Synthesis of water-based latexes using siloxane-derived surfactants and investigation of their use in pigment printing applications

Open Access
02-07-2025

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Authors: Sinan Karademir; Ayfer Saraç Özkan
Published in: Journal of Coatings Technology and Research | Issue 5/2025

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Abstract

The article investigates the synthesis of poly(vinyl acetate-co-butyl acrylate) latexes using three types of silicone surfactants at varying concentrations near their critical micelle concentration (CMC). The study highlights the significant influence of surfactant type and concentration on the physicochemical properties of the latexes, including viscosity, particle size, zeta potential, and surface tension. Notably, the amphoteric surfactant ABIL® B 9950 demonstrated superior performance, providing balanced stabilization and high conversion rates. The latexes were extensively characterized, and their stability was monitored over a year. The most stable latexes were then evaluated for their performance in pigment printing applications on cotton fabrics. The results showed that the latex synthesized with ABIL® B 9950 at a concentration of 0.16 wt.% (AB-50-016) exhibited the most compatible results in terms of washing fastness, rubbing fastness, hand feel, and color yield. This research provides valuable insights into the development of high-performance, environmentally friendly binders for the textile industry, offering a new perspective on the use of silicone-based surfactants in latex formulations.

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Introduction

Emulsion polymerization is a widely used method to produce a variety of commercially important polymeric materials, including architectural coatings, synthetic rubber, adhesives, paints, paper coatings, and textile applications. Water's thermal conductivity allows for efficient control and removal of the heat generated during the reaction; it maintains its fluidity even at high solids content, and high molecular weight polymers with accelerated polymerization rates can be obtained. Latexes can be applied directly to surfaces without any additional processing needed. Thus, application becomes easier in terms of production, and costs are reduced. Additionally, it is environmentally friendly because it eliminates toxicity and flammability issues that are associated with other polymerization methods.^1‐6

In emulsion polymerization, monomer blends can be used to improve and modify the properties of products. Vinyl acetate monomer, when copolymerized with other monomers such as vinyl chloride, methacrylate, or acrylate, can produce useful, durable latexes with a variety of molecular and particle morphological properties for different industries. The properties of the polymers also depend on the molecular composition of the monomers and their mixing ratios.

Vinyl acetate (VAc)/butyl acrylate (BuA) emulsion copolymer is a frequently preferred industrial latex. Acrylate copolymers are known for their ability to increase the bond strength of adhesives by forming thin, transparent, flexible, high-gloss, and durable films that form strong bonds between materials. They are pervasive in paints, coatings, and the textile industry to produce water-repellent coatings and color-fastness enhancing materials. The VAc/BuA copolymerization system is characterized by large differences in reactivity ratios (rVAc = 0.05 and rBuA = 5.5), propagation rate constants (kp(VAc) = 4000 L/mol/s and kp(BuA) = 200 L/mol/s), and glass transition temperatures (Tg(VAc) = 32 °C and Tg(BuA) = − 54 °C). Since, these properties enable the synthesis of a wide variety of latexes, the VAc/BuA copolymer is of great interest. The semi-continuous polymerization system provides a more homogeneous distribution of the particles of both monomers.^5,7‐13

Xinghai et al.¹⁴ investigated the effect of the preparation method on the polymerization products. Findings indicated that the semi-continuous monomer addition process resulted in a stable latex with a narrow particle distribution and high monomer conversion. Ovando-Medina et al.¹⁵ emphasize the importance of surfactant concentration and monomer addition rate in achieving desired polymer properties and conversion in emulsion polymerization processes.

In recent years, new research on silicone surfactants has shown that they increase the efficiency of microemulsions due to their high surface activity and are useful for applications, where silicone content provides a performance advantage. Polysiloxane-based block copolymers provide important features such as high hydrophobicity, higher thermal stability, flexibility, optical transparency, and biocompatibility.^16,17

A silicone surfactant contains a permethylated siloxane group coupled with one or more polar groups. Graft copolymers are most commonly composed of polar groups attached to a polydimethylsiloxane backbone. The general configurations of silicone surfactants are shown in Fig. 1. One or more different types of hydrophilic groups (R = anionic, cationic, zwitterionic, or nonionic)^18‐21 are covalently bonded onto hydrophobic siloxane backbones of different chain lengths. The Si–O bond energy of hydrophobic groups (about 460.5 kJ/mol) is quite high compared to the C–C (304.0 kJ/mol) and C–O (358.0 kJ/mol) bond energies that are found in conventional carbon chain surfactants.²²

Fig. 1

General structure of silicone surfactants

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The polar groups in these surfactants are usually nonionic polyether groups such as polyoxyethylene (PEO) or polypropylene (PPO).²³ Ethylene oxide (EO) groups that occur by ethoxylation, form polyethylene glycol (PEG) chains that add a hydrophilic end to surfactants, improve water affinity, and decrease interfacial tension. On the other hand, propylene oxide (PO) groups create polypropylene glycol (PPG) segments, which increase both flexibility and hydrophobicity. When PEG and PPG segments are combined, the hydrophobic PO segments naturally tend to oil, solid, or air interfaces, creating an amphipathic structure that balances hydrophilic and hydrophobic properties.^16‐21,24

ABIL^® B 8843 (polysiloxane polyether copolymers) (INCI)²⁵ is a nonionic, nontoxic²⁶ silicone surfactant. Its commercial name is PEG/PPG-14/0 Dimethicone, which contains an average of 14 moles of EO (the number of mers in the silicone chain (m, n), the number of EO groups (x) and propylene oxide groups (y), and the degree of polymerization m = 13, n = 5).^27‐31

ABIL^® 88184 is a nonionic silicone surfactant. Its commercial name is PEG/PPG-20/6 Dimethicone (m = 38, n = 7), and its chemical structure is an alkoxylated derivative of Dimethicone containing an average of 20 moles of EO and 6 moles of PO.³²

ABIL^® B 9950 is an amphoteric silicone surfactant (a + b = 3 to 50) that improves washing fastness. Its commercial name is Dimethicone Propyl PG-betaine.^33,34

In the textile industry, silicone surfactants offer antistatic properties, softness, and effective sterilization and disinfection capabilities, while also providing a good softening effect to fibers. These surfactants are both safe and long-lasting.³⁵

The pigment printing technique has become the most preferred technique in the textile industry in recent years due to its economic, environmental, and toxicological advantages. The advantage of this technique is that the print quality is better, it can be applied to almost any fiber or mixture, and a notable feature distinguishing pigment printing from certain other techniques is eliminating the need for washing subsequent to the fixation process. In this technique, pigments are fixed to the fiber with binders. The binder plays a crucial role in determining the overall fastness properties of the prints. Additionally, the binder can provide other properties, such as gloss, matte, or hand feel, to the final printed material. Overall, the binder is a key component in the printing process that ensures the longevity and quality of the printed design.^36‐38

In conclusion, the structural versatility of silicone surfactants enables their use across a broad spectrum of applications. Their ability to achieve low surface and interfacial tensions, combined with unique wetting and spreading capabilities, underscores their importance in advancing surface science and material application.

Our research aims to investigate the physicochemical properties of latexes prepared with different types of silicone surfactants and their performance in pigment printing textile applications. Poly(vinyl acetate-co-butyl acrylate) copolymer latexes were synthesized by the semi-continuous emulsion polymerization method with a fixed VAc/BuA ratio of 85:15. In the recipe, the amount of ammonium persulfate (APS), N-methylol acrylamide, and polymerization duration (2.5 h) were kept constant. Three types of silicone-based surfactants were used, and samples were synthesized at five concentrations (0.08, 0.12, 0.16, 0.20, and 0.24 wt.%) close to their critical micelle concentration for each. Brookfield viscosity, particle size, zeta potential, polydispersity index of particle size (PDI), pH, theoretical solid content (TSC), practical solid content, conversion, and surface tension results are reported. Rubbing, washing, color fastness, and standard performance tests were carried out on cotton woven and knit fabrics to assess the potential of latex products derived from silicone surfactants as textile binders for pigment printing.

