NOVEL HYDROPHILIC SOFTENERS FOR TISSUE AND TOWEL APPLICATIONS Authors

Dr. Craig Poffenberger Senior Scientist Goldschmidt Chemical Corp. Dublin, Ohio

Ms. Yvonne Deac Marketing/R&D Manager Goldschmidt Steinau, Germany

Mr. William Zeman Manufacturing Goldschmidt Chemical Corp. Janesville, Wisconsin

ABSTRACT Cationic surfactants, primarily fatty-alkyl quaternary ammonium compounds, are extensively used as softener/debonders in the production of premium tissue, paper towels, and fluff pulp. A new generation of wet-end softeners has been developed to overcome many of the performance shortcomings of the commercial products. Test results will demonstrate that the new specialty surfactants exhibit premium water absorbency while enhancing bulk and maintaining softness. The way in which the products are constructed determines the balance of absorbency and softness, which traditionally have been mutually exclusive in fatty-based softeners. The new softener/debonders have also been designed to provide beneficial environmental behavior through incorporation of ester functionalities that undergo facile hydrolyses that leads to improved biodegradation. As these new softener/debonders are solvent-free fluids, are very low odor, are very thermally stable, and are highly substantive to fibers, many of the environmental and safety concerns at the plant site are also circumvented whether the products are added in the wet-end or administered topically. INTRODUCTION In the premium tissue market, the following ranking represents the 3 primary characteristics employed by the consumer to evaluate product quality and performance (1): 1. Softness 2. Absorbency 3. Strength This order of preferred attributes is rearranged for premium quality paper towels (1): 1. Absorbency 2. Strength 3. Softness Several techniques are available to the tissue and towel manufacturer to respond to and adjust these performance characteristics. One such method, introduction of wet-end softener/debonders to the tissue furnish, usually modifies all three of these properties. CH3 + R-N-R CH3

X-

Figure 1. Typical Difatty Quaternary Ammonium Softener/Debonder for Tissue

Due to the presence of large fatty alkyl chains and the affinity of the cationic charge of the ammonium salt towards the negatively charged fibers, hydrogen bonding between separate fibers is disrupted (2). This debonding results in a reduction in strength as measured by tensile and a bulk enhancement as determined by sheet density. Although increased voids are created for accumulation of liquids in the tissue or towel, the fatty groups of the debonders are hydrophobic which causes a net reduction in absorbency. On the other hand, the fatty moieties are responsible for imparting the lubricating, soft feel to the fibers. These properties are qualitatively compared against softener/ debonder dosage in Figure 2.
25

INCREASING PROPERTY---->

20

TENSILE

SOFTNESS

15

10

ABSORBENCY
5

DENSITY
0 0 1 3 5 INCREASING DEBONDER DOSAGE----> 8 10

Figure 2: Impact of Softener/Debonders on Tissue Properties Clearly, there is a predicament with most commercial wet-end debonders: increased softness is often accompanied by an undesired loss of absorbency. To mitigate against this decreased absorbency, many softener/debonders are formulated to include rewet aides. Solvents are also used to dilute the effective concentration of the hydrophobic softener, for ease of handling and for increased water dispersibility. The use of these additives leads to the presence of materials which contribute to VOC levels and which can accumulate in whitewater systems. Another environmental concern is the biodegradability of the fatty-based quaternary ammonium softener/debonders. Many in use today exhibit biodegradation profiles under 40%. In fact, one softener used for fabric care (and also tissue) has been discontinued in northern Europe due to its accumulation in river sediments. Therefor, the evolving trend for new softeners is the construction of quaternary ammonium compounds that incorporate ester funtionalities (3-6). As shown in the sequence below, these esters are subject to hydrolytic cleavage which generates readily biodegradable fatty acids.

R2 + R1C(O)-O-CH2CH2NCH2CH2-O-C(O)R1 CH3 H2O H2O

R2 + HOCH2CH2NCH2CH2OH CH3

+ 2 R1C(O)OH FATTY ACID

R2 = CH3, CH2CH2OH Figure 3. Fatty Ester Quats as Cleavable Surfactants for Improved Biodegradation

The objective of the work herein is to describe how tissue and toweling softener/debonders can be designed so as to balance hydrophobic and hydrophilic properties, to improve biodegradability with ester funtionalities, and to eliminate or significantly reduce the need for formulating solvents and rewet aides. This paper summarizes the test data that we have collected on handsheet trials with a new class of fatty ester quaternary ammonium tissue softeners conducted at our laboratories in Ohio and Germany. EXPERIMENTAL Preparation of New Softener/Debonder AROSURF Z-QUAT ESTER QUATS As shown below, the new ester quats are prepared in a straightforward 3-step process (7). The first step involves ethoxylation of a primary fatty amine. This intermediate is then esterified with fatty acid to form a mixture of mono- and diesters. The final step is quaternization with an alkylating agent to form a quaternary ammonium salt of an amine ethoxylate ester.

