WO1993007199A1 - Polyesters sulfones et utilisation de ces derniers dans des produits transformables en compost tels que des couches jetables - Google Patents

Polyesters sulfones et utilisation de ces derniers dans des produits transformables en compost tels que des couches jetables Download PDF

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Publication number
WO1993007199A1
WO1993007199A1 PCT/US1992/008173 US9208173W WO9307199A1 WO 1993007199 A1 WO1993007199 A1 WO 1993007199A1 US 9208173 W US9208173 W US 9208173W WO 9307199 A1 WO9307199 A1 WO 9307199A1
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mole
radical
polyester
fibers
polyesters
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PCT/US1992/008173
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English (en)
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Francis Glenn Gallagher
Cathy Jane Hamilton
Steven Michael Hansen
James Alan Romesser
Hyunkook Shin
Raymond Frank Tietz
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E.I. Du Pont De Nemours And Company
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Publication of WO1993007199A1 publication Critical patent/WO1993007199A1/fr

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the 5 products include fibers, films, foams, coated papers, extruded nets, molded objects and nonwovens and disposable products such as diapers from such products.
  • the products are degradable to innocuous materials under conditions used in municipal solid waste composting systems.
  • polyesters and derivative products which have low ingredient costs and yet provide strength and toughness properties adequate for end uses such as in disposable diapers.
  • R is about 97.5 to 99.9 mole % para-phenylene (abbreviation T) and about 0.1 to 2.5 mole % of an alkali metal or alkaline earth metal 5- sulfoisophfhalate radical (abbreviation 5SI) and wherein G is about 60 to 80 mole % -CH2-CH2- (abbreviation 2G) and about 20 to 40 mole % -(CH2)2-0-(CH2)2- (abbreviation DEG), and fibers, non-woven sheet, films and combinations thereof, and disposable diapers comprising such materials.
  • T para-phenylene
  • 5SI alkali metal or alkaline earth metal 5- sulfoisophfhalate radical
  • G is about 60 to 80 mole % -CH2-CH2- (abbreviation 2G) and about 20 to 40 mole % -(CH2)2-0-(CH2)2- (abbreviation DEG), and fibers, non-woven sheet, films and combinations thereof, and disposable diapers compris
  • Patent Nos.5,097,004 and 5,097,005 provided other polyesters containing 5SI radicals.
  • PC Applications QP-4691-A, QP-4850Aand DP-4955-A disclose useful compostable products provided from additional polyesters containing sulfonate radicals other than 5SI, for example 4SP, referred to therein and hereinafter.
  • the present invention provides compostable products from such copolyesters derived from 4SP, as a sulfonate radical.
  • a novel fiber and film forming polyester consisting essentially of recurring structural units of the Formulae: -[-C(0)-R-C(0)-OGO-] a -[-C(0)-Q-0-] b - wherein about 0.1 to about 2.5 mole % of R is 4SP, an alkali metal or alkaline earth metal salt of a 4-sulfophthalic radical, up to about 40 mole % of R is a radical D selected from the group consisting of a chemical bond and one or more divalent, non-aromatic, CI-CJQ hydrocarbylene radicals, and the remainder of R is a divalent aromatic radical, with at least about 85 mole % of said remainder being p-phenylene (T), wherein G is up to about 30 mole % of a polyethylene ether radical E selected from the group consisting of DEG and TEG,
  • G is selected from the group consisting of a radical F, being a polyalkylene ether of molecular weight at least about 250, and of hydrocarbylene radicals -(CH2)2* (i-e., 2G), -(CF-2)3- (i.e., 3G) and -(CH 2 ) 4 - (i.e., 4G), and wherein the structural units of the formula:-
  • [-C(0)-R-C(0)-OGO-] a contain amounts of radicals D and/or E and/or F that are at least S, wherein S is the total of d + e + f, wherein d is the mole % of radical D, e is one quarter of the mole % of radical E, and f is the mole % of radical
  • x is an integer, such hydroxy acid having a melting point at least 5 C below its decomposition temperature
  • Q is selected from the group consisting of a chemical bond and hydrocarbylene radicals -(CH2) n - > where n is an integer from 1 to 5, -C(R ' )H-, and -C(R ' )HCH2-, wherein R ' is selected from the group of -CH3 and -CH2CH3, and wherein "a” and “b” are mole fractions of the polymer, and the mole fraction "a” may be 0.6 to 1 and, correspondingly, mole fraction "b” may be 0 to 0.4.
  • inventions include fibers, foams, films and coatings of the above polyesters and nonwovens of the fibers.
  • the invention also contemplates disposable products, such as diapers, which contain an absorbent body portion, with, on at least one surface, a water permeable nonwoven sheet composed of the polyester fibers, a water impermeable film of the polyester, or a combination thereof.
  • polyesters derived for example from terephthalic acid (abbreviation T), a metal salt of a 4-sulfophthalic acid (abbreviation 4SP), ethylene glycol (abbreviation 2G) and diethylene glycol (abbreviation DEG), undergo degradation when subjected to the conditions of high humidity and temperature that typically characterize composting operations.
