Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
• • 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
  • 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
  • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C08L31/04—Homopolymers or copolymers of vinyl acetate
• • 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
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
  • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
  • D04H1/66—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions at spaced points or locations
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
  • D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
  • D06M11/62—Complexes of metal oxides or complexes of metal salts with ammonia or with organic amines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
  • D06M15/05—Cellulose or derivatives thereof
  • D06M15/09—Cellulose ethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
• • 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
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
  • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
  • C08J2201/0545—Precipitating the polymer by adding a non-solvent or a different solvent from an aqueous solvent-based polymer composition
  • C08J2201/0547—Precipitating the polymer by adding a non-solvent or a different solvent from an aqueous solvent-based polymer composition the non-solvent being aqueous
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/04—Alginic acid; Derivatives thereof

Definitions

• 117-38 13 Claims ABSTRACT OF THE DISCLOSURE Methods of controlling the migration of resin binders in the manufacture of bonded nonwoven fabrics from fibrous webs comprising the use of a resin binder composition comprising: (1) a synthetic resin; (2) a water soluble, polymeric, carboxylic thickener; and (3) a metal ammine, complex coordination compound capable of releasing ions of said metal to control the total migration of the resin binder during its deposition on the fibrous web.
• the present invention relates to porous, absorbent fibrous sheet materials and to their methods of manufacture. More particularly, the present invention is concerned with the so-called bonded, nonwoven textile fabrics, i.e., fabrics produced from textile fibers without the use of conventoinal spinning, weaving, knitting or felting operations. Although not limited thereto, the invention is of primary importance in connection with nonwoven fabrics derived from oriented or carded fibrous webs composed of textile-length fibers, the major proportion of which are oriented predominantly in one direction.
• Typical of such fabrics are the so-called Ma'sslinn nonwoven fabrics, some of which are described in greater particularity in US. Patents 2,705,687 and 2,705,688, issued Apr. 5, 1955, to D.R. Petterson et a1. and I. S. Ness et al., respectively.
• Another aspect of the present invention is its application to nonwoven fabrics wherein the textile-length fibers were originally predominantly oriented in one direction but have been reorganized and rearranged in predetermined designs and patterns of fabric openings and fiber bundles.
• Typical of such latter fabrics are the so-called Keybak bundled nonwoven fabrics, some of which are described in particularity in US. Patents 2,862,251 and 3,033,721, issued Dec. 2, 1958 and May 8, 1962, respectively, to F. Kalwaites.
• Still another aspect of the present invention is its application to nonwoven fabrics wherein the textilelength fibers are disposed at random by air-laying techniques and are not predominantly oriented in any one direction.
• Typical nonwoven fabrics made by such procedures are termed isotropic nonwoven fabrics and are described, for example, in US. Patents 2,676,363 and 2,676,364, issued Apr. 27, 1954, to C. H. Plummer et a1.
• nonwoven fabrics which comprise textilelength fibers and which are made basically by conventional or modified aqueous papermaking techniques such as are described in greater particularity in pending patent application Ser. No. 4,405, filed Jan. 20, 1970 by P. R. Glor and A. H. Drelich, and now abandoned.
• Such fabrics are also basically isotropic and generally have like properties in all directions.
• the conventional base starting material for the majority of these nonwoven fabrics is usually a fibrous web comprising any of the common textile-length fibers, or mixtures thereof, the fibers varying in average length from approximately one-half inch to about two and one-half inches.
• Exemplary of such fibers are the natural fibers 3,706,595 Patented Dec. 19, 1972 ice such as cotton and wool and the synthetic or manmade cellulosic fibers, notably rayon or regenerated cellulose.
• textile length fibers of a synthetic or man-made origin may be used in various proportions to replace either partially or perhaps even entirely the previouslynamed fibers.
• Such other fibers include: polyamide fibers such as nylon 6, nylon 66, nylon 610, etc.; polyester fibers such as Dacron, Fortrel and Kodel; acrylic fibers such as Acrilan, Orlon and Creslan; modacrylic fibers such as Verel and Dynel; polyolefinic fibers derived from polyethylene and polypropylene; cellulose ester fibers such as Arnel and Acele; polyvinyl alcohol fibers; etc.
• These textile length fibers may be replaced either partially or entirely by fibers having an average length of less than about one-half inch and down to about onequarter inch.
• These fibers, or mixtures thereof are customarily processed through any suitable textile machinery (e.g., a conventional cotton card, a Rando-Webber, a papermaking machine, or other fibrous web producing apparatus) to form a web or sheet of loosely associated fibers, weighing from about grains to about 2000 grains per square yard or even higher.
