US3419422A - Paper sized with an isocyanate-modified silicone - Google Patents

Paper sized with an isocyanate-modified silicone Download PDF

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Publication number
US3419422A
US3419422A US523257A US52325766A US3419422A US 3419422 A US3419422 A US 3419422A US 523257 A US523257 A US 523257A US 52325766 A US52325766 A US 52325766A US 3419422 A US3419422 A US 3419422A
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Prior art keywords
paper
water
silicone
isocyanate
sizing
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US523257A
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Enrico J Pepe
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Union Carbide Corp
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Union Carbide Corp
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Priority to BE652572D priority Critical patent/BE652572A/xx
Priority to FR987069A priority patent/FR1406429A/fr
Priority to DE1493328A priority patent/DE1493328C3/de
Priority to NL6410323A priority patent/NL6410323A/xx
Priority to GB36331/64A priority patent/GB1084855A/en
Priority to US523257A priority patent/US3419422A/en
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Priority to GB3909/67A priority patent/GB1184742A/en
Priority to FR92759A priority patent/FR1509553A/fr
Priority to US707365A priority patent/US3584024A/en
Priority to US706701A priority patent/US3511866A/en
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Publication of US3419422A publication Critical patent/US3419422A/en
Priority to BE727989D priority patent/BE727989A/xx
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Assigned to MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. reassignment MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: STP CORPORATION, A CORP. OF DE.,, UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,, UNION CARBIDE CORPORATION, A CORP.,, UNION CARBIDE EUROPE S.A., A SWISS CORP.
Assigned to UNION CARBIDE CORPORATION, reassignment UNION CARBIDE CORPORATION, RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: MORGAN BANK (DELAWARE) AS COLLATERAL AGENT
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule

