Biopolymer composition with additives

Abstract

This invention relates to novel compositions comprising (A) 65 to 99.4 wt.% of a biopolymer selected from the group consisting of polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate-butylene adipate (PBSA), thermoplastic starch (TPS), polyhydroxyalkanoates (PHA), polybutylene adipate-butylene terephthalate (PBAT), polybutylene sebacic acid-butylene terephthalate (PBST), polyhydroxybutyrate (PHB), polycaprolactone (PCL), cellophane (CA), and mixtures thereof; (B) 0.5 to 30 wt.% of a vinyl acetate-based homopolymer, copolymer, or terpolymer; and (C) 0.1 to 5 wt.% of organopolysiloxane particles comprising (1) 100 parts by weight of a polymer derived from the general formula RrSiO (4‑r / 2) (I) at least one polyorganosiloxane of the unit, wherein R is the same or different and represents a substituted or unsubstituted hydrocarbon residue and r represents 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.1; (2) 1 to 200 parts by weight of reinforced or unreinforced fillers or mixtures thereof; (3) 0.01 to 20 parts by weight of an additive containing boric acid for the production of granular materials; and (4) if desired, additional auxiliaries selected from the group consisting of processing aids, softeners, pigments and stabilizers, wherein the organopolysiloxane particles have a particle size of 1 to 100 mm.

Description

Technical Field

[0001] This invention relates to compositions comprising biopolymers and additives. Background Technology

[0002] Biopolymers are polymers that are made wholly or partially from renewable raw materials and / or are biodegradable. They are intended to replace petroleum-based plastics. Typically, the processing conditions for bioplastics are more difficult and their mechanical properties are often insufficient.

[0003] US2017 / 313912 A1 discloses a composition of polylactic acid (PLA), polyvinyl acetate and a plasticizer for membrane applications.

[0004] US2005 / 0004296 A1 describes a method for producing organopolysiloxane particulate material and the use of organopolysiloxane particulate material as an additive in thermoplastics. Summary of the Invention

[0005] The aim is to optimize or improve the surface properties, mechanical properties, and processing of biopolymers by adding additives.

[0006] This objective is achieved through the present invention.

[0007] The present invention provides a composition comprising

[0008] (A) 65% to 99.4% by weight, preferably 85% to 90% by weight, of a biopolymer selected from the group consisting of:

[0009] Polylactic acid (PLA),

[0010] Polybutylene succinate (PBS)

[0011] Polybutylene succinate adipate (PBSA)

[0012] Thermoplastic starch (TPS),

[0013] Polyhydroxyalkanoate (PHA)

[0014] polybutylene adipate-terephthalate (PBAT),

[0015] Polybutylene sebacate terephthalate (PBST)

[0016] Polyhydroxybutyrate (PHB)

[0017] Polycaprolactone (PCL),

[0018] And cellophane (CA),

[0019] (B) 0.5% to 30% by weight, preferably 10% to 15% by weight, of vinyl acetate-based homopolymers, copolymers, or terpolymers, and

[0020] (C) 0.1% to 5% by weight, preferably 1% to 2% by weight, of organopolysiloxane particles, said organopolysiloxane particles comprising

[0021] (1) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula

[0022] R r SiO (4-r / 2)

[0023] Wherein, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.1.

[0024] (2) 1 to 200 parts by weight of reinforced or unreinforced fillers or mixtures thereof

[0025] (3) 0.01 to 20 parts by weight of boric acid-containing additives, used in the production of particulate materials, and

[0026] (4) Optional additional additives, said additives being selected from the group consisting of: processing aids, plasticizers, pigments, and stabilizers.

[0027] Organopolysiloxane particles have a particle size of 1 to 100 mm.

[0028] The condition is that the content of components (A), (B) and (C) by weight % is based on the total weight of the composition in each case.

[0029] The present invention also provides a method for producing a composition, said method being carried out by mixing the following:

[0030] (A) 65% to 99.4% by weight, preferably 85% to 90% by weight, of a biopolymer selected from the group consisting of:

[0031] Polylactic acid (PLA),

[0032] Polybutylene succinate (PBS),

[0033] Polybutylene succinate-butylene adipate (PBSA)

[0034] Thermoplastic starch (TPS),

[0035] Polyhydroxyalkanoate (PHA),

[0036] Polybutylene adipate-terephthalate (PBAT),

[0037] Polybutylene sebacate-butylene terephthalate (PBST)

[0038] Polyhydroxybutyrate (PHB)

[0039] Polycaprolactone (PCL),

[0040] and cellophane (CA),

[0041] and

[0042] (B) 0.5% to 30% by weight, preferably 10% to 15% by weight, of vinyl acetate-based homopolymers, copolymers, or terpolymers, and

[0043] (C) 0.1% to 5% by weight, preferably 1% to 2% by weight, of organopolysiloxane particles, said organopolysiloxane particles comprising

[0044] (5) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula

[0045] R r SiO (4-r / 2)

[0046] Wherein, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.1.

