Polymeric Pigments and Paint Formulation

OBJECTIVE AND SCOPE OF INVESTIGATION

The main objectives of the entire work is to synthesize a polymeric pigment (also called Core Shell emulsion polymer ) and use it in paint to partially replace white pigment Titanium dioxide. In this work , about 15 % of Titanium dioxide will be tried to replace. The general method of approach will be : 1. Preparation of a soft core (copolymer) by emulsion polymerization using Butyl acrylate, Methyl methacrylate and Methacrylic acid as monomers. 2. Using the above formed core as seed , formation of a hard polymer shell by emulsion polymerization over it. Monomers used are Styrene and Acrylonitrile. 3. Characterization of Polymeric pigment synthesized. 4. Formulating a white decorative emulsion paint using TiO 2 in one batch 5. Formulating a white decorative emulsion paint using 85% TiO 2 and 15% synthesized Polymeric pigment. 5. Comparing the properties of two paints.

Polymeric Pigments and Paint Formulation

POLYMERIC PIGMENTS

1. Introduction :
Titanium dioxide is the most widely used white pigment because of its brightness and very high refractive index. It provides excellent whiteness and opacity to the paint coatings. However due to its very high cost, several alternatives have been developed which can replace some part of TiO2 thus reducing cost of paint without affecting its properties. Polymeric Pigments are one of the novel developments. Polymeric pigments are the dried form of core-shell emulsion which provides opacity/hiding power to the paint formulation to which they are added. They behave as if they are pigments once the water gets evaporated. Their concentration in formulation is higher than that of additives and lesser than pigments. They serve as a partial replacement for TiO2 pigments which are very costly and thus reduce the cost per liter of a formulation.

2. Polymeric pigments
These belong to a class of pigments that use the difference in the refractive index of two polymers that are polymerized as layered spherical particles. They are core shell type of polymers that is they comprise a softer core made of one polymer and harder shell made of the other one. They are synthesized by continuous emulsion polymerization. The polymeric pigment particles suspended in emulsion have a core which is initially filled with water. When the emulsion is allowed to dry , the water from the core diffuses through the shell and
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Polymeric Pigments and Paint Formulation

gets evaporated. Thus the particle gets an encapsulated air void which is mainly responsible for scattering. They use the principle of continuous reflection of light before it is thrown back into atmosphere. The general structure and mechanism of formation can be shown as:

3. Advantages of Polymeric Pigments

Polymeric pigments have an encapsulated air void which is responsible for scattering of light. This gives us the freedom of formulating a low PVC composition with all the resistance properties kept at its best and still achieving the desired opacity. As compared to other organic pigments and inorganic extenders present in the system, these have low binder demand. That is they have low oil absorption value when measured on (v/v) basis. [Generally oil absorption value is measured as wt. of oil required to wet 100 gms of a given pigment. In (v/v) basis, we measure it as volume of oil required to wet give volume of pigment]. So it saves our cost on resin part. One of the reasons for the less binder demand is the uniform spherical shape of these particles. In case of spherical systems, surface area to volume ratio is lower as compared with other geometries. The diameter of inorganic extenders is high than polymeric pigments, but
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Polymeric Pigments and Paint Formulation

being non- spherical in nature, extenders have same oil absorption (v/v) as compared to their polymer counterparts. In case of core shell polymer , because of low binder demand, CPVC is high i.e. the region in which we can adjust PVC is broad as compared to others and this allows us in formulating paints with high PVC values, but still get good resistance. [As contrast to others, at high PVC, the resistance of film is poor]. They have low density as compared to organic pigments and extenders. They have small particle size than the general film thickness, uniform particle size distribution, thus have very high gloss. They serve as a replacement for TiO2 in formulation which is very costly. Thus it helps in reducing the overall cost of the formulation. As it partially replaces non-durable extender, durability of paint is increased. Without polymeric pigment paints lighten over a period because of chalking , so by using them this problem can be solved TiO2 and others exhibit the phenomenon of crowding whereas these pigments do not. Here with increasing PVC, scattering efficiency increases too. Here the source of scattering is encapsulated air voids, which scatter light to equal extent irrespective of void conc. So in this formulation scattering is independent of inter particle distance. So no need of going for above CPVC formulation. If we go, we will have more hiding.

Polymeric Pigments and Paint Formulation

4. Synthesis techniques
The synthesis of polymeric pigment requires two step emulsion polymerization. Thus the pigment particles obtained are in dispersed form in water. To know how synthesis of core shell emulsion takes place , first we briefly discuss about emulsion polymerization.

4.1 Emulsion Polymerization

Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the oil) are emulsified (with surfactants) in a continuous phase of water. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and comprise many individual polymer chains. The particles are stopped from coagulating with each other because each particle is surrounded by the surfactant; the charge on the surfactant repels other particles electro statically. Emulsion polymerization is used to manufacture several commercially important polymers. Many of these polymers are used as solid materials and must be isolated from the aqueous dispersion after polymerization. In other cases the dispersion itself is the end product. A dispersion resulting from emulsion polymerization is often called latex. They are finding increasing acceptance and are preferred over solvent-based products in these applications as a result of their eco-friendly characteristics due to the absence of VOCs (Volatile Organic Compounds) in them.