1. R1-NH2

EO

R1-N[(CH2CH2O)YH]2 (CH2CH2O)YC(O)R2

2. R1-N[(CH2CH2O)YH]2 + 2 R2C(O)OH

R1-N (CH2CH2O)YC(O)R2

+ 2H2O

(CH2CH2O)YC(O)R2 3. R1-N (CH2CH2O)YC(O)R2 + (CH3)2SO4

(CH2CH2O)YC(O)R2 R1-N+-CH3 (CH2CH2O)YC(O)R2 + CH3SO4-

Figure 4. Synthesis Scheme for New Softener/Debonder Ester Quats The finished quaternary products are obtained in high yield at 100% actives in a physical form ranging from solid pastes to easy to handle liquids. The esters of the amine ethoxylates formed in the second step of the reaction are isolated as low viscosity liquids. Handsheet Preparation and Testing at Both Laboratories All furnishes, virgin and recycled, were provided by tissue manufacturers. Handsheets treated with softener/debonders were prepared according to TAPPI test Method T205 sp-95 and conditioned according to TAPPI test Method T402 om93. Handsheet tensile and density were measured according to TAPPI test method T220 sp-96. Absorption rate and capacity data were collected according to TAPPI Method T561 pm-96. Where applicable, handsheets were also treated with commercial softener/debonders manufactured by Goldschmidt Chemical Corporation for performance comparison with the new ester quats. These products are hereinafter referred to as COMM A and COMM B. Typical softener/debonder dosages were 0.05-0.4% by weight of fiber. Hand panels were conducted to measure and rank the relative softness of treated fibers. Tensile reduction was also used as an indicator of increased sheet softness in lieu of handpanels during much of the screening developmental stage. Testing of New Softener/Debonder Ester Quats The rate of exhaustion and the substantivity of the new ester quats was determined by extraction of treated handsheets, followed by titration for % quaternary. Thermogravimetric Analyses were performed with neat samples on a Dupont Instruments 951 Thermogravimetric Analyzer.

PERFORMANCE OF THE QUAT ESTERS OF AMINE ETHOXYLATES There are several structural components of the new ester quaternary ammonium compounds which can be varied in response to the performance requirement(s) of the tissue softener/debonder. These include the degree of ethoxylation, the degree of esterification, the composition of the fatty amine, and the composition of the fatty acids used for esterification. For the sake of brevity, hand panels demonstrated the following trends as a function of composition: 1. Diesters that have a total of 3 fatty groups afford a higher level of softness as compared to monoesters with only 2 total fatty groups 2. Diesters prepared from long-chained fatty acids impart the highest level of softness 3. Softness is improved when the fatty group of the amine ethoxylate is saturated and when the fatty acids used for esterification are saturated. Recognizing that the fatty groups in terms of number and composition are the primary contributors to softness, the factors influencing absorbency were studied in extensive detail in both laboratories. These will be reviewed in the following sections. Degree of Esterification Since the diester derivatives of the amine ethoxylate quats impart premium softness, there was concern that the presence of the 3 hydrophobic fatty moieties would result in a tissue/towel product with a substantially reduced absorbency. To test this possibility, handsheets were prepared with one of these new softener/debonder compositions wherein only the degree of esterification differed. The test data is presented in Figure 5. Since the absorbency capacity and rate data mirror each other, only the capacity data will be reported here to indicate the trends for both.

30 25 20 15 10 5 0 BLANK MONOESTER DIESTER ABSORBENCY TENSILE

5 4 3 2 1 0

Figure 5. Tensile Reduction and Absorbency Changes on a SW/HW Fiber Blend Treated with the New Softener/Debonders Indeed, the absorbency of the diester is lower than the monoester species, but it is important to note that the absorbency of the SW/HW fiber blend treated with the diester species is virtually the same as the untreated blank. In other words, the treated handsheet, which is softer and bulkier, has the same absorbency as the untreated sheet, so the diester represents an acceptable compromise of performance. Degree of Ethoxylation An improvement in the sheet absorbency was predicted and subsequently confirmed when amines with higher degrees of ethoxylation were converted to the esters. What was not anticipated was the improvement in the handling and liquidity of quaternary ammonium derivatives of the higher ethoxylates.

