Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/53—Polyethers; Polyesters
• • 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
  • C08J2301/06—Cellulose hydrate
• • 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
  • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

• the method of this invention comprises treating a fibrous or non-fibrous water-insoluble hydrophilic cellulosic sheet with an aqueous solution of a polyalkylene glycol buffered with a buffering agent to a pH of from about 5 to about 8.
• the water-insoluble, hydrophilic cellulosic sheets of this invention are fibrous, non-fibrous or a combination of these forms.
• woven and nonwoven sheets, paper and the like which contain a substantial proportion of water-insoluble, hydrophilic cellulosic fibers; laminates of fibrous cellulosic sheets and films of fibrous sheets coated with cellulosic films to provide greater'wet-strength or other beneficial properties; and cellulosic films usually prepared by extrusion of a cellulosic solution in the form of a pellicle and the coagulation of the pellicle.
• a preferred sheet material for this invention is regenerated cellulose film based on the greater amount of commercial use of the product. Paper coated with viscose which is subsequently regenerated and hydroxyethyl cellulose ether films are examples of other more commercially important sheets which are used for this invention.
• the polyalkylene glycols which are useful for this invention are those which have a softening or plasticizing effect on the cellulosic sheets.
• the polyalkylene glycols are those wherein the alkylene radical has from two to five carbon atoms and the average molecular weight ranges from about 150 to about 1,000. More preferably, the polyalkylene glycol is a polyethylene glycol having an average molecular weight of from about 250 to about 600.
• the glycol plasticizers or softeners can be present in the sheet or film in an amount ranging from about percent up to about 120 percent based on the weight of the cellulosic material.
• amounts of the glycols in the upper portion of this range, starting at about 75 percent, are preferred while conventional plasticization requires amounts in the middle or lower portion of the given range.
• the more highly plasticized sheets present a more severe deterioration problem on aging.
• the polyalkylene glycols are preferably incorporated in the'sheets and filmsof this'invention by passing the sheet or film through an aqueous bath containing the glycol.
• the concentration of the bath will depend on the desired pick-up, and to a lesser extent, on the construction of the fibrous or nonfibrous sheet and the residence time of the sheet in the bath.
• the amount of plasticizer in theaqueous treating bath to obtain the desired amount in the sheet will range,.for example, from about 5 to about 40 percent based on the weight'of the bath.
• aqueous plasticizer composition examples include spraying and padding. While usually not economically desirable, volatile organic solvents can be used to incorporate the polyalkylene glycol, as well as other constituents of this invention, into the sheet. 1
• the buffering agent employed to buffer the cellulosic sheet is any agent which will maintain the pHof the plasticized sheet within the range of about 5 to about 8.5 for at least several months at room temperature.
• buffering agents useful for this purpose include dibasic sodium phosphate-monobasic potassium phosphate, sodium hydroxide-potassium acid phthalate, sodium hydroxide-monobasic potassium phosphate, sodium hydroxide-boric acid, Borax-boric acid, dipotassium phthalate-potassium acidphthalate, monoba'sic sodium phosphate-dibasic sodium phosphate,dibasic sodium phosphate-citric acid, sodium citratecitric acid, sodium carbonate-sodium bicarbonate and the like.
• Aqueous solutions of the buffering agent meeting the given pH requirement are readily prepared by those skilled in the art and as shown, for example, in Langes Handbook of Chemistry, Ninth Edition.
• the buffering agent is, most preferably, introduced into the cellulosic sheet by incorporating it in the glycol plasticizer bath although it may also be introduced in a subsequent treatmentor bath.
• the sheets of this invention which are prepared by passage through an aqueous bath buffered within a range of about 5 to'about 8.5 will, on drying to'normal moisture regain, maintain substantially the same pH values as the treatment bath.