• shorter fibers such as wood pulp fibers or cotton linters
• wood pulp fibers or cotton linters may be used in varying proportions, even up to 100%, where such shorter length fibers can be handled and processed by available apparatus.
• Such shorter fibers have lengths less than A inch.
• the resulting fibrous web or sheet regardless of its method of production, is then subjected to at least one of several types of bonding operations to anchor the individual fibers together to form a self-sustaining web.
• One method is to impregnate the fibrous web over its entire surface area with various well-known bonding agents, such as natural or synthetic resins.
• Such over-all impregnation produces a nonwoven fabric of good longitudinal and cross strength, acceptable durability and washability, and satisfatcory abrasion resistance.
• the nonwoven fabric tends to be somewhat stifi and boardlike, possessing more of the properties and characteristics of paper or board than those of a Woven or knitted textile fabric. Consequently, although such overall impregnated nonwoven fabrics are satisfactory for many uses, they are still basically unsatisfactory a's general purpose textile fabrics.
• Another well-known bonding method is to print the fibrous webs with intermittent or continuous straight or wavy lines, or areas of binder extending generally transversely or diagonally across the web and additionally, if desired, along the fibrous Web.
• the resulting nonwoven fabric as exemplified by a product disclosed in the Goldman Patent 2,039,312 and sold under the trademark Masslinn," is far more satisfactory as a textile fabric than over-all impregnated webs in that the softness, drape and hand of the resulting nonwoven fabric more nearly approach those of a woven or knitted textile fabric.
• the nominal surface coverage of such binder lines or areas will vary widely depending upon the precise properties and characteristics of softness, drape, hand and strength which are desired in the final bonded product.
• the nominal surface coverage can be designed so that it falls within the range of from about 10% to about 50% of the total surface of the final product. Within the more commercial aspects of the present invention, however, nominal surface coverages of from about 12% to about 40% are preferable.
• nonwoven fabrics bonded with such line and area binder patterns have had the desired softness, drape and hand and have not been undesirably stiff or board-like.
• nonwoven fabrics have also possessed some disadvantages.
• the relatively narrow binder lines and relatively small binder areas of the applicator which are laid down on the fibrous web possess specified physical dimensions and interspatial relationships as they are initially laid down.
• the binder concentration in the binder area is lowered and rendered less uniform by the migration of the binder into adjacent fibrous areas.
• One of the results of such migration is to make the surface coverage of the binder areas increase whereby the effect of the intermittent bonding approaches the effect of the over-all bonding. As a result, some of the desired softness, drape and hand are lost and some of the undesired properties of harshness, stiffness and boardiness are increased.
• Resins, or polymers as they are often referred to herein as interchangeable terms, are high molecular weight organic compounds and, as used herein, are of a synthetic or man-made origin. These synthetic or manmade polymers have a chemical structure which usually can be represented by a regular repeating small unit, referred as a mer, and are formed usually either by an addition or a condensation polymerization of one or more monomers. Examples of addition polymers are the polyvinyl chlorides, the polyvinyl acetates, the polyacrylic res ns, the polyolefins, the synthetic rubbers, etc. Examples of condensation polymers are the pulurethanes, the polyamides, the polyesters, etc.
• Emulsion polymerization is one of the most commonly used.
• Emulsion polymerized resins notably polyvinyl chlorides, polyvinyl acetates, and polyacrylic resins
• Such resins are generally produced by emulsifying the monomers, stabilizing the monomer emulsion by the use of various surfactant systems, and then polymerizing the monomers in the emulsified state to form a stabilized resin polymer.
• the resin polymer is usually dispersed in an aqueous medium as discrete particles of colloidal dimansions (1. to 2 microns diameter or smalle and is generally termed throughout the industry as a resin dispersion, or a resin emulsion or latex.”
• the average particle size in the resin dispersion is in the range of about 0.1 micron (or micrometer) diameter, with individual particles ranging up to 1 or 2 microns in diameter and occasionally up to as high as about 3 or 5 microns in size.
• the particle sizes of such colloidal resin dispersions vary a great deal, not only from one resin dispersion to another but even within one resin dispersion itself.
• the amount of resin binder solids in the resin colloidal aqueous dispersion varies from about A solids by weight up to about 60% by weight or even higher solids, generally dependent upon the nature of the monomers used, the nature of the resulting polymer resin, the surfactant system employed, and the conditions under which the polymerization was carried out.