As shown in Figure 6, for a homologous series of these ester quats, one observes an increase in absorbency capacity as the degree of ethoxylation increases from 2 to 10 and, finally, to 15 moles of EO for the fatty amine precursor.

15 10 5 0 B LA N K 2 10 15
TENS IL E A B S O RB ENCY

2.5 2 1.5 1 0.5 0

Figure 6. Tensile and Absorbency as a Function of the Degree of Ethoxylation There is very little variation between the ethoxylate species in terms of tensile reduction, but, at the higher levels of ethoxylation, the absorbency capacities have recovered to that of the untreated material. Therefor, the sheets have excellent absorbency, softness, and bulk as a result of the treatment with these hydrophilic amine ethoxylate ester quats. For a homologous series of these ester quats where only the degree of ethoxylation is varied, one finds the following changes in the physical state of the materials: Table I. Physical Characteristics as a Function of Ethoxylation Moles of EO 2 6 8 10 12 15 Appearance at 20 C Hard Paste Paste Flowable Paste Thick, Hazy Liquid Flowable Liquid Liquid

Increasing liquidity with increasing ethoxylation is a very fortuitous happenstance as the test data also demonstrates that these materials are the best balances of softening/debonding and absorbency performance. Also, as the degree of ethoxylation increases, the aqueous solubility/dispersibility increases, so the need for solvents as formulation aides is diminished. The environmental benefits of solvent removal will be discussed below. Fatty Acid Type Although tallow is the predominant source for fatty acids and their derivatives in the United States, concerns about mad cow disease or B.S.E. in Europe has created a shift towards consumption of natural fatty acids from vegetable sources. This, combined with religious and cultural aversions to animal tallow in various parts of the world, led to preparation of identical offsets, in terms of the degree of ethoxylation and esterfication, of these new ester quats from tallow and partially-hardened palm stearine.

Figure 7 demonstrates that the tallow and palm derivatives are comparable in debonding performance as measured by tensile reduction. However, the palm ester quat exhibits a reduced absorbency. This is attributable to the increased saturation of the fatty chain for the palm which renders the material slightly more hydrophobic (7).

10 8 6 4 2 0
S W /H W B L AN K TAL L O W P AL M
A B S O RB ENCY

2 1.5 1 0.5 0

TENS IL E

Figure 7. Tensile and Absorbency for Tallow- and Palm -Based Offsets of A New Ester Quat However, since the net loss of absorbency is relatively minor, the hydrophilic polyethoxylate chains are able to compensate for this. As a consequence, the combination of tallow and palm derivatives allows for these products to be suitable for global consumption. Performance Comparison versus Commercial Products After optimization of the structural properties of these new softener/debonders, their performance was compared with commercial softener/debonders. In Figure 8, tensile and absorbency data are provided for handsheets which were treated with two commercial softener/debonders and one of these new ester quats. On a typical SW/HW (60/40) tissue fiber blend, the data shows that the new ester quat A is a very effective debonder and that it is more absorbent than either of the two commercial materials. Interestingly, both commercial products are formulated for ease of handling and COMM B even contains absorbency aides. In other words, ester quat A at 100% actives is more absorbent than a formulated product containing a lower amount of hydrophobic quat and an absorbency aide additive.

14 12 10 8 6 4 2 0 B L A NK COMM A COMM B ES TER QUA T A

2 .5 2 1 .5 1 0 .5 0

TENSIL E

A BS ORB ENCY

Figure 8. Tensile and Absorbency for a New Ester Quat Compared against Commercial Products

Generally, furnishes containing recycled fibers do not debond particularly well due to presence of permanent bonds and increased levels of fines and anionic trash which scavenge the debonder. As depicted below, a SW/RF blend responds better to ester quat B than to a commercial debonder, since the tensile is more reduced and absorbency is increased.

