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Meeting the Requirements of Todays Furniture Industry through Applied Polyurethanes Technology

Chen Jian
Shell Seraya Research Laboratory, Singapore

Jeremy Shears
Shell Seraya Research Laboratory, Singapore

Meeting the Requirements of Todays Furniture Industry through Applied Polyurethanes Technology
Chen Jian and Jeremy Shears
Shell Seraya Research Laboratory, Shell Eastern Petroleum (Pte) Ltd, Singapore SUMMARY
Asia Pacific is one of the fastest growing regions in terms of the production of flexible slabstock foam. Much of this foam is used as a cushioning material in the manufacture of upholstered furniture. Increasingly, furniture manufacturers demand a wider range of cushioning materials having improved performance characteristics, such as the hardness range, durability and comfort. This is to satisfy the requirements of high quality furniture both within the region and for export to other regions, such as Europe and North America. This paper will describe how these demands can be met through the selection of the appropriate polyol and other formulation ingredients. Recent developments in polyols technology by Shell Chemicals has lead to an extension of the range of hardness of flexible slabstock foams, from super soft foams to high load bearing foams. The correct choice of polyol, or combination of polyols, allows the foam manufacturer to tailor the hardness to the requirements of various components of upholstered furniture. To meet the demand for cushioning materials with superior support properties and the long-term retention of these characteristics, high resilience foam is assuming increasing importance in Asia Pacific. We will describe how a range of high resilience foams, of varying density and hardness, can be prepared with the polyol CARADOL MD30-02.

INTRODUCTION
Density and hardness are two key properties of flexible polyurethane foams. The fact that these two properties can be varied independently over a wide range by the balanced selection of formulation ingredients, makes flexible polyurethane foam one of the most versatile of materials. In recent years, Shell Chemicals has contributed to this formulation flexibility by introducing into the market a range of polyols, which can be used in combination with a conventional slabstock polyol, such as CARADOL SC56-01 or CARADOL SC56-02, to control foam hardness. This range includes the polymer polyol, CARADOL SP33-03, a conventional slabstock polyol containing a Styrene Acrylonitrile (SAN) dispersed solid phase, which is used to make high load bearing foams. At the other end of the hardness range, the additive polyol CARADOL SA36-02 can be used to make soft foam grades 1. Another trend within the market in Asia Pacific is the desire for foam cushioning materials with superior support and comfort characteristics provided by high resilience foams. To meet this demand the high resilience polyol, CARADOL MD30-02 was developed and introduced to the market.

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EXPERIMENTAL
Polyols and other materials used CARADOL SC56-01: 3000 MW all PO conventional polyol, hydroxyl value 56 mg KOH/g CARADOL SC56-02: 3000 MW PO/EO conventional polyol, hydroxyl value 56mg KOH/g CARADOL SP33-03: high solids SAN polymer polyol for high load bearing slabstock foam applications, hydroxyl value 33 mg KOH/g CARADOL SA36-02: hydrophilic, high reactivity polyol for the production of soft and super-soft foams, hydroxyl value 36 mg KOH/g CARADOL MD30-02: polymer polyol for high resilience foam, hydroxyl value 30 mg KOH/g CARADATE- 80: commercial grade TDI-80/20, i.e. toluene di-isocyanate, blend of 80% wt 2,4isomer and 20% wt 2,6-isomer DBTDL: DEOA: dibutyltin dilaurate diethanolamine

Physical property measurement Foams were cured at room temperature for at least 48 hours before cutting. Subsequently, they were conditioned for at least 16 hours at 23C and 50% relative humidity prior to testing. The tests were carried out according to ASTM D3574 (tensile strength, elongation at break and compression set), DIN 53577 (compression load deflection) and DIN 53576 B or C (indentation load deflection).

MANUFACTURE OF HIGH LOAD BEARING FOAMS USING CARADOL SP33-03


High load bearing foams exhibit increased hardness at a given density compared to foams based on conventional slabstock polyols. Such foams find a wide variety of applications including as a cushioning material in upholstered furniture and mattresses, as a packaging material and as a padding layer in shoes. These foams can be produced using a high solids polymer polyol, such as CARADOL SP33-03. The increased hardness can be explained by the reinforcing filler effect of the microscopic Styrene Acrylonitrile (SAN) particles contained in the polymer polyol. The highest foam hardness can be achieved by using the pure polymer polyol, but intermediate hardness is achievable by using a combination of CARADOL SP33-03 and a conventional polyol, such as CARADOL SC56-01 or CARADOL SC56-02. By selecting the proper blend ratio, it is possible to tailor the hardness to the requirements of the final application: the more polymer polyol, the harder the foam as shown in Figure 1 for a foam of density 25 kg/m3.

