US3238010A - Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts - Google Patents

Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts Download PDF

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Publication number
US3238010A
US3238010A US102085A US10208561A US3238010A US 3238010 A US3238010 A US 3238010A US 102085 A US102085 A US 102085A US 10208561 A US10208561 A US 10208561A US 3238010 A US3238010 A US 3238010A
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Prior art keywords
paper
weight
parts
latex
ionic
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US102085A
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Emile E Habib
Nimoy Melvin
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WR Grace and Co
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WR Grace and Co
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Priority to GB940771D priority Critical patent/GB940771A/en
Priority to DEG29738A priority patent/DE1165987B/de
Priority to FR828845A priority patent/FR1258646A/fr
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Priority to US102085A priority patent/US3238010A/en
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Classifications

    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D21H17/08—Isocyanates
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene

Definitions

  • This invention relates to a method of treating paper to improve the physical properties of the same.
  • the basic difliculty with this process is that it was found necessary, in each and every case, to dissolve the isocyanate in a non-reactive solvent in order to use the isocyanate in the treatment of paper. If this is not done, the isocyanate, when used for treatment, reacts predominantly at a fairly rapid rate, with the active hydrogens present in the latex system, forming insoluble di-urea compounds. When this happens, a substantial quantity of the isocyanate is consumed and thereby becomes unavailable to cross-link the elastomeric polymer and the paper.
  • our process comprises treating a sheet of paper with a latex containing a polyfunctional isocyanate in unreactive form, and then regenerating the isocyanate in active form, while in contact with the paper.
  • a polyfunctional isocyanate in unreactive form, and then regenerating the isocyanate in active form, while in contact with the paper.
  • all polyfunctional isocyanates are herein referred to as isocyanate.
  • our process comprises impregnating a sheet of paper with a latex containing an isocyanate in unreactive form, drying the paper at a temperature below 140 C., and heating the impregnated paper to a temperature above 140 C. to regenerate the isocyanate in a form which is reactive to both the cellulosic fibers in the paper and the elastomeric chain in the latex.
  • an isocyanate in unreactive form is incorporated into the aqueous latex most generally by means of an emulsion.
  • the isocyanate is one in which the reactive groups of the isocyanate molecule have been rendered inactive at ordinary temperatures by the formation of a chemical complex, which complex when heated, decomposes to regenerate the isocyanate molecule in the freely reactive form. Paper is thus impregnated with latex containing this isocyanate in unreactive form. Subsequently, this treated sheet is dried and then is heated and the isocyanate groups contained therein are thereby regenerated.
  • cmpounds which contain free isocyanate groups are, most generally, very reactive compounds and that the free isocyanate groups of these types of compounds will react with practically any active hydrogen compound, i.e. a compound containing a hydrogen which may normally be replaced with sodium.
  • the free isocyanate groups even react with the hydrogen and hydroxyl groups present in the cellulosic chain of the paper and in the elastomeric chain of the polymer.
  • the cellulosic fibers appear to be interconnected to each other by means of elastorneric chains which tie the fibers into a network wherein the elastomeric chains are bonded to the cellulosic fibers by means of urethane bonds.
  • ISOCYANATES There are many organic molecules containing isocyanate groups which will react with the polymer in the latex and with the cellulose fibers in the paper. In general, any of the polyisocyanates in the following classes, due to their chemical nature are reactive With groups containing e: an active hydrogen.
  • Suitable isocyanates include the aliphatic diisocyanates such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propylene- 1,2 butylene-1,2, butylene-2,3, butylene-1,3, ethylidene, and butylidene diisocyanate; the aromatic diisocyanates such as m-phenylene, p-phenylene, 4,4-diphenyl, 1,5- naphthalene, and 1,4-naphthalene diisocyanate; the cycloalkylene diisocyanates such as cyclopentylene-l,3, cyclohexylene-l,4, and cyclohexylene-1,2; the aliphatic aromatic diisocyanates such as 4,4-diphenylene methane, 2,4- tolylene, 4,4-tolidene, and 1,4-xylylene diisocyanate; the nuclear substituted aromatic isocyanates such as
  • the active isocyanate group is reacted with a chemical agent which renders the isocyanate group inactive at ordinary temperatures, but which degenerates thereby regenerating the isocyanate, in active form, upon heating to temperatures above about 140 C.
  • a chemical agent which renders the isocyanate group inactive at ordinary temperatures, but which degenerates thereby regenerating the isocyanate, in active form, upon heating to temperatures above about 140 C.
  • aceto-acetic ester diethylmalonate
  • mercaptans such as 2-mercapto-benzothiazole
  • lactams such as epsilon-caprolactams, delta-valerolactam, gamma-butyrolactam, and beta-propiolactam
  • imides such as succinimide and phthalimide