  • terephthalic acid abbreviation T
  • 4SP a metal salt of a 4-sulfophthalic acid
  • 2G ethylene glycol
  • DEG diethylene glycol
  • copolyesters which may be made by copolymerization with 4-sulfophthalic acid (4SP) will hydrolyze readily. Not all such copolymers are acceptable in the end uses contemplated.
  • the polymers should exhibit the desired physical properties, and be processable under practical conditions, but the products of hydrolysis should desirably have the potential to be digested by the organisms likely to be found in waste disposal facilities and compost. This cannot be achieved by all monomers used in preparing other copolyesters.
  • terephthalic acid is decomposed substantially completely in such a test over 28 days, and that ethylene glycol and polyethylene glycol (with MW 250 and 3500) are also satisfactorily digested by organisms typical of those found in waste disposal systems; typically, as the molecular weight increases, degradation generally becomes slower.
  • Non-aromatic acids such as adipic acid and glutaric acid
  • carbonic acid gives carbon dioxide and water directly.
  • sodium 4-sulfophthalate radicals to decompose readily under the test conditions indicated may prove advantageous over other sulfonated ingredients.
  • Sodium dimethyl 5-sulfoisophthalate for example, has shown slower degradation in some tests. In this regard, it should be recognised that the rate and extent of decomposition is affected significantly by selection of particular organisms and other specifics during composting.
  • a preferred polyester of the invention is that indicated by the abbreviation 2G-T/6/4SP(78.4/20/1.6), where the numbers connote the mole percentages of the various diacid monomeric units in the polyester. Such abbreviations to connote compositions on a mole % basis will be used throughout this specification.
  • polyesters provide useful materials having applications in end uses where containment of body fluids is necessary and disposability is desirable, e.g., in a degradable film or in a fabric or paper coated with a film which will conform easily to body contours yet act as an effective barrier to penetration of body fluids. It is especially preferred that such films or coated sheets should have a reduced tendency to rattle and rustle when flexed during body movements. Such a film or coated sheet must have adequate strength and • toughness to allow its survival during use. In order that it not leave objectionable residues when disposed of, it should disintegrate quickly when placed in proper waste disposal facilities and, ultimately, degrade substantially completely to innocuous materials, such as carbon dioxide, methane and water.
  • polyesters of the invention consist essentially of recurring structural units of the Formulae :
  • R is 4SP, an alkali metal or alkaline earth metal salt of a 4-sulfophthalic radical, up to about 40 mole % of R is a radical D selected from the group consisting of a chemical bond and one or more divalent, non-aromatic, C1-C10 hydrocarbylene radicals, and the remainder of R is a divalent aromatic radical, with at least about 85 mole % of said remainder being p-phenylene (T), wherein G is up to about 30 mole % of a polyethylene ether radical E selected from the group consisting of DEG and TEG,
  • G is selected from the group consisting of a radical F, being a polyalkylene ether of molecular weight at least about 250, and of hydrocarbylene radicals -(Ct-2)2- (i-e., 2G), -(CH )3- (i.e., 3G) and -(CH 2 ) 4 - (i-e., 4G), and wherein the structural units of the formula:-
  • [-C(0)-R-C(0)-OGO-] a contain amounts of radicals D and/or E and/or F that are at least S, wherein S is the total of d + e+ f, wherein d is the mole % of radical D, e is one quarter of the mole % of radical E, and f is the mole % of radical F, and wherein S is at least 5 mole %, wherein Q is derived from an hydroxy acid of formula
  • x is an integer, such hydroxy acid having a melting point at least 5 C below its decomposition temperature
  • Q is selected from the group consisting of a chemical bond and hydrocarbylene radicals -(CH2) n -, where n is an integer from 1 to 5, -C(R * )H-, and -C(R ' )HCH2 ⁇ , wherein
  • R * is selected from the group of -CH3 and -CH2CH3, and wherein "a” and “b” are mole fractions of the polymer, and the mole fraction "a” may be 0.6 to 1 and, correspondingly, mole fraction "b” may be 0 to 0.4.
  • the acid component preferably includes about 1.5 to 2 mole % 4SP.
  • This component is not only relatively costly but also excessively large amounts can render the polyesters water soluble and thus affect the fiber and film physical properties such as shrinkage.
  • Small amounts of 3-sulfophthalic acid may be present as an impurity in 4SP, especially in commercial material. As little as 0.1 mole % of 4SP contributes significantly to the degradability characteristics of the resultant fibers and films.
  • the metal ion is preferably an alkali metal such as sodium, potassium or lithium. However, alkaline earth metals such as magnesium are also useful.
  • the sodium salt 4-sulfophthalic acid has given very good results.
  • R radicals D Up to about 40 mole % of the R radicals, and advantageously, about 5 to 40 mole %, may be an alkylene or other residue from an organic C2- 2 non- aromatic dibasic acid. These are referred to as radicals D.
  • At least about 85 mole % is preferably T (para-phenylene), with optional inclusion of up to about 15 mole % of I (meta-phenylene).
  • Polyesters in which at least about 97.5 mole % of R is p-phenylene and the remainder is 4SP are also preferred, as being economically attractive.
  • G radicals up to about 30 mole %, and advantageously about 20 to 30 mole %, may be DEG and/or TEG (i.e., polyethylene ether radicals -(CH 2 ) 2 -0-(CH 2 )2- and -(CH2)2-0-(CH 2 )2-0-(CH 2 )2-, respectively). These are referred to as radicals E.
