CA1065294A - Absorbent articles and methods for their preparation - Google Patents
Absorbent articles and methods for their preparationInfo
- Publication number
- CA1065294A CA1065294A CA249,651A CA249651A CA1065294A CA 1065294 A CA1065294 A CA 1065294A CA 249651 A CA249651 A CA 249651A CA 1065294 A CA1065294 A CA 1065294A
- Authority
- CA
- Canada
- Prior art keywords
- polyamine
- polyamido
- film
- polyelectrolyte
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
Abstract
A B S T R A C T
This invention relates to a composition useful to form water swellable articles and to a method of pre-paring a water swellable polyelecrolyte coating, film, or fiber. The composition comprises (1) a soluble carboxylic polyelectrolyte characterized as a partially saponified polyacrylate polymer, (2) a soluble crosslinking agent reactive with carboxylate groups characterized as a polyamido-polyamine/epichlorohydrin adduct, and (3) a solvent consisting of water, lower alcohols, or mixtures thereof. The method comprises (a) forming the composition of a polyacrylate polymer, a polyamido-polyamine/epichlorohydrin adduct, and a solvent, (b) forming a coating, film, or fiber;
and (c) drying the coating, film, or fiber to crosslink the polyelectrolyte with the crosslinking agent and remove the excess solvent. The final products of the present invention are water swellable and are useful wherever aqueous solu-tions need to be absorbed. Examples of the diverse utilities include surgical sponges, catamenial tampons, diapers, meat trays, paper towels, disposable door mats, disposable bath mats, and disposable litter mats for household pets.
This invention relates to a composition useful to form water swellable articles and to a method of pre-paring a water swellable polyelecrolyte coating, film, or fiber. The composition comprises (1) a soluble carboxylic polyelectrolyte characterized as a partially saponified polyacrylate polymer, (2) a soluble crosslinking agent reactive with carboxylate groups characterized as a polyamido-polyamine/epichlorohydrin adduct, and (3) a solvent consisting of water, lower alcohols, or mixtures thereof. The method comprises (a) forming the composition of a polyacrylate polymer, a polyamido-polyamine/epichlorohydrin adduct, and a solvent, (b) forming a coating, film, or fiber;
and (c) drying the coating, film, or fiber to crosslink the polyelectrolyte with the crosslinking agent and remove the excess solvent. The final products of the present invention are water swellable and are useful wherever aqueous solu-tions need to be absorbed. Examples of the diverse utilities include surgical sponges, catamenial tampons, diapers, meat trays, paper towels, disposable door mats, disposable bath mats, and disposable litter mats for household pets.
Description
1~5Z94 The present invention comprises a composition useful to form water swellable articles of a carboxylic synthetic polyelectrolyte comprising tl) a soluble carboxy-lic polyelectrolyte, (2) a soluble crosslinking agent reactive with carboxylate groups, and (3) a solvent con-sisting of water, lower alcohols, or mixtures thereof characterized in that the carboxylic polyelectrolyte is a partially ~aponified polyacrylate polymer and the crosslinking agent is a polyamido-polyamine/epichlorohydrin adduct.
The present invention further comprises a method of preparing a water swellable polyelectrolyte coating, film, or fiber comprising the steps of (a) preparing a solu-tion containing (1) a carboxylic polyelectrolyte, (2) a soluble crosslinking agent reactive with carboxylate groups, and (3) a solvent consisting of water, lower alcohols ; or mixtures thereof; (b) forming a coating, film, or fiber from the solution; and (c) drying the coating, film, or fiber to cro~slink the polyelectrolyte with the crosslinking agent and remove the excess solvent characterized in that one employs a partially saponified polyacrylate polymer as the carboxylic polyelectrolyte and a polyamido-polyamine/
epichlorohydrin adduct as the crosslinking agent.
In order to obtain very high production rates of absorbant articles, it may be desirable to replace part or nearly all of the water in the polyelectrolyte solution with a lower alcohol such as, for example, methanol or ethanol.
This substitution results in lower solution viscosities at a given percent solids and promotes rapid drying.
17,656-F ~
.
.
~Ofà,~9~ , The final products of the present invention are water swellable and are useful wherever aqueous solutions need to be absorbed. Examples of the diverse utilities are surgical sponges, catamenial tampons, diapers, meat trays, paper towels, disposable door mats, disposable bath mats, and disposable litter mats for household pets.
