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EP2580277A1 - Matériau expansible biodégradable convenant à la production de pantoufles - Google Patents

Matériau expansible biodégradable convenant à la production de pantoufles

Info

Publication number
EP2580277A1
EP2580277A1 EP11725861.6A EP11725861A EP2580277A1 EP 2580277 A1 EP2580277 A1 EP 2580277A1 EP 11725861 A EP11725861 A EP 11725861A EP 2580277 A1 EP2580277 A1 EP 2580277A1
Authority
EP
European Patent Office
Prior art keywords
tributyl citrate
mater
zone
weight
starch
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Withdrawn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
EP11725861.6A
Other languages
German (de)
English (en)
Inventor
Frederic Mauch
Bruno Karl Wampfler-Von Rotz
Karl Kehl
Linda Christiane THÖNY-MEYER
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.)
Bioapply Sarl
Eidgenoessische Materialpruefungs und Forschungsanstalt
Original Assignee
Bioapply Sarl
Eidgenoessische Materialpruefungs und Forschungsanstalt
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 Bioapply Sarl, Eidgenoessische Materialpruefungs und Forschungsanstalt filed Critical Bioapply Sarl
Publication of EP2580277A1 publication Critical patent/EP2580277A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B3/00—Footwear characterised by the shape or the use
    • A43B3/10—Low shoes, e.g. comprising only a front strap; Slippers
    • A43B3/101—Slippers, e.g. flip-flops or thong sandals
    • A43B3/106—Disposable slippers; One-piece slippers
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • 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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • the present invention concerns biodegradable materials, in particular low weight elastic deformable materials.
  • Thick-walled flexible parts, made of cellulose are already commercially available.
  • Glycan Biotech offers plates of low density made of glycan (the term glycan refers to an oligosaccharide or
  • citrate esters are used in synthetic polymers (e.g. PVC) as well as in biopolymers, e.g. starch (see patent documents mentioned below).
  • Triethyl citrate and tributyl citrate are also used in thermoplastic compositions that are pharmaceutically acceptable (see EP 0 575 349) .
  • thermoplastic compositions that are pharmaceutically acceptable (see EP 0 575 349) .
  • plasticizers are liberated from the bulk at the surface (usually called bleeding) .
  • FR 2 923 488 discloses a composition
  • plasticizers comprising as plasticizers a composition of at least one citrate and at least one lipid.
  • starch is mentioned as a possible polymer, all examples were performed with poly (lactic acid).
  • starch based compositions that also include a further polymer such as biodegradable polyester and plasticizers .
  • the plasticizer may be selected from a broad variety comprising citrates. A much preferred plasticizer content is as high as 15 to 35 %
  • plasticizer optionally a plasticizer.
  • plasticizer not specified citrates are mentioned.
  • biodegradable polyester compositions that preferably comprise less than 50 % starch together with hydroxyl functional polyester and plasticizer comprising
  • US 2003/100635 discloses a complex biodegradable polimeric composition comprising 40 to 52 % of a starch component and several other polymeric
  • plasticizers are mentioned encompassing not further specified
  • citrates as well as blowing or foaming agents such as chemical blowing agents and the introduction of gases during processing.
  • blowing or foaming agents such as chemical blowing agents and the introduction of gases during processing.
  • blowing or foaming agents such as chemical blowing agents and the introduction of gases during processing.
  • Such materials may be used for the production of flip-flops.
  • foamed compounds can be foamed by chemical foaming.
  • foaming was made on extrusion equipment for foamed tube insulating, which is an open system, a density of 0.15 g/cm 3 could be realized if applying a temperature of 100- 110°C using sodium bicarbonate together with a polymeric acid, preferably an acid with carboxyl side groups like poly (acrylic acid) or ethylene acrylic acid copolymers, as foaming agent. If using injection moulding, however, a temperature of 170°C had to be used and the density obtained raised to 0.3 g/cm ⁇ .
