232] As can be seen from Table 11, Figure 5, and Figure 6, the probe composition of the present invention is suitable for measuring the CMC of various commercially available detergents by fluorescence spectroscopy, and the measurement results are in close agreement with the CMC results measured by the conventional surface tension method, with errors within an acceptable range and no impact on actual use.

[0233] (Example 5) The detergent solution under test was replaced with a directly prepared detergent solution and wash water used in different washing machine scenarios (washing with an industrial washing machine or washing with a household washing machine), where some detergents contain a fluorescent whitening agent. Using the two ACQ fluorescent probe compositions of the present invention, namely (A) CUR probe composition and (B) NR probe composition, the cmc was measured similarly with reference to Example 1 or Example 2, and the resulting fluorescence response value-detergent concentration curve is shown in Figure 7.

[0234] As can be seen from Figure 7, the probe composition of the present invention is applicable to measuring the CMC of detergent solutions or wash water in various usage scenarios using fluorescence spectroscopy, and the measurement results are in near agreement. In all cases, the CMC concentration of wash water from actual washing machines is higher than the CMC concentration of directly prepared detergent solutions, and the fluorescent whitening agent has little effect on the results and does not affect actual use.

[0235] (Example 6) By replacing the detergent solution under test with other commercially available products containing surfactant components such as fabric softeners, oxygen-based bleaches, and disinfectants, and performing measurements similarly with reference to Example 1 or Example 2, the results will enable the measurement of the detergent CMC value.

[0236] Figure 8 shows the fluorescence response value-detergent concentration curve when the CMC of other types of products containing surfactant components (fabric softeners, oxygen bleaches, disinfectants) was tested using the fluorescent probe composition of the present invention, with (A) being the CUR probe composition and (B) being the NR probe composition.

[0237] As can be seen from the results in Figure 8, the fluorescent probe method using the fluorescent probe composition of the present invention can still measure fluorescence intensity response values ​​for other types of products with added surfactants, and the measured CMC values ​​show a strong correlation with the amount of surfactant added to the product, demonstrating the high suitability of the fluorescent probe composition of the present invention.

[0238] Furthermore, as can be seen from Figure 8, when the concentration of fabric softener is very high, the clarity of the solution decreases significantly as the concentration of fabric softener increases, and the light transmittance of the solution also decreases. Therefore, the curve tends to decline after reaching its peak.

[0239] (Example 7) A "Zhizun Biotechnology (Whitening Type)" detergent solution was prepared referring to Examples 1 and 3. The amount of probe mother liquor added was adjusted to 400 μL using a CUR probe composition (probe mother liquor) with a probe concentration of 0.001 mg / mL, or the amount of probe mother liquor added was adjusted to 1 μL using an NR probe composition with a probe concentration of 100 mg / mL. The amount of organic solvent (auxiliary agent) added to the wash water under test and the probe operating concentration were both kept within the preferred range for measurement according to the present invention (i.e., the amount of solvent added does not exceed 4%, and the probe operating concentration does not exceed 10 μg / mL). Measurements were performed in both cases using a CD detector.

[0240] The measurement results are shown in Table 12. The CMC results measured in the two cases were 0.061 g / L and 0.171 g / L, respectively, demonstrating that the CMC of "Zhizun Biotechnology (Whitening Type)" detergent can be measured in both cases. Furthermore, when comparing the measured values ​​with the results under the same probe operating concentration in Table 8 (Reference Example 1, Reference Example 2), the errors were all within acceptable limits. It was found that when the amount of probe solution added and the probe operating concentration are within the range specified in this invention, the detergent CMC value can be measured, and its accuracy meets practical needs. [Table 12]

[0241] (Example 8) To achieve miniaturization of laundry equipment or detergent dispensing control systems, we customized the following fluorescence photoelectric detectors. The specifications were as follows: 1) Including an excitation filter (430nm), a dichroic mirror, and an emission filter (495nm), the light source has a peak wavelength of 430nm, a bandwidth of 420nm to 440nm, an operating current of 0.02A, an operating voltage of 5V, and the detector's compatible wavelength range includes at least 480nm to 510nm. 2) Including an excitation filter (550nm), a dichroic mirror, and an emission filter (638nm), the light source has a peak wavelength of 550nm, a bandwidth of 540nm to 560nm, an operating current of 0.02A, an operating voltage of 5V, and the detector's compatible wavelength range includes at least 620nm to 650nm.

