EP1025180A1 - Copolyesters aliphatiques-aromatiques utilisees en couches de liaison des adhesifs pour les enductions par extrusion - Google Patents

Copolyesters aliphatiques-aromatiques utilisees en couches de liaison des adhesifs pour les enductions par extrusion

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Publication number
EP1025180A1
EP1025180A1 EP98956292A EP98956292A EP1025180A1 EP 1025180 A1 EP1025180 A1 EP 1025180A1 EP 98956292 A EP98956292 A EP 98956292A EP 98956292 A EP98956292 A EP 98956292A EP 1025180 A1 EP1025180 A1 EP 1025180A1
Authority
EP
European Patent Office
Prior art keywords
mole
aliphatic
acid
group
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98956292A
Other languages
German (de)
English (en)
Inventor
Bruce William Foster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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Filing date
Publication date
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP1025180A1 publication Critical patent/EP1025180A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • A61L15/58—Adhesives
    • 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
    • A61L15/58—Adhesives
    • A61L15/585—Mixtures of macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

  • This invention relates to the use of biodegradable copolyesters and copolyester blends as adhesives and particularly the use of aliphatic-aromatic copolyesters and blends thereof as an adhesive tie-layer.
  • the aliphatic-aromatic copolyesters and blends thereof are useful in providing an adhesive tie-layer for dissimilar materials and particularly for materials having a surface energy of less than about 50 dynes/centimeter (cm).
  • nonwoven web refers to a web structure composed of individual fibers or threads which are, typically, randomly interlaid and are bonded or intertwined without weaving or knitting.
  • nonwoven fabrics have been widely used for garments, carpets, diapers, sanitary articles, and industrial materials, such as wipers or towels.
  • Fibrous materials which have been used in the formation of nonwoven fabrics include polyolefins, such as, polypropylene, aromatic polyesters, such as PET and polybutylene terephthalate (PBT), polyamides such as nylon and cellulosics such rayon.
  • Nonwoven fabrics can be made using a variety of known methods and processes, such as meltblowing, spunbonding and carded web process.
  • Such materials may not be ideally situated for a specific application, having only a few certain desired properties. Very often it is desirable to coat a substrate having one set of properties to impart new properties to the composite.
  • the material must be comfortable to the wearer and preferably is biodegradable.
  • most nonwoven materials are fluid permeable. Thus, the fabric would not prevent body fluids from contacting the wearer.
  • the nonwoven material must be coated or covered with a material that prevents fluids from entering the garment and desirably, is still breathable so as not to detract from the comfort of the wearer.
  • An ideal material that provides such barrier properties is cellulose acetate proprionate (CAP). Unfortunately, it is difficult to get CAP to adhere to a non-woven fabric. Therefore, one or more tie-layers must be used between CAP layer and the non-woven fabric to get the proper adherence.
  • CAP cellulose acetate proprionate
  • tie-layers are available in the prior art for adhering one layer to another. However, this becomes more difficult when the layers tied together are dissimilar in properties. This problem becomes even more difficult when the tie-layer must not interfere with the desirable properties of the various but dissimilar layers. Again, using medical garments as an example, the tie-layer must not interfere with the favorable barrier properties of the external layer (i.e., CAP) or the wearability of the internal layer (i.e., non-woven fabric).
  • CAP barrier properties of the external layer
  • the internal layer i.e., non-woven fabric
  • a further problem is that in many applications a composite comprising two or more layers having a tie-layer in between one or more of the layers must be "environmentally-friendly", e g , it must be readily disposable and desirably is biodegradable This is particularly true in medical garments, since used medical garments are often likely to be contaminated with potentially hazardous body fluids, such as blood. Disposable medical garments which are worn once and then disposed of have become the standard and are often mandated for use Thus, any tie-layer used in such composites must also be readily disposable
  • biodegradable aliphatic-aromatic copolyesters can successfully be used as an adhesive tie-layer for bonding a variety of dissimilar materials.
