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Accepted: 2 October 2017

DOI: 10.1111/jocd.12454

ORIGINAL CONTRIBUTION

Examining polyquaternium polymers deposition on human


excised hair fibers

Javad Shokri PharmD, PhD1,2 | Maryam Shamseddini Lori PharmD3 |


Farnaz Monajjemzadeh PharmD, PhD4,2

1
Dermatology & Dermopharmacy Research
Team (DDRT), Tabriz University of Medical Summary
Sciences, Tabriz, Iran Background: Polyquaterniums (PQs) as important ingredients of hair products are
2
Faculty of Pharmacy, Tabriz University of
synthetic cationic polymers and are used in commercial hair volumizers and condi-
Medical Sciences, Tabriz, Iran
3
Student Research Committee, Tabriz tioners.
University of Medical Sciences, Tabriz, Iran Methods: Three different grades of polymers including PQ 87, 68, and 46 with vari-
4
Food and Drug Safety Research Center,
ous concentrations were used, and their hair deposition efficacy was measured at 5
Tabriz University of Medical Sciences,
Tabriz, Iran different pH values using hair diameters measurements by digital micrometer. Depo-
sition durability of polymer layer on the hair surface was tested by a defined wash-
Correspondence
Dr Farnaz Monajjemzadeh, Pharm-D, PhD of ing test. Optical microscopic images and polarized light images were also taken from
Pharmaceutics, Associate Professor of
treated and untreated samples for further investigation. Attenuated total reflectance
Pharmaceutical and cosmetic control, Faculty
of Pharmacy, Tabriz University of medical (ATR) spectral were recorded from hair samples to prove the polymer deposition
sciences, Tabriz, Iran.
and probable interaction with hair fibers.
Email: Monajjemzadehf@yahoo.com
Results: PQ-68 with the highest molecular weight (300 kDa) at pH = 9 exhibited
the best hair deposition efficacy. The results revealed that the deposition of poly-
mers is directly proportional to the pH values. The best results were seen at pH = 9,
and at the lowest pH (pH = 5), the efficiency of polymers was approximately equal
to zero. The best resistance against washing was shown by PQ-44 at pH = 6. ATR
successfully tracked the presence of the polymers on the hair fibers and also pro-
posed specific wave numbers for each polymeric agent, individually.
Conclusions: In general, two main parameter which can mainly influence the deposi-
tion efficacy of PQs are the type of polymer or its molecular weight and also the
positive charge density on the polymer molecules.

KEYWORDS
cationic polymer, deposition, FTIR spectroscopy, hair treatment, polymers and surfactants,
polyquaternium

1 | INTRODUCTION compounds and silicone derivatives have been introduced and


widely utilized to supplement the Cs performance. Polymeric
The hair conditioners and hair volumizers belong to the same active ingredients may be cationic or nonionic. Silicon derivatives
group in the hair care products in the case of active ingredients, may be cationic, anionic, or nonionic in nature. Cationic polymers
and the difference is mainly related to the polymer type and the act with film-forming properties and also electrostatic attractions
concentration of the polymers in the formulations. The first gener- and thus have higher volumizing and conditioning efficacy than
ations of these active ingredients are cationic surfactants (CSs) nonpolymeric types of conditioners. These polymers are also com-
such as cethyl trimethyl ammonium bromide (CTAB) or other quat- patible with the human skin. Cationic polymers can be used alone
ernized ammonium surfactants.1-3 In the last decades, polymeric as volumizers but anionic or nonionic silicones should be used

J Cosmet Dermatol. 2017;1–8. wileyonlinelibrary.com/journal/jocd © 2017 Wiley Periodicals, Inc. | 1


2 | SHOKRI ET AL.