Experimental

Chemicals

Commercially available VAc and BuA (CHT Turkiye Chemistry Inc.) monomers were directly used without purification. N-Methylol acrylamide (Amol) (CHT Turkiye Chemistry Inc.) was used as a stabilizing co-monomer, and ammonium persulfate ((NH4)₂S₂O₈ (Merck) (APS)) was used as a thermal initiator. Nopco-1497 (Turkish-Henkel Chemicals Industry Co.) was used as an antifoam agent, and sodium bicarbonate (NaHCO₃, Merck) was used as a buffer to keep the pH of the reaction medium between 4.5 and 5.5. All substances were used without further purification. Deionized water was used in analyses and syntheses. ABIL^® B 8843 (Evonik Personal Care), ABIL^® B 9950 (Evonik Personal Care), and ABIL^® 88184 (Evonik Personal Care), were used, and Fig. 2 presents their separate molecular structures. In each recipe, the surfactant concentration was calculated to be 0.08, 0.12, 0.16, 0.20, and 0.24 wt.%. The CMC values of these surfactants were determined by diluting aqueous stock solutions prepared at various concentrations.^26,28,39 The measurements were taken at specific intervals using the du Nouy ring method. A graph was created as a result of the obtained data. The surfactant concentrations were plotted against the corresponding surface tension values, with the results shown in Table 1. The challenges in calculating HLB values for silicone-based surfactants and the detailed methodologies are provided in the supplementary file. For the pigment printing formulations pigment, BEZAPRINT Blue TB (CHT Turkiye Chemistry Inc.) and as a thickener (Synthetic-Acrylate based thickener) (CHT Turkiye Chemistry Inc.) were used. A standard VAc/BuA latex, STD, was provided by CHT Turkiye Chemistry Inc. for comparison purposes.

Fig. 2

Chemical structures of ABIL series

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Table 1

Recipe for copolymerization of VAc and BuA: different surfactant types and concentrations

Components	Constituents	Amount (wt%)
Monomer blend/monomer ratio (85/15)	Vinyl acetate (VAc)	37.15
Monomer blend/monomer ratio (85/15)	Butyl acrylate (BuA)	6.56
Different type Silicone Surfactant		Sample codes
	ABIL® B 8843 (CMC = 0.074 mg/mL)	AB-43-008	AB-43-012	AB-43-016	AB-43-020	AB-43-024
	ABIL® 88184 (CMC = 0.078 mg/mL)	AB-84-008	AB-84-012	AB-84-016	AB-84-020	AB-84-024
	ABIL® B 9950 (CMC = 0.082 mg/mL)	AB-50-008	AB-50-012	AB-50-016	AB-50-020	AB-50-024
	Different Concentration (wt % )	0.08	0.12	0.16	0.2	0.24
Stabilizing co-monomer	Amol/N-methylol acrylamide (NMA)	1.88
Initiator	Ammonium persulfate (APS)	0.24
Buffer	Sodium bicarbonate (NaHCO3)	0.12
Anti-foam agent	Nopco V-1497	0.10
Deionized water	Deionized water	Calculated to provide the total recipe formula according to the varying amount of surfactant
Total		100.00

Synthesis of latexes

Poly(vinyl acetate-co-butyl acrylate) latexes were synthesized in a 250-mL three-necked round-bottom flask with one central neck and two vertical side necks.

The central neck of the 3-necked flask was equipped with a reflux condenser to prevent evaporation and ensure the recycling of monomers and water from the reaction medium. Other necks were equipped with a dropping funnel and thermometer. The experimental setup is shown in Fig. 3. A magnetic stirrer with a heater was used for heating and mixing purposes. During the emulsion polymerization, the constant stirring rate was 400 rpm, and the reaction medium temperature was kept constant at 72–74 °C. Since, there could be a difference of approximately 3–4 °C between the temperature at the bottom of the flask and the liquid surface during the reaction, it was important to constantly control the temperature.

Fig. 3

The experimental setup

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Therefore, the flask was kept in the silicone bath until it reached a constant temperature. The outside of the flask was insulated with aluminum foil to reduce heat transfer to the environment. The total reaction period was nearly 2.5 h.

Synthesis was made using 3 different silicone surfactants (ABIL^® B 8843, ABIL^® B 88184, and ABIL^® B 9950) at 5 different concentrations (0.08, 0.12, 0.16, 0.20, and 0.24 wt.%) for each surfactant type. According to changes in the amount of surfactant, the water amount was adjusted in the total recipe. The appropriate amounts of water for the latexes were calculated by adhering to the basic recipe for the synthesis of latexes, as shown in Table 1.

The polymerization process was carried out as follows: from the total water specified in the recipe, 6.3 g was reserved for dissolving ammonium persulfate (APS). The remaining water was divided equally, with half added to a three-necked flask and the other half to a beaker for preparing the pre-emulsion. The pre-emulsion was prepared by adding vinyl acetate (VAc), butyl acrylate (BuA), N-methylolacrylamide (NMA), and two-thirds of the total emulsifier into the beaker. The mixture was stirred at 400 rpm for 30–40 min using a magnetic stirrer, with the beaker covered to prevent evaporation.

In the three-necked flask, the remaining one-third of the emulsifier, sodium bicarbonate (NaHCO₃), and Nopco V-1497 were added to the water and stirred at 400 rpm. The mixture was heated to 70 °C and maintained at this temperature for at least 10 min.

The total APS and the reserved water for dissolving APS were divided into 10 equal parts. Each portion of APS was dissolved in an equal volume of water, and the first portion of APS was added to the flask once the flask mixture reached 72 ± 1 °C. The total pre-emulsion in the beaker was divided into 9 equal volumes. When 1 portion of APS was added, 1 volume of pre-emulsion was dropped into the flask with a dropping funnel at approximately 15 min intervals.

The final portion of APS was dissolved in water and added to the flask. The reaction mixture was heated to 80 °C, stirred for another 15 min until complete polymerization was achieved, and then slowly cooled to room temperature. This procedure ensured a controlled and efficient polymerization process. After the latexes were cooled, they were filtered through a filter sock.

Characterization of the copolymer latexes

Experimental and theoretical solid contents, conversions of latexes

To determine the experimental (practical) and theoretical solid amounts of the obtained latexes,

To ensure minimum evaporation, we prepared aluminum foil pouches and weighed their tares beforehand. Nearly 1 g of each latex was weighed into aluminum foil pouches with a Precisa XB 220A SCS balance (m₁). Samples were heated in an oven at 105 ± 2 °C for 2 h, and all the water in the latex was allowed to evaporate. Once the water had evaporated completely, the samples were placed in a desiccator and cooled to room temperature. The remaining solid content of the latexes was re-weighed using the precise balance (m₂). Equation (1) was used to experimentally calculate the percent solids of each latex based on the weighing results.

$$\% {\text{ Solid}} = \left[ {\left( {m_{1} } \right) - \left( {m_{2} } \right)/\left( {m_{1} } \right)} \right]*100$$

(1)

Calculating the theoretical solid contents (TSC) of the obtained latexes was performed using equation (2) and % by weight in the emulsion polymerization recipe.

$${\text{TSC}}\,\left( \% \right) = \left( {{\text{VAc }} + {\text{ BuA}}} \right)\% + 0.{95}\, \times \,{\text{NMA}}\% \, + \,0.{76} \times {\text{Emulsifier}}\% \, \, + \,{\text{APS }}\% \, + \,{\text{NaHCO}}_{{3}} \%$$

(2)

We calculated %conversions using equation (3) gravimetrically. The experimental and practical solid percentages calculated for latexes were used to determine the percentage conversions of polymers.

$$\% {\text{ Conversion}} = \left( {\% \,{\text{Solid/TSC}}} \right)*100$$

(3)

Stability analyses of latexes (determination of viscosity, particle size, zeta potential, and polydispersity index (PDI))

The viscosities of latexes were measured at 19 °C using a Brookfield Programmable DV-II + model viscometer and spindle number 4. After mixing for a minimum of 3 min, the viscosities of each latex were measured in centipoise (cP).

Latex samples were measured using a Brookhaven 90 Plus zeta sizer to determine particle sizes, zeta potentials, and polydispersity indexes.

Surface tension

The Sigma 701 model multipurpose tensiometer was used to measure surface tension by using a Pt du Nouy ring at 25 °C.

Fourier transform infrared spectroscopy (FTIR)

For FTIR analysis, the samples are dried at 50 °C in the oven, and then the formed films are mixed with a small quantity of KBr and pressed into tablets. The chemical groups and composition of the samples were analyzed using a Perkin Elmer Spectrum Two Fourier transform infrared spectrometer. For every sample, it was observed that roughly the same peaks and graphs formed, and the spectrum of one sample is shown in Fig. 11.

Differential scanning calorimeter (DSC)

The sample was tested as freeze-dried. The glass transition temperature (T_g) of samples was measured by a Perkin Elmer Jade DSC differential scanning calorimeter. For this, 3.7 mg of sample was weighed into a standard DSC hermetic alumina crucible. For each sample, the following program was applied: hold for 2 min. at − 70 °C, heat to 170 °C at 20 °C/min, hold for 1 min. at 170 °C, cool to − 70 °C at 10 °C/min, hold for 3 min. at − 70 °C, heat from − 70 °C to 115 °C at 20 °C/min

Storage stability

Figure 4 presents comparative images of the synthesized latexes, showing samples both immediately after synthesis (in the top three rows) and after one year of storage (in the bottom three rows). The samples that maintained their stability after a 1-year period are AB-43-008, AB-43-012, AB-43-016, AB-43-024, AB-84-016, AB-84-020, AB-84-024, AB-50-008, AB-50-012, AB-50-016, AB-50-020, and AB-50-024. Among these, the samples suitable for use in pigment printing applications are AB-43-008, AB-43-016, AB-84-020, AB-50-008, AB-50-012, AB-50-016, and AB-50-020.