  • tertiary alcohols such as ter-amyl, tertiary butyl, dimethyl ethenyl carbinol, dimethyl phenyl carbinol, methyl diphenyl carbinol, triphenyl carbinol, 1- nitro tertiary butyl carbinol, l-chlorotertiary butyl carbinol, and triphenyl silinol
  • secondary aromatic amines such as diphenyl-amine
  • diaryl compounds such as diphenylamine, o-ditolyl amine, m-
  • the polymeric latices used in this treatment must be non-ionic in nature. It has been found that the stability of the blocked isocyanate to premature cleavage is excellent in non-ionic latices and poor in either anionic or cationic latices.
  • the polymeric systems, which are used, however, must contain labile hydrogen or hydroxy groups with which the isocyanate, when regenerated in active form, may react.
  • the polymeric latices which are preferably used are polymers which can be made in non-ionic systems. Examples of non-ionic latices are those containing polyvinyl acetate, copolymers of vinyl acetate, and copolymers of butadiene-acrylonitrile such as that commercially available under the trade name of Hycar 1872.
  • the reactivity of the polymeric system may be further enhanced by increasing the number of labile hydrogen or hydroxy groups present in the system. This may be accomplished, in the case of polyvinyl acetate, by a partial hydrolysis of the system. It may also be accomplished, in the case of both polymers and copolymers of vinyl acetate, by introducing reactive groups into the molecule during the polymerization of the monomer, such as by incorporating hydroxy bearing emulsifying agents into the reactive charge during the emulsion polymerization of the monomer. It has been noted that only about 50% of such hydroxy bearing material has been recovered after the polymerization reaction has been completed indicating that the hydroxy bearing material, which has not been recovered, had been incorporated into the polymer. There are a number of hydroxy bearing materials which may be used for this grafting technique, such as polyvinyl alcohol, hydroxy-ethyl cellulose and carboxymethyl cellulose.
  • the paper which is to be treated by this method should be sufficiently porous that the ingredients of the impregnating composition will not be filtered out by the paper during treatment.
  • the minimum degree of necessary porosity is controlled by the particle size of the particular polymer present in the latex. Particle size, of course, varies depending not only on the method of producing the polymer but also on the specific monomers used in the process. Since the method of producing suitable porous papers is an art itself which is well known to the paper industry it is not considered necessary to consider this subject in detail.
  • the isocyanate material in the unreactive or blocked state is introduced into the latex in the form of a dispersion or of an emulsion in water.
  • a dispersion in water may be formed by ball milling the blocked isocyanates in the presence of water and a dispersion agent.
  • a rather satisfactory emulsion may be formed by dissolving the blocked isocyanate in ethyl acetate, and then adding the solution to a warm aqueous solution containing sodium alkyl naphthalene sulfate, alkyl aryl sodium sulfonate, and ammonium caseinate.
  • the ammonium caseinate functions as a stabilizer for the emulsion
  • the sodium naphthalene sulfate functions as a wetting agent for the system
  • the alkyl aryl sodium sulfonate functions as a dispersing agent for the organic phase.
  • the paper may be impregnated with the impregnation compound in a number of ways. These include beater impregnation, wet web impregnation and dry web impregnation. For convenience the examples that follow were made by dry web impregnation by passing paper through a bath containing the latex solution in which the blocked isocyanate was dispersed. After impregnation, the paper was further processed by passing the same through a conventional press or calender in order to squeeze out the excess impregnant. Subsequently, this paper was heated at a low temperature to substantially dry it and then heated to a temperature between about 100 C. and 180 C.
  • the following examples show how various blocked isocyanates are dispersed in a vinyl acetate copolymer latex and how these dispersions are used to treat paper. All formulations given herein are on the dry base for all ingredients. The treated sheets were then conditioned by maintaining them at a temperature of about F. and a relative humidity of about 50% for 14 to 16 hours. After conditioning, the treated sheets were tested to determine their tensile strength.
  • Example I a blocked isocyanate was emulsified and then dispersed in a vinyl acetate copolymer latex which was later used to treat paper.
  • Example I 50 parts by weight of the reaction product of toluene, 2,4-diisocyanate, trimethylol propane and phenol were ground into a coarse powder and disolved in ethyl acetate. This solution was then emulsified in another solution containing 3 parts by weight of ammonium caseinate, 5 parts by weight of sodium alkyl naphthalene sulfate, and 0.5 part by weight of alkyl aryl sodium sulfonate dissolved in 23 parts by weight of warm water. The emulsion was then homogenized and stirred until the temperature of the emulsion was below about 110 F.
  • Table I sets forth the results obtained when the amount of blocked isocyanate in the system is varied.
  • the papers were impregnated at a level of about 20 parts by weight of polymer per 100 parts by weight of paper. It is clear that the wet tensile strength and wet elongation of the impregnated paper increase as the amount of blocked isocyanate in the impregnant is increased. The increase in wet tensile is quite rapid as the amount of isocyanate is increased to 20 parts by weight. The optimum amount of isocyanate in the impre'gnant is between and parts by weight. The wet tensile strength of a sheet treated with such an impregnant would be 8 to 9 times that of a control sheet which was not treated with isocyanate. Also, the effect on elongation closely follows that of the tensile.