Polymeric Pigments and Paint Formulation

Advantages of emulsion polymerization include: High molecular weight polymers can be made at fast polymerization rates. By contrast, in bulk and solution free radical polymerization, there is a tradeoff between molecular weight and polymerization rate. The continuous water phase is an excellent conductor of heat and allows the heat to be removed from the system, allowing many reaction methods to increase their rate. Since polymer molecules are contained within the particles, viscosity remains close to that of water and is not dependent on molecular weight. The final product can be used as is and does not generally need to be altered or processed.

4.2 Polymeric Pigment Synthesis

The synthesis of polymeric pigments is usually done by two step emulsion polymerization technique. The second stage monomers are polymerized in the presence of seed latex particles. The resulting latexes are thus known as core-shell latex, implying a particle structure with the initially polymerized polymer located at the centre of the particle, and the later formed polymers becoming incorporated into the outer shell layer. The core may be solid polymer particle or hydrogel and shell is made of hard polymer. Osmotic Swelling is a basic synthesis technique for polymeric pigments. Some alternate methods are also discussed below.

4.2.1 Osmotic Swelling

The development of hollow particles by osmotic swelling typically requires the synthesis of a structured particle, such as a core-shell latex, by sequential emulsion polymerization. The

Polymeric Pigments and Paint Formulation

core or a component of the core is designed to be ionizable based on different chemical approaches, e.g. pH change, hydrolysis. A subsequent swelling process imbibes water into the center of the particle. This water leaves a void upon evaporation, as, for example, during the drying of a coating formulation. Structural factors such as composition, core - shell ratio, and network structure are critical to obtaining a stable hollow morphology. The basic principle involves making a structured particle with a carboxylated core polymer and one or more outer shells. The ionization of the carboxylated core with a base under the appropriate temperature conditions expands the core by osmotic swelling to produce hollow particles with water and polyelectrolyte in the interior.

The polymerization should be such that the hydrophobic shell completely encapsulates the hydrophilic core. Such core-shell emulsion is then heated in the presence of a base such as sodium hydroxide or ammonia to a temperature above the softening point of the shell polymer. However a volatile base is preferred in order that coatings formulated with these particles are not damaged by the presence of permanent base. The base neutralizes the core polymer forming a polyelectrolyte within the particle. The subsequent imbibing of water into the interior due to osmotic pressure leads to expansion and void formation. Once expanded, the structure must be stable to any temperature changes.

Polymeric Pigments and Paint Formulation

Typically, the shells of these particles are high glass transition temperature (Tg) thermoplastics like styrene or acrylonitrile. The art involved in developing a thermally stable shell that both transports water and base is considerable.

Although, in principle, formation of such a particle is straightforward, surface energies would favor the formation of a polar surface dispersed in a polar medium such as water: the opposite morphology to that suggested above. Thermodynamic equilibrium would favor particles with a hydrophobic core encapsulated with hydrophilic alkali-swellable shells. Such equilibrium conditions, however, are hard to achieve in an emulsion polymerization, as has been mentioned.

Polymeric Pigments and Paint Formulation

Other molecular and processing characteristics can overcome this thermodynamic tendency, namely molecular structure (i.e. cross-link density), conversion kinetics, and additives such as surfactants, and monomer feed profile. Some of the essential requirements inherent to hollow latexes made by osmotic swelling for commercial applications are: 1. The swellable core of the particles should be of sufficient volume relative to the volume of the particle to form a micro void inside the particle sufficient to scatter light efficiently. This efficiency is defined by the diameter of the void relative to the wavelength of visible light and the thickness of the shell. The void volume fractions of commercial hollow products are typically from 30 to 50%. 2. The shell should have the appropriate transport properties as adjusted by the composition and network structure to facilitate the transport of water into the interior of the particle. 3. The shell must have thermoplastic flow properties at the expansion temperature and be sufficiently cohesive and uniform to maintain the integrity of the particle. Yet it must be strong enough to avoid collapse during further processing or application conditions, e.g. the compressive forces experienced during drying and film formation in a coating.

Polymeric Pigments and Paint Formulation

4.2.2 Alternate Methods

The incorporation of high levels of carboxylic acid into an emulsion copolymer has several disadvantages. Copolymers of polar materials do not absorb surfactants well, leading to instability and coagulation. Further, polarizable monomer can partition significantly into the water phase of the emulsion, leading to the formation of oligomeric species which can behave as dispersants or flocculants depending on their molecular weight. With structured particles having the core made from a carboxylic acid copolymer, full encapsulation of the core polymers is problematic. The core tends to remain at the polymerwater interface. As an alternative approach, Rohm & Haas developed technology which did not depend on osmotic swelling based on copolymerized ionic monomers. In this case, they imbibe low molecular weight organic acids such as benzoic acid or acid anhydrides into the cores for later encapsulation followed by ionization with a base. Avoiding copolymerization of an ionic comonomer into a core seed was also possible with the use of vinyl acetate monomer. Instead of an acrylic ester composition leading to ionic groups along the main chain of the copolymer, a polyvinyl acetate containing core is initially polymerized. After hydrolysis, this comonomer produces hydroxyl groups along the chain as well as acetic acid. With this technology, either acid or basic conditions may be used to accomplish the hydrolysis and osmotic swelling.

