1. Introduction
Hair cosmetics were developed to provide solutions for hair loss functions such as recovery for damaged hair, straightening for curly hair, color care, and scalp care [
1,
2,
3,
4]. Additionally, research is being conducted on defense mechanisms to prevent damage that occurs when using hot air tools and during cleaning due to surfactant penetration [
5]. Recently, the scope of hair care has been widely expanded through research on chemical damage caused not only by oxidation and reduction due to dyeing, perms, etc., but also by ultraviolet rays and metal ions [
6,
7].
Hair detangling is an important area in the hair market that has always been in demand from consumers, but it is also an area that has not yet been independently resolved. While detangling can effectively improve tangles by softening the rough texture of damaged hair with oil and other products [
8], it has not received much attention. When hair becomes tangled, friction increases during combing, which is a direct cause of hair breakage [
9]. Increasing combability is a major challenge in the hair care market as it always causes stress to consumers regardless of whether they use a comb or their hand. Research on combability has been conducted, focusing on their effects on the scalp and studying brushing behaviors [
10,
11,
12]. The research focused on the effects of combing on hair itself, specifically examining damage such as the hair breakage that occurs during combing [
13,
14,
15,
16]. To our knowledge, there has been no report on an evaluation method to determine the degree of tangling that occurs during combing.
There are many formulation products for mists or leave-in creams on the global market that act as hair detanglers. Although the size of the hair tangling prevention market is not yet large, hair cosmetics with detangling functions along with efforts to reduce the stress consumers feel when combing their hair are taking up a significant portion of the market. Therefore, as the detangling effect is considered more important in the hair care market, it is obvious that it will be used as an indicator of the function of hair care products in the future. It is difficult to set standards for this effect in the cosmetics industry because various advertisements report on sensory evaluation including detangling efficacy based on customer experience group sensory values that are evaluated according to unknown standards for each advertisement [
17].
Observing the detangling effect on the hair is important from the perspective of hair health care [
9,
18,
19,
20,
21]. Many commercial shampoos and treatments use cationic polymers, silicones, oils, and fatty acids to provide detangling benefits [
22]. Cationic polymer and oil complexes have different hair absorption efficiencies due to coacervate formation, so it is important to optimize their composition within the formulation [
23]. Most people with curly hair prefer products that moisturize and minimize damage, as their hair is prone to dryness and breakage [
24]. Despite this market interest and approach, there is no way to objectively quantify the extent of detanglement. Although it is necessary to demonstrate the efficacy of hair detangling through an official evaluation, the industry does not know what type of hair tress should be evaluated, so there have been many difficulties in evaluating the degree of this effect [
10,
25]. In order to solve this problem, this study was conducted to establish an effective evaluation method for the first time by setting conditions for the evaluation of hair tangle prevention.
In order to evaluate the effectiveness of hair detangling products, hair tresses with the same degree of tangles are required, and objective indicators that can relatively reflect the degree of tangles between hairs must be established to evaluate the efficacy. In this study, we first established a method to produce tangled tresses. We designed the section detangling rate as an objective quantitative means to determine whether it could be appropriately applied to the evaluation of anti-tangling efficacy.
2. Materials and Methods
2.1. Materials
Sodium laureth sulfate (SLES) was obtained from LG Household and Healthcare (Seoul, Republic of Korea). Wella bleach (Blondor, Wella, Petit-Lancy, Switzerland) was used to treat agent 1 for 5 min and agent 2 for 20 min, followed by washing with SLES 10%. The rice bran extract, Inositol, was purchased from Tsuno (Wakamiya, Japan).
2.2. Treamtent of Hair
Hair under 25 cm was purchased from Phoenix Korea (Seongnam, Republic of Korea). Hair above 25 cm from Chinese individuals was purchased from Bulex (Happy Call, Seoul, Republic of Korea). To remove surface lipids and impurities, all hair was lathered for 45 s with a 10% SLES solution according to weight and then rinsed twice for 2 min. The hair was made to an appropriate weight as needed, glued, and left to dry naturally for two days. For the upper part, 1 cm of hair was cut off, and the lower part was cut to a total length of 15 cm or 25 cm. Treated hair was left overnight in a room with constant temperature and relative humidity (25 °C and 50%, respectively). When treated with a commercially available treatment, 10% of the weight of the tress was washed 7 times in the same manner as SLES.
