US2897094A - Process of treating latex impregnated paper with an isocyanate and resultant article - Google Patents

Process of treating latex impregnated paper with an isocyanate and resultant article Download PDF

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Publication number
US2897094A
US2897094A US429119A US42911954A US2897094A US 2897094 A US2897094 A US 2897094A US 429119 A US429119 A US 429119A US 42911954 A US42911954 A US 42911954A US 2897094 A US2897094 A US 2897094A
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US
United States
Prior art keywords
paper
isocyanate
latex
treated
impregnated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US429119A
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English (en)
Inventor
Norman J Hayes
William C Ross
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WR Grace and Co
Original Assignee
WR Grace and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL86080D priority Critical patent/NL86080C/xx
Priority to DENDAT1066986D priority patent/DE1066986B/de
Priority to BE537751D priority patent/BE537751A/xx
Application filed by WR Grace and Co filed Critical WR Grace and Co
Priority to US429119A priority patent/US2897094A/en
Priority to FR1128989D priority patent/FR1128989A/fr
Priority to GB12670/55A priority patent/GB774243A/en
Priority to CH336688D priority patent/CH336688A/de
Application granted granted Critical
Publication of US2897094A publication Critical patent/US2897094A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment
    • 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
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/11—Isocyanate and carbonate modification of fibers
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31569—Next to natural rubber
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31591—Next to cellulosic
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31826—Of natural rubber
    • Y10T428/31841—Next to cellulosic

