Composite material and its use

Abstract

The techniques disclosed herein relate to a methodology for tailoring the properties of raw materials to provide a final composite material with unique pre-selected mechanical properties.

Description

Technical Field

[0001] The present invention generally relates to a method for manufacturing polymer composite materials and their use.

Background Art

[0002] Polymers and products made therefrom account for a significant portion of the solid waste of local governments. These materials are virtually non-biodegradable and include those that are difficult to recycle. Although manufacturers generally desire to produce biodegradable materials that contribute to sustainability and reduce the environmental impact associated with the disposal of such polymers, extremely large amounts of contaminated polymers are still being produced and discarded.

[0003] For many years, researchers have attempted to produce functional, i.e., not only having certain desired properties, but also safe polymer compositions with limited or reduced environmental impact. These attempts are described, for example, in any of the following references [1] -

[24] .

Prior Art Documents

Patent Documents

[0004] [1] International Patent Publication No. 07 / 010553 [2] International Patent Publication No. 13 / 029018 [3] Japanese Patent Application Laid-Open No. 2009091011 [4] International Patent Publication No. 17 / 214187 [5] International Patent Publication No. 13 / 044266 [6] Japanese Patent No. 4265200 [7] International Patent Publication No. 04 / 037919 [8] International Patent Publication No. 16 / 083667 [9] International Patent Publication No. 14 / 003369

[10] International Patent Publication No. 11 / 098122

[11] International Patent Publication No. 06 / 117801

[12] International Patent Publication No. 06 / 082471

[13] International Patent Publication No. 02 / 053640

[14] International Patent Publication No. 02 / 053610

[15] International Patent Publication No. 07 / 049952

[16] International Patent Publication No. 15 / 142564

[17] International Patent Publication No. 03 / 082970

[18] International Patent Publication No. 91 / 02023

[19] International Patent Publication No. 15 / 145457

[20] International Patent Publication No. 17 / 112878

[21] International Patent Publication No. 95 / 20013

[22] International Patent Publication No. 04 / 074367

[23] International Patent Publication No. 07 / 015261

[24] U.S. Patent No. 7,993,738

SUMMARY OF THE INVENTION

[0005] The inventors of the technology disclosed herein have developed a novel method for modifying the properties of raw materials in order to replace polymers that deteriorate over a long period, such as plastics, with new materials whose deterioration has been pre-adjusted. The composite materials of the present invention provide various end products configured based on the selection of materials, and when those materials are combined according to the present invention, they result in a final composite material having uniquely selected mechanical properties. It is an essential feature of the technology disclosed herein that a composite material or product having a predetermined lifespan can be adjusted, that is, it can be determined during manufacturing how quickly the composite material or product will deteriorate. By selecting an appropriate set of manufacturing parameters including material composition, amount of material, processing conditions, etc., a product having a predetermined lifespan can be adjusted. Such products will, for example, decompose when coming into contact with water or will naturally deteriorate after a pre-designed period has elapsed, leaving less toxic decomposition products that can sometimes be easily taken up by naturally occurring microorganisms.

[0006] Generally, the present invention provides a composite material (i.e., a raw material or a product) containing an aggregate of a polymer material and a non-polymer material in a combination or amount that imparts various properties to the composite material. By adjusting any of the amounts of PVOH, the crosslinked portion, and the bioplastic, the properties can be further adjusted to suit the purpose. Such properties include OTR and / or gas permeability, water solubility (or water degradation), thermal stability, heat seal, and mechanical properties such as tensile strength, Young's modulus, maximum elongation, flexibility, rigidity, shrinkability, or stretchability.

[0007] As disclosed herein, the compositions according to the present invention are aggregates of the disclosed components in a form (composition and amount) suitable for undergoing chemical treatment to provide a solid composite material. The composite material is based on the components of the originating composition and contains those components, while some of the components may be in a reactive or crosslinked form in the composite material. The composite materials of the present invention can be provided as raw materials, as masterbatches, in a partially processed form, or in the form of a final product. Non-limiting examples of composite forms include masterbatches, granular raw materials, powder raw materials, fibers, sheets of any thickness, polymer blocks, and any final product form.

[0008] Accordingly, in a first of its objectives, the present invention is a composition comprising A - poly(vinyl alcohol) (PVOH), B - at least one crosslinking compound (e.g., as described herein, selected from polymers, copolymers, and non-polymer materials), C - at least one additional bioplastic, and D - optionally at least one additive is provided.

[0009] In some embodiments, the compositions of the present invention A - poly(vinyl alcohol) (PVOH) in an amount in the range of 30 to 99% by weight, B - at least one crosslinking compound present in an amount in the range of 0.1 to 20% by weight, At least one additional bioplastic in an amount in the range of 0.1 to 50% by weight, and D - Optionally, at least one additive in an amount in the range of 0.1 to 20% by weight is included.

Mode for Carrying Out the Invention

[0010] Poly(vinyl alcohol) (PVOH) is a highly hydrophilic water-soluble polymer. The degree of hydroxylation determines its physical, chemical, and mechanical properties. The lower the number of residual acetate groups, the lower its water solubility and the higher its glass transition temperature. Furthermore, the degree of hydroxylation affects the maximum moisture absorption of water acting as a plasticizer and thus affects the mechanical and physical properties of the polymer. With an increase in water uptake, the tensile strength, modulus of elasticity, and hardness decrease, while the impact resistance and elongation at break increase significantly. Any form of PVOH is included in the invention disclosed herein.

[0011] Films made from PVOH have good heat sealability, excellent barrier properties against gases such as oxygen and carbon dioxide, and are biocompatible, biodegradable, and non-toxic. However, the films are highly hydrophilic and very susceptible to water-derived degradation, and thus are not substantially usable. In order to impart desired mechanical properties to PVOH while controlling the rate of degradation upon exposure to water, the compositions of the present invention further contain one or more additives or materials in a specific amount or a specific material ratio that change the properties of PVOH and impart one or more desired properties to the composition or the composite material made therefrom.

[0012] In some embodiments, at least one crosslinking compound is a compound capable of binding or crosslinking to PVOH. As shown, the crosslinking compounds are selected from polymers, copolymers, and non-polymeric materials, each of which has a functional group capable of binding to the PVOH backbone or any functionality present thereon.

[0013] In some embodiments, at least one crosslinking compound is a polymer or oligomer that can crosslink or bind to PVOH. Typically, the crosslinking or binding to PVOH is inherently chemical, i.e., through the formation of covalent bonds. In other examples, the binding may be physical, i.e., the polymer chains may be intertwined. Regardless of the type of binding, the crosslinking molecule is selected to enable a binding that provides the desired physical and mechanical properties.

[0014] The crosslinking compound has a functional group that can bind to PVOH. Such a functional group may be an original functional group of the polymer or a functional group grafted, bonded, or added to the polymer to impart crosslinking ability. In some embodiments, the functional group is selected from alcohols, epoxides, anhydrides, carboxylic acids, amines, amides, glycidyl functional groups, aldehyde functional groups, esters, etc.

[0015] The polymer can be selected from ionomers, i.e., polymers having functional groups capable of forming ionic groups. In some embodiments, the ionomer is a polyacid optionally selected from poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), etc.

[0016] In some embodiments, the crosslinking compound is a polymer grafted with an anhydride such as maleic anhydride. In some embodiments, the polymer grafted with maleic anhydride is selected from polyethylene (PE), poly(lactic acid) (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), poly(butylene adipate-co-terephthalate) (PBAT), etc. In some embodiments, the crosslinking compound is polyethylene-graft-maleic anhydride.

[0017] In some embodiments, the crosslinking compound is a polymer having a carboxylic acid functional group. In some embodiments, the polymer is selected from poly(ethylene-co-acrylic acid) (PE-co-AA), poly(ethylene-co-methacrylic acid) (PE-co-MAA), poly(lactide-block-acrylic acid) (PLA-block-AA), PVOH having a carboxyl group, carboxymethyl cellulose (CMC), and the like.

[0018] In some embodiments, the polymer is poly(ethylene-co-acrylic acid).

[0019] In some embodiments, the polymer is a polymer having a glycidyl functional group.

[0020] In some embodiments, at least one crosslinking compound is a copolymer.

[0021] In some embodiments, the crosslinking compound is a low molecular weight crosslinking compound that is neither a polymer, an oligomer, nor a copolymer. The compound is typically selected from aldehyde compounds, such as a compound having one or more aldehyde functional groups, carboxylic acid compounds, such as a compound having one or more carboxylic acid functional groups, and the like.