The partially saponified polyacrylate polymers useful in this invention can be made by known techniques such as emulsion, suspension, bulk and solution polymeriza-tion techinques. The polymer before saponification is the result of reacting together a mixture of monomers which comprises (1) 30 to 92 percent by weight of an alkyl acrylate wherein the alkyl group has from 1 to 10 carbon atoms, an alkyl methacrylate wherein the alkyl group has from 4 to 10 carbon atoms, or mixtures thereof; (2) 8 to 70 percent by weight of an olefinically unsaturated carboxy-lic acid; and (3) 0 to 15 percent by weight of an omega hydroxyalkyl acrylate wherein the hydroxyalkyl groups has from 1 to 4 carbon atoms.
Examples of useful alkyl acrylate~ include methyl acrylate, ethyl acrylate, propyl acrylate and hexyl acrylate.
Examples of useful alkyl methacrylates include butyl meth-acrylate, hexyl methacrylate, octyl methacrylate and decyl methacrylate. Example of useful omega hydroxyalkyl acry-lates include 2-hydroxyethyl acrylate~ hydroxymethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
The olefinically unsaturated carboxylic acids useful in this invention are mono or polycarboxylic acids.
Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid.
17,656-F -2-~O~;SZ94 Examples of polycarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
The foregoing polyacrylates are then dissolved in an aqueous alkali metal hydroxide solution. The amount of hydroxide solution employed is sufficient to saponify some of the acrylate esters to alkali m~tal carboxylates and to neutralize the carboxylic groups of the polyacrylate to alkali metal carboxylates so that the saponified poly-acrylate polymer has from 30 to 70 weight percent alkali metal carboxylates. `~-The partially saponi~ied polyacrylate polymer is employed as a solution containing from 5 to 60 percent by weight of the polymer. It i9 preferred to use alkali--soluble latices having from 15 to 60 weight percent non-volatile polymer ~olids.
The polyamido-polyamine/epichlorohydrin adducts useful in this invention are well known in the art. They are prepared commercially by Hercules Incorporated under . :
U.S. Patent 2,926,154 and are known as Kymene~ 557 and Polycup~ 172. They are prepared by reacting a polyalky-lene polyamine with a saturated dicarboxylic acid having from 3 to 10 carbon atom~. The molar ratio of the poly-alkylene polyamine to dicarboxylic acid is from 0.8:1 to 1.4:1. The reaction temperature i~ from 110C. to 250C
and the reaction time is from 0.25 to 2 hours. The poly-amide so produced is reacted with epichlorohydrin. The molar ratio of epichlorohydrin to secondary amine groups of the polyamide is from 0.5:1 to 1.8:1. The reaction temperature is from 45C. to 100C. The pH o~ aqueous 301utions of the adduct is reduced to such an extent that 17,656-F _3_ 1065; :94 10 percent and 25 percent aqueous solutions thereof have a pH not in excess of 6 and 4, respectively. The structure of these adducts has been discussed in an article by M. E.
Carr, et al., ~ournal of Applied Polymeric Science, Volume S 17, pages 721-735 (1973).
In the preferred method of making water swellable films by the present invention, the above composition of the polyelectrolytas is spread on a flat plate or roller of metal, plastic, or other impervious substrate and dried to crosslink the polyelectrolyte and drive off the excess water and/or alcohol. The film is then peeled off the plate or roller by a scraper to recover the intact film for subsequent storage or use.
It is sometimes desirable to add a small amount of a surfactant to the polyelectrolyte composition to aid in flowing on and removing the continuous film from the water impervious substrate. A secondary benefit of using a surfactant is to increase the wettability of the final dry absorbent film. Either anionic or nonionic surfactants may be used. Example~ of the u~eful surfactants include sodium alkyl sulfonates and ethylene oxide derivatives of alkylated phenols.
Similarly, when an absorbent article i9 prepared, the article which is to be the substrate i9 coated with the composition of the polyelectrolyte and then the coating is cro~slinked. It is to be understood that for the pur-poses of this invention the coating step implies a complete coating or a discontinuous coating, thus when a fibrous substrate such as, ~or example, cellulose batting, paper, - 30 woven or non-woven cloth, and polyurethane foam are used 17,656-F _4_ ~o~sz9~
- as the substrate J the composition can be applied in a discontinuous manner, i.e. in a pattern of large dots, squares, or grid lines to retain the inherent flexibility of the fibrous substrate and at the same time vastly im-prove its water absorbency. Wood pulp can be coated by slurrying it in the polyelectrolyte composition ~ollowed by a ~luffing operation.
