US3849173A - Synthetic resin composition and methods of utilizing the same - Google Patents

Synthetic resin composition and methods of utilizing the same Download PDF

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US3849173A
US3849173A US26061372A US3849173A US 3849173 A US3849173 A US 3849173A US 26061372 A US26061372 A US 26061372A US 3849173 A US3849173 A US 3849173A
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Prior art keywords
synthetic resin
acid
resin composition
percent
porous materials
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A Drelich
G Lukacs
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Johnson and Johnson
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Johnson and Johnson
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Priority to US05260613 priority Critical patent/US3849173A/en
Priority to IN1281/CAL/73A priority patent/IN141141B/en
Priority to SE7307897A priority patent/SE414055B/xx
Priority to IT5049273A priority patent/IT985335B/it
Priority to BR423873A priority patent/BR7304238D0/pt
Priority to CA173,310A priority patent/CA1003985A/en
Priority to ZA00733846A priority patent/ZA733846B/xx
Priority to NL7307902A priority patent/NL7307902A/xx
Priority to GB2703473A priority patent/GB1430126A/en
Priority to AR24844573A priority patent/AR198840A1/es
Priority to AU56678/73A priority patent/AU470606B2/en
Priority to JP6458373A priority patent/JPS4966722A/ja
Priority to DE2329193A priority patent/DE2329193A1/de
Priority to FR7320844A priority patent/FR2187828B1/fr
Priority to US05/446,254 priority patent/US3931085A/en
Application granted granted Critical
Publication of US3849173A publication Critical patent/US3849173A/en
Priority to US05/575,560 priority patent/USRE28957E/en
Priority to IN1282/CAL/76A priority patent/IN144616B/en
Priority to SE7803939A priority patent/SE7803939L/xx
Anticipated expiration legal-status Critical
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    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • 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
    • D06M11/67—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 cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24826—Spot bonds connect components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2311—Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof

Definitions

  • ABSTRACT Methods of applying stable synthetic resin compositions to porons material the synthetic resin compositions comprising: (1) a synthetic resin; (2) a polyvalent metal complex coordination compound; and (3) a water-soluble, ionically active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration of said polyvalent metal salt, and substantially immediately destroying the stability of the synthetic resin compositions to precipitate the resin on the porous materials under controlled migration conditions.
  • the present invention relates to synthetic resin compositions and to methods of utilizing the same. More particularly, the present invention relates to synthetic resin compositions and to methods of applying such synthetic resin compositions to porous or absorbent materials and controlling their spreading, diffusing, or migrating thereon or their penetrating therein. Even 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 conventional 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.
  • MAS- SLINN nonwoven fabrics Typical of such fabrics are the so-called MAS- SLINN nonwoven fabrics, some of which are described in greater particularity in US. Pat. Nos. 2,705,687and 2,705,688, issued Apr. 5, 1955, to D. R. Petterson et al. 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. Pat. Nos. 2,862,25l 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. Pat. Nos. 2,676,363 and 2,676,364, issued Apr. 27, 1954 to C. H. Plummer et al.
  • nonwoven fabrics which comprise textile-length 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.
  • 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 inch to about 2% inches.
  • Exemplary of such fibers are the natural fibers such as cotton and wool and the synthetic or man-made 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 previously named fibers.
  • Such other fibers include: polyamide fibers such as nylon 6, nylon 66, nylon 610, etc.; polyester fibers such as Dacron, Fortrel and Kodeh 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 Amel 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 7% inch and down to about inch.
  • These fibers, or mixtures thereof, are customarily processed through any suitable textile machinery (e.g., a
  • 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 percent, 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 satisfactory abrasion resistance.
  • the nonwoven fabric tends to be somewhat stiff 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 over-all impregnated nonwoven fabrics are satisfactory for many uses, they are still basically unsatisfactory as 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 US. Pat. No. 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 printing of the resin binder on these nonwoven webs is usually in the form of relatively narrow lines, or elongated rectangular, triangular or square areas, or annular, circular, or elliptical binder areas which are spaced apart a predetermined distance which, at its maximum, is preferably slightly less than the average fiber length of the fibers constituting the web. This is based on the theory that the individual fibers of the fibrous web should be bound together in as few places as possible.
  • 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 percent to about 50 percent of the total surface of the final product. Within the more commerical aspects of the present invention, however, nominal surface coverages of from about 12 percent to about 40 percent 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 inter-spatial 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 overall 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 man-made polymers have a chemical structure which usually can be represented by a regularly 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,
  • condensation polymers are the polyurethanes, the polyamides, the polyesters, etc.
  • Emulsion polymerization is one of the most commonly used.
