Colouring plastics: fundamentals and trends

Colour masterbatches, or colour concentrates, find applications in many areas of plastics processing. Blow, injection and rotational moulding, extrusion, calendering, and wire and cable manufacturing all depend on them. The masterbatches contain a high loading of colourants, also known as pigments or dyes, in a carrier resin. Richard Abrams, Mir Ali, Paul Denton, Juan Igualada, Martin Groen and Eddy Gschwind of Ferro present an overview of the subject of colour with a view to understanding the complex tasks that colour engineers face.

What is colour ? Colour is all around us. It is important in our daily lives and we learn from birth to react to colours logically or emotionally. Colours have meaning, which vary from culture to culture and continent to continent. In many societies, it governs and controls traffic: red means stop, green means go, or acts as a warning: blue means cold, red means hot. Colour is also used to describe moods - green with envy, feeling blue or seeing red. Three things are required for the presence of colour. One may think of colour as the property of an object only, but without the presence of light, there is no way of seeing the colour. With light and an object present, there is still no colour without someone or something to detect it. Therefore, colour is defined by the presence of an object, a light source (illuminant) and an observer. The Illuminant: In order to see colours, energy typically in the form of light is required. Colour sensation is produced by physical stimuli associated with the various wavelengths in the visible portion of the electromagnetic spectrum. In order to understand colour better, we need to appreciate the origin of light. Light comes from a wide variety of sources and consists of electromagnetic radiation, a form of energy that propagates in a wave motion.

Figure 1: Visual colour spectrum

The best way to characterize lights is to see the composition of the light. All visible light is made up of a mixture of the colours of the spectrum, which combine in different proportions to make up each distinctive light. The way we measure and characterize lights is by a Spectral Power Distribution. In Figure 1, the visual colour spectrum starts at 400 nm and ends at 700 nm. Everything below 400 nm is called ultraviolet (UV) and everything above 700 nm is referred to as infrared (IR). The human eye cannot see ultraviolet or infrared light.

White light, as we see it, is composed of a select group of special colours; each one characterized by a specific range of wavelengths, which it absorbs. These are the colours of the spectrum - red, orange, yellow, green, blue and violet. Incandescence and luminescence are two common ways to create light. Incandescence is light from heat energy. Heating the filament of a light bulb to a high enough temperature will cause it to glow. The stars and sun glow by incandescence. Luminescence is also known as cold light. It is light from other sources of energy independent of heating and can be generated at room or even lower temperatures. Quantum physics explains luminescence through movements of electrons from their ground-state (lowest-energy level) into an excited (higher-energy) state. Returning to its ground-state, the electron gives back the energy in the form of a photon of light. If the interval between the two steps is short (some microseconds), the process is called fluorescence; if the interval is long (some hours), the process is called phosphorescence. The combination of these wavelengths in light can change depending on the light source. Therefore, colours look differently when compared under the influence of daylight, fluorescent light or sodium lamps. Natural sunlight varies widely. The character of sunlight can be very blue, especially near midday, looking north. Direct sunlight usually is seen as golden, but, near sunset, it can be bright red. Artificial light can be yellow, from sodium vapour, blue-green from mercury vapour or it can be yellow, from an incandescent light bulb, or varying colours from fluorescent light. The graphs in Figure 2 show average north sky daylight (Illuminant D65), a cool white fluorescent light (Illuminant F), and an incandescent light (Illuminant A).