Fig. 4

The appearance of the obtained latexes after synthesis and one year of storage

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Textile application methods

Determination of the textile application performance of samples in cotton knit and cotton woven fabrics

Among the prepared samples that maintained their colloidal stability without phase separation after approximately one year, the printability and fastness levels of the samples were investigated. Washing and rubbing fastness (wet and dry), hand feel, color yield, color strength (K/S), hydrophilicity, and pigment migration tests were applied to cotton woven and knit fabrics using the CHT Turkiye company's printing recipe and standard procedures. Pigmented cotton knit and cotton woven fabrics can be seen in Fig. 5.

Fig. 5

Appearances of fabrics: (a) cotton knit, (b) cotton woven

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Pigment printing

Pigment printing applications were performed with samples that maintained their stable structure at the end of one year.

Preparation of the printing paste recipe

The pigment printing pastes were prepared according to the following recipe in Table 2. Evaluations were made according to the standard binder application. In distilled water, we prepared the print paste by adding 120 g of binder per kilogram and 15 g of thickener. To achieve an approximate pH of 8–9, ammonia was added. Then, 0.1 wt.% liquid dispersion Bezaprint Blue TB pigment was added to each print paste. The viscosities of the final print pastes were 7000–9000 cPs, as determined with a Brookfield viscometer by using spindle number 4 at 20 rpm. Thickeners and binders are sensitive to polymers and electrolytes. Due to various factors, such as water hardness, electrolytes in the paint, etc., viscosity checks were carried out both before and after painting. If the product had low electrolyte sensitivity, we observed a decrease in consistency (viscosity), making it difficult to print. Until consistency could be pressed, the thickener was added again. Finally, 7000–20000 cP could be considered the viscosity that could be printed for pigment printing applications. It was more appropriate to use a small amount of thickener.

Table 2

Printing paste composition

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Pigment printing application

The printing pastes were applied to the fabrics using a flat-screen technique by Johannes Zimmer on the MINI MDF/749 Magnet sample printing machine with a squeegee. Printing was done on the template numbered 62 T/printing with a squeegee diameter of 12 mm, squeegee pressure of 3 bar, and squeegee speed of 4.5 m/min. The printed fabric was dried at 100 °C for 2 min and cured at 150 °C for 5 min.

Washing fastness

A testing method was used for determining the durability of colors against several wash conditions used for dyed and/or printed textile products. The method used washing and drying processes with a household washing machine according to ISO EN 6330/40ºCX3.

Rubbing fastness

According to British Standard Document BS EN ISO 105-X12 Textiles standard procedures, samples were tested with a "crockmeter". Both wet and dry rubbing tests were conducted to determine the color resistance of the fabrics. Tests were assessed using the Gray Scale shown in Fig. 6. A gray scale is an assessment tool used to evaluate color change and staining during colorfastness tests. The grayscale has values from 1 to 5. The highest fastness value is 5, and the lowest fastness value is 1.

Fig. 6

Grayscales are used for color staining and color change

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Color measurements

In the field of textiles, color attributes are commonly quantified through parameters such as color strength (K/S values), color difference (ΔE), and chromatic attributes (L*, a*, b*) as per the standards set by CIELab (CIE = “Commission Internationale de l’Eclairage’s”). Alongside CIELab's values of colorimetric parameters, the Metamerism Index (MI) is also taken into consideration. For the colorized fabric, K is its absorption constant, S is its scattering constant, and R is its reflectance fraction. The K/S value was calculated by the Kubelka–Munk equation, as shown in equation (4).

$$\frac{K}{S} = \frac{{1 - R_{\lambda \max }^{2} }}{{2R_{\lambda \max } }}$$

(4)

A color scale based on the opponent-color theory states that color receptors in the human eye perceive color pairs as opposites: light and dark, red and green, and yellow and blue. The values of colorimetric parameters (L*, a*, b*, C*, and h*) and the color strength (K/S value) of all samples were measured using the Data Color Benchtop Spectro 1000 family. DL values were taken according to the illuminant D65 (referring to daylight as the color reference) observer and the CIE 1964 (International Commission on Illumination) supplemental standard observer (10° observer)—Value indicates darkness, and value indicates lightness.^40,41

Hand feel

The fabric hand feel includes tests involving weaving, twisting, and squeezing actions, and these comparisons were analyzed and evaluated by experts at CHT Turkey Chemistry Inc. against fabrics treated with an external standard of commercial VAc-BuA (45% by weight) synthesized by CHT Turkey Chemistry Inc. It is important to note that hand feel evaluations are subjective and may vary among individuals due to differences in sensory perception and tactile differences. According to a scale ranging from 0 (roughest) to 100 (softest), fabrics are evaluated based on softness preference.

Hydrophobic properties of the printed fabrics

In cotton knit and woven fabrics, it was assessed according to the standard methods. Samples were evaluated according to the standard binder before and after dyeing. The products that pass water fastest and those that pass water slowly are evaluated between 1 and 10. 10 is the most hydrophilic value.

Results and discussion

Results of characterization measurements

Experimental and theoretical solid contents, conversions of latexes

Table 3 provides experimental and theoretical results for solid contents and conversion percentages of latexes. When all samples were compared, the experimental solids content results of 20 wt.% samples synthesized with ABIL^® B 9950 were closest to the theoretical solids calculation values, and the best conversions were obtained in the same sample with 99.8. This result is indicating efficient stabilization provided by the surfactant. This high experimental solid content ratios-to-TSC ratio reflects excellent process efficiency, minimal coagulation, and maximum monomer utilization.

Table 3

Brookfield viscosity, Particle size, Zeta potential, Polydispersity index of particle size (PDI), pH, Theoretical solid content (TSC), Practical solid content, %Conversion, Surface tension results of samples, respectively

	Brookfield viscosity (cP)			Particle size (nm)	Zeta potential (mV)	PDI	pH	TSC (%)	Solid content (%)	Conversion%	Surface tension (mN/m)
Latex sample	1 rpm	5 rpm	10 rpm
ABIL® 88184
AB-84-024	35.00	22.50	5.62	479.2	−15.41	0.005	3.94	46.04	44.9	97.5	39.05
AB-84-020	18.70	9.37	7.50	558.3	−13.22	0.005	4.46	46.01	44.1	95.8	39.90
AB-84-016	39.40	30.00	28.10	320.6	−15.38	0.155	4.38	45.98	45.1	98.1	44.09
AB-84-012	52.50	35.60	18.70	383.9	−21.65	0.005	3.78	45.95	45.5	99.0	45.84
AB-84-008	22.50	18.70	3.75	479.1	−9.11	0.098	3.95	45.92	43.3	94.3	45.87
ABIL® B 9950
AB-50-024	28.70	19.00	15.00	581.8	−20.13	0.005	4.30	46.04	45.4	98.6	43.59
AB-50-020	33.20	28.20	18.75	323.6	−75.67	0.183	3.72	46.01	45.9	99.8	42.74
AB − 50-016	38.70	33.70	20.10	518.7	−17.98	0.005	5.27	45.98	44.5	94.6	43.87
AB − 50-012	41.30	36.00	23.75	497.5	−15.38	0.06	4.92	45.95	43.7	95.1	42.73
AB − 50-008	50.20	37.50	28.20	429.4	−20.67	0.005	4.52	45.92	44.4	96.8	42.04
ABIL® B 8843
AB-43-024	18.70	15.00	7.50	556.3	−21.94	0.005	4.69	46.04	43.2	93.8	43.21
AB − 43-020	22.50	16.90	9.37	536.0	−16.66	0.005	4.11	46.01	44.0	95.6	43.62
AB − 43-016	56.20	30.00	11.20	500.5	−24.34	0.005	4.01	45.98	43.4	94.4	44.62
AB − 43-012	131.20	33.70	16.90	382.0	−18.5	0.039	4.26	45.95	44.5	96.8	43.65
AB − 43-008	150.00	37.5	20.60	373.0	−15.77	0.005	4.39	45.92	42.2	91.9	35.35

In a detailed study conducted by Kong et al.,^42,43 the semi-continuous emulsion polymerization of a vinyl acetate (VAc) and butyl acrylate (BuA) system was performed without the use of emulsifiers. This comparative analysis underscores the significant advantages of surfactant-stabilized emulsion polymerization over emulsifier-free systems:

Except for the ABIL^® B 8843 series, other data show that particle size reduction is consistent with other studies^7,44‐46 that solids content increases.