  • Emulsion polymerized resins notably polyvinyl chlorides, polyvinyl acetates, carboxylated styrene butadiene rubbers, and polyacrylic resins, are widely used throughout many industries.
  • 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 dimensions (1 to 2 microns diameter or smaller) 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 l 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 1/10 percent solids by weight up to about percent 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 pl-ls of from about 2 to about 1 1.
  • 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 percent to about 30 percent by weight, based on the weight of the porous or absorbent material is preferred.
  • Such resins have also found use in the coating industries for the coating of knitted fabrics, woven fabrics, paper, paper products, leather, and other materials.
  • the resins are also used as adhesives for laminating films, sheets and like materials or for bonding fibrous webs.
  • These resins have also found wide use as additives in the manufacture of paper, the printing industry, the painting 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 or 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 to spread into and throughout the porous material and does not remain merely on its surface.
  • the aqueous colloid tends to diffuse, spread or migrate 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 of migration which takes place due to the diffusion of the water and the resin, until the water is evaporated or otherwise driven off.
  • these methods disclose applying stable synthetic resin compositions under alkaline conditions to porous or absorbent materials which were previously treated and wetted with controlled concentrations or amounts of acidic media, aqueous media, or simply water.
  • synthetic resin compositions were applied to the pretreated porous or absorbent materials, their stability was altered and destroyed by the resulting altered acidic or dilutive conditions and they immediately coagulated and precipitated on the porous or absorbent materials under controlled migration conditions.
  • U.S. Pat. No. 3,706,595 discloses methods of applying stable synthetic resin compositions as described herein and having an alkaline pH to porous materials and controlling the migration of such stable synthetic resin compositions on such porous materials by destroying the stability of such synthetic resin compositions by diluting the same substantially immediately after being applied to such porous materials.
  • U.S. Pat. No. 3,720,562 discloses methods of applying stable synthetic resin compositions as described herein and having an alkaline pH to porous materials and controlling the migration of such stable synthetic resin compositions on such porous materials by destroying the stability of such synthetic resin compositions by acidifying the same-substantially immediately after being applied to such porous materials.
  • FIGURE A typical arrangement of such apparatus is shown in the FIGURE for illustrative but not for limitative purposes.
  • an adjustable upper rotatable back-up roll 10 rotating on a rotatable shaft 12, in adjustably controlled pressure contact with a lower rotatable engraved print roll or applicator roll 14 rotating on a rotatable shaft 16.
  • a lowermost rotatable pick-up roll 18 rotating on a rotatable shaft 20 and being partially immersed in a bath 22 of the synthetic resin composition, which pick-up roll 18 picks up the synthetic resin composition 24 and transfers it to the applicator roll 14 which applies it to a porous or absorbent material W passing through the adjustable pressure nip of back-up roll 10 and applicator roll 14. All these rolls are adjustable whereby the pressure applied to the porous or absorbent material W is adjusted to control the amount of pick-up of the synthetic resin composition 24 on the porous or absorbent material W.
  • a doctor blade 26 is employed to prevent build-up of the resin latex on the pick-up roll 18.
  • This apparatus is generally conventional and standard and other equivalent forms of apparatus are of use.
  • the premature coagulation and precipitation was evidenced primarily by a thickening or setting-up of the synthetic resin composition in the bath, particularly during the running of the operation.
  • a synthetic resin composition having a viscosity for example, a 1,000 centipoises, when originally prepared, thickened to a viscosity of 20,000 centipoises or higher in a period of 1 week storage, prior to plant operation.
  • a comparable synthetic resin composition when protected by the application of the present invention, thickened only slightly to a viscosity of 1,040 centipoises.
  • a stabilizing and anti-coagulating and precipitating agent comprising a water-soluble, ionically active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration of said polyvalent metal salt.
  • the addition of the stabilizing and anti-coagulating and anti-precipating agent serves to render the liberated polyvalent metal cations innocuous and ionically inactive by chemical reaction and precipitation or sequestration of the polyvalent metal cations.
  • the action of the stabilizing and anti-coagulating agent is thus actually a scavenging action. In this way, the synthetic resin is unaffected and the viscosity of the synthetic resin composition is relatively stabilized.
  • the removal of M from the system should shift the equilibrium to continuously form more ionic M cations to maintain the constancy of the value of the reaction constant k. Unexpectedly and surprisingly. this does not appear to happen, or to happen so slowly that we can increase the stability of a formulation from several hours to many weeks.
  • the improved synthetic resin compositions of the present invention comprise from about 0.1 percent to about 60 percent by weight on a solids basis of a colloidal synthetic resin and may be of a self cross-linking type, or an externally cross-linking type, or may not be cross-linked.