When light strikes an object, several phenomena can happen. Transmission occurs if the light passes through the object, which is the case with transparent colours. It is referred to as reflection if, for example, a green object reflects the part of the colour spectrum that represents green and all other light is absorbed. The reflection curve of white will show roughly equal intensities close to 100% reflection in all wavelengths of the spectrum. Refraction or scattering is when light changes direction as it passes from one medium to another, like from the polymer to a pigment or filler particle in a plastic part. Scattering is influenced by the difference in refractive index between a particle and its surroundings, particle size, and wavelength of light. An opaque colour shows a high level of scattering. A translucent colour shows a combination of transmission and scattering at the same time. Absorption exists if most wavelengths of the visible spectrum are absorbed. Black surfaces absorb nearly all light. Combinations of one or more effects exist. The Object: A product appears in a specific colour because the light, which is reflected from its surface, is made up exactly of wavelengths, which combine, to the colour observed. The object absorbs all other wavelengths. As an example, a blue object reflects the blue light spectrum, but absorbs red, orange, yellow, green and violet, which are most of the other wavelengths. A red object reflects the red spectrum but absorbs most of the orange, yellow, green, blue and violet. The colours black and white differ in their absorption behaviour. Strictly following the rules they are not really colours. A white object reflects all (or nearly all) colours while a black object absorbs most colours completely. In other words, whites represent a mixture of the colour spectrum and black the absence of them. Matching the colour of an object is complex and becomes more demanding with increased needs for appearance and effects. An object can be spherical or square, glossy or dull, transparent or opaque or translucent. It can appear metallic, fluorescent, pearlescent, or phosphorescent. The target can be a completely different material than that of the current match. Its colour can appear very different at various viewing angles. The gloss or texture of a sample can change its appearance significantly. A good deal of a colour engineer's skill lies in getting around these problems and the limitations in materials. The Observer: The defining observer is the human eye. No matter how carefully one matches a colour, an observer nearly always bases acceptance of a colour on visual judgement. Most of the time, this means a colour match can become highly subjective, since colour vision varies widely from individual to individual. Age, gender, inherited traits, way of viewing a sample - and even mood - can affect colour vision. Colour measurement Consequently, there is a need for a less-biased observer in the form of a colour-measuring device. This instrument is designed to provide an objective means of measuring, evaluating and aiding in matching colours. These instruments measure the amount of light that an object reflects in each part of the wavelength spectrum and develops a profile to describe that colour. The information about light source and observer can be described mathematically with three variables, which describe how we see a colour. The measured values relate to amounts of primary colours needed for matching a colour appearance. Information on characteristics of the sample can be used in identifying type and amount of colour pigment needed to match its colour. Two types of commonly used colour measurement equipment are a colorimeter and a spectrophotometer. Colour measuring equipment helps us to give an objective definition of the colour. Each colour has a fingerprint reflectance pattern in the spectrum. We look at the characteristics of a pigment where it absorbs light. The colorimeter measures colour through three wide-band filters corresponding to the spectral sensitivity curves and is therefore not very accurate, showing large differences between the various instrument manufacturers. However, colorimeters are less expensive than spectrophotometers. Modern spectrophotometers contain monochromators and photodiodes

that measure the reflectance curve of a product's colour every 10 nm or less. The analysis generates typically 30 or more data-points, with which an exacting colour composition can be calculated. The spectrophotometer can detect metamerism (matching under one light source, but not another), perform colour matching recommendations and is often also utilized as a quality control tool.

Figure 3: CIEAB diagram and coordinate system

For the measurement of colour, standard values are used worldwide, for example as determined by an organisation called CIE. CIE was founded in 1913 and stands for Commission Internationale de l'Eclairage (International Commission on Illumination). CIE has a technical committee, Vision and Colour, that has been a leading force in colorimetry since it first met to set its standards in Cambridge, England, in 1931. The values used by CIE are called L*, a* and b* and the colour measurement method is called CIELAB. L* represents the difference between light (where L*=100) and dark (where L*=0), a* represents the difference between green (-a*) and red (+a*) and b* represents the difference between yellow (+b*) and blue (-b*). With these co-ordinates, any colour can be defined as a place on the graph shown in Figure 3. Differences in L*, a*, b* or E* are represented as oL*, oa*, ob* or oE*, where oE* = o (oL*2+oa*2+ob*2). It represents the magnitude of the difference in colour, but does not indicate the direction of the colour difference. Another colour measurement system often used is the Munsell Colour System developed by A. Munsell, an American artist in 1898. Munsell desired to create a 'rational way to describe

