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WO1991013207A1 - POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS - Google Patents

POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS Download PDF

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Publication number
WO1991013207A1
WO1991013207A1 PCT/CA1990/000058 CA9000058W WO9113207A1 WO 1991013207 A1 WO1991013207 A1 WO 1991013207A1 CA 9000058 W CA9000058 W CA 9000058W WO 9113207 A1 WO9113207 A1 WO 9113207A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
polymer
paper
units
formula
Prior art date
Application number
PCT/CA1990/000058
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English (en)
Inventor
Robert H. Marchessault
Pierre F. Lepoutre
Peter E. Wrist
Original Assignee
Pulp And Paper Research Institute Of Canada
The Royal Institution For The Advancement Of Learning (Mcgill University)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pulp And Paper Research Institute Of Canada, The Royal Institution For The Advancement Of Learning (Mcgill University) filed Critical Pulp And Paper Research Institute Of Canada
Priority to US07/916,990 priority Critical patent/US5451456A/en
Priority to PCT/CA1990/000058 priority patent/WO1991013207A1/fr
Priority to CA002076038A priority patent/CA2076038C/fr
Priority claimed from CA002076038A external-priority patent/CA2076038C/fr
Publication of WO1991013207A1 publication Critical patent/WO1991013207A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters

Definitions

  • This invention relates to a method of preparing a coated or impregnated paper or other fibre construct, a coated or impregnated paper or other fibre construct, a latex for use in the pre ⁇ paration of paper or other fibre constructs and films, and self supporting films.
  • paper is surface treated in order to improve its properties.
  • an aqueous suspension of pigment particles and binder similar to a latex house paint, is applied at high speeds typically up to 100 km/h with roll or blade coaters.
  • the paper is then dried and calendered.
  • the finished surface is very smooth, uniform and glossy and gives excellent print quality particularly in multicolour printing.
  • the binders currently used in pigmented coatings are soluble polymers such as starch or polyvinyl alcohol or latexes based on styrene- butadiene, polyvinyl acetate or acrylic monomers.
  • the synthetic latex binders are not biodegradable.
  • Starch is biodegradable but has poor binding efficiency and is water-sensitive, a problem in multicolour offset printing where water is applied at each station, as well as in water-based gravure or flexographic printing.
  • the market for pigmented coated papers is growing extremely fast, currently about 10-15% per year, and it may be predicted that even the lower grades such as newsprint will be coated one way or another in the near future.
  • the size-press, and its newer versions,' are used to apply a number of chemicals that will change the surface and also the bulk properties of paper. Hydrophobicity, mechanical strength, grease resistance, release properties, friction, flammability, electrical conductivity are examples of properties that can be imparted to paper by such means.
  • Self-supporting polymer films are used in a variety of applications, for example, water imperme ⁇ able films in disposable diapers, and these films too, represent an environmental problem.
  • Self-supporting films which are biocom- patible are also employed for controlled delivery of drugs in the body.
  • Such films may be microporous with the drug being held within the micropores, or the film may form a capsule about the drug, and degrade slowly in the body to release the drug. It is important that the degradation products of such films be non-toxic in the body.
  • Thermoplastic polymers of bacterial origin are known which behave like polypropylene and related polyolefins, but which are biodegradable. These polymers form a family of poly S-hydroxyalkanoates based mainly on /3-hydroxyalkanoic acids containing 4 or 5 carbon atoms and are, more especially, isotactic crystalline polyesters of high molecular weight.
  • poly- ⁇ -hydroxyalkanoates and in particular poly- ⁇ -hydroxy-butyrate (PHB) and ⁇ - hydroxybutyrate-S-hydroxyvalerate) (PHB/V) copolymer are microbially produced in nature and can be synthesised on an industrial scale from a variety of bacteria, by fermentation technology. These polymers are in powder available commercially in a spray dried particle form.
  • This invention seeks to provide a latex for use in the preparation of a coated or impregnated paper which possesses the needed characteristics provided by conventionally employed binders, but which renders the paper biodegradable as well as more readily recyclable.
  • the invention also seeks to provide a biodegradable and more readily recyclable paper.
  • the invention seeks to provide a method of preparing a coated or impregnated paper with a latex in accordance with the invention.