  • colloidal synthetic resins include: polymers and copolymers of vinyl halides such as plasticized and unplasticized polyvinyl chloride, polyvinyl chloride-polyvinyl acetate, ehtylene-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, ethyl-butyl acrylate, ethyl hexyl acrylate, hydroxyethyl acrylate, dimethyl amino ethyl acrylate, etc.; polymers and copolymers of the polymethacrylic resins such as methyl methacrylate, ethyl methacrylate, isopropyl methacryl
  • 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, withinthe polymer chain. Also included within the inventive concept are the block polymers comprising relatively long blocks of different monomer units in a polymer chain and graft polymers comprising chains of one monomer attached to the backbone of another polymer chain.
  • the coordinating ligand is normally an acidic or proton donor group, especially those containing terminal hydroxy groups.
  • the colloidal synthetic resins possessing a hydroxycontaining coordinating ligand are obtained by copolymerizing: 1 from about 92 percent by weight to about 99 percent by weight of a monomer or a mixture of monomers of the group comprising vinyl halide, vinyl ester, or vinyl ether monomers including, for example, vinyl chloride, vinyl acetate and vinyl ethyl ether; olefin monomers such as ethylene and propylene; acrylic and methacrylic monomers including, for example, ethyl acrylate, ethyl hexyl acrylate, methyl acrylate, propyl acrylate, butyl acrylate, hydroxyethyl acrylate, dimethyl amino ethyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, N-isopropyl acrylamide, N
  • Anhydrides of such acids, where they exist, are also of use.
  • Other a,B-unsaturated acids are of use and include 2- sulfoethyl methacrylate, styrene sulfonic acid, vinyl phosphonic acid, etc.
  • more than one monomer may be included in the polymerization with the a,B-unsaturated acid.
  • An outstanding example of the use of more than one monomer is the polymerization of butadiene and styrene with an a,B-unsaturated acid such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, or itaconic acid.
  • Anhydrides, for example, maleic anhydride, are also of use.
  • 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 acidpolyacrylamide copolymers; carboxymethyl cellulose; carboxyethyl cellulose; carboxypropyl cellulose; polycarboxy-methyl hydroxyethyl cellulose; alginic acid; polymers of acrylic acid and acrylic acid esters; polymers of 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.
  • anionic and nonionic surfactants are added to the synthetic resin composition to create, enhance or to augment the triggering action which initiates the coagulation and precipitation of the synthetic resin.
  • anionic and nonionic surfactants are included in the synthetic resin composition in amounts ranging from about 0.01 percent to about 5 percent by weight, based on the weight of the synthetic resin solids.
  • Typical examples of such surfactants are: the alkyl aromatic sulfonic acids, alkyl sulfonic acids, the carboxylic acids, and other surfactants such as, for example, dodecyl benzene sulfonate, octyl benzene sulfonate, hexyl benzene sulfonate, octadecyl benzene sulfonate, octyl sulfonate, hexyl sulfonate, dodecyl sulfonate, octadecyl sulfonate, and the sodium and potassium fatty acid soaps containing from 5 to 18 carbon atoms.
  • anionic surfactants include sodium p-lmethyl 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 nalkyl 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-alkyl sulfates, containing from 6 to 18 carbon atoms, etc.
  • Non-ionic surfactants which are-useful within the principles of the present invention possess non-ionizing hydrophilic groups and include such surface-active agents as fatty acid mono-esters of polyglycerol and pentaerythritol. Specific examples are glycerol monostearate, glycerol mono-laurate, pentaerytritol monostearate, pentaerytritrol, mono-laurate, etc. Others include glycol esters of fatty acids, prepared by treating the acid with ethylene oxide.
  • Specific useful surfactants include: nonyl phenoxy poly (ethyleneoxy) ethanol; nonyl phenol polyglycol ether alcohol; polyethylene glycol monolaurate; polyoxyethylene oleyl ether; ethylene oxide condensates of castor oil; polyglycol palmitate amide; ethoxylated alkyl phenol; lauric diethanolamide; octyl phenoxy polyethoxy ethanol; difunctional block-polymers terminating in primary hydroxy groups; etc.
  • the specific surfactant which is selected for use in the-resin composition does not relate to the essence of THE POLYVALENT METAL COMPLEX COORDINATION COMPOUND
  • the polyvalent metal complex coordination compound is included in the resin composition in an amount equal to from about 0.01 percent by weight to about percent by weight, based on the weight of the previously mentioned synthetic resin or polymer solids.