  • Example 11 10 parts by weight of the reaction product of toluene 2,4-diisocyanate, trimethylol propane and phenol were emulsified as set forth in Example I. This emulsion was then added to 100 parts by weight of a mixture which contained varying ratios of a vinyl acetate copolymer latex (same as that used in Example I) and a resinous material commercially available under the tradename of Piccopale N-2. Sheets of impregnated base paper were then treated, conditioned and tested as heretofore set forth.
  • Dry Dry Wet 1 Expressed as parts by weight of impregnant. 2 Expressed as pounds per inch. 3 Expressed as percent.
  • Example 111 5 parts by weight of the reaction product of toluene 2,4-diisocyanate, trimethylol propane, and phenol was emulsified as set forth in Example I. This emulsion was then added to 100 parts by weight of a polyvinyl acetate latex (same as that used in Example I). Sheets of impregnated paper were then treated at various levels of impregnation, conditioned and tested as heretofore set forth.
  • Example IV Varying amounts of the reaction product of toluene 2,4-diisocyanate, trimethylol propane, and phenol were dispersed in 100 parts by weight of a vinyl acetate copolymer latex by means of a ball mill.
  • the latex used was the same as that described in Example I. Sheets of impregnation base paper were then treated with this dispersion, conditioned and tested as heretofore described.
  • Example IV the wet tensile strength of sheets treated by the emulsion technique (set forth in Example I) were compared with sheets treated by the technique used in Example IV.
  • the significant difference between these two methods is the manner in which the blocked isocyanate is dispersed in the latex.
  • These papers were impregnated at a level of about 22 parts by weight per It appears that no matter which technique is used the wet tensile strength of 21 treated sheet is greater than that of a control sheet which did not contain isocyanate.
  • the method of dispersing the isocyanate in the latex appears to have a significant effect on the Wet tensile strength of the sheet.
  • the wet tensile strength of a sheet treated according to procedure set forth in Example I is greater than a sheet treated by this procedure because the blocked isocyanate is more finely distributed in the latex when it is in emulsified form.
  • Example V the diphenylamine adduct of toluene 2,4-diisocyanate was prepared, emulsified and then dispersed in a vinyl acetate copolymer latex which was later used to treat paper.
  • Example V 17.4 grams toluene 2,4-diisocyanate were dissolved in 1000 ml. of toluene, 34 grams of diphenylamine were then added to this solution and it was stirred for 2 hours and then allowed to stand for 12 hours. The toluene was then distilled from the liquid at which time the liquid was cooled to 20 C. and filtered to separate the precipitate.
  • Example II 4 parts by weight of this isocyanate emulsion (parts in this case meaning emulsion solids) was then added to a non-ionic vinyl acetate copolymer latex containing 100 parts by weight of polymer.
  • This latex was the same as that utilized in Example I.
  • the sheets were tested for wet strength (as in Example I), conditioned and tested as heretofore described and the results appear in Table V. It clearly appears that the wet tensile of an impregnated sheet increases as the level of impregnation is raised.
  • Example VI the morpholine adduct of 4,4-methylene di-o-tolylisocyanate was prepared, emulsified, and then dispersed in a vinyl acetate copolymer latex which was later used to treat paper.
  • Example VII 28 grams of 4,4-methylene di-o-tolylisocyanate and grams of morpholine were mixed in 200 m1. of methyl ethyl ketone. The exothermic reaction which resulted was maintained at 40 C. after which a yellowish white precipitate was filtered off.
  • this precipitate (which was the morpholine adduct of 4,4-methylene di-o-tolylisocyanate) was dissolved in 47 /2 parts by weight of methyl Cellosolve. This solution was then added to 50 parts by weight of water and the isocyanate was precipitated in the form of a fine dispersion.
  • Recom- Blocked Isocyanate mended Proportion 1. Bis phenyl adduct of methylene bis(4-phenyllsocyanate) 8. 3 2. Reaction product of phenol and triphenyl methane triisocyanate 6. 7 3. Reaction product of morpholine and triphenyl methane triisocyanate 6. 5 4. Reaction product of diphenylamine and triphenyl methane triisocyanate 9.0 5. Reaction product of aceto-acetic ester and triphenyl methane triisocyanare 7. 9 6. Morphollne adduct of methylene bis(4-phenylisocyanate). 6. 4 7.
  • the tensile-product of the paper is of prime importance rather than the tensile alone.
  • the tensile-product is the product of the tensile per inch width of the paper multiplied by the percent elongation.
  • High tensile-products may be accomplished by varying the ingredients in the formulation which is used to treat the paper.
  • the elongation and tensile strength of a treated sheet may be varied when synthetic polymeric systems, such as butadiene-styrene and butadiene acrylonitrile are incorporated into the compound.
  • the addition polymer must be non-ionic in nature. If, however, it is not possible to use a non-ionic system for the polymer, a system should be used wherein each of the components, in and of itself, is stable.
  • the component which initially functions as a carrier for the isocyanate must be non-ionic in nature, while the other component may contain a material which is ionic in nature. When mixed, these two components will form an unstable system due to the effect of the ionic component upon the blocked isocyanate.