[0047] (6) 1 to 200 parts by weight of reinforced or unreinforced fillers or mixtures thereof

[0048] (7) 0.01 to 20 parts by weight of boric acid-containing additives, used in the production of particulate materials, and

[0049] (8) Optional additional additives, said additives being selected from the group consisting of: processing aids, plasticizers, pigments, and stabilizers.

[0050] Organopolysiloxane particles have a particle size of 1 to 100 mm.

[0051] The condition is that the content of components (A), (B) and (C) by weight % is based on the total weight of the composition in each case.

[0052] Biopolymers (A) are commercially available, such as polylactic acid (PLA) from Nature Works and Total-Corbion, polybutylene succinate (PBS) from MCPP-Europe, polybutylene succinate-butylene adipate (PBSA) from MCPP-Europe, thermoplastic starch (TPS) from Rodenburg Biopolymers, polyhydroxyalkanoate (PHA) from Biomer and Danimer Scientific, polybutylene adipate-butylene terephthalate (PBAT) from BASF, polybutylene sebacate-butylene terephthalate (PBST) from BASF, polyhydroxybutyrate (PHB) from Biomer and Danimer Scientific, polycaprolactone (PCL) from Dow-DuPont and Perstorp, and cellophane (CA) from FKuR.

[0053] The biopolymers used are preferably polylactic acid (PLA) and polybutylene succinate (PBS).

[0054] The vinyl acetate-based homopolymer, copolymer, or terpolymer used as additive (B) is preferably selected from those comprising the group consisting of: vinyl acetate homopolymers, copolymers of vinyl acetate and ethylene, copolymers of vinyl acetate and vinyl laurate, terpolymers of vinyl acetate, ethylene, and versatic ester, terpolymers of vinyl acetate, ethylene, and acrylate, terpolymers of vinyl acetate, vinyl laurate, and acrylate, and mixtures thereof.

[0055] Vinyl acetate-based homopolymers, copolymers, and terpolymers are commercially available. For example, vinyl acetate homopolymers and copolymers are manufactured by Wacker Chemie AG. Products that can be purchased commercially under the product name.

[0056] The additive (B) used is preferably a homopolymer of vinyl acetate and a copolymer of vinyl acetate and ethylene.

[0057] Additive (B) can be a fine powder (preferably with a d of about 100 μm). 50 It can be in the form of spherical balls (preferably with a maximum diameter of 2 mm), broken flakes (irregular shape), or as particles (preferably with a diameter of up to about 4 mm).

[0058] The additive (C) used is organopolysiloxane particles as described in US2005 / 0004296 A1 (in connection with reference), more specifically in paragraphs

[0009] through

[0054] .

[0059] Examples of hydrocarbon groups R are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, or tert-pentyl groups; hexyl groups, such as n-hexyl groups; heptyl groups, such as n-heptyl groups; octyl groups, such as n-octyl groups and isooctyl groups, such as 2,2,4-trimethylpentyl groups; nonyl groups, such as n-nonyl groups; decyl groups, such as n-decyl groups; dodecyl groups, such as n-dodecyl groups; octadecyl groups, such as n-octadecyl groups; cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl groups; aryl groups, such as phenyl, biphenyl, naphthyl, anthracene, and phenanthrene groups; alkylaryl groups, such as ortho-, meta-, and p-tolyl groups, xylyl groups, and ethylphenyl groups; and aralkyl groups, such as benzyl groups, α-phenylethyl groups, and β-phenylethyl groups.

[0060] Examples of substituted hydrocarbon groups R are haloalkyl groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and perfluorohexylethyl groups, as well as haloaryl groups, such as p-chlorophenyl and p-chlorobenzyl groups.

[0061] Group R is preferably a hydrogen atom group or a hydrocarbon group having 1 to 8 carbon atoms, more preferably a methyl group.