  • polyvalent metal complex coordination compounds of particular applicability when the porous or absorbent materials are pretreated with acidic media are: ammonium carbonato zirconate (NH4)3 l 3)3]' 2 ammonium heptafluoro zirconate (NH4)3 l 7] potassium tetracyano zincate K [Zn(CN) sodium tetrahydroxo zincate sodium tetrahydroxo aluminate potassium trioxalato aluminate
  • a metal complex coordination compound is one of a number of types of metal com- 45 plex compounds, usually made by addition of organic or inorganic atoms or groups 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 coordinate 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.
  • polyvalent metal complex coordi- 6O pentammine chloro chromium chloride crowns Cl c1 hexammine nickel chloride tetrammine dinitro cobalt nitrate l s)4( 2)2] a)3 hexammine cobalt chloride hexammine cobalt iodide hexammine cobalt nitrate 3)s] ah hexammine cobalt sulfate hexammine cobalt bromide hexammine nickel bromide hexammine nickel chlorate hexammine nickel iodide hexammine nickel nitrate tetrammine zinc carbonate tetrammine zinc sulfate tetrammine zinc nitrate diammine zinc chloride tetrammine zinc chloride diammine copper acetate tetrammine copper sulfate tetrammine copper hydroxide ammonium t
  • 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.
  • the water-soluble, ionically active ammonium or alkali metal salt of an acid (to be defined more particularly hereinafter) is present in the resin composition in an amount of from about 5 percent to about 90 percent molecular equivalent (stoichiometric basis) of the polyvalent metal which is present and which is to be precipitated ,or sequestered. That is to say, for example, if there is one mole of the polyvalent metal present, then there is from about 0.05 to 0.90 mole of the watersoluble, ionically active ammonium or alkali metal salt present.
  • Ammonium and alkali metal salts of acids naturally are selected from the group consisting of ammonium, lithium, sodium and potassium salts. Of these, ammonium is preferred. As a matter of fact, in many cases where there is sufficient ammonium or alkali metal hydroxide in the resin composition, the agent may be added in the acid form rather than in the salt form and the water-soluble, ionically active ammonium salt will be formed, in situ.
  • the above salts generally consist of the N11,, Na, etc., and salts of acids listed below.
  • acids suitable for application within the principles of the present invention are: inorganic mineral acids such as ortho-phosphoric acid, hypophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, chromic acid, orthoboric acid, metaboric acid, tetraboric acid, etc.; monobasic aliphatic organic acids, preferably having at least carbon atoms, such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc.; dicarboxylic aliphatic organic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, etc.; aliphatic hydroxy acids such as citric acid, glycollic acid, lactic acid, malic acid, tartaric acid, etc.; monocarboxylic aromatic organic acids such as benzoic acid,
  • chelating agents include: ethylene diamine tetraacetic acid (EDTA); ethylene diamine tetrapropionic acid (EDTPA); hydroxyethyl ethylene diamine triacetic acid (HEDTA); ammonia triacetic acid (NTA); N- hydroxyethyl diethylene triamine tetraacetic acid (HDTTA); etc.
  • EDTA ethylene diamine tetraacetic acid
  • EDTPA ethylene diamine tetrapropionic acid
  • HEDTA hydroxyethyl ethylene diamine triacetic acid
  • NTA ammonia triacetic acid
  • HDTTA N- hydroxyethyl diethylene triamine tetraacetic acid
  • a resin binder formulation suitable for bonding nonwoven fabrics having the following composition is prepared:
  • the viscosity of the above described composition is 1000 centipoises, as initially prepared.
  • the pH is on the alkaline side (9.0).
  • a one-pound sample is exposed to air for seven days and the viscosity undesirably increases to 20,000 centipoises.
  • Another one-pound sample is protected by the addition of 001 pound of a 25 percent solution of diammonium phosphate.
  • the onepound sample of the protected composition is exposed to air for seven days and the viscosity increases to only 1,040 centipoises. There is no excessive thickening or setting-up of the resin latex.
  • the beneficial results of the diammonium phosphate as an antithickneing and anti-coagulating agent are notable.
  • a resin binder formulation suitable for bonding nonwoven fabrics having the following composition is prepared:
  • the viscosity of the above-described composition is 560 centipoises, as initially prepared.
  • the pH is alkaline (9.2).
  • a 0.7-pound sample is exposed to air for 24 hours and the viscosity undesirably increases to 3,200 centipoises.
  • Another 0.7-pound sample is protected by the addition of 1 ml. of a 25 percent solution of diammonium phosphate.
  • the 0.7-pound sample of the protected composition is exposed to air for 24 hours and the viscosity increases to only 1,060 centipoises. There is no excessive thickening or setting-up of the resin latex.
