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WO1993007198A1 - Polyesters sulfones et utilisation de ces derniers dans des produits pouvant etre transformes en compost, tels que des couches jetables - Google Patents

Polyesters sulfones et utilisation de ces derniers dans des produits pouvant etre transformes en compost, tels que des couches jetables Download PDF

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Publication number
WO1993007198A1
WO1993007198A1 PCT/US1992/008172 US9208172W WO9307198A1 WO 1993007198 A1 WO1993007198 A1 WO 1993007198A1 US 9208172 W US9208172 W US 9208172W WO 9307198 A1 WO9307198 A1 WO 9307198A1
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WO
WIPO (PCT)
Prior art keywords
mole
polyester
polymer
fibers
group
Prior art date
Application number
PCT/US1992/008172
Other languages
English (en)
Inventor
Francis Glenn Gallagher
Cathy Jane Hamilton
Steven Michael Hansen
Hyunkook Shin
Raymond Frank Tietz
Original Assignee
E.I. Du Pont De Nemours And Company
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 claimed from US07/834,794 external-priority patent/US5171308A/en
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1993007198A1 publication Critical patent/WO1993007198A1/fr

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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
    • 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
    • A61L15/225—Mixtures of macromolecular compounds
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • 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.
  • SUBSTITUTE SHEET aerobically/anaerobically in composting but will continue to degrade in the soi or landfill. As long as water is present, they will continue to break down into lo molecular weight fragments which can be ultimately biodegraded by microorganisms completely into biogas, biomass and liquid leachate, as for 5 natural organics like wood.
  • polyesters and derivative products which have low l o ingredient costs and yet provide strength and toughness properties adequate for end uses such as in disposable diapers.
  • polyesters were provided and fibers, non-woven sheet, films and combinations thereof, and disposable diapers comprising such materials.
  • Such polyesters are useful for some end uses, 15 e.g., as described. It would, however, be desirable to provide additional degradable materials, having properties that may be better adapted for various end uses. In particular, it is desirable to provide additional polyesters that can be formed into films that have good toughness, with similar advantageous properties in many respects, and polyesters having good rates of hydrolysis.
  • polyesters of the aforesaid copending applications maybe advantageously modified by including in the molecule, usually instead of part of the para-phenylene (T) units, a proportion of a non-aromatic acid, such as adipic acid.
  • R is selected from the group consisting of a chemical bond and one or more divalent, non-aromatic, C -CIQ hydrocarbylene radicals, and the remainder of R is at least about 85 mole% p-phenylene radical
  • G is about 1 to 30 mole % of a polyethylene ether radical selected from the group consisting of -(CH 2 )2-0-(CH2)2- an£ -(CH 2 ) 2 -0-(CH 2 ) 2 -0-(CH 2 )2- the remainder of G is a hydrocarbylene radical selected from the group consisting of -(CH 2 ) 2 -, -(CH 2 )3-, and -(CH 2 )4- radicals, wherein Q is derived from an hydroxy acid of formula HO[-C(0)-Q-0-] x H, where x is an integer, such hydroxy acid having a melting point at least 5 C below its decomposition temperature, and is selected from the group consisting of
  • some of the G may be a radical of a polyalkylene glycol of
  • 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 from non- aromatic dibasic acids, such as adipic acid (abbreviation 6) and glutaric acid (abbreviation 5), as well as from terephthalic acid (abbreviation T), a metal sal of a 5-sulfoisophthalic acid (abbreviation 5SI), ethylene glycol (abbreviation 2 or other lower alkylene glycol (such as 3G and 4G), and polyethylene ether glycols (abbreviations DEG or TEG), and, if desired, a C2-C4 polyalkylene ether glycol of the indicated higher molecular weight (such as PEG), undergo degradation when subjected to the conditions of moisture and temperature tha typically characterize composting operations. It is also significant that the bulk the monomers resulting from degradation, i.e. the acids and the glycols, are readily digested by organisms in solid waste or compost to create carbon dioxid methane and water.
  • a preferred polyester of the invention is that indicated by the abbreviation 2G/DEG-T/5SI/5 and/or 6, containing up to 20 mole % of DEG, and containing 1.5 to 2 mole % of 5SI and 10 to 40 mole % of adipic and/or glutaric acid.
  • numbers are used to connote the mole percentages of the glycol and of the diacid monomeric units in the polyester, while any PEG content may be denoted in weight (w) % of the total polymer, if so indicated, or by numbers like the other mole percentages if not so indicated.
  • 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.
  • 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.