  • WO 2006/027671 discloses polyurethane
  • products comprising microsperes and expanding agents for producing low density foamed footwear products with integral skin.
  • foot beds can be produced. Another advantage is that no open pores must be sealed in a further production step because - contrary to cutting - no open pores are
  • biodegradable material of the present invention is on the one hand manifested by the features that it comprises (i) a polymer composition comprising as constituents starch and a biodegradable polyester, and (ii) at least one plasticizer, wherein said polyester is an unsubstituted aromatic-aliphatic copolyester, in particular
  • plasticizer is present in non beleeding amounts and selected from tributyl citrate, acetyl tributyl citrate and mixtures thereof in amounts of at most 15 % by weight referred to the weight of the total composition,
  • the present invention comprises a biodegradable flexible expansible material comprising (i) starch, (ii) a biodegradable polyester, (iii) plasticizers and (iv) a foaming agent, wherein the plasticizers are present in non bleeding amounts, wherein said plasticizers comprise at least one plasticizer selected from tributyl citrate, acetyl tributyl citrate and mixtures thereof in amounts of at most 15 % by weight referred to the weight of the total composition, and wherein the foaming agent comprises and preferably consists of expansible microspheres .
  • the starch and the polyester are used in the form of a polymer composition that optionally may comprise some additives.
  • a preferred polymer composition comprises starch in an amount of at least 85 % referred to the polymer composition,
  • Mater-Bi® (hereinafter referred to as "Mater-Bi”) , from Novamont, Novara (I).
  • Mater-Bi® had been developed to produce biodegradable films for packaging, e.g. shopping bags or wrappings. In order to develop a material based on Mater- Bi® suitable for slippers, the material had to be made more flexible and its density lowered.
  • Mater-Bi® is composed of more than 85% by weight of starch, a
  • polyester e.g poly (butylene-adipate-co-butylene- terephthalate) such as the polyester known as Ecoflex®, a product of BASF, and some plasticizers.
  • Ecoflex® a polyester known as Ecoflex®
  • BASF a product of BASF
  • plasticizers some plasticizers.
  • plasticizers and the density of thereof produced articles was reduced by adding a suitable foaming agent.
  • Starches that may be used in the scope of the present invention are any kind of starch but preferably thermoplastic starch derived from potatoe starch and corn starch .
  • biodegradable polyesters examples are:
  • PHA polyhydroxyalkanoates
  • PLA polylactic acid
  • PCL polycaprolactone
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • AAC aliphatic-aromatic copolyesters
  • PET polyethylene terephthalate
  • PBAT polybutylene adipate/terephthalate
  • PTMAT polymethylene adipate/terephthalate
  • adipate/terephthalate e.g. poly (butylene-adipate-co- butylene-terephthalate) , a polymer that does not comprise hydrophilic groups such as hydroxy groups attached, being presently preferred.
  • a much preferred polymer material i.e. the starch and polyester component, is Mater-Bi®.
  • citrates are known to be advantageous plasticizers , it was found that only very specific citrates can be used and, if bleeding shall be avoided, only in limited ranges. These citrates are tributyl citrate (TBC) and acetyl tributyl citrate (ATBC) .
  • Mater-Bi® is used TBC and ATBC are much preferably the only plasticizers present except for the plasticizers comprised in Mater-Bi, i.e. no plasticizers such as polyols like sorbitol, mannitol and glycerol, or lipids etc. are added to Mater-Bi®.
  • the material comprises a foaming agent, in particular a physical foaming agent such as expandable microspheres.
  • no plasticizer is liberated from the material at the surface and the material contains or consists of
  • the sum of the above mentioned ingredients amounting to at least about 98 % by weight of the total composition, preferably to 100 %.
  • a light weight foamed product may be produced by applying an injection moulding method comprising the steps of
  • metering injection, holding, cooling, and ejection, wherein the metering is performed in a metering zone comprising at least one feeding zone, at least one heating zone and an injection zone.