  • the invention seeks to provide a latex for use in the preparation of fibre constructs, for example, non-woven fabrics.
  • the invention seeks to provide a latex for use in the preparation of self- supporting biodegradable or recyclable films.
  • a latex which comprises a colloidal suspension in water of essentially non-crystalline particles of a poly- ⁇ -hydroxy- alkanoate polymer or copolymer.
  • a method of preparing paper which comprises adding to a paper construct a latex of the invention and processing the construct to form a paper coated or impregnated with the polymer or copolymer.
  • a method of treating a fibre construct comprising applying to the fibre construct a latex of the invention and drying the thus treated fibre construct.
  • the polymer coated paper is exposed to solvent vapour to effect penetration of the polymer into the paper.
  • the poly ⁇ -hydroxyalkanoate polymer or copolymer of the invention comprises monomer units of formula (I) :,
  • R is a straight or branched chain alkyl of 1 to 12 carbon atoms.
  • the invention contemplates homopolymers in which all units of formula (I) have the same alkyl substituent R, as well as copolymers formed from different monomer units of formula (I).
  • the latex of the invention may contain pigments or colour formulations as well as additives selected from surface active agents, dispersion agents and rheological adjuvants as well as anti- bacterials .
  • the paper of the invention has the appearance and performance of currently available papers with the added advantage of biodegradability and recyclability by conditions employed in the paper industry, i.e., alkaline hydrolysis.
  • the polymers and copolymers of the latex are an intracellular energy source for most bacteria and thus will degrade in landfill environments to oligomers of the -hydroxy acids and ultimately to carbon dioxide and water. This represents a significant advance for otherwise non-recyclable and wet-strength consumer paper products, fibre con ⁇ structs and films.
  • the polymers hydrolyse in alkaline media at a pH of 7.5 to 12, and the hydrolysis products disperse and re-emulsify without forming sticky deposits.
  • the recycling essentially occurs through the ease of hydrolysis of the poly- ⁇ -hydroxy- alkanoates which may be achieved chemically or enzymatically. Alternatively the recycling may employ a mechanical removal relying on the crystal ⁇ line character of the dried material.
  • the poly-S-hydroxyalkanoates are thermo ⁇ plastic and have characteristics which depend on their composition. Melting point ( T r -)' glass transition temperature (T )and crystallization rate y of butyrate/valerate copolymers decrease with increase in content of /5-hydroxyvalerate units, the latter increase also has a plastifying and softening effect on the polymer as well as increasing the elongation at break and the toughness.
  • the native, polymer or copolymer is pre ⁇ ferably in the form of virgin wet granules of the polymer or copolymer, by which is intended granules as produced in the fermentation and which have never been subjected to drying. These granules are essentially non-crystalline but the dried material is crystalline. In water these granules have a latex form similar to commercially available polystyrene and styrene-butadiene latices. The granules are white and generally produce a viscosity in water greater than that of their synthetic counterparts, for a given solids content.
  • the granules are polydisperse and typically range in diameter from 0.2 to 1.5 urn; scanning micrographs indicate that some granules are fused in pairs. Agglomeration treatments can be used to artificially increase the particle size.
  • An especially preferred class of polymers and copolymers within formula (I) comprises: a) 0 to 100%, preferably 65 to 100%, more preferably 70 to 100%, by weight of ⁇ -hydroxybutyrate units of formula (II):
  • a preferred homopolymer is the poly- ⁇ - hydroxy-butyrate homopolymer derived from monomer units of formula (II).
  • a preferred copolymer is derived from ⁇ -hydroxybutyrate units of formula (II) and up to 31%, preferably up to 21%, by weight, of ⁇ -hydroxyvalerate units of formula (III).