  • DEG and/or TEG polyethylene ether radicals -(CH 2 ) 2 -0-(CH 2 )2- and -(CH2)2-0-(CH 2 )2-0-(CH 2 )2-, respectively.
  • some of the G may be PAG (a radical of a polyalkylene glycol of MW at least about 250). This is referred to as radical F.
  • the remainder of G may be 2G, 3G and/or 4G (i.e. C2-C4 lower alkylene groups).
  • polyesters of the invention are not soluble in water (in contrast to like polyesters derivable from the same constituents but with very much higher mole percentages of 4SP). They also have relatively low glass transition temperatures, Tg.
  • R be a radical D and/or some of the G be a radical E and/or F.
  • at least 5 mole % of the R should be a radical D.
  • at least 5 mole % of the G should be PEG or other radical F.
  • at least 20 mole % of the G may desirably be a radical E (DEG and/or TEG).
  • the Tg of the polyester articles should be no higher than approximately the temperature at which degradation will take place. Since the temperatures in composting operations are often no higher than about 70 C, it is desired that the Tg of the polyester be no more than about 70 C, preferably about 65 C or below.
  • Commercial unmodified polyethylene terephthalate (abbreviation 2GT) polyester fibers have a higher Tg of about 80 C.
  • Such organic non-aromatic dibasic acid for radical D is preferably adipic and/or glutaric acid, but may be azelaic, succinic, sebacic or other acid, ranging from oxalic acid (C2) to dodecanoic acid (C12), s dibasic acids having larger numbers of carbon atoms are not yet commercially available.
  • C2 oxalic acid
  • C12 dodecanoic acid
  • s dibasic acids having larger numbers of carbon atoms are not yet commercially available.
  • the polyesters of the invention may be prepared by conventionally polycondensation techniques using, for example, as the glycol component, a combination of about 70 to 80 mole % of ethylene glycol with complementally about 20 to 30 mole % of diethylene glycol, and as the acid component, a combination of about 97.5 to 99.9 mole % of terephthalic acid with about 0.1 to 2.5 mole % of a metal salt of 4-sulfophthalic acid.
  • some of the glycol components or terephthalic acid can be replaced, respectively, by another glycol or by another acid, especially an aliphatic acid.
  • ester forming derivatives such as the dimethyl esters of the acids may be used.
  • polyesters of the invention it is possible for the polyesters of the invention to have a further significant reduction in their Tg values.
  • the replacement of some of the terephthalic acid with an aliphatic acid such as azelaic, succinic, adipic, sebacic or glutaric acid or the replacement of some of the ethylene glycol with another glycol such as triethylene glycol can lower the Tg even below 65 C.
  • the glycol component is preferably about 20 to 25 mole % DEG or TEG and about 75-80 mole % 2G, 3G or 4G, to achieve an optimum level of degradability without a major sacrifice to fiber and film physical properties such as tensile strength. Above about 40 mole % DEG such properties are adversely affected while with less than about 20 mole % DEG, the degradability may become inadequate, unless PEG (radical F) or an aliphatic acid (such as for radical D) is used instead or in addition.
  • a relative viscosity of at least 16, preferably at least about 18, is generally acceptable for melt spinning performance.
  • Minor amounts of polyfunctional branching agents, such as trimellitic acid residues, may be incorporated to modify melt rheology and film processing, 5 if desired.
  • the various monomeric components are charged to a polymerization vessel along with an antimony or other catalyst and subjected to polycondensation conditions to produce a linear polyester in which the units are randomly distributed along the molecular chain. It will be 0 understood that it is also possible, however, to first react two or more of the monomeric components to a prepolymer stage followed by addition of the remaining components and completion of the polymerization.
  • the polyesters of the invention are very hydrolytically sensitive, having a higher equilibrium moisture content than 2G-T resin and a faster moisture 5 regain rate. It is desirable that isolated flake be dried thoroughly, preferably to a moisture content below 400 ppm before reextrusion, and to maintain a nitrogen atmosphere around all possible air in leakage points, and to transfer polymer in warm condition (e.g., above about 50 C) from the dryer to the extruder.
  • the polyesters as isolated from the reactor usually have multiple melting points by DSC analysis. These are seen at temperatures which overlap those which might be used in drying 2G-T flake, making it difficult to dry these polymers without fusing the flake into a solid mass when they are rapidly heated to get fast economical drying rates. Slower heating to allow crystallization, after 5 which heating at higher temperatures for fast drying, is desirable.
  • a desirable procedure for preparing high molecular weight resins from rapidly polymerized lower molecular weight ones may be to use solid phase polymerization of low molecular weight flake. This procedure may desirably be carried out after or in combination with the crystallization procedure mentioned o above so that temperatures high enough for rapid polymerization can be attained without fusing of the flaked resin.
  • anticaking agents may be useful to prevent sticking, such as Cab-o-sil grade MS-75D, or other finely divided inert solids, like Ti ⁇ 2, talc, carbon black and clay.