[0022] In some embodiments, the aldehyde compound can be selected from monoaldehydes and dialdehydes. In some embodiments, the aldehyde is selected from formaldehyde, glutaraldehyde, glyoxal, malondialdehyde, succinaldehyde, phthalaldehyde, and the like.

[0023] In some embodiments, the carboxylic acid compound is selected from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and higher homologs. Alternatively, these carboxylic acids can be selected based on the number of carboxylate groups or basic groups that can be formed. Thus, in an equivalent manner, these compounds can be selected from monobasic acids, dibasic acids, tribasic acids, and their higher homologs. In some embodiments, the carboxylic acid compound is selected from citric acid, boric acid, humic acid, phthalic acid, terephthalic acid, malic acid, sulfo-succinic acid, isophthalic acid, aconitic acid, and the like.

[0024] Additional bioplastics (or simply "bioplastics") used in accordance with the present invention are polymers different from other polymer components used in the composition, and all of those polymers are substantially bioplastics. The additional bioplastics can be represented by natural polymers produced or derived from natural resources such as living cells, plants, and other natural resources. Such polymers can be completely natural or partially synthetic, i.e., those derived from nature and chemically modified to structurally modify the natural polymer. Also, the bioplastics used in accordance with the present invention can be represented by biodegradable or compostable polymers derived in part or completely from petrochemical resources.

[0025] In some embodiments, the additional bioplastics are selected from polypeptides and polysaccharides.

[0026] In some embodiments, the additional bioplastics are selected from aliphatic or aromatic polyesters, copolyesters, or polyester amides.

[0027] In some embodiments, the additional bioplastic is selected from poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polycaprolactone (PCL), poly(lactic acid) (PLA), cellulose and cellulose derivatives, starch, thermoplastic starch (TPS), chitosan, polyhydroxyalkanoates (PHA) such as polyhydroxybutyric acid (PHB).

[0028] Cellulose derivatives are either its crystalline derivatives or other amorphous forms of such materials. Non-limiting examples include nanocrystalline cellulose (NCC), microfibrillated cellulose, bacterial cellulose, hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC).

[0029] In some embodiments, the additional bioplastic is PEO.

[0030] In some embodiments, the additional bioplastic is PCL.

[0031] In some embodiments, the additional bioplastic is PEG.

[0032] In some embodiments, the composition comprises both PEO and PCL.

[0033] In some embodiments, the composition comprises PVOH, PAA, PEO, and optionally PCL.

[0034] At least one additive used in the composition of the present invention can be selected from inorganic additives, fillers or reinforcing agents, and can be selected from low molecular weight additives (molecular weight less than 1000 Da) that improve various properties such as processing aids, slip agents, light stabilizers, ultraviolet absorbers, flame retardants, antibacterial agents, antiviral agents, foaming agents, nucleating agents, antioxidants, antiblocking agents, antistatic agents, etc.

[0035] In some embodiments, the additive is a moisture absorbent. Such agents can be selected from CaO, CaCl2, LiCl, NaCl, CaI2, MgCl2, TiO2, CaCO3, aluminosilicate fillers, SiO2, and the like. In some embodiments, the additive is CaO.

[0036] In some embodiments, the additive is an inorganic salt containing a metal element or a non-metal element. In some embodiments, the inorganic salt is an inorganic salt of a metal selected from alkali metals and alkaline metals. In some embodiments, the inorganic salt is a salt of a transition metal. Non-limiting examples of inorganic salts include halide salts of metals selected from Li, K, Ca, Na, Mg, Mn, Zn, and the like. Typically, the inorganic salt is a halide salt (where the halide atom is the anion of the metal cation). In some embodiments, the inorganic salt is selected from LiCl, NaCl, CaCl2, CaI2, and MgCl2. In some embodiments, the inorganic salt is CaCl2.

[0037] In some embodiments, the composition used according to the present invention comprises poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), and poly(acrylic acid) (PAA). The composition can be treated to include one or more additional components mainly selected from inorganic salts, cellulose-derived substances, and chitosan.

[0038] The inorganic salts used to modify the properties of the solid composite materials of the present invention can be in any salt form of metal elements or non-metal elements. In some embodiments, the inorganic salts are inorganic salts of metals selected from alkali metals and alkaline metals. In some embodiments, the inorganic salts are salts of transition metals. Non-limiting examples of inorganic salts include halide salts of metals selected from Li, K, Ca, Na, Mg, Mn, Zn, etc. Typically, the inorganic salts are halide salts (where the halide atoms are anions of metal cations). In some embodiments, the inorganic salts are selected from LiCl, NaCl, CaCl2, CaI2, and MgCl2. In some embodiments, the inorganic salt is CaCl2.

[0039] Cellulose-derived substances are any such materials that contain or are based on cellulose or cellulose derivatives. In some embodiments, the cellulose-derived substances are cellulose, or its crystalline structures such as nanocrystalline cellulose (NCC), microfibrillated cellulose, bacterial cellulose. In some embodiments, the cellulose-derived materials are selected from hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC).

[0040] By selecting a material composition from the material families disclosed herein, at least one property of the solid polymer material can be adjusted during the manufacturing process. The properties that can be adjusted are mechanical, chemical, or physical properties selected from water degradation, gas permeability, rigidity, flexibility, and elasticity. More specifically, the properties that can be adjusted can be mechanical properties such as water solubility or water degradation, oxygen transmission rate (OTR) and / or gas permeability, thermal stability, heat seal, and tensile strength, Young's modulus, maximum elongation, flexibility, rigidity, shrinkage, or stretch properties.

[0041] The oxygen transmission rate (OTR) measures the amount of oxygen gas passing through the solid composite material according to the present invention at the measured temperature over a given period. Also, by increasing the amount of PVOH, the permeation of gases other than oxygen can be prevented. Such other gases can be, for example, carbon dioxide.

[0042] In some embodiments, the amount of PVOH, the amount of at least one crosslinking compound, and the amount of at least one additional bioplastic are selected to regulate the water degradation of the composite material formed from the composition.

[0043] As described above, the ability to adjust the composite material to a predetermined lifespan, i.e., how quickly it degrades, or put another way, how long it can maintain contact with moisture or water wetting before they degrade, is an essential feature of the technology disclosed herein. The composite materials of the present invention can be made more or less sensitive to hydrolysis by controlling the amount of crosslinking material and / or additional bioplastics utilized, such as PAA and / or PEO or materials derived from cellulose. As used herein, "water degradation" implies that when the solid composite material made from the composition of the present invention comes into contact with water, the composite material dissociates partially or completely. In some cases, the composite materials of the present invention can be stable against hydrolysis by water for a period, but will begin to degrade after that period. This is referred to herein as the product lifespan. Other products will only readily degrade in water when in contact with water for a certain period. Such products can be considered to have a chemical self-destruction switch that can be activated by exposing the composite material to water.

[0044] Water degradation can result in the dissociation of the composite material into parts that can be easily decomposed and further hydrolyzed or chemically digested by natural microorganisms. In the present invention, the stability against water can be tested, verified, or determined based on any such assay known in the art. In some embodiments, one or more of the following can be used. 1 - Measure the decomposition time or the rate until complete dissolution while stirring in water at room temperature. 2 - Determine the decomposition time or the rate until complete dissolution while stirring in water at a temperature higher than room temperature, or 3 - Biodegradability test.

[0045] For example, the rate of water degradation of the composite material of the present invention was determined as the time required for dissolution or decomposition of the composite material under accelerated conditions and stirring at ambient temperature under sink conditions at all times, i.e., conditions where the concentration of the composite material dissolved in water is negligible compared to the amount of water (3 digits). The composite material containing 0.4 - 0.55 wt% of PAA showed a degradation rate of ~1 mg / (min×cm 2 ). The composite material containing 0.6 - 1.4 wt% of PAA showed a hydrolysis rate of ~0.2 mg / (min×cm 2 ).

[0046] In some embodiments, water degradation increases with an increase in the amount of at least one additional bioplastic relative to the amount of at least one cross - linking material.

[0047] In some embodiments, water degradation stops or slows down or is delayed with a decrease in the amount of at least one additional bioplastic relative to the amount of at least one cross - linking material.

[0048] In some embodiments, at least one cross - linking material and at least one additional bioplastic are each present in a ratio of about 1:5. In some embodiments, the ratio is PAA:PEO, 1:5.

[0049] In some embodiments, the ratio is 2:8. The ratio is PAA:PEO, 2:8.

[0050] In some embodiments, the ratio of the combined amount of PEO and PAA to PVOH is 2:98, respectively. In other embodiments, the ratio of the total of PEO and PAA, PCL, and PVOH is PEO / PAA:PCL:PVOH, 2:5:93.