  • the invention also contemplates latices based on such polymers and copolymers derived from crystalline particles, by regenerating the essentially non-crystalline granules, ii) Manufacture of Latex
  • the poly- ⁇ -hydroxyalkanoates are syn- thesised by a variety of bacteria and thus may be produced industrially by application of standard fermentation techniques. a) • Fermentation
  • PHB hydroxyalkanoate
  • Most bacteria that can accumulate PHBs also have the ability to produce some copolymers. So far poly- ⁇ - hydroxyalkanoate (PHA) copolymer production has been demonstrated in Alcaligenes eutrophus, Bacillus megaterium, a species of Cyanobacteria, Alcaligenes latus, Pseudomonas pseudoflava, Pseudomonas cepacia and other bacteria. It has been demonstrated that Alcaligenes eutrophusis is only capable of synthesizing PHA whose monomers are C. , C,- or C ⁇ , this is due to enzymatic specificity. Pseudomonas oleovorans and other fluorescent pseudomonads can produce PHAs with a much wider range of monomer chain length when specific alkanes or alkanoic acids are used as the substrate.
  • Batch PHB production is generally a 2-step process.
  • the first stage involves the production of high protein biomass at an exponential rate.
  • the maximum specific growth rate for Alcaligenes eutrophus is about 0.42 h in mineral salts medium.
  • the cells produced in the first stage accumulate PHA intracellularly. Since the number of microorganisms remains constant, the rate of accumulation is linear.
  • the onset of the second stage begins after the exhaustion of a limiting nutrient other than carbon, usually the nitrogen and/or phosphorus source.
  • High density fermentations are suitable.
  • a final cell dry weight concentration of about 100 g L is desirable.
  • the oxygen requirements for the first stage of fermentation are much higher than the second stage.
  • P. cepacia growing on fructose in a mineral salts medium requires a maximum of about 10 itiM h of oxygen per gram of cellular protein during the first stage but only about half as much during the PHB accumulation phase. For this reason, use of different fermentors for each stage may be appropriate.
  • the kind of PHA formed depends on the type of carbon source supplied and the ratio of their concentration during the PHA accumulation phase. For example, if cells of A. eutrophus are placed in nitrogen source free medium with glucose as the sole source of carbon, 100% of the PHA monomers will be HB. If pentanoic acid is used as the sole carbon source, up to 90 moles % of the PHA will be HV " and 10 moles % HB. Addition of 4-hydroxybutyric acid results in its incorporation as a monomer as opposed to the usual 3-hydroxybutyric acid. Thus by con ⁇ trolled feeding of specified carbon sources, the desired copolymer composition can be obtained.
  • PHA molecular weight should suitably be as high as possible at the end of a fermentation as it may degrade during processing, especially at high temperatures. High concentrations of carbon sources such as methanol in the fermentor may result in lower molecular weight, b) Separation of PHA from Biomass
  • the solvent extraction method usually involves the use of a chlorinated solvent such as chloroform, dichloroethane or 1,1,2-trichlorethane. Acetic anhydride and propylene or ethylene carbonate can also be used. In most cases the PHA is sub ⁇ sequently precipitated by addition of the solution to methanol. Separation may also be achieved by differential digestion using sodium hypochlorite. This method is based on the fact that PHB is degraded less by aqueous hypochlorite than other biomass components. Generally the procedure consists of contacting the PHA-containing biomass with an aqueous hypochlorite solution containing 5% titratable chlorine. The residue may be purified by methods such as solvent washing, dialysis or recrystaliization.
  • Separation may also be achieved by enzymatic digestion in which an aqueous suspension of PHA-containing biomass is heat-shocked to between 100-150 C for a short period of time to denature protein, RNA and DNA and rupture the cell walls.
  • the pH is held at between 6 and 8 to avoid any PHA degradation.
  • Sequential treatments with enzymes such as proteases and phospholipase are used to dissolve unwanted biomass. This is followed by washing with anionic surfactants such as sodium dodecylsulphate with or without EDTA.
  • a gentle method to isolate native granules of PHA after cell lysis involves two phases formed by two selected water soluble polymers.
  • particles such as PHA granules from lysed cells are added to such a system, they tend to be distributed in one of the phases based on their surface energy. Such distributions generally occur quickly and the thermo- dynamic equilibrium can be simply represented by a phase diagram. They are characterized by an 85-99% water content, little difference in density between phases, low interfacial tension and relatively high viscosity. In contrast to the distribution of particles, separation of the two phases is usually slow. It can be, however, greatly increased by centrifugation.
  • One such system is a dextran 500 (5% w/w)-polyethylene glycol (3.5% w/w) system.