If desired, the water swellable film prepared as above can be used per se as the inner absorbent layer in baby diapers. It is sometimes advantageous that the film be disintegrated into flakes, strips or powders. This is accomplished, for example, by crushing or comminuting the film in a hammer mill or blenders. If long flat strips are desired, the film can be sliced widthwise with appropriate slicers.
In some instances, water swellable fibers are desired. These can be prepared by extruding the above composition of the polyelectrolytes into a bath comprising lower alkyl ketones such as, for example, acetone, methyl ethyl ketone, and diethyl ketone. Alcoholic composition~
may be extruded into a nonaqueous coagulant such as, for example, chlorinated hydrocarbons, i.e. methylene chloride and perchloroethylene. The soft extruded fibers are then removed from the bath by any convenient means ~uch as a three or five roll cluster and carried through a heated chamber at a temperature greater than 30C. and preferably in the range from 70 to 150C. to dry and to crosslink the polyelectrolyte fibers.
The absorbency of crosslinked polyelectrolytes (grams solution gelled per gram of polyelectrolyte) is 17,656-F -5-~.
~of~sz9'~
determined in the following manner using synthetic urine (0.27 N sodium chloride solution). A 0.5 gram sample of a crosslinked polyelectrolyte is weighed into a 250 ml beaker, 150 ml of a 0.27 N sodium chloride solution is poured into the beaker and the crosslinked polyelectrolyte is allowed to soak for 15 minutes at room temperature with occasional stirring. The swelled polyelectrolyte is then collected by filtration and the gel capacit~ is reported as grams of solution gelled per gram of polymer salt.
For the purposes of this invention, a moisture or water absorbent or water swellable polyelectrolyte is ~; defined as one which absorbs greater than 20 times its weight of synthetic ~0.27 ~ NaCl solution) or natural urine. Preferably, the absorbency should be in the range from 30 to 60 grams of 0.27 ~ ~aCl solution per gram of resin or polyelectrolyte. The level of crosslinking agent used i~ a variable factor which is dependent upon the particular polyelectrolyte used and the molecular weight of the polyelectrolyte. In general, the amount u~ed varies from the 0.5 to 5.0 percent based on the weight of the polyelectrolyte. However, this range i9 varied fo~ each polyelectrolyte in order to adjust the absorbency of the final crosslinked gel 90 that it is at least 20 and preferably in the range from 30 to 60 grams of 0.27 N NaCl solution per gram of resin.
A partially saponified polyacrylate polymer was prepared using the following procedure:
Three mixtures were made up having the following compositions:
. .
17,656-F -6-~ 1()65Z94 Mixture A
; 600 g deionized water 0.75 g dioctyl sodium sulfosuccinate 1.75 g sodium persulfate Mixture B
437.5 g ethyl acrylate 77.2 g methacrylic acid Mixture C
175 g deionized water
The present invention further comprises a method of preparing a water swellable polyelectrolyte coating, film, or fiber comprising the steps of (a) preparing a solu-tion containing (1) a carboxylic polyelectrolyte, (2) a soluble crosslinking agent reactive with carboxylate groups, and (3) a solvent consisting of water, lower alcohols ; or mixtures thereof; (b) forming a coating, film, or fiber from the solution; and (c) drying the coating, film, or fiber to cro~slink the polyelectrolyte with the crosslinking agent and remove the excess solvent characterized in that one employs a partially saponified polyacrylate polymer as the carboxylic polyelectrolyte and a polyamido-polyamine/
epichlorohydrin adduct as the crosslinking agent.
In order to obtain very high production rates of absorbant articles, it may be desirable to replace part or nearly all of the water in the polyelectrolyte solution with a lower alcohol such as, for example, methanol or ethanol.
This substitution results in lower solution viscosities at a given percent solids and promotes rapid drying.
17,656-F ~
.
.
~Ofà,~9~ , The final products of the present invention are water swellable and are useful wherever aqueous solutions need to be absorbed. Examples of the diverse utilities are surgical sponges, catamenial tampons, diapers, meat trays, paper towels, disposable door mats, disposable bath mats, and disposable litter mats for household pets.
The partially saponified polyacrylate polymers useful in this invention can be made by known techniques such as emulsion, suspension, bulk and solution polymeriza-tion techinques. The polymer before saponification is the result of reacting together a mixture of monomers which comprises (1) 30 to 92 percent by weight of an alkyl acrylate wherein the alkyl group has from 1 to 10 carbon atoms, an alkyl methacrylate wherein the alkyl group has from 4 to 10 carbon atoms, or mixtures thereof; (2) 8 to 70 percent by weight of an olefinically unsaturated carboxy-lic acid; and (3) 0 to 15 percent by weight of an omega hydroxyalkyl acrylate wherein the hydroxyalkyl groups has from 1 to 4 carbon atoms.