[0242] Using a spectrofluorometer and the customized fluorescence photoelectric detector described above, the CMC of the aqueous solution of "Zhizun Biotechnology (Whitening Type)" laundry solution was measured by referring to Example 1 or Example 2, and the results are shown in Table 13 below. [Table 13]

[0243] As can be seen from Table 13, the test results of the customized fluorescence photoelectric detector exhibit reproducibility and high accuracy, and the present invention can be used in miniaturized laundry equipment. [Industrial applicability]

[0244] By using the ACQ fluorescent probe composition of the present invention, it is possible to store it for a long time in the form of a stable probe solution, and it can be directly used for CMC measurement of surfactant solutions and determination of dirt cleaning concentration. In particular, it has important applications in detergent dispensing control in industrial washing machines, household washing machines, and household washer-dryers.

Claims

1. An ACQ fluorescent probe composition comprising a probe molecule and an auxiliary agent, used for directly measuring the CMC concentration of a surfactant, The aforementioned probe molecule is a fluorescent molecule that possesses aggregation-induced quenching (ACQ) properties. The aforementioned auxiliary agent comprises one or more non-volatile organic solvents, the boiling point of the organic solvent being 100°C or higher. The distance between the probe molecule and the Hansen solubility parameter of the organic solvent, i.e., the HSP distance Ra, is 17 (MPa). 1 / 2 An ACQ fluorescent probe composition characterized by the following:

2. The Hansen solubility parameter (HSP) δ of the probe molecule is 15 (MPa). 1 / 2 ~35 (MPa) 1 / 2 The ACQ fluorescent probe composition according to claim 1.

3. The ACQ fluorescent probe composition according to claim 1, wherein the solubility category of the probe molecule in the auxiliary agent is soluble or greater.

4. The difference in Hansen solubility parameters Δδ between the aforementioned additive and the probe molecule is -3 (MPa). 1 / 2 ~+12 (MPa) 1 / 2 The ACQ fluorescent probe composition according to any one of claims 1 to 3.

5. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein the viscosity of the auxiliary agent is 30 mPa·s or less.

6. The aforementioned additive is soluble in water and has a density of 0.9 g / cm³. 3 ~1.2 g / cm 3 The ACQ fluorescent probe composition according to any one of claims 1 to 3.

7. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein the flash point of the auxiliary agent is 60°C or higher.

8. The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein the probe molecule is an ACQ molecule whose emission method is based on a change in fluorescence intensity or a change in characteristic wavelength, and includes an ACQ molecule whose characteristic wavelength has a blueshift characteristic, an ACQ molecule whose characteristic wavelength has a redshift characteristic, and an ACQ molecule whose characteristic wavelength does not change.

9. The aforementioned probe molecule is one or more ACQ molecules selected from curcumin (CUR), Nile red (NR), coumarin (C480), rhodamine B (RhB), N-phenyl-1-naphthylamine (NPN), and pyrene (PYR). The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein the auxiliary agent includes one or more organic solvents selected from n-butanol, ethylene glycol, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide (DMF), diethylene glycol monoethyl ether (DGME), ethyl glycolate, polyethylene glycol 200 (PEG200), 1,3-butanediol, and 1,5-pentanediol.

10. The probe molecule is at least one ACQ molecule selected from curcumin (CUR), Nile red (NR), and coumarin (C480). The ACQ fluorescent probe composition according to any one of claims 1 to 3, wherein the auxiliary agent includes at least one organic solvent selected from N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), polyethylene glycol 200 (PEG200), and diethylene glycol monoethyl ether (DGME).

11. A solution preparation step for preparing a series of surfactant solutions of different concentrations, A probe addition step involves adding a fixed amount of probe solution to each of the aforementioned surfactant solutions, A detection step involves detecting the fluorescence response value of each surfactant solution using a detection means, The method includes, in this order, a determination step in which a fluorescence response value-concentration curve diagram having at least a first plateau region and an upward region is created based on the results obtained in the detection step, and the concentration corresponding to the inflection point where the fluorescence response value changes from the first plateau region to the upward region is determined as the cmc of the surfactant solution. A method for measuring the cmc of a surfactant solution, characterized in that the probe solution is the ACQ fluorescent probe composition described in any one of claims 1 to 10.

12. The method for measuring CMC according to claim 11, wherein in the determination step, the concentration corresponding to the intersection of the fitting line of the first plateau region and the fitting line of the rising region in the fluorescence response value-concentration curve diagram is determined as the CMC of the surfactant solution.

13. The CMC measurement method according to claim 11 or 12, wherein the amount of solvent added to the probe solution to 10 mL of the surfactant solution does not exceed 400 μL, and the probe operating concentration of the probe molecule does not exceed 10 μg / mL.