  • hydroxy acid residues may be incorporated. This may be effected by transesterification carefully to provide copolyesters containing, by weight of the copolyester, at least about 60% of glycol/diacid polyester as discussed and illustrated in first part of Formula (I) with up to about 40% consisting essentially of structural units of the formula [-C(0)-Q-0-], and wherein Q is such that the hydroxy acid HO-C(0)-Q-OH, which may be a polyhydroxy acid, has a melting point at least 5 C below its decomposition temperature, and Q is preferably -CH 2 -, -CH 2 -CH -, -CH 2 -CH 2 -CH 2 -, -(CH 2 ) 5 -, -C(CH 3 )H- , or -C(R')H-CH 2 -, where R' is selected from the group of -CH3 and -CH -CH3, similar to the copolyesters more fully
  • polyesters of the invention consist essentially of recurring structural units of Formula I
  • R is selected from the group consisting of a chemical bond and one or more divalent,non-aromatic, Ci-Cio hydrocarbon radicals, and the remainder of R is at least about 85 mole p-phenylene radical
  • G is about 1 to 30 mole % of a polyethylene ether radical selected from the group consisting of -(CH 2 ) 2 -0-(CH 2 ) - and -(CH 2 ) 2 -0-(CH 2 ) 2 -0-(CH 2 ) 2 - the remainder of G is a hydrocarbylene radical selected from the group consisting of -(CH 2 )2-5 -(CH2)3-, and -(CH 2 )4- radicals, wherein Q is derived from an hydroxy acid of formula HO[-C(0)-Q-0-] x H, where x is an
  • about 5 to 40 mole % should be an alkylene or other residue from an organic C 2 -C ⁇ 2 non aromatic dibasic acid, with at least about 85 mole % of the remainder (about 60 to 95 mole %) being T (para- phenylene), with optional inclusion of up to about 15% mole % of I (meta-phenylene) .
  • G radicals about 1 to 30 mole % are preferably DEG and/or TEG (i.e., polyethylene ether radicals -(CH 2 ) 2 -0-(CH 2 ) - and
  • PEG a radical of a polyafkylene glycol of MW at least about 250
  • 2G, 3G and/or 4G i.e. G2-C4 lower alkylene groups
  • the polymer contains sulfo groups, such as are described inU. S. Patent No. 3,018,272 (Griffing and Remington), the disclosure of which is hereby incorporated by reference.
  • the amount of sulfo groups in the polymer should be about 0.1 to 2.5 mole %.
  • about 0.1 to 2.5 mole % of the R may be 5SI and/or 4SP radicals, as described herein, or may be another sulfo group suggested by Griffing et al.
  • about 0.1 to 2.5 mole % of the G may be the sulfo group.
  • the content of sulfo group-containing radical is calculated with respect to the recurring structural units of the formula .
  • radicals may, however, be contained in other units, i.e., other than in the R or G units, for instance in end groups, if desired.
  • the radicals containing sulfo groups need not necessarily be aromatic, although 5SI and 4SP have given good results. Preferred amounts are about 1.5 to 2 mole %.
  • 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 5SI). They also have relatively low glass transition temperatures, Tg.
  • the Tg of the polyester fibers or films 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 Tg of about 80 C. Even a 2G-T polyester containing 2.5 mole % of 5SI has a Tg value of 76 C.
  • the replacement of some terephthalic acid with an aliphatic acid, such as azelaic, succinic, adipic, sebacic or glutaric acid, is advantageous in lowering the Tg.
  • the organic non-aromatic dibasic acid 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 as dibasic acids having larger numbers of carbon atoms are not yet commercially available.
  • C2 oxalic acid
  • C12 dodecanoic acid
  • the aforesaid parent applications provide for incorporating small amounts of such aliphatic acids. The more of such acid that is added, the more significant is the effect of such incorporation. It is not, however, desirable to lower the melting point of the
  • SUBSTITUTE polymer to such an extent as to impair its usefulness, depending on the desired end-use, and it is generally desirable to incorporate no more than about 40 mol % of such acid. Preferred amounts are 10-30 mole %.
  • the polyesters of the invention can have a further significant reductio in their Tg values.
  • a polyethylene ether glycol such as DEG or TEG (triethylene glycol)
  • Tg polyethylene ether glycol
  • the glycol component may advantageously contain a polyethylene ether radical, such as DEG or TEG, 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, as indicated by Tietz.
  • a polyethylene ether radical such as DEG or TEG
  • the acid component preferably includes about 1.5 to 2 mole % 5SI.
  • 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. As little as 0.1 mole % of 5SI contributes significantly to the degradability characteristics of the resultant fibers and films.