When treating the surface of the hair to change its properties, inositol was prepared as a 0.01% to 5% aqueous solution and the hair tress was soaked for 10 min, and then taken out, rinsed, and left to dry naturally.
To create hair tangles, tresses were fixed and rotated in a spinner (IKA Eurostar 40, Staufen, Germany). When detangling hair shorter than 25 cm, the experimenter held both ends of the hair and gently rotated it with the palm of a latex-gloved (Jahyun, Daejeon, Republic of Korea) hand. In both cases, 10 hair tresses were created. The hairs that were used once were not reused, but new hair tresses were used.
2.3. Formulation of Treatment
Treatment A is a commercially available detangler product containing water, cetearyl alcohol, dicetyldimonium chloride, cetrimonium chloride, parfum, dimethicone, cetyl esters, sodium benzoate, isopropyl alcohol, amodimethicone, trideceth-10, ricinus communis seed oil/caster seed oil, tartaric acid, niacinamide, panthenol, chlorhexidine digluconate, PEG-100 stearate, hexyl cinnamal, benzyl salicylate, and linalool as raw materials.
Treatment B is a commercial treatment formulated as water, etyl alcohol, bis-aminopropyl dimethicone, stearamidopropyl dimethylamine, glycerin, stearyl alcohol, glutamic acid, shea butter, argania spinosa kernel oil, panthenol, panthenyl ethyl ether, fragrance, benzyl alcohol, citric acid, disodium ethylene-diamine-tetraacetic acid, phenoxyethanol, methylchloroisothiazolinone, and methylisothiazolinone.
Treatment C is a commercial treatment formulated as water, cetearyl alcohol, dimethicone, glycerin, stearamidopropyl dimethylamine, behentrimonium chloride, shea butter, oleyl alcohol, macadamia seed oil, hydrolyzed soy protein, hydrolyzed vegetable protein, hydrolyzed collagen, hydrolyzed silk, arginine, lysine polypeptide, hydrolyzed keratin, glycine, and serine.
The treatment used in applying the evaluation method was made of water, cetearyl alcohol, behentrimonium chloride, macadamia seed oil, shea butter, octanediol and emulsifiers, with the addition of inositol.
2.4. Measurement of Detangling
Combing friction was measured using the commercial instrument MTT175 (Dia-Stron, East Anton, UK). This unit is equipped with an optional accessory that allows the load cell to be installed vertically, facing upwards, for combing. The hair tresses were pinned at the top and combed vertically from top to bottom. The combing limit is 9.8 N and the instrument is designed to stop combing if that limit is exceeded. Combs suitable for the experiment were purchased from Naver Shopping (Seongnam, Republic of Korea).
2.5. Contact Angle Measurement
Static contact angle measurements were taken at room temperature using a Sanyo camera with an FTA 32 (version 2.0). Ten strands of hair fibers were attached in parallel using adhesive tape and photographed using a DSA-100 (Krüss, Hamburg, Germany). The values obtained from a total of 10 measurements were averaged. The volume of the droplet was 0.3 μL. Contact angle data values were automatically analyzed using the Krüss Advance 1.8.0.4 program.
2.6. Scanning Electron Microscopy
The extent of cuticle lifting was confirmed using scanning electron microscopy (SEM). The SEM images of the hair were obtained using a Hitachi S 4800 instrument (Hitachi, Tokyo, Japan). Based on the SEM images, the hair was classified based on the degree of cuticle lifting. Pt was coated on the hair as a pretreatment. To classify the hair using SEM, numerous hair strands were randomly selected from a 4 g sample of hair and many photographs were taken.