14. The CMC measurement method according to claim 11 or 12, wherein the surfactant comprises at least one of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

15. The CMC measurement method according to claim 11 or 12, wherein the surfactant solution further comprises a fluorescent whitening agent.

16. A solution preparation step involves adding a predetermined amount of detergent to a washing machine containing a predetermined amount of water and clothes, stirring to mix uniformly, and then obtaining wash water. A sample collection step involves taking a sample from the aforementioned wash water and adding a small amount of probe solution to obtain the wash water to be measured. A detection step of detecting the fluorescence response value S of the water to be measured using a detection means, Based on whether the detected fluorescence response value S has reached or exceeded a preset cleaning response threshold value S 0 it is determined whether the detergent concentration of the measured washing water is the dirt cleaning concentration. When it has not reached the preset cleaning response threshold value S 0 the determination result is "no". When it has reached or exceeded the preset cleaning response threshold value S 0 the determination result is "yes", and a determination step The control step includes controlling the subsequent addition of the detergent in the solution preparation step based on the determination result of the determination step, and if the determination result is "no", returning to the solution preparation step and continuing to add a second predetermined amount of detergent, then performing the subsequent sample collection step, detection step and determination step, and if the determination result is "yes", stopping the addition of the detergent and outputting the determination result. A method for determining the concentration of dirt removal, characterized in that the probe solution is the ACQ fluorescent probe composition described in any one of claims 1 to 10.

17. The washing response threshold S 0 This is the fluorescence response value corresponding to the critical micelle concentration cmc of the wash water, or the dirt cleaning threshold concentration C. t This is the corresponding fluorescence response value, The aforementioned dirt cleaning threshold concentration C t This is the minimum concentration required to clean clothes with different types of stains, and is determined by the following equation 3: C t = cmc × (1 + a) (Equation 3) The method for determining the dirt cleaning concentration according to claim 16, wherein in equation 3, cmc is the critical micelle concentration of the washing water, a is the cleaning coefficient with a range of 0 ≤ a ≤ 10, and a is set to a different value corresponding to different types of dirt and degrees of dirt.

18. The washing response threshold S 0 However, this is determined by the following equation 4 or equation 5, S 0 =β×S max (Equation 4) S 0 =S blank +β×(S) max -S blank (Equation 5) Here, S max S is the maximum fluorescence intensity or maximum voltage response value of the wash water, or the second plateau value in the fluorescence response value-concentration curve diagram of the wash water, blank The method for determining the dirt washing concentration according to claim 16, wherein β is the background fluorescence intensity or minimum voltage response value of the washing water, or the first plateau value in the fluorescence response value-concentration curve diagram of the washing water, β is a threshold percentage with a unit of 100%, a range of 0 < β < 1, and β has different values ​​corresponding to different types of dirt and degrees of dirt.

19. In a washing machine, a solution preparation step is performed in which a first predetermined amount of detergent is put into an inner tub based on the weight of the laundry and the amount of water supplied, and the detergent is mixed with the water in the inner tub and stirred to obtain washing water or detergent solution. A sample collection step of taking a predetermined amount of the washing water or the detergent solution from the inner tub as a sample, The extraction step involves taking out a small amount of probe solution and adding it to the sample, A mixing step of mixing the sample and the probe solution to obtain the liquid to be measured, A detection step which involves detecting the fluorescence response value of the liquid to be measured and outputting a detection signal S, The detection signal S is received, and the detection signal S is set to a preset response threshold S. 0 Based on whether it reaches or exceeds the critical micelle concentration (cmc) or the preset cleaning threshold concentration (C), the detergent concentration of the liquid being measured is determined to be either the critical micelle concentration (cmc) or the preset cleaning threshold concentration (C). t A step of determining whether the washing threshold concentration C has reached the target concentration. t This involves a determination step of whether the critical micelle concentration (cmc) is equal to or greater than the above-mentioned critical micelle concentration, The control step includes controlling the subsequent addition of the detergent based on the determination result of the determination step, returning to the solution preparation step and continuing to add a second predetermined amount of the detergent to the inner tank if the determination result is that the critical micelle concentration or a preset cleaning threshold concentration has not been reached, and stopping the addition of the detergent if the determination result has already reached the critical micelle concentration or a preset cleaning threshold concentration. A detergent dispensing control method characterized in that the probe solution is the ACQ fluorescent probe composition described in any one of claims 1 to 10.