• resin colloidal dispersions or resin emulsions, or latexes, may be anionic, non-ionic, or even polyionic and stable dispersions are available commercially at pHs of from about 2 to about 11.
• the amount of resin which is applied to the porous or absorbent material varies within relatively wide limits, depending upon the resin itself, the nature and character of the porous or absorbent materials to which the resins are being applied, its intended use, etc.
• a range of from about 10% to about 30% by weight, based on the weight of the porous or absorbent material is preferred.
• Such resins have found use in the coating industries for the coating of woven fabrics, paper and other materials.
• the resins are also used as adhesives for laminating materials or for bonding fibrous webs.
• These resins have also found wide use as additives in the manufacture of paper, the printing industry, the decorative printing of textiles, and in other industries.
• the resin is colloidally dispersed in water and, when applied from the aqueous medium to a porous absorbent sheet material which contains additional water is carried by the water until the water is evaporated or otherwise driven off. If it is desired to place the resin only on the surface of the wet porous or absorbent sheet material and not to have the resin penetrate into the porous or absorbent sheet material, such is usually not possible inasmuch as diffusion takes place between the aqueous colloidal resin and the water in the porous material. In this way, the colloidal resin tends the spread into and throughout the porous material and does not remain merely on its surface.
• the aqueous colloid tends to diffuse and to wick along the individual fibers and to carry the resin with it beyond the confines of the nominal intermittent print pattern.
• the ultimate pattern goes far beyond that due to the spreading or migration which takes place due to the diffusion of the water and the resin, until the water is evaporated or otherwise driven off.
• our compositions and methods will allow this to be done. Furthermore, if it is desired that the resin be impregnated throughout the material, from one surface to the other surface, again, our composition and method will allow this to be done.
• the improved method involves the use of a resin dispersion which comprises from about 0.1% to about 60% by weight on a solids basis of a colloidal synthetic resin, from about 0.05% by weight to about 7% by weight, based on the weight of the colloidal synthetic resin solids of a water-soluble, polymeric, carboxylic thickener; and from about 0.01% by weight to about by weight, based on the Weight of the colloidal synthetic resin solids of a metal ammine complex coordination compound wherein the central metallic atom is chromium, nickel, zinc, or copper, said colloidal resin dispersion being stable at alkaline pHs in the presence of an excess of a complexing substance such as ammonium hydroxide and at certain concentrations or degrees of dilution but which is unstable at lesser concentrations or greater degrees of dilution when in the presence of heavy metal ions such as chromium, nickel, zinc, or copper.
• a resin dispersion which comprises from about 0.1% to about 60% by weight on a solids basis of a colloidal synthetic
• the synthetic resin may be selected from a relatively large group of synthetic resins well known in industry for bonding purposes and may be of a self crosslinking type, externally cross-linking type, or not crosslinked.
• synthetic resins include: Polymers and copolymers of vinyl ethers; vinyl halides such as plasticized and unplasticized polyvinyl chloride, polyvinyl chloride-polyvinyl acetate, ethylene-vinyl chloride, etc.; polymers and copolymers of vinyl esters such as plasticized and unplasticized polyvinyl acetate, ethylene-vinyl acetate, acrylic-vinyl acetate, etc.; polymers and copolymers of the polyacrylic resins such as ethyl acrylate, methyl acrylate, butyl acrylate, ethylbutyl acrylate, ethyl hexyl acrylate, hydroxyethyl acrylate, dimethyl amino ethyl acrylate, etc.
• These resins may be used either as homopolymers comprising a single repeating monomer unit, or they may be used as copolymers comprising two, three, or more different monomer units which are arranged in random fashion, or in a definite ordered alternating fashion, within the polymer chain.
• block polymers comprising relatively long 6 blocks of different monomer units in a polymer chain and graft polymers comprising chains of one monomer attached to the back-bone of another polymer chain.
• compositions and formulations containing these polymers must be stable at an alkaline pH range of from about 7 to about 10 /2 or even higher which is the range wherein they are utilized, with preferred pH ranges extending from about 7 /2 to about 10.
• alkaline pH range of from about 7 to about 10 /2 or even higher which is the range wherein they are utilized, with preferred pH ranges extending from about 7 /2 to about 10.
• Such stability is particularly required for these polymer dispersions, when existing at their normal concentration levels in the presence of water-soluble polymeric carboxylic thickeners, and metal ammine complex coordination compounds, as described herein.
