(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2013/116763 Al 8 August 2013 (08.08.2013) P O P CT

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every B32B 27/20 (2006.01) C08L 67/00 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/US20 13/024487 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 1 February 2013 (01 .02.2013) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, (26) Publication Language: English RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, (30) Priority Data: ZM, ZW. 61/594,638 3 February 2012 (03.02.2012) US (84) Designated States (unless otherwise indicated, for every (71) Applicant (for all designated States except US): ECO- kind of regional protection available): ARIPO (BW, GH, SPAN USA [US/US]; 300 Drakes Landing, Suite 200, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, Greenbrae, California 94904 (US). UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (72) Inventor; and EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, (71) Applicant (for US only): SANDERSON, Scott [US/US]; MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, 1339 Garman Drive, Chester Springs, PA 19425 (US). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, (74) Agent: ROSEDALE, Jeffrey, H.; Woodcock Washburn ML, MR, NE, SN, TD, TG). LLP, Cira Centre, 12th Floor, 2929 Arch Street, Phil Published: adelphia, PA 19104 (US). — with international search report (Art. 21(3))

(54) Title: COMPOSITIONS AND RELATED METHODS

Figure 1

(57) Abstract: Bioplastic compositions having favorable mechamcal and characteristics. Methods of forming these com positions and also workpieces formed from these compositions. The compositions comprising a polylactic acid; a polyhy- droxyalkanoate; a plurality of clay particles; a plurality of talc particles; and a modifier capable of facilitating mixing between the clay particles and the talc particles. The compositions suitably include a polylactic acid, a polyhydroxyalkanoate, a plurality of clay particles, a plurality of talc particles. The compositions also suitably include a modifier capable of facilitating mixing between the clay particles and the talc particles. The clay particles may have an average diameter in the range of from about 2 nm to about 100 nm; a diameter of 8 nm is considered suitable. BIOPLASTIC COMPOSITIONS AND RELATED METHODS

TECHNICAL FIELD [0001] The present invention relates to the field of bioplastic compositions. The present invention also relates to the field of incorporating particulate materials into biopolymers.

BACKGROUND [0002] Bioplastic materials, such as those made from naturally-derived polymers, have attracted interest as of late. The ability to fabricate such materials from sustainable sources makes the materials attractive, but have historically exhibited mechanical properties (e.g., brittleness, low resistance to fatigue) that renders them unsuitable for certain applications, such as living hinges. Accordingly, there is a need in the field for bioplastic compositions having improved mechanical properties.

SUMMARY [0003] In meeting the disclosed challenges, disclosed here are first compositions, the compositions comprising a polylactic acid; a polyhydroxyalkanoate; a plurality of clay particles; a plurality of talc particles; and a modifier capable of facilitating mixing between the clay particles and the talc particles. [0004] Also provided are workpieces. The workpieces suitably comprise first and second sections being connected by a living hinge formed by a composition according to the present disclosure. [0005] The present disclosure also provides processes. These processes suitably include molding a bioplastic composition at a meltflow value of from about 45 to about 80; the bioplastic is suitably a composition according to the present disclosure. [0006] Also provided are , the containers suitably including a portion comprising a composition according to the present disclosure. The containers suitably include a living hinge comprising a composition according to the present disclosure. [0007] This disclosure also provides methods. These methods include blending a polylactic acid; a polyhydroxyalkanoate; a plurality of clay particles; a plurality of talc particles; and a modifier capable of facilitating mixing between the clay particles and the talc particles.

BRIEF DESCRIPTION OF THE DRAWINGS [0008] The summary, as well as the following detailed description, is further understood when read in conjunction with the appended drawings. For the purpose of illustrating the disclosure, there are shown in the drawings exemplary embodiments of the disclosure; however, the disclosure is not limited to the specific methods, compositions, and devices disclosed. In addition, the drawings are not necessarily drawn to scale. In the drawings: [0009] Figure 1 depicts a side view of a package formed from a composition according to the present disclosure, wherein the package includes a living hinge formed from the disclosed composition;