Examples of useful alkyl acrylate~ include methyl acrylate, ethyl acrylate, propyl acrylate and hexyl acrylate.
Examples of useful alkyl methacrylates include butyl meth-acrylate, hexyl methacrylate, octyl methacrylate and decyl methacrylate. Example of useful omega hydroxyalkyl acry-lates include 2-hydroxyethyl acrylate~ hydroxymethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
The olefinically unsaturated carboxylic acids useful in this invention are mono or polycarboxylic acids.
Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid.
17,656-F -2-~O~;SZ94 Examples of polycarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
The foregoing polyacrylates are then dissolved in an aqueous alkali metal hydroxide solution. The amount of hydroxide solution employed is sufficient to saponify some of the acrylate esters to alkali m~tal carboxylates and to neutralize the carboxylic groups of the polyacrylate to alkali metal carboxylates so that the saponified poly-acrylate polymer has from 30 to 70 weight percent alkali metal carboxylates. `~-The partially saponi~ied polyacrylate polymer is employed as a solution containing from 5 to 60 percent by weight of the polymer. It i9 preferred to use alkali--soluble latices having from 15 to 60 weight percent non-volatile polymer ~olids.
The polyamido-polyamine/epichlorohydrin adducts useful in this invention are well known in the art. They are prepared commercially by Hercules Incorporated under . :
U.S. Patent 2,926,154 and are known as Kymene~ 557 and Polycup~ 172. They are prepared by reacting a polyalky-lene polyamine with a saturated dicarboxylic acid having from 3 to 10 carbon atom~. The molar ratio of the poly-alkylene polyamine to dicarboxylic acid is from 0.8:1 to 1.4:1. The reaction temperature i~ from 110C. to 250C
and the reaction time is from 0.25 to 2 hours. The poly-amide so produced is reacted with epichlorohydrin. The molar ratio of epichlorohydrin to secondary amine groups of the polyamide is from 0.5:1 to 1.8:1. The reaction temperature is from 45C. to 100C. The pH o~ aqueous 301utions of the adduct is reduced to such an extent that 17,656-F _3_ 1065; :94 10 percent and 25 percent aqueous solutions thereof have a pH not in excess of 6 and 4, respectively. The structure of these adducts has been discussed in an article by M. E.
Carr, et al., ~ournal of Applied Polymeric Science, Volume S 17, pages 721-735 (1973).
In the preferred method of making water swellable films by the present invention, the above composition of the polyelectrolytas is spread on a flat plate or roller of metal, plastic, or other impervious substrate and dried to crosslink the polyelectrolyte and drive off the excess water and/or alcohol. The film is then peeled off the plate or roller by a scraper to recover the intact film for subsequent storage or use.
It is sometimes desirable to add a small amount of a surfactant to the polyelectrolyte composition to aid in flowing on and removing the continuous film from the water impervious substrate. A secondary benefit of using a surfactant is to increase the wettability of the final dry absorbent film. Either anionic or nonionic surfactants may be used. Example~ of the u~eful surfactants include sodium alkyl sulfonates and ethylene oxide derivatives of alkylated phenols.
Similarly, when an absorbent article i9 prepared, the article which is to be the substrate i9 coated with the composition of the polyelectrolyte and then the coating is cro~slinked. It is to be understood that for the pur-poses of this invention the coating step implies a complete coating or a discontinuous coating, thus when a fibrous substrate such as, ~or example, cellulose batting, paper, - 30 woven or non-woven cloth, and polyurethane foam are used 17,656-F _4_ ~o~sz9~
- as the substrate J the composition can be applied in a discontinuous manner, i.e. in a pattern of large dots, squares, or grid lines to retain the inherent flexibility of the fibrous substrate and at the same time vastly im-prove its water absorbency. Wood pulp can be coated by slurrying it in the polyelectrolyte composition ~ollowed by a ~luffing operation.
If desired, the water swellable film prepared as above can be used per se as the inner absorbent layer in baby diapers. It is sometimes advantageous that the film be disintegrated into flakes, strips or powders. This is accomplished, for example, by crushing or comminuting the film in a hammer mill or blenders. If long flat strips are desired, the film can be sliced widthwise with appropriate slicers.