• the water soluble polymeric carboxylic thickener may be selected from a relatively large group of such materials which include, for example: polyacrylic acid; polymeric crotonic acid; copolymers of vinyl acetate and crotonic acid; copolymers of vinyl acetate and acrylic acid; polyacrylic 'acid-polyacrylamide copolymers; polymethacrylic acid; polymethacrylic acid-polyacrylamide copolymers; carboxymethyl cellulose; carboxyethyl cellulose; carboxypropyl cellulose; polycarboxymethyl hydroxyethyl cellulose; alginic acid; polymers of acrylic acid and acrylic acid esters; polymers of a,B-unsaturated carboxylic acids such as itaconic acid; etc.
• These water soluble, polymeric, carboxylic thickeners may be used in their acid forms but normally it is preferred to use their water soluble neutralized salts, that is, their sodium, potassium, lithium, ammonium, or like water soluble salts.
• metal ammine complex coordination compounds are:
• a metal ammine complex coordination compound is one of a number of types of metal complex compounds, usually made by addition of organic or inorgam'c atoms or groups such as ammonia (NH to simple inorganic compounds containing the metal atom.
• Coordination compounds are therefore essentially compounds to which atoms or groups are added beyond the number possible of explanation on the basis of electrovalent linkages, or the usual covalent linkages, wherein each of the two atoms linked donate one electron to form the duplet.
• the coordination compounds the coordinated atoms or groups are linked to the atoms of the coordination compound, usually by coordinate valences, in which both the electrons in the bond are furnished by the linked atoms of the coordinated group.
• colloidal synthetic resin, the water soluble polymeric carboxylic thickener and the metal ammine complex coordination compound exist together in a stable emulsion form and normally do not agglomerate, coagulate or precipitate, as long as the stable concentration levels of NH OH or degree of dilution are maintained.
• the resin immediately coagulates and agglomerates in place with no further spreading, diffusion or migration.
• the metal ammine complex coordination compound itself as exemplified by tetrammine zinc chloride [Zn(NH C12, ionizes to the divalent cation [Zn(NH and two anions Cl-, even in the presence of high pH, ammoniacal, colloidal latex and water soluble, polymeric carboxylic thickener. Yet, this complex cation has no apparent or appreciable effect on the colloidal latex or on the water soluble, polymeric carboxylic thickener and specifically does not form an insoluble precipitate with either of them, as might have been expected.
• the metal cation which is released from the metal ammine complex coordination compound also is capable of attacking or reacting with any other chemical compounds which are present and which possess anionic groups, particularly hydroxy, carboxy, sulfino, sulfo, and like acid groups.
• surfactant system which is anionic and contains surfactants such as alkyl aromatic sulfonic acids, alkyl sulfonic acids, the carboxylic acids, and other surfactants
• anionic surfactants include sodium p-l-methyl alkyl benzene sulfonates in which the alkyl group contains from 10 to 16 carbon atoms, the sodium di-n-alkyl sulfosuccinates in which the alkyl groups contain from 4 to 12 carbon atoms,'the potassium n-alkyl malonates in which the alkyl group contains from 8 to 18 carbon atoms, the potassium alkyl tricarboxylates in which the alkyl group contains from 6 to 14 carbon atoms, the alkyl betaines in which the alkyl group contains from 6 to 14 carbon atoms, the ether alcohol sulfates, sodium n-al'kyl sulfates, containing from 6 to 18 carbon atoms, etc.
• the amount of surfactant used may vary from about 0.1% to 5% by weight of the resin solids dependent on the type resin being polymerized and the conditions under which it is polymerized.
• the specific surfactant which is selected for use in the resin composition does not relate to the essence of the invention. It is merely necessary that it possess the necessary properties and characteristics to carry out its indicated function of stabilizing the resin composition prior to the time that coagulation and precipitation of the resin is required. Additionally, in the event that it is desired that the surfactant assist in or promote the coagulation and precipitation function, then it must possess the necessary anionic groups, as described hereinbefore, which are capable of reaction due to the presence of the metal cations released from the metal ammine complex coordination compound.
• the present inventive concept is operative with resins which have non-ionic or even polyionic emulsifying or stabilizing systems.
• the presence of an anionic surfactant system may be helpful in the controlled coagulation procedures described herein but it is not necessary or even especially advantageous in many cases.
• the mechanism of instant agglomeration, coagulation and precipitation of the colloidal resin binder may therefore be triggered subsequent to dilution by reaction of the metal cation with either the water soluble, polymeric carboxylic thickener or the anionic surfactant, or both.
• the dilution may be effected in different ways in order to activate the reaction mechanism.