  • other sulfo group-containing units may be included, as taught in U. S. Patent No.3,018,272.
  • the metal ion is preferably an alkali metal such as sodium, potassium or lithium. However, alkaline earth metals such as magnesium are also useful.
  • a 5-sulfoisophthalate that has given very good results is the sodium salt.
  • a relative viscosity of at least 16, preferably at least about 18, is generally acceptable for melt spinning performance.
  • the polyesters of the invention may be prepared by conventional polycondensation techniques using, for example, as the glycol component, a combination of about 15 to 20 % by weight of the polyalkylene glycol, with a complemental molecular amount of ethylene glycol, and, as the acid component, a combination of about 10 to 40 mole % of the non-aromatic acid, about 57 to 89.9 mole % of terephthalic acid and about 0.1 to 2.5 mole % of a metal salt of 5-sulfoisophthalic acid, which is a preferred component containing the sulfo groups. Any carbonic acid residues are conveniently introduced by transesterification. Optionally up to about 5 mole % of the ethylene glycol can be replaced by another glycol. In lieu of the mentioned dicarboxylic acids, ester- forming derivatives such as the dimethyl esters of the acids may be used.
  • 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 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, which may be polymeric, such as polyethylene adipat , polylactide, polyglycolide or polycaprolactone, and completion of the polymerization.
  • the monomeric components such as polyethylene adipat , polylactide, polyglycolide or polycaprolactone
  • the polyesters of the invention are very hydrolytically sensitive, having a higher equilibrium moisture content than 2G-T resin and a faster moisture regain rate. It is desirable that isolated flake be dried thoroughly, preferably o 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 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 mentione above so that temperatures high enough for rapid polymerization can be attained without fusing of the flaked resin.
  • a ticaking 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 Iinde Molecular Sieve 13X, type 9356, with a nominal pore size of lOA, obtained from Union Carbide Corporation.
  • a crystalline sodium aluminosilicate molecular sieve such as Iinde Molecular Sieve 13X, type 9356, with a nominal pore size of lOA, obtained from Union Carbide Corporation.
  • 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 b - 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 J.J. Smith) or by stretching and drawing embossed films of the thermoplastic polymers (British Patent 914,489 and 1,548,865 to Smith and
  • 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 “Principles of Stitch Through Technology” Nonwovens Fabrics Forum, Clemson University, Clemson, S C 1978 by J.D. Singelyn). Reinforcement can also be accomplished by adhesive bonding which includes impregnation of the web by a
  • 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. 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.
  • blowing process may also be used as an adhesive layer between other nonwove 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 powde 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 ma 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 and/or reinforced with fibers 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 disintegratabihty. Use of starch is particularly helpful, as taught in PCT Application (QP-4850-A), and in Example 11 herein.
  • the incorporation of finely divided particulates has likewise been found helpful, for instance incorporating similar amounts of calcium carbonate in similar compositions.
  • microporous films are taught by Moss in U. S. Patent No. 4,698,372, and similar techniques may be followed with products of the present invention.
  • Advantageous results have also been obtained by using blends with tartarates and citrates, such as dibutyl tartarate and triethyl citrate.
  • 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 endothe ⁇ nic 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 150C 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 benzyl alcohol to a colorimetric endpoint
  • Inherent viscosity is defined in "Preparative Methods of Polymer Chemistry", W. R. Sorenson and T. W. Campbell, 1961, p. 35. It is determined a a concentration of 0.5 g/100 ml of the indicated solvent at the indicated temperature, usually HFTP at 30 C.
  • Tensile Properties of fibers and yarns are 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% RH, 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.
  • Fabric samples are 1 inch X 8 inches (with 5 inches gauge length), are conditioned prior to testing, and are extended in a commercial testing machine at a rate of 100% per minute. Paper laminates in Examples 6 and 7 are tested as 1 inch wide strips at a 5 inch gauge length at 100% E/min after conditioning at 65% RH 70 F.
  • Results are reported as T/Emax/Eult/M/To (Tenacity at maximum load/Elongation at that load/Ultimate elongation at break/Initial Modulus/Toughness).
  • the corresponding units are Ib/in/oz/yd ⁇ , percent, percent, lb/in/oz/yd ⁇ and lb/in/oz/yd ⁇ , respectively.
  • 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 H S04-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 0.1 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 0 monochromator set to exclude copper K b radiation. Diffracted radiation 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 5 and 343. Crystallinity index is defined as
  • Crystallinity index has been o related to percent crystallinity determined by density (see U.S. 4,704,329, col
  • Copolyester resin 11 of Table 1 A was made to have the following composition:
  • composition may result from generation of DEG as a byproduct during polymerization and its incorporation in the copolymer in minor amounts.