  • a catalyst that comprises antimony or another heavy metal may be achieved, for instance, by using a crystalline sodium aluminosilicate molecular sieve such as Linde Molecular Sieve 13X, type 9356, with a nominal pore size of lO A, obtained from Union Carbide Corporation.
  • a crystalline sodium aluminosilicate molecular sieve such as Linde Molecular Sieve 13X, type 9356, with a nominal pore size of lO A, obtained from Union Carbide Corporation.
  • Such procedure is more fully described in U.S.P.5,041,525 (Jackson), but other methods of avoiding antimony may be used, if desired.
  • the particular mole percentages of the aforementioned components are desirably selected to provide a polyester which in fiber or film form has a Tg of 70 C or less, preferably of about 65 C or less.
  • polyesters of the invention are well suited for use as fibers or filaments in nonwoven sheets, they can be used to particular advantage in the form of cast and blown films, foams, coatings, laminates, molded articles, or wherever polyesters with such properties are desired.
  • Fibers and filaments herein are interchangeable terms in the general sense, but where a more specific acknowledgement of length is appropriate, the term “fibers” is intended to refer to short filaments as in "staple fibers". Hereafter only one of the terms may be used.
  • the polyesters of the invention may be converted to fibers or filaments by conventional melt spinning techniques. Deniers of 2 to 15 dpf are most common.
  • the filaments may be used as-spun(undrawn) or in a stretched (drawn or oriented) condition. Drawing to reduce denier or for increasing orientation can be accomplished by the usual procedures.
  • the polymer compositions of the invention can be formed into nonwoven fabrics via a number of processes. These may be roughly divided into spunbonded fabrics and those fabrics using staple fibers. These are discussed in "Encyclopedia of Textiles, Fibers and Nonwoven Fabrics", Ed. Martin Grayson, John Wiley and Sons, New York, 1984, pp 252-304.
  • the compositions described herein can be used in many such products.
  • Spunbonded nonwovens can be prepared by spinning and laying down simultaneously into webs of continuous filaments using known methods of distributing the threadline in the desired orientation in the web plane. Such webs can be thermally bonded under suitable conditions of time, temperature and pressure to strong fabrics with tensile properties which are usually superior to those obtained with staple webs.
  • Bonding can also be carried out by using suitable adhesives and both these methods may be used to make point bonded or area bonded fabrics. Needle punching may also be used to give the webs stability and strength.
  • Spunbonded fabrics can also be made by melt blowing wherein a stream of molten polymer is extruded into a high velocity stream of heated air and a bonded web formed directly on a screen conveyor from the resultant fibers.
  • Nonwoven fabrics can also be made by direct extrusion through a rotating die into a netlike product (US 3,959,057 JJ. Smith) or by stretching and drawing embossed films of the thermoplastic polymers (British Patent 914,489 and 1,548,865 to Smith and Nephew Research Ltd.).
  • Staple fibers can be made into nonwovens by several processes. Most of these can be classified into (1) web preparation and (2) reinforcing ("Manual of Nonwovens", Dr. Radko Krcma, Textile Trade Press, Manchester, England, pp 74-76, 1971). During web preparation, bales of staple fiber are opened and formed into a web having either a random orientation (via air, water or electrostatic deposition) or parallel or crosslaid orientation (via carding and plying).
  • Reinforcement to impart physical integrity and useful mechanical properties can be accomplished by mechanical means such as needlepunching or hydroentanglement (where water jets move fibers out of the plane of the web and entangle them) as in the spunlaced fabrics (US 3,485,706 to Du Pont) or by stitchbonding where a reinforcing thread is sewn through the web. (See: needlepunching or hydroentanglement (where water jets move fibers out of the plane of the web and entangle them) as in the spunlaced fabrics (US 3,485,706 to Du Pont) or by stitchbonding where a reinforcing thread is sewn through the web. (See
  • Reinforcement can also be accomplished by adhesive bonding which includes impregnation of the web by a water based resin binder solution or dispersion and subsequent evaporation of the water leaving a fabric which is composed typically of 60-70% by weight fiber and 30-40% by weight binder. Dry adhesive powders may also be applied to the staple web prior to a heating step to produce a powder-bonded nonwoven. Webs of thermoplastic staple fibers may also be reinforced by thermal bonding in which use is made of the ability of the fibers to soften and adhere to each other upon application of heat.
  • thermoplastic fibers As with the spunbonded fabrics these may be point bonded or area bonded. Heat may be applied by hot air (known as through air bonding) or by a pair of patterned and/or flat heated rollers which form a nip through which the web passes to achieve bonding. This process may be carried out with 100% thermoplastic fibers or with blends of thermoplastic fibers with fibers which do not thermally bond in the 100% form, i.e., cotton and rayon.
  • useful articles can also be made by laminating, extrusion melt coating or adhesively combining the above types of nonwoven fabrics with each other, with films or with staple webs in such a way as to confer desired properties on the combined fabric.
  • a fabric made by extrusion melt coating a thin, pinhole-free film of the compositions of this invention on a nonwoven, made by the spunbonded process or by thermally bonding staple from fibers of this invention alone or in combination with other compostable fibers such as cotton or rayon, is aesthetically pleasing and non-fluid permeable.
  • the compostable polyester fibers described herein may be used in all these methods of preparing nonwovens to yield fabrics which when subjected to composting conditions will be substantially degraded.