Definitions

  • Latex-treated papers are used in considerable quantity, largely in substitution for leather. Typical uses include insoles, midsoles, welting, heel pads, and plumper material in the shoe industry and as a base for the manufacture of artificial leather.
  • Such papers are normally manufactured from a pulp having a high alpha cellulose content (usually 80% or more), which has been but lightly beaten upon dispersion of the pulp fiber in water in a paper beater. Beating to a freeness of 7 to 15 seconds Williams is typical if the paper is to be saturated when dry. Sulfite and sulfate pulps are also used particularly if the latex deposition takes place in the paper beater, in which case, the beating may be continued until a higher freeness is achieved. Most of these papers are wet-laid felts made on normal paper-making machinery, but considerable quantities of air-laid felts are also used as saturating base and usually are converted into hathands and stays. For this reason, the term paper, as used herein, includes cellulosic felts of both wet or dry origin, for our process is equally useful with webs of either type.
  • the latex may be added to the paper-making slurry in the beater, in which case the rubber is coagulated on the surface of the fibers, for example, by the addition of alum.
  • the paper is formed from the treated slurry.
  • Latex-treated paper may also be formed by the Wet web process, in which the web is passed through an impregnating bath inserted in a paper-making machine after the web is formed, and the excess water has been removed but before the paper has been dried.
  • latex-treated paper may be formed by the dry web process, in which a finished, dry impregnating paper is resaturated with a latex composition and then redried. Dry web impregnation is the characteristic manner of latex-treating air-laid felts. Latex-treated papers made by any of these three processes appear to be equally suitable for use in practicing the present invention.
  • the effectiveness of the treatment depends upon two factors: the quantity of rubber impregnant and the quantity 'of isocyanate in the treating solution.
  • the treatment appears to be efiective with the various types of paper coming within the scope of the term latex-treated paper, irrespective of whether a conventional wet strength agent is utilized or not. It is likewise eifective "with the various types of latex useful for impregnating paper; with paper impregnated according to any of the conventional methods; with all available isocyanate resins and With any of the solvents useful for forming solutions of such isocyanates.
  • each of the tests enumerated herein was made according to the following procedure. Eight inch by ten inch sheets of a paperimpregnation base which contained no wet strength agent were impregnated by total immersion with a latex impregnating compound. This compound in each case, unless otherwise designated, was of 30% total solids and contained a latex of the designated rubber and minor amounts of stabilizer, anti oxid-ant, dormant coagulant, dye and a levelling agent for the dye-all according to conventional latex compounding practice. In each case, the total rubber hydrocarbon solids exceeded about of the total solids in the impregnating compound.
  • the impregnated sheet was drained, placed between sheets of blotting paper, and passed through a roller to simulate the squeeze roll used in commercial practice.
  • the paper was then dried to bone dryness at a temperature of approximately 230 F.
  • the dried latex-impregnated paper after being maintained for at least overnight at normal temperature and humidity, was heated to a temperature of 300350 F. in a circulating air oven for 2 to 3 minutes immediately before treatment to eliminate any possible variation that may be caused by differences in moisture content.
  • the dried sheets were then treated with a solution of an isocyanate resin. On a laboratory scale this was done by immersion, by spraying, or by roll application of the solution. Each method is equally effective, but of course, the effectiveness of the treatment depends upon the completeness of the saturation of the paper.
  • the wet sheet was placed between two sheets of blotting paper as before and passed under a roller to remove the excess fluid. The sheets were again dried in contact with a surface heated to a temperature of about 230 F. and conditioned in air at normal temperature and humidity overnight.
  • Heating is not essential but merely provides an easy method of removing the solvent. Samples dried at various temperatures ranging between room temperature and 350 F. have shown no noticeable difierence in properties provided there had been substantially complete solvent removal. .f
  • the tensile strength and elongation of the samples were then measured both wet and dry on a Scott tensile tester model X-3.
  • the wet samples were soaked in water at a temperature of F. for the time indicated.
  • the measurements were made on strips V2" by .4 with a one-inch initial gap between the jaws and with a rate of elongation of 12 inches per minute.
  • the tensile is reported in pounds corrected to an equivalent 1" strip, and the elongation is reported as elongation at break in percentage elongation. All tests were run in the machine direction of the paper.