These findings emphasize the advantages of surfactant-stabilized emulsion polymerization systems in industrial applications such as coatings and textile binders, where high solids contents, efficient monomer conversions, and stability are crucial for product quality and cost-effectiveness. Compared to emulsifier-free methods, surfactant-based systems exhibit superior performance, making them a preferred option for advanced latex production.

Stability analyses of latexes (viscosity, particle size, zeta potential, polydispersity index (PDI))

The viscosity of the synthesized latex samples was measured to evaluate the influence of surfactant type and concentration. The change in viscosity of the samples according to increasing surfactant concentration is shown in Fig. 7. Measurements were taken at 1, 5, and 10 rpm. Data for all results are given in Table 3.

Fig. 7

Brookfield viscosity changes with surfactant concentrations for ABIL^® B 8843, ABIL^® B 88184, and ABIL^® B 9950, respectively

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For the samples prepared with ABIL® 88184, the viscosity increased rapidly with increasing surfactant concentration, reached a peak at 0.16 wt.%, and then was followed by a gradual decline. This behavior is consistent with the dual stabilization mechanism attributed to the surfactant's PEG and PPG segments. These groups are effective in stabilizing the latex at lower concentrations depending on the steric effects of silicone surfactant. However, at higher concentrations, the stabilizing effect may diminish, causing a reduction in viscosity. This trend is in line with findings by Soni et al.,¹⁸ who demonstrated that surfactants with a more complex molecular architecture, such as those incorporating PEG and PPG, show significant viscosity changes depending on concentration. Specifically, they noted that surfactants initially stabilize the solution, but at higher concentrations, steric effects become dominant, leading to a reduction in viscosity due to weaker stabilization of latex particles. Therefore, PPG increases viscoelastic properties by increasing hydrophobic structures within the polymer matrix.⁴⁷

The viscosity of the latex synthesized with ABIL^® B 8843 decreased consistently with increasing surfactant concentration, as shown in Fig. 7. Surfactants with shorter EO chains provide less steric stabilization compared to longer-chain surfactants.⁴⁶ Karacetin et al.⁴⁸ reported in their study that viscosity decreased depending on both the surfactant concentration and the number of EO units. PEG segments provide strong interaction with water. The flexible structure of polysiloxane chains contributes to faster viscosity reduction and accelerated dehydration and demulsification. It indirectly reduces the viscosity of the emulsion by reducing surface tension and interfacial stability. The viscosity difference between emulsion phases also decreases, leading to the destabilization of stable emulsions. El-Sharaky et al.²⁶ reported that ABIL^® B 8843 showed the highest demulsification efficiency in their study. After one year, phase separation was observed in the latex prepared with ABIL^® B 8843 at a concentration of 0.20 wt.%, as shown in Fig. 4.

Our samples prepared with ABIL^® B 9950 revealed a gradual decrease in viscosity as the surfactant concentration increased. This trend underscores the amphoteric structure of ABIL^® B 9950, which contributes to balanced stabilization through a combination of steric and electrostatic effects. Similarly, Smid-Korbar et al.³⁴ reported that ABIL^® B 9950 exhibited excellent stabilization properties, maintaining stability performance at near points of its CMC due to reduced aggregation enabled by its unique amphoteric structure.

However, Jovanović et al.³³ observed a contrasting behavior in carboxymethylcellulose (cMc) solutions, where ABIL^® B 9950 caused a significant increase in viscosity at a 2% concentration. This difference likely stems from the interaction of the surfactant with the polymer matrix in their aqueous system, compared to our emulsion-based poly(vinyl acetate-co-butyl acrylate) latex system. These variations illustrate the system-dependent nature of ABIL^® B 9950's performance, where it adapts its behavior based on the surrounding matrix and interaction dynamics.

The results from both studies underline the versatility of ABIL^® B 9950 in various applications. Its ability to stabilize complex systems, modulate viscosity, and enhance interfacial properties makes it a valuable component in diverse industrial formulations. The differences in behavior between the systems in the studies by Jovanović et al.,³³ Smid-Korbar et al.³⁴ and in our study highlight the multifunctionality and adaptability of the samples obtained with ABIL^® B 9950 to changing application needs. Therefore, it is an effective surfactant for advanced material applications.

The particle size, zeta potential, and PDI measurements offer significant insights into the colloidal stability, homogeneity, and application potential of latex samples synthesized with silicone-based surfactants. All data are shown in Table 3. Figure 8 presents the variation in particle size due to surfactant concentrations; the zeta potential change graph is shown in Fig. 9.

Fig. 8

Particle size changes with surfactant concentrations for ABIL^® B 8843, ABIL^® B 88184, and ABIL^® B 9950, respectively

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Fig. 9.

Zeta potential changes with surfactant concentrations for ABIL^® B 8843, ABIL^® B 88184, and ABIL^® B 9950, respectively

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For the samples synthesized with ABIL^® B 88184, particle size first decreases and then increases with increasing concentrations of the surfactant. Stability first increases and then becomes constant. Stability on CMC is almost constant. Change in zeta potentials: between − 13.22 and − 21.65 (8 units, approx.). These are the latexes with the lowest stability compared to the others.

The observed trend suggests that surfactant concentrations close to the CMC optimize particle size reduction, but further increases might lead to agglomeration or reduced stabilization efficiency. Similar findings were reported by Xinghai et al.,¹⁴ who noted that surfactant concentrations near the CMC ensure optimal stabilization during semi-continuous polymerization.

For the samples synthesized with ABIL^® B 9950, particle size increases rapidly, and stability first decreases and then increases with increasing concentrations of the surfactant, but in general, it can be considered constant. Even at surfactant concentrations close to CMC, stable latex is formed, and among all samples, the latexes whose stability changes the least were obtained with this surfactant. Zeta potential values are changing between − 15.38 and − 20.67 (5 units, approx.). AB-50-020 is the most stable latex, with the lowest pH, and the most durability. 2nd latex with the lowest particle size. Viscosity is at average values. Additionally, ABIL^® B 9950's unique molecular structure minimizes particle aggregation and ensures long-term stability, aligning with findings by Smid-Korbar et al.³⁴ and Jovanović et al.³³ Both our results and the referenced studies emphasize the role of ABIL^® B 9950 in enhancing colloidal stability. In our latex systems, ABIL^® B 9950 significantly reduced particle aggregation at low concentrations and maintained stability over one year. Jovanović et al.³³ similarly reported an increase in the zeta potential of cMc particles upon the addition of ABIL^® B 9950, attributing this to its amphoteric structure, which increases the electronegativity of the particles. Smid-Korbar et al.³⁴ also highlighted its exceptional stabilization capabilities in emulsions, where its low CMC value prevented excessive molecular aggregation.

For samples synthesized with ABIL^® B 8843, particle size increases regularly, and stability increases first, and then does not change much with surfactant concentration; the change is in a narrow range. Zeta potential values are changing between − 15.77 and − 24.34 (9 units, approx.), and latexes have somewhat higher stability than ABIL^® B 88184.

These findings are consistent with established principles in colloidal chemistry that particle size and zeta potential are critical indicators of emulsion stability. Smaller particle sizes and higher absolute zeta potential values increase stability due to increased surface area and electrostatic repulsion, respectively. Similarly, Naghash et al.⁴⁹ reported in their studies on St/BA copolymers with silicone-modified samples that the morphologies of latexes depend on the silicone types.

Surface tension

Initially, the surface tension of water at 25 °C was measured as approximately 73,104 mN/m. Under optimum conditions, depending on their concentration and structures, silicone surfactants reduce surface tension to values as low as approximately 20 mN/m.²⁵ Based on our results, silicone surfactant concentrations close to CMC resulted in lower surface tensions than water. When the concentration of surfactants is below CMC, hydrophobic groups cannot align tightly. This causes the forces to act unequally on the liquid surface, diminishing the surface tension.⁵⁰ When surfactant concentration exceeds CMC, the liquid's surface tensions reach equilibrium. Surface tension is influenced by the amount of free emulsifier present in latex, with an increase in this amount leading to a decrease in surface tension. However, the emulsifiers' adsorption onto polymer particles reduces the concentration of free emulsifiers in the latex, consequently causing an increase in surface tension. The adsorption behavior of emulsifiers differs based on their properties and the properties of the polymer particles. Therefore, increasing the concentration of free emulsifiers in the latex prevents their adsorption onto the polymer particles and minimizes the polarity differences at the interfaces, effectively decreasing the surface tension. This effect is particularly pronounced in VAc-rich copolymer latexes, where the emulsifier concentration plays a critical role in stabilizing the system and enhancing interfacial properties.^45,51‐53

Kekevi et al.²³ mention in their study that the additional PPG group increases the hydrophobicity of the copolymer and causes a decrease in the surface tension values of the aqueous solutions of the copolymers. Furthermore, increasing the chain length of PPG and PEG increased the hydrophobic character of the copolymers and decreased the surface tension values of aqueous copolymer solutions.