  • staple webs of the polyester fibers, as well as blends of these fibers with cotton and rayon may be bonded by hydro entanglement, by needle punching, by wet resin bonding and by dry adhesive bonding. (The adhesives used should be chosen to allow the desired degradation under composting conditions.)
  • Thermally bonded staple webs of the described compostable polyester fibers can be made in the 100% form or webs containing a significant proportion of these fibers together with cotton and/or rayon may be thermally bonded to fabrics having useful mechanical properties.
  • Continuous or spun yarns prepared from the compositions described herein may be used to stitch bond webs of fibers such as cotton, rayon or blends of these fibers, or wood pulp, with the compostable polyester fibers of this invention resulting in fabrics which will degrade under composting conditions.
  • Spunbonded fabrics can be made by thermally bonding webs of continuous fibers prepared from the compostable polyester compositions described herein, and by blow spinning, direct extrusion to nets and drawing of embossed films.
  • compositions described herein can be melt extruded as films to coat spunlaced nonwoven fabrics which themselves may be composed of compostable fibers alone or in combination with wood pulp, rayon or cotton.
  • blowing agent used in foam extrusion, molten polymer is first mixed with a relatively small amount (e.g. 1 to 15 wgt %) of a blowing agent.
  • the blowing agent used does not have to be a true solvent for the polymer.
  • the blowing agents expand due to depressurization and/or volatilization to form a microcellular structure. Unlike in flash spinning, most of the blowing agents used do not leave but stay inside the foam.
  • Most commonly used blowing agents are: 1). gaseous materials such as nitrogen and carbon dioxide, 2). low boiling organic solvents such as hydrofluorocarbons (e.g.
  • HFC-134a, 152a, 125 hydrochlorofluorocarbons (e.g. HCFC-22, 123, 141b, 142b, 124), and hydrocarbons (e.g. isobutane, pentane).
  • chemical blowing agents are also used to make foams. Chemical blowing agents decompose at elevated temperatures or through chemical reaction to generate gases. Nucleating agents which are finely divided powders such as fumed silica are usually added to encourage the formation of small uniform cells.
  • Nonwoven webs of the compostable compositions made by the melt blowing process may also be used as an adhesive layer between other nonwoven fabrics.
  • compositions described herein have a great number of applications in products which are disposed of or potentially may be disposed of in composting systems.
  • compositions have utility in objects made by injection molding, injection blow molding, thermal forming of sheets, rotational molding of powder, extrusion, and pultrusion, which desirably can be disposed of and degraded in composting systems.
  • Agricultural mulch is a nonexclusive list of such end uses:
  • the invention can provide fluid impermeable sheets which are compostable in typical waste disposal facilities.
  • these sheets should not rattle or rustle objectionably and should have strength and toughness adequate for use in personal absorbent products, such as disposable diapers.
  • the fibers, films, foams and nonwoven fabrics prepared from the compositions of the present invention are of particular utility in disposable diapers since in that use they have an enhanced capability of being degraded in a composting operation.
  • Typical examples of disposable diaper constructions are given in U.S. Patents 3,860,003 (Buell) and 4,687,477 (Suzuki et al.), the disclosures of which are incorporated herein by reference. Items which can be made of the compostable compositions of this invention include:-
  • the backsheet film i.e., the water-impermeable outside layer
  • the backsheet film which may be a film which is 100% of the compostable composition or it may be a laminated sheet with a nonwoven or web of compostable fibers including cotton or rayon adhered to the film, or it may be a film adhered to a suitable grade of paper,
  • the topsheet i.e., the water permeable or inner layer, which is a film of a composition of the invention or a nonwoven fabric of the compostable fiber composition or a blend of the compostable fiber of this invention with cotton or rayon fiber, having a porosity suitable for passing urine quickly to the fluid absorbing pad between the topsheet and backsheet,
  • the fastening tapes which may optionally be made from films, or nonwovens of the compositions of the invention; the fastening tapes are typically coated with a pressure sensitive adhesive,
  • the frontal landing strip which may be made from films of this invention; the frontal landing strip is typically printed with a decorative design and coated with a pressure sensitive adhesive,
  • the flexible foam optionally inserted into the diaper under modest extension to gather the waist, leg openings, and/or barrier leg cuffs may be made from polymers of this invention
  • hot melt adhesives used to bond the diaper components to one another may be formulated to incorporate polymers of this invention
  • the leakage shield used at the diaper waist, in front and back may be made from films of this invention, and may be glued, thermally bonded, or sonically bonded to the topsheet or the topsheet and backsheet,
  • additives to the absorbent cellulose pulp core which may be short fibers, fibrids, synthetic pulp prepared by flash spinning, or some other mechanically dispersable and finely divided form made from polymers or fibers of this invention, and which serve to increase wet strength of the core, particularly when superabsorbent polymers have been incorporated and pulp content subsequently reduced,
  • diaper packaging which may comprise a bag made of film of compositions of this invention, or paper or cardboard coated with film of compositions of this invention.
  • the products of the invention may contain additives such as dyes, fillers, pigments, plasticizers, etc. Indeed, use of appropriate fillers or other additives may be helpful, as an acceptable way to enhance dismtegratability.