Dispensed foams Foam samples (55 x 55 x 50cm) were prepared on a Viking laboratory foam machine using a low pressure mixing technique. Ancillary chemicals were blended with the polyols in a manifold and then mixed with di-isocyanate at 3500rpm. The polyol and di-isocyanate were maintained at temperatures between 20 and 22C. Where indicated, some foams were also produced on commercial low and high pressure continuous foaming machines.

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MANUFACTURE OF SOFT FOAMS USING CARADOL SA36-02


Soft foam grades are used in some specific furniture applications, including as a seating or cushioning material, in mattresses (where it is often applied as a layer on top of a harder foam) and in pillows. Soft foams can be produced using an auxiliary blowing agent such as methylene chloride or carbon dioxide. However, these blowing agents are sometimes not preferred either due to practical constraints or, in the case of partially halogenated blowing agents, for environmental reasons. An alternative approach is to use the additive polyol, CARADOL SA36-02. This polyol allows a substantial reduction of the di-isocyanate index, even to levels below the stoichiometric amount. Inclusion of CARADOL SA36-02 prevents the processing problems usually encountered in low diisocyanate index formulations such as shatter splits and a reduced tin catalyst latitude.
Table 1: Effect of increasing the amount of polymer polyol used in a 16 kg/m3 density foam, based on CARADOL SC56-01

Figure 1: Effect of increasing CARADOL SP33-03 on the hardness of a 25 kg/m 3 foam

Tables 1 and 2 show in more detail the typical properties of machine made foams based on CARADOL SC56-01 and SC56-02 respectively, with different amounts of the high solids polymer polyol.

Another advantage of using CARADOL SA36-02 in the manufacture of these types of foam is that the foam has a very smooth and luxurious hand feel, compared to foams made with methylene chloride. This is partly due to the polymer modifying effect of the additive polyol, but also due to the fact that it is easier to produce foam with a fine and regular cell structure. Typical use levels of CARADOL SA36-02 are up to 15 pbw, the remainder being a conventional slabstock polyol, such as CARADOL SC56-01 or CARADOL SC56-02. However, because the additive polyol is hydrophilic it does not easily mix with the conventional polyol. Therefore it is preferable to dose the additive polyol from a separate stream directly into the manifold or mixing head of the foaming machine. Soft foam grades containing CARADOL SA36-02 have been run on practically all types of industrial slabstock machines, using standard ancillary chemicals (in

Table 2: The effect of increasing the amount of polymer polyol used in a 22 kg/m3 density foam, based on CARADOL SC56-02

CARADOL SP33-03 can be processed on most types of industrial foam machinery, providing it is capable of handling the relatively high viscosity which is inherent to high solids polymer polyols. Standard catalysts and ancillary chemicals can be used.

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some cases it may be necessary to increase the level of silicone surfactant slightly to improve the miscibility). Figure 2 shows the effect on foam hardness of applying different levels of CARADOL SA36-02, across the density range 21 to 44 kg/m 3, at a diisocyanate index of 100. A hardness reduction in the range of 30 to 40% can be observed with 14 pbw of the additive polyol. Table 3 shows some typical formulations and resulting physical properties of foams based on CARADOL SA36-02.

polyurethane foam is that it has excellent durability characteristics and will not lump during use. Typical super soft foam formulations and associated physical properties are illustrated in Table 4. It should be noted that these formulation process in a rather different manner compared with conventional foam grades. Firstly, no tin catalyst is used and, secondly, the cream time is very short (typically 4 to 5 seconds).