Figure 10 illustrates surface tension changes with surfactant concentrations. ABIL^® B 88184 is the surfactant that causes the greatest decrease in surface tension due to the PEG/PPG groups in its structure. ABIL^® B 8843 surfactant contains only PEG groups. First, the surface tension increased and then decreased. ABIL^® B 9950, which has an amphiphilic structure, did not cause a significant change in surface tension.

Fig. 10

Surface tension changes with surfactant concentrations for ABIL^® B 88184, ABIL^® B 9950,

Full size image

The observed reduction in surface tension, both in our results and in those of Smid-Korbar et al., ³⁴ further supports its ability to enhance interfacial stability, a key factor in ensuring uniform dispersion in emulsions.

The findings of Kim et al.²⁴ demonstrate that the structural properties of surfactants significantly influence their surface-active properties, including surface tension, cloud point (Cp), and sedimentation time. For silicone-based surfactants used at low concentrations, an increase in EO chain length raises the cloud point due to stronger hydrogen bonding between EO groups and water molecules. Conversely, an increase in the hydrophobic effect of PO groups lowers the cloud point.

Before reaching the CMC, surfactants effectively reduce surface tension, highlighting a clear relationship between surface tension and cloud point at low concentrations.

ABIL^® B 8843 respectively

The low surface tension observed for samples prepared with ABIL^® B 8843 at 0.08 wt.% can be attributed to the EO units in its structure. These EO units enhance hydrophilicity, facilitating strong hydrogen bonding with water and promoting efficient surfactant alignment at the air-water interface, thereby reducing surface tension. Additionally, EO units influence the cloud point, as phase separation in aqueous solutions of nonionic surfactants occurs at a specific temperature, determined by the balance between hydrophilic and hydrophobic groups. Therefore, carefully optimizing the ratio of EO to PO groups in surfactant formulations is essential for achieving the desired stability and performance characteristics.

El-Sharaky et al.²⁶ reported that nonionic star polymeric surfactants modified with silicone polyethers, such as ABIL^® B 8843, significantly reduce surface tension due to their rapid adsorption at the oil-water interface. The incorporation of ABIL^® B 8843 enhanced the hydrophilicity of the surfactant, lowering CMC and improving emulsion-breaking performance. At the critical micelle concentration, because of cloud point behavior, silicon-containing surfactants reduce surface and interfacial tension, which is consistent with our results.

Fourier transform infrared spectroscopy (FT-IR)

All samples exhibited similar FT-IR spectra. Figure 11 presents the FT-IR spectrum of sample AB-50-020. On the sample graph, a broad band between 3500 and 3000 cm⁻¹ is indicative of the typical O-H stretching, which can arise from free hydroxyl groups in water, hydrogen bonds, (N-H) intermolecular bonds, or Si-OH groups, observed specifically at 3349 cm⁻¹. Moreover, peaks around 2960 cm⁻¹ are attributed to the asymmetric C–H stretching vibrations from (CH₃) groups within acrylic or silicone matrices. A characteristic absorption peak at 1729 cm⁻¹ is related to carbonyl (C=O) in acrylic groups. Another peak seems nearly at 1665 cm⁻¹ from N–C=O. Additionally, a peak of methylene (CH₂) observed at 1434 cm⁻¹. Characteristic deformation vibrations of −CH₂, − CH₃, and −CH groups are evident at 1370 cm⁻¹. Within the copolymer, VAc displays a C–O stretching vibration at 1227 cm⁻¹, while BuA gives a C–O stretching vibration at 1173 cm⁻¹. Ester group vibrations for the O–C group of the acrylate polymer are observed at 1118 cm⁻¹, and 1019 cm⁻¹ was identified at the C–O etheric bond of PEG, Si–O–Si stretching vibrations on the backbone. Additionally, −C=C– peaks at 944 cm⁻¹, C–H (CH₃) at 800 cm⁻¹, and Si–C stretches of Si–(CH₃) could be seen at 796 cm⁻¹.^54,55

Fig. 11

FT-IR spectrum for AB-50-020

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Differential scanning calorimeter (DSC)

The glass transition temperature (T_g) of poly(vinyl acetate-co-butyl acrylate) copolymers is significantly influenced by the monomer composition, surfactant types, and their concentrations. T_g values of our samples are given in Table 4. Misra et al.⁵⁶ reported that the molecular weight distribution and branching degrees determine the glass transition temperature. Additionally, the semi-continuous polymerization method produced more homogeneous structures. Depending on the structures of ABIL^® B 88184 and ABIL^® B 8843, T_g also increases. Naghash et al.⁴⁹ explored the influence of varying types and concentrations of silicone on the properties of copolymers. An increase in both silicone concentration and silane content was observed to enhance the thermal stability of the copolymers, while significantly reducing the glass transition temperature (T_g).

Table 4

Glass transition temperature of samples

	T_g Onset (ºC)
	ABIL^® 88184
AB-84-020	38.42
	ABIL^® B 9950
AB-50-020	38.60
AB-50-016	35.87
AB-50-012	40.35
AB-50-008	35.50
	ABIL^® B 8843
AB-43-016	35.85
AB-43-008	36.55

Li et al.⁵⁷ reported that the conversion significantly influences the glass transition temperature (T_g), where higher conversion levels lead to T_g values approaching the theoretical predictions. St:BuA:MMA was used, and it was reported that as the monomer conversion increased, the glass transition temperature of the latex gradually decreased, and when the final conversion exceeded 90%, the Tg reached a plateau. In addition, as the BuA content decreased, the T_g reached values around 40 °C.

Misra et al. ⁵⁶ evaluated the T_g values based on BuA content in semi-continuous emulsion polymerization. For samples with BuA content close to 15% (e.g., B2 = 11), surface examinations revealed that a small amount of BuA contributes to smooth film formation, which persists for several days due to gradual coalescence. T_g values obtained via DSC measurements were 21 °C, whereas DMS measurements yielded 38 °C. These differences highlight the significant influence of measurement methods and durations on T_g results, underlining the complexity of T_g determination in such systems.

Ghorbani et al.⁴⁴ demonstrated that increasing the PDMS surfactant content (0–6 wt.%) substantially increased the glass transition temperature (Tg) of VA/BA copolymer latex, ranging from − 20.7 to 21.7 °C. This improvement was attributed to enhanced monomer distribution and a more uniform particle morphology. These findings align with the consistently higher experimental Tg values observed in this study compared to theoretical predictions, emphasizing the role of surfactant composition in influencing thermal properties.

Erbil ⁵⁸ reported that a single glass transition temperature (T_g) was observed for the semi-continuous copolymer latex films, which decreased linearly with increasing BA content, confirming the formation of a homogeneous copolymer structure. High conversion rates and controlled T_g variation indicate consistent product quality.

Seul et al. ⁵⁹ demonstrated that the copolymerization exhibited remarkable conversion rates exceeding 95% under optimal conditions (0.7 wt.% KPS, 15 wt.% PVA-217). Glass transition temperatures (T_g) showed a systematic decrease with increasing BA content, with experimental values consistently higher than theoretical predictions (e.g., at 3% BA: theoretical 32.4 °C, experimental 41.2 °C). The conversion efficiency showed inverse correlation with BA content, achieving maximum efficiency at 5% BA concentration. This relationship between composition, Tg, and conversion rates provides crucial datas for tailoring mechanical properties and film-forming characteristics for industrial applications.

Results of textile application

Pigment printing applications were performed on cotton knit and woven fabrics. Samples that were stable without phase separation after one year among the binders that we prepared in five different concentrations by weight (wt.%) using three different types of silicone surfactants were selected and evaluated with textile performance tests.

In the pigment printing method, it is also necessary to understand the washing and rubbing fastness, hand feel (touch), durability, and, depending on the intended application, other properties such as water repellency, wettability, and color fastness.

Washing fastness, rubbing fastness, hand feel, pigment migration, color yield, and wettability tests were performed with the samples we prepared for pigment printing, which is a widely used method in textiles. Standard washing tests were performed after pigment dyeing. Each printed fabric's dry and wet rubbing fastness has been tested. The obtained results were evaluated according to the results of the commercially used STD (VAc-BuA (45 wt.%) material. All tested fabrics are shown in Figs. 12 and 13. The photographs show the aspects of cotton knit and cotton woven fabrics before and after washing, respectively. The sample names can be seen on the fabrics. The sample order is the same for each fabric column. The last two columns indicate images of STD samples before and after washing.

Fig. 12

Appearance of cotton knit and cotton woven fabrics before and after washing test application

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Fig. 13

Rubbing fastness results of cotton woven and cotton knit fabrics in dry and wet tests

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In Tables 5, 6, and 7, the results of all textile tests are reported. The results of the rubbing fastness tests are shown in Fig. 13. When the results of the rubbing fastness tests were compared with the STD, more compatible results were observed in the wet rubbing fastness results for woven fabrics and the dry rubbing fastness tests for the two types of fabrics. The most compatible rubbing fastness results for knit and woven fabrics were obtained for the AB-50-016 sample.