[0062] Other examples of group R are vinyl, allyl, methalyl, 1-propenyl, 1-butenyl and 1-pentenyl, 5-hexenyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, ethynyl, propynyl and 1-propynyl groups.

[0063] In a further preferred embodiment of the invention, group R is an alkenyl group having 2 to 8 carbon atoms, more preferably a vinyl group.

[0064] The polyorganosiloxane (1) is preferably a highly viscous material. Preferably, the polyorganosiloxane (1) has a viscosity of 1,000,000 to 100,000,000 mm at 25°C. 2 Viscosity / s (measured according to DIN 1342-2, 2003-11).

[0065] The polyorganosiloxane (1) is preferably a diorganopolysiloxane having trialkylsiloxy, trimethylsiloxy, dimethylhydroxysiloxy or dimethylvinylsiloxy as end groups.

[0066] The polyorganosiloxane (1) is preferably a diorganopolysiloxane that is end-capped with trialkylsiloxy, preferably trimethylsiloxy, and consists of dimethylsiloxane units in the range of 70 to 100%, preferably 90 to 100%, and alkenylmethylsiloxane units (preferably vinylmethylsiloxane units) in the range of 0 to 30%, preferably 0 to 10%.

[0067] A single type of polyorganosiloxane (1) or a mixture of at least two different types of polyorganosiloxane (1) can be used.

[0068] An example of reinforced filler (2) is one with at least 50m 2 / g of BET surface area of ​​fumed silica or precipitated silica.

[0069] The silica fillers mentioned may be hydrophilic or they may have been hydrophobicized by known methods. Their use is preferred.

[0070] Examples of non-reinforced fillers (2) are quartz powder, diatomaceous earth, calcium silicate, zirconium silicate, zeolite, metal oxide powders such as aluminum, titanium, iron or zinc oxide powders, barium silicate, barium sulfate, calcium carbonate, gypsum, and polytetrafluoroethylene powder. Fiber components such as glass fiber and plastic fiber can also be used as fillers. The BET surface area of ​​these fillers is preferably less than 50 m². 2 / g.

[0071] In each case, based on 100 parts by weight of the polyorganosiloxane (1), the organopolysiloxane particles according to the invention contain filler (2) in an amount preferably 1 to 200 parts by weight, more preferably 30 to 100 parts by weight.

[0072] Additive (3) containing boric acid is described in EP 1 028 140 A1, the related disclosure of which is intended to form part of this application and to enable the production of completely free-flowing organopolysiloxane particulate materials. Additive (3) preferably consists essentially of boric acid and water, and optionally a fatty acid salt, wherein the water is preferably deionized or of higher purity, and in each case is added to the polyorganosiloxane (1) in an amount preferably from 0.01 to 20 parts by weight, preferably from 0.1 to 4 parts by weight, and more preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of the polyorganosiloxane (1). The water acts as a solvent for the boric acid and is preferably removed prior to granulation.

[0073] The fatty acid salts optionally present in the boric acid additive (3) are preferably salts of metals Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Ni, Pb, Sn, Sr, Zn, and higher fatty acids, resin acids, and naphthenic acids, such as stearates, palmitates, oleates, linoleates, resin salts, laurates, caprylates, ricinoleates, 12-hydroxystearates, naphthenicates, tallates, etc. Fatty acids having more than 12 carbon atoms up to 30 carbon atoms are preferred, and fatty acids having more than 16 carbon atoms up to 26 carbon atoms are particularly preferred, especially stearates, particularly calcium stearate. The amount of fatty acid salt present in the boric acid additive composition is preferably 0.1% to 10% by weight, preferably 0.2% to 6% by weight, and more preferably 0.3% to 4% by weight.

[0074] Examples of plasticizers that can be used as component (4) in organopolysiloxane particulate materials are those that are end-capped with trimethylsiloxy or hydroxyl groups and have a maximum thickness of 5000 mm at 25°C. 2 Dimeric organosiloxanes or diphenylsilanediols with a viscosity of / s. The dimer organosiloxanes are preferably formed from dimethylsiloxane units and / or vinylmethylsiloxane units.

[0075] After the individual components (1)-(4) are preferably combined in a kneader at a temperature preferably 100-250°C, more preferably 120-200°C, the composition is granulated using conventional granulation equipment (such as perforated plates and rotary knives) to provide a completely free-flowing particulate material. The resulting organopolysiloxane particles have a particle size of 1 to 100 mm, preferably 2 to 50 mm. The organopolysiloxane particles according to the invention preferably have a typical cylindrical particle structure with a diameter preferably 3 to 10 mm, more preferably 4 to 8 mm, and a height preferably 2 to 10 mm, more preferably 3 to 8 mm.