[0051] Alternatively or additionally, in the compositions of the present invention, the amount of at least one crosslinking material can be 0.4 to 0.5 wt% or 0.9 to 1.1 wt%.

[0052] The mechanical properties of flexibility, rigidity, and elongation can be similarly adjusted by selecting appropriate relative amounts of PEO, PAA, cellulose, and / or at least one inorganic salt. As is known in the art, the flexibility or pliability of a composite material measures the rigidity of the product. The more flexible the product, the less rigid it is. Flexibility is measured as the resistance of the composite material to deformation in response to a force applied to the composite material. As the amount of PAA in the core formulation increases relative to the other components, the product becomes harder and less extensible.

[0053] Table 1 shows an exemplary list of the compositions according to the present invention. It should be noted that (as shown in Table 2), each composition can include a predefined amount of materials that impart the desired properties to the composite material made therefrom.

[0054] An exemplary composite material containing 1% PAA and 5% cellulose material showed a lower sealing temperature compared to a composite material containing 1.5% PAA and 1% cellulose material. Similarly, a composite material containing 1% PAA and 5% cellulose material showed a faster hydrolysis time (decomposed in 10 - 15 minutes, measured under stirring at room temperature) compared to a composite material containing 1.5% PAA and 1% cellulose material, which showed a medium range of decomposition time (decomposed in 20 - 25 minutes, measured under stirring at room temperature).

[0055] A composite material containing an amount of PAA in the range of 0.1 to 2% by weight can be adjusted to be susceptible or resistant to hydrolysis. The greater the amount of PAA present (i.e., an amount close to the limit of 2% by weight), the slower the observed hydrolysis. A smaller amount of PAA (i.e., an amount close to the limit of 0.1% by weight) allows for faster hydrolysis.

[0056] Similarly, a composite material containing an amount of PEO in the range of 1 to 10% by weight can be adjusted to be susceptible or resistant to hydrolysis. The greater the amount of PEO present (i.e., an amount close to the limit of 10% by weight), the faster the observed hydrolysis.

[0057] TIFF0007710645000001.tif127170

[0058] As shown in Tables 1 and 2, as the three relative amounts of PAA increase (see Table 1), the seal temperature (i.e., the temperature required to bond two polymer materials) increases (see Table 2), and water degradation slows down. As the amount of PEO increases, water degradation is promoted (fast under stirring at room temperature).

[0059] TIFF0007710645000002.tif119170

[0060] Compositions 6 and 9 contain the same amount of PEO, but Composition 9 contains five times more PAA. As shown in Table 2, compared to the composite material formed from Composition 6, which decomposed rapidly, the composite material made from Composition 9 decomposed slowly when in contact with water. The seal temperature of the composite material made from Composition 6 was low, while the temperature of the composite material consisting of Composition 9 increased as expected with the increase in the amount of PAA.

[0061] When Composition 6 is modified by increasing the amount of PAA to produce a composite material consisting of a composition such as Composition 7, the water dissolution rate decreases and the seal temperature increases. This is also consistent with the decrease in the dissolution rate due to the relatively decreased amount of PEO.

[0062] TIFF0007710645000003.tif144170

[0063] An exemplary composite material containing 1% PAA and 5% PCL showed a lower sealing temperature compared to a composite material containing 2% PAA and 1% PCL, and a composite material containing 1% PAA and 5% PEO showed a faster hydrolysis time (decomposed in 10 - 15 minutes, measured under stirring at room temperature) compared to a composite material containing 2% PAA and 1% PEO, which showed a slow range of decomposition time (decomposed in 40 - 50 minutes, measured under stirring at room temperature).

[0064] As shown in Table 3, with the increase in the relative amount of PCL, the sealing temperature (i.e., the temperature required to bond two polymer materials) decreased. Compositions 17, 20, and 21 had a medium heat - seal temperature, and compositions 18, 19, and 22 had a much lower heat - seal temperature. Increasing the amount of PAA shortened the hydrolysis time (under stirring at room temperature). Thus, Compositions 14 and 21 had a much longer hydrolysis time. The amount of PEO can finely adjust the decomposition time. When a larger amount of PAA was used, the solubility of Composition 13 was faster than that of Composition 11, and the dissolution rate of Composition 16 was higher compared to that of Composition 15.

[0065] Thus, the composition of the present invention can contain an amount of PVOH that is 80 - 85 wt%, 80 - 90 wt%, 80 - 99 wt%, 85 - 99 wt%, 90 - 99 wt%, 78 - 85 wt%, or 78 - 90 wt%.

[0066] In some embodiments, the amount of at least one crosslinking component is 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 7 wt%, 0.1 to 10 wt%, 0.1 to 12 wt%, 0.1 to 15 wt%, 0.1 to 17 wt%, 0.1 to 0.2 wt%, 0.1 to 0.3 wt%, 0.1 to 0.4 wt%, 0.1 to 0.5 wt%, 0.1 to 0.6 wt%, 0.1 to 0.7 wt%, 0.1 to 0.8 wt%, 0.1 to 0.9 wt%, 1 to 20 wt%, 3 to 20 wt%, 5 to 20 wt%, 7 to 20 wt%, 9 to 20 wt%, 10 to 20 wt%, 12 to 20 wt%, 15 to 20 wt%, or 17 to 20 wt%.

[0067] In some embodiments, the amount of at least one bioplastic is 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 7 wt%, 0.1 to 10 wt%, 0.1 to 12 wt%, 0.1 to 15 wt%, 0.1 to 17 wt%, 0.1 to 19 wt%, 0.1 to 20 wt%, 0.1 to 22 wt%, 0.1 to 25 wt%, 0.1 to 27 wt%, 0.1 to 30 wt%, 0.1 to 32 wt%, 0.1 to 35 wt%, 0.1 to 37 wt%, 0.1 to 40 wt%, 0.1 to 43 wt%, 0.1 to 45 wt%, 0.1 to 47 wt%, 1 to 5 wt%, 1 to 7 wt%, 1 to 10 wt%, 1 to 12 wt%, 1 to 15 wt%, 1 to 17 wt%, 1 to 20 wt%, 1 to 22 wt%, 1 to 25 wt%, 1 to 27 wt%, 1 to 30 wt%, 1 to 32 wt%, 1 to 35 wt%, 1 to 37 wt%, 1 to 40 wt%, 1 to 42 wt%, 1 to 45 wt%, 1 to 47 wt%, 3 to 20 wt%, 5 to 20 wt%, 7 to 20 wt%, 9 to 20 wt%, 10 to 20 wt%, 12 to 20 wt%, 15 to 20 wt%, 17 to 20 wt%, 5 to 20 wt%, 5 to 25 wt%, 5 to 30 wt%, 5 to 35 wt%, 5 to 40 wt%, 5 to 45 wt%, or 5 to 50 wt%.

[0068] In some embodiments, the amount of at least one additive is 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 7 wt%, 0.1 to 10 wt%, 0.1 to 12 wt%, 0.1 to 15 wt%, 0.1 to 17 wt%, 0.1 to 0.2 wt%, 0.1 to 0.3 wt%, 0.1 to 0.4 wt%, 0.1 to 0.5 wt%, 0.1 to 0.6 wt%, 0.1 to 0.7 wt%, 0.1 to 0.8 wt%, 0.1 to 0.9 wt%, 1 to 20 wt%, 3 to 20 wt%, 5 to 20 wt%, 7 to 20 wt%, 9 to 20 wt%, 10 to 20 wt%, 12 to 20 wt%, 15 to 20 wt%, or 17 to 20 wt%.

[0069] In some embodiments, PVOH is present in an amount of 73 to 96.5, 68.5 to 89.8, 77.5 to 96.3, 67.5 to 91.5, 72 to 95, 71 to 85, 81 to 90, 68 to 81, 75 to 84, 60 to 78, 91.5 to 99.3, 87.5 to 98.7, 94.6 to 82.5, 87 to 93.3, 83 to 98.7, 78.5 to 94.3, 79.5 to 93.8, 68 to 93.5, 81.5 to 93.7, 73.5 to 93.3, 82 to 98.6 or 77.5 to 98.2 wt%, at least one crosslinking compound is present in an amount of 0.1 to 1.5, 1.5 to 2.5, 1 to 2.5, 1.5 to 4, 1, 1.5 to 2, 1.5 to 2, 5, 0.1 to 0.5, 0.5 to 2, 0.1 to 0.5 or 1 to 2 wt%, and / or at least one bioplastic is present in an amount of 1.5 to 10, 5 to 10, 1.5 to 5, 1.5 to 4, 5, 2, 10, 0 to 1, 1 to 5, 5 to 10, 0.1 to 1 or 0.1 to 1 wt%, and the composition optionally contains at least one additive.