• the porous or absorbent fibrous material may be pre-treated by being pre-wet with a suflicient quantity of an aqueous medium, preferably water, whereby the colloidal resin composition immediately becomes sufiiciently diluted.
• the colloidal resin composition may be first printed on the porous or absorbent fibrous material and then substantially immediately treated with the aqueous medium such as water to effect the dilution whereupon the colloidal resin particles substantially immediately agglomerate or coagulate in place with no further spreading, diffusion or migration.
• Me is a metal such as disclosed herein, 9: is a whole number from 2 to 8 (and more commonly 2, 4 or 6), and Y is an anion such as chloride, iodide, bromide, sulfite, sulfate, nitrite, nitrate, carbonate, acetate, borate, phosphate, citrate, chlorate, oxalate, etc.
• Me and Y normally form compounds, the formation of which can be explained on the basis of electtovalent linkages, or the usual covalent linkages, wherein each of the two atoms linked donate one electron to form the duplet.
• the amount of the water applied to the fibrous web varies widely, depending upon many factors, the most important of which is the nature, concentration, properties and characteristics of the synthetic resin, the metal ammine complex coordination compound, and the surfactant system in which they are stabilized.
• the amount of water applied to the fibrous web is in the range of from about 140% to about 280%, and preferably from about 160% to about 220%, based on the Weight of the fibrous web being treated.
• Such amounts are controlled by the use of suitable conventional vacuum apparatus, nip-rolls, squeeze-rolls, etc.
• the amount of water which is applied to the fibrous web prior to the printing of the resin binder also affects the degree of control exercised over the coagulation and migration.
• the degree of coagulation may be lowered even more and the degree of migration may be increased by the inclusion in the pre-wetting water of a small amount of an alkaline or basic material such as ammonium hydroxide.
• the pH remains alkaline, just as it does in other variations of this invention, and the coagulation and precipitation are purely the result of the dilution.
• the total migration of the resin binder solids may be reduced to as little as about 50% or less beyond the originally deposited area. In some instances, the migration is relatively negligible. Normally, however, the increase in area of the resin binder solids, even under the most adverse conditions, does not materially exceed about 200%. Such values are to be compared to increases in binder migration of at least about 300% and up to about 800% when emulsion polymerized resins are applied to fibrous porous absorbent sheet materials, unaided by the principles disclosed herein.
• the concentration of the binder resin solids in the binder area is correspondingly increased when utilizing the principles of the present invention and is in the range of from about 50% by weight to about 120% by weight, and more normally from about 60% to about 80% by weight, based on the weight of the fibers in the binder area.
• a fibrous card web weighing about 570 grains per square yard and comprising 100% rayon fibers 1 /2 denier 10 and 1 /2 inches in length is intermittently print bonded by the rotogravure process using an engraved roll having 6 horizontal wavy lines per inch. The width of each line as measured on the engraved roll is 0.024 inch.
• composition by weight of the resin binder formulation used for the intermittent print-bonding is:
• the fibrous card web is pretreated or pre-moistened with a large amount of water to the extent of about 190% moisture based on the weight of the fibers in the web.
• the extra dilution with water is sufficient by itself to upset the stability of the resin dispersion when applied to the web and it instantly coagulates and precipitates on the very wet fibrous Web.
• the printed web is then processed, dried and cured.
• the width of the binder line in the finished product is about 0.054 inch which represents a controlled total migration of about
• the surface coverage of the binder is about 32.4%.
• the percent binder in the bonded nonwoven fabric is about 17.4%.
• the concentration of binder in the binder area is about 54%, based on the weight of the fibers therein.
• the resulting nonwoven fabric has excellent strength, excellent softness, drape and hand, and excellent crossresilience.
• Example II The procedures of Example I are followed substantially as set forth therein with the exception that grams of American Cyanamid curing resin Cyrez 933, an aminoform melamine formaldehyde type external cross-linking agent, is added to the formulation. The results are good and are generally comparable to those obtained in Example I, except that this sample has improved wet-abrasion resistance and very good launderability. The resulting bonded nonwoven fabric also finds commercial acceptance.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the ethylene-vinyl acetate copolymer is replaced by 7 pounds of 46% solids latex of Goodrich 2671, a self cross-linking acrylic copolymer containing ethyl acrylate and acrylonitrile. The results are good and are generally comparable to those obtained in Example II. The resulting bonded nonwoven fabric also finds commercial acceptance.