Table 4: Super soft foams based on CARADOL SA36-02

SELECTING THE RIGHT FORMULATION FOR SPECIFIC APPLICATIONS: Formul8


Figure 2: Effect of CARADOL SA36-02 on foam hardness (foams based on CARADOL SC56-02, index 110 or 100 as stated)

The range of foams required by the furniture industry is becoming increasingly wide. Hence choosing the right formulation is sometimes not straightforward. Factors to take into account include the foam physical property requirements which must be met, the types of raw materials which can be handled on a particular foaming machine and, not least in todays economic climate, the foam cost. To assist the foam manufacturer in this selection process, Shell Chemicals has developed a foam property prediction program, called Formul8 2. This allows the user to input a particular formulation and the program predicts the foam physical properties and estimates the foam cost. This way it is possible to work out starting formulations, which can then be fine-tuned to obtain the exact properties required, thereby saving time and money in the development of new foam grades or optimizing existing ones. The prediction program is based on data obtained from both industrial and laboratory

Table 3: Physical properties of soft foam grades based on CARADOL SA36-02

CARADOL SA36-02 can also be used to make super soft foams. In this case the polyol is not used as an additive, but as the main polyol (typically 70 to 80 pbw) in combination with a conventional slabstock polyol such as CARADOL SC56-02. This type of foam is used as a surface wrap in upholstered furniture. In some furniture this function is provided by polyester fibre, but the advantage of

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foam production, using a variety of different polyols, under a range of environmental conditions. These data were analysed using statistical techniques to develop specific correlations which are the basis of the prediction program. As illustrated in Figure 3, Formul8 allows the user to select the preferred polyol, or combination of polyols, water level, auxiliary blowing agent and di-isocyanate index. The program then presents a prediction of the foam density, hardness, tensile strength and elongation properties. If the raw material prices are entered, an approximation of the foam cost is also presented. It should also be noted that the environmental process conditions are required to be entered as these can strongly influence the foam properties. For example, atmospheric pressure affects the foam density and relative humidity affects the foam hardness. Thus another use for the Formul8 program is to optimize the formulation depending on the prevailing atmospheric (weather) conditions. For example, it is a well-known phenomenon that under increased humidity, the foam tends to be softer than when the atmosphere is less humid. This can be a problem if the customer requires a specific hardness. If one wishes to obtain exactly the same hardness when the humidity is higher, one solution is to increase the di-isocyanate index slightly. An indication of the magnitude of increase required can be obtained from Formul8.

Furthermore, the prevailing weather systems can affect the atmospheric pressure, which in turn affects the foam density. Differences in atmospheric pressure also explain why foam produced in plants at elevated altitudes has a lower density than foam produced at sea level, when identical formulations are applied.

MANUFACTURE OF HIGH RESILIENCE FOAMS USING CARADOL MD30-02


Whilst conventional polyurethane foams still represent the majority of foams manufactured, an increasingly important cushioning material is high resilience (HR) foam. HR foam was developed by the industry to satisfy the requirements for cushioning materials with superior support characteristics and the long-term retention of these characteristics. HR foams are available in a wide density range and different degrees of stiffness. Such foams are generally used in high quality upholstered furniture and bedding applications and are characterized by a soft initial touch, followed by a high support factor at further compression. This is illustrated by the stress-strain compression curves in Figure 4, derived from DIN53577 compression load deflection (CLD) measurement. By contrast to the curve for a typical conventional foam, the HR curve shows that as the degree of compression is increased, so the force also gradually increases, indicating a continuous load bearing ability throughout the compression cycle.

Figure 3: A screen shot of the Formul8 foam property prediction program

Figure 4: Typical stress-strain curves for conventional and HR foams (derived from DIN 53577 Compression Load Deflection test)

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Shell Chemicals has developed a unique polyol for the manufacture of HR foams known as CARADOL MD30-02. Standard catalysts and silicone surfactants designed for HR foams are used in processing. The foam density and hardness can be controlled by selecting an appropriate water level and di-isocyanate index (Figure 5). Hardness can be further fine-tuned by selecting the proper level of cross-linker (diethanolamine; DEOA) as shown in Figure 6. The wide range over which these parameters can be varied, whilst maintaining processability, is an important feature of formulations based on CARADOL MD30-02. The range of density/hardness is shown in Figure 7.

Excellent foam properties have also been realised during industrial scale production on a variety of foam machinery (Table 5), including both high and low pressure machines. The enhanced stability of the foam during rise means that processing of CARADOL MD30-02 is particularly easy. In spite of this superior stability, the foam is usually very open (i.e. possessing a high air porosity) due to the efficient cell opening characteristics of the polymeric solids in the polyol. This means that only minimal crushing of the foam is required after curing. The data in Table 5 show that excellent ball rebound resilience, tensile and compression set values are obtained. Moreover, the high sag factors show that the foams are capable of sustaining a gradual increase in load bearing during compression. Put simply this means that the foams exhibit excellent support characteristics when used as a cushioning material in upholstered furniture.