with a cationic polymer as adjuvant.4-7 Volumizing polymers have


2.3 | Methods
been divided into natural polymers (such as guar gum, car-
rageenan, and xanthan), semisynthetic (such as quaternized guar or
2.3.1 | Preparation of polymeric solutions
cationic polysaccharides)8 and synthetic (PQs, silicones, and amine
oxides). PQs are one of the mostly used conditioners and volumiz- Polymeric solutions were prepared by dissolving different mass per-
ers in commercial hair care products, and their usage was signifi- centages of tested PQs in distilled water. Polymers were accurately
cantly increased in recent years due to their desired weighted, and distilled water was added to reach the required vol-
supplementary effects. These polymers can be used in both rinsing ume. The solutions were homogenized by stirring in 500 rpm for
and nonrinsing (leave on) conditioners and volumizers with no 20 minutes at room temperature. The resulting solutions were
need for any organic solvent or co-solvent additive owing to their adjusted to the desired pH by gradually adding diluted sodium
high water solubility. There are various types of PQs with very hydroxide or hydrochloric acid solutions (based on the desired pH of
different physicochemical characteristics. Molecular weight and the polymer solution) to a determined pH value, while stirring in the
molecular charge density are the main characteristics of these presence of pH-meter electrode. Six percent’s (1, 2, 3, 4, 5 and 6%
polymers. Molecular weight of PQs varies in a wide range from w/w) at 5 different pH values (5, 6, 7, 8, and 9) for any of the PQs
40 kDa (in PQ-16) to 1000 kDa (in PQ-11). Charge density of (PQ-87, PQ-68, and PQ-44) were prepared for the next step.
PQs also varies from 0.5 (in PQ-68 and PQ-44) to 6.1 meq/g (in
PQ-16) at pH = 7. Charge density is directly related to the num-
2.3.2 | Preparation of hair samples
ber and power of positive groups of molecules and is inversely
related to their molecular weights.9-11 The differences between In this study, the human natural and uncolored female hair fibers
PQ grades result from the composition of their monomers. The were used as sample hair tresses. Due to high fiber to fiber and inter
current monomers utilized in synthesis of PQs are vinyl-pyrroli- fiber variability, the hair samples of different persons were separated
done (VP), methacrylamide (VI), vinyl-immidazole (VA), dimethy- and divided into small groups with 20 hair fibers in each. To mini-
laminoethyl-methacrylate (DMAEMA), vinyl-caprolactam (VCap), and mize errors, each series of experiments were performed on the hair
quaternized vinyl-immidazole (QVI). PQs are also used in pharma- of only one person. The samples were prepared from the lower parts
ceutical industries as antimicrobial preservative or contact lens dis- of the hair shafts.
infectants.12-14
In this research, the deposition efficacy of PQs (various molecular
2.3.3 | Treating of samples with polymers
weights) and durability of the maintenance at different pH values and
concentrations were examined on excised human hair fibers by means The hair samples were treated by gently floating of hair samples in
of hair volume measurements, microscopic imaging, and ATR (FTIR) fresh polymer solutions for 30 s at 35°C. After 30 s, the hair sam-
analysis. ples were withdrawn from the solutions and dried using a hair dryer,
after gently rinsing with distilled water to remove the residuals and
un-bonded polymers from the hair fibers. “Without Polymer” con-
2 | MATERIALS AND METHODS
trols were also performed for each pH condition.
In this study, we attempted to simulate the normal usage condi-
2.1 | Materials
tion of no rinse hair conditioners due to increase extendibility of the
Polyquaternium 87, Polyquqternium 68, and Polyquaternium 44 results to the real situation. Many people use these conditioning
were received as a gift from BASF Chemical Co, Germany. Sodium products immediately after bath prior to drying of hairs by electric
hydroxide and hydrochloric acid were prepared from Merck chemical hair dryer, and thus, we selected this process for our study.
co, Germany.

2.3.4 | Measurement of hair fibers diameters


2.2 | Equipments
Hair diameters were measured by digital micrometer with 0.1 mm
ATR spectrophotometer (Bruker optics, Billerica, MA, USA), digital accuracy after complete drying of the hair fibers. Measurement was
micrometer with 0.1 lm accuracy (Mitotoyo, 0-25 mm, performed three times for each hair fiber, and the median of three
15
0.001 mm, Japan), optical microscope (Carl Zeiss, Jena, Ger- measurements was considered as the real diameter of the hair. The
many) equipped to digital camera (dino lite, AnMo Electronics, average of 20 hair diameters in each sample was considered as the
Hsinchu, Taiwan), dermatoscope equipped with a polarized light final diameter for the calculation of increasing volume efficiency of
imaging accessory (KC Tech Co Ltd, Anseong, Korea), dissolution each polymer solution. The hair fiber diameters of untreated hair
tester USP apparatus II (Erweka DT6K, Heusenstamm, Germany), samples “Without Polymer controls” were also measured for compar-
digital balance (AND GT-200, 0.0001 g, Japan), digital pH-meter ison of treating process on the deposition efficacy of different PQs
(Metrohm, Switzerland), air shaker-incubator (Heidolph, Germany). on the hair fibers.
SHOKRI ET AL. | 3

presence of polymeric layer on the surface of the hair samples.