  • Use of starch is particularly helpful, as taught in PCT Application (QP-4850-A).
  • the incorporation of finely divided particulates has likewise been found helpful, for instance incorporating similar amounts of calcium carbonate in similar compositions. As the incorporation of large amounts of such a filler may increase the tendency of articles to embrittle to an extent that could be undesirable for certain end uses, it may be desirable to take steps such as adding a plasticizer to counter such tendency.
  • Polyester glass transition temperatures. Tg are obtained by using a Du Pont model 2910 Differential Scanning Calorimeter. Samples are heated under a nitrogen atmosphere at a rate of 20 C/min. to a temperature 10-20 C above the melting point, then the melt is cooled using the rapid air quench capability of the instrument. The Tg is determined from the second cycle scan done at 20 C/min. using the internal software to determine the inflection point of the baseline shift.
  • Polymer melting point m.p., is determined on the first heating cycle as described in Tg determination. The temperature at which the highest endothermic peak occurs is reported as the polymer melting point.
  • Mn Number average molecular weight. Mn, is determined by gel permeation chromatography (gpc) versus a standard polyethylene terephthalate sample with an Mn of 22000 and a weight average molecular weight of 44000. Polymers are dissolved in and the analysis is run using HFIP (hexafluoroisopropanol) containing O.OIM sodium trifluoroacetate as the solvent.
  • HFIP hexafluoroisopropanol
  • O.OIM sodium trifluoroacetate O.OIM sodium trifluoroacetate
  • a Waters model 150 C ALC/GPC instrument, or its equivalent, is used with two Zorbax PSM-S biomodal columns (sold by E. I. du Pont de Nemours and Company) (or equivalent) in series at 30 C. A refractive index detector was used and data collected at 100 intervals and analyzed via software provided by the instrument supplier.
  • Carboxyl end groups are determined by titration of an o-cresol solution of the polymer at 115 C with KOH in ben2yl alcohol to a colorimetric endpoint using bromophenol blue as the indicator. Results are reported in eq./lO ⁇ grams of polymer.
  • Tensile Properties of fibers and yarns are sometimes coded as T/E/M/To for tenacity, elongation, initial modulus, and toughness and are reported in their conventional units of grams per denier, percent, grams per denier, and grams per denier. These are measured on conditioned (65% RF1, 70 F) samples (3 inch gauge length) in a commercial testing machine at the rate of extension of 50% per minute (unless otherwise indicated). Toughness (To) is measured as the integrated area under the stress-strain curve.
  • Relative viscosity is the ratio of the viscosity of a solution of 0.8 gram of polyester dissolved in 10 ml of hexafluoroisopropanol (HFIP) containing 80 ppm H2SO4 to the viscosity of H2S04-containing HFIP itself, both measured at 25 C in a capillary viscometer and expressed in the same units.
  • HFIP hexafluoroisopropanol
  • Crimp index is measured by straightening a crimped tow by application of about O.l gpd load. Then 0.5 gm clips 66.6 cm apart are attached to the extended tow. The tow is then cut 11.2 cm beyond each clip to give a sample of 90 cm extended length. The sample is suspended vertically, hanging freely from one of the clips to allow retraction to crimped length. After about 30 sees., clip to clip distance is measured.
  • Lc is the clip-to-clip distance in the free-hanging state.
  • Crystallinity index is measured by first obtaining a diffractogram as described by Blades (U.S. Patent No. 3,869,429, col. 12) with some modifications.
  • the high intensity X-ray source is a Phillips XRG-3100 with a long fine focus copper tube. Diffraction is analyzed with a Phillips single axis goniometer equipped with a thetacompensating slit and a quartz monochromator set to exclude copper K b radiation. Diffracted radiation is collected in step scanning mode in 0.025 steps with a 1.5 sec. per step count time.
  • the digital data so collected are analyzed by a computer and smoothed by a running fit to second order polynomial.
  • the computer is programmed to define a straight base line which joins the diffractogram tangentially at about 113 and 343. Crystallinity index is defined as
  • This Example describes the preparation of the dimethyl ester of 4- sulfophthalic acid (4SP), its polymerization in a copolymer of the composition
  • This mixture was heated slowly to 220 C (bath temperature) and methanol distillate was collected.
  • the molten prepolmer was then transferred to a polymer tube with a side arm a finely drawn capillary N2 tube inserted with the tip near the bottom of the tube.
  • the polymer tube was immersed in a dimethyl phthalate vapor bath and polymerization was carried out by removing glycol vapor first at laboratory vacuum for 1 hour then at 0.3 mm Hg pressure for 2.5 hours.
  • the polymer was molded into a 7/8 inch diameter plug and spun from an electrically heated vessel in a press-spinning apparatus through 3 holes 0.009 inch diameter x 0.027 inches long, at a temperature of 245 C, a delivery rate of 0.7 cc/min., and a windup speed of 27 m/min. These fibers were drawn 5.5X over a 100 C hot pin.
  • T/E/M/To 2.5/36/46.S/.65 (gpd/%/gpd/gpd/gpd) (19 dpf) when tested on an Instron at 3 inch gage length and an elongation rate of 50%/min.