Definitions

  • the invention relates to paper making.
  • this invention is directed to a method for sizing paper or similar cellulosic fibers and the article of manufacture derived therefrom.
  • Cellulosic fibers constitute the bulk of finished paper.
  • a wide variety of internally contained or surface carried ingredients are employed to impart particular desired properties to the paper.
  • These ingredients include fillers such as clay, chalk, and other oxides or salts of metals, dyes and colorant materials, mordants, retention aids, wet strength agents, sizing agents, and the like.
  • Paper is sized in order to increase its resistance to penetration by liquids, particularly water.
  • the most common sizing system is rosi soap (sodium rosinate) and papermakers alum (aluminum sulfate).
  • rosi soap sodium rosinate
  • alum aluminum sulfate
  • hydrocarbon and natural waxes, starch, sodium silicate, glues, casein, synthetic resins, latices, etc. have been employed as sizing agents.
  • Silicones containing relatively large amounts of methylhydrogen siloxane heretofore have been reported as sizing agents for paper. Such materials suffer from three major shortcomings, however: (a) considerable time is required to develop lasting water resistance under conventional paper treating conditions, (b) the useful lift of the silicone is shortened to impractical time periods when the silicone is used in conjunction with catalysts 3,419,422 Patented Dec. 31, 1968 which shorten the necessary cure time, and (c) the presence of even small amounts of alum in the paper further retards the development of water resistance.
  • the sizing agents contemplated by the present invention contain no silanic hydrogen.
  • a further object of this invention is to provide a method for rending cellulosic materials adhesive.
  • the objects of this invention are achieved by sized cellulosic fibers, such as paper, characterized by the presence on at least the surface portion thereof of an isocyanate-rnodified silicone compound.
  • the isocyanatemodified silicone compound is present on the cellulosic substrate in an amount at least suflicient to enhance the resistance of the cellulosic substrate to wetting by an aqueous medium.
  • the amount of the isocyanate-modified silicone present in or on the final product depends on the intended end use of the product. As soon as some increase in resistance to wetting is discernible, as compared to the untreated state, the treated cellulosic fiber can be deemed sized.
  • the degree of sizing can be carried on until a substantially continuous layer of the sizing agent, i. e., the isocyanatemodified silicone, is deposited on the surface. In the latter case the porosity of the sized material is considerably reduced.
  • the material is sized to such a degree, i.e., hard sized, the material will exhibit release or abhesive, properties.
  • the thickness of the addition product layer on the surface of the sized cellulosic material usually does not exceed about one-half mil. Thicker layers can be produced of course; however, no additional commensurate benefits can be gained thereby.
  • the isocyanate-modified silicone compound loading typically can be in the range from about 0.2 to about 3 weight percent, based on the weight of the dry fibers.
  • the method of this invention can be practiced either before, during, or after the paper forming operation.
  • the isocyanate-modified silicone can be contacted with or applied to the paper fibers by itself, as a solution in a compatible solvent, or as an emulsion.
  • typical compatible solvents are the aliphatic or aromatic solvents such as hexane, mineral spirits, kerosene, toluene, xylene, and the like. Also compatible are the halogenated solvents such as perchloroethylene and the like.
  • any of the conventional anionic, cationic, non-ionic emulsifiers, or compatible mixtures thereof, may be utilized.
  • the amount and the exact type of emulsifier is generally determined by practical considerations with respect to the applyication procedure followed, emulsion stability, and minimum interference to the hydrophobing properties of the addition product.
  • nonionic emulsifiers such as polyvinyl alcohol, trimethylnonylpolyethyleen glycol/nonyl phenyl polyoxyethylene glycol ether blends, polyoxyethylene sorbitan monooleate,
