JP6033581B2 - Fast foam test evaluation method and measuring device - Google Patents

Description

  The present invention relates to a method for evaluating the foaming speed (rapid foaming property) of a cleaning agent and a measuring apparatus used for the method.

  Conventionally, as a method for evaluating the foaming property of a solution such as a surfactant, a flow-down method (Pouring method), an agitation method (Beating method), a rotation method (Rotating method), a stirring method (Stirring method), a shaking method (Shaking method) etc. are known.

  Since these evaluation methods are static observation methods and the measurement is performed at the time of equilibration after foaming, the change in foaming over time, particularly the foaming speed (initial foaming speed / There was a drawback that the fast foaming property) could not be observed under uniform conditions.

  An example of the dynamic foaming evaluation method is an air supply method (Bubbling method). Non-Patent Document 1 describes a measurement example by an air supply method, but bubbles are generated by aeration. Therefore, the mechanism is different from the foaming of a cleaning composition, and the rate of disappearance of bubbles is mainly evaluated. Will be. For this reason, when a detergent composition mainly composed of a surfactant having a large amount of foam and a large contribution to the stability is evaluated, there is a problem that the air flow rate is directly measured as the foam amount.

  As a method for carrying out comprehensive foaming evaluation, Patent Document 1 collects and measures foams generated by sliding an object to be cleaned and a cleaning liquid while sliding a protrusion (with a torque meter). An evaluation method is described. This technique is an excellent method capable of observing foaming characteristics of a cleaning composition and an object to be cleaned under actual use, and is a measurement method capable of dynamic measurement.

  However, in this evaluation method, it takes a long time to collect the foam, and this also includes a defoaming factor in the evaluation result. The evaluation method is not sufficient.

  Further, the structure of the apparatus is complicated, the reproducibility between the apparatuses is poor, and there is a concern that the evaluation result varies depending on the state of wear or the like of the hair or protrusion to be evaluated. In addition, there is concern about poor cleaning properties, and it is difficult to evaluate continuously.

Patent No. 3520690

Journal of Japan Society on Water Environment, Vol. 23 (2000) No. 2 pp.122-125

  That is, until now, no simple evaluation method has been found for the foaming speed (rapid foaming property). Moreover, since the influence of an antifoaming factor becomes large in a measurement result, so that the time until measurement after foaming becomes long, the evaluation method which can be measured immediately after foaming was calculated | required.

  The present invention is intended to solve the above-described problems of the prior art, and an object of the present invention is to provide an apparatus capable of evaluating the rapid foaming property at the actual use concentration of the cleaning agent.

  The present inventors have found that the amount of foam generated in a specific measuring device can be measured immediately in the quick foam property evaluation by stirring the cleaning agent, and the measured value is based on sensory evaluation. It was confirmed that there was a strong correlation with the preliminary report evaluation, and the present invention was completed.

In other words, the present invention comprises a cylindrical bubble generator having a stirring portion and a measuring portion, and further having two holes opened on the upper bottom surface for connection between the two, and the center of the hole for the stirring portion on the upper bottom surface of the foam generator. Is placed at a position different from the center of the bubble generator so that it does not overlap the hole of the measurement part,
The stirrer is set to generate foam with a stirring blade,
The measuring unit has a scale to measure the volume in the vertical direction,
A fast foaming evaluation method characterized by rotating a stirring blade of a stirring unit in a state where the foam generator is filled with a measurement liquid and collecting the generated foam in the measuring unit, and measurement for evaluating the fast foaming property Relates to the device.

  The apparatus of the present invention makes it possible to evaluate the rapid foaming property at the actual use concentration of the cleaning agent.