  • this fluid system is used to treat paper in the manner heretofore described. Normal take up of the compound by the paper during treatment will consume the compound before substantial destabilization takes place and further destabilization will then proceed after the polymer is in place in the paper.
  • Example VIII A typical two component system is set up in Example VIII.
  • Example VIII Component A.4 parts by weight of the reaction product of toluene 2,4diisocyanate, trimethylol propane and phenol were emulsified in a manner similar to that in Example I. This emulsion and 0.2 part by weight of a modified sodium polyacrylate were then dispersed in 30 parts by weight of a vinyl acetate copolymer latex. This latex was the same as that in Example I.
  • Component B 0.5 part by weight of ammonium caseinate was added, with stirring, to 70 parts by weight of a 50:50 butadiene styrene synthetic rubbery polymeric latex. Subsequently 2 parts by weight of an antioxidant and 0.3 part by weight of the sodium salt of tetraacetic acid ethylenediamine was added to this liquid. The systern was mixed and 1% of ammonia (based on the wet wet of the system) was added thereto with stirring.
  • Component A was uniformly dispersed in Component B and the resulting fluid mixture was used to treat paper in the manner heretofore described.
  • wet tensile strength is obtained when a 50:50 copolymer of buta diene-styrene synthetic polymer is substituted for the vinyl copolymer acetate latex in the basic formulations.
  • a higher level of wet tensile may be obtained when mixtures of the vinyl acetate copolymer with 50:50 butadiene styrene copolymer are used.
  • the mixed system in any case, however, is stable for at least 24 hours after mixing. Therefore, the paper may be impregnated with the polymeric system (including the isocyanate) and destabilization will take place while the polymer is in place in the paper. It has been found that when a twocomponent system is used that a satisfactory cure may be obtained at temperatures as low as about 120 F. in as little as 3 days. This is especially adaptable to paper making practices because the paper may be treated, rolled warm, and held for several days prior to shipment.
  • a method of improving the physical properties of cellulose paper which comprises: impregnating said paper with a composition consisting essentially of a substantially non-ionic polymeric vinyl acetate latex wherein the chain portion of the vinyl acetate polymer contains hydrogen and hydroxy groups as substituents on said chain, said groups being capable of reacting with isocyanate groups, and an aqueous emulsion of a polyisocyanate adduct which is stable in the presence of the non-ionic latex and non-reactive until heated to a temperature which regenerates free isocyanate groups in reactive form, substantially drying the treated paper at a temperature below the temperature at which free isocyanate groups are regenerated, and heating the dried paper to a temperature above about 140 C. for a period of time sufficient to provide free isocyanate groups which react with the hydrogen and hydroxy groups in the paper and the polymer.
  • a method of improving the physical properties of cellulose paper which comprises: impregnating said paper with a composition consisting essentially of a substantially non-ionic polymeric vinyl acetate latex wherein the chain portion of the vinyl acetate polymer contains hydrogen and hydroxy groups as substituents on said chain, said groups being capable of reacting with isocyanate groups, and an aqueous emulsion of between 2.5 and 123 parts by weight based on 100 parts by weight of said polymeric latex solids, of a polyisocyanate adduct selected from the groups consisting of the phenol adducts of triphenyl methane triisocyanate, toluene-2, 4-diisocyanate, and 4,4-methylene di-o-tolylisocyanate; the aceto-acetic ester adducts of methylene bis(4-phenylisocyanate), triphenyl methane triisocyanate, toluene-2,4-diisocyanate, and
  • polymeric component of the latex is comprised of a vinyl acetate-dibutyl maleate copolymer.
  • adduct is the morpholine adduct of 4,4'-methylene di-o-tolylisocyanate.
  • adduct is the adduct of toluene-2,4-diisocyanate, trimethylol propane and phenol.
  • a method of improving the physical properties of cellulose paper which comprises: impregnating said paper with a composition comprised of between 50 to 100 parts by weight of substantially non-ionic vinyl acetate copolymer latex solids wherein the vinyl acetate chain portion of said copolymer contains hydrogen and hydroxy groups as substituents on said chain capable of reacting with isocyanate groups, an aqueous emulsion of about 4 parts by weight of the adduct of toluene-2,4-diisocyanate, trimethylol propane and phenol, said adduct being stable in the presence of the non-ionic latex and non-reactive until heated to a temperature which regenerates free isocyanate groups in reactive form, and up to 50 parts by weight of a substantially non-ionic butadiene-styrene copolymer latex; substantially drying the treated paper at a temperature below the temperature at which free isocyanate groups are regenerated; and heating the dried paper to a temperature in the range of about 120 F.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US102085A 1959-06-02 1961-03-31 Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts Expired - Lifetime US3238010A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB940771D GB940771A (enrdf_load_stackoverflow) 1959-06-02
DEG29738A DE1165987B (de) 1959-06-02 1960-05-23 Verfahren zur Verbesserung der physikalischen Eigenschaften von Papierbahnen
FR828845A FR1258646A (fr) 1959-06-02 1960-06-01 Amélioration de la résistance du papier par traitement avec des isocyanates polyfonctionnels
US102085A US3238010A (en) 1959-06-02 1961-03-31 Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts

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US81748859A 1959-06-02 1959-06-02
US102085A US3238010A (en) 1959-06-02 1961-03-31 Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts

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Cited By (18)

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Publication number Priority date Publication date Assignee Title
US3413144A (en) * 1965-03-23 1968-11-26 Union Carbide Corp Polyurethane coated articles
US3492081A (en) * 1965-06-08 1970-01-27 Container Corp Method of treating paper with isocyanates blocked with cyclohexanol
US3505001A (en) * 1965-11-26 1970-04-07 Hooker Chemical Corp Process for treating cellulosic materials
US3529990A (en) * 1966-09-24 1970-09-22 Bayer Ag Process of finishing textile materials
US3531429A (en) * 1965-06-17 1970-09-29 Standard Brands Chem Ind Inc Method for producing modified rubbery latices
US3639157A (en) * 1968-07-18 1972-02-01 Bayer Ag Process for finishing textile materials with a polymer of a vinyl compound and the reaction product of a polyol and an organic polyisocyanate
US3887427A (en) * 1971-07-15 1975-06-03 Kema Nord Ab Process for sizing cellulose fibers
US3989458A (en) * 1973-04-16 1976-11-02 Commonwealth Scientific And Industrial Research Organization Compositions containing bisulphite adducts of polyisocyanates and method of use
DE2612783A1 (de) * 1976-03-25 1977-09-29 Hoechst Ag Blockierte polyisocyanate aus biuretgruppenhaltigem polyisocyanat und acetessigsaeurealkylester
US5576382A (en) * 1996-05-05 1996-11-19 Arco Chemical Technology, L.P. Aqueous polyurethane dispersions based on polyether polyols of low monol content
US5747392A (en) * 1996-11-19 1998-05-05 Hi-Tex, Inc. Stain resistant, water repellant, interpenetrating polymer network coating-treated textile fabric
US6143132A (en) * 1992-04-06 2000-11-07 Bayer Aktiengesellschaft Process for imparting wet strength to paper
US6207250B1 (en) 1995-03-21 2001-03-27 Hi-Tex, Inc. Treated textile fabric
US6251210B1 (en) 1996-08-07 2001-06-26 Hi-Tex, Inc. Treated textile fabric
US6488813B2 (en) * 2000-08-01 2002-12-03 Dai-Ichi Kogyo Seiyaku Co., Ltd. Blocked urethane prepolymers as paper wet strength agent
US6492001B1 (en) 1996-08-07 2002-12-10 Hi-Tex, Inc. Treated textile fabric
US20030083427A1 (en) * 2001-10-31 2003-05-01 Dai-Ichi Kogyo Seiyaku Co., Ltd. Composition for increasing wet strength of paper including water-soluble blocked urethane prepolymers
US20070021019A1 (en) * 2005-07-21 2007-01-25 Hi-Tex, Inc. Treated textile fabric