2.7. Atomic Force Microscope
To measure topography, images were evaluated using an atomic force microscope (NX-10, Park Systems, Suwon, Republic of Korea) with an NSC36/Cr-Au cantilever (Parksystems, Suwon, Republic of Korea). The cantilever had a typical spring constant of 0.60 N·m−1 and a radius of 35 nm. The surface (50 μm by 50 μm) of a total of three hairs was scanned in contact mode. Data were analyzed using XEI 5.2.4 software without any separate flattening operation.
3. Results
3.1. Establishment of Hair Tangle Evaluation Method
To determine the degree of hair tangles, the MTT175 device was used. It is dedicated to measuring friction on hair and fiber strands and can measure the force applied to hair fibers by attaching a comb to an evaluation device with a force measurement sensor. Studying and objectively quantifying the effects of hair detangling products on hair requires standardized hair detangling samples. In terms of hair characteristics between races, African hair appears curly, so it is easy to study curly hair types using African hair [
26]. However, African hair has the disadvantage of being very expensive to obtain and the degree of curling varies between samples, making it difficult to obtain objective results. Artificially permed straight hair can be an alternative, but it has the disadvantage of requiring an evaluation of hair damage because perming causes chemical damage [
27].
If the length of the hair exceeds 25 cm, the centrifugal force acting on the hair when the tress rotates does not reach the end of the hair, causing tangles. In this case, when the hair tress is wetted with water equivalent to the weight of the tress and then rotated, the adhesive force between the hair strands and the weight of the hair tress increase, increasing the tilting of the hair tress and further increasing tangles. At this time, if the rotational agitation speed exceeds 300 rpm, the water applied to the tress flies away, eliminating tangles in the tress during rotation. Therefore, there was no need to increase the rotation speed beyond 300 rpm, and the degree of entanglement depending on the rotation speed was constant at rotation speeds of 300 rpm or lower. In this experiment, the stirring speed was fixed at 150 rpm.
Healthy, chemically undamaged hair was held in a shaker and spun. The relationship between the rotation time and the maximum friction force during combing after tangling the hair by rotating it in a stirrer is shown in
Figure 1. The experiments were conducted using untreated hair and tresses of hair washed with two types of commercial treatment. A comb made of carbon-reinforced plastic with a tooth spacing of 4 mm was used.
The maximum combing friction of treatment-treated hair tresses was lower than that of untreated hair. It was expected that friction would increase due to increased entanglement as the stirring time increased, but in reality, the combing friction reached its peak and then decreased after rotating for more than 5 min.
The advantage of the method used in
Figure 1 is that multiple spinners can be operated simultaneously to produce many tresses. However, this method could only be applied when the hair length was at least 25 cm or longer. As the length of the hair becomes shorter, the centrifugal force due to rotation increases, so the resistance acting on the hair itself decreases, preventing the hair from becoming tangled. Currently, sample costs are higher for hair lengths longer than 25 cm, so it is more efficient to use short hair to obtain a large number of samples. Additionally, the evaluation method in
Figure 1 is suitable for evaluating the detangling function of leave-in cream. Therefore, a different evaluation method was designed that can be applied to single-shot tresses and wash-off formulations, which are generally less expensive.
Ultimately, the method chosen was to hold the top and end of the tresses by hand and rotate them to cause tangles. The relationship between hand-spun hair bundles and combing friction is shown in
Figure 2A. When straight tresses were placed in the palm of the hand and rotated, the degree of tangling in the hair became more severe as the number of rotations increased; once the hair was tangled, it could no longer be untangled naturally. On the other hand, when hair exceeding 25 cm in length was turned by hand, it did not tangle properly due to the long length; however, the device appeared to effectively cause tangles.
Figure 2B is an experimental image in which tangles were measured using a combability tester. The combability measurement device used in the experiment was set to stop the experiment after applying 9.8 N force to ensure sensory safety. When brushing hair, the distance the comb moves is limited by the tangles in the hair. If the tangles are severe, the force applied to the comb can reach up to 9.8 N and the distance the comb can travel is shortened. If the tangles are weak, the comb can move a longer distance. If the tangles are very light, the force applied to the comb will not reach 9.8 N and pass through the entire hair tress, in which case its value is considered unmeasurable. When the force applied to the comb reaches 9.8 N, the distance the comb moves is divided by the total tress length of 150 mm to obtain the section detangling rate; the larger this value, the better the detangling function is considered to be.