  • Sonication or ultrasound can also be used to break cell walls in a preliminary step of granule isolation. Usually lysozyme and EDTA are added to aid in the process. The granules can then be iso ⁇ lated by methods such as density gradient centri- f gation and cesium chloride or glycerol. c) Latex
  • the latex thus separated from the biomass is an aqueous colloidal dispersion in which the colloidal particles of the poly-S-hydroxyalkanoates are in their native, virgin wet state.
  • the latex has the form of a white smooth slurry of pleasant fruity odour.
  • X-ray diffraction patterns reveal that the colloidal particles or granules after drying are of good crystallinity, however, in the native, virgin wet state the granules are essentially non-crystalline, by which is intended that the granules are not crystalline or exhibit only weak crystallinity.
  • the dispersion is very fluid and easily foamed by shaking.
  • the latex is readily diluted with water and can be readily rinsed off a surface to which it is applied, in contrast to aqueous dispersions formed from the spray dried powder which leaves a residue.
  • the latex may be modified for use in the invention by the addition of pigments and also by the addition of a surface active agent, for example, soap or detergent, a dispersion agent to improve or enhance the spreadability, rheological adjuvants and anti-bacteriostatic agents.
  • a surface active agent for example, soap or detergent
  • a dispersion agent to improve or enhance the spreadability
  • rheological adjuvants and anti-bacteriostatic agents for example, soap or detergent, a dispersion agent to improve or enhance the spreadability.
  • the latex more especially contains 10 to 50%, preferably 15 to 30%, more preferably 20 to 25%, by weight, of the poly- ⁇ S- hydroxyalkanoate.
  • a typical latex of the invention may contain, in weight % based on dry solids: latex solids - 10 to 15 parts by weight pigment - 50 to 65 parts by weight surface active or dispersing agents up to 0.03% by weight of pigment rheological aids up to 0.03% by weight of pigment bacteriostatic agents up to 0.1% by weight of solids.
  • the latex solids in this formulation are to be understood to be the polymers and copolymers of formula (I); the pigment may be, for example, clay of titanium dioxide.
  • the surface active or dispersing agents and the rheological aids are typically present in an amount up to about 0.1%, by weight, of the solids content of the latex.
  • the latex may also contain synthetic latex polymers and copolymers, for example, styrene- butadiene, and water soluble polymers, for example, carboxymethyl cellulose and starch. These polymers and copolymers may, for example, comprise up to 10 parts by weight of the solids, iii) Film Formation
  • a film can be made from the latex by casting a dilute solution of 15-25% w/w solids on an impervious surface and allowing the water to evaporate slowly at room temperature. Heating the air dry film in a drying oven at a temperature 30 degrees below T causes moderate fusion.
  • ' m are white, opaque and have a microporous structure as shown by electron micrographs.
  • the surface energy of these films has a high "polar" component.
  • Air dried or partially fused films can be hot pressed, suitably at 100-140°C, and 1000-5000 psi, to produce flexible and translucent films of average to high crystallinity. They are weakly birefringent but non-spherulitic.
  • the hot fusion treating of HPB/V copolymer films containing 21%, by weight, ⁇ > -hydroxyvalerate produces films of increased total surface energy as compared with HPB films and provides water imperviousness.
  • Dense, transparent films are also formed by exposing air dried films to solvent or liquid vapour atmospheres, such as chloroform and other halogenated solvents, ethylene or propylene carbonate, acetic anhydride, dimethylformamide, ethylaceto acetate, triolein, acetic acid and alcohols.
  • solvent or liquid vapour atmospheres such as chloroform and other halogenated solvents, ethylene or propylene carbonate, acetic anhydride, dimethylformamide, ethylaceto acetate, triolein, acetic acid and alcohols.
  • the films are smooth but not very flexible. They show x-ray crystallinity but are not birefringent.
  • These films are self-supporting and may be used as such or laminated to paper or other substrates.
  • Coated paper was made by treating base- stock, cardboard, or any other paper substrate with a color formulation containing from 20 to 100% PHB/HV latex, with HV content ranging from 0 to 100%.
  • the coating can be applied onto the substrate with a metering rod, bird applicator, size press or the like. Once dry, either by air exposure, infra-red, induction, convection or microwave oven, the coated substrate was subjected to heat and/or pressure treatment, i.e. hot or cold press, calendering and the like.