[0076] The particle size of the organopolysiloxane particles is determined by the diameter of the perforated plate used.

[0077] The organopolysiloxane particles used as additive (C) are commercially available, for example from Wacker Chemie AG. Product name.

[0078] In addition to components (A) to (C), the compositions according to the invention may also contain other components (D), such as fillers, pigments, stabilizers, and antioxidants.

[0079] The packing material used can be reinforced or unreinforced.

[0080] Reinforcing filler (i.e., having at least 50m) 2An example of a filler with a BET surface area of ​​greater than 50 m² / g is... 2 Fumed silica, precipitated silica, or silicon-aluminum mixed oxides with a BET surface area of ​​ / g. The fillers mentioned can be hydrophobized, for example, by treatment with organosilanes, silazanes, or siloxanes, or by etherification of hydroxyl to alkoxy groups.

[0081] Non-reinforced filler (i.e., with a thickness of less than 50m) 2 Examples of fillers with a BET surface area of ​​ / g include calcium carbonate, powdered quartz, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonite such as bentonite, molecular sieves including zeolites such as sodium aluminum silicate, metal oxides such as aluminum oxide or zinc oxide or mixed oxides thereof, metal hydroxides such as aluminum hydroxide, barium sulfate, gypsum, silicon nitride, silicon carbide, and boron nitride.

[0082] The compositions according to the invention contain filler in an amount preferably 5 to 40% by weight, and more preferably 10 to 15% by weight.

[0083] The preferred method for compounding the compositions of the present invention is a twin-screw extruder, such as a commercial co-rotating twin-screw extruder. The length-to-diameter ratio (L / D ratio) of the screw is preferably >30, more preferably >40.

[0084] The temperature during the incorporation of additives (B) and (C) into the biopolymer depends on the melt state of the biopolymer. It must not exceed recommended temperatures. During the incorporation of additives (B) and (C) into the biopolymer, temperatures from 170°C to 220°C, preferably from 175°C to 210°C, are preferred. After incorporation at elevated temperatures on suitable processing equipment, the resulting compound can be further processed using conventional techniques, such as injection molding, blow molding, compression molding, or vacuum forming, to produce the corresponding plastic.

[0085] The addition of additive (B) offers the advantage of compatibility with biopolymers, particularly polylactic acid (PLA). Furthermore, additive (B) allows for the production of high-performance polymer blends from PLA, other biopolyesters, and combinations of starch with organic and inorganic fillers. The use of additive (B) in combination with PLA is particularly suitable for blown film extrusion and injection molding applications.

[0086] Adding additive (B) to polybutylene succinate (PBS) can significantly reduce the recrystallization rate of PBS, thereby maintaining its constant properties. Flexibility or rigidity can be adjusted as needed by the proportion of the selected additive type (B) and by adding polylactic acid (PLA). Higher proportions of organic or inorganic fillers can also be used without adversely affecting the physical properties.

[0087] However, the combination of additive (B) and additive (C) alone yields biopolymers with significantly better processability. Furthermore, compared to bioplastics treated with additive (B) alone or additive (C) alone, bioplastics treated with the combination of additive (B) and additive (C) show significant improvements in surface properties and mechanical parameters. Here, the combination of the two additives (B) and (C) produces a synergistic effect.

[0088] The use of the combination of the two additives (B) and (C) of the present invention in bioplastics enables the production of molded parts and films with better mechanical and surface properties than those produced by using only one additive (B) or (C). Detailed Implementation

[0089] Example

[0090] 1. Production of compositions 1 to 18

[0091] Eighteen compounds were compounded on a KraussMaffei Berstorff ZE-25 twin-screw extruder with a length / diameter ratio of 47 and a screw diameter of 25 mm, at a temperature of 185°C, a screw speed of 250 rpm, and a throughput of 10 kg / h. The compositions of the 18 compounds are given in Table 1 below. The compounding conditions for the relevant compounds are listed in Table 2. For this purpose, all components of the granular material were mixed to form a dry blend, and the dry blend was metered into the feed zone of the extruder by gravimetric analysis. Similarly, all powdered components were mixed to form a dry blend, and this dry blend was also metered into the feed zone of the extruder by gravimetric analysis. The resulting extrudate was granulated with UWG and cooled.