  • the tie-layer can be formed into a contiguous film providing an impermeable barrier to liquids, and possibly other environmental health hazards such as fungus, pollen, and microbial viruses and bacteria, and yet having a high moisture vapor transmission rate (MVTR) so that, when used in a composite garment, the garment can have good wearability.
  • MVTR moisture vapor transmission rate
  • the present invention provides a method for adhesively securing at least two materials together, and advantageously, materials of dissimilar properties to form a laminated web.
  • the present invention provides a method for adhesively securing two materials together wherein the adhesive includes an aliphatic- aromatic copolyester.
  • Another aspect of the invention is for a method for adhesively securing two materials together wherein the adhesive includes a binary and/or ternary blend of an aliphatic-aromatic copolyester and a cellulose ester.
  • the laminate is capable of being used in diverse composites such as medical garments, coated papers, and wet or dry packaging applications.
  • the figure illustrates a schematic representation of an exemplary process for foming a laminated composite of the present invention.
  • biodegradable aliphatic-aromatic copolyesters can be used as an adhesive tie layer for bonding a variety of materials, and particularly dissimilar materials, and more particularly materials having a surface energy of less than about 50 dynes/cm.
  • a portion of at least one of the layers to be positioned in a facing relationship relative to the other layer is coated with a co-compatible adhesive material having an aliphatic-aromatic copolyester and/or a blend of a cellulose ester and an aliphatic-aromatic copolyester.
  • the laminate if to be used as a fabric for a disposable garment, has a surface energy gradient from low to high relative to the layer positioned adjacent to or in contact with the wearer's skin.
  • the laminated composite of the invention is formed from a first layer material 10 which is typically unwound from a supply roll 12 and travels in the direction as indicated.
  • a tie layer composition 14 is coated onto the surface 16 of first layer material 10, which is adapted to be positioned in a facing relationship with a second material 18.
  • the coated first layer is then mated to the second material, preferably CAP or CAB, which then passed through the nip rolls 20.
  • Materials suitable for use in forming the layers of the laminate include natural and synthetic materials with synthetic materials being preferred.
  • suitable materials include nonwoven webs of synthetic fibers. The webs can be made using extrusion processes well known to those skilled in the nonwoven art, such as meltblowing, spunbonding, and carded web.
  • nonwoven webs have discontinuous, spaced regions that impart fluid mobility through the web.
  • the nonwoven web may be a single layer or a multi-layered material.
  • the nonwoven web may be elastic or extensible, in that the material is capable of being stretched in at least one direction when a biasing force is applied and then substantially returns to its pre- stretched shape or configuration.
  • substantially returns means the nonwoven web has less than about 5 percent permanent deformation, as measured 24 hours after the biasing force has been removed from the nonwoven web.
  • the nonwoven web may also be a composite made up of a mixture of two or more different fibers and particles. Such mixtures may be formed by adding fibers and particles to the gas stream in which the meltblown fibers are carried resulting in an intimate intermingling of meltblown fibers and other materials. Desirably, the materials have a surface energy of less than about 50 dynes/cm, preferably, less than about 45 dynes/cm and most preferably less than about 30 dynes/cm.
  • the preferred tie layer composition includes a biodegradable copolyester and desirably, includes one or more, including blends thereof, of the biodegradable aliphatic-aromatic copolyesters, (AAPE), described in U.S. Patent Nos. 5,661, 193; 5,599,858; 5,580,911; and 5,446,079 the entire disclosures of each being incorporated herein by reference. More specifically, the aliphatic-aromatic copolyesters useful in the present invention can be linear random copolymers preferably having repeating units of:
  • R 1 and R 3 are the same and are selected from the groups consisting of C 2 -C 8 alkylene or oxylalkylene;
  • R 2 is selected from one or more of the groups consisting of Co-C 8 alkylene or C -C 4 oxyalkylene, and the mole % of R 2 is from about 95-35%;
  • R 4 is selected from the group of C ⁇ -Cio aryl, and the mole % of R 4 is from about 5-65%o.