[0070] In some embodiments, the composition of the present invention comprises PVOH, PAA and PEO in amounts selected respectively from the following. - 73 to 96.5 wt%, 0.1 to 1.5 wt% and 1.5 to 10 wt%, - 68.5 to 89.8 wt%, 0.1 to 1.5 wt% and 5 to 10 wt%, - 77.5 to 96.3 wt%, 1.5 to 2.5 wt% and 1.5 to 5 wt%, -67.5 to 91.5 wt%, 1 to 2.5 wt%, and 1.5 to 5 wt%, -72 to 95 wt%, 1.5 to 4 wt%, and 1.5 to 4 wt%, -71 to 85 wt%, 1 wt%, and 5 wt%, -81 to 90 wt%, 1.5 to 2 wt%, and 2 wt%, -68 to 81 wt%, 1.5 to 2 wt%, and 5 wt%, -75 to 84 wt%, 5 wt%, and 5 wt%, -60 to 78 wt%, 5 wt%, and 10 wt%, -91.5 to 99.3 wt%, 0.1 to 0.5 wt%, and 0 to 1 wt%, -87.5 to 98.7 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt%, -94.6 to 82.5 wt%, 0.1 to 0.5 wt%, and 5 to 10 wt%, -87 to 93.3 wt%, 0.5 to 2 wt%, and 0 to 1 wt%, -83 to 98.7 wt%, 0.5 to 2 wt%, and 1 to 5 wt%, -78.5 to 94.3 wt%, 0.5 to 2 wt%, and 5 to 10 wt%, -79.5 to 93.8 wt%, 0.1 to 0.5 wt%, and 5 to 10 wt% (further optionally containing PCL in an amount in the range of 1 to 5 wt%), -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (further optionally containing PCL in an amount in the range of 5 to 10 wt%), -81.5 to 93.7 wt%, 0.1 to 1.5 wt%, and 0 to 1 wt% (further optionally containing PCL in an amount in the range of 5 to 10 wt%), -73.5 to 93.3 wt%, 0.5 to 1.5 wt%, and 5 to 10 wt% (further optionally containing PCL in an amount in the range of 1 to 5 wt%), -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt% (further optionally containing PCL in an amount in the range of 1 to 5 wt%), or -77.5 to 98.2 wt%, 0.5 to 1.5 wt%, and 0.1 to 1 wt% (further optionally containing PCL in an amount in the range of 5 to 10 wt%).

[0071] The compositions exemplified herein demonstrate and embody a novel method for modifying at least one property of a solid composite material derived from a combination of materials disclosed herein, such as combinations comprising poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), and poly(acrylic acid) (PAA).

[0072] The composite materials of the present invention are considered to be solid and can be manufactured with one or more improved properties as disclosed herein. These properties can be imparted based on the intended use of the composite material. The composite materials of the present invention can be manufactured in various shapes, sizes, and forms and can be manufactured by various processing techniques known in the field of polymeric materials.

[0073] Accordingly, the present invention further contemplates composite materials in non-specific forms and includes the following. - At least one material selected from among polymer materials that are easily crosslinkable in combination (these polymers can be selected from poly(vinyl alcohol), poly(acrylic acid), and glutaraldehyde), - At least one additional bioplastic material selected to be insoluble in water (the material is also selected to be biodegradable. By including such materials, the amount of materials such as poly(vinyl alcohol), poly(acrylic acid), glutaraldehyde, etc. can be reduced. The combination of a material such as poly(vinyl alcohol), poly(acrylic acid), or glutaraldehyde and a biodegradable material selected from water-insoluble materials is designed to finely tune the sensitivity to water. In some embodiments, the water-insoluble material is selected from among cellulose-derived materials such as hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), and / or chitosan), - At least one material selected from among hygroscopic materials (such materials can be ionic materials such as calcium salts, e.g., CaCl2), and - At least one material selected from among biodegradable plastics (non-limiting examples include PEO).

[0074] Further provided, in some embodiments, is a polymer composition in the form of a solid composite material comprising a combination of poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), and poly(acrylic acid) (PAA) (referred to herein as the core combination), optionally together with at least one material selected from inorganic salts, cellulose-derived substances, and chitosan.

[0075] The present invention further provides raw materials composed of poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), and at least one material selected from inorganic salts, cellulose-derived substances, chitosan, and formaldehyde.

[0076] In some embodiments, the composite material of the present invention comprises poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), and at least one material selected from inorganic salts, cellulose-derived substances, chitosan, and formaldehyde.

[0077] The composite material of the present invention can be made into any shape and form as a substantially one-dimensional object, such as a fiber, a two-dimensional object, such as a sheet or film, or a three-dimensional object. In some embodiments, the composite material is in the form of a material sheet or film. In other embodiments, the composite material can be made into a three-dimensional product by manipulating a composite sheet or film or by any one method selected from casting, blowing, injection, injection molding, extrusion, etc. Non-limiting examples of three-dimensional products that can be manufactured include storage chambers and containers, boxes, tubes, liners, advertising stands and billboards, exhibition facilities and panels, automotive components, bags, accessories, parts of clothing, pipes, rods, etc.

[0078] In some embodiments, the composition of the present invention comprises the following. A - Poly(vinyl alcohol) (PVOH) in an amount in the range of 30 to 99% by weight In some embodiments, the amount of PVOH in the composition is 30 to 40% by weight, 30 to 45% by weight, 30 to 50% by weight, 30 to 55% by weight, 30 to 60% by weight, 30 to 65% by weight, 30 to 70% by weight, 30 to 75% by weight, 30 to 80% by weight, 30 to 85% by weight, 30 to 90% by weight, 40 to 45% by weight, 40 to 50% by weight, 40 to 60% by weight, 40 to 70% by weight, 40 to 80% by weight, 40 to 90% by weight, 50 to 60% by weight, 50 to 70% by weight, 50 to 80% by weight, 50 to 90% by weight, 60 to 70% by weight, 60 to 80% by weight, 60 to 90% by weight, 70 to 80% by weight, 70 to 90% by weight, 80 to 85% by weight, 80 to 90% by weight, 80 to 99% by weight, 85 to 99% by weight, 90 to 99% by weight, 78 to 85% by weight, or 78 to 90% by weight. B - At least one cross - linking compound selected from polymers, copolymers, and non - polymeric materials in an amount in the range of 0.1 to 20% by weight In some embodiments, the amount of this component in the composition of the present invention is 0.1 to 1% by weight, 0.1 to 2% by weight, 0.1 to 4% by weight, 0.1 to 5% by weight, 0.1 to 7% by weight, 0.1 to 10% by weight, 0.1 to 12% by weight, 0.1 to 15% by weight, 0.1 to 17% by weight, 0.1 to 0.2% by weight, 0.1 to 0.3% by weight, 0.1 to 0.4% by weight, 0.1 to 0.5% by weight, 0.1 to 0.6% by weight, 0.1 to 0.7% by weight, 0.1 to 0.8% by weight, 0.1 to 0.9% by weight, 1 to 20% by weight, 3 to 20% by weight, 5 to 20% by weight, 7 to 20% by weight, 9 to 20% by weight, 10 to 20% by weight, 12 to 20% by weight, 15 to 20% by weight, or 17 to 20% by weight. C - At least one biodegradable plastic in an amount in the range of 0.1 to 50% by weight In some embodiments, the amount of the biodegradable plastic is 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 7 wt%, 0.1 to 10 wt%, 0.1 to 12 wt%, 0.1 to 15 wt%, 0.1 to 17 wt%, 0.1 to 19 wt%, 0.1 to 20 wt%, 0.1 to 22 wt%, 0.1 to 25 wt%, 0.1 to 27 wt%, 0.1 to 30 wt%, 0.1 to 32 wt%, 0.1 to 35 wt%, 0.1 to 37 wt%, 0.1 to 40 wt%, 0.1 to 43 wt%, 0.1 to 45 wt%, 0.1 to 47 wt%, 1 to 5 wt%, 1 to 7 wt%, 1 to 10 wt%, 1 to 12 wt%, 1 to 15 wt%, 1 to 17 wt%, 1 to 20 wt%, 1 to 22 wt%, 1 to 25 wt%, 1 to 27 wt%, 1 to 30 wt%, 1 to 32 wt%, 1 to 35 wt%, 1 to 37 wt%, 1 to 40 wt%, 1 to 42 wt%, 1 to 45 wt%, 1 to 47 wt%, 3 to 20 wt%, 5 to 20 wt%, 7 to 20 wt%, 9 to 20 wt%, 10 to 20 wt%, 12 to 20 wt%, 15 to 20 wt%, 17 to 20 wt%, 5 to 20 wt%, 5 to 25 wt%, 5 to 30 wt%, 5 to 35 wt%, 5 to 40 wt%, 5 to 45 wt%, or 5 to 50 wt%. At least one additive in an amount in the range of D - 0.1 to 20 wt% In some embodiments, the amount of the additive in the composition of the present invention is 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 7 wt%, 0.1 to 10 wt%, 0.1 to 12 wt%, 0.1 to 15 wt%, 0.1 to 17 wt%, 0.1 to 0.2 wt%, 0.1 to 0.3 wt%, 0.1 to 0.4 wt%, 0.1 to 0.5 wt%, 0.1 to 0.6 wt%, 0.1 to 0.7 wt%, 0.1 to 0.8 wt%, 0.1 to 0.9 wt%, 1 to 20 wt%, 3 to 20 wt%, 5 to 20 wt%, 7 to 20 wt%, 9 to 20 wt%, 10 to 20 wt%, 12 to 20 wt%, 15 to 20 wt%, or 17 to 20 wt%.