Table 5

Textile applications measurement values include rubbing fastness (dry and wet), washing fastness, hand feel, color yield, pigment migration (which refers to the relative evaluation of the color difference between the front and back sides of the fabric for all samples), and wettability for cotton knit and cotton woven fabrics

	Cotton knit fabric							Cotton woven fabric
	Rubbing fastness		Washing fastness	Hand Feel	Color Yield	Pigment Migration	Wettability (hydrophilicity) (seconds)	Rubbing fastness		Washing fastness	Hand Feel	Color Yield	Pigment Migration	Wettability (Hydrophilicity) (seconds)	Thickener Usage (g/kg)
	Dry	Wet	DL*		DL*			Dry	Wet
Latex sample
ABIL^® 88184
AB-84-020	3–4	2	2.31	100	−2.06	90	5	3–4	2–3	−1.12	85	0.99	90	4	15.2
ABIL^® B 9950
AB-50-020	3–4	1–2	−0.14	80	−1.57	100	6	3–4	2–3	1.31	80	−0.41	100	7	15.2
AB-50-016	3–4	2–3	−0.05	90	−2.14	95	8	3–4	3	0.24	85	0.51	95	8	15.2
AB-50-012	3–4	1–2	2.15	95	−0.88	90	8	3–4	2–3	−1.15	90	0.78	90	8	15.85
AB-50-008	3–4	1–2	0.9	100	0.26	85	10	3–4	2–3	0.44	95	0.93	85	9	15.77
ABIL^® B 8843
AB-43-016	3–4	1–2	0.17	70	−1.61	95	5	3–4	2–3	0.67	80	1.13	95	4	15.2
AB-43-008	3–4	1–2	−1.07	80	−1.08	100	5	3–4	2–3	0.64	85	0.88	95	5	15.2
STD BuA-VAc Binder (45%)
STD BuA-VAc Binder (45%)	4–5	3–4	STD	100	Standard	100	5	4–5	4	STD	95	STD	100	3	15.6

*DL values are taken according to D 65 light. − value indicates darkness + value indicates lightness

Table 6.

CMC decision and metamerism index (MI) for dyed cotton fabrics

Cotton knit fabric
Sample	Illuminant/observer	DL*	Da*	Db*	DC*	Dh*	Decision	CMC DE	Metamerism Index	Description
ABIL^® 88184
AB-84-020	D65/10°	−2.06	1.42	0.58	−1.19	0.97	Fail	1.21		Darker	More red	More yellow
	F11/10	−2.04	1.71	0.71	−1.18	1.42	Fail	1.39	0.61	Darker	More red	More yellow
	A/10°	−1.86	2.11	0.88	−1.88	1.3	Fail	1.32	0.45	Darker	More red	More yellow
ABIL^® B 9950
AB-50-020	D65/10°	−1.57	1.25	0.92	−1.41	0.66	Fail	1		Darker	More red	More yellow
	F11/10	−1.49	1.57	1.12	−1.53	1.17	Fail	1.17	0.54	Darker	More red	More yellow
	A/10°	−1.32	2.21	1.31	−2.29	1.15	Fail	1.2	0.80	Darker	More red	More yellow
AB-50-016	D65/10°	−2.14	1.24	−0.17	−0.44	1.17	Fail	1.22		Darker	More red	More blue
	F11/10	−2.31	1.78	−0.33	−0.19	1.8	Fail	1.56	1.04	Darker	More red	More blue
	A/10°	−2.08	1.54	−0.15	−0.7	1.38	Fail	1.28	0.44	Darker	More red	More blue
AB-50-012	D65/10°	−0.88	0.72	0.88	−1.12	0.22	Pass	0.62		Darker	More green	More yellow
	F11/10	−0.83	1.12	1.01	−1.3	0.77	Pass	0.79	0.52	Darker	More green	More yellow
	A/10°	−0.68	1.61	1.17	−1.86	0.71	Pass	0.82	0.82	Darker	More green	More yellow
AB-50-008	D65/10°	0.26	0.14	0.55	−0.55	−0.15	Pass	0.27		Lighter	More red	More yellow
	F11/10	0.26	0.59	0.57	−0.72	0.39	Pass	0.38	0.44	lighter	more red	More yellow
	A/10°	0.37	0.85	0.7	−1.05	0.33	Pass	0.45	0.82	lighter	more red	more yellow
ABIL^® B 8843
AB-43-016	D65/10°	−1.61	1.14	−0.45	−0.15	1.22	Fail	1.04		Darker	More red	More blue
	F11/10	−1.82	1.74	−0.71	0.18	1.87	Fail	1.42	1.03	Darker	More red	More blue
	A/10°	−1.6	1.35	−0.49	−0.31	1.4	Fail	1.07	0.39	Darker	More red	More blue
AB-43-008	D65/10°	−1.08	0.82	0.64	−0. 96	0.41	Pass	0.68		Darker	More red	More yellow
	F11/10	−1.07	1.27	0.7	−1.04	1	Pass	0.89	0.61	Darker	More red	More yellow
	A/10°	−0.91	1.57	0.89	−1.6	0.84	Pass	0.84	0.64	Darker	More red	More yellow
STD BuA-VAc Binder (45%)
	D65/10°	−2.36	0.82	−1.44	0.88	1.4	Fail	1.42		Darker	More red	More blue
	F11/10	−2.75	1.29	−2.06	1.6	1.84	Fail	1.84	1.37	Darker	More red	More blue
	A/10°	−2.57	−0.12	−1.81	1.59	0.88	Fail	1.46	1.68	Darker	More green	More blue

Cotton woven fabric
Sample	Illuminant / Observer	DL*	Da*	Db*	DC*	Dh*	Decision	CMC DE	Metamerism Index	Description
ABIL^® 88184
AB-84-020	D65/10°	0.99	0.4	1.27	−1.32	−0.17	Pass	0.71		Lighter	More red	More yellow
	F11/10	1.33	0.27	1.82	−1.83	−0.17	Pass	0.98	0.87	Lighter	More red	More yellow
	A/10°	1.3	1.71	1.81	−2.43	0.54	Fail	1.12	1.84	Lighter	More red	More yellow
ABIL^® B 9950
AB-50-020	D65/10°	−0.41	1.52	1.88	−2.34	0.61	Fail	1.02		Darker	More red	More yellow
	F11/10	0.1	1.13	2.76	−2.95	0.46	Fail	1.14	0.99	Lighter	More red	More yellow
	A/10°	0.1	3.27	2.77	−4.04	1.41	Fail	1.56	2.11	Lighter	More red	More yellow
AB-50-016	D65/10°	0.51	0.67	1.65	−1.78	−0.09	Pass	0.75		Lighter	More red	More yellow
	F11/10	0.94	0.39	2.38	−2.4	−0.19	Fail	1.03	1	Lighter	MORE red	more yellow
	A/10°	0.9	2.18	2.33	−3.12	0.67	Fail	1.22	1.97	Lighter	More red	More yellow
AB-50-012	D65/10°	0.78	0.83	2.05	−2.21	−0.11	Pass	0.96		Lighter	More red	More yellow
	F11/10	1.29	0.54	2.93	−2.97	−0.18	Fail	1.3	1.22	Lighter	More red	More yellow
	A/10°	1.27	2.75	2.9	−3.9	0.88	Fail	1.56	2.52	Lighter	More red	More yellow
AB-50-008	D65/10°	0.93	0.75	2.32	−2.42	−0.3	Fail	1.08		Lighter	More red	More yellow
	F11/10	1.56	0.23	3.34	−3.29	−0.59	Fail	1.52	1.49	Lighter	More red	More yellow
	A/10°	1.47	2.66	3.28	−4.18	0.6	Fail	1.66	2.61	Lighter	More red	More yellow
ABIL^® B 8843
AB-43-016	D65/10°	1.13	0.3	1.45	−1.44	−0.35	Pass	0.81		Lighter	More red	More yellow
	F11/10	1.52	0.1	2.04	−2.01	−0.4	Fail	1.11	0.97	Lighter	More red	More yellow
	A/10°	1.46	1.61	2.06	−2.6	0.32	Fail	1.19	1.91	Lighter	more Red	More yellow
AB-43-008	D65/10°	0.88	0.45	1.43	−1.48	−0.2	Pass	0.74		Lighter	More red	More yellow
	F11/10	1.25	0.28	2.03	−2.04	−0.21	Fail	1.01	0.91	Lighter	More red	More yellow
	A/10°	1.22	1.82	2.03	−2.68	0.52	Fail	1.15	1.89	Lighter	More red	More yellow
STD BuA-VAc Binder (45%)
	D65/10°	−0.1	−0.09	0.81	−0.69	−0.43	Pass	0.38		Darker	More green	More yellow
	F11/10	0.06	−0.19	0.95	−0.87	−0.43	Pass	0.42	0.22	Lighter	More green	More yellow
	A/10°	0.02	0.19	1.07	−1.01	−0.41	Pass	0.41	0.35	Lighter	More red	More yellow

Table 7.