• Some care must be taken in the use of water containing alkaline salts, such as tap water, to prepare the buffered baths since someof the buffering agent may precipitate. If the water is alkaline, someacid, for example, sulfuric acid should be added to bring the pH down to 7 and then the buffering agent may be'added.
• the pH of the film is defined as the pH .of a liquid consisting of 250 ml. of distilled water containing 5 gms. of test film. 'This test liquid is prepared by cutting sufficient /2 inch squares of the test. film to weigh 5- gms. The 5 gms. of film is placed into250 ml. of distilled water contained in a 500 ml. Erlenmeyer flask and a stopper inserted on-the top of the flask. The flaskis shaken for 15 minutes at room temperature and the pH of the resulting liquid is determined on a standard the plasticizing bath although secondary baths or' sprays may be employed for this purpose.
• the antioxidant is incorporated in the cellulosic sheet in amounts which effectively inhibit oxidation of the glycol constituent. Preferably, amounts ranging from about 50 to about 1,000 parts of antioxidant, preferably 100 to 400 parts, per million parts polyalkylene glycol are used. If the antioxidant is applied by passing the cellulosic sheet through an aqueous bath, the bath may contain, for example, between 50 and 400 parts per million of antioxidant.
• the cellulosic sheets After the cellulosic sheets have been treated as required in accordance with this invention, they are dried and usually rolled up for storage and later shipment to customers.
• EXAMPLE a A 12 inch by 8 inch sample of water washed, wet gel (never dried) film of regenerated cellulose, freshly prepared by the viscose process, was treated by immersing it in a one liter aqueous solution of 30 percent polyethylene glycol having an average molecular weight of about 400 at a bath temperature of 50C.
• the acidity of the film was measured as the number of milliequivalents of acid per gm. of the film conditioned at 45.percent relative humidity for 4 hours.
• glycol plasticized, buffered cellulose films did not develop any odor or acidity on aging at 65C. for at least 4 weeks. It is estimated that the glycol in the film would not deteriorate appreciably for at least a year at 25C.
• the films containing both buffer and antioxidant also showed the same excellent stability. It is believed that the antioxidant significantly increases the induction period for the start of oxidation of the glycol and will offer additional long range protection against deterioration in combination with the buffering agent.
• Table II demonstrate the bane fits of the method of this invention for the continuous preparation of polyalkylene glycol plasticized cellulosic sheets.
• Polyalkylene glycol plasticizing baths can be used for much longer periods without producing sheets which are subject to early deterioration.
• Table II also shows the added benefit of the antioxidant-buffer combination in the plasticizer bath.
• Fibrous and non-fibrous water-insoluble, hydrophilic cellulosic sheets containing a plasticizing amount of a polyalkylene glycol having an average molecular weight of at least 250 and a buffering agent which buffers the plasticized sheet .to a pH of between about 5 and about 8.5;
• polyalkylene glycol is a polyethylene glycol having an average molecular weight ranging between about 250 and about 8.
• a method of preparing a deterioration resistant polyalkylene glycol plasticized, water-insoluble, hydrophilic cellulosic sheet which comprises passing a waterinsoluble, hydrophilic cellulosic sheet in contact with an aqueous medium containing-a polyalkylene glycol million parts of said glycol.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Cosmetics (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Priority Applications (8)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22895758

Family Applications (1)

Country Status (8)

Cited By (5)

Families Citing this family (1)

• 1972
  • 1972-03-24 US US00237911A patent/US3840395A/en not_active Expired - Lifetime
  • 1972-12-11 GB GB5703472A patent/GB1420609A/en not_active Expired
  • 1972-12-12 CA CA158,909A patent/CA997523A/en not_active Expired
  • 1972-12-18 ZA ZA728933A patent/ZA728933B/xx unknown
  • 1972-12-22 DE DE2262913A patent/DE2262913A1/de active Pending
  • 1972-12-22 FR FR7246054A patent/FR2176666B1/fr not_active Expired
  • 1972-12-28 IT IT33722/72A patent/IT974756B/it active
• 1974
  • 1974-06-10 BE BE145249A patent/BE816127Q/fr active

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