  • Excellent emulsions exhibiting very good sizing properties have been obtained by premixing the non-ionic emulsifier, water, and the isocyanate-modified silicon compound in a suitable container and then passing the resulting admixture through a homogenizer at a relatively high (about 4500 p.s.i.) pressure.
  • wet end sizing The adition of the sizing agent to the paper fibers prior to the time when they are interfelted into a relatively low water content, self-supporting sheet is conventionally referred to as Wet end sizing.
  • dry end sizing the process is conventionally termed dry end sizing.
  • the sizing agent When, according to this invention, the sizing agent is applied to the Wet end of the papermaking process it can be applied in a water dispersible form such as ian aqueous emulsion, for example. As such it can be added to the water dispersed pulp at any time up until the fibers are picked up on the wire or cylinder of the paper machine. Preferably the addition is carried out after the beating operation which produces fibers from the starting material.
  • the optimum procedure for applying the sizing agent according to this invention at the dry end of the papermaking process depends on such factors as the type of papermaking equipment available, weight and speed of the paper, the desired degree of sizing, etc. Any conventional technique of application, such as a water box on a calender, tub sizing, size press, transfer roll, spraying, and the like, can be employed.
  • the conventional method comprises dipping the cloth in a treating bath which contains the sizing agent.
  • the sizing agents for the present invention are those isocyanate-modified silicone compounds which are (A) represented by the general formula Qu ]a SiX4(e+b) wherein Y can be a divalent or trivalent aliphatic or aromatic radical which is a member of the group consisting of a hydrocarbon, a hydrocarbon ester, and a hydrocarbon ether, the hydrocarbon portion of the foregoing being saturated or unsaturated;
  • Q can be an oxy (O-), thio (S), azo (N:N-),
  • NC-N carbamate substituted carbamate ureylene r t r
  • R can be a monovalent aliphatic hydrocarbon, a monovalent cycloaliphatic hydrocarbon, a monovalent aliphatic halohydrocarbon, or a monovalent cycloaliphatic halohydrocarbon radical;
  • R can be a divalent aliphatic or aromatic hydrocarbon radical which is a member of the group consisting of a hydrocarbon, a hydrocarbon ether, a hydrocarbon ester, and a hydrocarbon tertiary amine, the foregoing being with or without substituents containing no active hydrogen such as halo groups, nitro groups, oggo groups,
  • X can be a member of the group consisting of hydrogen, fluorine, chlorine, and hydrocarbonoxy (OR') groups; and a a has a value from 1 to 3 inclusive, b, has a value from 0 to 2 inclusive, with the proviso that the value of (a-f-b) is from 1 to 3 inclusive, d has a value from 1 to 2 inclusive, and e has a value from ()to 1 inclusive; (B) organosiloxane homopolyrners represented by the formula (II) R'b wherein Y, Q, R, R, a, b, d, and e represent the same groups and have the same numerical values specified in Formula I above; and (C) siloxane copolymers composed essentially of from about 0.1 to about 99.9 mole percent of units represented by Formula II and complementarily from about 99.9 to about 0.1 mole percent of units represented by the general formula wherein R" can be hydrogen or the same groups as represented by R in Formula 1 above, and
  • R Illustrative of the radicals represented by R are the straight or branched chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, nbutyl, isoamyl, hexyl, decyl, octadecyl and the like; the cyclic alkyl groups such as cyclopentyl, cyclohexyl, bicycloheptyl, and the like; the aryl groups such as phenyl, naphthyl, p-phenylphenyl, and the like; the alkaryl groups such as neophyl, tolyl, xylenyl, and the like; the aralkyl groups such as benzyl, phenylethyl, and the like, the haloalkyl groups such as chloromethyl, chloroethyl, bromoethyl, chlorohexyl, and the like; the haloary
  • R Illustrative of the radicals represented by R are the alkylene groups such as methylene, propylene, ethylethylene, octylene, and the like; the cycloaliphatic radicals such as and the like; the hydrocarbon ether groups such as CH CH OCH CH 'CH CH CH OCH CH(CH and the like; the hydrocarbyl ester groups such as -CH2CH(CH3) C"O"CH2GH2 OH2CH2CHn?