  • More preferred AAPE are those wherein R 1 and R 3 are the same and are selected from C 2 -C 4 alklyene; R 2 is selected from one or more of the groups consisting of C 2 -C ⁇ alkylene or C oxyalkylene, and the mole % of R 2 is from about 95-40%; R 4 is l,4-disubstituted-C6 aryl, and the mole % of R 4 is from about 5-60%.
  • the most preferred compositions for these AAPE are those prepared from the following diols and diacids (or polyester forming derivatives thereof) in the following mole %>, based on 100 mole percent acid and 100 mole percent diol:
  • Glutaric acid (30-65%); diglycolic acid (0-10 mol %); terephthalic acid (25- 60%); 1,4-butanediol (100 mole %).
  • Succinic acid (30-85%); diglycolic acid (0-10%); terephthalic acid (5-60%); 1,4-butanediol (100 mole %).
  • Adipic acid (30-65%); diglycolic acid (0-10%); terephthalic acid (25-60%); 1,4-butanediol (100 mole %).
  • Such compositions are commercially available from Eastman Chemical
  • AAPE poly(tetramethylene glutarate-co- terephthalate-co-diglycolate) [50/45/5], poly(tetramethylene glutarate-co-terephthalate)
  • the aliphatic-aromatic copolyester can be blended, preferably with cellulose esters, to form binary and ternary blends.
  • the cellulose esters useful in formulating the blend can be a cellulose triester or a secondary cellulose ester.
  • cellulose triesters include cellulose triacetate, cellulose tripropionate, or cellulose tributyrate.
  • secondary cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. These cellulose esters are described in U.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147,
  • cellulose esters useful in the present invention can be prepared using techniques known in the art or are commercially available, e.g., from Eastman
  • the cellulose esters useful in the present invention have at least 2 anhydroglucose rings and typically have between 2 and 5,000 anhydroglucose rings; also, such polymers typically have an inherent viscosity (IV) of about 0.2 to about 3.0 deciliters/gram, preferably about 1 to about 1.5, as measured at a temperature of 25° C. for a 0.5 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
  • IV inherent viscosity
  • the DS/AGU of the cellulose esters useful herein ranges from about 1.7 to about 3.0.
  • Preferred esters of cellulose include cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), and the like CAP and CAB are more preferred cellulose esters
  • CAP and CAB are more preferred cellulose esters
  • the most preferred ester of cellulose is CAP
  • the preferred esters of cellulose for blending with aliphatic- aromatic copolyesters are CAP and CAB
  • the preferred ester of cellulose is CAP having a DS/AGU of 2 1 to 2 85 wherein the DS/AGU of acetyl ester is 1% to 50% of the total ester content
  • the most preferred CAPs have a DS/AGU of 2 5 to 2 75 wherein the DS/AGU of acetyl ester is 4%> to 30 % of the total ester content
  • the preferred esters of cellulose for blending with aliphatic-aromatic copolyesters and/or polymeric compounds, biodegradable additives, or hydrophobic agents are CAP and CAB
  • the preferred ester of cellulose is CAP having a DS/AGU of 1 7-3 0 wherein the DS/AGU of acetyl ester is 1% to 50% of the total ester content
  • the most preferred CAP's have a DS/AGU of 2 5-2 75 wherein the DS/AGU of acetyl ester is 4%-30% of the total ester content
  • the aliphatic-aromatic copolyesters that are useful in such blends in the present invention are random copolymers and preferably comprises repeating units of
  • R 5 and R 7 are independently selected from one or more of the following groups consisting of C 2 -C ⁇ 2 alkylene or oxyalkylene, C 2 and C 12 alkylene or oxyalkylene substituted with one to four substituents independently selected from the group consisting of halo, C ⁇ -Cio aryl, and C ⁇ -C 4 alkoxy, C5-C10 cycloalkylene, C5.C10 cycloalkylene substituted with one to four substituents independently selected from the group consisting of halo, C 6 -C 10 aryl, and C ⁇ -C alkoxy