2.3.5 | Washing test
Using this method, one can take IR spectral directly from intact hair
Washing test was carried out to evaluate the durability and mainte- without the need for sample preparation currently used in conven-
nance of polymer layers deposited on the hair fibers. For this test, tional IR spectroscopy. The spectral were taken from intact hair,
dissolution tester equipment was utilized (Erweka DT6K Dissolution treated hair, and pure polymeric film of each polymer. Polymeric
tester Germany, USP II apparatus). Washing test was performed at a films were prepared by evaporation of solvents of polymeric solution
predetermined temperature (35°C) at a constant paddle shaft speed in air incubator at 40°C.
(50 rpm) using a normal hair shampoo as a detergent. Hair samples
which were treated with various polymer solutions were put into the
2.3.9 | Statistical analysis
bottom of the dissolution tester cells containing 500 mL distilled
water and 10 g normal hair shampoo as a detergent. Cell contents All measurements were performed in triplicates. Hair fibers in each
were steered with standard paddles at 0.5 g rotation speed for test were at least equal to 20 fibers. Whenever necessary, the
5 minutes. After 5 minutes, samples were withdrawn and dried with means were compared using ANOVA test and the error was defined
warm air circulation. Each sample was washed three times with at the level of 0.05.
24 hours intervals. After each washing and drying, the diameters of
the samples were measured by digital micrometer.
3 | RESULTS AND DISCUSSION

2.3.6 | Calculations 3.1 | Results of optical microscopy


The changes in diameter and volume of the hair samples, thickness
The images of optical microscope from treated and untreated hair
of the polymeric layer, and related standard deviations were calcu-
samples obviously showed an increment in the hair diameter after
lated from below equations:
treating with different polymeric solutions. The samples of optical
D2 – D1 images of hair are shown in Figures 1 and 2. As shown in these fig-
Diameter change percent ¼  100 (1)
D1 ures, the treated hair is significantly thicker than the same hairs
without polymer treatment. This confirmed the results of diameter
D2 – D1
Polymeric layer thicknes ¼ (2) measurements using manual micrometer apparatus.
2
 
D2 3
Volume change percent ¼  100  100 (3) 3.2 | Results of ATR spectroscopy
D1
The ATR spectral of intact hair and treated hair fibers with three
STDEV
%RSD ¼  100: (4) polymers at three pH values are shown in Figures 2, 3, 4, 5, and 6.
Mean
These spectral confirmed the presence of polymeric layer on the hair
where D1 is untreated hair fibers “Without Polymer controls” mean fibers and propose a significant binding of the PQs to hair keratin
diameter, D2 is treated hair fiber samples mean diameter, and for all tested polymers.
STDEV is the standard deviation of data series related to each Untreated hair fiber ATR spectrum shown in Figure 3 illustrates
sample series. the main keratin vibrations which can vary between different races.

2.3.7 | Microscopic imaging


Two types of microscopic imaging were performed including optical
microscope imaging and polarized light imaging. Optical microscope
equipped with 5 MP digital camera and measuring software was
used for confirming the results of diameter measurements by digital
micrometer.
Microscopic imaging with polarized light was carried out for eval-
uating the deposition efficacy of different polymers on the hair sur-
face characteristics and ability of the polymers for improvement of
superficial properties of the hair.

2.3.8 | ATR spectroscopy


FTIR spectral were measured by ATR technique for the assessment F I G U R E 1 Optical Microscope image from untreated (below) and
of probable polymer-keratin interaction and confirmation of the treated (above) the same hair shaft in pH = 5 with PQ-44 solution
4 | SHOKRI ET AL.

tracked using certain vibrational peaks. An IR vibrational marker for


PQ 87 was seen at 1373 cm1, while vibration at 1279 was
assigned as a characteristic peak for PQ 68. Three main markers
were related to the PQ 44 at 1278, 1344, and 1726 cm1. These
findings prove the binding of the polymers to the hair fibers by a sci-
entific method and can be used in qualitative and also quantitative
determination. Some researchers have reported similar markers in
forensic medicine aspects. ATR studies revealed FTIR characteristics
of the polymers and provided a proof for their localization on the
hair fibers in intact hair.17,18