  • the alkylene groups such as methylene, propylene, ethylethylene, octylene, and
  • R is an alkylene group containing from 1 to about 22 carbon atoms or a phenylene up-
  • Illustrative of the radicals represented by Y are the alkylene groups such as ethylene, propylene, butylene, octylene, octadecylene, dodecylene, and the like; the alkylidene groups such as l-propanyl-B-ylidene, l-butanyl- 4-ylidene, and the like; the arylene groups such as phenylene, naphthenylene, and the like; the alkenylene groups such as vinylene, propenylene, and the like; the hydrocarbon ether groups such as CH CH OCH CH CH CH CH OCH CH(CH and the like; the hydrocarbon ester groups such as lLtOll NCO 2 (CHM NCO
  • copolymers and homopolymers can be in the form of cyclics, linear fluids, branched fluids, gums, etc., depending upon the functionality of the component units.
  • Particularly preferred as sizing agents for paper are 6 the isocyanate-modified silicone systems of the general type wherein R is an alkylene group; R is an alkyl group or an aryl group; Z is an alkoxy group, an aroxy group, or a siloxane group having the formula R SiO b can have a value from 0 to 2, inclusive; x can have a value from 1 to 10 and preferably from 1 to y can have a value from 1 to 10 and c has a value of with the further proviso that the ratio of y-t-c to x is not greater than 10 and preferably is in the range from about 5 to about 500.
  • these sizing agents can be prepared readily by contacting an aminohydrocarbylsilane or aminohydrocarbylsiloxane with phosgene, optionally in the presence of an inert organic solvent, at reaction temperatures to form the desired silicone isocyanate.
  • aminohydrocarbylsilanes are employed having the general formula wherein Y, Q, R, R", a, b, a, and e represent the same groups and values as in Formula I, and Z represents hydrogen or OR' groups.
  • the homopolymers and copolymers of Formulae II and III are prepared from the starting materials represented by the general formula KHZNMYQQR P w and aminohydrocarbylsiloxane copolymers represented by the general formula respectively, wherein Y, Q, R, R, a, b, d, e, and f represent the same groups and values as in Formulae II and III, and g and h are integers such that the units of the formula RSiO represent from 0.1 to 99.9 mole percent of the copolymer.
  • reaction of the aminoalkyl or aminoaryl silicone with phosgene proceeds by a two-step reaction in which the products of the first reaction are a canbamic acid chloride and an amine hydrochloride, which intermediates are each converted to the desired isocyanate by additional phosgene.
  • these reactions can be illustrated by the following (J representing the grouping YQ R supra): I? HzN-J-SiE 00012 HCLNHrJSiE ClC-NHJSi HCl'NIiZJSlE
  • the first reaction (1) is favored by relatively low temperatures, generally of the order of about C. to about C.
  • the seuond reaction (2) is generally favored by elevated temperatures.
  • reaction of phosgene with the amino group of the starting silicon compounds is favored, particularly at lower temperatures over the competing reaction of phosgene with any hydrocarbonoxy groups bonded to silicon which happen to also be present in the same starting compounds.
  • some hydrocarbonoxy substituents are converted to chlorine su'bstituents, thereby giving rise to a mixed reaction product which is readily separated by conventional procedures such as distillation.
  • Chlorine attached to silicon is readily replaced by fluorine by contacting the chlorine-containing product with sodium fiuorosilicate at moderately elevated temperatures.
  • a preferred means of obtaining intimate contact between the reactant materials is the utilization of an inert organic solvent medium in which at least the phosgene is soluble and preferably the aminohydrocarbyl silicone also.
  • inert organic solvent medium in which at least the phosgene is soluble and preferably the aminohydrocarbyl silicone also.
  • conventional solvents are toluene, benzene, chlorobenzene, 4-chloro-ethylbenzene, xylene, and carbon tetrachloride.
  • the solvent is a high boiling halogenated hydrocarbon.
  • superatrnospheric pressures can be employed, with provision being made for the removal of HCl from the reaction system. Reactions are generally carried out under normal atmospheric or slightly reduced pressures using an inert gas purge such as nitrogen or helium.
