Patent GB-604904-A (GB)
Title: Emulsions and their use in forming water-resistant film coatings
IPC: C09D103/00
Filed: 1943-04-21
Abstract: A film-forming emulsion comprises a water-immiscible phase and an aqueous phase, the latter containing a water-dispersible film-forming polyhydroxylated substance convertible to a less water-soluble film by drying in the presence of a water-insolubilising agent therefor comprising an antimony compound reactive therewith, which compound is also present in the aqueous phase.  The emulsion is advantageously of the oil-in-water type and may contain a dye or pigment or components thereof.  Specified film-forming substances are starch and its degradation products (e.g. dextrines, enzyme-modified starches, chlorinated or oxidized starches), natural gums (e.g. locust bean gum or gum tragacanth), polyvinyl alcohols, and mixtures thereof; and the antimony compound may be antimonious oxide, or especially a compound containing pentavalent antimony, e.g. sodium antimonate, the acid and neutral potassium pyroantimonates, antimony pentoxide, orthoantimonic acid and the precipitate obtained from reaction of aqueous solutions of potassium pyroantimonate and antimony trifluoride or antimony lactate. Specified water-immiscible liquids are aliphatic and hydrogenated petroleum hydrocarbons, benzene, toluene, xylene, terpenes and alcohols or esters having no solvent action on the dyes if used. The water-immiscible phase may also have dissolved therein a binder, e.g. ethyl cellulose, cellulose acetate, nitrocellulose, rubber, polymerized butadiene or chloroprene, polymerized olefines, natural resins such as gum dammar, bodied fatty oils and synthetic resins of the cumarone, indene, glyceryl phthalate, phenol-formaldehyde and urea-formaldehyde types; such binder may or may not be plasticised.  The polyhydroxylated material may contain auxiliary agents for specific purposes, such as thinning agents (e.g. enzymes or various salts or other compounds, such as sodium silicofluoride, antimony trifluoride, ammonium oxalate, sodium perborate or persulphate, or citric, lactic or acetic acid) or plasticising agents.  The products may be used as coating compositions for a variety of materials, including sheet materials, board-like products and fabricated articles such as boxes, bottles or tubes.  In examples: (1) an aqueous phase prepared by mixing chlorinated corn starch, locust bean gum and potassium pyroantimonate, dissolving them in water and adding an emulsifying agent, e.g. sodium lauryl sulphate, and an oil or solvent phase, e.g. a solution of a sodium alkyl sulphonate such as Twitchell oil XXX in a hydrogenated petroleum hydrocarbon, are homogenized to form an oil-in-water emulsion, and, if desired, a dye, e.g. Aridye SX Green (the word "Aridye" is a Registered Trade Mark), is added; (2) as in (1) but with the addition to the oil phase of a binder, e.g. a low viscosity ethyl cellulose; (3) an oil phase made by adding copper naphthenate to Varsol (hydrocarbon oil) is emulsified in the aqueous phase of (1) with the addition of Modinal D emulsifying agent (the word "Modinal" is a Registered Trade Mark), after which Aridye Green DX colour (a water-immiscible solvent-dispersed pigment dye containing an oil-soluble resin) is added, and during the addition the emulsion is reversed to a water-in-oil type.ALSO:A film-forming emulsion comprises a water-immiscible phase and an aqueous phase, the latter containing a water-dispersible film-forming polyhydroxylated substance convertible to a less water-soluble film by drying in the presence of a water-insolubilising agent therefor comprising an antimony compound reactive therewith, which compound is also present in the aqueous phase.  The emulsion is advantageously of the oil-in-water type, and may contain a dye or pigment or components thereof.  Specified film-forming substances are starch and its degradation products (e.g. dextrines, enzyme-modified starches, chlorinated or oxidized starches), natural gums (e.g. locust bean gum or gum tragacanth), polyvinyl alcohols, and mixtures thereof; and the antimony compound may be antimonious oxide, or especially a compound containing pentavalent antimony, e.g. sodium antimonate, the acid and neutral potassium pyroantimonates, antimony pentoxide, orthoantimonic acid and the precipitate obtained from reaction of aqueous solutions of potassium pyroantimonate and antimony trifluoride or antimony lactate. Specified water-immiscible liquids are aliphatic and hydrogenated petroleum hydrocarbons, benzene, toluene, xylene, terpenes and alcohols or esters having no solvent action on the dyes if used. The water-immiscible phase may also have dissolved therein a binder, e.g. ethyl cellulose, cellulose acetate, nitro-cellulose, rubber, polymerised butadiene or chloroprene, polymerised olefines, natural resins such as gum dammar, bodied fatty oils and synthetic resins of the cumarone, indene, glyceryl phthalate, phenol-formaldehyde and urea-formaldehyde types; such binder may or may not be plasticised.  