  • the resulting material is of comparable strength, gloss, brightness and overall performance to commercially available coated paper products.
  • a "wet strength" composite material was made by placing a layer of partially fused PHB/HV latex film on top or/and bottom of a sheet of paper or board. The resulting product can be hot pressed or solvent treated using the same conditions mentioned above to produce a two or three ply paper laminate containing paper or board encased or covered with a transparent hydrophobic polymer layer.
  • Impregnated "wet strength" material was also made by dipping or spraying paper or board substrates with a mixture containing from 15 to 100% PHB/HV latex with an HV content ranging from 0 to 100%. Once dry, the material may be pressed, calendered or solvent treated to produce a sheet where the individual cellulose fibers are covered and reinforced with the fused polymer.
  • Impregnation may also be achieved employing standard paper making techniques by adding the latex to a paper-forming fibre suspension prior to paper formation and allowing the latex to adsorb on the fibres.
  • paper construct is employed to identify paper and paper- forming fibre suspensions.
  • Example 2 An air dried or partially fused film as in Example 1 above was placed inside Mylar (Trade Mark) sheets and wrapped in aluminum foil. It was subsequently hot pressed in a polymer molding press set at 100 C, a pressure of 5000 psi was applied for about 1 minute. the resulting film was x-ray crystalline, uniformly birefringent but non-spherulitic. Complete fusion imparted transparency, toughness and more flexibility to the film. If stretched at room temperature, it shows appreciable necking and turns completely white and opaque. The film elongation at break on hand stretching is at most 30%. The crystallinity of these films does not seem to change in time.
  • Example 2 An air dried film prepared as in Example 1 was placed inside a desiccator containing a small amount of chloroform. After a 24 hour period the film was allowed to air dry at room temperature. Chloroform vapour and the dry film combine to produce an extremely smooth and tough film. It was very transparent but not birefringent. The film showed x-ray crystallinity.
  • a coated strip of paper prepared as in Example 4 above was placed between Mylar (Trade Mark) strips and wrapped in aluminum foil. .
  • the wrapped coated paper was hot pressed at 100 C, at a pressure of 5000 psi for about 1 minute.
  • the polymer coating fused and adhered strongly onto the paper. It was transparent and glossy, comparable to styrene-butadiene latex-coated basestock paper.
  • a coated strip of paper prepared as in Example 4 was placed inside a desiccator containing a small amount of chloroform. After a 24 hour period the strip was allowed to air dry at room temperature. The paper strip lost its opacity and it was impossible to detect with respect to sideness of the original coating application. The fused polymer coating migrated to the body of the paper, an impregnated paper product was obtained.
  • Hot pressed film strips prepared as in Example 2 were immersed in a cultured broth contain ⁇ ing 100 ml of activated sludge (Water treatment plant Weg Montagnes). Mineral salts, microelement solution and glucose as the only carbon source in the nutrient feed were added to the culture at a rate of 0.60 ml/h. Temperature, pH and agitation rate were 24 + 1°C, 7.0 pH units and 600 rpm. The air inflow was kept at a constant rate of 0.9 L/h. The polymer strips (50.0 mm x 10.0 mm x 1.0 mm), were held inside the broth on supports and fixed by stainless steel thread.
  • a PHA coated piece of paper prepared and treated as in Example 5 was shredded and placed in an aqueous NaOH, pH 11.0 solution.
  • the resulting mixture is treated in a fibre disintegration for a period of 30 minutes to several hours, depending on temperature which can range from room temperature to 60 C, then washed to neutrality.
  • the fibres are subsequently formed and air dried to a suitable paper handsheet.

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Abstract

Latex à base d'une suspension colloïdale dans l'eau composée pour l'essentiel de particules non cristallines de polymère, de copolymère ou de β-hydroxyalcanoates, par exemple β-hydroxybutyrate et β-hydroxyvalérate. Ledit latex peut être utilisé dans la fabrication de films ou de papiers autoporteurs biodégradables et facilement recyclables.