  • Paper to be sized can be made using any type of wood, pulping procedure, bleaching procedure, etc.
  • the paper can also contain fillers such as clay, titanium dioxide, calcium carbonate, and the like, and can also contain the conventional papermakers additives such as starch, rosin, and wet strength resins.
  • Typical types of paper that can be sized in accordance with the present invention are made from (1) reclaimed ground wood, (2) unbleached soft wood-kraft, (3) bleached soft wood and mixed hardwood; the soft woods having been prepared by the sulfate, sulfite, or soda process, (4) highly hydrated pulps supercalendered to a smooth, dense paper, and the like.
  • Sizing is complete as soon as the paper treated with the sizing agent in accordance with this inveniton has dried. It is usually not necessary to subject the treated paper to elevated temperatures to effect a cure. Of course, elevated temperatures can be employed during drying without any adverse effect provided the degradation temperatures of the fiber, paper or the sizing agent are not exceeded.
  • sizing is effective as soon as a sufficient amount of the sizing agent is deposited on the cellulosic fibers to enhance the wetting resistance of the paper as compared to that of an untreated sample of the same fibers.
  • relatively small amounts of the sizing agent are necessary to attain this end.
  • a satisfactory size of paper used for the manufacture of gypsum board was obtained with about 0.2 lb. of the instant sizing agent per one ton of lb./ 1000 sq. ft. paper.
  • the amount of the sizing agent necessary to impart abhesive properties to paper is dependent upon the porosity of the paper. Usually the loadings are in the range from about 0.01 to about 4 pounds of the sizing agent per 3000 square feet of paper. Loadings in the range from about 0.1 to about 2 pounds per 3000 square feet of paper are preferred.
  • a catalyst such as dibutyltin dilaurate can be utilized to enhance a cure if desired.
  • Other suitable catalysts are strong bases, nitrogen compounds such as triethylene diamine, tetramethyl guanidine, the N-alkylethyleneimines, etc., organotitanium compounds, organotin compounds, metals such as lead, iron, tin, and the like.
  • T ypica-l of such materials are starch, polyvinyl alcohol, carboxymethyl cellulose, gum, urea formaldehyde resins, melamine-formaldehyde resins, rosin, the sulfonium methyl sulfate salt of acrylic acid-acrylamide copolymers, amineepichlorohydrin derivatives, and the like.
  • the presence of the commonly employed wash-and-wear resins used in conjunction with cotton fabrics is not precluded.
  • Paper handsheets were made in a Noble and Wood sheetmold using a mixture of 50 wt. percent bleached kraft softwood and 50 wt. percent bleached sulfite softwood. About 25 wt. percent clay was also added to the foregoing mixture. The resulting paper sheets were then dried for about 3 minutes at about 88 C. F.) in a Noble and Wood drum drier. The paper weighed about 2.5 grams per handsheet or about 46 pounds per 3000 ft.
  • the diluted emulsion containing the isocyanate-modified silicone was then applied on the handsheets using a laboratory calender operating at about 400 ft./ min. and equipped with a water box on the lower roll so as to give a silicone loading on the handsheet of about 0.1 weight percent, based on the dry weight of the paper.
  • the paper was dried for about 3 minutes at about 88 C. (190 F.) and conditioned overnight at about 24 C. (75 R).
  • Water resistance was measured using a tester which indicates the time for water to penetrate the paper.
  • the time for water penetration was about 52 seconds whereas water penetrated an untreated sample of the same paper in less than one second.
  • the dilute silicone emulsion was then aged for about 7 hours at room temperature and then applied on paper in the aforedescribed manner.
  • the treated paper had a water penetration time of about 47 seconds which is within the experimental limits, i.e., the performance of the aged emulsion was about the same as that of the fresh emulsion. This demonstrates the stability of the paper sizing emulsion of this invention.