The hair tress was treated with three commercially available wash-off treatments with an anti-tangling function, and the tress was rotated in the palm of the hand to tangle it. The greater the degree of detangling, the further the comb will travel when combing the tangled hair.
As shown in
Figure 2C, in the case of treatment A, the measurement reached 9.8 N within the length of the tress when combed, even after five rotations. When using treatments B and C, which provide strong softness to the hair, the amount of tangling was low and the comb passed through, even when tangling five times, so there was no measurement value. It was confirmed that as the number of tangles increases, the distance at which the comb stops becomes shorter.
The static friction of all treatments could be measured after 15 rotations. If the number of tangles increases beyond 15, the degree of tangles in the hair increases and the difference between treatments decreases, reducing the discriminatory ability of the experiment. Therefore, the suitable number of hair rotations was considered to be 15 and this value was selected.
Hair tangles occur when the entire hair is not straightened. As combing progresses, the amount of hair that is not straightened and the force applied to the comb both increase. In other words, the force applied to the comb always increases as the combing distance increases. First, in this experiment, the maximum value during combing was measured to select the optimal comb needed to measure the degree of tangles. For this purpose, a 2 g hair tress with a length of 25 cm was used and the minimum amount of tress that could prevent tangles was used.
Figure 3A is a graph measuring the force between combs using nine types of combs with different degrees of spacing between the teeth. The force applied to the tress was measured using a comb with tooth spacing varying from 1 mm to 10 mm. It has been shown that the larger the comb tooth spacing, the greater the friction.
In order to select the most optimized comb for combability, the maximum moving distance value according to the comb tooth spacing was measured and the section detangling rate was evaluated by dividing the moving distance by the tress length of 150 mm.
Figure 3B shows data obtained regarding the force applied to hair washed with three types of commercially available treatment. The treatment used in this experiment is the same as the treatment used in
Figure 2. Comparing the tangle strength of the three treatments, the order was treatment B > treatment C > treatment A, excluding the comb with 1 mm spacing. The discriminatory ability of the treatment was found to be the greatest when tangled hair was combed with a comb with tooth spacing of 3 mm and 4 mm. Of the two combs, the comb with the lowest deviation across
n = 10 experimental measurements had a tooth spacing of 4 mm. Through this experiment, it was confirmed that the ideal comb tooth spacing for tangle evaluation was 4 mm.
3.2. Analysis of the Causes of Hair Tangles
The standardization of tangled tresses and a tress evaluation method for hair tangle assessment were achieved. To find out whether this assessment method is suitable for hair evaluation, it is necessary to know how to approach detangling.
When hair is combed, the area where tangles occur is the area furthest from the hair root. In hair that was 25 cm long, tangles occurred from the second half of the 19 cm section. To investigate the characteristics of this tangled hair portion, the contact angle was measured as shown in
Figure 4. Since hair can be more easily damaged the farther away it is from the root, the area closer to the hair root was also measured and the degree of damage to the hair was compared. In this case, the contact angle for the straight part was observed to be 95° to 96° regardless of the distance from the hair root. However, when the contact angle of the hair tangle area was measured, it was evaluated as 102°.
To further confirm the condition of the tangled part observed in
Figure 4, the surface was observed using SEM images. The part of the same hair strand that has no tangles and the part that always becomes tangled during combing were cut out and imaged; they are shown in
Figure 5. The area where tangles do not occur is the area located directly above the area where tangles occur.