PCT/CA1990/000058 1990-02-21 1990-02-21 POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS WO1991013207A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US07/916,990 US5451456A (en) 1990-02-21 1990-02-21 Latex of poly-β-hydroxyalkanoates for treating fiber constructs and coating paper
PCT/CA1990/000058 WO1991013207A1 (fr) 1990-02-21 1990-02-21 POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS
CA002076038A CA2076038C (fr) 1990-02-21 1990-02-21 Poly.beta.hydroxyalcanoates pour la fabrication de pellicules ou de papiers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/CA1990/000058 WO1991013207A1 (fr) 1990-02-21 1990-02-21 POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS
CA002076038A CA2076038C (fr) 1990-02-21 1990-02-21 Poly.beta.hydroxyalcanoates pour la fabrication de pellicules ou de papiers

Publications (1)

Publication Number Publication Date
WO1991013207A1 true WO1991013207A1 (fr) 1991-09-05

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Cited By (37)

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WO1993010308A1 (fr) * 1991-11-12 1993-05-27 Imperial Chemical Industries Plc Structure presentant une resistance a l'eau controlee
EP0550490A1 (fr) * 1990-09-26 1993-07-14 E.I. Du Pont De Nemours And Company Pate de cellulose liee par des resines contenant de l'acide polyhydroxy
WO1994008090A1 (fr) * 1992-10-02 1994-04-14 Cargill, Incorporated Papier pourvu d'un couchage en polymere de lactide stable a la fusion et procede de fabrication
EP0613790A1 (fr) * 1993-02-16 1994-09-07 Canon Kabushiki Kaisha Moyen d'enregistrement, procédé d'enregistrement par jet d'encre en l'utilisant et article imprimé par jet d'encre
US5352244A (en) * 1992-09-02 1994-10-04 Norlab, Inc. Process for tracing liquid flow with a dye-impregnated paper strip
US5391423A (en) * 1992-06-26 1995-02-21 The Procter & Gamble Company Biodegradable, liquid impervious multilayer film compositions
US5417679A (en) * 1991-06-26 1995-05-23 The Procter & Gamble Company Disposable absorbent articles with biodegradable backsheets
US5422387A (en) * 1991-06-26 1995-06-06 The Proctor & Gamble Company Biodegradable, liquid impervious films
EP0662097A1 (fr) 1992-09-28 1995-07-12 Monsanto Company Composition polymere
US5475080A (en) * 1992-10-02 1995-12-12 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
WO1996000263A1 (fr) * 1994-06-23 1996-01-04 Stichting Onderzoek En Ontwikkeling Noord Nederland (Soonn) Procede de production d'un revetement en polyhydroxyalcanoate biodegradable a l'aide d'une dispersion aqueuse de polyhydroxyalcanoate
US5489470A (en) * 1994-01-28 1996-02-06 The Procter & Gamble Company Biodegradable copolymers and plastic articles comprising biodegradable copolymers
WO1996003468A1 (fr) * 1994-07-25 1996-02-08 Imperial Chemical Industries Plc Composition de revetement aqueuse produisant des revetements a durete precoce et resistance a l'adhesion ameliorees
US5498692A (en) * 1994-01-28 1996-03-12 The Procter & Gamble Company Biodegradable copolymers and plastic articles comprising biodegradable copolymers
US5502116A (en) * 1994-01-28 1996-03-26 The Procter & Gamble Company Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate
US5685756A (en) * 1994-01-28 1997-11-11 The Procter & Gamble Company Nonwoven materials comprising biodegradable copolymers
US5918747A (en) * 1994-06-01 1999-07-06 The Procter & Gamble Company Process for recovering polyhydroxyalkanoates using centrifugal fractionation
US5939467A (en) * 1992-06-26 1999-08-17 The Procter & Gamble Company Biodegradable polymeric compositions and products thereof
US5990271A (en) * 1994-01-28 1999-11-23 The Procter & Gamble Company Films and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate comonomer units
US6077931A (en) * 1998-12-21 2000-06-20 The Procter & Gamble Company Biodegradable PHA copolymers