[0010] Figure 2 depicts a view of the interior of the package shown in Figure 1, with the living hinge in an opened position; [0011] Figure 3 depicts a view of the package of Figures 1 and 2, with the living hinge in a closed position; [0012] Figure 4 depicts a side view of the package of Figure 3, with the living hinge in a closed position; and [0013] Figure 5 illustrates the package of Figures 1-4, including non-limiting dimensions for the various portions of the package.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS [0014] The present disclosure may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this disclosure is not limited to the specific devices, methods, applications, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claims. Also, as used in the specification including the appended claims, the singular forms "a," "an," and "the" include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. [0015] The term "plurality", as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable. Any documents cited herein are incorporated herein by reference in their entireties for any and all purposes. [0016] In a first aspect, the present disclosure provides compositions. The compositions suitably include a polylactic acid (available from, e.g., Natureworks), a polyhydroxyalkanoate (available from, e.g., Metabolix, Tepha, Greenbio, PHB Industrial SA), a plurality of clay particles, a plurality of talc particles. The compositions also suitably include a modifier capable of facilitating mixing between the clay particles and the talc particles. [0017] The clay particles may have an average diameter in the range of from about 2 nm to about 100 nm; a diameter of 8 nm is considered especially suitable. Clays from Thailand are considered especially suitable. Without being bound to any particular theory, the presence of clay allows one to impart a lubricity to the composition that assists in releasing the composition from a mold without having to add a release agent. The clay may also confer strength, stretch, ductility, elasticity, or any of the foregoing onto the composition. [0018] Talc particles may be purchased commercially. Talc particles may have a size in the range of from 2 nm up to 10, 20, or even 50 micrometers. Talc particles having a diameter in the range of from about 50 nm to about 150 nm are especially suitable. [0019] The modifier may be one or more chemical components or compositions that acts to bring the clay and the talc together so as to form an integrated composition and to prevent the formation of layers that may in turn delaminate. Suitable modifiers include block copolymers, graft copolymers and crosslinking peroxides. Suitable graft copolymers can be selected from the Modiper™ A series from the NOF Corporation in Japan, which can be selected from one or more of the following: E/VA-graft-mPMMA

E/GMA : Poly(ethylene-stat-glycidyl methacrylate), (85/1 5 t ) E EA : Poly(ethyiene-stat-ethyi acryiate), (80/20wt%) E/VA : Poly (ethy ene-stat-vinyl acetate), (85/ wt%) Ε/ Α/ΜΑ : Po[y(eihyleTie-stat-eihyl a ry ate-stat-ma ei anhydride) (85/ 2/3wi%) PSAN : Poly(styrene-stai~acr o itri le), (7Q/3Q †% ) mPMMA : modified PMMA

[0020] Suitable block copolymers include any of the styrene block copolymers as well as acrylic block copolymers. Examples of styrene block copolymers include the Kraton™ G SEBS and SEPS polymers, such as the styrene-ethylene -propylene block types, available from Kraton Performance Polymers, Inc. [0021] Suitable crosslinking peroxides are commercially available from AkzoNobel under the Perkadox™ trade name. Suitable Perkadox™ crosslinking peroxides can include one or more of the following:

[0022] The one or more modifiers may be present at a weight percentage of from about

1 to about 99% , from about 2 to about 50%>, or even from about 3 to about 5%. [0023] The polylactic acid (PLA) of the disclosed compositions may be amorphous or crystalline; crystalline polylactic acid is considered especially suitable. Exemplary polylactic acid may be purchased from Natureworks or other commercial vendors. [0024] The polyhydroxyalkanoate (PHA) may be amphorhous or crystalline; crystalline polyhydroxyalkonate is considered especially suitable. PLA may be present in a wt% of from about 5% to about 85%, or from about 15% to about 75%, with 60% being especially suitable. [0025] PHA may be present in a wt% in the range of from about 10% to aout 90%, or from about 20% from about 80%, or even from about 40% to about 60%. Clay may be present in the range of from about 1 wt% to about 50 wt%, or even from about 2 wt% to about 10 wt%. Talc may be present in the range of from about 1 wt% to about 50 wt%, or from 5 wt% to about 10 wt% or about 20 wt%. The modifier is suitably present in the range of from about 0 wt% to about 15 % or about 20 wt%>, with 5 wt%> being especially suitable. [0026] The compositions may be characterized as having a heat distortion temperature of greater than about 60 °C, about 70 °C, or even higher than about 80 °C or even higher than about 90 °C. [0027] The compositions may include other additives. Such additives include, e.g., colorants, antimicrobials, metals, Ti02, TAIC cross linking agent, Trigonox 301 and Stabiol P, and the like. Other cross-linkers, stabilizers, fire retardants, plasticizers, and the like may be added. Some additives may act to marry talc and clay to the other materials. A crosslinker may be used to bind the talc and clay to the PLA, PHA, or both. In some embodiments, the user may bind clay and talc to one another and then mix the clay/talc with the PLA, PHA, or both. Nanoparticles (e.g., having a cross-sectional dimension in the range of from about 1 nm to about 1000 nm) of any composition may be incorporated into the disclosed compositions. Silver, gold, and carbon nanoparticles are all considered suitable for this application. Carbon nanotubes (single-wall and multi-wall) may also be incorporated into the disclosed compositions.

Additives (e.g., nanoparticles) may be present at from about 0.00001 wt%> to about 50 wt%>, or from about 0.1 wt%> to about 10 wt%>, or even at about 5 wt%>.