[0092] Table 1: Compositions 1 to 18

[0093]

[0094] Ingeo TM PLA 4043D Polylactic Acid (PLA), trade name Ingeo TM Biopolymer 4043D, NatureWorks

[0095] BioPBS TM FZ 91PM Polybutylene Succinate (PBS), trade name BioPBS TM FZ 91PM, Mitsubishi Chemical Performance Polymers (MCPP)

[0096] 2504 Vinyl acetate-ethylene copolymer, trade name 2504, WackerChemie AG

[0097] 2525 Vinyl acetate homopolymer, trade name 2525, Wacker Chemie AG

[0098] Particle-sized P+ organopolysiloxane granular material, trade name P+ (spherical particles) ( Pellet P+)Pellet P Plus), Wacker Chemie AG

[0099] Spherical S Organic Polysiloxane Particle Material, Trade Name Spherical S ( ( Pellet S)Pellet S), Wacker Chemie AG

[0100] Omyacarb 40GU Calcium Carbonate, trade name 40GU, ​​Omya GmbH

[0101] Table 2: Composition of the Composition

[0102] (See 1. Production of the composition)

[0103]

[0104]

[0105] During processing, when two additives are used, the maximum reduction in torque and power consumption is experienced in the compounding step.

[0106] The efficacy was determined and demonstrated by comparing the following: biopolymers in which both additives (B) and (C) have been added, i.e., wherein 10% or 15% by weight of... and 1% by weight Already added to biopolymers (compositions 3 and 6, and also 10 and 13), with

[0107] - Pure biopolymers, without additives or fillers (PLA, composition 1) and those with fillers (PBS+CaCO3, composition 8), and with...

[0108] - Adding additive (B) alone to the biopolymer, such as 10% or 15% by weight. (Compositions 2 and 5, as well as 9 and 12).

[0109] 2. Further processing

[0110] 2.1 Injection-molded sheets

[0111] The compounds from Table 1 were processed on an Engel ES 600 / 125 injection molding machine at 170-200°C, an injection rate of 30-80 mm / s, and a dynamic pressure of 5.4 bar to form injection-molded sheets with smooth surfaces and dimensions of 8 cm x 12 cm.

[0112] 2.2 Flow spiral

[0113] At 160-190°C, an injection rate of 50 mm / s, and a back pressure of 2 bar, the compound also produced a flow spiral with a depth of 1.6 mm on the same system.

[0114] 2.3 Blown Film

[0115] In addition, blown films are produced to obtain test samples.

[0116] 3. Produce test samples in the form of pressure plates.

[0117] At 180℃ and 10N / mm 2 Each compound was processed for 10 minutes under pressure into pressure plates of different thicknesses.

[0118] 4. Inspection and evaluation of test samples

[0119] The injection-molded sheet from 2.1 and the press sheet from 3 were stored for 2 days under standard climatic conditions at 23°C and 50% relative humidity.

[0120] 4.1 COF: Sliding characteristics

[0121] According to ISO 8295, COF plastics—films and sheets—determination of coefficient of friction.

[0122] COF is represented without elements and measured using a pressure plate.

[0123] Table 3a:

[0124]

[0125] Table 3b:

[0126]

[0127] Using a combination of two additives (B) and (C), sliding performance can be significantly improved by reducing sliding friction resistance. The coefficient of friction (CoF value) decreases. The synergistic effect of adding additives (B) and (C) is clearly visible.

[0128] 4.2 Flowing spiral

[0129] The flow spiral is generated according to 2.2.

[0130] Table 4a:

[0131]

[0132]

[0133] Table 4b:

[0134]

[0135] Very good results were achieved using a flow spiral. Additive (B) It significantly prolonged the flow path, while additive (C) It provides an additional boosting effect.

[0136] 4.3MFR: Melt mass flow rate

[0137] These values ​​were determined on particulate materials according to DIN EN ISO 1133.

[0138] Table 5:

[0139]

[0140] The melt mass flow rate profile in PBS was improved by adding both additives (B) and (C).

[0141] 4.4 Transparency

[0142] Use the injection-molded sheet to visually assess transparency.

[0143] The transparency of injection-molded sheets is affected Impact; with With further addition, there was almost no additional turbidity.

[0144] 4.5 ball drop

[0145] The ball drop test is performed according to standard DIN EN ISO 6272-2.