BEZEMA QC colormetric results and K/S values

	CIE lab color difference							CMC result DE
Sample	Light Source / Angle	DL*	Da*	Db*	DC*	Dh*	DE*	deIE	deIL	deIC	deIH	DE	Color Strength (K/S)
ABIL^® 88184
AB-84-020	D65/10°	2.31	−0.3	0.06	0.09	−0.29	2.34	1.1	1.08	0.04	−0.18	1.1	83.66%
	F11/10	2.41	−0.42	0.16	−0.03	−0.45	2.46	1.25	1.22	−0.01	−0.27
	A/10°	2.36	−0.03	0.18	−0.13	−0.12	2.37	1.2	1.2	−0.05	−0.06
ABIL^® B 9950
AB-50-020	D65/10°	−0.14	1.24	−1.06	0.36	1.59	1.64	0.97	−0.06	0.15	0.96	0.97	99.84%
	F11/10	−0.17	0.91	−1.08	0.77	1.18	1.42	0.77	−0.09	0.3	0.7
	A/10°	−0.16	0.83	−1.05	0.45	1.26	1.35	0.67	−0.08	0.16	0.65
AB-50-016	D65/10°	−0.05	0.38	−1.09	0.8	0.84	1.16	0.6	−0.02	0.33	0.50	0.6	102.82%
	F11/10	−0.23	0.47	−1.36	1.18	0.81	1.45	0.67	−0.12	0.46	0.48
	A/10°	-0.18	−0.13	−1.33	1.2	0.59	1.35	0.53	−0.09	0.43	0.3
AB-50-012	D65/10°	2.15	1.16	0.28	−0.8	0.89	2.46	1.18	0.99	−0.33	0.53	1.18	77.73%
	F11/10	2.41	0.78	0.69	−0.89	0.55	2.63	1.3	1.21	−0.35	0.33
	A/10°	2.4	1.95	0.77	−1.69	1.24	3.18	1.49	1.2	−0.61	0.63
AB-50-008	D65/10°	0.9	0.75	−0.6	0.18	0.94	1.32	0.71	0.42	0.07	0.57	0.71	90.59%
	F11/10	0.89	0.69	−0.61	0.39	0.83	1.28	0.68	0.44	0.15	0.5
	A/10°	0.92	0.83	−0.53	0.01	0.99	1.35	0.69	0.46	0	0.5
ABIL^® B 8843
AB-43-016	D65/10°	0.17	0.89	−0.61	0.15	1.07	1.09	0.65	0.08	0.06	0.64	0.65	96.91%
	F11/10	0.17	0.71	−0.61	0.4	0.84	0.95	0.53	0.09	0.15	0.5
	A/10°	0.18	0.74	−0.55	0.08	0.91	0.93	0.48	0.09	0.03	0.47
AB-43-008	D65/10°	−1.07	1.67	−1.11	0.23	1.99	2.27	1.3	−0.5	0.09	1.2	1.3	106.26%
	F11/10	−1.11	1.31	-1.13	0.74	1.57	3.45	1.13	−0.56	0.29	0.94
	A/10°	−1.08	1.16	−1.07	0.31	1.54	1.91	0.97	−0.55	0.11	0.79
	STD BuA-VAc Binder (45%)
	D65/10°	−2.36	0.82	−1.44	0.88	1.4	2.88	1.42	−1.08	0.37	0.84	1.42	124.06%
	F11/10	−2.75	1.29	−2.06	1.6	1.84	3.67	1.84	−1.35	0.63	1.09
	A/10°	−2.57	−0.12	−1.81	1.59	0.88	3.14	1.46	−1.27	0.57	0.45

	CIE lab color difference							CMC result DE
Sample	Light Source / Angle	DL*	Da*	Db*	DC*	Dh*	DE*	deIE	deIL	deIC	deIH	DE	Color Strength (K/S)
ABIL^® 88184
AB-84-020	D65/10°	−1.12	0.94	−0.34	−0.08	1	1.5	0.8	−0.53	−0.03	0.6	0.8	107.02%
	F11/10	−1.13	0.78	−0.32	0.14	0.83	1.41	0.76	−0.58	0.05	0.49
	A/10°	−1.1	0.75	−0.29	−0.13	0.79	1.36	0.7	−0.57	−0.04	0.4
ABIL^® B 9950
AB-50-020	D65/10°	1.31	−0.23	0.03	0.07	−0.22	1.33	0.63	0.62	0.03	−0.14	0.63	90.28%
	F11/10	1.37	−0.3	0.09	−0.01	−0.31	1.4	0.73	0.7	0	−0.18
	A/10°	1.33	−0.07	0.09	−0.05	−0.1	1.34	0.69	0.69	−−0.02	-0.05
AB-50-016	D65/10°	0.24	0	−0.57	0.52	0.24	0.62	0.28	0.11	0.21	0.15	0.28	100.82%
	F11/10	0.14	0.03	−0.73	0.71	0.2	0.75	0.3	0.07	0.27	0.12
	A/10°	0.15	−0.33	−0.72	0.78	0.08	0.8	0.29	0.08	0.28	0.04
AB-50-012	D65/10°	−0.14	−0.56	0.88	−0.56	−0.87	1.05	0.58	−0.07	−0.23	−0.53	0.93	108.12%
	F11/10	−0.03	−0.53	1.03	−0.88	−0.76	1.16	0.57	−0.02	−0.34	−0.45
	A/10°	−0.07	−0.23	0.98	−0.73	−0.69	1.01	0.44	−0.03	−0.26	−0.35
AB-50-008	D65/10°	0.44	0.54	0.14	−0.35	0.43	0.71	0.36	0.21	−0.15	0.26	0.36	92.78%
	F11/10	0.55	0.37	0.31	−0.39	0.29	0.73	0.36	0.28	−0.15	0.17
	A/10°	0.55	0.85	0.35	−0.73	0.56	1.07	0.48	0.28	−0.26	0.29
ABIL^® B 8843
AB-43-016	D65/10°	0.67	−0.47	−0.25	0.42	−0.32	0.85	0.41	0.32	0.17	−0.19	0.41	98.93%
	F11/10	0.64	−0.53	−0.32	0.44	−0.43	0.89	0.45	0.33	0.17	−0.25
	A/10°	0.59	−0.74	−0.36	0.69	−0.45	1.01	0.45	0.31	0.24	−0.23
AB-43-008	D65/10°	0.64	−0.13	−0.31	0.34	0.01	0.73	0.33	0.3	0.14	0.01	0.33	97.99%
	F11/10	0.65	−0.3	−0.32	0.38	−0.22	0.79	0.39	0.34	0.15	−0.13
	A/10°	0.6	−0.41	−0.35	0.51	−0.17	0.81	0.37	0.31	0.18	−0.09
	STD BuA-VAc Binder (45%)
	D65/10°	−0.1	−0.09	0.81	−0.69	−0.43	0.82	0.38	−0.05	−0.28	−0.26	0.38	98.52
	F11/10	0.06	−0.19	0.95	−0.87	−0.43	0.97	0.42	0.03	−0.33	−0.25
	A/10°	0.02	0.19	1.07	−1.01	−0.41	1.09	0.41	0.01	−0.36	−0.21

CIE stands for Commission Internationale de l´Eclairage (The International Commission on Illumination)

DL* = difference in lightness/darkness value (+ = lighter - = darker)

Da* = difference on red/green axis (+ = redder - = greener)

Db* = difference on yellow/blue axis (+ = yellower - = bluer)

DC* = difference in chroma (+ = brighter - = duller)

DH* = difference in hue

DE* = total color difference value

As the concentration of silicone surfactants increased in samples prepared with ABIL^® B 9950, the amount of pigment transfer to the back side of the fabrics also increased.

The results reported by Zhang et al.⁶⁰ showed that both the fastness and hardness properties of printed fabrics depend on the types and concentrations of binder used. Rodríguez et al.⁶¹ found that the amount of silicone grafted to the acrylic chains, not the total amount of silicone, was the main factor affecting the film properties in silicone grafted acrylic latexes prepared by the semi-continuous method with reactive vinyl groups. They reported that hydrophobicity, water resistance, and thermal stability properties increased with the amount of grafted silicone.

Coatings containing high levels of non-grafted silicone showed separate submicrometer silicone phases and exhibited low properties. It shows the importance of not using more silicone content than necessary in terms of product properties. It was also stated that the increase in silicone content increased the contact angle.