colour' that would use clear decimal notation instead of colour names. In 1905 he published A Colour Notation, which has been reprinted several times and is still a standard for colorimetry. Munsell modelled his system as an orb around whose equator runs a band of colours. The axis of the orb is a scale of neutral grey values with white as the North Pole and black as the South Pole. Extending horizontally from the axis at each grey value is a gradation of colour progressing from neutral grey to full saturation. With these three defining aspects, any of thousands of colours could be fully described. Munsell named these aspects, or qualities, hue, value, and chroma.
Table 1: Difference between visual and computer controlled colour-matching procedure Visual Colourist experience Visual assessment of the sample Selection of a combination of pigments Design of formulation, based on experience and on a library of previous matches Preparation of the formulation Visual assessment Estimation of necessary corrections Selection of a new combination of pigments (if necessary) Computer Preparation of calibration standards, reading and storage of their reflectance curves Measuring the sample Selection of possible pigments Data entry and calculation of possible formulations. Selection of a formulation Preparation of the formulation Reading of the sample Calculation of the correction Selection of a new combination of pigments (if necessary)

Munsell defined hue as the quality by which we distinguish one colour from another. He selected five principle colours: red, yellow, green, blue, and purple; and five intermediate colours: yellow-red, green-yellow, blue-green, purple-blue, and redpurple. He arranged these in a wheel measured off in 100 compass points. The colours were identified as R for red, YR for red-yellow, Y for yellow etc. Each primary and intermediate colour was allotted ten degrees around the compass and then further identified by its place in the segment. Munsell defined value as the quality by which we distinguish light colours from dark ones. Value is a neutral axis that refers to the grey level of the colour. It ranges from white to black. The value of a particular hue would be noted with the value after the hue designation. Chroma is the quality that distinguishes the difference from a pure hue to Figure 4: The Munsell System a grey shade. The chroma axis extends from the value axis at a right angle and the amount of chroma is noted after the value designation. Therefore, 7.5YR 7/12 indicates a yellow-red hue tending toward yellow with a value of 7 and a chroma of 12. However, chroma is not uniform for every hue at every value. Munsell saw that full chroma for individual hues might be achieved at very different places in the colour sphere. In the Munsell System, reds, blues, and purples tend to be stronger hues that average higher chroma values at full saturation, while yellows and greens are weaker hues that average fullest chroma saturation relatively close to the neutral axis.

Colour matching and appearance A colour match is often a combination of the colour engineer's visual perception and the measurement results of a PC-controlled measurement tool. Both have advantages, but neither one should be used alone. The information a colour engineer receives before the experiment is critical for the successful outcome of the match. Therefore, it is important to understand the objective and means of the plastic manufacturer. For example, the chemical nature of the specific resin to be coloured and the processing conditions will determine the correct masterbatch formulation. The main performance requirements that affect the selection process include: 1. Obtaining information on resin and type of processing equipment. This includes what type of polymer(s) are used and what is the end product. The process the customer intends to use is also important, such as injection or blow moulding, sheet or film extrusion. 2. Understanding the chemical resistance requirements of the plastic product. For example, if is it to be used in contact with acids, bases or organic solvents, the colourant of choice must be resistant to these chemicals. 3. Knowing the heat exposure during each processing step. The degree of heat the colourant has to withstand is predominantly determined by the maximum processing temperature and duration of exposure. 4. Protecting against ambient conditions. The long-term resistance of the final product against humidity, light, temperature and combinations of these can be greatly influenced by choosing suitable raw materials, which protect the polymer. For measuring the life of a certain product with regard to the colour, most colour engineers use the grey scale. The grey scale is a tool for describing the colour changes of an object that might occur under the influence of temperature, light (in particular UV radiation), and other weather conditions, during a certain period of time. This scale contains a range of 1 to 5, where 5 means that the colour of the object has not changed and 1 that a severe colour change has occurred. 5. Enabling usage in food approved products. The legislation in many countries bans specific raw materials in products and requires special approval for plastic ingredients used in contact with food or pharmaceuticals. For example, most heavy metals are highly regulated in food packaging. When developing masterbatches for food packaging colour engineers are not allowed to use pigments containing heavy metals. A close co-operation between customer and colour engineer is imperative to ensure compliance. 6. Offering the ability to reduce waste. Another legislative restriction found in many countries aims at reducing waste. Reducing the thickness of the plastic packaging achieves this goal. The colour engineer has to create a concentrate that can obtain the same level of opacity with a thinner product, by either adding more pigment to the concentrate or by using different types of pigments with higher colour strength. 7. Providing optimal colour quality and desired effects. The stability of the final product depends largely on the correct ingredients within the formulation, their degree of dispersion, resistance to migration, bleeding, crocking or bronzing. Effects like metallescent or luminescent looks will give the plastic the desired appearance. The more complex the desired effect becomes in the plastic product, the higher the cost of the raw materials. If any (or all) of the above questions cannot be answered properly, the chances of getting a correct match decrease considerably. For example, if the colour engineer is not informed that the customer wants to use the end product in warm climates for ten years, then sufficient UV-stabilisation will not be added to the colourant. Alternatively, if the colour engineer is not informed that a product has a life cycle of only six weeks, more expensive, but highly stable

