Classifications

• • A—HUMAN NECESSITIES
  • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
  • A47K—SANITARY EQUIPMENT; ACCESSORIES THEREFOR, e.g. TOILET ACCESSORIES
  • A47K7/00—Body washing or cleaning implements
  • A47K7/02—Bathing sponges, brushes, gloves or similar cleaning or rubbing implements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives

Definitions

• an alkaline cellulose solution such as viscose
• a poreforming material such as viscose
• Salt crystals such as decahydrated sodium sulfate (Glaubers salt)
• cotton, flax or hemp fibers have been employed as the fibrous material.
• This mixture is formed into a paste which is introduced into molds where coagulation and decomposition or regeneration are accomplished in a manner well known to those skilled in the art. Salts and other impurities are then washed from the shaped regenerated cellulose articles to form the regenerated cellulose sponge.
• the sponges are usually subjected to a softening bath consisting essentially of diethylene glycol or glycerol or the like dissolved in water.
• the cellulosic sponges are subject to degradation by molds and bacteria. Preservatives to resist degradation of cellulose are known but are diflicult to retain in a cellulosic sponge during use, since they tend to be leached therefrom during use which involves repeatedly immersing the sponge in water and squeezing excess Water there from. Water-insoluble preservatives do not lend themselves well to aqueous processing which is characteristic of the manufacture of cellulosic sponges.
• US. Patent 2,945,772 describes a cellulose sponge resistant to degradation by molds and bacteria which has incorporated therein a mixture of rosin amine and a quaternary ammonium halide.
• the product described in US. Patent 2,945,772 retains about 50% of its original tensile strength after being leached about fifty times and then subjected to a six day simulated soil burial test, and only 15-20% of its original tensile strength after same number of leaches and a thirteen day simulated soil burial test.
• the foregoing objects are accomplished by uniformly impregnating a cellulosic sponge material with a cationic rosin amine and/ or a cationic quaternary ammonium halide and then treating the impregnated cellulose sponge with an anionic surfactant.
• the anionic surfactant reacts with the cationic rosin amine and/or the cationic quaternary halide to form a water-insoluble precipitate which is resistant to leaching with water.
• the sponge material is first impregnated with a cationic surfactant comprising about a 2% aqueous solution of a rosin amine and/ or quaternary ammonium halide in suffiicent quantity to deposit about 1% of the rosin amine and/or quaternary ammonium halide throughout the sponge, the percentage being based on the weight of the cellulose in the sponge.
• a cationic surfactant comprising about a 2% aqueous solution of a rosin amine and/ or quaternary ammonium halide in suffiicent quantity to deposit about 1% of the rosin amine and/or quaternary ammonium halide throughout the sponge, the percentage being based on the weight of the cellulose in the sponge.
• the sponge is then impregnated with about a 1% aqueous solution of an anionic surfactant which reacts with the rosin amine and/ or the quaternary ammonium halide to form a relatively water-insoluble nonionic precipitate which is resistant to leaching by water and imparts to the sponge surprising resistance to degradation by molds and bacteria.
• an anionic surfactant which reacts with the rosin amine and/ or the quaternary ammonium halide to form a relatively water-insoluble nonionic precipitate which is resistant to leaching by water and imparts to the sponge surprising resistance to degradation by molds and bacteria.
• the sponge can be first impregnated with the anionic surfactant and subsequently impregnated with the cationic rosin amine and/ or the quaternary ammonium halide.
• the most useful rosin amine in the present invention is Rosin Amine D, dehydroabietyl amine manufactured by Hercules Powder Company; and the most useful quaternary ammonium halides are Arquad 16, an alkyl trimethyl ammonium chloride containing hexadecyl trimethyl ammonium chloride, 6% octadecyl trimethyl ammonium chloride and 4% octadecenyl trimethyl ammonium chloride manufactured by Armour & Company; and Hyamine 1622, a diisobutyl phenoxy ethoxyethyl dimethyl benzyl ammonium'chloride monohydrate manufactured by Rohm and Haas Company.
• the rosin amines useful in the present invention include primary amines derived from stabilized rosins and stabilized rosin acids wherein the carboxyl group has been converted into a --CH NH group. These include dehydroabietyl amine derived from dehydrogenated rosin; dihydroand tetra-hydroabietyl amines derived from hydrogenated gum or wood rosin; and the aforementioned amines derived from pure stabilized rosin acids.
• Stabilized rosin amine is meant to include primary amines having a ring structure of a stabilized rosin acid, sfich as dehydro-, dihydro-, tetrahydroor polyabietic acid or a mixture of such primary amines.
• dehydroabietyl amines and the other hydro abietyl amines refer to rosin amines wherein the aforementioned amines are the major constituents. It is not intended that minor amounts of other materials derived from the dehydrogenated rosins or hydrogenated rosins be excluded when preparing the aforementioned rosin amines.
• the quaternary ammonium halides useful in the present invention are those that are water soluble and in which the halogen is either fluorine, chlorine, bromine or iodine.