  • the method is performed with the injection zone having a barrel
  • the metering zone having a back pressure between 0.5 bar and 5 bar, preferably about 1 bar, and a screw rotation speed of 20 to 50 rpm, preferably about 30 rpm, and the holding is performed at a pressure between 0 and 10 bar, preferably built by the foaming agent only.
  • Figure 1 shows a typical stress-strain curve of Mater-Bi® NF01U and a mixture of 91% Mater-Bi® NF01U + 9% acetyl tributyl citrate.
  • Figure 2 shows the flexural modulus of Mater- Bi® plasticized with different quantities of acetyl tributyl citrate.
  • the unity of the content means g/100 g.
  • the 3-point flexural modulus and flexural stress at conventional deflection were determined according to ISO 178. Thickness of the samples was 4 mm.
  • Figure 3 shows flexural modulus vs. flexural stress at conventional deflection of Mater-Bi®
  • Figure 4 shows a suitable, flexibility enhancing sole design in top view.
  • Figure 5 shows a cross section through the sole of Figure 4 along line 5-5.
  • TBC tributyl citrate
  • ATBC acetyl tributyl citrate
  • TBC e.g. CITRFOL® Bl from Jungbunzlauer
  • ATBC e.g. CITRFOL® B2 from Jungbunzlauer
  • Mater-Bi® with the following properties:
  • a preferred fraction of ATBC was 5% to 10% (highest flexibility without bleeding)
  • Expandable microspheres were found to be suitable to foam the compound Mater-Bi® / TCB and/or ATBC, in particular Mater-Bi® / ATBC, and to reduce the density of the material by more than 50% in an injection moulding process.
  • the advantage of microsperes is that they do not foam due to a chemical reaction during production but have a gaseous substance incorporated within a compatible shell. The same effect may be obtained by directly using a gas, i.e. by gas injection during molding thereby avoiding the incorporation of the shell material of the microspheres.
  • the compound Mater-Bi® / TCB and/or ATBC in particular Mater-Bi® / ATBC
  • microspheres are that they can be homogenously distributed within the polymer composition and that nospecific means for gas injection have to be provided.
  • Example 1 Evaluation of the biopolymer based on starch
  • Biograde® BM, Bioplast® 2189 and Mater-Bi® NFOIU are biodegradable materials based on starch, which can be processed by extrusion.
  • the biopolymers were melted on a laboratory roll mill with two cylinders (Collin 100T) and blended with 10% of triglycerol. Several turn-overs were
  • the temperature of both cylinders was 170°C (Biograde®, Bioplast®) and 140°C (Mater-Bi®) , respectively.
  • the compounds were removed from the roll-mill and subjected to pressure moulding (conditions: 170°C (Biograde®, Bioplast®); 140°C (Mater-Bi®); 10 bar) to obtain material plates of about 140 x 140 x 3.5 mm.
  • Mater-Bi® NF01U had the lowest E-modulus and thus the highest elasticity. Mater-Bi® also showed a high value for the strain at rupture, thus indicating that this material is not brittle in contrast to Bioplast® and Biograde®. Therefore, Mater-Bi® NF01U was selected for further investigations.
  • Biopolymers of the type Mater-Bi® NF are based on natural raw materials (maize starch, derivatives of vegetable oils) as well as on synthetic biodegradable polyesters (http: //www.materbi .it) .
  • Mater-Bi® is produced by extrusion. During extrusion, the crystals of starch melt and additives can then be admixed.
  • the producer specifies Mater-Bi® NFOIU as a polymer blend based on starch, synthetic polyester and plasticizers, with the polyester being poly (butylene-adipate-co-butylene- .
  • Mater-Bi® NFOIU is a blend of two different phases [N. Tzankova Dintcheva, F.P. La Mantia, Polymer Degradation and Stability 92(2007)630-634]. Information on Mater-Bi products can be found in literature e.g.
