Paper making and fiber liberation – Processes and products – Non-fiber additive
Reexamination Certificate
2000-09-11
2002-07-09
Chin, Peter (Department: 1731)
Paper making and fiber liberation
Processes and products
Non-fiber additive
C524S099000, C162S168100, C162S168200
Reexamination Certificate
active
06416627
ABSTRACT:
The instant invention pertains to novel polymeric stabilizers which contain nitroxide, hydroxylamine or hydroxylammonium salt groups which are useful for preventing loss of brightness and for enhancing resistance to yellowing in pulp or paper still containing lignin. This performance is often further enhanced by the presence of one or more coadditives selected from the group consisting of the UV absorbers, the polymeric inhibitors, the nitrones, the fluorescent whitening agents and metal chelating agents. Combinations of hydroxylamines or their salts, benzotriazole or benzophenone UV absorbers and a metal chelating agent are particularly effective.
BACKGROUND OF THE INVENTION
High-yield and ultra high-yield wood pulps undergo rapid light induced discoloration, particularly when they are exposed to near ultraviolet radiation (wavelengths 300-400 nm) in indoor fluorescent light and daylight. This characteristic restricts their use to short-life, low-value paper products. High-yield and ultra high-yield wood pulps can be bleached to a high level of whiteness. If this whiteness could be stabilized against discoloration, these bleached high-yield pulps could displace significant amounts of more expensive fully-bleached, low-yield chemical pulps.
This discoloration is ascribed to the substantial lignin content of high-yield pulps totalling about 20-45% by mass. Phenoxy radicals are the key intermediates in the reaction mechanism. Several light induced reactions have been proposed to account for their formation such as abstraction of a hydrogen atom from phenolic groups, cleavage of the aryl ether bond of phenacyl aryl ether groups, or the breakdown of ketyl radicals fromed from saturated aryl-glyerol &bgr;-aryl ether structures in lignin. The phenoxy radicals are oxidized by other oxygen-centered radicals (alkoxy, peroxy, hydroxy and perhydroxy) to form yellow chromophores as taught by C. Heitner in “Photochemistry of Lignocellulosic Materials”, C. Heitner, J. C. Sciano, eds.; ACS Sym. Ser. 531, 1-25 (1993).
I. E. Arakin et al., Khymiya drevesiny (Chemistry of Wood), 1982, No. 2, 114 and A. D. Sergeev et al., ibid, 1984, No. 5, 20 disclosed that the use of iminoxyl radicals such as TEMPO (1-oxyl-2,2,6,6-tetramethylpiperidine) is useful in the delignification of wood using the one-stage oxygen-soda (alkaline) process, but made no mention or suggestion of any activity provided by TEMPO on preventing light-induced discoloration of paper or pulp made from such treated wood.
EP 717,143 and WO 97/36041 describe a multicomponent system for changing, reducing or bleaching lignin and lignin-containing materials which comprise an oxidation catalyst, and an N-hydroxyl mediator compound such as N-hydroxyphthalimide or a dialkyl-hydroxylamine. These references are aimed at the delignification of wood. There is no mention or suggest of any activity provided by the N-hydroxyl compounds in preventing the light-induced discoloration of paper or pulp made from such treated wood.
V. I. Khodyrev et al., Vysokomol soyed, A29, No. 3, 616 (1987) [Polymer Sci. U.S.S.R., 29, No. 3, 688 (1987)] show that the photoinitiated oxidation by oxygen causes weathering of cellulosic textile materials such as flax or cotton, and that the light stability of the cellulose could be improved by photostabilizers such as the UV absorbers, benzophenols and 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine. The UV absorbers offer no protection, and are actually detrimental. The authors noted that the stable nitroxyl radical interacts with alkyl radicals in the cellulose to afford its salubrious stabilizing activity. There is no suggestion by the authors that this stabilizing activity could be applied successfully in wood pulp and/or paper made therefrom.
M-K. Syler et al., J. Assn. Paper Pulp Tech, 29, 135 (1990) show that selected metal salts such as magnesium sulfate and lower alkanoic acids inhibit color reversion in bleached pulp.