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GB2288179B (en) * 1992-11-11 1997-06-11 Jujo Paper Co Ltd Aqueous polyolefin resin composition

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US2570253A (en) * 1946-10-25 1951-10-09 Minnesota Mining & Mfg Stable aqueous dispersions of copolymers of vinyl esters, neutral ethylenic polyesters, and acrylic acid, and method of making
US2897094A (en) * 1954-05-11 1959-07-28 Grace W R & Co Process of treating latex impregnated paper with an isocyanate and resultant article
US2994672A (en) * 1957-11-06 1961-08-01 Du Pont Adhesive comprising aqueous dispersion of water soluble polymer and phenolisocyanate adduct, cellulosic structure coated with same and process of preparing same
US2994671A (en) * 1956-10-17 1961-08-01 Du Pont Coating linear condensation polymers with a polyisocyanate adduct
US3001957A (en) * 1957-11-08 1961-09-26 Celanese Corp Aqueous latex comprising vinyl acetate polymer and amino ether of starch and method of coating fibrous sheet material therewith
US3005728A (en) * 1956-10-19 1961-10-24 Tee Pak Inc Cellulosic laminates
US3092601A (en) * 1959-10-01 1963-06-04 Union Carbide Corp Latex coating compositions

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DE897625C (de) * 1940-01-17 1953-11-23 Bayer Ag Verfahren zur Herstellung von hochmolekularen Polykondensationsprodukten
DE929322C (de) * 1942-03-15 1955-06-23 Hoechst Ag Verfahren zur Herstellung von Polyurethanen

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Publication number Priority date Publication date Assignee Title
US2570253A (en) * 1946-10-25 1951-10-09 Minnesota Mining & Mfg Stable aqueous dispersions of copolymers of vinyl esters, neutral ethylenic polyesters, and acrylic acid, and method of making
US2897094A (en) * 1954-05-11 1959-07-28 Grace W R & Co Process of treating latex impregnated paper with an isocyanate and resultant article
US2994671A (en) * 1956-10-17 1961-08-01 Du Pont Coating linear condensation polymers with a polyisocyanate adduct
US3005728A (en) * 1956-10-19 1961-10-24 Tee Pak Inc Cellulosic laminates
US2994672A (en) * 1957-11-06 1961-08-01 Du Pont Adhesive comprising aqueous dispersion of water soluble polymer and phenolisocyanate adduct, cellulosic structure coated with same and process of preparing same
US3001957A (en) * 1957-11-08 1961-09-26 Celanese Corp Aqueous latex comprising vinyl acetate polymer and amino ether of starch and method of coating fibrous sheet material therewith
US3092601A (en) * 1959-10-01 1963-06-04 Union Carbide Corp Latex coating compositions

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3413144A (en) * 1965-03-23 1968-11-26 Union Carbide Corp Polyurethane coated articles
US3492081A (en) * 1965-06-08 1970-01-27 Container Corp Method of treating paper with isocyanates blocked with cyclohexanol
US3531429A (en) * 1965-06-17 1970-09-29 Standard Brands Chem Ind Inc Method for producing modified rubbery latices
US3505001A (en) * 1965-11-26 1970-04-07 Hooker Chemical Corp Process for treating cellulosic materials
US3529990A (en) * 1966-09-24 1970-09-22 Bayer Ag Process of finishing textile materials
US3639157A (en) * 1968-07-18 1972-02-01 Bayer Ag Process for finishing textile materials with a polymer of a vinyl compound and the reaction product of a polyol and an organic polyisocyanate
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