20. The detergent dispensing control method according to claim 19, wherein the control step further includes a count limit step, in which a count threshold indicating the maximum number of times detergent is dispensed is set in advance, and after dispensing detergent once or more times, if the determination result of the determination step has not reached the critical micelle concentration or a predetermined washing threshold concentration, but the number of times the detergent has been dispensed has already reached the count threshold, the dispensing of detergent is stopped in the solution preparation step.

21. A detergent dispensing control system used to automatically control the amount of detergent dispensed into a washing machine, wherein the washing machine includes an inner tub used to hold laundry and water, a storage device used to store detergent, and a dispensing device used to dispense a first predetermined amount of the detergent into the inner tub and mix and agitate it with the water in the inner tub to obtain washing water or a detergent solution. The detergent dispensing control system is A liquid storage device used for storing probe solutions, A sample collection device used to collect a predetermined amount of the washing water or the detergent solution from the inner tub as a sample, A liquid extraction device used to take a small amount of probe solution from the liquid storage device and add it to the sample, A mixing device used to obtain a liquid to be measured by mixing the aforementioned sample with the aforementioned probe solution, A detection device used to detect the fluorescence response value of the liquid to be measured and to output a detection signal S, The detection signal S is received, and the detection signal S is set to a preset response threshold S. 0 Based on whether it reaches or exceeds the critical micelle concentration (cmc) or the preset cleaning threshold concentration (C), the detergent concentration of the liquid being measured is determined to be either the critical micelle concentration (cmc) or the preset cleaning threshold concentration (C). t A determination device used to determine whether the washing threshold concentration C has reached the target, wherein t This includes a device for determining whether the critical micelle concentration (cmc) is equal to or greater than the aforementioned critical micelle concentration, A CMC determination device is used to determine the critical micelle concentration of the detergent solution when there is no laundry in the inner tub, by using the dispensing device to dispense a predetermined amount of the detergent into the inner tub in several portions, and by repeatedly performing multiple sets of measurements using the liquid storage device, the sample collection device, the liquid extraction device, the mixing device, and the detection device, and based on multiple detection data corresponding to different detergent concentrations output by the detection device, The control device is used to control the subsequent dispensing of the detergent by the dispensing device of the washing equipment based on the determination result of the determination device, The determination result of the aforementioned determination device is the critical micelle concentration cmc or the preset washing threshold concentration C. t If the critical micelle concentration (cmc) has not been reached, the control device controls the dispensing device to continue dispensing a second predetermined amount of the detergent into the inner tub of the washing equipment, and the determination result of the determination device is that the critical micelle concentration (cmc) or the preset washing threshold concentration (C) has already been reached. t If the level reaches or exceeds a certain point, the control device controls the dispensing device to stop dispensing the detergent. A detergent dispensing control system characterized in that the probe solution is the ACQ fluorescent probe composition described in any one of claims 1 to 10.

22. The washing response threshold S 0 This is the fluorescence response value corresponding to the critical micelle concentration cmc of the detergent solution, or the dirt cleaning threshold concentration C. t This is the corresponding fluorescence response value, The critical micelle concentration (CMC) is the critical micelle concentration of the detergent solution measured in advance, or the critical micelle concentration of the detergent solution or wash water determined by online measurement using the CMC determination device. The aforementioned washing threshold concentration C t It is calculated using the following formula 3, C t = cmc × (1 + a) (Equation 3) Here, a is the cleaning coefficient, with a range of 0 ≤ a ≤ 10, and a is set to a different value corresponding to different types of dirt and degrees of dirt. Alternatively, the cleaning response threshold S 0 However, this is determined by the following equation 4 or equation 5, S 0 =β×S max (Equation 4) S 0 =S blank +β×(S) max -S blank (Equation 5) Here, S max S is the maximum fluorescence intensity or maximum voltage response value of the wash water, or the second plateau value in the fluorescence response value-concentration curve diagram of the wash water, blank The detergent dispensing control system according to claim 21, wherein β is the background fluorescence intensity or minimum voltage response value of the wash water, or the first plateau value in the fluorescence response value-concentration curve diagram of the wash water, β is a threshold percentage with a unit of 100%, a range of 0 < β < 1, and β has different values ​​corresponding to different types and degrees of soiling.

23. The detergent dispensing control system according to claim 21 or 22, wherein the control device is further configured with a count threshold indicating the maximum number of times detergent can be dispensed, and after the dispensing device has dispensed detergent once or more times, if the determination result of the determination device has not reached the critical micelle concentration or the preset washing threshold concentration, but the number of times the detergent has been dispensed has already reached the count threshold, the control device controls the dispensing device to stop dispensing the detergent.

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