  • Table IB shows polymers that contain a proportion of PEG (the mole % has been indicated) in addition to a proportion of glutaric acid, but the procedures are otherwise essentially as in Example 5 of USP 5,097,004.
  • Table IA indicates polymers that are similar, but do not contain PEG.
  • the aliphatic acid indicated was glutaric acid, except that the (6) indicates adipic acid, in items 3, 10-12, and 18.20 mole % of hexahydroterephthalic acid (HT) was used in addition to 20 mole % of glutaric acid or adipic acid, respectively, in items 17 and 18.
  • Item 19 is a polymer having the composition 2G/DEG(80/20)-T/DBE-3/5SI(77/21/2), where DBE-3 is a 90/10 mixture of dimethyl adipate and dimethyl glutarate that is commercially available from Du Pont.
  • the hydrolysis of this item and of items 11 and 12 have asterisks (*) because item 19 was hydrolysed at 60 C for 7 days, and items 11 and 12 were hydrolysed at 100 C for 8 hours, whereas other items in the Table were hydrolysed at 100 C for 24 hours.
  • polyesters of the invention in contrast with only 17% for A, which was a comparison, containing no 5SI.
  • the Toughness (To) of some films was excellent, whereas other items were not so tough (but generally hydrolysed quite rapidly).
  • 2G-T compositions with 40-60 mole % of combined DEG and glutaric acid content, with at least 30 mole % glutaric acid, and 1.6 mole% 5SI, are rubbery and useful as adhesives.
  • adipic acid in place of glutaric acid is
  • This Example shows the use of a low melting, water insoluble, polyester composition as a degradable compostable hot melt adhesive.
  • the capillary was removed from the molten polymer, and, after cooling, the polymer was recovered from the tube and ground into small particles in a Thomas mill using liquid nitrogen to embrittle the polymer. This flake, when dried at 100-130 C under laboratory vacuum, coalesced to a solid 0 block. The melting point was 114 C.
  • polyesters may blend them with plasticizers and/or tackifiers.
  • This Example shows the spinning to a fiber and hydrolysis testing of the fiber from the 2G-T/6/5SI (78/20/2), polymer prepared as item 11 in Table IA of Example 1.
  • the ground polymer was dried overnight under laboratory vacuum at about 90 C, then molded into a 7/8" diameter plug, which was placed in a press spinning apparatus and spun through a 5 hole-(.015 inch x .045 inch) spinneret at 231 C.
  • the filament yarn was led first around a pair of takeup rolls running at 400 m/min, then over a heated (70C) pin, about 3/4" in diameter, to draw rolls running at 500 m/min, and then onto a bobbin.
  • Example 3 demonstrates the preparation of foamed fibers from the same polymer as in Example 3.
  • the apparatus used consists of two high pressure cylindrical chambers, each equipped with a piston which is adapted to apply pressure to the contents of the vessel.
  • the cylinders have an inside diameter of 1.0 inch (2.5 cm) and each has an internal capacity of 50 cubic centimeters.
  • the cylinders are connected to each other at one end through a 3/32 inch (2.3mm) diameter channel and a mixing chamber containing a series of fine mesh screens used as a motionless mixer. Mixing is accomplished by forcing the contents of the vessel back and forth between the two cylinders through the motionless mixer.
  • a spinneret with a quick-acting means for opening the orifice is then attached to the channel through a tee.
  • the pistons are driven by high pressure water supplied by a hydraulic system.
  • the apparatus was charged with polymer pellets and solvent, then high pressure water, e.g. 1200 psi, was introduced to drive the piston to compress the charge.
  • the contents were then heated to mixing temperature and held at that temperature for about an hour or longer, during which time an alternating differential pressure of about 100 psi or greater was established alternatively between the two cylinders to force the contents through the mixing channel back and forth, from one cylinder to the other, to provide mixing and effect formation of a solution.
  • the solution temperature was then set to the desired spin temperature, and held there for about 15 minutes to equilibrate the temperature. Mixing was continued throughout this period. Finally, the spinneret orifice was opened, and the resultant flash-spun product collected.
  • the fiber obtained was about .033" in diameter and about 3500 dpf., i.e., about 46 % void volume.
  • This Example demonstrates the preparation of a copolyester fiber of the invention from ingredients which include a commercially available mixture ⁇ 90/10 dimethyl adipate/dimethyl glutarate (DBE-3, referred to Example 1 above), and hydrolysis testing of the fiber.