In some instances, water swellable fibers are desired. These can be prepared by extruding the above composition of the polyelectrolytes into a bath comprising lower alkyl ketones such as, for example, acetone, methyl ethyl ketone, and diethyl ketone. Alcoholic composition~
may be extruded into a nonaqueous coagulant such as, for example, chlorinated hydrocarbons, i.e. methylene chloride and perchloroethylene. The soft extruded fibers are then removed from the bath by any convenient means ~uch as a three or five roll cluster and carried through a heated chamber at a temperature greater than 30C. and preferably in the range from 70 to 150C. to dry and to crosslink the polyelectrolyte fibers.
The absorbency of crosslinked polyelectrolytes (grams solution gelled per gram of polyelectrolyte) is 17,656-F -5-~.
~of~sz9'~
determined in the following manner using synthetic urine (0.27 N sodium chloride solution). A 0.5 gram sample of a crosslinked polyelectrolyte is weighed into a 250 ml beaker, 150 ml of a 0.27 N sodium chloride solution is poured into the beaker and the crosslinked polyelectrolyte is allowed to soak for 15 minutes at room temperature with occasional stirring. The swelled polyelectrolyte is then collected by filtration and the gel capacit~ is reported as grams of solution gelled per gram of polymer salt.
For the purposes of this invention, a moisture or water absorbent or water swellable polyelectrolyte is ~; defined as one which absorbs greater than 20 times its weight of synthetic ~0.27 ~ NaCl solution) or natural urine. Preferably, the absorbency should be in the range from 30 to 60 grams of 0.27 ~ ~aCl solution per gram of resin or polyelectrolyte. The level of crosslinking agent used i~ a variable factor which is dependent upon the particular polyelectrolyte used and the molecular weight of the polyelectrolyte. In general, the amount u~ed varies from the 0.5 to 5.0 percent based on the weight of the polyelectrolyte. However, this range i9 varied fo~ each polyelectrolyte in order to adjust the absorbency of the final crosslinked gel 90 that it is at least 20 and preferably in the range from 30 to 60 grams of 0.27 N NaCl solution per gram of resin.
A partially saponified polyacrylate polymer was prepared using the following procedure:
Three mixtures were made up having the following compositions:
. .
17,656-F -6-~ 1()65Z94 Mixture A
; 600 g deionized water 0.75 g dioctyl sodium sulfosuccinate 1.75 g sodium persulfate Mixture B
437.5 g ethyl acrylate 77.2 g methacrylic acid Mixture C
175 g deionized water
2.0 g sodium bisulfite Mixture A was charged to a 2 liter reactor and heated to 40C. while under rigorous nitrogen purge.
Eighteen milliliters of Mixture B were added to the reactor followed by all of Mixture C. The remainder of Mixture B -was added to the reactor over the next 2.5 hours while the temperature was maintained between 39 and 41C.
The latex was then digested at 60C. for 1.5 hours and then cooled to 30C. and bottled. The latex contained 40.6 weight percent non-volatile polymer solids.
The latex so prepared was partially saponified by adding 1125 g of the latex in a small stream over a per-iod of 25 minutes to a slowly stirred solution of 187.16 g of 50 weight percent sodium hydroxide dissolved in 547.9 g of deionized water. ~fter all of ~he polymer had dissolved, the viscous solution was heated at 50C. for 22 hours. The resulting solution contained 25.4 weight percent solids and had a Brookfield viscosity of 16,200 cps at 25C. with a No. 5 spindle at 10 rpm. The polymer was analyzed and found to contain ester groups equivalent to 50 mole percent ethyl acrylate, with the remainder of the composition being equi-valent to sodium acrylate and sodium methacrylate.
17,656-F -7-:
1065~
Exam~le 1 A composition for forming a water swellable article was prepared by mixing 10 grams of the above described partially saponified polyacrylate polymer solu-tion with 0.099 grams of an aqueous solution of a polyamido--polyamine/epichlorohydrin adduct. The solution of the adduct contained 12.5 weight percent solids, had a pH
between 4.6 and 4.9 and a nitrogen content of 12.8 weight percent. The composition contained 0.5 weight percent crosslinking agent based on the dry weight of the poly-acrylate polymer.
Two water swellable films were prepared by casting the above described composition on a polished chrome plate using a 25 mil (0.635 millimeter) draw bar. After air drying, each film was lifted from the plate. One film was dried for 48 hours at 25C. in the laboratory.