In the hydrophilicity values shown in Table 3 obtained in our study, the samples obtained with ABIL^® B 9950 showed more hydrophilic properties with increasing concentrations of silicone surfactant. However, it can be understood from the results that the types and structural properties of silicone surfactants have different effects on hydrophilicity. According to the STD binder, hydrophilic properties decrease with silicone content, while they differ according to the type of silicone surfactant. While the highest hydrophilicity belonged to the STD binder, the lowest hydrophilicity was observed in the cotton knit fabrics of the AB-50-008 sample.

When the K/S values were compared to the standard sample, an increase was observed for the woven fabric samples AB-43-016, AB-50-012, AB-50-016, and AB-84-020.

AB-50-016 can be considered the most suitable concentration in terms of color yield, hand feel, and washing resistance, and AB-50-008 can be considered the most suitable concentration in terms of emulsion stability and product.

Due to the structure of the fabrics, different color yield results were obtained. While more vibrant and bright colors were obtained in woven, no differences were observed between the products in knitting. When evaluated according to the STD, better results were obtained in terms of the MI for woven fabrics.

Mahli et al.⁶² studied in detail the effects of surfactant types (anionic and nonionic) on color development and viscosity in pigment printing and reported that nonionic surfactants provide better color stabilization and development than anionic surfactants. They reported that nonionic surfactants at low concentrations provide advantages in terms of color matching but that increasing the number of EO units negatively affects color performance in red and yellow pigments. According to the data in Table 6 in our CMC and MI studies, especially in the samples obtained with the amphoteric

ABIL^® B 9950, the low CMC DE values indicate that this surfactant provides good color matching by minimizing color differences. However, it was observed that color matching performance decreased as the surfactant concentration increased. These findings indicate that amphoteric surfactants can offer a wider range of applications in pigment printing as an alternative to nonionic structures.

Color measurements on dyed fabrics were made with the Data Color Benchtop Spectro 1000 family device. The values are shown in Tables 6 and 7. The values in the tables show the evaluations according to the fabrics dyed with the prepared commercial standard (STD VAc/BuA 45% commercial binder).

10° Observer: Represents CIE 1964 Supplementary Standard Observer, covering an approximately 90 mm diameter circle viewed from 1-meter distance, D65/10° (Daylight Illuminant), F11/10° (Fluorescent Illuminant), A/10° (Tungsten Illuminant), and DL* values represent the relative lightness/darkness of the fabric, where negative values indicate darker tones compared to the reference standard. CMC Decision: Categorizes samples as "pass" or "fail" based on ΔE values, a quantitative metric of color difference relative to a standard. ΔE Values: Differences in color are calculated using equation (5). CIE Lab parameters (DL*, Da*, Db*, DC*, Dh*). Smaller ΔE values (< 1) are typically imperceptible to the human eye and indicate high fidelity in color reproduction.

$$\Delta E = \sqrt {\left( {\Delta L*} \right)^{2} + \left( {\Delta a*} \right)^{2} + \left( {\Delta b^{2} *} \right)}$$

(5)

Delta E (∆E): A metric used to measure the difference between two colors:

∆E ≤ 1: Not perceptible by the human eye

∆E = 2–10: Perceptible to varying degrees

∆E > 10: Clearly distinguishable

∆E > 100 Colors are exact opposite

Evaluations were done in the Tables 6 and 7 were done CIE-L * a * b* values express colors in terms of color as numbers.

DL* = difference in lightness/darkness value (+ = lighter − = darker)

Da* = difference on red/green axis (+ = redder - = greener)

Db* = difference on yellow/blue axis (+ = yellower - = bluer)

DC* = difference in chroma (+ = brighter - = duller)

DH* = difference in hue

DE* = total color difference value

Conclusions

The effects of silicone surfactant types and different concentrations close to CMC on the properties of the synthesized latexes were investigated. After synthesized samples, physicochemical tests were performed, such as viscosity, particle size, zeta potential, PDI, practical and theoretical solid content, conversion %, and surface tension measurements. After that, among the synthesized samples, those that remained stable after a waiting period of approximately one year were tested for pigment printing applications on cotton knit and cotton woven fabrics. Washing fastness, rubbing fastness, hand feel, pigment migration, color yield, and wettability tests were investigated with the samples we prepared for the pigment printing method, which is a widely used method in textiles. All findings were compared; more compatible results were obtained with the AB-50-016 sample synthesized with amphiphilic silicone surfactant.

There are studies in the textile industry that contribute to the development of environmentally friendly and high-performance binders.^63‐66 In terms of textile applications, the aim is to provide an alternative to traditional binder applications to achieve more satisfactory physical-mechanical fabric performance as well as optimum color properties, color yield, and color fastness. In this context, our study provides a new perspective to the literature by examining the effect of silicone-based surfactants on VAc-BuA latexes.

The lowest zeta potential in latex prepared with ABIL^® B 88184 was measured at − 21.65 mV in the AB-84-012 sample. It exhibited stable particle sizes ranging from 320.6 to 479.2 nm. Surface tension decreased with increasing surfactant concentration and reached the lowest value of 39.05 mN/m at 0.24 wt.%. This trend emphasized the effectiveness of the nonionic structure of ABIL 88184 in reducing the interfacial tension. Conversion rates were consistently in the range of 94.3-99%. Samples obtained with this surfactant did not provide long-term stability. ABIL^® B 88184 demonstrated strong interfacial activity, a property linked to its structural features incorporating PEG and PPG segments. However, its performance in stability and viscosity fluctuated at higher concentrations, as observed in both experimental data and previous studies. The sample that showed the highest stability was AB-84-020. It was observed that it gave applicable results when it met the standard in textile tests.

ABIL® B 8843, while acceptable in basic performance metrics, lagged behind the other surfactants due to its relatively weaker stabilization mechanisms. With increasing concentration, particle size increased (between 373.0 and 556.3 nm), while viscosity values decreased in the opposite way (20.60–7.50 cP). They were able to show sufficient performance in textile applications with AB-43-008 and AB-43-016 samples selected from the samples that could maintain their stability for 1 year.

ABIL^® B 9950, the Brookfield viscosity results exhibited a decreasing trend with increasing surfactant concentration, particularly evident at 10 rpm, where the viscosity dropped from 28.20 cP at 0.08 wt.% surfactant to 15.00 cP at 0.24 wt.%. The smallest particle size (323.6 nm) was achieved at a zeta potential of − 75.67 mV, indicating high colloidal stability.

Surface tension values have not changed much with higher surfactant concentrations, between 42.04 and 43.87 mN/m, suggesting enhanced interfacial stabilization. Furthermore, the conversion rate peaked at 99.8, demonstrating the superior efficiency of ABIL^® B 9950 in facilitating polymerization. According to the results of extensive tests, ABIL^® B 9950 exhibited superior performance due to its amphoteric structure, providing balanced electrostatic and steric stabilization. Its low surfactant concentrations near CMC resulted in latexes with exceptional colloidal stability, high conversion rates, and consistent particle size distributions.

Acknowledgments

The authors would like to sincerely thank CHT Türkiye Chemistry Inc. for their support in supplying specific chemicals and contributing to the pigment printing tests conducted as part of the textile applications.

Conflict of interest

The authors declare no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Metadata
Literature

Title: Synthesis of water-based latexes using siloxane-derived surfactants and investigation of their use in pigment printing applications
Authors: Sinan Karademir
Ayfer Saraç Özkan
Publication date: 02-07-2025
Publisher: Springer US
Published in: Journal of Coatings Technology and Research / Issue 5/2025
Print ISSN: 1547-0091
Electronic ISSN: 1935-3804
DOI: https://doi.org/10.1007/s11998-025-01091-x

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Springer Professional

Abstract

Publisher's Note

Introduction

Experimental

Chemicals

Synthesis of latexes

Characterization of the copolymer latexes

Experimental and theoretical solid contents, conversions of latexes

Stability analyses of latexes (determination of viscosity, particle size, zeta potential, and polydispersity index (PDI))

Surface tension

Fourier transform infrared spectroscopy (FTIR)

Differential scanning calorimeter (DSC)

Storage stability

Textile application methods

Determination of the textile application performance of samples in cotton knit and cotton woven fabrics

Pigment printing

Preparation of the printing paste recipe

Pigment printing application

Washing fastness

Rubbing fastness

Color measurements

Hand feel

Hydrophobic properties of the printed fabrics

Results and discussion

Results of characterization measurements

Experimental and theoretical solid contents, conversions of latexes

Stability analyses of latexes (viscosity, particle size, zeta potential, polydispersity index (PDI))

Surface tension

ABIL® B 8843 respectively

Fourier transform infrared spectroscopy (FT-IR)

Differential scanning calorimeter (DSC)

Results of textile application

Conclusions

Acknowledgments

Conflict of interest

Publisher's Note

ABIL^® B 8843 respectively