US6143947A (en) * 1996-01-29 2000-11-07 The Procter & Gamble Company Fibers, nonwoven fabrics and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate
US6160199A (en) * 1998-12-21 2000-12-12 The Procter & Gamble Company Absorbent articles comprising biodegradable PHA copolymers
US6174990B1 (en) 1998-12-21 2001-01-16 The Procter & Gamble Company Films comprising biodegradable PHA copolymers
WO2001049770A1 (fr) * 1999-12-30 2001-07-12 The Procter & Gamble Company Articles de restauration en plastique biodegradable
WO2001094697A3 (fr) * 2000-06-09 2002-05-10 Procter & Gamble Substrats enrobes biodegradables
WO2002034704A3 (fr) * 2000-10-27 2003-08-14 Metabolix Inc Compositions de monomeres d'ester d'acide alcanoique et leurs procedes de preparation
US6780903B2 (en) 1996-12-31 2004-08-24 Valtion Teknillinen Tutkimuskeskus Process for the preparation of polymer dispersions
US6828376B2 (en) * 1994-07-25 2004-12-07 Imperial Chemical Industries Plc Aqueous coating composition giving coatings having improved early hardness and tack-resistance
FR2862309A1 (fr) * 2003-11-17 2005-05-20 Roquette Freres Utilisation d'une dispersion aqueuse d'au moins un polymere biodegradable contenant au moins un agent stabilisant pour la preparation d'une composition pigmentaire aqueuse
FR2862310A1 (fr) * 2003-11-17 2005-05-20 Roquette Freres Utilisation d'une dispersion aqueuse d'au moins un polymere biodegradable contenant au moins un agent stabilisant pour la preparation d'une composition filmogene aqueuse
US7025980B1 (en) * 1999-09-14 2006-04-11 Tepha, Inc. Polyhydroxyalkanoate compositions for soft tissue repair, augmentation, and viscosupplementation
US7407987B2 (en) 2000-03-31 2008-08-05 Duke University Compositions and methods for treating hair loss using C16-C20 aromatic tetrahydro prostaglandins
US7455999B2 (en) 1998-01-22 2008-11-25 Metabolix, Inc. Transgenic systems for the manufacture of poly (3-hydroxy-butyrate-co-3-hydroxyhexanoate)
WO2011087438A1 (fr) * 2010-01-12 2011-07-21 Innventia Ab Matériau moulable
WO2014023319A1 (fr) 2012-08-10 2014-02-13 Synthomer Ltd. Procédé de fabrication d'une dispersion aqueuse de poly(hydroxyalcanoates)
US8728778B2 (en) 1998-03-30 2014-05-20 Metabolix, Inc. Microbial strains and processes for the manufacture of biomaterials
WO2024013134A1 (fr) 2022-07-13 2024-01-18 Centre National De La Recherche Scientifique Procede de preparation de film de poly-(beta)-hydroxyalcanoate

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EP0662097A1 (fr) 1992-09-28 1995-07-12 Monsanto Company Composition polymere
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WO1994008090A1 (fr) * 1992-10-02 1994-04-14 Cargill, Incorporated Papier pourvu d'un couchage en polymere de lactide stable a la fusion et procede de fabrication
US5852166A (en) * 1992-10-02 1998-12-22 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
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EP0613790A1 (fr) * 1993-02-16 1994-09-07 Canon Kabushiki Kaisha Moyen d'enregistrement, procédé d'enregistrement par jet d'encre en l'utilisant et article imprimé par jet d'encre
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US5990271A (en) * 1994-01-28 1999-11-23 The Procter & Gamble Company Films and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate comonomer units
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US6410096B1 (en) * 1994-06-23 2002-06-25 Stichting Onderzoek En Ontwikkeling Noord-Nederland (Soonn) Method for producing a biologically degradable polyhydroxyalkanoate coating with the aid of an aqueous dispersion of polyhydroxyalkanoate
WO1996003468A1 (fr) * 1994-07-25 1996-02-08 Imperial Chemical Industries Plc Composition de revetement aqueuse produisant des revetements a durete precoce et resistance a l'adhesion ameliorees