  • R 6 is selected from one or more of the following groups consisting of Co-C] 2 alkylene or oxyalkylene, C ⁇ -C ⁇ 2 alkylene or oxyalkylene substituted with one to four substituents independently selected from the group consisting of halo, C ⁇ -Cio aryl, and C ⁇ -C 4 alkoxy, Cs-Cio cycloalkylene, and C5-C10 cycloalkylene substituted with one to four substituents independently selected from the group consisting of halo, C ⁇ -Cio aryl, and C ⁇ -C 4 alkoxy
  • R 8 is selected from one or more of the following groups consisting of C ⁇ -Cio aryl, C ⁇ -Cio aryl substituted with substituted with one to four substituents independently selected from the group consisting of halo, C ⁇ -C 4 alkyl, and C ⁇ -C alkoxy
  • the aliphatic-aromatic copolyester has from about 10 to about 1,000 repeating units and preferably, from about 15 to about 600 repeating units
  • the mole %> of R 6 in the copolymer can range from 30 to 95%)
  • the mole % of R 8 can range from 5 to 70%>
  • a more preferred range is when the mole % of R 6 is from about 45 to 85%> and the mole % of R 8 is from about 15-55 mole %
  • the most preferred ranges for miscible blends is when R is gluta ⁇ c and the mole % of R 6 in the copolyester ranges from 70 to 85% and the mole % of R 8 range from 15-30 mole %>
  • the most preferred ranges for partially miscible blends is when R 6 is gluta ⁇ c and the mole %> of R 6 in
  • the aliphatic-aromatic copolyester has an inherent viscosity of about 0 4 to about 1 2 as measured at a temperature of 25° C for a 0 5 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane
  • alkyl and alkylene refer to either straight or branched chain moieties such as - CH 2 - CH 2 - CH 2 - CH 2 -and- CH 2 CH(X) - CH 2 -
  • all of the carbon atoms of the cycloalkyl and cycloalkylene moieties are not necessarily in the ring structure, e.g., a C cycloalkyl group can be cyclooctyl or dimethylcyclohexyl.
  • oxyalkylene refers to alkylene chains containing from 1 to 4 ether oxygen groups.
  • polyesters and copolyesters are well known in the art (U.S. Pat. No 2,012,267, incorporated herein by reference in its entirety.) Such reactions are usually carried out at temperatures from 150° C. to 300° C. in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof.
  • the catalysts are typically employed in amounts between 10 to 1000 ppm, based on total weight of the reactants.
  • a representative aliphatic polyester is the polycondensation product of dimethylglutarate and 1,6- hexanediol.
  • This polyester poly(hexamethylene glutarate), is produced when dimethylglutarate and 1,6-hexanediol are heated at approximately 210° C. for 4 hours and then at 260° C. for 1.5 hours under vacuum in the presence of 100 ppm of Ti.
  • a representative aliphatic-aromatic copolyester is poly(tetramethylene glutarate- coterephthalate) containing 30 mole per cent terephthalate.
  • This polyester is produced when dimethylglutarate, dimethyl terephthalate, and 1 ,4-butanediol are heated at 200° C. for 1 hour then at 245° C. for 0.9 hour under vacuum in the presence of 100 ppm of Ti present initially as Ti(O'Pr) 4 .
  • the aliphatic-aromatic copolyester for use in blending is prepared from any polyester forming combination of dicarboxylic acids or derivatives thereof, and diols.
  • Dicarboxylic acids may be selected from the group consisting of the following diacids; malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, diglycolic, itaconic, 1,3-cyclopentanedicarboxylic, 1,4- cyclohexanedicarboxylic, meleic, 1,3-cyclohexanedicarboxylic, 2,5-norbornanedicarboxylic, 1,4-terephthalic, 1,3-terephthalic, 2,6-naphthoic, 1,5-naphthoic, and ester forming derivatives thereof, and combinations thereof; and said diols are selected from the group consisting of
  • preferred aliphatic-aromatic copolyesters for blending include poly(tetramethylene glutarate-co-terephthalate-co-diglycolate) [50/45/5], poly(tetramethylene glutarate-co-terephthalate) [50/50], poly(tetramethylene glutarate- co-terephthalate) [60/40], poly(tetramethylene glutarate-co-terephthalate) [70/30], poly(tetramethylene glutarate-co-terephthalate [85/15], poly(tetramethylene glutarate- co-terephthalate) [70/30], poly(tetramethylene adipate-co-etrephthalate) [85/15], poly(tetramethylene succinate-co-terephthalate) [85/15], poly(tetramethylene-co- ethylene glutarate-co-terephthalate) [50/50] [70/30].