  • the beneficial results of the diammonium phosphate as an anti-thickening and anti-coagulating agent are notable.
  • Example III EXAMPLE IV
  • the procedures of Example II are followed substantially as set forth therein with the exception that the 0.7-pound sample is protected by the addition of 1 ml. of a 25 percent solution of the ammonium salt of ethylene diamine tetraacetic acid.
  • the sample of the protected" composition is exposed to air for 24 hours and the viscosity increases moderately to only 1,400 centipoises. There is no excessive thickening or setting-up of the protected resin latex.
  • the beneficial results of the ethylene diamine tetraacetic acid as an antithickening and anti-coagulating agent are notable.
  • Example V The procedures of Example IV are followed substantially as set forth therein with the exception that ethylene diamine tetraacetic acid is added rather than its ammonium salt.
  • the dispersion is sufficiently ammoniacal, that the ammonium salt is formed in situ. and subsequently protects the dispersion from coagulation and precipitation. No thickening or setting-up of the protected resin latex is noted. The results are generally comparable.
  • Example II The procedures of Example II are followed substantially as set forth therein with the exception that the 0.7-pound sample is protected by the addition of 1 ml. of a 12% percent solution of ammonium oxalate. The sample of the protected composition is exposed to air for 24 hours and the viscosity increases to only 1,600 centipoises. This increase in viscosity is significantly below the unprotected sample and is still acceptable. The beneficial results of such a small amount of ammonium oxalate as an anti-thickening and anticoagulating agent are notable.
  • a resin binder formulation suitable for bonding nonwoven fabrics having the following composition is prepared:
  • Plasticizer 0.13 Anionic surfactant (25%) 0.03 Corrosion inhibitor (20%) 0.03
  • the viscosity of the above-described composition is 7,400 centipoises, as initially prepared.
  • the pH is alkaline (9.3).
  • a 0.7-pound sample is exposed to air for 24 hours and the viscosity undesirably increases to 20,000 centipoises.
  • Another 0.7-pound sample is protected by the addition of 4 ml. of a 25 percent solution of diammonium phosphate.
  • the sample of the protected" composition is exposed to air for 24 hours, and the viscosity decreases. There is no evidence of any thickening or setting-up of the resin latex.
  • the beneficial results of the diammonium phosphate as an antithickening and anti-coagulating agent are notable.
  • a resin binder formulation suitable for bonding nonwoven fabrics having the following composition is prepared:
  • the viscosity of the above-described composition is 7,400 centipoises, as initially prepared.
  • the pH is alkaline (9.4).
  • a 0.7-pound sample is exposed to air for 24 hours and the viscosity increases to 20,000 centipoises.
  • Another 0.7-pound sample is protected by the addition of 1 ml. of a 25 percent solution of diammonium phosphate.
  • the 0.7-pound sample of the protected composition is exposed to air for 25 hours and the viscosity decreases to 2,800 centipoises.
  • the beneficial results of the diammonium phosphate as an anti-thickening and anti-coagulating agent are notable.
  • EXAMPLE IX A fibrous card web weighing about 750 grains per square yard and comprising percent bleached rayon fibers 1.5 denier and 1 9/16 inches in length is intermittently print bonded by the rotogravure process using an engraved roll having a diamond print pattern therein. Apparatus such as illustrated in the FIGURE is used. There are approximately four lines per inch in each of two directions, crossing to form a diamond pattern and each set of lines is approximately 30 to the cross axis of the fibrous web. The width of each line, as measured on the engraved print roll, is 0.024 inch.
  • the composition by weight of the resin binder formulation used for the intermittent print bonding is:
  • the fibrous card web is pretreated or premoistened with a large amount of water to an extent of 250 percent moisture, based on the weight of the fibers in the web.
  • the extra dilution with water is sufficient to destroy the stability of the resin dispersion when it is applied to the fibrous web by a rotogravure printing process and the resin dispersion immediately coagulates and precipitates in place on the very wet fibrous web.
  • the printed web is then processed, treated and cured as described in the previous referred-to patent applications.
  • the width of the binder line in the finished bonded nonwoven product is not more than about 0.048 inch which represents a controlled total migration of not more than about 100 percent.
  • the resulting bonded nonwoven fabric has excellent strength, excellent softness, and excellent drape and hand.
  • Example IX The procedures of Example IX are followed substantially as set forth therein with the exception that an increased amount of 0.06 pound of the 25 percent solution of diammonium phosphate is added to the 5.6- pound sample of the resin binder composition.
  • the pH of the resulting composition is 9.2 and the viscosity is 440 centipoises.