  • ingredients which include a commercially available mixture ⁇ 90/10 dimethyl adipate/dimethyl glutarate (DBE-3, referred to Example 1 above), and hydrolysis testing of the fiber.
  • the polymer composition was 2G/DEG(80/20)-T/5/6/5SI (77/2/19/2).
  • DBE-3 and 5SI were added to a mix tank containing ethylene glycol and catalysts.
  • the catalyst was a mixture of manganese acetate, antimony trioxide, sodium acetate, and tetrapropyltitanate in a mole ratio of 4.6/4.3/1.7/1, respectively.
  • the entire mixture was continuously fed from a mix tank to a first vessel, where ester interchange was carried out and diethylene glycol formed.
  • the temperatures in this vessel ranged from approximately 65 C at the top of the column to approximately 236 C at the bottom.
  • the vessel was operated at atmospheric pressure with a hold-up time of about 65 minutes.
  • Dimethyl terephthalate in molten form was directly metered into the first vessel. Pure uncatalyzed glycol was metered into the vessel to adjust the catalyst level to approximately 110 ppm Mn based on the polymer to be formed. The molar proportion of ethylene glycol to the acid components was approximately 2:1.
  • the low molecular weight material was then pumped to a third vessel, where the temperature was increased to about 268 C and the pressure reduced to about 60 mm Hg. Excess glycol was again removed through a vacuum system over a period of about 12 minutes.
  • the low molecular weight material was then transferred to a fourth vessel, where the temperature was controlled at approximately 277 C and the pressure reduced to 3-5 mm Hg. The pressure was automatically adjusted to maintain the polymer melt viscosity determined by an in-line viscometer. After about 200 minutes, the polymer was recovered, and found to have a relative viscosity (RV) of approximately 17.
  • RV relative viscosity
  • the polymer was then spun into amorphous monocomponent filaments by extruding through orifices (of about 0.38 mm diameter) of a spinneret maintained at 260 C. As the filaments left the spinneret, they were quenched with air at 21 C, collected into a bundle, and then about 0.4% of a spin finish was applied. The filaments were wound at 1050 yards per minute to give a yarn containing 900 filaments and a total denier of 6700.
  • Bundles of yarn were collected to form a tow of approximately 36,000 filaments, which were drawn in a single stage at a draw ratio of about 3.3X.
  • the fibers were crimped in a stuffer box crimper, and heat-set under essentially no restraint in an oven for 8 minutes at 72 C.
  • the resultant filaments had a denier of 2.0, a tenacity of 2.4 grams/denier, an elongation of about 86%, a crimp level of 13-14 crimps per inch, and a crimp index of approximately 17.
  • the initial Mn of the fiber (average of 2 determinations) was 34220. Hydrolysis of the fiber at 60 C in water for 1 day, reduced Mn to 9290 (avg of 2 det.), and after 2 days to 6480 and only powder remains, and after 7 days to
  • This Example shows the preparation of calendared laminates with different types and weights of paper using a degradable film of composition (2G/DEG(90/10)-T/5/5SI(73/25/2).
  • the laminates were prepared by making an assembly of a film, approximately 0.5 mil thick, and coated on release paper, in contact with a similar-sized sheet of the paper to be coated, and then passing this assembly through the nip between a heated polished metal top roll and an unheated resilient (silk) roll at a surface speed of 5 yd/min. at a temperature of 200 F and under a pressure of 10 tons.
  • Comparison samples numbered 7 to 12 in Table 6B, corresponding to numbers 1-6, respectively, were prepared similarly, except using a coating copolyester with 2G/DEG/PEG 600(86.4/6.5/7.1)- T/5SI(98/2), i.e. not according to the present invention.
  • Pieces of the laminates (3 - ⁇ 8" x 8") were placed in a rotary composter with about 0.5 cu yd ⁇ of mixed municipal solid waste (from which glass, cans and much of the light plastic and paper had been removed) and sewage sludge in the ratio of about 2/1.
  • the composter was rotated once a week and the temperature and moisture content monitored. After 1 week temperature was 60 C , moisture 46.9%: after 2 weeks they were 48.9 C, 47.2%; after 3 weeks 32.2 C, 56.9%. After 4 weeks the compost was removed and the samples retrieved by hand sorting. Table 6C gives the results. (Notice that samples 2 - 6) with the coating of this invention showed the most disintegration).
  • Example 4 describes extrusion-coated paper laminates, using the extrusion-coating procedure and apparatus described in Example 1 of USP 5,097,004, with temperatures in degrees F.