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Polymeric Pigments and Paint Formulation

5. Application
5.1 Architectural coatings: Pigments are a critical ingredient in architectural coatings serving to provide color, to hide the substrate, and to modify the performance of a coating, e.g. functional pigments can enhance corrosion resistance. Hiding is a critical coating property, and a large fraction of all paint formulations contains white pigment. Typically these are small fine particle size dispersions. Titanium dioxide is the major white opacifying pigment used in the coating industry, added because of its high refractive index compared to the coating binder polymers. However , as the level of TiO2 in paint film increases, its light scattering efficiency decreases due to the close packing or crowding of TiO2 particles. The light scattering properties of hollow latex particles make them an effective hiding additive for water-borne latex paints. The coatings industry has long recognized the utility of air as a hiding ingredient for paint. Hollow latex particles are a convenient and cost-effective way to introduce air voids into the paint film without increasing the porosity of the film. Even though the hollow particle shell, the air it contains, and the surrounding film forming paint binder are all transparent to light, there are significant differences in refractive index (air 1.0 and polymeric pigment 1.58). When light passes through one transparent material into another of different refractive index, it is scattered. Thus, light moving through a hollow particle will be scattered when it hits the air at the center of the particle. The light is refracted a second time when it encounters the shell on the other side of the void. The cumulative effects of multiple scattering events as the light beam travels through the film increases the hiding of the paint film. Thus, the use of hollow latex particles allows the paint manufacture to reduce some of the main hiding

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Polymeric Pigments and Paint Formulation

pigment in the paint, which is typically the titanium dioxide, without losing the hiding properties. The hollow latex particles also have a lower binder demand then that of the pigments they replace thus overall binder may be reduced in the formulation without adversely affecting paint performance. The optimum particle size of the hollow latex particle was determined empirically to be having a diameter of 0.50.6 mm with a void diameter of 0.250.3 mm. A number of models have been published on how to convert paint formulations to the use of hollow pigments. The commercial products sold into the coating market are uniform in particle size, typically between 0.4 and 0.5 mm, and have a void volume fraction of 2540%.They are typically supplied at approximately 40% weight solids. The addition of the hollow latex lowered the cost due to the need to use less TiO 2. Porosity, gloss and paint viscosity was not affected by the formulation change but hiding, brightness and wet scrub resistance was increased.

5.2 Paper coatings: In coated paper, solid polystyrene latex particles have been used for some time to enhance the sheet gloss and print gloss of coated paper. The solid polystyrene latex particles also reduce the density of the coating formulation because they are of lower density than the mineral pigments present. With hollow latex particles, both the particle size and the void volume have an impact on paper properties. The presence of a void within the particles significantly reduces the density of the plastic pigment and at the same time contributing to opacity. The presence of the void also has an impact on the response the paper properties have to the finishing process. Since the shell polymer is thermoplastic it will deform under

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Polymeric Pigments and Paint Formulation

stress that is applied during the calendaring process. This ability to deform leads to an improvement in the micro-smoothness of the sheet. The greater response of the hollow latex particles to calendaring is due to the voids making the particle more easily deformed by the calendar. The large hollow particle samples have a lower uncalendered gloss but a higher finished gloss. Less severe calendaring conditions may possibly be used if hollow latex particles are utilized in the coated paper formulation. The brightness and opacity of papers coating formulations containing hollow latex particles increase due to the light scattering capability of these particles described above. Since both brightness and opacity increase with the use of hollow latex particles, only a few of the hollow particles at the surface must deform during the calendering process. Obviously the ultimate impact of hollow latex particles on finished coated paper properties is dependent on several factors such as overall formulation composition, calendaring conditions, and base stock properties. An important note to make about the use of hollow latex particles in paper coatings is the fact that the optimum particle is a large diameter particle with a void in the range of 5055%. Since a large portion of the water is contained inside the particle these latex samples are supplied at relatively low weight solids. The rheology characteristics of these latex samples will be typical of samples with a solids content of double the actual weight solids. The material supplier often will quote effective solids on these products. The effective solids determine the rheology and runability characteristics of the formulations containing the hollow latex particles.

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Polymeric Pigments and Paint Formulation

6. Experimental work
6.1 Synthesis of Carboxylated latex particles (CORE) The Core shell emulsion was synthesized in a 500 ml four necked flask. Heating mantle and temperature controller were used to maintain proper thermodynamic conditions. The Teflon stirrer was attached to a motor whose R.P.M. could be controlled digitally. Two dropping funnels were used for continuous addition. In the first step of emulsion polymerization, Core was synthesized. The following monomers used for Core synthesis are: a) Methyl methacrylate (MMA) 1. Molecular formula : C5H8O2 2. Molecular mass : 100.12 gm/mole

3. Density : 0.94 g/cm3 @ 25 C, liquid 4. Tg of homopolymer : 106C 5. Melting point : -48 C 6. Boiling point : 101 C

b) Butyl acrylate (BA) 1. Molecular formula : C7H12O2 2. Molecular mass : 128.2 gm/mole

3. Density : 0.898 g/cm3 @ 25 C, liquid 4. Tg of homopolymer: - 49C 5. Melting point : - 64 C 6. Boiling point : 148 C

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Polymeric Pigments and Paint Formulation

c) Methacrylic acid (MAA) 1. Molecular formula : C4H6O2 2. Molecular mass : 86.06 gm/mole

3. Density : 1.015 g/cm3 @ 25 C, liquid 4. Tg of homopolymer : 228C 5. Melting point : 14 C 6. Boiling point : 161 C

All the monomers were washed by 5% sodium hydroxide solution followed by washing with distilled water to remove the inhibitors. The initiators Sodium persulfate (SPS), Ammonium persulfate (APS), Sodium meta bisulfite (SMBS) and surfactant Sodium lauryl sulphate (SLS) were used without purification. Deionized water was used in the synthesis of the latexes.