  • impregnating paper was impregnated with a 30% total solids impregnating compound containing GR-S latex type 2001 according to the procedure out lined above.
  • the sheets were then treated With a 2 /2% solution in toluene of each of six difierent typical isocyanates. These were the following:
  • Phenyl isocyanate (PI) Octa-decyl iso cyanate (ODI) OH3(OH2)11NC O Alpha-naphthyl isocyanate (ANI) Methylene bis (4 phenyl isocyanate) (MDI) m-Tolylene diisocyanate (TDI) NCO NCO
  • Triphenyl methane triisocyanate (TPM) NCO An untreated sheet and one treated with toluene were used as controls. The tensile properties were measured both for the dry sheets and for sheets which had been soaked in water maintained at 160 F. for twenty-four. This table clearly shows that, while treatment with any of the isocyanates results in improved strength without loss in extensibility of the treated paper, the effect is more noticeable in the case of the poly-isocyanates than in the case of the mono-isocyanates. Indeed, it will be noticed that the impregnated paper after treatment with a polyisocyanate solution is as strong, it not stronger, after a twenty-four hour immersion in Water at 160 F. than the impregnated but untreated paper when dry.
  • percent isocyanate in sheet appearing in Table I above and in several of the following tables, would appear to be in order.
  • concentration of isocyanate in the isocyanate solution remains unchanged as the solution is used up. Therefore, the quantity of isocyanate deposited upon the web has been estimated by weighing the sheet immediately before and immediately after treatment to obtain the total amount of solution imbibed by the web.
  • the quantity reported as percent isocyanate in sheet is the weight of isocyanate in that amount of solution expressed as a percentage of the Weight of the dry, untreated sheet.
  • Butadiene-styrene (GR-S latex type 2001) Butadiene-acrylonitrile (Hycar OR 25 1562) Neoprene (Neoprene N571) Natural (concentrated, centrifuged Liberian Hevea latex- Loxite 2109) v
  • Neoprene Neoprene N571 Natural (concentrated, centrifuged Liberian Hevea latex- Loxite 2109)
  • the amount of latex impregnant deposited upon the paper has been reported throughout in terms of the concentration of the impregnating compound.
  • impregnation with a 30% total solids GR-S compound results in an average increase in the Weight of the dry, impregnated sheet of approximately 71% based on the weight of the dry, unimpregnated sheet.
  • the range for individual samples was between 68 and 74%.
  • butadiene-acrylonitrile the average is 70% and the range 66 to 74%.
  • neoprene the average is 85% with a range 85-86%, and for natural rubber the average is 71% and the range 70-72%.
  • the treated sheet showed no sign of wear at the .end of 1,000 complete cycles and only slight wear at the end of approximately 6,000 complete cycles when the test was discontinued. At this point the thickness of the "abraded portion of the treated sheet was reduced by 0.004 of an inch or approximately 10%
  • latex-treated paper especially as re gards the abrasion resistance and tensile strength of that paper-when wet, are vastly improved if that paper is treated and preferably saturated with a solution of an isocyanate.
  • This efiect appears to be independent of the exact type of rubber latex used to form the latextreated paper and to be independent of the exact type of organic isocyanate (e.g., an organic compound containing the terminal group NCO) used for treating the paper, although as might be expected the diand tri-isocyanates are more effective when compared on a weight basis than the monoisocyanates.
  • the improvement in properties of the isocyanate-treated, latex-treated paper is progressive at a given latex impregnation, as the quantity of isocyanate deposited therein is increased with slight but noticeable improvements noted with treatment with solutions of an isocyanate in solvent as dilute as 0.01% and reading a maximum at a concentration between 2.5 and 5%.
  • the improvement in properties with treatment with a given solution of an isocyanate with paper impregnated With varying quantities of latex is progressive with increasing degrees of impregnation.
  • the drawing is a flow sheet illustrating the manner in which the preformed latex-impregnated paper is treated.
  • iso cyanate is a polyisocyanate selected from the class consisting of the diand tri-isocyanates.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
US429119A 1954-05-11 1954-05-11 Process of treating latex impregnated paper with an isocyanate and resultant article Expired - Lifetime US2897094A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL86080D NL86080C (es) 1954-05-11
DENDAT1066986D DE1066986B (es) 1954-05-11
BE537751D BE537751A (es) 1954-05-11
US429119A US2897094A (en) 1954-05-11 1954-05-11 Process of treating latex impregnated paper with an isocyanate and resultant article
FR1128989D FR1128989A (fr) 1954-05-11 1955-04-26 Perfectionnements aux papiers traités au latex
GB12670/55A GB774243A (en) 1954-05-11 1955-05-02 Improvements in latex-treated paper
CH336688D CH336688A (de) 1954-05-11 1955-05-02 Verfahren zur Verbesserung der Nassfestigkeit von mit Latex imprägniertem Papier