  • EXAMPLE II An aliquot of the emulsion prepared in Example I was admixed with cooked corn starch so as to obtain a starch to silicone ratio of about 13:1. The resulting blend was then diluted with water and applied to handsheets of 46 lb./ 3000 ft. paper. The paper was made from a pulp blend of 50 wt. percent sulfate softwood, 25 wt. percent sulfite softwood, and 25 wt. percent sulfite hardwood.
  • the starch/silicone blend was applied to the paper using a laboratory calender operating at about 200 ft./ min. and equipped with a water box so as to give a silicone loading on the paper of about 0.1 weight percent, based on the dry weight of the paper.
  • the paper was dried for about 3 minutes at about 88 C. (190 F.) using a drum drier.
  • the treated paper was tested for water repellency as. soon as it was removed from the drier by placing thereon drops of water.
  • the treated paper did not wet in 2 to 3 minutes which indicates good size. Without the treatment with the isocyanate-modified silicone the water drops wet the paper within several seconds.
  • EXAMPLE IH An aliquot of the emulsion prepared in Example I was applied to several types of paper using a laboratory calender equipped with a water box on the lower roll. In all cases the silicone loading on the treated paper was about 0.1 weight percent, based on the dry paper. After treating the paper was dried for about 3 minutes at about 88 C. (190 F.) and then conditioned for one dayat about 24 C. (75 F.) and 50% relative humidity. All of the treated paper was found to be water resistant, i.e., sized. The table below summarizes the types of paper treated.
  • the resulting paper was then dried for about 3 minutes at about 88 C. (190 F.).
  • the paper was water resistant as soon as it was dried.
  • Some of the paper manufactured in above manner was conditioned for about one day at about 24 C. (75 F.) and relative humidity and then tested for water resistance.
  • the time needed. for Water to penetrate the treated paper was in the range from about 35 to about 80 seconds.
  • the time needed for water to penetrate an untreated sample of similar paper was less than one second.
  • EXAMPLE V The isocyanate-modified silicone having the general formula (CHMNCO 2 was emulsified in water withabout 3 weight percent of trimethylnonylpolyethylene glycol ether and about 2 weight percent of nonylphenylpolyethylene glycol ether, based on the weight of the silicone present. To the resulting emulsion then was added the sulfonium methyl sulfate salt of an acrylic acid-'acrylamide copolymer as a retention aid (about 20 weight percent, based on the weight of silicone).
  • CHMNCO 2 The isocyanate-modified silicone having the general formula (CHMNCO 2 was emulsified in water withabout 3 weight percent of trimethylnonylpolyethylene glycol ether and about 2 weight percent of nonylphenylpolyethylene glycol ether, based on the weight of the silicone present.
  • sulfonium methyl sulfate salt of an acrylic acid-'acrylamide copolymer as a retention aid
  • the thus prepared emulsion was then admixed with a pulp suspension (50 wt.-percent bleached kraft, 25 Wt. percent bleached, sulfite, and 25 wt.-percent bleached soda hardwood) also containing about 20 wt.-percent clay and about 5 wt.-percent corn starch, based on the dry weight of pulp.
  • the pulp was at a consistency of about 23.7 grams per 18 liters of the suspension and the silicone concentration in the pulp suspension was about 0.5 weight percent, based on the dry weight of the pulp.
  • Unbleached graft pulp was beaten to a Canadian Freeness of about 505 ml. and diluted to about 23.7 grams of pulp per 18 liters of tap water. To the diluted pulp suspension then was added the above silicone emulsion in an amount to give a silicone concentration of about 0.5 weight percent, based on the pulp.
  • the thus produced paper was then conditioned for about one day at about 24 C. F.) and 50% relative humidity and then its water resistance was evaluated.
  • the time needed for water to penetrate the treated paper was in the range from about 41 to about 52 seconds.
  • the time needed for water to penetrate an untreated sample of similar paper was found to be less than one seconds.
  • EXAMPLE VI An isocyanate-modified silicone having the general formula K ahsiOhao 1 l 12 was emulsified in water with about weight percent of N- pellency using the AATCC Spray Test (Method 22-1952) cetylethylmorpholinium ethosulfate, based on the weight whereby 250 ml. of water is sprayed on the cloth and the of the solicone present. cloth evaluated for water repellency.