Preparation Of Core:
a) Mixture of monomers, MMA 23.37 g, MAA 1 g, BA 26.00 g were emulsified in a separate vessel using 0.7 g surfactant (SLS) and water 26 g. The pre-emulsion was made using a high speed disperser such that a homogenous solution was obtained. b) The reactor was charged with 120 g water and to it catalyst solution (APS 0.2 g with water 5 g) and SMBS 0.6 g was added directly with stirring at 200 r.p.m. The reaction temperature was raised to 55 oC and pre-emulsified monomer 4 g was added at a time. c) After 15 minutes, the rest of pre emulsion was added continuously at a speed of 10 ml/15 min. Simultaneously SMBS solution (.07 g in 20ml water) was added continuously such that it's addition rate was same as pre emulsion's addition.

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Polymeric Pigments and Paint Formulation

d) After the addition of pre-emulsion the reaction was hold for 1.5 hours at temperature of 60 C. After 1.5 hours, the heating was stopped and post addition was done. e) In post addition , redox catalysts Sodium Formaldehyde Sulphoxylate (SFS) .03 g and tert-Butyl hydroperoxide (t-BHP) .04 g were added. f) To maintain pH, buffer solution i.e. 0.6g of Ammonia solution (33%) was added. The mixture was stirred for another half hour and then emulsion was allowed to cool at room temperature. INGREDIENTS Reactor charge : 1. Deionized water 2. SLS 3. APS 4. SMBS Monomer Pre-Emulsion : 1. Deionized water 2. BA 3. MMA 4. MAA 5. SLS 16 26 23.37 1 0.7 125 0.6 0.2 0.6 QUANTITY (g.)

Continuous feed ( Reducing agent) : 1. Deionized water 2. SMBS 20 0.07

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Polymeric Pigments and Paint Formulation

Redox Catalyst and post addition 1. t-BHP 2. SFS 3. Ammonia (33%) 0.04 0.03 0.6

6.2 Synthesis of Core-Shell Latex particle (Polymeric Pigment) The synthesized core was analyzed for its properties. The properties were fairly agreeable and then it was used as seed for Core-Shell polymer. Like core, it is also synthesized by emulsion polymerization. The shell is made of hard monomers so as to give good pigmentary properties. The monomers used for Shell formation are:

a) Styrene 7. Molecular formula : C8H8 8. Molecular mass : 104.15 gm/mole

9. Density : 0.909 g/cm3 @ 25 C, liquid 10. Tg of homopolymer : 100C 11. Melting point : -30 C 12. Boiling point : 145 C

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Polymeric Pigments and Paint Formulation

b) Acrylonitrile 1. Molecular formula : C3H3N 2. Molecular mass : 53.06 gm/mole

3. Density : 0. 81 g/cm3 @ 25 C, liquid 4. Tg of homopolymer : 125C 5. Melting point : -84 C 6. Boiling point : 77 C

All the monomers were washed by 5% sodium hydroxide solution followed by washing with distilled water to remove the inhibitors. The initiator potassium persulfate (PPS) was used without purification. Deionized water was used in the synthesis of the latexes.

Preparation of Core-Shell:
a) The reactor was charged with 90 g of water and temperature was increased to 85 oC. b) 25 g of core latex prepared in stage 1 was added to the reactor slowly along with catalyst i.e. PPS solution (0.04 g in 10.00 g water). c) Then the monomer mixture styrene 55 g and Acrylonitrile 36 g was added slowly within 3 hours . Simultaneously catalyst solution PPS (0.53 g in 20 g water) was added slowly for 3 hours. d) After completion of feeding, the reaction was hold for 1 hour for complete conversion. e) Then ammonia solution (7.5 g in 15 g) water was added to the reaction mixture. The heating was stopped and emulsion was stirred for another 2 hours.

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Polymeric Pigments and Paint Formulation

INGREDIENTS

QUANTITY (g.)

Reactor Charge: 1. Deionized water 2. CORE LATEX 3. PPS 100 25 0.04

Monomer Mixture: 1. Styrene 2. Acrylonitrile 55 36

Continuous feed ( Catalyst ): 1. Deionized water 2. PPS 20 0.53

Post Addition: 1. Deionized water 2. Ammonia solution (33%) 15 7.5

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Polymeric Pigments and Paint Formulation

7. Characterization of Core and Polymeric pigment

The synthesized emulsions were characterized for: a) Non Volatile Matter content b) pH c) Viscosity d) UV-Visible Absorption Spectroscopy (UV-Vis) e) Fourier transform infrared spectroscopy (FTIR) f) Differential Scanning Calorimetry (DSC)

a) Total Solids Content or Non Volatile Matter content (NVM): A known weight of the paint sample was taken in a Petridis and allowed to be in oven at 1200c for about an hour. It was weighed and then kept back in oven. The heating was continued till constant weight was obtained. The difference between the two weights gives the amount of volatile material lost and hence the % NVM can be found out b) pH The pH of an emulsion is important for its stability. It is adjusted by adding liq. NH 3 It was measured by using pH paper and comparing with pH scale. c) Viscosity Viscosity was determined by using Brookfield Viscometer according to ASTM D2196-05 of appropriate spindle. It was reported in centipoises.