pigments may be used to get the right colour, and protect against weatherability, while making the final formulation cost prohibitive. Over the past decade consumers have become much more demanding. For example, in the packaging industry requirements are longer shelf life, fresher products and packaging that is easier to handle and easier to recognize. Demands in this industry are high UV-stability, improved barrier properties, and improved tear strength, antistatic and antifogging properties and a colour that helps differentiate their packaging from their competition. In the automotive industry looks, scratch resistance and cost reduction have become important issues, while in the appliance industry it is appearance, design and advice about colour trends. The tools - inorganic and organic colours Colourists work with a variety of pigments to reach the desired colour and effect. Typically, two main pigment classes, inorganic and organic, exist because of their chemical differences. Another group referred to as polymer-soluble dyes are organic colourants that dissolve in certain polymers when melted.
Table 2: Differences between inorganic and organic pigments and dyes inorganic Less expensive High stability High opacity Low colour strength Dull colours (often nontoxic) Bright colours (lead, cadmium Easy to process Easy to disperse Suitable for all thermoplastics Organic Moderate to expensive Low to high stability Low to medium opacity High colour strength Bright colours Dye More expensive Low stability Low opacity Very high colour strength Bright colours

Seldom found Difficult to process Difficult to disperse (small particle size) More or less suitable, depending on the pigment and polymer

Seldom found - more toxic) Difficult to mix at high concentration No dispersion required (dissolve in polymers) Not suitable for olefins - at very low levels in PS, PA, etc

Inorganic colours are based on oxides, salts, or complexes of metals in various oxidation states. Most inorganic colour pigments have a simple molecule structure, except for some mixed metal oxides, which have more complex shapes. The metals often require a special pre-treatment to make them suitable for use in plastics. Organic colours are based on carbon chemistry and typically do not contain any metals. These colours can have complex molecular structures, are produced through multi-stage synthesis and are often easier to mix with the polymer. Based on the requirements of the customer, the proper pigments are chosen to achieve the desired performance. Often, a combination of organic and inorganic pigments is used to obtain the desired colour and effect. The main difference between both classes is summarized in Table 2. Dispersion and distribution of colorants Besides matching the colour, the masterbatch needs to ensure dispersion of pigment and facilitate the distribution of the colour in the plastic. Dispersion is the separation of particles of pigment from each other through wetting the surface of the pigment with the polymer