[0079] In some embodiments, the composition of the present invention comprises an amount of PVOH of 73 to 96.5, 68.5 to 89.8, 77.5 to 96.3, 67.5 to 91.5, 72 to 95, 71 to 85, 81 to 90, 68 to 81, 75 to 84, 60 to 78, 91.5 to 99.3, 87.5 to 98.7, 94.6 to 82.5, 87 to 93.3, 83 to 98.7, 78.5 to 94.3, 79.5 to 93.8, 68 to 93.5, 81.5 to 93.7, 73.5 to 93.3, 82 to 98.6 or 77.5 to 98.2% by weight, an amount of at least one cross-linking compound disclosed herein of 0.1 to 1.5, 1.5 to 2.5, 1 to 2.5, 1.5 to 4, 1, 1.5 to 2, 1.5 to 2, 5, 0.1 to 0.5, 0.5 to 2, 0.1 to 0.5 or 1 to 2% by weight, and / or an amount of at least one bioplastic of 1.5 to 10, 5 to 10, 1.5 to 5, 1.5 to 4, 5, 2, 10, 0 to 1, 1 to 5, 5 to 10, 0.1 to 1 or 0.1 to 1% by weight, and the total amount of the components (including additives if present) adds up to 100%.

[0080] In some embodiments, the composition of the present invention further comprises at least one additive.

[0081] In some embodiments, the composition of the present invention comprises the materials of the above groups (A), (B) and (C), for example, PVOH, PAA and PEO, respectively, as follows. - 73 to 96.5% by weight, 0.1 to 1.5% by weight and 1.5 to 10% by weight, - 68.5 to 89.8% by weight, 0.1 to 1.5% by weight and 5 to 10% by weight, - 77.5 to 96.3% by weight, 1.5 to 2.5% by weight and 1.5 to 5% by weight, - 67.5 to 91.5% by weight, 1 to 2.5% by weight and 1.5 to 5% by weight, - 72 to 95% by weight, 1.5 to 4% by weight and 1.5 to 4% by weight, - 71 to 85% by weight, 1% by weight and 5% by weight, - 81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, - 68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, - 75 to 84% by weight, 5% by weight, and 5% by weight, - 60 to 78% by weight, 5% by weight, and 10% by weight, - 91.5 to 99.3% by weight, 0.1 to 0.5% by weight, and 0 to 1% by weight, - 87.5 to 98.7% by weight, 0.1 to 0.5% by weight, and 1 to 5% by weight, - 94.6 to 82.5% by weight, 0.1 to 0.5% by weight, and 5 to 10% by weight, - 87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, - 83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, - 78.5 to 94.3% by weight, 0.5 to 2% by weight, and 5 to 10% by weight, - 79.5 to 93.8% by weight, 0.1 to 0.5% by weight, and 5 to 10% by weight (optionally further containing PCL in an amount in the range of 1 to 5% by weight), - 68 to 93.5% by weight, 0.1 to 0.5% by weight, and 1 to 5% by weight (optionally further containing PCL in an amount in the range of 5 to 10% by weight), - 81.5 to 93.7% by weight, 0.1 to 1.5% by weight, and 0 to 1% by weight (optionally further containing PCL in an amount in the range of 5 to 10% by weight), - 73.5 to 93.3% by weight, 0.5 to 1.5% by weight, and 5 to 10% by weight (optionally further containing PCL in an amount in the range of 1 to 5% by weight), - 82 to 98.6% by weight, 1 to 2% by weight, and 0.1 to 1% by weight (optionally further containing PCL in an amount in the range of 1 to 5% by weight), - 77.5 to 98.2% by weight, 0.5 to 1.5% by weight, and 0.1 to 1% by weight (optionally further containing PCL in an amount in the range of 5 to 10% by weight)

[0082] The present invention further provides a method for manufacturing an object or composite material according to the present invention. The method is modified according to the manufacturing rules described herein, - forming a core composition containing PAA and PEO, and - treating the core composition with either a composition containing PVOH or an additional material described herein. It includes all components compounded into a single homogeneous composition and processed under conditions such that 1D, 2D, or 3D objects can be obtained.

[0083] The present invention further - forming a core composition containing, for example, PVOH, PEO, and PAA, - treating the core composition with at least one additional material selected from, for example, inorganic salts, cellulose-derived substances, chitosan, and formaldehyde as described above, all components are compounded into a single homogeneous composition and processed under conditions such that 1D, 2D, or 3D objects can be obtained and provides a method including this.

[0084] As described above herein, for example, in order to adjust the hydrolysis rate, a composite material containing an amount of PAA in the range of 0.1 to 2% by weight can be adjusted to be more or less susceptible to hydrolysis. The greater the amount of PAA present (i.e., an amount close to the limit of 2% by weight), the slower the observed hydrolysis. A smaller amount of PAA (i.e., an amount close to the limit of 0.1% by weight) allows for faster hydrolysis. Similarly, a composite material containing an amount of PEO in the range of 1 to 10% by weight can be adjusted to be more or less susceptible to hydrolysis. The greater the amount of PEO present (i.e., an amount close to the limit of 10% by weight), the faster the observed hydrolysis. A smaller amount of PEO (i.e., an amount close to the limit of 1.5% by weight) allows for slower hydrolysis at a constant PAA concentration.

[0085] In some embodiments, the method of the present invention includes the step of preparing a formulation containing PVOH.

[0086] In some embodiments, the formulation containing PVOH is added to or combined with a pre-made formulation containing PEO, and in some embodiments, the combined formulation can be mixed to obtain a homogeneous formulation.

[0087] In some embodiments, the PVOH-PEO formulation is added to or mixed with a formulation consisting of pre-made PAA under conditions that enable cross-linking of PAA and PVOH. In some embodiments, cross-linking is enabled by adding at least one acid at a temperature from room temperature (RT, 23 - 30 °C) to 230 °C (or a temperature from 120 - 150 °C or 150 - 230 °C). In some embodiments, the temperature is 50 - 150 °C or 150 - 230 °C. In some embodiments, the acid can be selected from mineral acids and organic acids. In some embodiments, the acid is selected from sulfuric acid, HCl, nitric acid, etc. In some embodiments, the combination of PVOH, PEO and PAA is further treated with or mixed with at least one inorganic salt. In some embodiments, the inorganic salt is as defined above herein.

[0088] In some embodiments, the combination of PVOH, PEO and PAA is further treated with or mixed with at least one cellulose-based material selected as detailed above herein and PVOH.

[0089] Compounding the components together into a single homogeneous composition can be done under mixing at a temperature between room temperature (23 °C - 30 °C) and 120 - 230 °C or 150 - 230 °C. Once the homogeneous composition is formed, it can then be operated on or processed under industrially acceptable conditions to obtain the final composite product. Such methods include one or more of casting, blowing, injection and extrusion.

[0090] The present invention further provides exemplary composite materials prepared and characterized as herein, which composite materials are formed of the compositions listed in Tables 1 and 3. Accordingly, the present invention further contemplates the compositions listed in Tables 1 and 3 named as Composition 1 - 22 herein.

[0091] Also provided are composite materials formulated with the aforementioned compositions named as Composition 1 - 22 as defined.

