US2650172A - Moistureproofing of nonfibrous cellulosic material - Google Patents

Moistureproofing of nonfibrous cellulosic material Download PDF

Info

Publication number
US2650172A
US2650172A US7206549A US2650172A US 2650172 A US2650172 A US 2650172A US 7206549 A US7206549 A US 7206549A US 2650172 A US2650172 A US 2650172A
Authority
US
United States
Prior art keywords
article
cellulosic
polymerization product
moistureproofing
styrene
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
Inventor
William O Brillhart
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.)
Akzo Nobel UK PLC
Original Assignee
American Viscose Corp
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
Application filed by American Viscose Corp filed Critical American Viscose Corp
Priority to US7206549 priority Critical patent/US2650172A/en
Application granted granted Critical
Publication of US2650172A publication Critical patent/US2650172A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31884—Regenerated or modified cellulose

Definitions

  • This invention relates to improvements in non-fibrous cellulosic articles. More particularly it relates to the treatmentof regenerated cellulose sheets or films with an aqueous alkaline medium containing an anchoring agent for filmforming surface coatings whereby slightly alkaline sheets or filmswhich are not embrittled by age, and to which the surface coating firmly adheres, are obtained.
  • anchoring agents have had the disadvantage that they are acidic or revert to an acidic condition when the cellulosic article is dried after it has been treated with them. This is undesirable because cellulosic articles which comprise an acid tend to become brittle and fragile on ageing due to acid degradation of thecellulose. Such articles cannot be stored safely for any appreciable period of time. In order to avoid this difliculty it is necessary to treat the article, after application cfthe anchoring agent, to bring it to neutral or alkaline condition. y
  • the principal object of this invention is to produce cellulosic articles, for example sheets or films, which are slightly alkaline as produced, and which can be given a topor surface coating of a film-forming substance or composition which imparts moistureproof, vapor proof, and/or heat-sealing characteristics to the cellulosic article, whereby the, surface coating is firmly anchored to the cellulosic article andis resistant to loosening or sloughing 01f when the article is exposed to moisture
  • Another object is to provide an improved method for conditioning cellulosic articles forreception of a surface or top coating wherein the anchoring age nt is applied from aqueous alkaline medium.
  • the objects of the invention are accomplished by treating cellulosic articles such as sheets, films, pellicles, tubes, filaments, etc., with aqueous alkaline medium containing a resin comprising a polymerization product of styrene and maleic anhydride containing 50 mol per cent of styrene in the polymer molecule, in the form of a water-soluble salt of an alkaline agent selected from the group consisting of ammonia and amines having up to four carbons, and thereafter heating the treated cellulosic article to dry the article and insolubilize the resin under controlled conditions such that the amount of alkaline agent such as the amine or ammonia volatilized during the heating and insolubilizing step is not sufficient to effect conversion of the resin to the free acid state.
  • aqueous alkaline medium containing a resin comprising a polymerization product of styrene and maleic anhydride containing 50 mol per cent of styrene in the polymer
  • the cellulosic articles may be of regenerated cellulose prepared from solutions of cellulose xanthate or cuprammonium cellulose, or they may be of a cellulose ester orether, such as cellulose acetate, cellulose nitrate, ethyl cellulose, methyl cellulose, etc. which materials contain free hydroxyl groups and are hydrophilic in character.
  • an ammonium or amine salt of the styrenemaleic anhydride polymerization product is incorporated directly in the aqueous softening bath, such as theglycerol bath, on the casting machine for producing regenerated cellulose sheets, and thus the anchoring agent is applied to the gel sheet as it passes through the glycerol bath, after the sheet has been purified and washed, while it is in substantially neutral, Water-laden condition, and prior to initial drying thereof.- The sheet is then dried under controlled conditions of time and temperature such that the styrene-maleic anhydride polymerization product iS insolubilized without sufficient evolution of ammonia or amine to convert the anchoring agent to the acid condition.
  • This curing of the resin without reversion thereof to the free acid state is accomplished by drying the impregnated sheet orfilm and simultaneously curing the resin ,atrelatively low temperatures ofL50-80i. C. ,for a short period of from 1 to 5 polymerization product to an acid condition, and then applying to the article a film-forming moistureproofing agent.
  • aqueous alkalme medium also contains a quaternary ammonium salt as a catalyst for said insolubilization.
  • a method as in claim 1 wherein the aqueous alkaline medium also contains 4.
  • a method for the production of a moistureproof cellulosic article which comprises applying to a hydrophilic cellulosic article, while it is in materials, said anchoring agent being a water-soluble salt of a medium, ture of from 50 to 80 to dry the article and 5.
  • a method as in claim 4 wherein the cellulosic article comprises regenerated cellulose.
  • cellulosic article comprises regenerated cellulose and the aqueous alkaline medium also contains glyclosic article comprises regenerated cellulose and the aqueous alkaline medium also contains a the aqueous alkaline medium also contains a plasticizer for the cellulosic article and a quaternary ammonium salt as a catalyst for said insolubilization.
  • a composite film comprising a cellulosic base, a moistureproof coating, and, disposed between the base and the moistureproof coating, an