As a result of classification based on the cuticle surface, out of a total of 16 straight hairs, 3 were confirmed to be hairs partially lacking cuticles, and 13 were healthy hairs with transparent cuticle edges. However, in the tangled area, 12 hairs were assessed as having at least partial cuticle deficiency and 4 hairs were assessed as having healthy cuticles. Therefore, it is determined that the cuticles of tangled hair are not in good condition. This suggests that the cuticle damage seen in the SEM images may be related to hair entanglement. Healthy hair has at least seven cuticles that are 500 nm thick, and these peel off when damaged [
9]. When the cuticle is removed, the lower cuticle may be the outermost layer, but the cortex may also be exposed [
28]. To determine whether the irregular shape of the cuticle seen in tangled hair reflects both the cuticle and the cortex below it, an analysis was performed using AFM, which can measure phase. As shown in
Figure 6A, the cuticle of straight hair was apparent, but the cuticle of tangled hair had unclear edges and could be seen to be broken.
As a result of observing the cuticle surface height in
Figure 6B, it can be seen that the height of the tangled hair is significantly lower than the height of the untangled cuticle. Considering that the healthy cuticle height is 500 nm, the cuticle of tangled hair is at a fairly low level.
3.3. Approach to Detangling Research Using Hair Detangling Evaluation
SEM and AFM measurements showed that the cuticle surface of the tangled area was uneven, resulting in increased interfacial tension and increased contact angle. Under the hypothesis that this induced degree of hydrophobicity would cause entanglement, we tried varying the degree of surface hydrophobicity. To make the hair hydrophilic, a treatment containing hydrophilic ingredients was applied to the hair and then washed. In order to change the hydrophilicity of the tangled cuticle, the cuticle was coated with a cosmetic ingredient of glucose rings using rice bran extract (Inositol, Tsuno, Japan), and the resulting OH groups attached to the hair surface to increase the moisturizing effect [
29]. It was evaluated whether lowering the surface contact angle to the level of non-tangling straight hair would lower the degree of tangling.
As a result of measuring the contact angle by changing the concentration of the aqueous solution used to soak the hair from 0.01% to 5%, the contact angle of the tangled hair changed from 103° to 95°. The section detangling rate of the section of hair treated in this way is shown in
Figure 7. The contact angle value of the straight part was selected as a control. When OH groups were applied to the hair surface, it can be seen that the detangling section rate increased as the contact angle decreased. It was observed that the d/d
0 value increased exponentially as the contact angle became similar to the control.
4. Discussion
In
Figure 1, the reason why friction is lower when combing treated hair compared to untreated hair is because the conditioning ingredients contained in the treatment are absorbed into the hair and make it smooth. It was expected that the longer the hair was spun, the more tangles would form, but it was observed that the tangles decreased after about 5 min. This is because the water applied to the hair to promote tangling naturally evaporates after 5 min and the tangling effect of the water begins to decrease.
The section detangling rate was evaluated using three commercially available treatments. The degree of tangling was adjusted according to the softness of each treatment. When tangling was performed using the palm of the hand for more than 15 times, all experiments reached 9.8 N during combing for hair tresses that were 15 cm long. If the number of rotations was fewer than 15, measurement was not possible because the comb passed through tresses washed with treatment, which were often soft due to oils or polymers. Since the ability to distinguish between treatments decreased when used more than 15 times, it was concluded that 15 palm rotations was the most appropriate.
The wider the spacing between the teeth of the comb, the greater the maximum friction when combing. This appears to increase the amount of hair that moves between the teeth of the comb when brushing, which increases the amount of force required to move the comb.
Each treatment offers varying levels of softness depending on its polymer or oil formulation [
30]. To develop effective treatment products, it is important to be able to distinguish meaningful differences in efficacy between treatments. If the spacing between the comb teeth is narrow, a lot of tangled hair can be caught between the combs, making it difficult to distinguish the degree of tangling. Conversely, if the spacing between combs is wider, the area covered by the comb becomes smaller, which has the disadvantage of reducing the ability to distinguish between treatments. As a result, it was found that the middle comb spacing of 4 mm was the most appropriate for differentiating between treatments in terms of detangling efficacy.