3.3 | Effect of molecular weights and charge


density of polymers on their deposition efficiency
Figure 7 shows the hair volume enhancement for three different
F I G U R E 2 Optical Microscope image from untreated (below) and polymers at 5 various pH values. Molecular weights of PQ-68, PQ-
treated (above) the same hair shaft in pH = 5 with PQ-68 solution
44, and PQ-87 are 300, 200, and 150 kDa and their charge densities
are 0.5, 1, and 1.8, respectively. As shown in this figure, molecular
Cysteine makes the major contribution to keratin structure in almost weight is an important factor in the deposition efficacy of polymer
all races. Cysteine is a naturally occurring, sulfur-containing amino at high pH values. The best volumizing power at high and or low pH
acid and is responsible for the disulfide linkages within the keratin values belonged to PQ-68 and PQ-87, respectively. These results
protein. The amide functionality in keratin results in three different show that MW is a key factor at high pH values, whereas the charge
vibrational peaks in IR region namely Amide I, II, and III which appear density is the most important factor at the low pH values. Other
at different wave numbers. In this study, the main amide vibrations concentrations of polymers (1%, 2%, 3%, 4%, and 5% w/w) also
were observed at 1639, 1529, and 1234 cm1. Other untreated hair showed similar results to that of 6% solution.
IR characteristic peaks were seen at 1460, 1052, and 1000 cm1
which can be attributed to C-H deformations and Cysteine monox-
ide and cysteic acid, respectively. Oxidative stresses of hair dryers or
3.4 | Effect of polymer concentration on volumizing
sunshine, bleaching or waving, result in a chemical deformation of
efficiency of PQs
Cysteine and its conversion to Cysteine monoxide, Cysteine dioxide, The volumizing efficacy of three polymers with different concentra-
and cysteic acid.16,17 Researchers have concluded that even in tions at different pH values is shown in Figures 7, 8, 9, and 10. As
untreated hair fibers, there are oxidative signs of age and environ- shown in these figures, the deposition efficiency of all polymers
mental conditions. Figures 4, 5, and 6 depict the ATR spectrum of increases with increase in the concentration of polymers in the solu-
untreated hair compared with different polymeric solutions at vari- tions. These results show that increasing the polymer concentration
ous pH values along with polymeric films for PQ 87, 67, and 44, results in thicker deposit of polymer layer on the surface of the hair
respectively. The presence of these PQs on the hair fibers can be fibers. The effect of concentration of volume enhancers is very

FIGURE 3 ATR spectrum of untreated


hair
SHOKRI ET AL. | 5

F I G U R E 4 ATR spectrum of untreated


hair (above), Pure PQ-87 film and treated
hair with PQ-87 in pH = 5, 7, and 9,
respectively

F I G U R E 5 ATR spectrum of untreated


hair (above), Pure PQ-68 film and treated
hair with PQ-68 in pH = 5, 7, and 9,
respectively

significant in all polymers but in polymer PQ-68, a plateau was seen of hair care products should be optimized based on the volumizing
at 5% w/w concentration which shows that this concentration is the efficacy and tissue irritancy. Using pH values above 9 can irritate the
optimum concentration for this purpose. The effect of polymer skin and should be avoided and pH values lower than 7 will reduce
concentration on volumizing efficacy is shown at all pH values. The the deposition efficacy of the final product. The statistical difference
statistical difference was significantly based on ANOVA results (P- was significantly based on ANOVA results (P-value < .05).
value < .05). Deposition durability of polymer layer on the hair surface was
tested by a defined washing test.
The washing test described here is a self-defined procedure by
3.5 | Effect of the polymer solutions pH value on
the authors. According to Society of Hair Testing guidelines for drug
deposition efficiency of PQs
testing in hair, a precise definition of the hair washing procedure
Effect of various pH values of the polymeric solutions on hair vol- being able to remove surface contaminations should be
ume expanding efficacy of PQs is shown in Figures 7, 8 and 9. The introduced.19
efficacy of all polymers increased with increase in the pH value of Thus, in hair washing tests, it is important to define the proce-
the polymeric solutions regularly. This effect was seen in all polymer dure completely and keep all parameters constant during the study.
concentrations. pH is one of the important factors in formulation of Different washing medium volumes, washing agent, and stirring
hair care products. The pH value of the polymer in the formulation rate and also washing durations have been used by different
6 | SHOKRI ET AL.