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Description

Patented Aug. 25, 1953 MOISTUREPRO OFING OF NONFIBROUSE CELLULOSIC MATERIAL W lliam] 0. Brillhart, Signor to American mington, Del., a cor Fredericksburg, Viscose Corporation, Wilporation of Delaware:
Va., as-
No Drawing. Application January 21, 1949 Serial No. 72,065
This invention relates to improvements in non-fibrous cellulosic articles. More particularly it relates to the treatmentof regenerated cellulose sheets or films with an aqueous alkaline medium containing an anchoring agent for filmforming surface coatings whereby slightly alkaline sheets or filmswhich are not embrittled by age, and to which the surface coating firmly adheres, are obtained.
It is desirable, in the manufacture of sheets and films of hydrophilic cellulosic materials, i
such as regenerated cellulose and cellulose ethers and esters containing free hydroxyl groups, to provide the sheets and films with a surface coating for improving certain characteristics of the cellulosic article, such as its moistureproof, vapor proof, and/or heat sealing characteristics. A number of substances ,and compositions have been proposed for this purpose. However, it has been recognized that when the treated sheets are used to package materials of high moisture content, or come in contact withan atmosphere of high humidity or a medium actually containing liquid water, the cellulosic base tends to swell, and the surface coating tends to loosen and slough off. A number of different materials have been proposed for use as an intermediate anchoring agent between thehydrophilic cellu: lose and the surface coating. Some of these anchoring agents have had the disadvantage that they are acidic or revert to an acidic condition when the cellulosic article is dried after it has been treated with them. This is undesirable because cellulosic articles which comprise an acid tend to become brittle and fragile on ageing due to acid degradation of thecellulose. Such articles cannot be stored safely for any appreciable period of time. In order to avoid this difliculty it is necessary to treat the article, after application cfthe anchoring agent, to bring it to neutral or alkaline condition. y
Other anchoring agents havehad the disad vantage that they mustbe applied from organic solvents, entailing expensive solvent recovery processes. i
The principal object of this invention is to produce cellulosic articles, for example sheets or films, which are slightly alkaline as produced, and which can be given a topor surface coating of a film-forming substance or composition which imparts moistureproof, vapor proof, and/or heat-sealing characteristics to the cellulosic article, whereby the, surface coating is firmly anchored to the cellulosic article andis resistant to loosening or sloughing 01f when the article is exposed to moisture Another object is to provide an improved method for conditioning cellulosic articles forreception of a surface or top coating wherein the anchoring age nt is applied from aqueous alkaline medium. Another object 12 Claims. (01. 11776) is to produce cellulosic articles which adhere firmly to film-forming moistureproofing agents or compositions in contact with moisture and which do not become brittle with use or on long storing either before or after application of the moistureproofing agent. Other objects of the invention are to provide a simple, practical method of applying an anchoring agent to cellulosic articles from an alkaline solution which does not require any change in conventional processes for manufacturing such articles. Other objects will appear hereinafter.