The whole explanatory drawing of the measuring device for quick-foam property evaluation. Formula 1 to 4 with the apparatus of FIG. 1 Plot of foam amount / time, linear regression line Formula 1 to 20 seconds of time in FIG. 2 Foam amount / time plot, linear regression line Comparative example Formula 1 to 4 by air-flow measurement Plot of foam amount / time Plot of regression line slope / sensory evaluation point of formulas 1 to 4 obtained in FIG. 3, primary regression line

  The present invention is characterized in that the stirrer and the measurement unit are separated from the center of the foam generator, so that the water surface of the outer periphery of the foam generator rises due to the flow of cleaning liquid in the foam generator, and the blades of the stirrer It has the advantage of being always in contact with the measuring solution, and has a feature that enables evaluation without stopping the generation of bubbles at a constant amount.

  The position of the stirring blade for foaming force evaluation by the conventional stirring method (Stirring method) is at the center of the stirring blade and the center of the measurement vessel, and eventually the generation of foam proceeds because the stirring blade is immersed in the foam. There was no problem. In addition, since the foam is sheared many times by high rotation stirring, the foam becomes fine, and there is a problem that the foam quality is different from the actual foaming.

  That is, the conventional stirring method (Stirring method) has a problem in the sustainability of the constant foaming force in units of time necessary for dynamic foaming observation. In the present invention, this problem is solved by removing the position of the stirring portion from the center of the container.

  In the present invention, since the generated foam can be collected and measured immediately after generation by the measurement unit, the defoaming factor after foaming can be reduced as much as possible, and the concentration and time are the same as the conditions for actually foaming by hand. It has the characteristic that it is a quick-foam property evaluation method which can be evaluated by.

  In addition, the measurement results of the measurement method of the present invention are characterized by high accuracy and reproducibility, a simple structure of the apparatus, and a good detergency.

  Hereinafter, the measuring apparatus of the method of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is an overall explanatory view of a measuring apparatus for the method for evaluating rapid foaming according to the present invention.

The measuring apparatus shown in FIG.
A foam generator comprising a container C and a lid B with two holes;
A stirring unit including a stirring motor D, an overflow prevention frame E, and a stirring blade F is provided.

  The measuring part A is set to one of the two holes opened in the upper bottom surface of the bubble generator. The volume of foam generated in the foam generator is measured, and a transparent cylindrical body is provided with a scale, and the upper surface and the lower surface are opened. C, which is the diameter of the measuring part A, is smaller than the radius a of the foam generator, is located off the center of the foam generator, and is measured on a line connecting the center of the stirring part and the center of the foam generator. More preferably, the center of the part A is located.

  The stirring unit is set to the remaining one of the two holes opened in the upper bottom surface of the bubble generator. A stirring motor D, an overflow prevention frame E, and a stirring blade F are provided. A leakage prevention frame E is installed in the connection hole of the stirring portion so that the cleaning liquid and the generated bubbles do not overflow at the time of evaluation. The height g of the overflow prevention frame E may be any height as long as the cleaning liquid and the bubbles do not overflow. However, if it is too high, it is difficult to install the stirring blade F, so 20 to 30 mm is desirable.

  The diameter b of the stirring section and the diameter of the stirring blade F are the same or have a gap of 10 mm or less (the diameter of the stirring blade is smaller). In order to reduce the measurement error while smoothly installing the stirring blade F, it is preferable that the diameter of the stirring portion is 1-2 mm larger than the diameter of the stirring blade F.

  The stirring blade F determines the horizontal position so that the center position of the stirring blade is the same as the center of the stirring section, and the vertical position of the blade is tested when the stirring blade is at a static value in the test solution filled with the bubble generator. Adjust to submerge in liquid. That is, the uppermost part of the stirring blade is adjusted to a position below the lid of the foam generator. With regard to the shape of the stirring blade, any shape such as a turbine blade, paddle blade, screw blade, etc. can be measured.

  The foam generator is composed of a container C and a lid B with two holes, but is preferably formed from transparent plastic or transparent glass. The two-hole lid B of the foam generator is preferably detachable from the container C in order to facilitate cleaning of the apparatus and preparation of the test solution. The container C and the lid B are in close contact during measurement so that the sample liquid does not leak during evaluation.