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Polymeric Pigments and Paint Formulation

d) UV-Visible Absorption Spectroscopy (UV-Vis) Ultraviolet-visible spectroscopy refers to absorption spectroscopy in the UV-visible spectral region. This means it uses light in the visible and adjacent (near-UV and nearinfrared (NIR)) ranges. The absorption in the visible range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum, molecules undergo electronic transitions. When the light is absorbed, transitions takes place from the ground state to the excited state. Thus the absorption spectra is recorded for a particular compound. The instrument used in ultraviolet-visible spectroscopy is called a UV/Vis. spectrophotometer. It measures the intensity of light passing through a sample (I), and compares it to the intensity of light before it passes through the sample (Io). The ratio I / Io is called the transmittance, and is usually expressed as a percentage (%T). The absorbance, A, is based on the transmittance: A = log (%T / 100%)

e) Fourier transform infrared spectroscopy (FTIR) FTIR is the subset of spectroscopy that deals with the infrared region of the

electromagnetic spectrum. It covers a range of techniques, the most common being a form of absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify compounds and investigate sample composition. The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and farinfrared, named for their relation to the visible spectrum. The far-infrared, approximately 40010 cm1 (100030 m), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The mid-infrared, approximately 4000400

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Polymeric Pigments and Paint Formulation

cm1 (302.5 m) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The higher energy near-IR, approximately 140004000 cm1 (2.50.8 m) can excite overtone or harmonic vibrations. Infrared spectroscopy exploits the fact that molecules absorb specific frequencies that are characteristic of their structure. These absorptions are resonant frequencies, i.e. the frequency of the absorbed radiation matches the frequency of the bond or group that vibrates. The energies are determined by the shape of the molecular potential energy surfaces, the masses of the atoms, and the associated vibronic coupling. f) Differential Scanning Calorimetry (DSC) Differential scanning calorimetry or DSC is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference are measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Generally, the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time. The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned. The main application of DSC is in studying phase transitions, such as melting, glass transitions, or exothermic decompositions. These transitions involve energy changes or heat capacity changes that can be detected by DSC with great sensitivity. Glass transitions may occur as the temperature of an amorphous solid is increased. These transitions appear as a step in the baseline of the recorded DSC signal. This is due to the sample undergoing a change in heat capacity; no formal phase change occurs.

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Polymeric Pigments and Paint Formulation

PAINT FORMULATION

1. Emulsion Paints
The introduction of synthetic emulsion polymers in emulsion form presented a stunning start towards the development of paints. They are not only comparable to conventional solvent based coatings but also far superior in some instances. Moreover since the sole solvent is water only, emulsion paints are free from VOCs, this advantage has put emulsion paints a step ahead of others for decorative paints. Today, where we concerned with the environmental effects of the paint industry, the diversion towards the water based products is definitely desired.

2. Paint Ingredients
Emulsion based paint mainly consist of emulsion as pigments, binders and additives such as wetting and dispersing agent, thickener, defoamer, buffer etc. a) Pigments Pigments are used to provide a visual effect, mainly colour and opacity. Having achieved the required colour and opacity, it is also important to ensure the pigment will remain essentially insoluble in the system in which it is used and will give the required physical properties, such as light fastness, weatherability, and resistance to chemicals

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Polymeric Pigments and Paint Formulation

Hiding power is the ability of a pigmented coating to obliterate the surface. It is dependent on the ability of the film to absorb and scatter light. Naturally, the thickness of the film and the concentration of the pigment play a fundamental role. A key factor in the opacity of a pigment is its refractive index (RI), which measures the ability of a substance to bend light. The opacifying effect is proportional to the difference between the refractive index of the pigment and that of the medium in which it is dispersed. This is one of the main reasons why titanium dioxide is now almost universally used as the white pigment in paint. Titanium dioxide absorbs almost no light, yet its ability to scatter light due to high refractive index ensures that at a high enough concentration it will cover all the substrate being coated. There is a new class of pigments called Polymeric Pigments. They use the difference in the refractive index of two polymers that are polymerized as layered spherical particles. They are core shell type of polymers that is they comprise a softer core made of one polymer and harder shell made of the other one. They are synthesized by continuous emulsion polymerization. The polymeric pigment particles suspended in emulsion have a core which is initially filled with water. When the emulsion is allowed to dry, the water from the core diffuses through the shell and gets evaporated. Thus the particle gets an encapsulated air void which is mainly responsible for scattering. They can partially replace inorganic pigment like TiO2 without changing the opacity or major properties of paint. The advantages of polymeric pigments have been discussed in previous section. There are other types of pigment that are used for specific purposes, such as extenders. Extenders do not usually affect the colour or opacity of a paint film, but may play an