  • the pulp was at a consistency water temperature of about 71 C. (160 F.), and washof about 23.7 grams per 18 liters of the suspension, and 10 ing cycle A. After each wash cycle the cloth was air dried.
  • Paper produced using the recycled White water was conditioned for about one day at about 24 C. (75 F.)
  • Emulsions were prepared from an isocyanate-modified silicone compound (about 20 parts by weight), polyoxyethylene esters of mixed fatty acids and resin acids (about 1 part by weight), N-cetylethyl morpholinium ethosulfate (about 1.1 parts by weight), and water (about 78 parts by weight).
  • a control emulsion was prepared ream glassine Paper using an applicator bat made by 3 slhcone on having the general formula wrapping a steel rod (No.
  • the glassine paper treated in the aforedescribed man- A first catalyst emulsion was prepared by admixing dinor was then tested for water repellency and for abhesive butyltin dilaurate (about 37.5 parts by weight), polyoxyor release properties.
  • ethylene sorbitan monooleate about 2.96 parts by on the treated paper no wetting was observed, whereas weight
  • a mixture of monoand di-glycerides of fatuntreated paper was readily wetted by a water drop.
  • fatty acids about 0.74 part by weight
  • wapressure sensitive cellophane tape was applied to the surter (about 57.8 parts by weight).
  • a second catalyst emul- 60 face of the treated paper, firmly pressed on by rubbing the sion was prepared by admixing zinc octoate (about 39 applied tape with a finger, and subsequentlyremoved, the parts by weight), polyoxyethylene sorbitan monooleate removal was very easy, and no paper fibers were stuck (about 3.12 parts by weight), a mixture of monoand dito the removed tape.
  • zinc octoate about 39 applied tape with a finger, and subsequentlyremoved, the parts by weight
  • polyoxyethylene sorbitan monooleate removal was very easy, and no paper fibers were stuck (about 3.12 parts by weight), a mixture of monoand dito the removed tape.
  • carglycerides of fat-forming fatty acids about 0.78 part by ried out with untreated glassine paper the removal of weight
  • water about 57.1 parts by weight
  • Th6 aqueous emulsion was then PP t0 commel'clal 3.
  • the treated paper was observed to be water repellent.
  • CHmNCO Pressure sensitive cellophane tape when applied to the li(OC2H5)2 [wfimsiolm treated paper, released easily without any pickup of paper o fibers, and subsequently did adhere to untreated paper L l 2 when applied thereto.
  • the surgical adhesion tape did nOt pick isocyanate thef ein directly bonded to organo group up any fibers upon removal from the treated paper and which in turn jis bonded to silicon of the silicone by a did adhere to untreated paper when applied thereto subcarbon t ili b sequent to the removal of the surgical tape from the surface of the treated paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Silicon Polymers (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US523257A 1963-09-06 1966-01-27 Paper sized with an isocyanate-modified silicone Expired - Lifetime US3419422A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
BE652572D BE652572A (enrdf_load_stackoverflow) 1963-09-06 1964-09-02
FR987069A FR1406429A (fr) 1963-09-06 1964-09-03 Composés isocyaniques d'organosilicium et leur procédé de préparation
DE1493328A DE1493328C3 (de) 1963-09-06 1964-09-04 Isocyanatgruppen enthaltende Organopolysiloxane und Verfahren zu deren Herstellung
NL6410323A NL6410323A (enrdf_load_stackoverflow) 1963-09-06 1964-09-04
GB36331/64A GB1084855A (en) 1963-09-06 1964-09-04 Organosilicon isocyanate compounds and process for preparing same
US523257A US3419422A (en) 1963-09-06 1966-01-27 Paper sized with an isocyanate-modified silicone
GB3909/67A GB1184742A (en) 1963-09-06 1967-01-26 Modified Cellulosic Fibres and Fibrous Products having Resistance to Wetting by Aqueous Media
FR92759A FR1509553A (fr) 1963-09-06 1967-01-27 Fibres cellulosiques encollées au moyen de silicones modifiées par un isocyanate
US707365A US3584024A (en) 1963-09-06 1968-02-07 Condensable isocyanato substituted siloxanes and phosgenation process for making same
US706701A US3511866A (en) 1963-09-06 1968-02-07 Isocyanatoalkyl halo silanes and methods for making same
BE727989D BE727989A (enrdf_load_stackoverflow) 1963-09-06 1969-02-06