Further, the shape of the container C is preferably configured with a smooth curve on the side surface, and more preferably a cylindrical shape, in order for the generated foam to be smoothly captured by the measurement unit A.
Only the connection part of the measurement part A and the stirring part is opening the lid | cover B with 2 holes.

The relationship between the diameter a of the bubble generator, the diameter of the stirring portion = the diameter b of the overflow prevention frame E, and the diameter c of the measurement portion A may be in the range of the following formulas (1) to (3). More preferred.

1 / 3a <b <2 / 3a (1)

1 / 4a <c <1 / 2a (2)

a> (b + c) (3)

When b is larger than the range of the formula (1), the center of the stirring blade F is close to the center of the container C, so that the liquid in the foam generator does not turbulent during measurement, and the generation of foam proceeds. The problem that does not happen. Moreover, when b becomes smaller than the range of Formula (1), since the stirring blade F is too small than the container C, in addition to the problem of slow foam formation, the flow of the liquid deteriorates and the stirring blade F Bubbles overflow from the portion, causing a problem that the bubbles are not captured in the measurement unit A.

  When c becomes larger than the range of the expression (2), the hole of the measurement unit A includes the center of the bubble generator. The center of the foam generator is the place where the test liquid level becomes the lowest at the time of measurement (the test liquid in the foam generator also flows in the direction along the rotation of the stirring blade in the foam generator, and the test liquid level is caused by centrifugal force. Is transformed into a mortar, with the bottom of the mortar at the center of the foam generator). Therefore, there is a problem that the bubbles captured by the measuring unit A easily return to the bubble generator, leading to a decrease in measurement accuracy.

  Moreover, since the stirring blade F and the measurement part A are located on the lid with two holes, it is necessary to satisfy Expression (3).

  A method of using the apparatus of FIG. 1 will be described.

  The apparatus is pumped up to the above conditions, and the test solution is injected from the stirring blade opening, or the two-hole lid B is removed from the container C and the cleaning agent is injected. At this time, the sample solution is filled so that bubbles do not remain in the bubble generator, and the amount of liquid is adjusted to prepare for measurement so that the liquid level becomes the same height as the upper part of the stirring blade F.

Test solution to be evaluated The test solution to be evaluated is measured after adjusting to a concentration higher than the CMC of the cleaning composition to be measured, particularly a concentration at the time of actual use. At this time, it is possible to evaluate the foaming power of impurity loading by adding dilution media with hard water and adding dirt, etc., and changing the detergent concentration according to the situation to be evaluated Can do.

  The actual measurement is started by rotating the stirring motor D at a constant speed after preparing the measurement in the manner described above. Since bubbles are collected in the measurement part A immediately after the motor rotation, the amount of bubbles is recorded every certain time, and the quick bubble property is evaluated.

  The measurement time scale measures the bubble volume collected in the measurement unit A every 5 seconds from the start of rotation and records it for a certain time (for example, 60 seconds) or measures until the bubble volume does not fit in the measurement unit A.

  The device of the present invention has the feature that the foaming property can be recorded simultaneously with the rotation of the motor, and dynamic observation can be performed. Therefore, it was possible to evaluate the initial foaming force, which was difficult to measure by the conventional methods, and the validity of the result confirmed that the present inventors had a strong correlation with the evaluation by the monitor.

  In addition, after the initial foaming is measured in the present invention, the foam generation is also stopped by stopping the motor, so that the disappearance of the foam generated by recording the foam amount every certain time is observed and evaluated. Can do.

Less than,
The present invention measurement method will be described with reference to Examples, Comparative Examples and Reference Examples.

  The following samples were prepared and used in Examples, Comparative Examples and Reference Examples.

  In each sample, the result of measuring the loss miles test JIS K 3362, which is a kind of flow-down method (Pouring method), at 40 ° C. and the sample concentration of 0.25% is shown.