The objects of the invention are accomplished by treating cellulosic articles such as sheets, films, pellicles, tubes, filaments, etc., with aqueous alkaline medium containing a resin comprising a polymerization product of styrene and maleic anhydride containing 50 mol per cent of styrene in the polymer molecule, in the form of a water-soluble salt of an alkaline agent selected from the group consisting of ammonia and amines having up to four carbons, and thereafter heating the treated cellulosic article to dry the article and insolubilize the resin under controlled conditions such that the amount of alkaline agent such as the amine or ammonia volatilized during the heating and insolubilizing step is not sufficient to effect conversion of the resin to the free acid state. In this Way, cellulosic articles which are slightly alkaline are obtained.
The cellulosic articles may be of regenerated cellulose prepared from solutions of cellulose xanthate or cuprammonium cellulose, or they may be of a cellulose ester orether, such as cellulose acetate, cellulose nitrate, ethyl cellulose, methyl cellulose, etc. which materials contain free hydroxyl groups and are hydrophilic in character.
In the preferred embodiment of the invention, an ammonium or amine salt of the styrenemaleic anhydride polymerization product is incorporated directly in the aqueous softening bath, such as theglycerol bath, on the casting machine for producing regenerated cellulose sheets, and thus the anchoring agent is applied to the gel sheet as it passes through the glycerol bath, after the sheet has been purified and washed, while it is in substantially neutral, Water-laden condition, and prior to initial drying thereof.- The sheet is then dried under controlled conditions of time and temperature such that the styrene-maleic anhydride polymerization product iS insolubilized without sufficient evolution of ammonia or amine to convert the anchoring agent to the acid condition. This curing of the resin without reversion thereof to the free acid state is accomplished by drying the impregnated sheet orfilm and simultaneously curing the resin ,atrelatively low temperatures ofL50-80i. C. ,for a short period of from 1 to 5 polymerization product to an acid condition, and then applying to the article a film-forming moistureproofing agent.
as in claim 1 wherein the aqueous alkalme medium also contains a quaternary ammonium salt as a catalyst for said insolubilization.
3. A method as in claim 1 wherein the aqueous alkaline medium also contains 4. A method for the production of a moistureproof cellulosic article which comprises applying to a hydrophilic cellulosic article, while it is in materials, said anchoring agent being a water-soluble salt of a medium, ture of from 50 to 80 to dry the article and 5. A method as in claim 4 wherein the cellulosic article comprises regenerated cellulose.
6. A method as in claim 4 wherein the cellulosic article comprises regenerated cellulose and the aqueous alkaline medium also contains a plasticizing agent for the cellulose.
7. A method as in claim 4 wherein the cellulosic article comprises regenerated cellulose and the aqueous alkaline medium also contains glyclosic article comprises regenerated cellulose and the aqueous alkaline medium also contains a the aqueous alkaline medium also contains a plasticizer for the cellulosic article and a quaternary ammonium salt as a catalyst for said insolubilization.
10. A composite film comprising a cellulosic base, a moistureproof coating, and, disposed between the base and the moistureproof coating, an
ated cellulose.
12. A composite film as defined in claim 11 wherein the sheet of regenerated cellulose is plasticized with glycerol.
WILLIAM O. BRILLI-IART. References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,976,679 Fikentscher et a1. Oct. 9, 1934 2,047,398 Voss et a1 July 14, 1938 2,168,535 Nuesslein et a1 Aug. 8, 1939 2,252,091 Muller et a1 Aug. 12, 1941 2,327,760 Bestian et a1 Aug. 24, 1943 2,341,413 Pense et a1 Feb. 8, 1944 2,356,879 Pense et al Aug. 29, 1944 2,394,009 Pollard Feb. 5, 1946 2,432,542 RitZl Dec. 16, 1947 2,467,436 Lanning Apr, 19, 1949 2,469,407 1 Powers et al. May 10, 1949 2,469,408 Powers et al May 10, 1949 2,469,409 Powers et a1 May 10, 1949 2,486,804 Seynor et al Nov. 1, 1949 FOREIGN PATENTS Number Country Date 466,817 Great Britain June 7, 1937 497,335 Great Britain Dec. 15, 1938

Claims (1)