• Example IV The procedures of Example II are followed substantially as set forth therein with the exception that the ethylene-vinyl acetate copolymer is replaced by 7 pounds of a 55 solids latex of National Starch Resyn 2345, a copolymer of polyvinyl acetate and an acrylate containing 10% by weight of di-octyl phthalate plasticizer. The results are good and are generally comparable to those obtained in Example II except that this product has good wet-abrasion resistance and has very good launderability. The resulting bonded nonwoven fabric also finds commercial acceptance.
• Example V The procedures of Example I are followed substantially as set forth therein with the exception that the ethylene-vinyl acetate copolymer is replaced by 7 pounds of a 46% solids latex of Goodrich Geon 576, a plasticized polyvinyl chloride-lower alkyl acrylate copolymer stabilized with an anionic surfactant. The results are good and are generally comparable to those obtained in Example I except that this product has very good heat sealing properties. The resulting bonded nonwoven fabric also finds commercial acceptance.
• Example VI The procedures of Example I are followed substantially as set forth therein with the exception that the ethylene-vinyl acetate copolymer is replaced by 7 pounds of a 50% solids latex of Rohm & Haas HA-8, a self cross-linking polyethyl acrylate copolymer stabilized with a non-ionic surfactant. The results are good and are generally comparable to those obtained in Example I. The resulting bonded nonwoven fabric also finds commercial acceptance particularly as a wet wiping cloth.
• Example VII The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1 pound of a 1% solution of the sodium salt of Hercules Carboxymethylcellulose 7H3S, having a high degree of polymerization in excess of about 1000, a high molecular weight in excess of about 200,000, a high viscosity of 900-3000 centipoises, maximum viscosity, 1% solution, at 25 C., and a degree of carboxymethyl substitution in the range of from about 0.65 to about 0.85 D5.
• the results are good and are generally comparable to those obtained in Example II.
• the resulting bonded nonwoven fabric also finds commercial acceptance.
• Example VIII The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1 pound of a 9% solution of the sodium salt of Hercules Carboxymethylcellulose 7M, having a degree of polymerization in excess of 500, a medium molecular weight greater than about 70,000, a medium viscosity 30-100 centipoises, malximum viscosity, 1% solution, 25 C., and a degree of carboxymethyl substitution in the range of from about 0.65 to about 0.85 D5. The results are good and are generally comparable to those obtained in Example H. The resulting bonded nonwoven fabric is also commercially acceptable.
• the thickening agent is 1 pound of a 9% solution of the sodium salt of Hercules Carboxymethylcellulose 7M, having a degree of polymerization in excess of 500, a medium molecular weight greater than about 70,000, a medium viscosity 30-100 centipoises, malximum viscosity, 1% solution, 25 C.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1 pound of a 9% solution of the sodium salt of Hercules Carboxymethylcellulose 12M8, having a medium molecular weight in excess of about 100,000, a medium viscosity of 400-800 centipoises, 2% solution, 25 C., and a degree of carboxymethyl substitution in the range of from about 1.2 to about 1.4 BS. The results are good and are generally comparable to those obtained in Example II. The resulting bonded nonwoven fabric finds commercial acceptance.
• the thickening agent is 1 pound of a 9% solution of the sodium salt of Hercules Carboxymethylcellulose 12M8, having a medium molecular weight in excess of about 100,000, a medium viscosity of 400-800 centipoises, 2% solution, 25 C., and a degree of carboxymethyl substitution in the range of from about 1.2 to about 1.4 BS.
• the results are good and are generally comparable to those obtained in
• Example IX The procedures of Example IX are followed substantially as set forth therein with the exception that 1 pound of a 9% solution of the sodium salt of Hercules Carboxymethylcellulose 9M8 having a molecular weight of about 100,000 is used as the thickening agent. The results are good and are generally similar to 11956 Obtained in Example IX.
• Example IX The procedures of Example IX are followed substantially as set forth therein with the exception that the sodium salt of Hercules Carboxymethylcellulose 7M1 and 7H4 are used.
• 7M1 has a medium molecular weight, a medium carboxymethyl substitution of 0.65-0.85 D.S., and a low viscosity range in centipoises at 25 C. of 50-100 for a 2% concentration.
• 7H4 has a high molecular weight, a medium carboxymethyl substitution of 0.65-0.85 D.S., and a high viscosity range in centipoises at 25 C. of 2500-4500 for a 1% concentration.
• the results are good and are generally comparable to those obtained in Example IX.
• the resulting bonded nonwoven fabric is acceptable commercially.