[0146] Damage levels 1-5:

[0147]

[0148] Table 6a:

[0149]

[0150] Table 6b:

[0151]

[0152] When a combination of the two additives was used, the drop ball test showed that the surface was less severely damaged.

[0153] 4.6 Wear Test

[0154] Wear testing according to DIN 53516 - Testing of rubber and elastomers: Wear determination.

[0155] Table 7a:

[0156]

[0157] Table 7b:

[0158]

[0159] Depending on the type of product used The type of additive (B) affects whether wear is reduced, or even worsened by the occurrence of greater wear. Adding additive (C) It not only reduces wear but also compensates for the adverse effects of additive (B) on wear. The synergistic effect of adding additives (B) and (C) is clearly visible.

[0160] 4.7 Erichsen scratch test (Germany): Scratch resistance

[0161] The German company, Elysium, conducts scratch tests according to PV3974 - scratch resistance test.

[0162] The German Elysin scratch hardness tester (model 430P-I) is used to apply a scratch to a smooth injection-molded plate of size 2.1 at a speed of 1000 mm / min with a force of 10 N.

[0163] The scratches were evaluated using optical microscopy methods via confocal microscopy.

[0164] Table 8a:

[0165]

[0166] Table 8b:

[0167]

[0168] Additive (B) Adding PLA and PBS has a detrimental effect on scratching depth. This can be mitigated not only by adding additives (C) This compensates for the damage and can significantly improve scratch resistance. The synergistic effect of adding additives (B) and (C) is clearly visible. In this case, 2% by weight is recommended. The dosage.

[0169] 4.8 Tensile Test

[0170] Tensile testing was performed using DIN EN ISO 527 1B.

[0171] Table 9a:

[0172]

[0173]

[0174] Table 9b:

[0175]

[0176] In tensile tests, the systems containing fillers showed a significant improvement in elongation at break. Additives (B) and (C) and The combination of ) is proven to be valid here.

[0177] 4.9 Tear Spread Test

[0178] According to DIN 53515 version 01 / 1990 and based on Graves with notches, tear propagation tests are performed on blown films using angular samples.

[0179] Table 10a:

[0180]

[0181] Table 10b:

[0182]

[0183] In summary, the addition of additives (B) and (C) to biopolymers in this invention leads to the following advantageous results:

[0184] During processing, when two additives are used, the maximum reduction in torque and power consumption is experienced in the compounding step.

[0185] Sliding characteristics:

[0186] The coefficient of friction was determined using a CoF measuring device. The combination of these two additives improves sliding characteristics. The combination of additives (B) and (C) produces a synergistic effect.

[0187] Flow path:

[0188] In subsequent processing using the injection molding machine, it was found that additive (B) significantly extended the flow path, while additive (C) brought about an additional reinforcing effect.

[0189] Melt mass flow rate (MFR)

[0190] The melt mass flow rate profile was improved by adding additives (B) and (C) to PBS.

[0191] transparency:

[0192] It was found that the transparency of the injection-molded sheet was affected by additive (B); with further addition of additive (C), almost no additional turbidity was observed.

[0193] Ball drop test:

[0194] When a combination of the two additives (B) and (C) was used, the performed drop ball test showed less severe surface damage. More specifically, the addition of additive (C) enhanced this effect.

[0195] Abrasion resistance:

[0196] Wear resistance was measured using a friction wheel test. Depending on the type of additive (B), wear decreased or even increased. Adding additive (C) almost completely compensated for this effect / reduced wear. This also applies to both plastic types. The combination of the two additives (B) and (C) produces a synergistic effect.

[0197] Scratching depth:

[0198] Adding additive (B) to PLA and PBS has an adverse effect on scratch depth. This can be compensated for by adding additive (C), and a significant improvement is achieved, namely, improved scratch resistance, especially at higher doses of additive (C). The combination of the two additives (B) and (C) produces a synergistic effect.

[0199] Tensile test:

[0200] In tensile tests, the system containing the filler showed a significant improvement in elongation at break. The combination of additives (B) and (C) proved effective in this study.

[0201] Due to synergistic effects, the addition of additives (B) and (C) according to the present invention improves the surface properties of bioplastics such as scratch and abrasion resistance, mechanical properties, and processability.