  • the aliphatic-aromatic copolyest
  • the aliphatic acid residue, -CO-R 10 -CO- is present in an amount "b” ranging from 30 to 95 mol percent, preferably 55 to 60 mol percent, and contains 3 to 40 carbon atoms, preferably 3 to 12 carbon atoms.
  • the aromatic acid residue, -CO-Ar-CO- is present in an amount "d” ranging from 5 to 70 mol percent, preferably 40 to 45 mol percent, and contains from 8 to 40 carbon atoms, preferably 8 to 14 carbon atoms.
  • the diol residues, -O-R 9 - and -O-R H -O-, which contain from 2 to 20 carbon atoms are present in an amount a of 0 to 100 mol percent and in an amount "c" of 100 to 0 mol percent, respectively.
  • the mole percent of the acid components and diol components are each based on 100 mole percent.
  • the aliphatic acid components are preferably selected from the group consisting of malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1,3-cyclopentane-dicarboxylic, 1,4-cyclohexanedicarboxylic, 1,3-
  • SUBST ⁇ UTE SHEET (RULE 25) cyclohexnedicarboxyhc, diglycolic, itaconic, maleic and 2,5-norbornaned ⁇ carboxyhc Hydroxy acids such as 4-(hydroxymethyl) cyclohexanecarboxyhc acid, hydroxypivahc acid, 6-hydroxyhexano ⁇ c acid, glycohc acid, lactic acid and ester forming derivations thereof may also be used as aliphatic acid components to make these co-polyesters
  • the aromatic acid components are preferably selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl 1,3-propanediol, 1,3-butanediol, 1,4-butaned ⁇ ol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4- trimethyl-l,6-hexaned ⁇ o
  • the branching agent is represented by "(BA) X ", wherein "x" is the weight percent of the branching agent The weight percent ranges from 0 01 to 10 percent, preferably 0 1 to 1 0 weight percent
  • the branching agent preferably has a weight average molecular weight of about
  • the branching agent may be a polyol having 3-6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups or a hydroxy acid having a total of 3-6 hydroxyl and carboxyl groups
  • Representative low molecular weight polyols that function as branching agents include glycerol, t ⁇ methylolpropane, 1,2,4-butanet ⁇ ol, pentaerythritol, 1,2,6- hexanet ⁇ ol, sorbitol, 1, 1,4,4,-tetrak ⁇ s (hydroxymethyl) cyclohexane, tris(2- hydroxyethyl) isocyanurate, and dipentaerythritol
  • Particular branching agent examples of higher molecular weight polyols are triols derived by condensing alkylene oxides having 2-3 carbons, such as ethylene oxide and porpylene oxide with polyo
  • polycarboxylic acids that may be used as branching agents include hemimelhtic acid, t ⁇ mellitic acid, t ⁇ mesic acid, pyromellitic acid, benzene tetracarboxylic acid, benzophenone tetracarboxylic acid, 1, 1,2,2,-ethanetetracarboxyhc acid, 1, 1,2-ethanet ⁇ carboxyl ⁇ c acid, 1,3,5-pentanetricarboxyl ⁇ c acid, and 1,2,3,4- cyclopentanetetra-carboxylic acid
  • the acids may be used as such, preferably they are used in the form of their lower alkyl esters or their cyclic anhydrides in those instances where cyclic anhydrides can be formed
  • hydroxy acids as branching agents include malic acid, citric acid, tarta ⁇ c acid, 3-hydroxygluta ⁇ c acid, mucic acid, t ⁇ hydroxygluta ⁇ c acid, and 4- (beta-hydroxyethyl)phthal ⁇ c acid Such hydroxy acids contain a combination of 3 or more hydroxyl and carboxyl groups
  • Especially preferred branching agents include t ⁇ mellitic acid, t ⁇ mesic acid, pentaeryth ⁇ tol, t ⁇ methylol propane and 1,2,4-butanet ⁇ ol
  • polyesters and copolyesters are well known in the art, such as disclosed in U S Pat No 2,012,267
  • Such reactions are typically operated at temperatures from 150° C to 300° C in the presence of polycondensation catalysts such as titanium isopropoxide, manganese diacetate antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof
  • the catalysts are typically employeed in amounts between 10 to 1000 parts per million (ppm), based on total weight of the reactants
  • a branched random aliphatic-aromatic copolyester of the present invention is poly(tetramethylene adipate-co-terephthalate) branched with 0 5 weight percent pentaeryth ⁇ tol and containing 43 mole percent terephthalate
  • This copolyester is produced when dimethyladipate, dimethyl terephthalate, pentaeryth ⁇ tol and 1,4- butanediol are heated at 190° C for 1 hour, 200° C for 2 hours, 210° C for 1 hour, then at 250° C for 1 5 hours under vacuum in the presence of 100 ppm of Ti present initially as Ti(O'Pr) 4
  • the copolyester is typically pelletized after formation for use in extrusion foaming
  • Another branched random copolyester of the present invention is poly(tetramethylene adipate-co-terephthalate) branched with 0 3 weight percent pyromellitic dianydnde and containing 43 mole percent terephthalate
  • This copolyester is produced via reactive extrusion of linear poly (tetramethylene adipate-co- terephthalate) with pyromellitic dianhyd ⁇ de using an extruder
  • an adhesive tie-laver can be formed by extruding the
  • These coatings can have the following structures: Substrate / A Substrate / A / B Substrate / B / A
  • Substrate / C / B / A Substrate / A / B / C Substrate A / B / C / B / A
  • Substrate A / B / C / B / A are accomplished using techniques known to those skilled in the art of co-extrusion coating and laminating.
  • the laminator section of the line included an unwind station, flame and corona discharge pre-treating stations, a nip, or lamination station with a chilled metal roll and rubber nip roll, a secondary unwind station (for laminating), and a rewind station.
  • the line was 42" (107 cm) wide, and was capable of running up to speeds of 2000 feet per minute (610 meters per minute).
  • the foil adhesion numbers were for 1 inch strips separated on a tensile tester according to ASTM D-92. Values are the average of 5 specimens.
  • the CAP is coated onto a polyester nonwoven because it provides a desirable combination of barrier to body fluids and a high moisture transmission rate, thereby providing a breathable, comfortable material.
  • the CAP is extrusion coated directly onto aluminum foil.
  • the plastic layer would generally provide a heat seal medium and barrier to hold in the contents, while the foil will protect the contents from atmospheric oxygen and hence spoilage.
  • the copolyester exhibits no measurable adhesion to the foil.
  • aliphatic-aromatic copolyester of the present invention imparts excellent adhesion to materials having different surface energies as well as composed of normally incompatible materials.
  • the examples further show that the aliphatic-aromatic copolyester of the present invention imparts excellent adhesion to polymers, cellulosics and foils.
  • the examples also show that the aliphatic-aromatic copolyester of the present invention imparts excellent adhesion to bleached board and polyester nonwoven, when co-extruded with CAP at a thickness of 3 to 7 microns, and excellent adhesion to aluminum foil at a thickness greater than about 3 microns.
  • the CAP and aliphatic-aromatic copolyester were coated onto the following substrates a) unprimed aluminum foil, b) woven polyethylene fabric; and c) 350 gsm bleached carton stock, or paperboard
  • the adhesion results are summarized in Table 4 below
  • LDPE 4.2 melt flow, 0.924 density polyethylene EMA (24) - 24% methyl-acrylate ethylene copolymer
  • compatibility with the 24% methacrylate EMA copolymer was acceptable at 20%> EMA.