carrier to form the colour concentrate. Distribution is the spreading of this concentrate evenly through the polymer without streaks. Dispersion: Pigment particles easily form aggregates, where the particles are firmly adhered to each other. It generally requires aggressive grinding to break up these aggregates. Agglomerates, on the other hand, can be broken fairly easily. Figure 5 shows the general problem. The strength of a pigment depends on dispersion, in particular. The number of colour sites largely determines the strength of a pigment. Breaking agglomerates of two pigment particles doubles the strength of the system. A 40-micron agglomerate of onemicron particles can contain up to 64,000 particles. A dye is usually stronger than a Figure 5: Pigment dispersion and agglomeration pigment, since a dye is dissolved, and each molecule becomes a colour site. Dispersion is generally a two-step process. A pigment agglomerate is broken up by physical force. The agglomerate can be crushed, pulled apart or shattered by an impact. The pressure of crushing can also create new agglomerates by squeezing particles together. Many organic pigments show this tendency of compaction, which can occur at different stages of the production process. In order to prevent particles of the same chemical make adhering to each other they have to be coated (wetted) by a different substance. Only then will they have a lower tendency to stick together. This other substance can be a wetting agent or polymer. The wetting material coats the pigment and allows pigment particles to slide over one another instead of sticking to each other. One popular type of wetting agent is a surface-active agent (surfactant), which has a molecule with a polar end to bind to pigments, since they are often polar molecules, and a non-polar end to bind the polymer. A common example is stearic acid, which has a polar acid group attached to a hydrocarbon backbone. Wetting agents are usually lubricating. Too much lubricant can prevent the necessary force from reaching the pigment. The agglomerates roll and are not sheared apart. One consideration in Figure 6: Relation between surface area and particle size determining how much surfactant to use is the surface area of the pigment. Inorganic pigments typically have small surface areas, about 4m2 per gram. Carbon black can have more than 300m2 per gram. Obviously, carbon black would need more surfactant. Figure 6 shows the surface area as a function of particle size. Distribution of colour is a shared responsibility between the colour concentrate producer and the plastic manufacturer. For example, a hard colour concentrate will not flow as well as the polymer it is being letdown into. It will mix poorly, leaving specks and streaks. The letdown ratio is a consideration in good mixing. If the letdown is 1%, and the pellets of concentrate and resin are roughly equal in size, there is only one pellet of concentrate for each hundred pellets of resin. The one pellet must break down and spread among the hundred pellets of natural resin. Consequently, a soft resin that can flow easily, and ideally, melts before the letdown resin, is best for the carrier. A pigment dispersed in the concentrate can increase the

viscosity, making mixing even more difficult. UV additive formulations can also make mixing difficult and cause streaks. Conventional pellet concentrates are usually used at 2% to 4%, to make the product look more even. New trends are towards smaller concentrate pellets. Pellets half the size of the resin pellets at 1% have one colour pellet for every 50 and not 100 resin pellets. Designing appearance The colour concentrate allows the manufacturer to produce plastics with desired colour, optical effects and specific physical properties. Appearance is critical for many products and a key differentiator for plastic producers and their clients. For example, designing interference or flip-flop colours, which change depending on the viewing angle requires a good understanding of the matter. In order to match an interference colour, the colour engineer works in two steps. Firstly, the base colour is matched. The interference effect is then added by typically using mineral-coated mica. By looking at the moulded part from different angles, the light will be reflected in different ways from the mica Figure 7: overview of different optical effects particles, causing a change in colour. Actually, the colour does not change, but the reflection effect of the mica particles will be more or less visible, causing the interference effect. There are a number of new effects and recent trends in designing colour masterbatches. Figure 7 below shows an overview of the different optical effects. Opaque plastics: The opacity of an object is determined by measuring how much light is transmitted through the object. Opacity of a colour is critical to its appearance. The usual way to measure opacity is to measure reflectance over white and over black in order to determine the contrast ratio. A contrast ratio of 98% is considered one-coat hiding in paints. A colour engineer needs to know the desired opacity and thickness of the plastic part. With this information the colourist can formulate the required pigment concentration in the masterbatch. Pearlescent plastics: These contain pigments that are applied to generate a pearl-like, iridescent effect. Typically, the pigments are thin, metal oxide coated mica platelets, usually less than one micron thick and between 5 to 100 microns long with a high refractive light index. The metallic oxide coatings have the ability to reflect or suppress specific wavelengths of incident light causing a soft, silky appearance. The platelets can change colour depending on the viewing angle. Which wavelengths are reflected or suppressed depends on the thickness of the metallic oxide coatings. The pigments typically have to be well dispersed in the plastic matrix to prevent agglomeration. Light scattering, either by the resin of the compound or by other pigments, needs to be avoided since this interferes with the reflection of the platelets. Usually, oxides of iron- or titanium-coated mica are the leading pearlescent pigments, which contain superior chemical and processing stability. The automotive industry, for example, is always looking for new colour shades and effects like pearlescent finishes.