Note 2: The 0-minute data of the Ross Miles test is a value obtained by subtracting the stable liquid level height after 5 minutes from the bubble height at the moment when the flow ends, and as a result, is a static observation value. The properties are different from the initial foaming to be measured in the present invention.

  This test method can only be considered at a level where the foaming power of Formula 1 is relatively large compared to other formulas.

Reference example 10 persons are selected as panelists for sensory evaluation, and the foaming quality (rapid foaming) when formulas 1 to 4 are foamed by hand for 20 seconds is defined as 5 levels based on formula 3 (3.0) as follows: Evaluated.
Evaluation of good foaming 5: Good 4: Slightly good 3: Same as prescription 3: 2: Somewhat bad 1: Calculate the average score of bad evaluation results, and the calculated average value is over 4.5 Very good (◎)
Good in the case of 3.5 to 4.5 (○)
Normal in case of 2.5-3.5 (△)
If it is less than 2.5, it is bad (×)
Went as.
The evaluation results are shown in Table 4.

Example Fast foaming property evaluation method of the present invention In the measuring apparatus of FIG.
As the measurement part A, a 200 mL graduated cylinder having a diameter of 33 mm and a height of 260 mm was used.
As the foam generator container C, a 200 mL transparent plastic cylindrical container having a diameter of 100 mm and a height of 26 mm was used.
The stirring section had a diameter b of 50 mm, a stirring blade F using 6 inclined paddle blades with a diameter of 50 mm, and the rotation speed by the stirring motor D was set to 300 rpm.

  In the quick foam property evaluation method using this apparatus, a test solution adjusted to an active agent concentration of 1% of formulations 1 to 4 was used.

  The surfactant concentration of 1% in the test solution is a concentration corresponding to the concentration diluted with water when the cleaning composition is bubbled for cleaning.

  After assembling the apparatus, about 200 mL of the test solutions of Formulations 1 to 4 were injected from the stirring blade opening to the same height as the top surface of the stirring blade F, being careful not to generate bubbles in the container B.

  Bubbles generated by the stirring blade F immediately after the stirring motor D is rotated are supplemented by the measurement unit A. FIG. 2 shows the result of recording the amount of bubbles captured by the measurement unit A every 5 seconds for 60 seconds from the start of rotation. The measurement is completed when the measurement time has passed 60 seconds or the amount of bubbles has reached 200 mL.

  The measurement results are shown in Table 3 and FIG. The straight line drawing in FIG. 2 is a linear regression line by the least square method of the measured values of each prescription.

  According to this measurement method, foaming is generated at a constant speed due to motor agitation. Therefore, bubble breakage (loss related to bubble breakage and bubble collection efficiency due to this measurement system) / foam removal (bubble capture) When there is no bubble breakage over time after collection, it has a prescription-specific inclination. The slope having a ml / sec dimension of the regression line obtained from the measured value of 20 seconds or less, which is relatively strong in linearity, is excellent for use in evaluating the rapid foaming property of the test solution. This numerical value agrees well with the actual sensory evaluation as described later. According to the study of the present inventor, the slope of the primary regression line of data of the amount of trapped foam (ml) and time (sec) up to 20 seconds after foaming with the same apparatus used in this experiment is 7.5 or more. The speed of foaming can be confirmed sensuously, and it becomes a standard when formulating a fast foaming detergent.

Comparative Example 1 Evaluation of dynamic foaming by insufflation method Evaluation was performed with reference to the method described in Reference Document 1. A glass filter for supplying fine foam is attached to the bottom of a glass tube with a tower height of 50 cm and an inner diameter of 2.5 cm, air is used as the aeration gas, and the flow rate is adjusted to 0.3 L / min with an air pump and flow meter. Vented into the tower. In the sample for evaluation, activators A to D were adjusted to an activator concentration of 0.1%, and 100 mL was injected along the wall surface from the upper part of the glass tube. The height of the foam from the liquid / foam interface within 60 seconds immediately after aeration was measured with a ruler. The result is shown in FIG.