[0092] In the method of the present invention, the final product produced from a raw material containing PVOH, PEO, and PAA and, optionally, one or more additional materials selected from, for example, inorganic salts, cellulose-derived substances, chitosan, and glycerol can be imparted with desired properties or a set of properties by modifying, fine-tuning, or tweaking the method for its production. The method of the present invention can be modified by changing the amount of the material ratio between two or more components (i.e., PVOH, PEO, and PAA) included in the core combination or between any component of the core combination and any other component of the material combination (e.g., inorganic salts, cellulose-derived substances, chitosan, and glycerol), by changing the additional components added to the core combination, by changing or modifying the processing conditions of the method for making the solid product, or by selecting a specific process sequence. Examples of the effects these modifications have on the properties of the final solid product are shown below in this specification.

[0093] The method of the present invention includes the step of controlling the weight / weight ratio (w / w) between (a) two or more materials selected from PVOH, PEO, and PAA, or (b) at least one material selected from PVOH, PEO, and PAA and at least one other material selected from inorganic salts, cellulose-derived substances, chitosan, and formaldehyde, and provides an option to modify the properties of the solid composite material by selecting the material ratio between any two materials of the combination of cores containing PVOH, PEO, and PAA, for example, between PVOH and PEO, or PVOH and PAA, or PEO and PAA, or between any one of PVOH, PEO, and PAA and any one of inorganic salts, cellulose-derived substances, chitosan, and formaldehyde. Non-limiting pairs of materials whose relative weight amounts (in grams or weight %) affect at least one property of the solid end product include PVOH and PEO, PVOH and PAA, PEO and PAA, PVOH and inorganic salts, PVOH and cellulose-containing substances, PVOH and chitosan, PVOH and formaldehyde, PEO and inorganic salts, PEO and cellulose-derived substances, PEO and chitosan, PEO and formaldehyde, PAA and inorganic salts, PAA and cellulose-derived substances, PAA and chitosan, and PAA and formaldehyde.

[0094] As shown in the examples described herein, increasing the amount of inorganic salt (calcium salt, such as calcium chloride, etc.) relative to at least one component of the combination of cores results in an improvement in the elongation ability of the solid product obtained from the combination of cores and the composition containing at least one inorganic salt.

[0095] Similarly, increasing the amount of PVOH relative to PAA increases the OTR. Increasing the amount of PAA relative to PVOH increases the rigidity.

[0096] Moreover, changing the relative amount of PEO affects the stability of the product in water. Increasing the amount of PEO relative to either PAA or PVOH increases the solubility in water (or decreases the water resistance and increases the hydrolyzability), and enhances the flexibility of the material. Similarly, increasing the amount of cellulose-derived substances (such as HPMC) relative to any of the core components decreases the water solubility of the solid final product.

[0097] An embodiment of the invention demonstrating the ability to adjust some of the properties detailed herein is shown in FIG. 1.

[0098] As used herein, the terms "ratio," "material ratio," or "weight / weight (w / w) ratio" imply the amount of a component of a combination (out of the total weight of the combination) relative to the amount of another component of the combination (out of the total weight of the combination). For example, the ratio between PVOH and PEO relates to the relative amount of PVOH compared to the amount of PEO in the combination. The ratio is expressed as an absolute weight value. For example, a ratio of PVOH:PEO of 1:1 indicates that each component of the combination is present in the same amount. An increase in the ratio stated with respect to one component means an increase in the amount of that particular component relative to the other component. For example, if the amount of PVOH increases relative to PEO, the stated ratio will be greater than 1:1, for example 2:1 or higher. When the term "about" is used with respect to a stated ratio or amount, it means a ratio or amount within ±10% of the stated value. For example, a ratio of about 1:1 is a ratio between (0.9 and 1.1):(1.1 and 0.9).

[0099] Accordingly, in another aspect of the invention, a method for manufacturing a solid composite material having a predefined hydrolysis rate is provided, the method comprising the following. - During the process of manufacturing the solid composite material, -(a) between two or more materials selected from poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), and poly(acrylic acid) (PAA), or - (b) at least one material selected from PVOH, PEO, and PAA, and at least one other material selected from inorganic salts, cellulose-derived substances, chitosan, and formaldehyde controlling the weight / weight ratio (weight / weight) therebetween.

[0100] In some embodiments, the "predetermined hydrolysis rate" is the rate at which the composite material of the present invention decomposes upon contact with water. The rate may be measured in units of grams per minute, or may simply be measured by the time it takes for the article to begin to decompose. As previously described herein, a composite material containing an amount of PAA in the range of 0.1 to 2 wt% can be adjusted to be more or less susceptible to hydrolysis. The more PAA present (i.e., an amount close to the 2 wt% limit), the slower the observed hydrolysis. A smaller amount of PAA (i.e., an amount close to the 0.1 wt% limit) allows for faster hydrolysis. Similarly, a composite material containing an amount of PEO in the range of 1.5 to 10 wt% can be adjusted to be more or less susceptible to hydrolysis. The more PEO present (i.e., an amount close to the 10 wt% limit), the faster the observed hydrolysis. A smaller amount of PEO (i.e., an amount close to the 1.5 wt% limit) allows for slower hydrolysis.

[0101] Thus, in some embodiments, a method for manufacturing a solid composite material having a predetermined hydrolysis rate includes the following. (a) varying the amount of PAA to be 0.1 to 2 wt% (when the amount of PAA in the composite material is large (1 to 2 wt%), hydrolysis is slower, and when the amount of PAA is small (0.1 to 1 wt%), hydrolysis is faster), or (b) varying the amount of PEO to be 1.5 to 10 wt% (when the amount of PEO in the composite material is large (3 to 10 wt%), hydrolysis is faster, and when the amount of PEO is small (1.5 to 3 wt%), hydrolysis is slower).

[0102] In some embodiments, a composite material containing 0.4 to 0.55 wt% of PAA in PVOH is ~1 mg / (min×cm2 ) showed the rate of decomposition. The composite material containing 0.6 - 1.4 wt% of PAA in PVOH showed a hydrolysis rate of ~0.2 mg / (min×cm 2 ).

[0103] Also provided is a method for modifying at least one property of a solid composite material formed from the composition according to the present invention, the method comprising treating a composition comprising an amount of PAA and an amount of PEO with a composition comprising an amount of PVOH and optionally at least one additive, wherein the amount of PAA, the amount of PEO and optionally the amount of PVOH are selected to modify at least one property under conditions that allow compounding of PAA, PEO and PVOH, and optionally at least one additive, into a solid composite material having at least one property.

[0104] In some embodiments, the at least one property is water degradation.

[0105] In some embodiments, the amount of PAA and the amount of PEO are each in a ratio of about 1:5.

[0106] In some embodiments, the amount of PAA and the amount of PEO are in a ratio of about 2:8. In some embodiments, the ratio is PAA:PEO, 2:8.

[0107] In some embodiments, the ratio of the total amount of PEO and PAA to the amount of PVOH is 2:98, respectively.

[0108] In some embodiments, the ratio of the total amount of PEO and PAA, the amount of PCL, and the amount of PVOH is PEO / PAA:PCL:PVOH, 2:5:93.

[0109] In some embodiments, the amount of PAA is 0.4 - 0.5 wt%.

[0110] In some embodiments, the amount of PAA is 0.9 - 1.1 wt%.

[0111] In some embodiments, the amount of PVOH is 80-85 wt%, 80-90 wt%, 80-99 wt%, 85-99 wt%, 90-99 wt%, 78-85 wt%, or 78-90 wt%.

[0112] In some embodiments, the amount of PAA is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

[0113] In some embodiments, the amount of PEO is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-10 wt%, 1-12 wt%, 1-15 wt%, 1-17 wt%, 1-20 wt%, 1-22 wt%, 1-25 wt%, 1-27 wt%, 1-30 wt%, 1-32 wt%, 1-35 wt%, 1-37 wt%, 1-40 wt%, 1-42 wt%, 1-45 wt%, 1-47 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, 17-20 wt%, 5-20 wt%, 5-25 wt%, 5-30 wt%, 5-35 wt%, 5-40 wt%, 5-45 wt%, or 5-50 wt%.