After drying, it had an absorbency of 50 grams of 0.28 N
sodium chloride solution per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. After drying, it had an absorbency of 54 grams of 0.27 N sodium chloride solution per gram of film.
A water swellable film was prepared by casting the above described composition on an aluminum plate heated to 150C. using a 25 mil (0.635 millimeter) draw bar. The plate with the cast film was dried for 2 minutes in an oven heated to 150C. After drying, the crosslinked polymer film was scraped off the plate with a razor blade.
It had an absorbency of 50 grams of 0.27 N sodium chloride solution per gram of film.
17,656-F -8-1~65Zg~ ,~
ExamPle 2 A composition for forming water swellable articles was prepared by mixing 10 grams of the polyacrylate polymer solution with 0.119 grams of the crosslinking agent solution described in Example 1. The composition contained 0.6 weight percent crosslinking agent based on the dry weight of the polyacrylate polymer.
Three water swellable films were prepared by casting the above described composition on a polished chrome plate as in Example 1. One film was dried for 48 -~
hours at 25C. in the laboratory. After drying it had an absorbency of 54 grams of 0.27 ~ sodium chloride solution per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. After drying, it had an absorbency of 51 grams of 0.27 ~ sodium chloride solution per gram of film. The third film was dried for 25 minutes in an oven heated to 95C. After drying, it had an absor-bency of 50 grams of 0.27 N sodium chloride solution per gram of film.
Example 3 A composition for forming water swellable articles was prepared by mixing 10 grams of the polyacrylate polymer solution with 0.168 gram of the crosslinking agent solution as described in Example 1. The composition contained 0.8 weight percent crosslinking agent based on the dry weight o~ the polyacrylate polymer.
Three water swellable films were prepared by casting the above described composition on a polished chrome plate as in Example 1. One film was dried for 48 17,656-F -9-10~ 9~
hours at 25C. in tha laboratory. After drying, it had an absorbency of 46 grams of 0.27 ~ sodium chloride per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. Aftar drying, it had an absorbency of 38 grams of 0.27 N sodium chloride solution par gram of film. The third film was dried for 25 minutes in an oven - heated to 95C. After drying, it had an absorbency of 37 grams of 0.27 N sodium chloride per gram of film.
17,656-F -10-
Eighteen milliliters of Mixture B were added to the reactor followed by all of Mixture C. The remainder of Mixture B -was added to the reactor over the next 2.5 hours while the temperature was maintained between 39 and 41C.
The latex was then digested at 60C. for 1.5 hours and then cooled to 30C. and bottled. The latex contained 40.6 weight percent non-volatile polymer solids.
The latex so prepared was partially saponified by adding 1125 g of the latex in a small stream over a per-iod of 25 minutes to a slowly stirred solution of 187.16 g of 50 weight percent sodium hydroxide dissolved in 547.9 g of deionized water. ~fter all of ~he polymer had dissolved, the viscous solution was heated at 50C. for 22 hours. The resulting solution contained 25.4 weight percent solids and had a Brookfield viscosity of 16,200 cps at 25C. with a No. 5 spindle at 10 rpm. The polymer was analyzed and found to contain ester groups equivalent to 50 mole percent ethyl acrylate, with the remainder of the composition being equi-valent to sodium acrylate and sodium methacrylate.
17,656-F -7-:
1065~
Exam~le 1 A composition for forming a water swellable article was prepared by mixing 10 grams of the above described partially saponified polyacrylate polymer solu-tion with 0.099 grams of an aqueous solution of a polyamido--polyamine/epichlorohydrin adduct. The solution of the adduct contained 12.5 weight percent solids, had a pH
between 4.6 and 4.9 and a nitrogen content of 12.8 weight percent. The composition contained 0.5 weight percent crosslinking agent based on the dry weight of the poly-acrylate polymer.
Two water swellable films were prepared by casting the above described composition on a polished chrome plate using a 25 mil (0.635 millimeter) draw bar. After air drying, each film was lifted from the plate. One film was dried for 48 hours at 25C. in the laboratory.
After drying, it had an absorbency of 50 grams of 0.28 N
sodium chloride solution per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. After drying, it had an absorbency of 54 grams of 0.27 N sodium chloride solution per gram of film.
A water swellable film was prepared by casting the above described composition on an aluminum plate heated to 150C. using a 25 mil (0.635 millimeter) draw bar. The plate with the cast film was dried for 2 minutes in an oven heated to 150C. After drying, the crosslinked polymer film was scraped off the plate with a razor blade.