Figure 8: Moulded plastic parts with knit-line (right) and without knit-line (left)

Fluorescent plastics: These materials contain pigments that possess the unique capability to absorb light energy in the visible and UV range and re-emit it at different wavelengths. This results in a bright glowing plastic in daylight, which is dark without light. This is also the main difference when compared with phosphorescent plastics, which contain an afterglow generating effect pigment. Fluorescent pigments typically consist of an organic moiety. Some molecules with fluorescent capabilities also show phosphorescent behaviour. The pigment is usually mixed into the plastic matrix and shows highest fluorescent intensity when applied over white surfaces. Phosphorescent plastics: These contain pigments that have the capability of absorbing light energy at one wavelength and releasing it in packets at a lower wavelength. The energy release is delayed and the re-emission process varies by pigment type and can last for several hours depending on length and size of the excitation process. Most common are inorganic oxides, like doped zinc sulphide complexes. The ZnS crystal lattice contains implanted metal-ions such as Sr+, Ca2+, Li+, Cd2+ or other metals in low concentrations. Organic pigments are also known to provide similar effects. Products containing these kinds of pigments are known for their special effects like glow-in-the-dark. Red, green and yellow are the most common colours observed in industries focusing on toys, safety, highway and road markings, and related industries. Metallescent plastics: Manufacturers often have to use metal or follow a two step paint process, applying a primer and a liquid coating in a post fabrication process to generate a metallic look. Over the past decade the automotive, household goods and electronic industries have looked at a number of ways to replace metal or paint in an attempt to reduce weight and organic solvents, while maintaining a metallic appearance. Polymers containing metallic flakes are designed to mimic metal. A metallic look is typically generated through the use of aluminium, copper or mixtures of these metals. The actual size of the flakes will vary, but typically range from 0.1 m to 2.0 m in thickness and 0.5m to 200m in diameter. When incorporated into a resin, the flakes have a tendency to orient themselves in a multilayered position. The metallic effect varies depending on how parallel the flakes are to the surface, flake size, and shape. The characteristic colour can be described as whiter, brighter or greyer, and darker, and is again related to particle size distribution. The lightness or greyness is provided by the amount of light reflected from the surface of the flake. Generally, as the particle size distribution becomes finer, the colour becomes darker. However, through particle size separation techniques, it has become possible to provide grades with a very small average particle size while maintaining a high degree of brightness. Smaller particles provide more opacity and hiding power, while larger particles cause higher reflectivity and therefore brightness of the object. Colours that vary with angle are particularly difficult to match. A metal looks light in colour when viewed head-on (face angle), but darker at an angle (flop angle).

Solving the formulation puzzle and complying with the processing conditions will not be sufficient in delivering the desired colour and effect. Metallic, pearlescent and iridescent formulations, for example, have a tendency to create flow lines in the plastic product. These streaks or lines are often caused by a combination of processing equipment and metallic pigment. In particular, at the injection point of an injection-moulding machine, the flow lines are very difficult to eliminate. The shear during the production process causes the metallic pigments to break, fold, bend, or distort from the original shape and size, eventually creating a flow line. The flow line can easily be seen in the final product because the light that falls on the distorted pigment area is reflected in different ways depending on the vertical orientation of the edges of the pigments, causing the knit, weld or flow line effect (see Figure 8). The challenge for colour engineers is now beyond chemistry. Success requires a good understanding and close co-operation with process engineers and mould designers to offer the electronic, telecommunication, automotive, appliances, furniture, consumer goods and related industries with the desired metallic look. Recently, new generations of metallic masterbatches have been introduced that have the ability to reduce significantly the flow lines in a plastic. In some cases these flow lines can be almost completely eliminated by a combination of process and no-knit metallic pigment technology. This technology looks promising and should be transferable to many other polymer families, including polyolefins, engineered thermoplastics, PVC, TPE, TPO, polyurethane and other commonly used resins, made by various manufacturing technologies like extrusion, blow or injection moulding and related processes.