  • the results are generally comparable to those obtained in Example IX and the resulting bonded nonwoven fabric has excellent strength, excellent softness and excellent drape and hand.
  • Example XI The procedures of Example IX are followed substantially as set forth therein with the exception that a further increased amount of 0.12 pound of 25 percent solution of diammonium phosphate is added to a 5.6- pound sample of the resin binder composition.
  • the pH of the resulting dispersion is 9.2 and its viscosity is 360 centipoises.
  • the control of the application of the protected synthetic resin composition to the fibrous web is very good.
  • the viscosity of the synthetic resin composition at the outset is 600 centipoises and this value does not change materially throughout the operation of the binder application. There is no evidence of any premature coagulation or precipitation of the resin binder composition in the bath and there is no undesirable thickening or setting up of the resin prior to being applied to the fibrous web.
  • the resulting bonded nonwoven fabric has excellent strength, excellent softness, and excellent drape and hand. It is acceptable to the industry.
  • the viscosity of the dispersion as initially prepared is 880 centipoises and the pH is 9.5. A sample of the resin is exposed to air and the viscosity thereof increases to 20,000 centipoises in 24 hours.
  • a 0.7-pound sample of the resin dispersion is protected by the addition thereto of 1 ml. of a 25 percent solution of diammonium phosphate. After 24 hours, the viscosity of the resin dispersion is 840 centipoises. After 48 hours, the viscosity increases to 1,600 centipoises.
  • the results are generally comparable to the results obtained in Example IX.
  • the bonded nonwoven fabric is processed with no production difficulties. There is no thickening or setting-up of the resin latex in the applicator bath. There is no premature coagulation or precipitation in the bath of resin latex.
  • the resulting bonded nonwoven fabric has excellent strength, excellent softness, and excellent hand and drape.
  • ammonium palmitate 3. the sodium salt of ethylene diammine tetraacetic acid
  • the results are generally comparable to the results obtained in Example I. There is no excessive thickening or setting-up of the resin latex. The beneficial results of the anti-thickening and anti-coagulating agent are notable.
  • Example IX The results are generally comparable to the results obtained in Example IX. There is no excessive thickening or setting up of the resin latex in the bath. The beneficial results of the anti-thickening and anticoagulating resin are notable. The properties of the bonded nonwoven fabric are generally comparable to those obtained in Example IX.
  • the viscosity of the above described composition is 1200 centipoises as initially prepared.
  • the pH is alkaline (pH 9.3 Upon exposure to air for 4 days, the viscosity undesirably increases to 1920 centipoises.
  • a 0.67-pound sample of the above resin composition is protected by the addition of 1.5 ml. of a 25 percent solution of diammonium phosphate. At the end of four days exposure to air, the viscosity has risen only slightly to 1,400 centipoises.
  • the viscosity of the above described composition is 240 centipoises.
  • the composition is alkaline and has a pH of 9.3. Upon exposure to air for 4 days, the viscosity of the composition increases to 520 centipoises.
  • a 0.65-pound sample of the above resin composition is protected by the addition of 2 ml. of 25 percent diammonium phosphate.
  • the viscosity of the resulting composition is 240 centipoises which, after four days,
  • a method of applying a stable synthetic resin composition having an alkaline pH to porous materials and controlling the migration thereon which comprises: applying to porous materials a stable synthetic resin composition having an alkaline pH and comprising: (1) from about 0.1 percent to about 60 percent by weight on a solids basis of a synthetic resin; (2) from about 0.01 percent to about percent by weight, based on the weight of said synthetic resin of a polyvalent metal complex coordination compound; and (3) a watersoluble, ionically-active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration of said polyvalent metal salt, said salt being capable of sequestering or precipitating the metal in said polyvalent metal complex coordination compound and being present in an amount of from about 5 percent to about 90 percent molecular equivalent on a stoichiometric basis of said polyvalent metal and substantially immediately destroying the the stability of said synthetic resin composition to coagulate and precipitate the resin on said porous materials under controlled