[0114] In some embodiments, PVOH is present in an amount of 73 to 96.5, 68.5 to 89.8, 77.5 to 96.3, 67.5 to 91.5, 72 to 95, 71 to 85, 81 to 90, 68 to 81, 75 to 84, 60 to 78, 91.5 to 99.3, 87.5 to 98.7, 94.6 to 82.5, 87 to 93.3, 83 to 98.7, 78.5 to 94.3, 79.5 to 93.8, 68 to 93.5, 81.5 to 93.7, 73.5 to 93.3, 82 to 98.6 or 77.5 to 98.2 wt%, PAA is present in an amount of 0.1 to 1.5, 1.5 to 2.5, 1 to 2.5, 1.5 to 4, 1, 1.5 to 2, 1.5 to 2, 5, 0.1 to 0.5, 0.5 to 2, 0.1 to 0.5 or 1 to 2 wt%, and / or PEO is present in an amount of 1.5 to 10, 5 to 10, 1.5 to 5, 1.5 to 4, 5, 2, 10, 0 to 1, 1 to 5, 5 to 10, 0.1 to 1 or 0.1 to 1 wt%, and the composition optionally contains at least one additive.

[0115] In some embodiments, the composition contains PVOH, PAA and PEO in amounts respectively selected from the following. - 73 to 96.5 wt%, 0.1 to 1.5 wt% and 1.5 to 10 wt%, - 68.5 to 89.8 wt%, 0.1 to 1.5 wt% and 5 to 10 wt%, - 77.5 to 96.3 wt%, 1.5 to 2.5 wt% and 1.5 to 5 wt%, - 67.5 to 91.5 wt%, 1 to 2.5 wt% and 1.5 to 5 wt%, - 72 to 95 wt%, 1.5 to 4 wt% and 1.5 to 4 wt%, - 71 to 85 wt%, 1 wt% and 5 wt%, - 81 to 90 wt%, 1.5 to 2 wt% and 2 wt%, - 68 to 81 wt%, 1.5 to 2 wt% and 5 wt%, - 75 to 84 wt%, 5 wt% and 5 wt%, - 60 to 78 wt%, 5 wt% and 10 wt%, - 91.5 to 99.3 wt%, 0.1 to 0.5 wt% and 0 to 1 wt%, - 87.5 to 98.7 wt%, 0.1 to 0.5 wt% and 1 to 5 wt%, -94.6 to 82.5 wt%, 0.1 to 0.5 wt%, and 5 to 10 wt%, -87 to 93.3 wt%, 0.5 to 2 wt%, and 0 to 1 wt%, -83 to 98.7 wt%, 0.5 to 2 wt%, and 1 to 5 wt%, -78.5 to 94.3 wt%, 0.5 to 2 wt%, and 5 to 10 wt%, -79.5 to 93.8 wt%, 0.1 to 0.5 wt%, and 5 to 10 wt% (optionally further containing PCL in an amount in the range of 1 to 5 wt%), -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally further containing PCL in an amount in the range of 5 to 10 wt%), -81.5 to 93.7 wt%, 0.1 to 1.5 wt%, and 0 to 1 wt% (optionally further containing PCL in an amount in the range of 5 to 10 wt%), -73.5 to 93.3 wt%, 0.5 to 1.5 wt%, and 5 to 10 wt% (optionally further containing PCL in an amount in the range of 1 to 5 wt%), -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt% (optionally further containing PCL in an amount in the range of 1 to 5 wt%), or -77.5 to 98.2 wt%, 0.5 to 1.5 wt%, and 0.1 to 1 wt% (optionally further containing PCL in an amount in the range of 5 to 10 wt%)

[0116] Thus, the degradation profile, i.e., the pace or rate at which the composite material degrades upon contact with water and perhaps how further degradation proceeds, will depend on any of the factors described herein. In some embodiments, the water degradation is adjusted by increasing the amount of PEO relative to PAA, thereby increasing the water degradation. In some embodiments, the water degradation is adjusted by increasing the amount of PAA relative to PEO, thereby decreasing the water degradation. In other embodiments, the water degradation is adjusted by decreasing the amount of PEO relative to PAA, thereby decreasing the water degradation. In other embodiments, the water degradation is adjusted by decreasing the amount of PAA relative to PEO, thereby increasing the water degradation.

[0117] An increase in the amount of PEO or PAA relative to the amount of PAA or PEO does not necessarily mean an increase in the amount of PEO / PAA over the amount of PAA / PEO, and the increase in that amount should be sufficient to increase / decrease water degradation. The degree of increase / decrease in amount depends, inter alia, on the initial amount of PEO / PAA in the composition, further effects associated with the increase / decrease in the amount of PEO / PAA, the desired degradation profile, and other factors.

[0118] The present invention also provides a method for adjusting the water degradation profile of a solid composite material formed with a composition according to the present invention, the method comprising treating a composition comprising an amount of PAA and an amount of PVOH and optionally at least one additive, together with an effective amount of PEO, the effective amount being selected to increase or decrease the water degradation of the solid composite material, the method being carried out under conditions that allow compounding of PAA, PEO and PVOH, and optionally at least one additive, into a solid composite material having a water degradation profile.

[0119] Also provided is a method for setting the onset of water degradation of a solid composite material comprising PVOH, the method comprising the following. - Selecting the amount of at least one crosslinking material and the amount of at least one additional bioplastic that, in combination, accelerate or delay the water degradation of the solid composite material when adjusting the preparation of a composition comprising PVOH, at least one crosslinking material and at least one additional bioplastic, and - Thermally treating the composition to form the solid composite material.

[0120] As used herein, the expression "setting the onset of water degradation" means determining in advance the rate at which the composite material will decompose, or in other words, whether it will decompose immediately in water, decompose later, or not degrade in water at all. By selecting the components of the composition from which the composite material is made, as disclosed herein, the onset of degradation can be predetermined by a simple experimental protocol. As disclosed herein, by determining the rate of decomposition, the earliest point in time at which the composite material will decompose and degrade can be determined. Without being bound by theory or decomposition mechanism, depending on the form of the composite material, such as a film or granules, the cascade of decomposition can be completed and the onset of decomposition can be determined. For example, in the degradation of a composite material in the form of a film, after initial deformation, the film breaks, crumbles into particles, and can subsequently dissolve. Therefore, the onset of degradation can be regarded as the stage of initial deformation.

[0121] Therefore, the method of the present invention is configured to produce a polymer composite material according to the present invention. The composite material can be characterized by a rate of water degradation of about 1 mg / (min·cm 2 ), or about 0.2 mg / (min·cm 2 ) or 0.001 mg / (min·cm 2 ) to 5 mg / (min·cm 2 ) or more. Some composite materials are configured to degrade immediately, some are configured to degrade days, weeks, or months after manufacture, and still others are made so as not to degrade.

[0122] As described above, the method of the present invention can include the step of forming the composite material into a desired form, such as in the form of granules, in the form of a masterbatch, or in the form of a 1D, 2D, or 3D object.

[0123] Also provided are objects comprising or consisting of the composite material of the present invention as disclosed herein and their use.

Brief Description of the Drawings

[0124] To better understand the subject matter disclosed in this specification and to illustrate how it can be actually implemented, embodiments will be described with reference to the accompanying drawings, merely as non-limiting examples. Those drawings are as follows.

Figure 1

Figure 2

Figure 3

Examples

[0125] Example 1 PAA and ground thermoplastic PVOH were mixed at a ratio of 1:99, extruded from a die with a diameter of 3 mm at 50 rpm and 190 - 210 °C using a twin-screw co-rotating extruder with L / D 40, and the resulting polymer strands were passed through an air-cooling system and a pelletizer.

[0126] Example 2 PAA, HPMC and ground thermoplastic PVOH were mixed at a ratio of 1:10:89, extruded from a die with a diameter of 3 mm at 50 rpm and 190 - 210 °C using a twin-screw co-rotating extruder with L / D 40, and the resulting polymer strands were passed through an air-cooling system and a pelletizer.

[0127] Example 3 PEO and PAA were mixed together at a ratio of 8:2, extruded from a die with a diameter of 3 mm at 50 rpm and 80 °C using a twin-screw co-rotating extruder with L / D 40, and the resulting polymer strands were passed through an air-cooling system and a pelletizer. The resulting PEO / PAA pellets were further mixed with PVOH at a ratio of 2:98, extruded from a die with a diameter of 3 mm at 150 rpm and 190 - 210 °C using a twin-screw co-rotating extruder with L / D 40 equipped with a devolatilization system, and the resulting polymer strands were passed through an air-cooling system and a pelletizer.

[0128] Example 4 Mix PEO and PAA together at a ratio of 8:2, extrude through a die with a diameter of 3 mm at 50 rpm and 80 °C using a co-rotating twin-screw extruder with L / D 40, and pass the resulting polymer strands through an air-cooling system and a pelletizer. The resulting PEO / PAA pellets were further mixed with PCL and PVOH at a ratio of 2:5:93, and extruded through a die with a diameter of 3 mm at 150 rpm and 190 - 210 °C using a co-rotating twin-screw extruder with L / D 40 equipped with a devolatilization system, and pass the resulting polymer strands through an air-cooling system and a pelletizer.