Applications Claiming Priority (1)

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US429119A US2897094A (en) 1954-05-11 1954-05-11 Process of treating latex impregnated paper with an isocyanate and resultant article

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US2897094A true US2897094A (en) 1959-07-28

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US (1) US2897094A (es)
BE (1) BE537751A (es)
CH (1) CH336688A (es)
DE (1) DE1066986B (es)
FR (1) FR1128989A (es)
GB (1) GB774243A (es)
NL (1) NL86080C (es)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3049442A (en) * 1959-09-03 1962-08-14 Ibm Process for manufacturing cured magnetic tapes utilizing an isocyanate accelerator
US3103437A (en) * 1959-04-10 1963-09-10 Hardening
US3238010A (en) * 1959-06-02 1966-03-01 Grace W R & Co Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts
US3260104A (en) * 1962-10-22 1966-07-12 Exxon Research Engineering Co Apparatus for fluid analysis
US3506480A (en) * 1969-02-24 1970-04-14 Gen Mills Inc Oil filter paper and process of preparing same
US3606992A (en) * 1967-08-28 1971-09-21 Warnaco Inc Abrasion and wrinkle resistant cotton containing fabric and method of manufacture
US4119746A (en) * 1977-06-14 1978-10-10 W. R. Grace & Co. Cross-linking resin saturant and method
US4587141A (en) * 1983-12-15 1986-05-06 U.S. Plywood Corporation Laminated panel and process
US4617223A (en) * 1984-11-13 1986-10-14 The Mead Corporation Reinforced paperboard cartons and method for making same
WO1992015441A1 (en) * 1991-02-28 1992-09-17 Network Graphics, Inc. Paperboard containers and method of making same
US6620459B2 (en) 2001-02-13 2003-09-16 Houston Advanced Research Center Resin-impregnated substrate, method of manufacture and system therefor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085027A (en) * 1961-01-30 1963-04-09 Us Rubber Co Polyurethane coated fabric filled with isocyanate free elastomer and method of making same
BE757409A (fr) * 1969-10-15 1971-04-13 Kalle Ag Procede pour la preparation d'un materiau textile plan, lie pardes agents chimiques, a base de fibres synthetiques, presentant un pouvoir eleve d'absorption de la vapeur d'eau

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2107304A (en) * 1934-06-27 1938-02-08 Raybestos Manhattan Inc Process of impregnating fibrous materials
US2282827A (en) * 1939-11-13 1942-05-12 Du Pont Resinous product and method of making
US2430479A (en) * 1941-07-23 1947-11-11 Du Pont Bonding of laminates by means of isocyanates
US2439514A (en) * 1941-07-23 1948-04-13 Du Pont Composite structures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2107304A (en) * 1934-06-27 1938-02-08 Raybestos Manhattan Inc Process of impregnating fibrous materials
US2282827A (en) * 1939-11-13 1942-05-12 Du Pont Resinous product and method of making
US2430479A (en) * 1941-07-23 1947-11-11 Du Pont Bonding of laminates by means of isocyanates
US2439514A (en) * 1941-07-23 1948-04-13 Du Pont Composite structures

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3103437A (en) * 1959-04-10 1963-09-10 Hardening
US3238010A (en) * 1959-06-02 1966-03-01 Grace W R & Co Method of reacting cellulose paper and specific non-ionic latices containing hydrogen and hydroxy groups in the polymer chain with polyisocyanate adducts
US3049442A (en) * 1959-09-03 1962-08-14 Ibm Process for manufacturing cured magnetic tapes utilizing an isocyanate accelerator
US3260104A (en) * 1962-10-22 1966-07-12 Exxon Research Engineering Co Apparatus for fluid analysis
US3606992A (en) * 1967-08-28 1971-09-21 Warnaco Inc Abrasion and wrinkle resistant cotton containing fabric and method of manufacture
US3506480A (en) * 1969-02-24 1970-04-14 Gen Mills Inc Oil filter paper and process of preparing same
US4119746A (en) * 1977-06-14 1978-10-10 W. R. Grace & Co. Cross-linking resin saturant and method
US4587141A (en) * 1983-12-15 1986-05-06 U.S. Plywood Corporation Laminated panel and process
US4617223A (en) * 1984-11-13 1986-10-14 The Mead Corporation Reinforced paperboard cartons and method for making same
WO1992015441A1 (en) * 1991-02-28 1992-09-17 Network Graphics, Inc. Paperboard containers and method of making same
US6620459B2 (en) 2001-02-13 2003-09-16 Houston Advanced Research Center Resin-impregnated substrate, method of manufacture and system therefor
US20040063891A1 (en) * 2001-02-13 2004-04-01 Colvin John C. Resin-impregnated substrate materials

Also Published As

Publication number Publication date
FR1128989A (fr) 1957-01-14
CH336688A (de) 1959-02-28
GB774243A (en) 1957-05-08
BE537751A (es) 1900-01-01
DE1066986B (es) 1900-01-01
NL86080C (es) 1900-01-01

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