  • the polymer compositions are given in the Table 7A for the components other than 2G-T.
  • the polymer of item 3 was prepared by a method similar to that of Example 5 herein, while the others were prepared by methods similar to that of Example 1 of USP 5,097,004.
  • the resin was placed in a hopper above the inlet of a 1 inch (2.5 cm) extruder (Echlin Mfg. Company Serial #0717) with an 18 inch wide film die with a 0.007 inch gap.
  • An 18 inch wide non woven fabric was led continuously at a speed of 47-106 ft/min through an extrusion coating machine made by Bertek Inc. of St. Albans, VT.
  • the paper to be coated (2 ply, 11 inch wide roll of household paper towel-Bounty brand made by Procter & Gamble Cincinnati, Ohio 45202) was fed over this support fabric, and the assembly was led through a
  • Item 4 contains adipic (6) residues, whereas the others contain glutaric
  • Example 7 describes preparation of extrusion-coated nonwoven fabrics, essentially as described in Example 7, except that the coating was extruded directly onto non-woven fabrics instead of onto paper.
  • the resin had been previously crystallized and then dried as described hereinbefore, and sealed in airtight bags, and was poured from such bags directl into the hopper to minimize contact with air.
  • the hopper was sealed, and the resin was preheated by recirculating dry, hot air (air temperature 100-150 deg F, ⁇ -20 deg F dew point) for 1 hour prior to extrusion.
  • Nonwoven fabric B coated with 0.5 mil of composition DEG/(5)/5SI 10/25/2 ((Item 15, Table IA)) was composted in a municipal co-composting IPS facility in Fairfield, CT, in a mixture of shredded yard waste and sewage sludge- (1:1 sludge:yard waste). The compost was turned once every working day. had an initial moisture content of 60% and a neutral pH. Forced aeration was used to control the temperature, with actual temperature of the compost running from 43-65 deg C for the 21-24 day composting cycle. At the end of the composting ycle, the residual fragments of coated nonwoven fabrics were recovered. Upon
  • Films of polymer of composition 2G/DEG(90/10)-T/5/5SI(58/40/2) (14 of Table IA) were tested, using 100% of such polymer and blends with com starch using a Brabender as described in Example 1 (of copending PCT Application QP-4850-A). The films were pressed as described in Example 1 (of QP-4850-A). Samples of film about 3-4" in diameter were tagged by bolting between two marked 1" x 1" x 1/16" polytetrafluoroethylene sheets and placed in a rotary composter with 2/1 municipal solid waste and sewage sludge for 28 days, as described in Example 6.
  • This Example describes the preparation of paper laminates with polyesters containing comstarch filler and their degradation by composting.
  • the 75% starch blend was too stiff to flow readily enough (under these conditions) to form a good laminate.
  • This Example shows the preparation of starch/copolyester and starch/copolyester/biodegradable additive compositions continuously in a twin screw extruder, injection molding of some of the compositions and their evaluation in composting.
  • the polymer pellets were dried overnight in a large tray dryer at 80 C with hot dry air recirculation to a moisture content of less than 0.04%.
  • Corn starch (Corn Products 3005 from CPC International, Inc.), and rice starch (Sigma Chemicals catalogue #S7260) were dried overnight in a large tray vacuum oven at 90 C and less than 1 mm Hg vacuum to a moisture content of less than 1%, and stored in sealed containers until used.
  • Blends of polymer pellets and starch were made by manually tumbling the materials in plastic bags.
  • the dry (room temperature) starch was added to warm polymer pellets from the dryer, and the (stili warm) mixture fed to the extruder.
  • polyethylene adipate (RUCOFLEX) was used, the polymer and RUCOFLEX were blended first to assure uniform distribution of RUCOFLEX in the warm polymer, prior to addition of the starch.
  • a 60% polymer 1 40% comstarch B 60% polymer 1, 40% rice starch C 55% polymer 1, 40% comstarch, 5% RUCOFLEX D 60% polymer 2, 40% comstarch E 60% polymer 2, 40% rice starch
  • the blends were placed in the feed hopper (with nitrogen purge) of a
  • the RUCOFLEX® lowers die pressure and melt temperature, while improving strand surface smoothness. Samples A, B, D, and E were stiff and brittle while samples C and F were flexible and tough, showing the advantage of using the RUCOFLEX®.
  • composition D a piece of the extrudate from composition D was immersed in room temperature water for 91 hrs. It showed a 1.2% gain in weight, a 4.7% increase in diameter and a 1% loss in length.
  • composition C and F pellets were dried overnight in a large tray drier at 80 C with hot dry air recirculation.