  • a method of applying a stable synthetic resin composition having an alkaline pH to porous materials and controlling the migration thereon which comprises: applying to porous materials a stable synthetic resin composition having an alkaline pH and comprising: (1) from about 0.1 percent to about 60 percent by weight on a solids basis of a synthetic resin; (2) from about 0.01 percent to about 5 percent by weight, based'on the weight of said synthetic resin of a polyvalent meta] complex coordination compound; (3) a water-soluble, ionically active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration 'of said polyvalent metal salt, said salt being capable of sequestering or precipitating the metal in said polyvalent metal complex coordination compound and being present in an amount of from about 5 percent to about percent molecular equivalent on a stoichiometric basis of said polyvalent metal and (4) a water-soluble polymeric carboxylic thickener; and substantially immediately destroying the stability of said
  • a method of applying a stable synthetic resin composition having an alkaline pH to porous materials and controlling the migration thereon which comprises: applying to porous materials a stable synthetic resin composition having an alkaline pH and comprising: (1) from about 0.1 percent to about 60 percent by weight on a solids basis of a synthetic resin; (2) from about 0.01 percent to about 5 percent by weight, based on the weight of said synthetic resin of a polyvalent metal complex coordination compound; (3) a water-soluble, ionically active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration of said polyvalent metal salt, said salt being capable of sequestering or precipitating the metal in said polyvalent metal complex coordination compound and being present in an amount of from about 5 percent to about percent molecular equivalent on a stoichiometric basis of said polyvalent metal; (4) a water-soluble polymeric carboxylic thickener; and (5) a surfactant, and substantially immediately

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US05260613 US3849173A (en) 1972-06-07 1972-06-07 Synthetic resin composition and methods of utilizing the same
IN1281/CAL/73A IN141141B (it) 1972-06-07 1973-05-31
SE7307897A SE414055B (sv) 1972-06-07 1973-06-05 Sett att pafora en syntetisk hartskomposition pa porosa material, serskilt textilmaterial och att reglera migreringen derpa
BR423873A BR7304238D0 (pt) 1972-06-07 1973-06-06 Composicao de resina sintetica e processo para aplicacao das mesmas
CA173,310A CA1003985A (en) 1972-06-07 1973-06-06 Synthetic resin compositions and methods of utilizing the same
ZA00733846A ZA733846B (en) 1972-06-07 1973-06-06 Improved synthetic resin compositions and methods of utilizing the same
NL7307902A NL7307902A (it) 1972-06-07 1973-06-06
GB2703473A GB1430126A (en) 1972-06-07 1973-06-06 Synthetic resin compositions and methods of utilizing the same
IT5049273A IT985335B (it) 1972-06-07 1973-06-06 Perfezionamento nelle composi zioni di resina sintetica e nei relativi procedimenti di impie go come leganti o adesivi
AU56678/73A AU470606B2 (en) 1972-06-07 1973-06-07 Improved synthetic resin compositions and methods of utilizing thesame
JP6458373A JPS4966722A (it) 1972-06-07 1973-06-07
AR24844573A AR198840A1 (es) 1972-06-07 1973-06-07 Composicion de resina sintetica para tratar materiales o fibras porosas o absorbentes y metodo de aplicacion
DE2329193A DE2329193A1 (de) 1972-06-07 1973-06-07 Kunststoffmasse mit einem alkalischen ph-wert und verfahren zu ihrer verwendung
FR7320844A FR2187828B1 (it) 1972-06-07 1973-06-07
US05/446,254 US3931085A (en) 1972-06-07 1974-02-27 Synthetic resin compositions
US05/575,560 USRE28957E (en) 1972-06-07 1975-05-08 Synthetic resin compositions and methods of utilizing the same
IN1282/CAL/76A IN144616B (it) 1972-06-07 1976-07-17
SE7803939A SE7803939L (sv) 1972-06-07 1978-04-07 Syntetiska hartskompositioner

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US4016312A (en) * 1974-05-30 1977-04-05 Akzo N.V. Method of coating a cellulosic substrate with an adherent polymeric coating
US4233345A (en) * 1979-04-23 1980-11-11 Johnson & Johnson Baby Products Company Thin-skin stabilization of pads of fluffed pulp
US4244991A (en) * 1975-12-15 1981-01-13 Toyota Jidosha Kogyo Kabushiki Kaisha Method of applying water paint
US4562097A (en) * 1980-05-09 1985-12-31 Union Carbide Corporation Process of treating fabrics with foam
US5549928A (en) * 1993-11-17 1996-08-27 The Procter & Gamble Company Process of making absorbent structures and absorbent structures produced thereby
US5840403A (en) * 1996-06-14 1998-11-24 The Procter & Gamble Company Multi-elevational tissue paper containing selectively disposed chemical papermaking additive