  • the copolymer was made by the following procedure: In a 500 ml reaction kettle fitted with a distillation head, a N2 inlet and a stirrer were placed:
  • This mixture was heated slowly to 220 C (bath temperature) and methanol distillate was collected.
  • the molten prepolymer was then transferred to a polymer tube with a side arm and a finely drawn capillary N2 inlet tube was inserted with its tip near the bottom of the tube.
  • the polymer tube was immersed in a diphenyl ether vapor bath and polymerization was carried out by removing glycol vapor, first at laboratory vacuum for 1.5 hours, then at 0.3 mm Hg pressure for 4 hours.
  • the polymer had a reddish color.
  • the biodegradability of the ultimate product from hydrolysis of the sulfonated dicarboxylic acid monomer sodium 4-sulfophthalic acid (4SP) was determined by a CO2 Production Test designed to determine the rate and extent of conversion of the carbon content of the test material to CO2 by the microorganisms in an activated sludge acclimated by prior exposure to the test substance.
  • test was carried out on 2 liters of combined test medium, test substance, and inoculum in 4L Erlenmeyer flasks shaken at 110 rpm in a temperature range of 21.8-23.5 C.
  • the test medium was water contaimng 1 ml 2.25% magnesium sulfate solution, -1 ml 2.75% calcium chloride solution,2 ml pH 7.2 phosphate buffer solution (Fisher SP341-1), 4 ml 0.025% ferric chloride solution and 1 ml 4% ammonium sulfate solution per liter.
  • the acclimated inoculum was prepared in individual semicontinuous activated sludge (SCAS) units using activated sludge from the Ayondale Sewage Sludge Treatment Plant, Avondale, Pa.
  • the solids were adjusted to 2500 mg/L and the test substance gradually increased to 40 mg/L concentration.
  • the units were maintained at 40 mg/L while being fed synthetic sewage daily until the sludges were used as a source of innoculum for the CO2 generation study.
  • the innoculum was prepared by homogenizing 400 ml of liquor from the SCAS unit in a blender for
  • the ratio of carbon incorporated in biomass to carbon released as C0 2 will vary depending on the organic substrate, experimental conditions and the microorganisms metabolizing the substance. Generally the amount of C0 produced will not be 100% of the total amount possible, even though 100% of the carbon initially added may be metabolized.
  • the near equivalence of theoretical C0 generated for 4SP and glucose during the 28 day period is taken as indicating substantially complete biodegradation of 4SP.

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Abstract

Cette invention concerne de nouveaux polyesters, des fibres et des films, des non tissés fabriqués avec les fibres et des produits jetables fabriqués avec les polyesters, tels que des couches. Lesdits produits sont dégradables dans les conditions typiques des procédés de compostage des déchets, nécessitent un faible coût pour ce qui concerne les ingrédients et possèdent cependant les propriétés de résistance et de solidité nécessaires à l'utilisation finale comme c'est le cas pour les couches jetables. Les polyesters sont principalement constitués de téréphtalates de polyalkylène copolymérisés avec un dérivé d'acide 4-sulfophtalique de métaux alcalino-terreux ou de métaux alcalins, et d'autres ingrédients tels que des polyéthylène éther glycols et/ou des diacides non aromatiques, tels que des acides adipique et glutarique.
PCT/US1992/008173 1991-10-01 1992-10-01 Polyesters sulfones et utilisation de ces derniers dans des produits transformables en compost tels que des couches jetables WO1993007199A1 (fr)

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US77101991A 1991-10-01 1991-10-01
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US76941791A 1991-10-01 1991-10-01
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US07/769,414 1991-10-01
US07/771,019 1991-10-01
US83479792A 1992-02-13 1992-02-13
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014741A1 (fr) * 1993-11-24 1995-06-01 E.I. Du Pont De Nemours And Company Ameliorations se rapportant a des copolyesters compostables, ainsi qu'aux produits obtenus a partir de ces copolyesters
WO1997002375A1 (fr) * 1995-06-30 1997-01-23 Kimberly-Clark Worldwide, Inc. Fibres et non-tisses composites hydrodegradables
US5916678A (en) * 1995-06-30 1999-06-29 Kimberly-Clark Worldwide, Inc. Water-degradable multicomponent fibers and nonwovens
US5976694A (en) * 1997-10-03 1999-11-02 Kimberly-Clark Worldwide, Inc. Water-sensitive compositions for improved processability
EP1043377A2 (fr) * 1999-04-09 2000-10-11 National Starch and Chemical Investment Holding Corporation Adhésifs thermofusibles à base de polyesters sulfonés comprenant un indicateur d' humidité
WO2001010928A1 (fr) * 1999-08-09 2001-02-15 E.I. Du Pont De Nemours And Company Film polyester aromatique oriente biodegradable et procede de fabrication