[0028] Unless indicated otherwise, as used herein throughout the specification, "wt%>" generally refers to weight percent based on total weight of the composition. [0029] Also provided are workpieces. The workpieces suitably include a first section and a second section, the first and second sections being connected by a living hinge formed of a composition according to the present disclosure. The first and second sections of the workpiece may comprise a composition according to the present disclosure. In some embodiments, the workpiece is a formed from a composition according to the present disclosure. One such exemplary container is shown by Figures 1-5. In some embodiments, the entire container is formed from the disclosed compositions. [0030] Also provided are methods. The methods include molding a bioplastic composition at a meltflow value of about 45 to about 80, the bioplastic suitably being a composition according to the present disclosure. Such meltflow values allow the user to form - thin walls, complex molds, different thicknesses in different parts of a mold, and even allow dense material packing into a mold. Such meltflow values also allow a user to work with higher- pressure molding than other existing bioplastic materials. The disclosed materials are also capable of supporting a finish, sheen, or color that is not supported by existing bioplastic materials. [0031] The disclosed materials also permit comparatively low temperature processing. The processing temperatures may be 10, 20, or even 25 or 30% lower than the processing temperatures for comparable petroleum-based materials. As a consequence, lower molding temperatures allow for faster cooling in molds. [0032] In traditional processes, molds are run at comparatively hot temperatures. By comparison, the disclosed materials pack densely into molds. Because cooling times contribute to overall cycle times, one may cool the mold (e.g., by a radiator-type structure, or even by a cooling jacket). A mold may be run at only about 30 °C, about 35 °C, or even about 40 °C for the disclosed materials, whereas molds for traditional may be run at 45 °C. [0033] Items formed from the disclosed compositions may be subject to an annealing process. A part may be taken out of a mold and then placed onto a sister mold (skeleton mold). Thus process may, without being bound to any single theory, this may help to align the microstructure of the parts. [0034] Demolding may be accomplished by application of air pressure. For example, air may be exerted through an aperture in a mold so as to de-mold an item. Such an aperture may even be constructed so that it lies behind a door, slider, or other portion of the mold in order that the aperture is shielded from the molded part during molding and then, once molding is complete, a slider or door moves to reveal the aperture and air may be exerted through the aperture to force the part out of the mold. [0035] A user may form the disclosed compositions into a variety of configurations. Containers, shells, packages, and the like are all suitable forms. Electronics components and are considered especially suitable, as are other retail packaging. What is Claimed:

1. A composition, comprising:

a polylactic acid;

a polyhydroxyalkanoate;

a plurality of clay particles;

a plurality of talc particles; and

a modifier capable of facilitating mixing between the clay particles and the talc particles.

2. The composition of claim 1, wherein the polylactic acid comprises crystalline polylactic acid, amorphous polylactic acid, or both.

3. The composition of claim 1, wherein the polyhydroxyalkanoate comprises crystalline polyhydroxyalkanoate, amorphous polyhydroxyalkanoate, or both.

4. The composition of claim 1, wherein the composition is characterized as having a heat distortion temperature of greater than about 80 °C.

5. The composition of claim 4, wherein the composition is characterized as having a heat distortion temperature of greater than about 90 °C.

6. The composition of claim 1, wherein a clay particle has an average diameter in the range of from about 2 nm to about 100 nm;

7. The composition of claim 1, wherein a talc particle has an average diameter in the range of from about 2 nm up to about 50 micrometers.

8. The composition of claim 1, further comprising Ti02, a colorant, TAIC cross linking agent, Trigonox 301, Stabaol P, a cross-linker, a stabilizer, a lubricant, or any combination thereof. 9. The composition of claim 1, wherein the polylactic acid is present in a wt% of from about 5% to about 85%.

10. The composition of claim 1, wherein the polyhydroxyalkanoate is present in a wt% in the range of from about 10% to aout 90%.

11. The composition of claim 1, wherein the clay is present in the range of from about 1wt% to about 50 wt%>.

12. The composition of claim 1, wherein the talc is present in the range of from about 1 wt% to about 50 wt%>

13. The composition of claim 1, wherein the modifier is suitably present in the range of from about 0 wt%> to about 20 wt%>.

14. A workpiece, comprising:

first and second sections being connected by a living hinge formed by a composition according to claim 1.

15. The container of claim 14, wherein at least one of the first and second sections is formed from the composition according to claim 1.

16. A process, comprising:

molding a bioplastic composition at a meltflow value of from about 45 to about 80.

17. The process of claim 16, wherein the bioplastic composition is a composition according to claim 1.

18. A container, comprising:

A portion comprising a composition according to claim 1. 19. The container of claim 18, further comprising a living hinge comprising a compostion according to claim 1.