It had an absorbency of 50 grams of 0.27 N sodium chloride solution per gram of film.
17,656-F -8-1~65Zg~ ,~
ExamPle 2 A composition for forming water swellable articles was prepared by mixing 10 grams of the polyacrylate polymer solution with 0.119 grams of the crosslinking agent solution described in Example 1. The composition contained 0.6 weight percent crosslinking agent based on the dry weight of the polyacrylate polymer.
Three water swellable films were prepared by casting the above described composition on a polished chrome plate as in Example 1. One film was dried for 48 -~
hours at 25C. in the laboratory. After drying it had an absorbency of 54 grams of 0.27 ~ sodium chloride solution per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. After drying, it had an absorbency of 51 grams of 0.27 ~ sodium chloride solution per gram of film. The third film was dried for 25 minutes in an oven heated to 95C. After drying, it had an absor-bency of 50 grams of 0.27 N sodium chloride solution per gram of film.
Example 3 A composition for forming water swellable articles was prepared by mixing 10 grams of the polyacrylate polymer solution with 0.168 gram of the crosslinking agent solution as described in Example 1. The composition contained 0.8 weight percent crosslinking agent based on the dry weight o~ the polyacrylate polymer.
Three water swellable films were prepared by casting the above described composition on a polished chrome plate as in Example 1. One film was dried for 48 17,656-F -9-10~ 9~
hours at 25C. in tha laboratory. After drying, it had an absorbency of 46 grams of 0.27 ~ sodium chloride per gram of film. Allowance was made for moisture absorbed from the air. The second film was dried for 10 minutes in an oven heated to 95C. Aftar drying, it had an absorbency of 38 grams of 0.27 N sodium chloride solution par gram of film. The third film was dried for 25 minutes in an oven - heated to 95C. After drying, it had an absorbency of 37 grams of 0.27 N sodium chloride per gram of film.
17,656-F -10-
Claims (8)
1. A composition useful to form water swellable articles of a carboxylic synthetic polyelectrolyte com-prising (1) a soluble carboxylic polyelectrolyte, (2) a soluble crosslinking agent reactive with carboxylate groups, and (3) a solvent consisting of water, lower alcohols, or mixtures thereof, characterized in that the carboxylic polyelectrolyte is a partially saponified polyacrylate polymer and further characterized in that the crosslinking agent is a polyamido-polyamine/epichlorohydrin adduct.
2. A composition as in Claim 1 characterized in that the polyamido-polyamine/epichlorohydrin adduct is prepared by (1) reacting a polyalkylene polyamine with a saturated dicarboxylic acid having 3 to 10 carbon atoms, the molar ratio of polyalkylene polyamine to dicarboxylic acid being from 0.8:1 to 1.4:1, thereby producing a poly-amide; (2) reacting the polyamide with epichlorohydrin, the molar ratio of epichlorohydrin to secondary amine groups of the polyamide being from 0.5:1 to 1.8:1; and (3) reducing the pH of an aqueous solution of the polyamido--polyamine/epichlorohydrin adduct to such an extent that 10 percent and 25 percent solutions thereof have a pH not in excess of 6 and 4, respectively.
3. The composition of Claim 2 characterized in that the partially saponified polyacrylate resin is present in the range of from 5 to 60 percent by weight based upon the amount of solvent.
4. The composition of any one of Claims 1, 2, or 3 characterized in that the polyamido-polyamine/epichlorohydrin adduct is present in the range from 0.5 to 5 percent by weight based upon the amount of partially saponified poly-acrylate polymer.
5. A method of preparing a water swellable poly-electrolyte coating, film, or fiber comprising the steps of (a) preparing a solution containing (1) a carboxylic polyelectrolyte, (2) a soluble crosslinking agent reactive with carboxylate groups, and (3) a solvent consisting of water, lower alcohols, or mixtures thereof; (b) forming a coating, film, or fiber from the solution; and (c) drying the coating, film, or fiber to crosslink the polyelectrolyte with the crosslinking agent and remove the excess solvent characterized in that one employs a partially saponified polyacrylate polymer as the carboxylic polyelectrolyte and a polyamido-polyamine/epichlorohydrin adduct as the crosslinking agent.