  • E-BA-MA terpolymers there was no compatibility with a 16.5% BA material, Example 17, and poor compatibility with a 5.5%> BA terpolymer, when the E-BA-MA material constituted 60 to 80% of the blend, Examples 20 and 21.
  • the 5.5% BA terpolymer was blended from 20 - 25%, a material with superior processability resulted.
  • These particular blends also exhibit improved adhesion to polyethylene fabrics and paper substrates, as show in Table 6 below:
  • aliphatic-aromatic copolyesters are useful as adhesive materials in various diverse applications to bond dissimilar materials. It will be recognized by those of skill in the art in possession of the present invention that these bonding materials will bond together one or more materials such as paper, metals, plastics, fabrics, and the like. These adhesive materials are particularly useful as tie-layers in such applications as paper coating for water- based inks, and as a packaging material to protect foil linings from corrosive contents.
  • the aliphatic-aromatic copolyesters are also useful as films when used in co-extrusions with, for instance, extrusion coating grades of polyester and with cellulosic plastics to various substrates.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Hematology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une couche de liaison d'adhésif comprenant des copolyesters aliphatiques-aromatiques biodégradables. Ces copolyesters aliphatiques-aromatiques conviennent particulièrement pour un film biodégradable et/ou imper-respirant ou des enductions par extrusion. Ces matériaux conviennent pour des coextrusions destinées à la liaison de polyesters et de plastiques cellulosiques sur divers substrats. De préférence, le substrat présente une tension superficielle inférieure à environ 50 dynes/cm.
EP98956292A 1997-10-31 1998-10-28 Copolyesters aliphatiques-aromatiques utilisees en couches de liaison des adhesifs pour les enductions par extrusion Withdrawn EP1025180A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US6380197P 1997-10-31 1997-10-31
US63801P 1997-10-31
US17933498A 1998-10-27 1998-10-27
US179334 1998-10-27
PCT/US1998/022893 WO1999023187A1 (fr) 1997-10-31 1998-10-28 Copolyesters aliphatiques-aromatiques utilisees en couches de liaison des adhesifs pour les enductions par extrusion

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EP1025180A1 true EP1025180A1 (fr) 2000-08-09

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US6475618B1 (en) 2001-03-21 2002-11-05 Kimberly-Clark Worldwide, Inc. Compositions for enhanced thermal bonding
SG121017A1 (en) * 2004-09-16 2006-04-26 Jen Chang Kuo An improved backup board
US8227658B2 (en) 2007-12-14 2012-07-24 Kimberly-Clark Worldwide, Inc Film formed from a blend of biodegradable aliphatic-aromatic copolyesters
FI20115226A0 (fi) * 2011-03-07 2011-03-07 Stora Enso Oyj Kuumasaumautuva pakkausmateriaali, sen valmistusmenetelmä ja siitä valmistettu pakkaus
NL2025240B1 (en) * 2020-01-20 2021-09-08 Huhtamaki Molded Fiber Tech Bv Biodegradable multi-layer packaging element, such as a foil or wrap, for a food product, packaging unit with such packaging element, and method for manufacturing such packaging element

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UST100504I4 (en) * 1980-03-31 1981-04-07 Sublett Bobby J Copolyester hot-melt adhesives
US4419507A (en) * 1982-01-25 1983-12-06 Eastman Kodak Company Copolyester adhesives
IT1197270B (it) * 1986-09-25 1988-11-30 Ausimont Spa Composizioni adesive termofusibili a base di poliesteri
DE59006526D1 (de) * 1990-10-16 1994-08-25 Kufner Textilwerke Gmbh Schmelzklebermasse zum rasterförmigen Beschichten von Flächengebilden, insbesondere von Einlagestoffen.
ES2113542T3 (es) * 1992-06-26 1998-05-01 Procter & Gamble Composiciones para peliculas multicapa biodegradables e impermeables a los liquidos.

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Title
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