The contact angle was measured between the part of the same hair near the hair root and the 19 cm area where the tangle occurred. When a drop of water is dropped on hair, the water is absorbed between the hairs and the shape of the drop changes. This causes the contact angle to change continuously, so all measurements were taken 10 s after dropping the drop. After measuring 10 hairs, it was found that there was no difference in the contact angle between the 5 cm and 19 cm parts from the hair root, indicating that the hair was healthy and without damage. After evaluating the contact angle between the tangled and untangled areas at the same distance of 19 cm from the hair root, the contact angle of the tangled area was found to be larger. Hair damage directly affects 18-methyleicosanoic acid (18-MEA), the outermost surface lipid layer of the hair [
31]. When the hair surface is damaged, 18-MEA is damaged and the hair becomes hydrophilic [
1]. The reason the measured contact angle may be larger may be because the surface is more hydrophobic.
Unexpectedly, the contact angle of the tangled hair was higher than that of the detangled part, as shown in
Figure 4. The relationship between contact angle
θ and surface roughness
is defined by the following formula:
where
A is the adhesion tension, and
is the force vector at the interface between water and surface [
32]. From the relationship between the contact angle and surface roughness of the surface of biomaterials, it was revealed that hydrophilicity increases as the surface microstructure increases compared to the macrostructure [
33,
34,
35]. Accordingly, if the degree of hydrophobicity is the same, the unevenness of the hair surface can change, increasing surface tension and thus increasing the contact angle. In this experiment, considering that the contact angles of the 5 cm portion and the 19 cm portion of the hair root were similar, the degree of hydrophobicity determined through the surface lipid represented by 18-MEA appears to have not changed. Therefore, it is thought that the irregularities and roughness on the surface are different where entanglement occurs.
As a result of observing the hair using SEM images, it was found that while the cuticles were evenly distributed in the hair in the untangled area, many areas where the cuticle was peeled off were found in the hair in the tangled area. This surface irregularity appears to increase the surface tension and thus the contact angle. This appears to be related to the health of the cuticle due to tangles, or to the cuticle being damaged by physical stimulation due to tangles when brushing.
As a result of AFM observation, the cuticle of the tangled hair was not partially flat, and a low cuticle of about 100 nm in height was found. No flat areas were found, meaning that the cortex was not exposed. It is suggested that the cuticles had been worn away, such as from brushing or other damaging factors.
The difference between tangled hair and straight hair lies in the cuticles. To prevent tangles, damaged cuticles must be returned to their original state. They should also present similar physical properties to untangled cuticles.
To our knowledge, the technology for restoring cuticle shape currently does not exist. Instead, it was decided to change the contact angle from 103° to 95° by coating it with a weak hydrophilic material. A method of changing pH under alkaline conditions can be used to achieve hydrophilicity [
36]. The adsorption of nanoparticle or sugar materials is also an approach to imparting hydrophilicity to the surface [
37,
38]. It is a well-known fact that sugar has the effect of preventing water loss in hair [
39]. KAO uses erythritol, which has four OH groups, as a moisturizing ingredient. In this study, rice bran extract with six OH groups was employed.
The factors that make up the properties of hair include the radius of curvature, thickness, and contact angle [
9,
19,
20,
21]. Among these, the contact angle is a representative physical characteristic that distinguishes between chemically damaged hair, mechanically damaged hair, healthy hair with conditioner applied, and untreated hair [
40]. In this study, the contact angle of the immersed tangled hair became more hydrophobic as the content of rice bran extract increased. The fact that the contact angle of the tangled hair changed to the level of untangled hair means that the physical properties of the cuticle became similar.
Based on the results of the tress tangling method and evaluation method described above, the improvement in the section detangling rate according to the change in contact angle was determined. The fact that an improvement in tangle rate is observed as the state of the cuticle becomes similar to that of detangled hair means that the detangling efficacy can be evaluated through the section detangling rate in this evaluation method. The fact that the section detangling rate increases as the hair becomes more hydrophilic means that conditioners or treatments for detangler are effective if they have moisturizing properties.
In the future, further modeling work on the relationship between fiber length, thickness and entanglement probability is needed to better understand how entanglement forms. Hair tangles need to be studied not only by physical factors but also by how tangles occur, depending on the amount and internal structure of the proteins that make up the hair.