6. A method as in Claim 5 characterized in that the polyamido-polyamine/epichlorohydrin adduct is prepared by (1) reacting a polyalkylene polyamine with a saturated dicarboxylic acid having 3 to 10 carbon atoms, the molar ratio of the polyalkylene polyamine to dicarboxylic acid being from 0.8:1 to 1.4:1, thereby producing a polyamide;
(2) reacting the polyamide with epichlorohydrin, the molar ratio of epichlorohydrin to secondary amine groups of the polyamide being from 0.5:1 to 1.8:1, and (3) reducing the pH of an aqueous solution of the polyamido-polyamine/
epichlorohydrin adduct to such an extent that 10 percent and 25 percent aqueous solutions thereof have a pH not in excess of 6 and 4, respectively.
(2) reacting the polyamide with epichlorohydrin, the molar ratio of epichlorohydrin to secondary amine groups of the polyamide being from 0.5:1 to 1.8:1, and (3) reducing the pH of an aqueous solution of the polyamido-polyamine/
epichlorohydrin adduct to such an extent that 10 percent and 25 percent aqueous solutions thereof have a pH not in excess of 6 and 4, respectively.
7. The method of Claim 6 characterized in that the partially saponified polyacrylate resin is employed in the range of from 5 to 60 percent by weight based upon the amount of solvent.
8. The method of any one of Claims 5, 6, or 7 characterized in that the polyamido-polyamine/epichlorohydrin adduct is employed in the range of from 0.5 to 5 percent by weight based upon the amount of partially saponified polyacrylate polymer.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56588075A | 1975-04-07 | 1975-04-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065294A true CA1065294A (en) | 1979-10-30 |
Family
ID=24260507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA249,651A Expired CA1065294A (en) | 1975-04-07 | 1976-04-06 | Absorbent articles and methods for their preparation |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US4076673A (en) |
| JP (2) | JPS51132262A (en) |
| AU (1) | AU510180B2 (en) |
| BE (1) | BE840443R (en) |
| CA (1) | CA1065294A (en) |
| DE (1) | DE2614662A1 (en) |
| FI (1) | FI66634C (en) |
| FR (1) | FR2307011A2 (en) |
| GB (1) | GB1549994A (en) |
| IT (1) | IT1061221B (en) |
| NL (1) | NL7603638A (en) |
| NO (1) | NO144492C (en) |
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-
1976
- 1976-04-05 DE DE19762614662 patent/DE2614662A1/en active Granted
- 1976-04-06 FR FR7610009A patent/FR2307011A2/en active Granted
- 1976-04-06 CA CA249,651A patent/CA1065294A/en not_active Expired
- 1976-04-06 AU AU12695/76A patent/AU510180B2/en not_active Expired
- 1976-04-06 NO NO761176A patent/NO144492C/en unknown
- 1976-04-06 IT IT48888/76A patent/IT1061221B/en active
- 1976-04-07 GB GB14205/76A patent/GB1549994A/en not_active Expired
- 1976-04-07 BE BE165889A patent/BE840443R/en not_active IP Right Cessation
- 1976-04-07 JP JP51039134A patent/JPS51132262A/en active Pending
- 1976-04-07 NL NL7603638A patent/NL7603638A/en not_active Application Discontinuation
- 1976-04-07 FI FI760940A patent/FI66634C/en not_active IP Right Cessation
- 1976-09-27 US US05/727,106 patent/US4076673A/en not_active Expired - Lifetime
-
1977
- 1977-04-29 US US05/792,163 patent/US4132695A/en not_active Expired - Lifetime
-
1988
- 1988-02-17 JP JP63034952A patent/JPS63254153A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1549994A (en) | 1979-08-08 |
| JPS51132262A (en) | 1976-11-17 |
| US4076673A (en) | 1978-02-28 |
| DE2614662C2 (en) | 1988-08-25 |
| FI66634B (en) | 1984-07-31 |
| AU510180B2 (en) | 1980-06-12 |
| NO144492B (en) | 1981-06-01 |
| FR2307011A2 (en) | 1976-11-05 |
| DE2614662A1 (en) | 1977-01-27 |
| US4132695A (en) | 1979-01-02 |
| BE840443R (en) | 1976-10-07 |
| FI760940A (en) | 1976-10-08 |
| NO144492C (en) | 1981-09-09 |
| JPS63254153A (en) | 1988-10-20 |
| FR2307011B2 (en) | 1979-05-11 |
| AU1269576A (en) | 1977-10-13 |
| FI66634C (en) | 1984-11-12 |
| NO761176L (en) | 1976-10-08 |
| JPH0125781B2 (en) | 1989-05-19 |
| IT1061221B (en) | 1983-02-28 |
| NL7603638A (en) | 1976-10-11 |
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