  • Each composition was injection molded, using a 6 oz Van Dorn injection molding machine with the following characteristics;
  • the extruder heater temperature was set at 200 C and the mold was cooled to 20 to 25 C.
  • the injection cycle used was - 1 second boost (1200 psig), 30 seconds inject (600 psig), 15 second hold (0 psig).
  • Ram speed was operated at maximum, screw speed was 60 RPM, and screw back pressure was 50 psig.
  • compositions C and F were placed in a rotary composter (Kemp Compostumbler) with a mixture of 50% municipal solid waste and 50% municipal waste water treatment sludge and allowed to compost for 28 days, turning every week and adding water after two weeks to maintain greater than 40% moisture.
  • the composition C plaque and bar broke into fragments during this treatment.
  • the composition F plaque and bar were substantially intact but all the samples could easily be broken by bending.
  • Gpc analysis of the polyester showed a 31% reduction in Mn for the Composition C
  • the cost of the degradable materials be as low as possible.
  • the main components of the polyesters may generally be such as are available at low cost in large volumes, such as ethylene glycol, 1,4 butylene glycol and terephthalic acid.
  • Inclusion of a small fraction of groups such as carbonate esters generally provides enough fast degrading links so hydrolysis will result in reduction of the molecular weight of the polyester below that at which physical properties are appreciable and/or to the point that microorganisms can digest the residue.
  • aliphatic glycol carbonates in particular tend to decompose at temperatures which are relatively low compared to the melting points of low cost 2GT and 4GT polyesters.
  • copolymers of 2GT or 4GT may be chosen such as have melting points below the decomposition temperatures of the aliphatic polycarbonates used.
  • the poly(diethylene glycol carbonate) polyol used in some of the polymer syntheses described herein may be prepared by the reaction of ethylene carbonate with ethylene glycol or diethylene glycol as an initiator in the presence of a catalyst such as sodium stannate and purified as described in J. Poly Sci Vol 38, 463-476 (1989).
  • a catalyst such as sodium stannate and purified as described in J. Poly Sci Vol 38, 463-476 (1989).
  • Other methods of producing suitable polycarbonates include; the reaction of carbon dioxide with an epoxide (S. Inoue, H.Koinuma, and T. Tsuruta, Poly. Lett, Vol 7, 287, (1969) and Makromol. Chem. Vol 155, p 61 (1972); the reaction of phosgene with glycols; and the reaction of dialkyl or diphenyl carbonate with glycols.
  • Example 12 describes the preparation of a copolymer having the composition 2G/DEG(90/10)-T/l/5/5SI(63/10/25/2), where the "1" represents a carbonate radical, as well as a comparison of a similar composition without 5SI.
  • An oligomer of diethylene glycol carbonate was prepared using a procedure from J. Appl Poly. Sci. Vol. 38, pp 463-476 (1989), combined with an oligomer
  • the flask was heated slowly to an internal temperature of 220 C, as methanol was distilled off. The temperature was then decreased to 200 C and 7.9 g of the above oligomer were added, and the mixture stirred for 30 min.
  • the melt was transferred to a polymer tube which has a side arm and a finely drawn N -inlet capillary tube was inserted to the bottom of the tube.
  • the polymer tube was heated in a glycol vapor bath (198 C), and polymerization carried out for about 1 hr, at house vacuum, and 20 hours at 0.3 mm Hg pressure.
  • the copolymer was made by the following procedure:
  • Fiber spinning was carried out as described in Example 3 herein through a 5 hole spinneret with 0.015" dia x 0.045" long holes, at a spinneret temperature of 204-220 C at a delivery of about 0.7 cc/min, taken up on a roll running at 40 o m/min. and drawn 2X over a hot pin at 80 C.
  • Fiber properties were T/E/M/To
  • This Example shows the preparation of a 2G-T/6(80/20) copolyester 10 endcapped with 0.8 mole % sodium m-carboxy benzene sulfonate groups and its evaluation in hydrolysis vs. a copolyester of the same composition without endcapping with the sulfonate.
  • the polymer was made by the procedure in Example 13 with the following ingredients:
  • the polymerization was carried out in a dimethyl phthalate vapor bath for 1 hour at laboratory vacuum and 4 hrs at 0.5 mm Hg pressure.
  • the polymer obtained had a reddish color.
  • a film about 4-5 mils thick was made by hot pressing some of the polymer between polytetrafluoroethylene films at 225 C.
  • Four l"x4" strips of film 25 were placed in 250 ml of deionized water and refluxed for 24 hrs.