1. IN THE PRODUCTION OF CELLULOSIC ARTICLES THE IMPROVEMENT WHICH COMPRISES APPLYING TO THE ARTICLE WHILE IT IS IN THE FORM OF A WET GEL PRIOR TO INITIAL DRYING THEREOF AS A STEP IN ITS MANUFACTURE, AN AQUEOUS ALKALINE MEDIUM CONTAINING A WATER-SOLUBLE SALT OF A POLYMERIZATION PRODUCT OF STYRENE AND MALEIC ANHYDRIDE CONTAINING ABOUT 50 MOL PER CENT OF STYRENE IN THE POLYMER MOLECULE, SAID SALT BEING FORMED WITH AN ALKALINE AGENT SELECTED FROM THE GROUP CONSISTING OF AMMONIA AND AMINES HAVING UP TO FOUR CARBONS, REMOVING EXCESS TREATING MEDIUM, AND THEREAFTERHEATING THE CELLULOSIC ARTICLE UNDER CONTROLLED CONDITIONS OF TEMPERATURE AND TIME TO DRY THE ARTICLE AND INSOLUBLIZE THE POLYMERIZATION PRODUCT WITHOUT VOLATILIZING SUFFICIENT ALKALINE AGENT TO CONVERT THE POLYMERIZATION PRODUCT TO AN ACID CONDITION, AND THEN APPLYING TO THE ARTICLE A FILM-FORMING MOISTUREPROOFING AGENT.
US7206549 1949-01-21 1949-01-21 Moistureproofing of nonfibrous cellulosic material Expired - Lifetime US2650172A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US7206549 US2650172A (en) 1949-01-21 1949-01-21 Moistureproofing of nonfibrous cellulosic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US7206549 US2650172A (en) 1949-01-21 1949-01-21 Moistureproofing of nonfibrous cellulosic material

Publications (1)

Publication Number Publication Date
US2650172A true US2650172A (en) 1953-08-25

Family

ID=22105336

Family Applications (1)

Application Number Title Priority Date Filing Date
US7206549 Expired - Lifetime US2650172A (en) 1949-01-21 1949-01-21 Moistureproofing of nonfibrous cellulosic material

Country Status (1)

Country Link
US (1) US2650172A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111425A (en) * 1963-11-19 Coating regenerated cellulose
US3179532A (en) * 1960-04-25 1965-04-20 Du Pont Anchor coating of a water-soluble salt of a copolymer of an acrylate and an acrylic ester
US3192066A (en) * 1961-06-12 1965-06-29 Olin Mathieson Process for preparing moistureproof film
US3652316A (en) * 1969-01-23 1972-03-28 Itt Rayonier Inc Heat-sealable hydroxyethyl cellulose film and process for preparing same

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1976679A (en) * 1930-05-26 1934-10-09 Ig Farbenindustrie Ag Production of dispersions
US2047398A (en) * 1930-06-26 1936-07-14 Ig Farbenindustrie Ag Artificial resins and process of making them
GB466817A (en) * 1937-04-02 1937-06-07 Reginald John William Reynolds Improvements in the treatment of cellulosic material
GB497335A (en) * 1936-06-17 1938-12-15 British Cellophane Ltd Improvements in or relating to the preparation of coated materials
US2168535A (en) * 1936-04-29 1939-08-08 Ig Farbenindustrie Ag Textile material and a process of preparing it
US2252091A (en) * 1937-08-24 1941-08-12 Du Pont Moistureproof sheet
US2327760A (en) * 1940-07-19 1943-08-24 Bestian Herbert Fibrous materials
US2341413A (en) * 1939-09-27 1944-02-08 Pense Walter Process of preparing coatings and the materials thus obtained
US2356879A (en) * 1939-12-12 1944-08-29 Pense Walter Process of preparing lustrous coatings
US2394009A (en) * 1943-04-30 1946-02-05 American Cyanamid Co Treatment of cellulosic materials
US2432542A (en) * 1944-07-13 1947-12-16 Du Pont Method of producing coated cellulosic sheets
US2467436A (en) * 1943-12-18 1949-04-19 Du Pont Plasticized hydroxylated polymeric film and method of making same
US2469409A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials
US2469408A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile material
US2469407A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials
US2486804A (en) * 1947-10-08 1949-11-01 Henry H Frede And Company Coating cellulosic textiles with maleic anhydride-styrene copolymer and solid polyethylene glycol