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Polymeric Pigments and Paint Formulation

important role in the film properties such as reinforcement, gloss (usually to make the film less glossy), hardness, etc. They can also affect the properties of the paint itself, such as its rheological properties, settling characteristics, or simply its cost. b) Binders Formulation of most coatings usually starts with the selection of the main film former or binder even though most of the properties are extensively modified by pigmentation. Mainly two types of binders are used Emulsion polymers and Alkyds. The former are polymeric dispersions carried in water, while the later are solutions of oil-modified polyesters carried in hydrocarbon solvents. Emulsion polymerization is very well established as the route to dispersion binders with diverse properties. Characteristically free radical initiators are used to polymerize monomers of low water solubility to produce an insoluble polymer. Paint properties will be influenced by the choice of monomers, particle size, and stabilizer system. The effect of monomer type on mechanically related properties can be interpreted through the Tg. Hard monomers included methyl methacrylate, vinyl acetate, styrene etc. while the soft monomers are n-alkyl acrylates, alkyl maleates etc. Most latexes used in the decorative market are copolymers or terpolymers with the ratios chosen to suit specific sectors. In very general terms softer polymers will favour extensibility, exterior durability, and film integration, while hard polymers give lower dirt retention, gloss retention, and scrub resistance.

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Polymeric Pigments and Paint Formulation

c) Surfactants Surfactants help to reduce surface tension and improve wetting and spreading (wetting agents); aid in dispersion of pigments. They comprise very minor portion of paint. Anionic surfactants are major type used to improve wetting and dispersion of pigments. Both anionic dispersant and non-ionic wetting agents contribute to overcome pigment floating and settling. Each pigment particle requires a particular amount to disperse and stabilize it. Excessive amounts of surfactants should not be used because this can lead to colour and other appearance changes Non-ionic surfactant: Stearic hindrance takes place when the hydrophobic portion of a nonionic surfactant is absorbed onto the surface of pigment particles. The long hydrophilic chain in the liquid medium and it acts as a bumper that prevents the stabilized pigment particles from too closely approaching each other. This is mechanism by which non-ionic surfactant functions. Ionic surfactant: When the hydrophilic portion of the surfactant is adsorbed on the pigment particles, the ionic portion of the molecule or hydrophile will be found in liquid phase. This charged portion of the molecule will repel particles that contain like electrostatic charges on other particles with the result, a stabilized system. d) Thickeners Paint requires a thickener to yield the viscosity that will hold the paint ingredients in a homogeneous state and also contribute to its rheological properties. For water borne coatings most commonly used thickeners are cellulose thickeners. Hydroxy ethyl cellulose, carboxymethyl cellulose are most commonly used. These thickeners are non-ionic water
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Polymeric Pigments and Paint Formulation

soluble polymers in powder form. These powders dissolve in either hot or cold water and may be surface treated to prevent agglomeration. e) Defoamers Although foam may occur as an interfering factor during paint production, most problem arises when it cause surface defects during the application process. Defoaming agents are additional adjuncts in the latex paints. They are required to suppress or eliminate any foam that tends to develop during manufacture or in container filling operations. In an aqueous formulation, it is almost impossible to totally eliminate all foams. The correct foam control agent will help to prevent foam, but of most importance, will allow the dried film to be free of foam and any resultant film defects that might result from an air void in the film. f) pH Stabilizers Styrene acrylics, acrylics latexes achieve their maximum stability in alkaline systems. Consequently, the systems are usually adjusted to pH of 9.0 to 9.5. Aqueous ammonia was used earlier days, but now days AMP-95 (2-amino-2-methyl-1-propanol) is most commonly used as pH stabilizer.

3. Formulation Of Paint
Ball Mill and a Dispersing Equipment High Speed Disperser were used to prepare paint. The equipment consisted of a pitch blade turbine type impeller which rotates at high speed. Following sequence is to be followed for paint manufacturing:

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Polymeric Pigments and Paint Formulation

GRIND STAGE

Ingredients

Nature

Batch A 100% TiO2 (g.)

Batch B 85% TiO2 (g.) 10 0.3 0.2 1.2 0.25 5 15.3 5 9 5

Water TAMOL 731 from BASF Ltd. TRITON (Dow-Rohm& Haas) Di Ethylene Glycol Natrosol Plus(Dow-Rohm & Haas) Pidicryl 8261 (Pidilite Ltd.) TiO2 (Tronex , Australia) China Clay Talc

_ Anionic Surfactant Non ionic Surfactant Wet edge Additive Thickener 50% pure Acrylic Binder Pigment

10 0.3 0.2 1.2 0.25 5 18 5 9

Extenders CaCO3 5

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Polymeric Pigments and Paint Formulation

LET DOWN STAGE

Ingredients

Nature

Batch A 100% TiO2 (g.)

Batch B 85% TiO2 (g.) 20 0.4 0.2 1 0.25 30

Water TAMOL 731 from BASF Ltd. TRITON (Dow-Rohm& Haas) Di Ethylene Glycol Natrosol Plus(Dow-Rohm & Haas) Pidicryl 8261 (Pidilite Ltd.) SYNTHESIZED POLYMERIC

_ Anionic Surfactant Non ionic Surfactant Wet edge Additive Thickener 50% pure Acrylic Binder

20 0.4 0.2 1 0.25 30

Pigment PIGMENT Liquor Ammonia (33%) BYK 022 ( Dow-Rohm & Haas ) Sodium hexametaphosphate pH stabilizer Defoamer Buffer

7.68

0.15 0.2 0.2

0.15 0.2 0.2

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Polymeric Pigments and Paint Formulation