  The surfactant concentration of the measurement liquid of the example is 1%, whereas the surfactant concentration of this comparative example is set to 0.1%. When measured at 1%, the surface activity is too high, and thus the disappearance of bubbles is unlikely to occur. Therefore, the surfactant concentration was successively lowered and measured, and the measurement at 0.1% when the difference between the samples began to appear was set as the measurement condition. This indicates that the dynamic foaming force observation by the air supply method is not suitable for the performance evaluation of the surfactant.

In the result of FIG. 4, the amount of foam after 60 seconds is prescription 1> prescription 2> prescription 3> prescription 4. This order is consistent with the result of sensory evaluation, but it is large enough to detect the difference between the groups of prescriptions 1 to 3 and prescription 4.
When the measurement results of Examples, Comparative Examples, and Reference Examples are arranged, the results shown in Table 1 are arranged.

The data obtained by the measurement method of the present invention has a very good correlation coefficient of 0.99 and corresponds to the data obtained by sensory evaluation in parallel.
Even in the foaming force evaluation by the insufflation method, which is a representative of conventional dynamic foaming measurement, the difference in the initial foaming properties in the groups of Formulas 1 to 3 and Formula 4 can be observed, but the order of sensory evaluation does not necessarily reflect Not done. Moreover, the correlation with sensory evaluation is low compared with the measurement method of the present invention.

  FIG. 5 is a correlation diagram between the slope m of the regression line measured by the method of the present invention and the average score of sensory evaluation.

  The measured value of the present invention corresponds well to sensory evaluation, and the slope m of the regression line measured by the method of the present invention is 7.5 or more. Excellent foaming property of 5 points or more.

  A very good correlation was found between the result of the measuring apparatus in FIG. 1 and the sensory evaluation of the fast foaming property.

  On the other hand, when a device similar to the air supply type foam amount measuring device is used, it must be diluted to a measured concentration of 0.1% and an active agent concentration of 1-2% actually used. The foaming results did not show a good correlation with the sensory evaluation.

  By using a specific measuring device, it is possible to easily and stably measure the initial foaming force, for which the numerical value is difficult in the conventional measuring method.

  By this measurement method, the data of initial foaming can be converted into a numerical value, and by comparing the measured values, a more excellent prescription with fast foaming properties can be drawn in a short time.

A Measuring part B 2-hole lid of foam generator C Foam generator container D Stirring motor E Overflow prevention frame F Stirring blade

Claims (2)

Stirring unit and the measurement unit and, further a two-hole aperture is not a cylindrical bubble generator above bottom for connection to both the center of the hole for agitation of the foam generator on bottom foam generator It is arranged at a position different from the center of the measurement unit so that it does not overlap the hole of the measurement unit, the stirring unit is set to generate foam by the stirring blade, the measurement unit has a cylindrical shape, and the volume in the vertical direction a fast foaming evaluation method using the measuring device for fast foam evaluation scales Ru chopped der to measure,
In a state where the foam generator is filled with the measurement liquid, the stirring blade of the stirring unit is rotated, and the generated foam is collected by the measuring unit .
Including speed foaming evaluation method to assess the rate of foaming of the test solution by performing comparison based on the volume of the collected foam in time measuring section from activates the stirring section. It includes a stirring unit, a measuring unit, further a cylindrical bubble generator is two-hole aperture on the bottom surface for connection to both,
The center of the hole for the stirring part on the bottom surface of the foam generator is installed at a position different from the center of the foam generator so as not to overlap the hole of the measurement part,
The stirrer is set to generate foam with a stirring blade,
The measuring part has a cylindrical shape and is a measuring device for quick foaming evaluation in which a scale for measuring the volume is engraved in the vertical direction.