• Preferred quaternary halides include lauryl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride, cetyl dimethyl ethyl ammonium chloride, tridecyl benzyl hydroxyethyl imidazolinium chloride, lauryl pyridium chloride, myristamido propyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, and diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride.
• the corresponding fluorides and iodides are also useful in practicing this invention.
• the anionic surfactant useful in this invention can be any one of a large number of such compounds which are well known, such as those described in Encyclopedia of Chemical Technology, by Kirk et al., vol. 13, pp. 521- 528, published 1954 by Interscience Publishers, Inc., New York, NY.
• the most useful anionic surfactants include sodium N-methyl-N-palmitoyl taurate, sodium dioctyl sulfosuccinate, salts of alkyl aryl sulfonates, such as the ammonium or alkali metal (e.g.
• the rosin amine and quaternary ammonium halide can be prepared in several ways.
• the rosin amine and the quaternary ammonium halide can be first mixed together and then emulsified by slowly adding water while agitating the mixture.
• the mixture can be dissolved in a solvent such as diethylene glycol.
• the quaternary ammonium halide can first be dissolved in water to form a solution.
• the rosin amine can be slowly added with constant stirring. After additional dilution with water, this solution of the mixture can be used as the first or second impregnating bath. If the cationic impregnant mixture is used as the second impregnating bath for forming the insoluble preservative, it can be added to the sponge-softener bath.
• the impregnating compositions can be applied to the sponge by soaking, spraying or by alternately squeezing the sponges and applying the liquid between rolls.
• the degree of protection to deterioration imparted to the sponge varies with the amount of insoluble preservative (reaction product of anionic and cationic surfactants) incorporated in the sponge, and can be regulated by the concentration of the anionic and cationic surfactants in the separate impregnating baths; the length of time of treatment; and the temperature of the processing, and amount of squeezing to which the sponge is subjected.
• the cationic rosin amine and/ or quaternary ammonium halide is dissolved and/ or dispersed to the extent of about .2% in water.
• the cellulose sponge prepared in the conventional manner as described in US. Patents 2,280,022 and 2,295,823, is passed through the solution or dispersion, the exposure being about three to five minutes. After excess solution or dispersion is squeezed from the sponge, the quantity of rosin amine and/or quaternary ammonium halide remaining represents about 1% of the weight of the cellulose in the sponge.
• the sponge Before the sponge is dried, it is immersed in an aqueous solution of anionic surfactant of about stoichiometric concentration which reacts with the rosin amine and/or quaternary ammonium halide to form a water-insoluble, non-ionic precipitant in the sponge.
• anionic surfactant of about stoichiometric concentration which reacts with the rosin amine and/or quaternary ammonium halide to form a water-insoluble, non-ionic precipitant in the sponge.
• Useful products can be made by impregnating the cellulose sponge with as little as about .1%, and as much as about 5% or higher of the cationic rosin amine and/ or cationic quaternary ammonium halide, based on the weight of cellulose in the sponge. If amounts less than about .1% are used, there is no significant improvement with respect to resistance to degradation of the sponge. If amounts appreciably greater than about 5.0% are used, there is no appreciable improvement in resistance to degradation and other valuable properties of the sponge may be deleteriously aifected.
• the preferred amount of anionic surfactant incorporated in the sponge in accordance with this invention is the amount which will react stoichiometrically with the cationic compound(s) introduced in the sponge.
• Useful products can be made by incorporating greater or lesser amounts of the anionic compounds.
• the amount of anionic compound can be that which reacts with only about 50% of the cationic compound
• the amount of the cationic compound corresponds to about .2% based on the weight of the cellulose sponge.
• a cellulose sponge made in a conventional manner, such as in accordance with US. Patent 2,280,022, and washed free of the Glaubers salt is immersed in a .2% aqueous solution of Arquad 16 hexadecyl trimethyl ammonium chloride, 5% octadecyl trimethyl ammonium chloride, and 4% octadecenyl trimethyl ammonium chloride) to saturate the sponge.
• the excess solution is squeezed from the sponge by passing it between squeeze rolls.
• the weight of the solution remaining in the sponge equals about 4 to 5 times the weight of the sponge thus distributing throughout the sponge about 1% of the Arquad 16 based on the weight of the cellulose in the sponge.
• the sponge containing the Arquad 16 While the sponge containing the Arquad 16 is still wet, it is immersed in a 1% aqueous solution of sodium dodecyl benzene sulfonate until the sponge is thoroughly saturated. The excess solution of the sulfonate is squeezed from the sponge and the solution remaining distributed throughout the sponge is approximately the amount to react in stoichiometric proportion with the Arquad 16.
• the cationic surfactant (Arquad 16) reacts with the anionic surfactant (sodium dodecyl benzene sulfonate) within the sponge to form in situ a water-insoluble preservative.
• test specimens were separated into four groups of nine each.
• Another group was not leached, another group was leached with water three times and another group was leached with water fifty times.