Procedure to be followed Water Surfactant

M I L L B A S E L E T D O W N

Mix well and then add Thickener Form a uniform jelly Wet Edge additive Emulsion Mix well and then add TiO2 China Clay Talc CaCO3 Grind the mix for about 1.5 2 hours Water Surfactants Emulsion Mill Base Mix well and then add Thickener Wet Edge additive Agitate well Ammonia Defoamer Buffer Agitate well

In second batch, Synthesized Core-Shell Emulsion was added in Let Down Stage.
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Polymeric Pigments and Paint Formulation

4. Analysis of Paint
The Paint formulated was analyzed for : a) Non Volatile Matter Content b) Viscosity c) Weight per liter d) Finish of dispersion e) Gloss at 20o and 60o f) Computer Colour Matching ( CCM )

1) Total Solids Content or Non Volatile Matter content (NVM): A known weight of the paint sample was taken in a Petridis and allowed to be in oven at 1200c for about an hour. It was weighed and then kept back in oven. The heating was continued till constant weight was obtained. The difference between the two weights gives the amount of volatile material lost and hence the % NVM can be found out 2) Viscosity Viscosity was determined by using Brookfield Viscometer according to ASTM D2196-05 of appropriate spindle. It was reported in centipoises. 3) Weight per liter Weight per liter was calculated according to IS: 1964. Initially the dry, empty weight per liter cup was weighed. It was then filled with the emulsion sample so that it overflows the vent cap. The cup was weighed again after cleaning the excess paint. The difference

31

Polymeric Pigments and Paint Formulation

between the two weights gives the weight of the paint sample held in the volume of 100ml of cup from which the weight per litre of paint was found out. 4) Finish of dispersion The fineness of grind or dispersion was found according to ASTM D 1210-05, according to which the finish was checked with the help of Hegmen gauge. The paint was taken at the 0 end of the Hegmen gauge kept in horizontal position. It was then drawn with the help of the applicator along with grooves. The gauge was viewed immediately to the paint surface was designated as the finish of the paint. 5) Gloss at 20o and 60o The gloss of the paint was found using Gloss meter at 20 o and 60o. For each panel five readings were taken at different positions and the average was calculated. 6) Computer Colour Matching In this analysis , it matches if two shades of colour are equal and upto what extent. CCM measures the % reflectance of colour and also Lab Colour Space values ( L* ,a* ,b*). Lab color space is a color-opponent space with dimension L for lightness and a and b for the color-opponent dimensions, based on nonlinearly-compressed CIE XYZ color space coordinates. It is designed to approximate human vision. It aspires to perceptual uniformity, and its L component closely matches human perception of lightness. It can thus be used to compare shades and make accurate color balance corrections by modifying output curves in the a and b components, or to adjust the lightness contrast using the L component. C value is also calculated by CCM which gives chroma or intensity of colour.

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Polymeric Pigments and Paint Formulation

RESULTS AND DISCUSSION

a) Core and Polymeric pigment ( Core-Shell ): ANALYSIS Composition i) N.V.M. ii) pH iii) Viscosity (cPs) CORE BA , MMA , MAA 19.02 % 4 30 CORE-SHELL CORE , Styrene , ACN 35.15% 9 70

i) N.V.M. The NVM of Core and Core-Shell is nearly same as the theoretical calculation. It means the extent of conversion is fairly decent. ii) pH The Core shows acidic nature which is because of the presence of carboxylic acid due to Methacrylic acid. Though the emulsion is stable at room temperature. The Core-Shell pigment is basic in nature due to addition of ammonia. Ammonia neutralizes acidic group of core to form amide and water. iii) Viscosity The viscosity here is dependent on % solids. In Core, it is less as NVM is less as compared to Polymeric pigment. However both are emulsions so their viscosity is not high.

33

Polymeric Pigments and Paint Formulation

iv) UV- Visible Absorption Spectroscopy (UV-Vis) The UV-Vis is done only on Core-Shell to find its absorption peak and compare it with that of TiO2. Below are the Absorption graphs of TiO2 and synthesized Core-Shell.

Absorption graph of TiO2

Absorption graph of Polymeric Pigment

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Polymeric Pigments and Paint Formulation

The Maximum absorbance of TiO2 is at 210 nm while for Polymeric pigment it is 222 nm (shown by arrow 2 in figure). Both absorb mainly in Ultraviolet region. Thus Core-Shell show nearly similar absorbance properties to TiO2. v) Fourier transform infrared spectroscopy (FTIR) The Core and Core-Shell were analyzed for the function groups present using FTIR. Below are the FTIR graphs.

FTIR for CORE The peaks at various positions identifies the functional group present in Core thus telling us about the presence of reactants.