  • Polyeste /polyether polyurethane 25%) caused a higher flexibility but requested also
  • Glycerol (23 - 30%); diglycerol (15 -.25%); polyglycerol-3 (17 - 25%); PEG-2000 (5%) and ethoxylated (20 EO) sorbitane tristearate (10%) and diglycerol (20%) .
  • plasticizers did not result in good products, i.e. either the material was too smeary or the flexibility was not improved.
  • ATBC was pre-mixed in an industrial mixing machine with Mater-Bi® (passage 1) or with Mater-Bi® already blended with a certain amount. of ATBC (passages 2-3) . The mixture was then charged into the feeder of the extruder. Other feeding methods would also be possible, e.g. addition of the plasticizer by side feeding. The following parameters were used:
  • Feeding zone 120°C (could be varied from 115 to 140°C)*
  • Barrel zone 1 135°C (120 ... 150°C)*
  • Feeding speed 300 (relative to an
  • Screw rotation speed 135 (relative to an internal scale of the machine)
  • Granulation speed 29 (relative to an internal scale of the granulator)
  • Coloured BioSlip e.g. BioSlip blue
  • a coloured, e.g. blue master batch to BioSlip in a fourth passage.
  • flexural stress and flexural modulus show pairs of values that are on a straight line having a positive slope.
  • the linearity indicates that both parameters similarly depend on the content of acetyl tributyl citrate and that the strain - stress curves have similar shapes.
  • Example 4.1 Foams produced on the laboratory scale
  • Example 1 Materials of Example 1 were compounded on a laboratory roll mill with two cylinders (Collin 100T) . The temperature of both cylinders was set at 130°C - 140°C when the plasticizer was added. In order to obtain a sufficient homogeneity several material turn-overs were performed. After having decreased the temperature of both cylinders to 115°C - 120°C, the foaming agent was added. Afterwards, the compounds were removed from the roll-mill and subjected to a moulding press (conditions: 125°C, 10 bar) to obtain material plates of about 140 x 140 x 3.5 mm. In order to investigate the foaming process, round or rectangular coupons were cut from the plates. The coupons were heated up to the individual reaction temperature of the investigated foaming agent to initiate a quick and complete foaming process. This was done using different sources of heat: heating furnace, microwave oven, and moulding press.
  • EXPANCEL 909 DUX 80 consisting of 20% - 30% isopentane and >70% copolymer CAS 38742-70-0
  • EXPANCEL 461 DU 40 consisting of 10% -
  • EXPANCEL 950 MB 80 comprising 10 - 14% isooctane, 2 - 6% isobutane, >50% copolymer CAS 38742-70- 0, and approx. 35% ethylene vinyl acetate copolymer
  • EXPANCEL 930 MB 120 comprising 9 - 14% isooctane, 2 - 6% isobutane, >50% copolymer CAS 38742-70- 0, and approx. 35% ethylene vinyl acetate copolymer
  • EXPANCEL 461 DU 40 shows maximum expansion at 142°C - 150°C Since injection moulding of plasticized Mater-Bi® requires processing temperatures of 160°C - 180°C, expandable microspheres with maximum expansion at 175°C - 190°C (EXPANCEL 909 DUX 80) and at 195°C - 210°C (EXPANCEL 930 MB 120) were additionally investigated. With EXPANCEL 909 DUX 80, an expansion factor of 2.7 could be reached, when adding 1% or 2% of this agent to Mater-Bi® plasticized with 20% - 25% of glycerol
  • Example 4.2 Up-scaling to an industrial moulding injection machine: production of foamed slippers
  • Feeding zone 140°C (120 to 150°C)* Barrel zone 1: 160°C (140 to 175°C)*
  • Barrel zone 2 175°C (165 - 185°C)*
  • Injection zone 175°C (165 - 185°C)*
  • Cooling time 50 s
  • the temperature of the feeding zone can be varied between 120°C and 150°C. Below 120 °C the material became more and more viscous (peak melting temperature (DSC): 116°C). In order to prevent the foaming agent from expansion in the feeding zone, the temperature should not exceed 150 °C.