F I G U R E 6 ATR spectrum of untreated


hair (above), Pure PQ-44 film and treated
hair with PQ-44 in pH = 5, 7 and 9,
respectively

F I G U R E 7 Enhancement of hair volume by three PQs n different


pHs in 6% concentration F I G U R E 8 Volume enhancement efficacy of PQ-87 in different
pHs with different concentrations

researchers.20–22 For example, a similar duration of 5 minutes was


selected by Baeck et al. in hair washing test, but other parameters substance on the hair tresses and measuring the efficacy of the
20
were different. The presented method herein is derived from a washing test in removing oil contamination. The oil was chemically
pharmacopeia apparatus for pharmaceutical dissolution testing similar to sebaceous glands secretion and belongs to triglycerides
from pharmaceutical dosage form dissolution tests (GB Caleva Inc., named Oleoyl polyoxyl-6 glycerides (Labrafilâ, Gattefosse). The
UK) and is able to keep washing medium temperature, stirring rate contaminated hair was immersed in the washing medium prepared
and also volume at a constant defined value (Figure 11). The vali- by dissolving 10 g of a normal washing shampoo in the dissolu-
dation was made, and accuracy, precision, and reproducibility of tion apparatus vessel containing 500 mL of water. Temperature
the method in removing surface contamination were measured by was set at 35°C  0.5 at a constant paddle shaft speed of 0.5 g.
a validation test which was performed by applying an oily The weight of the hair tresses was measured after the washing,
SHOKRI ET AL. | 7

F I G U R E 9 Volume enhancement efficacy of PQ-68 in different


pHs with different concentrations

FIGURE 11 The washing test apparatus

The weight of the hair tresses after and before washing by the
defined procedure was used to calculate the accuracy as below:

Wcontaminated  Wafterwashing
Accuracy ¼  100:
Winitial

As the washing test purpose is based on decontamination, here


the accuracy of decontamination can be assumed as the washing
test accuracy.
Accuracy of the washing was in calculated as 96.5-97.6 percent
in removing oil contamination. The repeatability was measured as
0.551% and 0.451% (RSD) for interday and intraday precision,
respectively. The best resistance against washing was shown by PQ-44
at pH = 6.

4 | CONCLUSION

PQs have very good features for formulation of hair care products
due to their high skin compatibility, low toxicity, low irritancy, and
low interaction with other formulation ingredients especially anionic
surfactants.24,25,26 Some important parameters should be taken into
F I G U R E 1 0 Volume enhancement efficacy of PQ-44 in different
consideration to achieve an ideal quality and efficacy of such prod-
pHs with different concentrations
ucts. Different grades of PQs have different MWs and charge densi-
and this was repeated for three different hair samples within a ties. Higher molecular weight PQs have higher volumizing power at
day. The test was again repeated the day after, and the within pH values above Thus in formulations with acidic pH values, PQs
day and intraday differences were reported based on Relative with higher charge densities are preferred. The best pH range in the
Standard Deviation (RSD) based on ICH guidelines.23 formulation of these products is assigned to be between 7 and 9.
8 | SHOKRI ET AL.

Concentration of polymers in the final preparation is also an impor- 13. Peace JH, Ahlberg P, Wagner M, Lim JM, Wirta D, Branch JD.
tant factor for the quality assurance of PQs. Higher concentrations Polyquaternium-1–preserved travoprost 0.003% or benzalkonium
chloride–preserved travoprost 0.004% for glaucoma and ocular
result in higher volume expanding power but each polymer may have
hypertension. Am J Ophthalmol 2015;160:266-274.
an optimum concentration in the final product preparation. 14. Alasino RV, Garcia LG, Gramajo AL, Pusterla JP, Beltramo DM, Luna
JD. Ocular biocompatibility of polyquaternium 10 gel: functional and
morphological results. Journal of Materials Science: Materials in Medi-
ORCID
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Farnaz Monajjemzadeh http://orcid.org/0000-0001-9369-5136 15. Gao T. Evaluation of hair humidity resistance/moisturization from
hair elasticity. J Cosmet Sci. 2007;58:393.
16. Chan K, Kazarian S, Mavraki A, Williams D. Fourier transform infra-
red imaging of human hair with a high spatial resolution without the
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