[0129] Figure 2 shows the effect of PAA on the dissolution of PVOH. Compounds containing 0%, 0.5%, 1%, 1.5% and 2% PAA in PVOH were prepared by reactive extrusion. Then, the samples were pressed to 200 microns from each compound and the dissolution was examined with stirring at room temperature. Record the time of initial deformation (D), film tearing (T), crushing into particles in water (P) and dissolution (S). Generally, as the PAA concentration in the compound increases, deformation, tearing, crushing into particles and dissolution become slower.

[0130] Figure 3 shows the effect of PEO on the dissolution of PVOH. Compounds containing 0%, 1%, 5% and 10% PEO in PVOH were prepared by reactive extrusion with a constant concentration of PAA (0.5%). Then, the samples were pressed to 200 microns from each compound and the dissolution was examined with stirring at room temperature. Record the time of initial deformation (D), film tearing (T), crushing into particles in water (P) and dissolution (S). Generally, as the PEO concentration in the compound increases, deformation, tearing, crushing into particles and dissolution are promoted.

[0131] In addition to dissolution kinetics, several further physico-mechanical parameters of the compound were characterized (data not shown). Polymer pellets were processed into 100 μm films at 200 °C using a cast extruder. The cast films were conditioned for 48 h at 23 ± 2 °C and 50 ± 5% RH in accordance with ASTM E171 / 71M-11 (reaffirmed 2015), Standard Practice for Conditioning and Testing Flexible Barrier Packaging. Tests were carried out under the same temperature / humidity conditions as above. Tensile properties of the films were measured based on ASTM D882-18, Standard Test Method for Tensile Properties of Thin Plastic Sheeting. For this purpose, strip test specimens 25.4 mm wide and 250 mm long were cut from the film using a dual blade shear cutter according to Procedure B specified in ASTM D6287-17, Standard Practice for Cutting Film and Sheeting Tests Specimens. Five test specimens were tested for each film. The tests were carried out using a Lloyd Instruments (UK) LRX 5K tensile testing machine equipped with a 500 N load cell and line grips in accordance with ASTM D882. The initial distance between the grips was 100 mm. All test specimens were tested at a grip separation speed of 500 mm / min along the machine direction (MD) of the film. According to these measurement results, increasing the PAA content in the compound increased the tensile strength, breaking stress and Young's modulus, while the elongation at break decreased.

[0132] The exemplary composite material containing 1% PAA showed higher tensile strength, breaking stress and Young's modulus than the composite material containing 0.5% PAA, and the elongation at break of the composite material containing 1% PAA was smaller than that of the composite material containing 0.5% PAA.

[0133] Another exemplary composite material containing 1% PAA showed lower tensile strength, breaking stress and Young's modulus than the composite material containing 1.5% PAA, and the elongation at break of the composite material containing 1% PAA was larger than that of the composite material containing 1.5% PAA.

[0134] Another exemplary composite material containing 0.5% PAA showed higher tensile strength, breaking stress and Young's modulus than the composite material without PAA, and the elongation at break of the composite material containing 0.5% PAA was smaller than that of the composite material without PAA.

Claims

**Claim 1** A composition comprising: A - poly(vinyl alcohol) (PVOH) in an amount in the range of 30 to 99% by weight; B - at least one crosslinking compound present in an amount in the range of 0.1 to 20% by weight and having a functional group capable of binding to PVOH, said functional group being a carboxylic acid selected from among dicarboxylic acids, tricarboxylic acids and higher homologues, at least one crosslinking compound; C - at least one additional biodegradable polymer in an amount in the range of 0.1 to 50% by weight, said at least one additional biodegradable polymer being at least one additional biodegradable polymer selected from poly(ethylene oxide) (PEO), polycaprolactone (PCL), cellulose and cellulose derivatives, starch, thermoplastic starch (TPS), chitosan and polyhydroxyalkanoate (PHA), and D - optionally, at least one additive in an amount in the range of 0.1 to 20% by weight in an anhydrous combination. **Claim 2** The composition according to claim 1, wherein said at least one crosslinking compound is selected from polymers, copolymers and non-polymeric materials and has a functional group capable of binding to PVOH. **Claim 3** The composition according to claim 2, wherein said at least one crosslinking compound is a polymer or oligomer having a functional group selected from alcohol, epoxide, anhydride, carboxylic acid, amine, amide, glycidyl functional group, aldehyde functional group or ester. **Claim 4** The composition according to claim 2, wherein said polymer is a polyacid, optionally poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMAA). **Claim 5** The composition according to claim 1, wherein said at least one crosslinking compound is a polymer having a carboxylic acid functional group, said polymer being optionally selected from poly(ethylene-co-acrylic acid) (PE-co-AA), poly(ethylene-co-methacrylic acid) (PE-co-MAA), poly(lactide-block-acrylic acid) (PLA-block-AA), PVOH having a carboxyl group and carboxymethylcellulose (CMC). The composition according to claim 1. **Claim 6** The composition according to claim 5, wherein said polymer is poly(ethylene-co-acrylic acid). **Claim 7** The composition according to claim 1, wherein the at least one additional bioplastic is selected from aliphatic or aromatic polyesters, copolyesters, and polyester amides.

8. The composition according to claim 1, wherein the at least one additional bioplastic is TPS.

9. The composition according to claim 1, wherein the at least one additive is selected from inorganic additives, fillers, reinforcing agents, processing aids, slip agents, light stabilizers, ultraviolet absorbers, flame retardants, antibacterial agents, antiviral agents, foaming agents, nucleating agents, antioxidants, antiblocking agents, and antistatic agents.

10. The amount of the PVOH, the at least one crosslinking compound, and the at least one additional bioplastic is selected to regulate the water degradation of the composite material formed of the composition, where water degradation is the partial or complete dissociation of the composite material when the composite material comes into contact with water, and the water degradation stops or decelerates or delays with a decrease in the amount of the at least one additional bioplastic relative to the amount of the at least one crosslinking material, and the at least one additional bioplastic is optionally PEO. The composition according to claim 1.

11. A method of modifying at least one property of a solid composite material formed of the composition according to claim 1, where the property is water solubility or water degradation, oxygen transmission rate (OTR) and / or gas permeability, thermal stability, heat seal, and mechanical properties, and water degradation is the partial or complete dissociation of the solid composite material when the solid composite material comes into contact with water. Including treating a composition containing an amount of PAA and an amount of PEO together with a composition containing an amount of PVOH and optionally at least one additive, where the amount of the PAA, the amount of the PEO, and optionally the amount of the PVOH are selected to modify the at least one property, and the compounding of the PAA, PEO, and PVOH, and optionally at least one additive, into the solid composite material having the at least one property is carried out under conditions that allow it. A method.

12. The method according to claim 11, wherein the at least one property is water degradation.

13. Treating a composition comprising an amount of PAA, an amount of PVOH, and optionally at least one additive, together with an effective amount of PEO, wherein the effective amount is selected to increase or decrease the water degradation of the solid composite material, water degradation being the partial or complete dissociation of the solid composite material when the solid composite material comes into contact with water, and wherein the PAA, PEO, and PVOH, and optionally at least one additive, are carried out under conditions such that they can be compounded into a solid composite material having a water degradation profile, a method for adjusting the water degradation profile of a solid composite material formed of the composition according to claim 1.

14. A method of setting the onset of water degradation of a solid composite material comprising PVOH formed of the composition according to claim 1, wherein water degradation is the partial or complete dissociation of the solid composite material when the solid composite material comes into contact with water, - When adjusting a composition comprising PVOH, at least one crosslinking material, and at least one additional bioplastic, selecting the amount of the at least one crosslinking material and the at least one additional bioplastic that, in combination, accelerate or delay the water degradation of the solid composite material, and - Heat-treating the composition to form the solid composite material comprising, a method.

15. A polymer composite material formed of the composition according to claim 1.

16. The composite material according to claim 15, in the form of a granular material or in the form of a masterbatch.

17. An object comprising the composite material according to claim 15.

18. A composition, A - poly(vinyl alcohol) (PVOH) in an amount in the range of 30 to 99% by weight, B - at least one crosslinking compound present in an amount in the range of 0.1 to 20% by weight, C - at least one additional bioplastic in an amount in the range of 0.1 to 50% by weight, and D - optionally, at least one additive in an amount in the range of 0.1 to 20% by weight comprising, wherein the at least one additional bioplastic is thermoplastic starch (TPS), a composition.

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