Claims

1. A composition comprising (A) 65% to 99.4% by weight of a biopolymer, wherein the biopolymer is selected from the group consisting of: Polylactic acid, Polybutylene succinate, Polybutylene succinate-butylene adipate Thermoplastic starch, Polyhydroxyalkanoates, Polybutylene adipate-terephthalate, Polybutylene sebacate-terephthalate, Polyhydroxybutyrate, Polycaprolactone, cellophane and their mixtures, (B) 0.5% to 30% by weight of vinyl acetate-based homopolymers or copolymers, and (C) 0.1% to 5% by weight of organopolysiloxane particles, said organopolysiloxane particles comprising (1) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula R r SiO (4-r / 2) (I) in, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.

1. (2) 1 to 200 parts by weight of reinforced filler or non-reinforced filler or mixtures thereof, (3) 0.01 to 20 parts by weight of a boric acid-containing additive, said boric acid-containing additive being used in the production of particulate materials, and (4) Optional additional additives, said additives being selected from the group consisting of plasticizers, pigments, and stabilizers. The organopolysiloxane particles have a particle size of 1 to 100 mm. The condition is that the content of components (A), (B) and (C) by weight % in each case is based on the total weight of the composition.

2. The composition according to claim 1, characterized in that, The vinyl acetate-based homopolymers or copolymers used are selected from those grouped into the following: Vinyl acetate homopolymer, A copolymer of vinyl acetate and ethylene. A copolymer of vinyl acetate and vinyl laurate. A terpolymer of vinyl acetate, ethylene, and tertiary carbonate. A terpolymer of vinyl acetate, ethylene, and acrylate. A terpolymer of vinyl acetate, vinyl laurate, and acrylate. And their mixtures.

3. The composition according to claim 1 or 2, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane having trialkylsiloxy, dimethylhydroxysiloxy or dimethylvinylsiloxy as end groups.

4. The composition according to claim 1 or 2, characterized in that, The polyorganosiloxane (1) has a strength of 1,000,000 to 100,000,000 mm at 25°C, as determined according to DIN 1342-2, 2003-11. 2 Viscosity per second.

5. The composition according to claim 1 or 2, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane with trimethylsiloxy group as the end group.

6. A method for producing the composition according to claim 1, said method being carried out by mixing the following: (A) 65% to 99.4% by weight of a biopolymer, wherein the biopolymer is selected from the group consisting of: Polylactic acid, Polybutylene succinate, Polybutylene succinate-butylene adipate Thermoplastic starch, Polyhydroxyalkanoates, Polybutylene adipate-terephthalate, Polybutylene sebacate-terephthalate, Polyhydroxybutyrate, Polycaprolactone, cellophane and their mixtures, and (B) 0.5% to 30% by weight of vinyl acetate-based homopolymers or copolymers, and (C) 0.1% to 5% by weight of organopolysiloxane particles, said organopolysiloxane particles comprising (1) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula R r SiO (4-r / 2) (I) in, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.

1. (2) 1 to 200 parts by weight of reinforced filler or non-reinforced filler or mixtures thereof, (3) 0.01 to 20 parts by weight of a boric acid-containing additive, said boric acid-containing additive being used in the production of particulate materials, and (4) Optional additional additives, said additives being selected from the group consisting of plasticizers, pigments, and stabilizers. The organopolysiloxane particles have a particle size of 1 to 100 mm. The condition is that the content of components (A), (B) and (C) by weight % in each case is based on the total weight of the composition.

7. The method according to claim 6, characterized in that, The vinyl acetate-based homopolymers or copolymers used are selected from those grouped into the following: Vinyl acetate homopolymer, A copolymer of vinyl acetate and ethylene. A copolymer of vinyl acetate and vinyl laurate. A terpolymer of vinyl acetate, ethylene, and tertiary carbonate. A terpolymer of vinyl acetate, ethylene, and acrylate. A terpolymer of vinyl acetate, vinyl laurate, and acrylate. And their mixtures.

8. The method according to claim 6 or 7, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane having trialkylsiloxy, dimethylhydroxysiloxy or dimethylvinylsiloxy as end groups.

9. The method according to claim 6 or 7, characterized in that, The polyorganosiloxane (1) composed of units of formula (I) has a strength of 1,000,000 to 100,000,000 mm at 25°C, as determined according to DIN 1342-2, 2003-11. 2 Viscosity per second.

10. The method according to claim 6 or 7, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane with trimethylsiloxy group as the end group.