The polyhydroxylated material may contain auxiliary agents for specific purposes, such as thinning agents (e.g. enzymes or various salts or other compounds such as sodium silicofluoride, antimony trifluoride, ammonium oxalate, sodium perborate or persulphate, or citric, lactic or acetic acid) or plasticizing agents.  The products are applicable particularly in the printing of textiles, but also for coating, impregnating, sizing, finishing and otherwise treating a variety of materials, e.g. woven, knit and sheet materials made from cellulose, linen, wool, cellulose esters and ethers and synthetic polyamides.  In examples: (1) an aqueous phase prepared by mixing chlorinated corn starch, locust bean gum and potassium pyroantimonate, dissolving them in water and adding an emulsifying agent, e.g. sodium lauryl sulphate, and an oil or solvent phase, e.g. a solution of a sodium alkyl sulphonate such as Twitchell oil in a hydrogenated petroleum hydrocarbon, are homogenized to form an oil-in-water emulsion, and, if desired, a dye, e.g. Aridye SX Green (the word "Aridye" is a Registered Trade Mark), is added; the product may be used for coating previously dyed materials, or, when a dye is present, for printing textiles, e.g. cotton fabric; (2) as in (1), but with the addition to the oil phase of a binder, e.g. a low viscosity ethyl cellulose; (3) an oil phase made by adding copper naphthenate to Varsol (hydrocarbon oil) is emulsified in the aqueous phase of (1) with the addition of Modinal D emulsifying agent (the word "Modinal" is a Registered Trade Mark), after which Aridye Green DX colour (a water-immiscible solvent-dispersed pigment dye containing an oil-soluble resin) is added, and during the addition the emulsion is reversed to a water-in-oil type; the dye may be replaced by Monastral Green B (chlorinated copper phthalocyanine), Monastral Blue BF (copper phthalocyanine), Lithosol Pink, red iron oxide or yellow ochre; the product may be used for printing camouflage material.  Other dyes and components specified are vat dyes and their leuco esters (e.g. sulphuric esters), Heliogen colours, and stabilized mixtures of diazo compounds and naphthol coupling components (including naphthoic acid derivatives), or the diazo compound alone, the coupling component being applied separately.ALSO:A film-forming emulsion comprises a water-immiscible phase and an aqueous phase, the latter containing a water-dispersible film-forming polyhydroxylated substance convertible to a less water-soluble film by drying in the presence of a water-insolubilising agent therefor comprising an antimony compound reactive therewith, which compound is also present in the aqueous phase.  The emulsion is advantageously of the oil-in-water type, and may contain a dye or pigment or components thereof. Specified film-forming substances are starch and its degradation products (e.g. dextrines, enzyme-modified starches, chlorinated or oxidized starches), natural gums (e.g. locust bean gum or gum tragacanth), polyvinyl alcohols, and mixtures thereof; and the antimony compound may be antimonious oxide, or especially a compound containing pentavalent antimony, e.g. sodium antimonate, the acid and neutral potassium pyroantimonates, antimony pentoxide, orthoantimonic acid and the precipitate obtained from reaction of aqueous solutions of potassium pyroantimonate and antimony trifluoride or antimony lactate.  Specified water-immiscible liquids are aliphatic and hydrogenated petroleum hydrocarbons, benzene, toluene, xylene, terpenes and alcohols or esters having no solvent action on the dyes if used.  The water-immiscible phase may also have dissolved therein a binder, e.g. ethyl cellulose, cellulose acetate, nitro - cellulose, rubber, polymerised butadiene or chloroprene, polymerised olefines, natural resins such as gum dammar, bodied fatty oils and synthetic resins of the cumarone, indene, glyceryl phthalate, phenol-formaldehyde and urea-formaldehyde types; such binder may or may not be plasticised.  The polyhydroxylated material may contain auxiliary agents for specific purposes, such as thinning agents (e.g. enzymes or various salts or other compounds such as sodium silicofluoride, antimony trifluoride, ammonium oxalate, sodium perborate or persulphate, or citric, lactic or acetic acid) or plasticising agents.  The products are applicable particularly in the printing of textiles, but also for coating, impregnating, sizing, finishing and otherwise treating a variety of materials, e.g. woven, knit and sheet materials made from cellulose linen, wool, cellulose esters and ethers and synthetic polyamides.  In examples: (1) an aqueous phase prepared by mixing chlorinated corn starch, locust bean gum and potassium pyroantimonate, dissolving them in water and adding an emulsifying agent, e.g. sodium lauryl sulphate, and an oil or solvent phase, e.g. a solution of a sodium alkyl sulphonate such as Twitchell oil XXX in a hydrogenated petroleum hydrocarbon, are hom