• Each leach consisted of immersing the sponge in fresh water until .it was thoroughly wet, then removing and wringing the s'ponge.
• Control A a mixture of Rosin Amine D and Arquad 16 (Example 1 of US. Patent 2,945,772) was added to the sponge and the sodium dodecyl benzene sulfonate bath was omitted; for Control B only Arquad 16 was added to the sponge and the sodium dodecyl ben zene sulfonate bath was omitted; and for Control C where no preservative was added.
• a cellulose sponge prepared in the conventional manner is immersed in an aqueous bath containing about 0.08% Rosin Amine D and 0.6% Arquad 16. The excess solution is squeezed from the sponge by passing the sponge between squeeze rolls. The sponge is thus impregnated throughout with about 1% of the combined ingredients, based on the weight of the dry cellulose in the sponge. While the sponge is still wet, it is immersed in a 1% aqueous solution of sodium dodecyl benzene sulfonate until the sponge is thoroughly saturated.
• Example III Sponge specimens of Example III and the Controls A, B, and C prepared as described above were concurrently exposed to the modified soil burial test in the manner described in Example I.
• Table III shows the results for the sponges treated according to the present example after zero, three and fifty leaches followed by exposure to seven days of rotting and then tested for tensile strength as described in Example I Table III Percent Tensile Strength Retained (Average of 9 Specimens) After Seven Previously Leeched Example Control Control III A B C EXAMPLE IV A cellulose sponge cloth approximately .08 inch thick reinforced with a 6 x 6 mesh (threads per inch) net of cotton is immersed in an 0.20% aqueous solution of Arquad 16.
• the excess solution is squeezed from the sponge cloth by passing the sponge between squeeze rolls.
• the sponge cloth is thus impregnated throughout with about 1% of Arquad 16, based on the weight of the dry cellulose in the sponge cloth. While the sponge cloth is still wet, it is immersed in a 1% aqueous solution of sodium dodecyl benzene sulfonate until the sponge is thoroughly saturated.
• the excess solution is squeezed from the sponge, and the sponge is impregnated throughout with the amount of sodium dodecyl benzene sulfonate to react in stoichiometric proportions with the cat ionic compounds.
• a Control D for Example IV was prepared in a similar manner except that only the Hyamine-1622 preservative was added and the sodium dodecyl benzene sulfonate was omitted.
• a weight loss determination is made rather than a tensile strength loss after the modified soil burial test, since the fabric insert does not decay at the same rate as cellulose sponge and thus the tensile strength loss is not a true measure of the amount of degradation of the cellulose sponge.
• the sponge cloth was tested for resistance to degradation when exposed to mold and bacteria in the following manner:
• Example IV Twenty-seven specimens of Example IV and a similar number for the control were separated into three sets of nine each.
• the bags of sponge cloths were placed in a heated cabinet maintained at 36 l C. for seven days. The bags were turned over after about three days.
• Example Control V D Percent Weight Retained After Seven Days Exposure to Number of Times Sponges Previously Rotting Conditions Leeched Example Control V D While the above described invention will find its greatest utility in the treatment of cellulose sponges, it is also useful in treating other cellulose structures, such as, e.g., woven, knitted and non-woven fabrics containing cellulose fibers to render them rot resistant.
• A419 ⁇ resistant cellulose sponge structure having incorpprated therein a water-insoluble reaction product of (a) a cationic compound selected from the class consisting of alrosin amine, a quaternary ammonium halide and mixtures thereof; arTlTbj'an anionic surfactant.
• a rot resistant cellulose sponge structure having incorporated therein the water-insoluble reaction product of (1) a cationic quaternary ammonium halide and (2) an anionic alkaline salt of an alkyl aryl sulfonate.
• a rot resistant cellulose sponge structure having incorporated therein the water-insoluble reaction product of (1) a quaternary ammonium chloride and (2) the sodium salt of an alkyl aryl sulfonate.
• a rot resistant cellulose sponge structure having incorporated therein the Water-insoluble reaction product of (1) a cationic mixture of a rosin amine and a quaternary ammonium halide and (2) an anionic alkaline salt of an alkyl aryl sulfonate.
• a process for rendering cellulose sponge structures rot resistant which comprises impregnating said structure with a cationic material selected from the class consisting of a rosin amine, a quaternary ammonium halide and mixtures thereof, separately incorporating an anionic surfactant in said structure, causing said anionic and cationic material to react and form in situ a water-insoluble preservative within said structure.
• a cationic material selected from the class consisting of a rosin amine, a quaternary ammonium halide and mixtures thereof, separately incorporating an anionic surfactant in said structure, causing said anionic and cationic material to react and form in situ a water-insoluble preservative within said structure.

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Citations (3)

• 1961
  • 1961-09-27 US US140988A patent/US3197327A/en not_active Expired - Lifetime
• 1962
  • 1962-09-06 GB GB3416962A patent/GB964569A/en not_active Expired
  • 1962-09-20 FR FR910021A patent/FR1345614A/fr not_active Expired
  • 1962-09-26 BE BE622916A patent/BE622916A/fr unknown

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