35

Polymeric Pigments and Paint Formulation

For Ester group conformation: 1654.3 cm-1 For Aliphatic group conformation: 2954 , 2874 cm-1 For carboxylic group ( COOH ) : 1731.8 cm-1

102.5 %T 100
1 9 4 7 .9 7 2 9 4 5 .1 0 2 2 3 7 .2 7 1 8 7 7 .5 7

97.5

95

92.5
1 4 9 3 .7 7 1 4 5 3 .2 6

90

87.5

85
7 5 9 .9 0

82.5

80 4000 3750 Core Shell Latest 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 1/cm

3 0 2 5 .1 4

FTIR for CORE-SHELL For Ester group conformation: 1877 cm-1 For Aliphatic group conformation: 2946.6 cm-1 For carboxylic group ( COOH ) : 1730 cm-1 For aromatic group conformation : 1423 , 1453 cm-1
6 9 9 .1 5

1 7 3 0 .0 3

36

Polymeric Pigments and Paint Formulation

For ammonia conformation : 3028 cm-1 For nitrile group conformation : 2237 cm-1 Thus the FTIR graph shows that all the raw materials have reacted and are present in our compound. vi) Differential Scanning Calorimetry (DSC) The glass transition temperature of both Core and Core-Shell are found using Tg. Since core is a simple copolymer it should show only 1 Tg value. Core-Shell should show three Tg values i.e. 3 shifts in baseline. It shows Tg of Core, Interface and Shell. Below are the DSC curves:

DSC Curve of CORE

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Polymeric Pigments and Paint Formulation

Only one Tg is shown in Core at 6.2 oC. It matches roughly with the theoretical calculated value of 8.3 oC. It may be concluded that reactants have reacted stoichiometrically.

DSC Curve of CORE-SHELL The DSC curve here shows 2 Tg only. At Interface Tg is 34.93 oC and for shell it is 111.48 oC. The Tg for Core could not be shown as the amount of Core present in Core-Shell is very small and after drying, the volume of polyelectrolyte in core decreases significantly. Thus its presence was not detected easily.

38

Polymeric Pigments and Paint Formulation

b) Paint: Batch A and Batch B Batch A: 100 % TiO2 Batch B: 85% TiO2 and 15% Dried Polymeric Pigment (w/w%)

ANALYSIS i) N.V.M. ii) Viscosity iii) WPL iv) Fineness of grind v) Gloss @ 20o @ 60o

BATCH A 48.27%

BATCH B 46.20%

1.36 5+

1.35 5+

2.5 6.1

2.62 7.8

i) N.V.M. The NVM of both the paints were found to be nearly same to their theoretical value. However paint A has more TiO2 pigment having high density thus its NVM is greater than paint B ii) Viscosity The Viscosity of paint A is slightly greater than paint B due to more amount of TiO2.

39

Polymeric Pigments and Paint Formulation

iii) WPL The weight per liter of Paint A is slightly grater than paint B due to high density of TiO 2 pigment as compared to polymeric pigment. iv) Fineness of grind Both the paints show same fineness of grind or dispersion. This means core-shell pigment is easily dispersible in Emulsion paints. v) Gloss As the amount of pigment and extender is high in both paints and due to nature of binder, sufficient gloss was not obtained. However the gloss of paint B is slightly greater than paint A. Thus addition of polymeric pigment helps in increasing gloss. vi) Computer Colour Matching Glass panels were coated with Paint A and B. After drying they were analyzed for optical properties using CCM Spectraflash SF300. Following are the results :

ANALYSIS

STANDARD WHITE TILE

PAINT A

PAINT B

% Reflectance L* a* b* c h

83.34 94.10 -0.62 -0.27 0.67 203.74

68.54 89.61 -1.82 -1.39 2.29 217.28

59.17 86.02 -2.09 -3.56 4.12 239.60

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Polymeric Pigments and Paint Formulation

The L* a* b* values of both the paints are comparable. Thus addition of polymeric pigment has no effect in change of colour. Infact after looking at the value of c (chroma), Paint B shows more brightness as compared to paint A. Thus by CCM testing we can say that the optical properties of paint have not been tampered by addition of polymeric pigment in its formulation.

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Polymeric Pigments and Paint Formulation

CONCLUSIONS

The synthesis of Polymeric Pigment by emulsion polymerization is an eco-friendly way of producing pigment which can partially replace TiO2 concentrations in paints. Though cost is the major factor for TiO2 replacement, Polymeric pigments can also show some better properties when incorporated. They increase the gloss and brightness of paint without compromising on other properties. They have less binder demand as compared to inorganic pigments due to their uniform spherical shape. Thus high CPVC paints can be formulated with Polymeric pigments. They also eliminate the problem of crowding experienced by TiO2 pigments. Thus we can conclude that incorporation of polymeric pigments in paints helps in increasing the property of paint with cutting of raw material cost.

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Polymeric Pigments and Paint Formulation

REFERENCES

1. A.K. Khana, B.C. Raya, S.K. Dolui ; Preparation of core-shell emulsion polymer and optimization of shell composition with respect to opacity of paint film ; Progress in Organic Coatings 62 (2008) 6570 2. McDonald, C.J.; Devon, M.J. Hollow latex particles: synthesis and applications Advances in Colloid and Interface Science (2002), 99, p.181213. 3. ROPAQUE ULTRA E Opaque Polymer, Product Description, Rohm and Hass Pvt. Ltd. 4. Fasano, D.M.; Williams E. JR. Opaque Polymers Handbook of Coating Additives Vol. 2, Marcel Dekker Inc., 1992. 5. Nobuyuki, I; Tooru, M.; Ichirou O.; Masayuki H.; Kiyoshi K. Cross-linked hollow polymer particles by emulsion polymerization Colloids and Surfaces A: Physiochemical and Engineering Aspects (1999), 153, p.311-316. 6. Malshe V.C.; Sikchi M. , Basics of Paint Technology I, Color Publications Ltd., 2004

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