• EXAMPLE XIII The procedures of Example II are followed substantially as set forth therein with the exception that the thickener is the sodium salt of Hercules Carboxymethylcellulose 7L2, having a low molecular weight of about 45,000, a degree of polymerization of about 200, a viscosity range in centipoises at 25 C. of 18 maximum at 2% concentration. An effect is noted but the results are not sufiicient as to be commercially warranted.
• Example XIV The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1% pounds of a 3% solution of the sodium salt of Hercules Carboxymethylcellulose 4M6, having a medium molecular weight of about 100,000, a medium viscosity, and a low degree of carboxymethyl substitution in the range of from about 0.38 to about 0.48 D8. The results are good and are generally comparable to those obtained in Example II. The resulting bonded nonwoven fabric finds commercial acceptance.
• the thickening agent is 1% pounds of a 3% solution of the sodium salt of Hercules Carboxymethylcellulose 4M6, having a medium molecular weight of about 100,000, a medium viscosity, and a low degree of carboxymethyl substitution in the range of from about 0.38 to about 0.48 D8.
• the results are good and are generally comparable to those obtained in Example II.
• the resulting bonded nonwoven fabric finds commercial acceptance.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1 pound of a 10% solution of the sodium salt of Goodyear Carboset 514 polyacrylate copolymer. The results are good and are generally comparable to those set forth in Example II. The resulting bonded nonwoven fabric finds commercial acceptance.
• the thickening agent is 1 pound of a 10% solution of the sodium salt of Goodyear Carboset 514 polyacrylate copolymer.
• the results are good and are generally comparable to those set forth in Example II.
• the resulting bonded nonwoven fabric finds commercial acceptance.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the thickening agent is 1 pound of a 10% solution of a neutralized sodium salt of Rohm & Haas Acrysol A-S polyacrylate homopolymer. The results are good and are generally comparable to those set forth in Example II. The resulting bonded nonwoven fabric finds commercial acceptance.
• the thickening agent is 1 pound of a 10% solution of a neutralized sodium salt of Rohm & Haas Acrysol A-S polyacrylate homopolymer.
• the results are good and are generally comparable to those set forth in Example II.
• the resulting bonded nonwoven fabric finds commercial acceptance.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the thickener is 1 pound of a 5% solution of a sodium salt of Kelco Kelgin XL alginate water soluble, polymeric, carboxylic thickener. The results are good and are generally comparable to those obtained in Example II. The resulting bonded nonwoven fabric finds commercial acceptance.
• Example II EXAMPLES XVIII AND XIX
• the procedures of Example II are followed substantially as set forth therein with the exception that the 50 milliliters of zinc tetrammine chloride is: (a) increased to milliliters; and (b) decreased to 35 milliliters.
• the results in both cases are good and are generally comparable to those obtained in Example H.
• the resulting bonded nonwoven fabrics are commercially acceptable.
• Example II The procedures of Example II are followed substantially as set forth therein with the exception that the volume of zinc tetrammine chloride is increased from 50 milliliters to 100 milliliters and the amount of Acrysol 51 thickener is increased from 1 lb. to 1 /2 lbs. The results are good and are generally comparable to those obtained in Example II, except that it is noted that practically all of the resin binder is on one face of the nonwoven fabric whereby it may be more easily plied to another fabric or to another material.
• Example II EXAMPLES XXI AND XXII
• the procedures of Example II are followed substantially as set forth therein with the exception that the zinc tetrammine chloride is replaced by an equivalent amount of: (a) zinc tetrammine sulfate; (b) zinc tetrammine carbonate; and (c) copper diammine acetate.
• the results in all three cases are good and are generally comparable to those obtained in Example II.
• the resulting bonded nonwoven fabrics find commercial acceptance.
• a method of applying a synthetic resin binder to a fibrous web of overlapping, intersecting fibers and controlling its migration thereon which comprises: applying to a fibrous Web of overlapping, intersecting fibers a stable, colloidal aqueous dispersion having an alkaline pH comprising: 1) a synthetic resin; (2) a Water-soluble, polymeric carboxylic synthetic resin; and (3) a metal amine complex coordination compound; and substantially immediately diluting said dispersion whereby a metal cation is released from said metal ammine complex coordination compound to substantially immediately destroy the stability of said dispersion and coagulate said resin with a minimum of migration on said fibrous web.
• the metal ammine complex coordination compound has the formula Me(NH Y wherein Me is a metal selected from the group consisting of chromium, nickel, zinc, and copper; x is a whole number from 2 to 8, inclusive; and Y is an anion.
• metal ammine complex coordination compound is zinc tetrammine sulfate.