11. A composition comprising (A) 65% to 99.4% by weight of a biopolymer, wherein the biopolymer is selected from the group consisting of: Polylactic acid, Polybutylene succinate, Polybutylene succinate-butylene adipate Thermoplastic starch, Polyhydroxyalkanoates, Polybutylene adipate-terephthalate, Polybutylene sebacate-terephthalate, Polyhydroxybutyrate, Polycaprolactone, cellophane and their mixtures, (B) 0.5% to 30% by weight of vinyl acetate-based homopolymers or copolymers, and (C) 0.1% to 5% by weight of organopolysiloxane particles, said organopolysiloxane particles comprising (1) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula R r SiO (4-r / 2) (I) in, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.

1. (2) 1 to 200 parts by weight of reinforced filler or non-reinforced filler or mixtures thereof, (3) 0.01 to 20 parts by weight of a boric acid-containing additive, said boric acid-containing additive being used in the production of particulate materials, and (4) Optional additional additives, said additives being processing aids, The organopolysiloxane particles have a particle size of 1 to 100 mm. The condition is that the content of components (A), (B) and (C) by weight % in each case is based on the total weight of the composition.

12. The composition according to claim 11, characterized in that, The vinyl acetate-based homopolymers or copolymers used are selected from those grouped into the following: Vinyl acetate homopolymer, A copolymer of vinyl acetate and ethylene. A copolymer of vinyl acetate and vinyl laurate. A terpolymer of vinyl acetate, ethylene, and tertiary carbonate. A terpolymer of vinyl acetate, ethylene, and acrylate. A terpolymer of vinyl acetate, vinyl laurate, and acrylate. And their mixtures.

13. The composition according to claim 11 or 12, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane having trialkylsiloxy, dimethylhydroxysiloxy or dimethylvinylsiloxy as end groups.

14. The composition according to claim 11 or 12, characterized in that, The polyorganosiloxane (1) has a strength of 1,000,000 to 100,000,000 mm at 25°C, as determined according to DIN 1342-2, 2003-11. 2 Viscosity per second.

15. The composition according to claim 11 or 12, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane with trimethylsiloxy group as the end group.

16. A method for producing the composition according to claim 11, said method being carried out by mixing the following: (A) 65% to 99.4% by weight of a biopolymer, wherein the biopolymer is selected from the group consisting of: Polylactic acid, Polybutylene succinate, Polybutylene succinate-butylene adipate Thermoplastic starch, Polyhydroxyalkanoates, Polybutylene adipate-terephthalate, Polybutylene sebacate-terephthalate, Polyhydroxybutyrate, Polycaprolactone, cellophane and their mixtures, and (B) 0.5% to 30% by weight of vinyl acetate-based homopolymers or copolymers, and (C) 0.1% to 5% by weight of organopolysiloxane particles, said organopolysiloxane particles comprising (1) 100 parts by weight of at least one polyorganosiloxane composed of units of the following general formula R r SiO (4-r / 2) (I) in, R is the same or different and is substituted or unsubstituted hydrocarbon group, and r is 0, 1, 2 or 3, provided that the average value of r is in the range of 1.9 to 2.

1. (2) 1 to 200 parts by weight of reinforced filler or non-reinforced filler or mixtures thereof, (3) 0.01 to 20 parts by weight of a boric acid-containing additive, said boric acid-containing additive being used in the production of particulate materials, and (4) Optional additional additives, said additives being processing aids, The organopolysiloxane particles have a particle size of 1 to 100 mm. The condition is that the content of components (A), (B) and (C) by weight % in each case is based on the total weight of the composition.

17. The method according to claim 16, characterized in that, The vinyl acetate-based homopolymers or copolymers used are selected from those grouped into the following: Vinyl acetate homopolymer, A copolymer of vinyl acetate and ethylene. A copolymer of vinyl acetate and vinyl laurate. A terpolymer of vinyl acetate, ethylene, and tertiary carbonate. A terpolymer of vinyl acetate, ethylene, and acrylate. A terpolymer of vinyl acetate, vinyl laurate, and acrylate. And their mixtures.

18. The method according to claim 16 or 17, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane having trialkylsiloxy, dimethylhydroxysiloxy or dimethylvinylsiloxy as end groups.

19. The method according to claim 16 or 17, characterized in that, The polyorganosiloxane (1) composed of units of formula (I) has a strength of 1,000,000 to 100,000,000 mm at 25°C, as determined according to DIN 1342-2, 2003-11. 2 Viscosity per second.

20. The method according to claim 16 or 17, characterized in that, The polyorganosiloxane (1) is a diorganopolysiloxane with trimethylsiloxy group as the end group.

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