35 30 25 20 15 10 5 0 S W /R F B L A NK CO MM B ES T ER Q U A T B A B S O R B EN C Y

3 2 1 0

T EN S IL E

Figure 9. Tensile and Absorbency for A New Ester Quat Using a Softwood/Recycle Fiber Blend Hand panels on treated sheets produced on a semi-continuos sheetmaker confirmed that ester quat B outsoftened COMM B. This data in combination with the tensile and absorbency data demonstrate that these new materials compare favorably with incumbent products. ENVIRONMENTAL PROPERTIES OF THE QUAT ESTERS OF AMINE ETHOXYLATES Biodegradation The construction of these new hydrophilic softener/debonders with ester functionalities results in materials with very good environmental and fish toxicity profiles. Many of the commercial softener/debonders are less than 40% biodegradable as measured by the 28 day Sturm test. As presented in the table below, the new ester quats exhibit an improved biodegradability which is actually very good for quaternary ammonium softeners. From the data, it is evident that esters such as those represented in Figure 3 that do not have the long polyethoxylate chain are more biodegradable. However, numbers in the 60-70% theoretical CO2 range are excellent for quats and confirm that these materials will be ultimately biodegradable. Table II. Comparative Biodegradation of Fatty Ammonium Salts MATERIAL Ditallowdimethylammonium Quat(Figure 1) Difatty Ester Quats from TEA or MDEA(Figure 3) DMS Quats of Esters of Amine Ethoxylates Acid Salts of Esters of Amine Ethoxylates % BIODEGRADATION <40% >80% 52-60% 58-70%

Substantivity Figure 10 confirms that this new class of softener/debonders exhausts rapidly and completely onto the tissue fiber blend. The test dosage of 0.4% closely approaches the saturation point wherein all the active sites on the fiber are depleted.

0.5
THEORETICAL

0.4 0.3 0.2 0.1 0 0.5 1 MINUTES 2 5

Figure 10. Substantivity of New Softener/Debonder on a SW/HW Fiber Blend as Function of Time This rapid and complete exhaustion of the new ester quats implies that there will be no build-up of unreacted material in the whitewater system. It is also very important to point out that the ester quat in this substantivity test was one that is a liquid at 100% actives. Since there are no solvents present as formulation or rewet aides, the combined beneficial effects include: 1. No accumulation of solvents nor unreacted softener in the whitewater contributing to foam and environmental load. 2. Reduced materials hindering runnability such as solvent interference with the Yankee adhesive. 3. No solvents with low flash points. 4. No VOC emissions from solvents.

THERMAL STABILITY OF THE NEW ESTER QUATS In Figure 11, Thermogravimetric (TGA) diagrams for one of the new ester quats and a home laundry dryer sheet softener are presented. Basically, the diagrams represent weight loss versus temperature. This technique identifies where thermal decomposition begins. As expected for a softener exposed to the heat of a clothes dryer, the quaternary ammonium salt is stable to about 280C. For the commercial dryer softener, one observes a 10% weight loss up to 280C, which corresponds to volatilization of a high flash solvent. The TGA diagram for the new ester quat shows that it is also stable to 280C and that, up to this temperature, there are no volatiles of any type generated. Clearly, these new materials will be robust to the temperature conditions encountered at the skin of a Yankee dryer or those used in the newer TAD processes for drying the tissue web.

< --N e w E s te r Q u a t D ry e r Q u a t-->

Figure 11. TGA Diagram for a New Ester Quat and a Dryer Sheet Softener CONCLUSIONS A new class of hydrophilic softener/debonders has been developed in response to continued demands by tissue and toweling manufacturers for new products which, in addition to imparting a premium softness, contribute to absorbency and also exhibit good biodegradability. These new materials can be designed for performance: the key for increased hydrophilicity is the incorporation of ethoxylate functionalities and the key for improved biodegradation and softening is the formation of fatty esters. The presence of several fatty groups in the quaternary ammonium debonder ensures that these materials soften and lubricate tissue surfaces. Another outcome of the design of these new ester quats is that they can be used at 100% actives without the need for solvents which have low flash points, which contribute to VOC emissions, which can accumulated in the water cycle, and which create foam. The liquid nature of these materials and their intermediates affords many opportunities for their consumption in tissue and toweling applications. Several are undergoing active investigation.

LITERATURE CITED 1. 2. 3. 4. 5. 6.
7.

Quarles, R. P., Tappi Journal 79(7): 88(1996). Poffenberger, C. A. and Jenny, N., Evaluation of Cationic Debonding Agents in Recycled Paper Feedstocks, Proceedings from the 1996 Tappi Recycling Symposium, New Orleans, La. Pi, R., Paper Technology, October 1998: 47(1998). Phan, D. V., and Trokhan, P. D., U.S. Patent 5,262,007. Phan, D. V., and Trokhan, P. D., U.S. Patent 5,264,082. Levinson, M. I., Journal of Surfactants and Detergents 2(2): 223(1999). Poffenberger, C. A., Zeman, W., and Deac, Y., U.S. Patent Application Serial Number 09/307,521.