  • the temperature of the zones “barrel 2" and “injection” preferably is kept between 165°C and 185°C. Splay marks around the gate could be lowered by decreasing the temperature of the zones "barrel 2" and "injection” from 175°C to 165°C. However, this improvement went along with a delamination of a thin layer of material around the gate. This
  • injection phase Again, injection speed and injection time were chosen as low and as long as
  • Holding phase When foaming with expandable microspheres, the holding pressure has to be set to zero (recommendation from AKZO NOBEL, the producer of the EXPANCEL microspheres). A higher holding pressure would hamper microspheres to expand.
  • Cooling phase Cooling time was rather long because a mass of 120 g - 140 g had to be cooled. Shorter cooling times were found to 1ead to a post-expansion of the ejected sample.
  • BioSlip 91% Mater-Bi® + 9% ATBC EXPANCEL 930 MB 120 contains 9 - 14%
  • EXPANCEL 950 MB 80 contains 10 - 14%
  • BioSlip blue was produced by addition of a blue masterbatch to BioSlip during compounding according to example 2.
  • EXPANCEL and green dye were mixed with BioSlip just before injection moulding.
  • the weight of sole decreased from 143.9 g to 119.9 g when the content of the foaming agent EXPANCEL 950 MB 80 was increased from 5% to 10% .
  • the density of samples of the lot numbers 4, 6 and 10 was determined according to ISO 845.
  • the density of the other samples was calculated using the weights quoted in table 4, whereas the slight shrinkage of some samples was not respected.
  • the sole 1 is provided with grooves 2 arranged in different directions, e.g. longitudinal grooves 2b of different length are arranged in the center of the sole 1, and grooves 2a perpendicular thereto are arranged in the lateral regions whereas central parts 3 comprise fewer grooves in order to provide better stability.
  • grooves 2 arranged in different directions, e.g. longitudinal grooves 2b of different length are arranged in the center of the sole 1, and grooves 2a perpendicular thereto are arranged in the lateral regions whereas central parts 3 comprise fewer grooves in order to provide better stability.
  • biodegradable flexible material comprising (i) a polymer composition comprising as constituents starch and a biodegradable polyester, and (ii) at least one plasticizer, wherein said polyester is an unsubstituted aromatic-aliphatic copolyester, in particular poly (butylene-adipate-co-butylene- terephthalate ) , and wherein said plasticizer is present in non bleeding amounts and selected from tributyl citrate, acetyl tributyl citrate and mixtures thereof in amounts of at most 15 % by weight referred to the weight of the total composition, preferably at most 12.5 % by weight,
  • the polymer composition comprises starch in an amount of at least 85 % referred to the polymer composition, a
  • the plasticizer comprises . up to 15 %,. preferably up to 12.5 % tributyl citrate, or wherein the plasticizer comprises up to 12.5%, preferably up to 10 % acetyl tributyl citrate.
  • foaming agent is expansible microspheres
  • a method for producing a foamed product comprising one of the materials described above, by applying an injection moulding method comprising the steps of metering, injection, holding, cooling, and ejection, wherein the metering is performed in a metering zone comprising at least one feeding zone, at least one heating zone and an injection zone,
  • the injection zone has a barrel temperature between 2°C and 35°C below the barrel
  • the metering zone has a back pressure between 0.5 bar and 5 bar, preferably about 1 bar, a screw rotation speed of 20 to 50 rpm, preferably about 30 rpm, and
  • the holding is performed at a pressure between 0 and 10 bar, preferably built by the foaming agent only,
  • plasticizers comprise the plasticizers in non bleeding amounts, and wherein said plasticizers comprise at least one plasticizer selected from tributyl citrate, acetyl tributyl citrate and mixtures thereof in amounts of at most 15 % by weight referred to the weight of the total composition, and wherein the foaming agent is expansible microspheres.