  • One sample strip was removed after 2, 4, 8 and 24 hrs.
  • Mn was determined on the samples by gpc with the following results:-
  • the mixture was placed in the hopper of a single screw volumetric feeder( K-tron, Model No 7)from which it free falls to the inlet of a 28 mm Wemer and Pfleiderer twin screw extmder with a vacuum port( maintained at house vacuum) attached to a 10 inch wide film die with about a 0.010 inch gap.
  • a dry nitrogen purge was maintained in the feed hopper and the feed throat of the extmder.
  • the extmder was operated at 150 RPM screw speed with a heater temperature (C) profile of
  • the extruded polymer films were electrostatically pinned on an 8 inch diameter smooth quench dmm maintained at 26 C with cold water and collected on release paper using a standard tension roll.
  • the quench dmm speed was adjusted from 5 to 15 ft per minute to obtain film samples from about 8 mils to 1.5 mils thick.

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Abstract

Cette invention concerne de nouveaux polyesters, des fibres et des films, des non-tissés fabriqués avec ces fibres et des produits jetables à base de ces polyesters tels que des couches. Ces produits sont dégradables dans les conditions typiques des processus de compostage des déchets, ont un faible coût pour ce qui concerne les ingrédients et possèdent cependant les propriétés de résistance et de solidité nécessaires à une utilisation finale comme couches jetables. Les polyesters sont principalement constitués de téréphtalate de polyalkylène copolymérisé avec un diacide non aromatique tel que des acides adipique et glutarique, et contenant du di- ou triéthylène glycol et des groupes sulfo de métaux alcalino-terreux ou de métaux alcalins, tels qu'un dérivé métallique d'acide 5-sulfo-isophtalique.
PCT/US1992/008172 1991-10-01 1992-10-01 Polyesters sulfones et utilisation de ces derniers dans des produits pouvant etre transformes en compost, tels que des couches jetables WO1993007198A1 (fr)

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US07/834,794 US5171308A (en) 1990-05-11 1992-02-13 Polyesters and their use in compostable products such as disposable diapers

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WO1998012245A1 (fr) * 1996-09-20 1998-03-26 Basf Aktiengesellschaft Dispersion aqueuse d'un polyester biodegradable et son utilisation
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
WO2013079378A3 (fr) * 2011-12-01 2013-08-29 Basf Se Procédé de fabrication de papier chargé en utilisant des fibres de polyester et/ou de polyalkylènecarbonate biodégradables
US8940135B2 (en) 2011-12-01 2015-01-27 Basf Se Production of filled paper using biodegradable polyester fibers and/or polyalkylene carbonate fibers
JP2017020147A (ja) * 2015-07-15 2017-01-26 三菱レイヨン・テキスタイル株式会社 改質ポリエステル繊維を含む抜蝕加工織編物及びその製造方法

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TWI480295B (zh) * 2012-08-31 2015-04-11 Tai Yuen Textile Co Ltd 表面具有熱融膠的透氣防水薄膜與其形成方法

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WO1998012245A1 (fr) * 1996-09-20 1998-03-26 Basf Aktiengesellschaft Dispersion aqueuse d'un polyester biodegradable et son utilisation
US6103858A (en) * 1996-09-20 2000-08-15 Basf Aktiengesellschaft Aqueous dispersion of a biodegradable polyester and its use thereof
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
AU781686B2 (en) * 1999-08-09 2005-06-09 E.I. Du Pont De Nemours And Company Biodegradable oriented aromatic polyester film and method of manufacture
WO2013079378A3 (fr) * 2011-12-01 2013-08-29 Basf Se Procédé de fabrication de papier chargé en utilisant des fibres de polyester et/ou de polyalkylènecarbonate biodégradables
US8940135B2 (en) 2011-12-01 2015-01-27 Basf Se Production of filled paper using biodegradable polyester fibers and/or polyalkylene carbonate fibers
JP2017020147A (ja) * 2015-07-15 2017-01-26 三菱レイヨン・テキスタイル株式会社 改質ポリエステル繊維を含む抜蝕加工織編物及びその製造方法
EP3323913A4 (fr) * 2015-07-15 2018-07-11 Mitsubishi Chemical Corporation Fibre de polyester modifié, tissu tissé et tricoté à finition opale contenant la fibre et son procédé de fabrication
US20180209074A1 (en) * 2015-07-15 2018-07-26 Mitsubishi Chemical Corporation Modified polyester fiber, etching finished woven and knitted fabric containing the fiber, and method for producing same

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TW211030B (fr) 1993-08-11

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