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30700363A 1963-09-06 1963-09-06
US523257A US3419422A (en) 1963-09-06 1966-01-27 Paper sized with an isocyanate-modified silicone

Publications (1)

Publication Number Publication Date
US3419422A true US3419422A (en) 1968-12-31

Family

ID=26975488

Family Applications (1)

Application Number Title Priority Date Filing Date
US523257A Expired - Lifetime US3419422A (en) 1963-09-06 1966-01-27 Paper sized with an isocyanate-modified silicone

Country Status (6)

Country Link
US (1) US3419422A (enrdf_load_stackoverflow)
BE (1) BE652572A (enrdf_load_stackoverflow)
DE (1) DE1493328C3 (enrdf_load_stackoverflow)
FR (1) FR1509553A (enrdf_load_stackoverflow)
GB (2) GB1084855A (enrdf_load_stackoverflow)
NL (1) NL6410323A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0099049A1 (en) * 1982-07-06 1984-01-25 Dow Corning Corporation Method for preparing silicone-treated starch
US4495226A (en) * 1982-07-06 1985-01-22 Dow Corning Corporation Method for preparing silicone-treated starch
US20160024243A1 (en) * 2013-03-15 2016-01-28 Hempel A/S Polysiloxane modified polyisocyanates for use in coatings
CN109336917A (zh) * 2013-06-04 2019-02-15 塞勒创尼克斯公司 腈-取代的硅烷和电解质组合物和包含它们的电化学装置
CN113292591A (zh) * 2021-06-23 2021-08-24 唐山三孚新材料有限公司 1,3-双(异氰酸酯基烷基)-1,1,3,3-四甲基二硅氧烷的合成方法与应用
CN116351338A (zh) * 2021-12-27 2023-06-30 万华化学集团股份有限公司 一种光气法制备异氰酸酯基烷氧基硅烷的系统和方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5831110A (en) * 1997-10-23 1998-11-03 Chisso Corporation Fluorine-containing siloxane compound and process for production thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2893898A (en) * 1956-01-16 1959-07-07 Bradford Dyers Ass Ltd Method of rendering materials water-repellent
US3012006A (en) * 1958-04-24 1961-12-05 Dow Corning Fluorinated alkyl silanes and their use
US3170891A (en) * 1962-09-14 1965-02-23 Dow Corning Silicone isocyanates
US3178391A (en) * 1958-10-31 1965-04-13 Bayer Ag Isocyanates and isothiocyanates and a process for producing the same
US3179622A (en) * 1962-03-26 1965-04-20 Dow Corning Polysiloxane isocyanates
US3179713A (en) * 1962-03-26 1965-04-20 Dow Corning Organopolysiloxane isocyanate composition for imparting scuff resistance and water repellency to leather

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2893898A (en) * 1956-01-16 1959-07-07 Bradford Dyers Ass Ltd Method of rendering materials water-repellent
US3012006A (en) * 1958-04-24 1961-12-05 Dow Corning Fluorinated alkyl silanes and their use
US3178391A (en) * 1958-10-31 1965-04-13 Bayer Ag Isocyanates and isothiocyanates and a process for producing the same
US3179622A (en) * 1962-03-26 1965-04-20 Dow Corning Polysiloxane isocyanates
US3179713A (en) * 1962-03-26 1965-04-20 Dow Corning Organopolysiloxane isocyanate composition for imparting scuff resistance and water repellency to leather
US3170891A (en) * 1962-09-14 1965-02-23 Dow Corning Silicone isocyanates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0099049A1 (en) * 1982-07-06 1984-01-25 Dow Corning Corporation Method for preparing silicone-treated starch
US4495226A (en) * 1982-07-06 1985-01-22 Dow Corning Corporation Method for preparing silicone-treated starch
US20160024243A1 (en) * 2013-03-15 2016-01-28 Hempel A/S Polysiloxane modified polyisocyanates for use in coatings
CN109336917A (zh) * 2013-06-04 2019-02-15 塞勒创尼克斯公司 腈-取代的硅烷和电解质组合物和包含它们的电化学装置
CN113292591A (zh) * 2021-06-23 2021-08-24 唐山三孚新材料有限公司 1,3-双(异氰酸酯基烷基)-1,1,3,3-四甲基二硅氧烷的合成方法与应用
CN116351338A (zh) * 2021-12-27 2023-06-30 万华化学集团股份有限公司 一种光气法制备异氰酸酯基烷氧基硅烷的系统和方法

Also Published As

Publication number Publication date
DE1493328A1 (de) 1969-04-24
BE652572A (enrdf_load_stackoverflow) 1964-12-31
GB1084855A (en) 1967-09-27
DE1493328C3 (de) 1978-04-06
GB1184742A (en) 1970-03-18
NL6410323A (enrdf_load_stackoverflow) 1965-03-08
FR1509553A (fr) 1968-01-12
DE1493328B2 (de) 1977-08-11

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