20. A method, comprising:

blending a polylactic acid;

a polyhydroxyalkanoate;

a plurality of clay particles;

a plurality of talc particles; and

a modifier capable of facilitating mixing between the clay particles and the talc particles.

2 1. The method of claim 20, further comprising blending the clay particles and the talc particles to form a first admixture, and mixing the first admixture with the polylactic acid, the polyhydroxyalkanoate, or both.

22. The composition of claim 1, further comprising a population of nanoparticles.

23. The composition of claim 22, wherein the population of nanoparticles is present at from about 0.00001 wt% to about 10 wt%

INTERNATIONALSEARCH REPORT International application No. PCT/US 13/24487

A . CLASSIFICATION OF SUBJECT MATTER IPC(8) - B32B 27/20, C08L 67/00 (201 3.01 ) USPC - 428/336, 528/272 According to International Patent Classification (IPC) o to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC(8)- B32B 27/20, C08L 67/00 (2013.01); USPC- 428/336, 528/272

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Patents and NPL (classification, keyword; search terms below)

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) PubWest, PatBase (USPTO, EPO, JPO, WlPO, PCT), GoogleScholar (PL, NPL), FreePatentsOnline (USPTO, EPO, JPO, WlPO, NPL); search terms: polyhyddroxyalkanoate, polylactic, acid, PLA, talk, day, particle, powder, granule, nanoparticle, flour, amorphous, crystal, workpiece, mold, mould, bioplastic, living, hinge

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X US 2012/0041 109 A1 (KRISHNASWAMY), para [0004], [0010], [001 1], [0016], [0020], [0023], 1-13, 16-18, 20-23 [0026], [0027], [003η , [0062], [0121], [0127], [0154], [0157]-[0159], [0171], [0176], [0182]- Y [0187], [0193] 14

Y US 2009/0024161 A 1 (BONUTTI et al.) 22 January 2009 (22.01 .2009), para [0193], [021 1], 14 [0272], [0492]

Y, P US 2012/ 0135169 A1 (TANGELDER et al.) 3 1 May 2012 (31 .05.2012), para [0027]-[0140] 1-14, 16-18, 20-23

Y US 201 1/0162955 A 1 (BUTZLOFF et al.) 07 July 201 1 (07.07.201 1), para [0004]-[0082] 1-14, 16-18, 20-23

Y US 2004/0225269 A 1 (ZHAO et al.) 11 November 2004 ( 11.1 1.2004), para [0007]-[01 10] 1-14, 16-18, 20-23

Y US 2002/0143136 A1 (NODA et al.) 03 October 2002 (03.10.2002), para [001 1]-[0088] 1-14, 16-18, 20-23

Further documents are listed in the continuation of C. | |

* Special categories of cited documents: |a t document published after the international filing date or priority A" document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand " to be of particular relevance ' principle or theory underlying the invention "E" earlier application or patent but published on or after the international "χ " document of particular relevance; the claimed invention cannot be filing date considered novel or cannot be considered to involve an inventive

" L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other γ „ d m t 0 particular relevance; the claimed invention cannot be special reason (as specified) considered to involve an inventive step when the document is "O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art

"P" document published prior to the international filing date but later than & document member of the same patent family the priority date claimed Date of the actual completion of the international search Date of mailing of the international search report 19 March 2013 (19.03.2013) AP R 2013 Name and mailing address of the ISA/US Authorized officer: Mail Stop PCT, Attn: ISA/US, Commissioner for Patents Lee W. Young P.O. Box 1450, Alexandria, Virginia 22313-1450 PCT Helpdesk: 571-272-4300 Facsimile No. 571-273-3201 PCT OSP: 571-272-7774 Form PCT ISA 2 10 (second sheet) (July 2009) INTERNATIONAL SEARCH REPORT International application No. PCT/US 13/24487

Observations where certain claims were found unsearchable (Continuation of item 2 of first sheet)

This international search report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons:

Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely

Claims Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such extent that no meaningful international search can be carried out, specifically:

Claims Nos.: 15 · 9 because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a).

Box No. ΠΙ Observations where unity of invention is lacking (Continuation of item 3 of first sheet)

This International Searching Authority found multiple inventions in this international application, as follows:

1 I I As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims.

2. As all searchable claims could be searched without effort justifying additional fees, this Authority did not invite payment of additional fees.

3. As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims for which fees were paid, specifically claims Nos.:

No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.:

The additional search fees were accompanied by the applicant's protest and, where applicable, the payment of a protest fee. The additional search fees were accompanied by the applicant's protest but the applicable protest fee was not paid within the time limit specified in the invitation. No protest accompanied the payment of additional search fees.

Form PCT/ISA/2 10 (continuation of first sheet (2)) (July 2009)