  • the biodegradable flexible expansible material wherein the starch and the polyester are constituents of a polymer composition comprising starch in amounts of at least 85% by weight of the polymer composition and wherein about 10 % of the constituents are water soluble, - one of the biodegradable flexible
  • polyester is a poly (butylene-adipate-co-butylene- terephthalate)
  • expansible materials described above wherein at least the starch and polyester components, preferably all components except the citrate plasticizers, are Mater-Bi® NF01U,
  • plasticizer comprises up to 15 %, preferably up to 12.5 % tributyl citrate, or wherein the plasticizer comprises up to 12.5%, preferably up to 10 % acetyl tributyl citrate,
  • expansible microspheres are composed of
  • perfumes 0 to 1.5 % of perfumes, the sum of the above mentioned ingredients amounting to at least about 98 % by weight of the total composition, preferably to 100 %,
  • a method for producing a foamed product comprising the material of any one of claims 1 to 17, by applying an injection moulding method comprising the steps of metering, injection, holding, cooling, and ejection, wherein the metering is performed in a metering zone comprising at least one feeding zone, at least one heating zone and an injection zone, and
  • the injection zone has a barrel temperature between 2°C and 35°C below the barrel
  • the metering zone has a back pressure between 0.5 bar and 5 bar, preferably about 1 bar, a screw rotation speed of 20 to 50 rprn, preferably about 30 rpm, and
  • the holding is performed at a pressure between 0 and 10 bar, preferably built by the foaming agent only.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un matériau souple biodégradable convenant à la production au moins de la semelle de pantoufles biodégradables, ledit matériau comprenant de l'amidon, un polyester biodégradable et un plastifiant choisi parmi le citrate de tributyle, l'acétyl citrate de tributyle et leurs mélanges en des quantités sans ressuage d'au plus 15 % en poids par comparaison avec le poids de la totalité du mélange. L'invention porte également sur un matériau à expansion physique, tel que des microsphères.
EP11725861.6A 2010-06-08 2011-06-07 Matériau expansible biodégradable convenant à la production de pantoufles Withdrawn EP2580277A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH9102010 2010-06-08
PCT/CH2011/000137 WO2011153653A1 (fr) 2010-06-08 2011-06-07 Matériau expansible biodégradable convenant à la production de pantoufles

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CN112048122A (zh) * 2020-09-18 2020-12-08 泉州师范学院 一种可生物降解pbst/eva中底鞋材及其制备方法
CN112724453A (zh) * 2020-12-23 2021-04-30 快思瑞科技(上海)有限公司 母粒材料、发泡母粒制备方法及工程塑料制备方法
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CN113583400A (zh) * 2021-08-27 2021-11-02 浙江新恒泰新材料有限公司 一种可降解发泡材料及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1232894B (it) 1989-08-03 1992-03-05 Butterfly Srl Articoli espansi di materiale plastico biodegradabile e procedimento per la loro preparazione
IT1245408B (it) 1991-02-20 1994-09-20 Butterfly Srl Composizioni polimeriche biodegradabili a base di amido e di polimero termoplastico
US6025417A (en) 1996-02-28 2000-02-15 Biotechnology Research & Development Corp. Biodegradable polyester compositions with natural polymers and articles thereof
US7037959B1 (en) 1999-04-12 2006-05-02 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable polymer compositions methods for making same and articles therefrom
US7071249B2 (en) 2001-10-05 2006-07-04 William Ho Biodegradable starch resin and method for making same
WO2006027805A1 (fr) 2004-09-08 2006-03-16 Elachem S.R.L. Composition et processus de realisation de produits expanses a faible densite
WO2008014573A1 (fr) 2006-08-04 2008-02-07 Plantic Technologies Ltd Polymère moulable biodégradable
FR2923488B1 (fr) 2007-11-08 2011-01-28 Ct Valorisation Ind Agro Ressources Utilisation d'un melange citrate/lipide comme plastifiant, et composites contenant un tel melange.

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Title
See references of WO2011153653A1 *

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