• metal ammine complex coordination compound is zinc tetrammine carbonate.
• metal ammine complex coordination compound is zinc tetrammine chloride.
• metal ammine complex coordination compound is copper diammine acetate.
• said aqueous dispersion comprises: from about 0.1% to about 60% by weight of said synthetic resin; from about 0.05% to about 7% by weight, based on the weight of said resin, of said water soluble, polymeric carboxylic thickening agent; and from about 0.01% to about by weight, based on the weight of said resin, of said metal ammine complex coordination compound.
• a method of applying a synthetic resin binder to a fibrous web of overlapping, intersecting fibers and control ling its migration thereon which comprises: applying to a fibrous web of overlapping, intersecting fibers a stable, colloidal aqueous dispersion having an alkaline pH comprising: (1) a synthetic resin; (2) a water soluble, polymeric, carboxylic thickening agent; and (3) a metal ammine complex coordination compound, said dispersion being applied to said fibrous web in a predetermined, intermittent print pattern of spaced discrete areas; and substantially immediately diluting said aqueous dispersion whereby a metal cation is released from said metal ammine complex coordination compound to substantially immediately destroy the stability of said aqueous dispersion and to coagulate said synthetic resin in said spaced discrete areas with a minimum of migration therefrom.
• a method of applying a synthetic resin binder to a fibrous web of overlapping, intersecting fibers and controlling its migration thereon which comprises: applying to a fibrous web of overlapping, intersecting fibers a stable, colloidal aqueous dispersion having an alkaline pH comprising: (l) a water-soluble, polymeric, carboxylic synthetic resin; and (2) a metal ammine complex coordination compound; and substantially immediately diluting said dispersion whereby a metal cation is released from said metal ammine complex coordination compound to substantially immediately destroy the stability of said dispersion and coagulate said resin with a minimum of migration on said fibrous web.
• a method of applying a synthetic resin binder to a fibrous web of overlapping, intersecting fibers and controlling its migration thereon which comprises: applying to a fibrous Web of overlapping, intersecting fibers a stable, colloidal aqueous dispersion having an alkaline pH comprising: (1) a water soluble, polymeric, carboxylic synthetic resin thickening agent; and (2) a metal ammine complex coordination compound, said dispersion being applied to said fibrous web in a predetermined, intermittent print pattern of spaced discrete areas; and substantially immediately diluting said aqueous dispersion whereby a metal cation is released from said metal ammine complex coordination compound to substantially immediately destroy the stability of said aqueous dispersion and to coagulate said synthetic resin in said spaced discrete areas with a minimum of migration therefrom.
• a method of applying a stable resin composition to porous materials and controlling the migration thereon which comprises: applying to porous materials a stable resin composition having an alkaline pH and comprising: (1) a water-soluble, polymeric, carboxylic resin; and (2) a metal ammine complex coordination compound; and substantially immediately diluting said resin composition to substantially immediately destroy the stability of said resin composition and coagulate said resin whereby the migration of said resin on said porous materials is controlled.
• a method of applying a stable resin composition to porous materials and controlling the migration thereon which comprises: applying to porous materials a stable resin composition having an alkaline pH and comprising: (1) a Water-soluble, polymeric, carboxylic resin; (2) a metal ammine complex coordination compound; and (3) a synthetic resin; and substantially immediately diluting said resin composition to substantially immediately destroy the stability of said resin composition and coagulate said resins whereby the migration of said resins on said porous materials is controlled.

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Cited By (18)

• 1971
  • 1971-01-22 US US109026A patent/US3706595A/en not_active Expired - Lifetime
  • 1971-08-10 CA CA120,247A patent/CA973645A/en not_active Expired
  • 1971-08-16 AU AU32390/71A patent/AU464802B2/en not_active Expired
  • 1971-08-16 FR FR7129839A patent/FR2122385B1/fr not_active Expired
  • 1971-08-17 SE SE7110450A patent/SE394699B/xx unknown
  • 1971-08-19 NL NL7111450.A patent/NL166992C/xx not_active IP Right Cessation
  • 1971-08-20 DE DE19712141862 patent/DE2141862A1/de not_active Ceased
  • 1971-08-20 GB GB3919971A patent/GB1356817A/en not_active Expired
  • 1971-08-20 BR BR5457/71A patent/BR7105457D0/pt unknown
  • 1971-08-20 ZA ZA715579A patent/ZA715579B/xx unknown
  • 1971-08-21 JP JP6395371A patent/JPS5517151B1/ja active Pending

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