Figure 5: Efect of TDI index on the hardness of HR foams based on CARADOL MD30-02

Figure 6: Effect of cross-linker (DEOA) on the hardness of HR foams based on CARADOL MD30-02

Table 5: Formulations and properties of HR foams based on CARADOL MD30-02 - silicone and flame retardant levels omitted. (Sag factor is the ratio of the ILD force at 65% divided by the force at 25% compression)

Figure 7: The density/hardness range of HR foams based on CARADOL MD30-02 at different TDI indices and DEOA levels

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CONCLUSIONS
Furniture manufacturers increasingly demand a wider range of cushioning materials having specified performance characteristics. This is to satisfy the furniture design requirements within Asia Pacific, but also for export purposes. Thanks to the versatility of polyurethane foam technology, these demands can be met through the careful selection of raw materials, especially the polyols used: High load bearing foams can be produced using the polyol CARADOL SP33-03, either alone or in combination with a conventional slabstock polyol. The hardness can be controlled by selecting the amount of polymer polyol used in the formulation. At the other end of the hardness range, soft foams can be produced using the special additive polyol, CARADOL SA36-02, in combination with a conventional slabstock polyol. These foams have a luxurious hand feel and can be prepared without auxiliary blowing agents. Super soft foams, which are becoming increasingly used as a surface wrap in upholstered furniture in place of polyester fibres, can be manufactured using CARADOL SA36-02 as the main polyol. The Formul8 foam prediction program can assist the foam manufacturer in selecting the most suitable formulation for a particular foam grade, taking into account physical property and cost requirements, as well as the environmental conditions at the foam plant. Increasingly, high resilience foams are used in furniture. Superior quality HR foams, exhibiting excellent support characteristics can be produced using the special HR polyol, CARADOL MD30-02.

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ACKNOWLEDGEMENTS
The authors would like to thank the members of Shell Chemicals flexible polyurethanes groups at the Shell Seraya Research Laboratory, Singapore and the Monnet Centre International Laboratory, Louvain-la-Neuve, Belgium, in particular Jurgen Maebe, who made this work possible.

BIOGRAPHICAL NOTES

Chen Jian Chen Jian joined the Shell Seraya Research Laboratory in Singapore in 1996 as Market Development Manager, North East Asia. He graduated from the Beijing Institute of Chemical Technology in 1983 with a Bachelor of Science degree in Chemical Engineering and Process Control. He joined Shell China in 1989 as Project Assistant in the chemicals department based in Beijing. He later became Project Development Manager and then Business Development Manager prior to his assignment in Singapore.

Jeremy Shears After completing a PhD at the University of Bristol, Jeremy Shears joined the Shell Research Centre at Sittingbourne, UK, in 1986. In 1992 he transferred to the Shell Research & Technology Centre, Louvain-la-Neuve, Belgium, where he was responsible for research & development and technical service in flexible slabstock applications. He subsequently moved to Shell Markets Middle East in Dubai, UAE in 1997, where he was polyols Market Development Manager for the Middle East & Africa. Since October 1999 he is the Manager of the Shell Seraya Research Laboratory in Singapore, as well as the Propylene Oxide Derivatives Market Development Manager for Asia Pacific.

1 The information contained in this publication is, to the best of our knowledge, true and accurate, but any recommendations or suggestions which may be made are without guarantee, since the conditions of use are beyond our control. Furthermore, nothing contained herein shall be construed as a recommendation to use any product in conflict with existing patents covering and material or its use. Royal Dutch /Shell Group and Shell companies have their own separate identities but in this document the expressions Shell and Group are used to refer to companies of the Royal Dutch/Shell group in general. These expressions are also used where no useful purpose is served by identifying the particular company or companies. CARADOL and CARADATE are Shell trade names. 2 The Formul8 prediction program has been developed to provide only an indicative prediction of physical properties of urethane foam from known Shell formulation ingredients, and should only be used for such purposes. In proceeding to use the program, the user hereby acknowledges and accepts, that Shell and its affiliates, and the directors and employees thereof, and the authors of this program, shall not be held responsible for, and shall be indemnified and held harmless by user, from any claims, proceedings, liabilities, losses, damages, costs (including legal costs) and expenses whatsoever arising relating to the use of the program.

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