Paper making and fiber liberation – Processes and products – Non-fiber additive
Reexamination Certificate
1999-10-25
2001-07-24
Silverman, Stanley S. (Department: 1731)
Paper making and fiber liberation
Processes and products
Non-fiber additive
C162S168300, C162S184000, C162S185000, C162S164100, C162S157100, C162S157600, C162S158000, C162S009000, C162S017000, C162S019000, C162S100000, C008S116100
Reexamination Certificate
active
06264791
ABSTRACT:
TECHNICAL FIELD
The invention relates to methods for making high wet performance webs.
BACKGROUND OF THE INVENTION
Webs having a high strength when they become wet (known in the art as wet strength) are useful for many applications. One application for such webs is as premoistened tissues, often used by travelers for cleansing the body. Such webs or tissues must maintain sufficient strength when stored in wet conditions for an extended period of time to withstand wiping and rubbing actions. Other applications for high wet strength webs is in articles that need to maintain integrity when wetted with body fluids, such as urine, blood, mucus, menses and other body exudates.
In the art of papermaking, chemical materials exist for improving the wet strength of paper. These materials are known in the art as “wet strength agents” and are commercially available from a wide variety of sources. For example, a polyamide/polyamine/epichlorohydrin resin is often used to enhance the wet strength of paper. This cationic resin is typically added to the papermaking slurry whereupon it bonds to the anionically charged cellulose. During the papermaking process the resin crosslinks and eventually becomes insoluble in water. The agent thus acts as a “glue” to hold the paper fibers together and enhances the wet strength of the paper. However, one needs to use chlorine in order to remove the resin and recycle products containing this resin, which presents environmental problems.
Cationic resins have other disadvantages, such as reacting with other anionic additives which it may be advantageous to add to the paper and, in many cases, increasing the dry strength of the paper as well, resulting in a less soft paper. Moreover, the effectiveness of cationic wet strength agents can be limited by low retention of the agent on the cellulose fiber.
The use of formaldehyde and various formaldehyde addition products to crosslink cellulosic fibers is known in the art. However, formaldehyde is an irritant and a known carcinogen. Crosslinking with compounds comprising formaldehyde at elevated temperatures can be particularly rapid relative to many other crosslinkers, requiring times as low as 1 to 10 seconds. However, for higher molecular weight compounds and for formaldehyde-free crosslinkers in general, much longer reaction times are found.
Other references disclose absorbent structures containing individualized, crosslinked fibers, wherein the crosslinking agent is selected from the group consisting of C
2
to C
8
dialdehydes, with glutaraldehyde being desired. The cost associated with producing fibers crosslinked with dialdehyde crosslinking agents such as glutaraldehyde may be too high to result in significant commercial success.
The use of monomeric polycarboxylic acids to impart wrinkle resistance to cotton fabrics is known. A cellulosic material was impregnated with a solution of the polycarboxylic acid and a catalyst, followed by drying the material and then curing the material in an oven at 150° C. to 240° C. for 5 seconds to 30 minutes.
The prior art also teaches a method of imparting wrinkle resistance to cellulosic textiles by crosslinking monomeric cyclic aliphatic hydrocarbons having multi carboxylic acid groups to the cellulose. Curing is said to be performed at about 150° C. to 240° C. for 5 seconds to 30 minutes.
The use of C
2
to C
9
monomeric polycarboxylic acids to make individualized, crosslinked cellulosic fibers having primarily intra-fiber crosslinking (crosslinks between cellulose units in a single fiber) and purportedly having increased absorbency has been taught.
Polyacrylic acid has been taught as a crosslinking agent, preferably as a copolymer with polymaleic acid. The fibers were fiberized prior to curing to make individualized, crosslinked cellulosic fibers having primarily intra-fiber crosslinking. The fibers are purportedly useful in absorbents. The crosslinking was achieved using temperatures of about 120° C. to 160° C.
Various resinous maleic anhydride compositions have been used in conjunction with paper products. For example, prior art discloses paper products coated with a composition including an amine salt of a low molecular weight C
6
to C
24
olefin/maleic anhydride copolymer in combination with a bisulfite. Such paper products exhibit release properties. Various amine salts of half esters of maleic anhydride/alpha-olefin copolymers have been disclosed as useful paper sizing or water holdout agents. Similarly, prior art discloses paper products impregnated with a sizing and wet strength agent of a reaction product of an alkyl tertiary amino alcohol and a copolymer of maleic anhydride/styrene or derivatives thereof. The use of an agent consisting of epoxide resins and maleic anhydride copolymers as an agent for imparting wet strength is known.
Polymeric treatment agents for adding wet strength to paper, which can be applied to a slurry or to a paper web, wherein curing times are said to range from 5 minutes to 3 hours, with a desired time range of 10 to 60 minutes, have been disclosed. The application of a polymeric polyacid, a phosphorous containing accelerator, and an active hydrogen compound to a paper web followed by curing at 120° C. to 400° C. for 3 seconds to 15 minutes has also been disclosed.
Accordingly, what is needed is a method of improving the wet performance of cellulosic based webs using non-formaldehyde crosslinking agents that can be cured in a one step process.
SUMMARY OF THE INVENTION
The present invention is directed to methods for making high wet performance webs. It has been discovered that wet performance can be improved by application of polymeric anionic reactive compounds to a cellulosic fibrous web followed by curing of the compound to crosslink the cellulose fibers. Rapid development of high wet performance can be achieved using flash curing in which the treated cellulosic webs are cured by application of high temperature in a short period of time, desirably in under one minute, more desirably in less than 15 seconds and most desirably in less than one second. The resulting tissue has high wet resiliency, high wet strength, and a high wet:dry tensile strength ratio.
The polymeric anionic reactive compounds useful in the methods are compounds that will cause crosslinking between the cellulose fibers. In one embodiment, the polymeric anionic reactive compounds include monomeric units having two carboxylic acid groups on adjacent atoms so that the carboxylic acid groups are capable of forming cyclic anhydrides which, at elevated temperature or other initiating force, will form an ester bond with the hydroxyl groups of the cellulose. Polymers, including copolymers, terpolymers, block copolymers, and homopolymers, of maleic acid are especially desired.
Curing is achieved by flash curing which refers to the application of intense energy over a brief period of time to rapidly drive the formation of covalent bonds between the polymeric anionic reactive compound and the cellulosic fibers. Typically, the web or at least the surfaces of the fibers in the web will be briefly heated to a temperature generally above about 160° C., desirably in the range of about 200° C. to 350° C. and most desirably above about 220° C., in the range of about 250-320° C. in a time desirably under about one minute, more desirably in less than 15 seconds, more desirably under about five seconds, even more desirably under about two seconds, and most desirably under about one second. Unlike prior methods for curing polycarboxylic acids and related polymeric crosslinking agents, the present methods provide dwell times in a curing section or heating unit that are short enough to permit curing of a treated web at industrially useful speeds for production or conversion of tissue and other papers. By way of example, industrially useful speeds can be about 70 meters per minute or greater, more specifically about 200 meters per minute or greater, more specifically still about 300 meters per minutes or greater, and most specifically about 600 meters per minute or greater.
The prese
Lindsay Jeffrey D.
Sun Tong
Halpern Mark
Kilpatrick & Stockton LLP
Kimberly--Clark Worldwide, Inc.
Silverman Stanley S.
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