P. Fornier de Violet et al., Cellulose Chem. Tech., 24, 225 (1990) show that the use of UV absorbers and hydrogen donor agents such as thiols, ascorbic acid, etc. help prevent the photoinduced discoloration of hydrogen peroxide bleached wood pulp, but that chain breakers such as hindered phenols and hindered amines (having >N-H or >N—CH
2
— moieties) had no or even a detrimental effect on preventing photoinduced discoloration.
R. Agnemo et al., 6th International Symposium on Wood and Pulping Chemistry, Appita, 1991, confirmed that free hydroxyl radicals plus lignin lead to undesirable photoyellowing in pulp and paper.
S. Omori et al., J. Assn. Paper Pulp Tech, 48, 1388 (1993) describes the effect of antioxidants and UV absorbers on light reversion and concludes that the combination of an antioxidant and UV absorber prevents color reversion and has a synergistic effect in that activity.
M. Paulsson et al., 8th International Symposium Wood and Pulping Chemistry, Helsinki, 1995, show that efficient photostabilization of unbleached paper or hydrogen peroxide bleached TMP pulp can be achieved by acetylation.
There have been a number of different approaches proposed to inhibiting the yellowing of mechanical pulps. These include: radical scavengers and antioxidants; UV screens; elimination of chromophores after their formation; chemical modification of lignin by alkylation or acetylation; polymeric inhibitors; and two types of coadditives used in combination. Z-H. Wu et al., Holzforschung, 48, (1994), 400 discuss the use of radical scavengers like phenyl-N-tert-butyinitrone to reduce the formation of chromophores during mechanical pulping and give a more light-stable pulp.
C. Heitner, “Chemistry of Brightness Reversion and It Control, Chapter 5”, in Pulp Bleaching-Principles and Practice, C. W. Dence, D. W. Reeve, Eds., TAPPI, Atlanta, 1996, pp 183-211, summarizes the state of the art in the thermal and light-induced yellowing of lignin-containing pulps such as thermomechanical (TMP) and chemithermomechical (CTMP) pulps, showing the seriousness of these undesirable effects discusses generally the then current prior art methods used to attack this problem. These include bleaching, the use of phosphites, UV absorbers, polyalkylene glycols and free radical scavengers such as ascorbic acid, thiols, thioethers, dienes and aliphatic aldehydes and chelating agents such as ethylenediaminetetra-acetic acid (EDTA). The author concluded that, although much progress had been made, much still remains to be done before a successful and practical solution to this loss of brightness and undesirable yellowing of lignin-containing pulp and/or paper is found.
Copending applications Ser. Nos. 09/119,567; 09/234,253; Nos. 60/116,687 and 60/116,688 describe potential solutions where the use of selected hindered amine nitroxides, hindered amine hydroxylamines, N,N-dialkylhydroxyamines or their salts in combination with selected UV absorbers and metal chelating agents is seen to prevent loss of brightness and to enhance resistance to yellowing in mechanical or chemical pulp or paper, particularly mechanical pulp or paper still containing significant amounts of lignin.
The instant invention provides novel polymeric materials which contain nitroxide, hydroxylamine or hydroxylammonium salt groups which either alone or in combination with UV absorbers, metal chelating agents and/or fluorescent whitening agents are useful in preventing loss of brightness and in enhancing resistance to yellowing in pulp or paper still containing lignin.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention discloses novel polymeric materials with pendant nitroxide, hydroxylamine or hydroxyammonium salt groups which are water compatible, either water soluble or water dispersible, and have high affinity for pulp and paper made therefrom. These stabilizers when applied to pulp which still contains lignin alone or in combinations with UV absorbers, metal chelating agents, fluorescent whitening agents, sulfur containing inhibitors, phosphorus containing compounds, nitrones, benzofuran-2-ones and/or stabilizing polymers effective ligh
Cunkle Glen T.
Devore David
Thompson Thomas F.
Chin Peter
Ciba Specialty Chemicals Corporation
Hall Luther A. R.
Hug Eric
Stevenson Tyler A.
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