US6022610A (en) * 1993-11-18 2000-02-08 The Procter & Gamble Company Deposition of osmotic absorbent onto a capillary substrate without deleterious interfiber penetration and absorbent structures produced thereby
US20190315083A1 (en) * 2015-08-13 2019-10-17 Puma SE Method for producing a sports glove, particularly a goalkeeper's glove

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* Cited by examiner, † Cited by third party
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US4171391A (en) * 1978-09-07 1979-10-16 Wilmington Chemical Corporation Method of preparing composite sheet material
CA1269789A (en) * 1984-04-10 1990-05-29 Ronald James Thompson Copolymer latex impregnated non-woven web of fibers

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US3536518A (en) * 1967-03-10 1970-10-27 Johnson & Johnson Method of applying print pattern of resin to fibrous sheet material
US3539434A (en) * 1967-12-27 1970-11-10 Goodrich Co B F Nonwoven compositions having improved aging properties
US3578485A (en) * 1967-08-03 1971-05-11 Kuraray Co Method of producing a coated paper
US3594210A (en) * 1969-04-17 1971-07-20 Johnson & Johnson Method of controlling resin deposition on absorbent materials
US3647507A (en) * 1970-01-07 1972-03-07 Johnson & Johnson Resin composition containing a polyacrylic acid-polyacrylamide copolymer and method of using the same to control resin composition
US3650805A (en) * 1967-06-30 1972-03-21 Saburo Imoto Method of manufacturing coated paper
US3674726A (en) * 1970-09-04 1972-07-04 Scott Paper Co Paper coating composition coagulatable by heating
US3706595A (en) * 1971-01-22 1972-12-19 Johnson & Johnson Method of applying a resin binder to a substrate

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US3536518A (en) * 1967-03-10 1970-10-27 Johnson & Johnson Method of applying print pattern of resin to fibrous sheet material
US3649330A (en) * 1967-03-10 1972-03-14 Johnson & Johnson Composition containing metal salts and method of utilizing the same to control resin deposition
US3720562A (en) * 1967-03-10 1973-03-13 Johnson & Johnson A method of bonding non woven fabrics
US3650805A (en) * 1967-06-30 1972-03-21 Saburo Imoto Method of manufacturing coated paper
US3578485A (en) * 1967-08-03 1971-05-11 Kuraray Co Method of producing a coated paper
US3539434A (en) * 1967-12-27 1970-11-10 Goodrich Co B F Nonwoven compositions having improved aging properties
US3594210A (en) * 1969-04-17 1971-07-20 Johnson & Johnson Method of controlling resin deposition on absorbent materials
US3647507A (en) * 1970-01-07 1972-03-07 Johnson & Johnson Resin composition containing a polyacrylic acid-polyacrylamide copolymer and method of using the same to control resin composition
US3674726A (en) * 1970-09-04 1972-07-04 Scott Paper Co Paper coating composition coagulatable by heating
US3706595A (en) * 1971-01-22 1972-12-19 Johnson & Johnson Method of applying a resin binder to a substrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016312A (en) * 1974-05-30 1977-04-05 Akzo N.V. Method of coating a cellulosic substrate with an adherent polymeric coating
US4244991A (en) * 1975-12-15 1981-01-13 Toyota Jidosha Kogyo Kabushiki Kaisha Method of applying water paint
US4233345A (en) * 1979-04-23 1980-11-11 Johnson & Johnson Baby Products Company Thin-skin stabilization of pads of fluffed pulp
US4562097A (en) * 1980-05-09 1985-12-31 Union Carbide Corporation Process of treating fabrics with foam
US5549928A (en) * 1993-11-17 1996-08-27 The Procter & Gamble Company Process of making absorbent structures and absorbent structures produced thereby
US6022610A (en) * 1993-11-18 2000-02-08 The Procter & Gamble Company Deposition of osmotic absorbent onto a capillary substrate without deleterious interfiber penetration and absorbent structures produced thereby
US5840403A (en) * 1996-06-14 1998-11-24 The Procter & Gamble Company Multi-elevational tissue paper containing selectively disposed chemical papermaking additive
US6117525A (en) * 1996-06-14 2000-09-12 The Procter & Gamble Company Multi-elevational tissue paper containing selectively disposed chemical papermaking additive
US20190315083A1 (en) * 2015-08-13 2019-10-17 Puma SE Method for producing a sports glove, particularly a goalkeeper's glove

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AU5667873A (en) 1974-12-12
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IN141141B (it) 1977-01-22
SE414055B (sv) 1980-07-07
ZA733846B (en) 1975-01-29
NL7307902A (it) 1973-12-11
BR7304238D0 (pt) 1974-07-18
IN144616B (it) 1978-05-20
FR2187828B1 (it) 1978-09-15
DE2329193A1 (de) 1974-01-03
IT985335B (it) 1974-11-30
AU470606B2 (en) 1976-03-25
AR198840A1 (es) 1974-07-24
CA1003985A (en) 1977-01-18
GB1430126A (en) 1976-03-31
SE7803939L (sv) 1978-04-07

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