US6300405B2 (en) * 1998-06-30 2001-10-09 General Electric Company Polyester molding composition
US6444761B1 (en) 1999-12-28 2002-09-03 Kimberly-Clark Worldwide, Inc. Water-soluble adhesive compositions
US6814974B2 (en) 2000-05-04 2004-11-09 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6828014B2 (en) 2001-03-22 2004-12-07 Kimberly-Clark Worldwide, Inc. Water-dispersible, cationic polymers, a method of making same and items using same
US6835678B2 (en) 2000-05-04 2004-12-28 Kimberly-Clark Worldwide, Inc. Ion sensitive, water-dispersible fabrics, a method of making same and items using same
WO2005092948A2 (fr) * 2004-03-19 2005-10-06 Eastman Chemical Company Polyesters biodegradables en anaerobie

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JPS4895495A (fr) * 1972-03-23 1973-12-07
FR2388008A1 (fr) * 1977-04-19 1978-11-17 Du Pont Pellicules de polyester modifie utilisables notamment dans les pellicules photographiques
EP0226439A1 (fr) * 1985-12-09 1987-06-24 W.R. Grace & Co.-Conn. Produits polymères et leur fabrication
USRE32741E (en) * 1982-07-09 1988-08-30 Toray Industries, Inc. Polyester fiber and method for the production thereof
EP0311943A1 (fr) * 1987-10-12 1989-04-19 Akzo N.V. Produit hygiénique absorbant
WO1989008558A1 (fr) * 1988-03-09 1989-09-21 Rhone-Poulenc Films Films polyester composites a adherence amelioree et leur procede d'obtention
WO1991002015A1 (fr) * 1989-08-08 1991-02-21 The Pennsylvania Research Corporation Polyesters hydrodegradables
US5097004A (en) * 1990-05-11 1992-03-17 E. I. Du Pont De Nemours And Company Novel polyesters and their use in compostable products such as disposable diapers

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JPS4895495A (fr) * 1972-03-23 1973-12-07
FR2388008A1 (fr) * 1977-04-19 1978-11-17 Du Pont Pellicules de polyester modifie utilisables notamment dans les pellicules photographiques
USRE32741E (en) * 1982-07-09 1988-08-30 Toray Industries, Inc. Polyester fiber and method for the production thereof
EP0226439A1 (fr) * 1985-12-09 1987-06-24 W.R. Grace & Co.-Conn. Produits polymères et leur fabrication
EP0311943A1 (fr) * 1987-10-12 1989-04-19 Akzo N.V. Produit hygiénique absorbant
WO1989008558A1 (fr) * 1988-03-09 1989-09-21 Rhone-Poulenc Films Films polyester composites a adherence amelioree et leur procede d'obtention
WO1991002015A1 (fr) * 1989-08-08 1991-02-21 The Pennsylvania Research Corporation Polyesters hydrodegradables
US5097004A (en) * 1990-05-11 1992-03-17 E. I. Du Pont De Nemours And Company Novel polyesters and their use in compostable products such as disposable diapers

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Chemical Abstracts, vol. 81, no. 2, 1973, (Columbus, Ohio, US), see abstract no. 4455x, & JP,A,48095495 (MITSUBISHI RAYON CO.) 7 December 1973, see abstract; registry number 51816-70-7 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014741A1 (fr) * 1993-11-24 1995-06-01 E.I. Du Pont De Nemours And Company Ameliorations se rapportant a des copolyesters compostables, ainsi qu'aux produits obtenus a partir de ces copolyesters
WO1997002375A1 (fr) * 1995-06-30 1997-01-23 Kimberly-Clark Worldwide, Inc. Fibres et non-tisses composites hydrodegradables
US5916678A (en) * 1995-06-30 1999-06-29 Kimberly-Clark Worldwide, Inc. Water-degradable multicomponent fibers and nonwovens
US5976694A (en) * 1997-10-03 1999-11-02 Kimberly-Clark Worldwide, Inc. Water-sensitive compositions for improved processability
US6121170A (en) * 1997-10-03 2000-09-19 Kimberly-Clark Worldwide, Inc. Water-sensitive compositions for improved processability
US6300405B2 (en) * 1998-06-30 2001-10-09 General Electric Company Polyester molding composition
EP1043377A3 (fr) * 1999-04-09 2002-01-09 National Starch and Chemical Investment Holding Corporation Adhésifs thermofusibles à base de polyesters sulfonés comprenant un indicateur d' humidité
EP1043377A2 (fr) * 1999-04-09 2000-10-11 National Starch and Chemical Investment Holding Corporation Adhésifs thermofusibles à base de polyesters sulfonés comprenant un indicateur d' humidité
WO2001010928A1 (fr) * 1999-08-09 2001-02-15 E.I. Du Pont De Nemours And Company Film polyester aromatique oriente biodegradable et procede de fabrication
US6444761B1 (en) 1999-12-28 2002-09-03 Kimberly-Clark Worldwide, Inc. Water-soluble adhesive compositions
US6814974B2 (en) 2000-05-04 2004-11-09 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6835678B2 (en) 2000-05-04 2004-12-28 Kimberly-Clark Worldwide, Inc. Ion sensitive, water-dispersible fabrics, a method of making same and items using same
US6828014B2 (en) 2001-03-22 2004-12-07 Kimberly-Clark Worldwide, Inc. Water-dispersible, cationic polymers, a method of making same and items using same
WO2005092948A2 (fr) * 2004-03-19 2005-10-06 Eastman Chemical Company Polyesters biodegradables en anaerobie
WO2005092948A3 (fr) * 2004-03-19 2007-01-04 Eastman Chem Co Polyesters biodegradables en anaerobie

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