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1976679A (en) * 1930-05-26 1934-10-09 Ig Farbenindustrie Ag Production of dispersions
US2047398A (en) * 1930-06-26 1936-07-14 Ig Farbenindustrie Ag Artificial resins and process of making them
US2168535A (en) * 1936-04-29 1939-08-08 Ig Farbenindustrie Ag Textile material and a process of preparing it
GB497335A (en) * 1936-06-17 1938-12-15 British Cellophane Ltd Improvements in or relating to the preparation of coated materials
GB466817A (en) * 1937-04-02 1937-06-07 Reginald John William Reynolds Improvements in the treatment of cellulosic material
US2252091A (en) * 1937-08-24 1941-08-12 Du Pont Moistureproof sheet
US2341413A (en) * 1939-09-27 1944-02-08 Pense Walter Process of preparing coatings and the materials thus obtained
US2356879A (en) * 1939-12-12 1944-08-29 Pense Walter Process of preparing lustrous coatings
US2327760A (en) * 1940-07-19 1943-08-24 Bestian Herbert Fibrous materials
US2394009A (en) * 1943-04-30 1946-02-05 American Cyanamid Co Treatment of cellulosic materials
US2467436A (en) * 1943-12-18 1949-04-19 Du Pont Plasticized hydroxylated polymeric film and method of making same
US2432542A (en) * 1944-07-13 1947-12-16 Du Pont Method of producing coated cellulosic sheets
US2469409A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials
US2469408A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile material
US2469407A (en) * 1945-12-01 1949-05-10 Monsanto Chemicals Treatment of textile materials
US2486804A (en) * 1947-10-08 1949-11-01 Henry H Frede And Company Coating cellulosic textiles with maleic anhydride-styrene copolymer and solid polyethylene glycol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111425A (en) * 1963-11-19 Coating regenerated cellulose
US3179532A (en) * 1960-04-25 1965-04-20 Du Pont Anchor coating of a water-soluble salt of a copolymer of an acrylate and an acrylic ester
US3192066A (en) * 1961-06-12 1965-06-29 Olin Mathieson Process for preparing moistureproof film
US3652316A (en) * 1969-01-23 1972-03-28 Itt Rayonier Inc Heat-sealable hydroxyethyl cellulose film and process for preparing same

Similar Documents

Publication Publication Date Title
US2511229A (en) Process for the preparation of cellulose sulfate
AU2015204026B2 (en) Production of poly alpha-1,3-glucan films
US2495232A (en) Cellulose derivatives and process of preparing same
US2650172A (en) Moistureproofing of nonfibrous cellulosic material
US2569932A (en) Cross-linked hydrolyzed interpolymer of vinyl acetate and allylidene diacetate and process
US3345200A (en) Method of preparing cellulose film having improved durability
US2252091A (en) Moistureproof sheet
CN105968398B (en) A kind of low-temperature alkali fuel cell anion-exchange membrane and preparation method thereof
US2575443A (en) Process for the manufacture of moistureproof sheet material
US2829944A (en) Method of extruding an aqueous particulate dispersion of finely divided cellulose
US2390780A (en) Process of making coated textile materials and the articles produced therefrom
US2525676A (en) Heat sealable regenerated cellulose film and methods of making same
US2459927A (en) Process of manufacturing regenerated cellulose sheet material
CN113603920B (en) Method for secondary crosslinking of protein-based composite membrane material assisted by water vapor
US2721150A (en) Coated cellulosic pellicles and methods of producing the same
GB1559644A (en) Method for the water resistance of pullulan
US2122418A (en) Product and process of preparing same
US2636804A (en) Process of treating polyvinyl alcohol fibers
US2159007A (en) Composite article and method for producing same
US2784052A (en) Process of preparing waterproof films, fabrics, filaments, and yarns of regenerated cellulose containing within a waterproof addition polymer and products produced therefrom
US2406905A (en) Method for producing cellulosic structures
US2917397A (en) Cellulosic pellicle and method of preparation
US2328679A (en) Cellulosic structure
US2025044A (en) Application of new organic ethers
US3016283A (en) Resin spun viscose