US6828376B2 (en) * 1994-07-25 2004-12-07 Imperial Chemical Industries Plc Aqueous coating composition giving coatings having improved early hardness and tack-resistance
GB2291648B (en) * 1994-07-25 1998-11-25 Ici Plc Aqueous coating composition giving coatings having improved early hardness and tack-resistance
US6143947A (en) * 1996-01-29 2000-11-07 The Procter & Gamble Company Fibers, nonwoven fabrics and absorbent articles comprising a biodegradable polyhydroxyalkanoate comprising 3-hydroxybutyrate and 3-hydroxyhexanoate
US6780903B2 (en) 1996-12-31 2004-08-24 Valtion Teknillinen Tutkimuskeskus Process for the preparation of polymer dispersions
US8049065B2 (en) 1998-01-22 2011-11-01 Metabolix, Inc. Transgenic systems for the manufacture of poly(2-hydroxy-butyrate-co-3-hydroxyhexanoate)
US7455999B2 (en) 1998-01-22 2008-11-25 Metabolix, Inc. Transgenic systems for the manufacture of poly (3-hydroxy-butyrate-co-3-hydroxyhexanoate)
US7504556B2 (en) 1998-01-22 2009-03-17 Metabolix, Inc. Transgenic systems for the manufacture of poly(2-hydroxy-butyrate-co-3-hydroxyhexanoate)
US8728778B2 (en) 1998-03-30 2014-05-20 Metabolix, Inc. Microbial strains and processes for the manufacture of biomaterials
US8748139B2 (en) 1998-03-30 2014-06-10 Metabolix, Inc. Microbial strains and process for the manufacture of biomaterials
US6174990B1 (en) 1998-12-21 2001-01-16 The Procter & Gamble Company Films comprising biodegradable PHA copolymers
US6160199A (en) * 1998-12-21 2000-12-12 The Procter & Gamble Company Absorbent articles comprising biodegradable PHA copolymers
US6077931A (en) * 1998-12-21 2000-06-20 The Procter & Gamble Company Biodegradable PHA copolymers
EP2088198A2 (fr) 1999-01-22 2009-08-12 Metabolix, Inc. Systèmes transgéniques pour la fabrication de poly(3-hydroxy-butyrate-co-3-hydroxyhexanoate)
US7025980B1 (en) * 1999-09-14 2006-04-11 Tepha, Inc. Polyhydroxyalkanoate compositions for soft tissue repair, augmentation, and viscosupplementation
WO2001049770A1 (fr) * 1999-12-30 2001-07-12 The Procter & Gamble Company Articles de restauration en plastique biodegradable
US7407987B2 (en) 2000-03-31 2008-08-05 Duke University Compositions and methods for treating hair loss using C16-C20 aromatic tetrahydro prostaglandins
WO2001094697A3 (fr) * 2000-06-09 2002-05-10 Procter & Gamble Substrats enrobes biodegradables
AU2001269779B2 (en) * 2000-06-09 2005-05-05 Meredian, Inc. Biodegradable coated substrates
CN100529256C (zh) * 2000-06-09 2009-08-19 宝洁公司 可生物降解的涂敷基材
WO2002034704A3 (fr) * 2000-10-27 2003-08-14 Metabolix Inc Compositions de monomeres d'ester d'acide alcanoique et leurs procedes de preparation
FR2862309A1 (fr) * 2003-11-17 2005-05-20 Roquette Freres Utilisation d'une dispersion aqueuse d'au moins un polymere biodegradable contenant au moins un agent stabilisant pour la preparation d'une composition pigmentaire aqueuse
WO2005052075A1 (fr) * 2003-11-17 2005-06-09 Roquette Freres Utilisation d’une dispersion aqueuse d’au moins un polymere biodegradable contenant au moins un agent stabilisant pour la preparation d’une composition filmogene aqueuse
FR2862310A1 (fr) * 2003-11-17 2005-05-20 Roquette Freres Utilisation d'une dispersion aqueuse d'au moins un polymere biodegradable contenant au moins un agent stabilisant pour la preparation d'une composition filmogene aqueuse
WO2011087438A1 (fr) * 2010-01-12 2011-07-21 Innventia Ab Matériau moulable
WO2014023319A1 (fr) 2012-08-10 2014-02-13 Synthomer Ltd. Procédé de fabrication d'une dispersion aqueuse de poly(hydroxyalcanoates)
WO2024013134A1 (fr) 2022-07-13 2024-01-18 Centre National De La Recherche Scientifique Procede de preparation de film de poly-(beta)-hydroxyalcanoate
FR3137916A1 (fr) 2022-07-13 2024-01-19 Centre National De La Recherche Scientifique Procédé de préparation de film de poly-β-hydroxyalcanoate

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