Bio-based scoring compositions and articles

Abstract

The present invention is a bio-based homogeneous composition comprising a bio-based polymer and a bio-based wax, wherein the bio-based wax comprises less than about 20% of the bio-based homogeneous composition. The bio-based composition has an elastic modulus of at least about 0.5 GPa and an elastic modulus of at least about 0.1 mJ / mm 3 has a strain energy density of

Description

[Technical Field]

[0001] The present invention relates generally to the field of scoring articles, and more particularly to bio-based scoring compositions and articles. [Background technology]

[0002] Scoring pads are widely used for cleaning surfaces in the home, such as surfaces in vehicles. Scoring pads are typically used with water and soap or detergent, with the scoring side of the pad being used to clean surfaces, such as dishes, utensils, glasses, pots, pans, grills, walls, floors, countertops, vehicle surfaces, and windows.

[0003] Scoring materials are manufactured in many forms, including nonwoven webs (e.g., the low-density nonwoven abrasive webs described in U.S. Pat. No. 2,958,593). After manufacture, the web of scoring material may be cut into pieces of a size suitable for hand use (e.g., the individual rectangular pads described in U.S. Pat. No. 2,958,593), or may be designed to be separated by the end user into convenient sizes as needed (e.g., as described in International Publication No. WO 00 / 006341 and U.S. Pat. No. 5,712,210). An example of a non-scratch scoring pad is sold under the trademark "Scotch-Brite" by 3M Company, St. Paul, Minnesota. TM Some are sold under the "

[0004] Preferred nonwoven fibrous scoring materials are low-density, open-structure materials with a relatively high void volume. While these types of scoring materials exhibit effective cleaning (because the voids retain material removed from the surface being cleaned), they are easily cleaned by simply rinsing with water or other cleaning solutions, allowing for reuse. Nevertheless, many scoring materials are intended for only a limited number of reuses and are then discarded. Because they are often used to clean kitchen work surfaces, cookware, and tableware, from a hygienic standpoint, it is desirable to discard these products before they become contaminated. However, as consumers become more environmentally conscious, they are becoming reluctant to use disposable products unless they are known to be recyclable or to decompose quickly without producing harmful by-products. Therefore, consumers are increasingly seeking more sustainable products. [Brief explanation of the drawings]

[0005] The present disclosure can be more fully understood from a consideration of the detailed description of various embodiments of the disclosure in connection with the accompanying drawings, in which:

[0006] [Figure 1] FIG. 1 is a cross-sectional view of a scoring article comprising a bio-based homogeneous composition of the present invention.

[0007] [Figure 2] FIG. 1 is a top view of a pattern used in an example of the present application.

[0008] While the foregoing drawings illustrate several embodiments of the present disclosure, other embodiments are contemplated as described herein. In all cases, the present disclosure presents the invention by way of example and not limitation. It is to be understood that numerous other modifications and embodiments can be devised by those skilled in the art which fall within the scope and spirit of the principles of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Summary of the Invention] In one embodiment, the present invention is a bio-based homogeneous composition comprising a bio-based polymer and a bio-based wax, wherein the bio-based wax comprises less than about 20% of the bio-based homogeneous composition. The bio-based composition has an elastic modulus of at least about 0.5 GPa and a modulus of at least about 0.1 mJ / mm 3 has a strain energy density of

[0010] In another embodiment, the present invention is a scoring article comprising a nonwoven substrate and a bio-based composition secured to the nonwoven substrate. The bio-based composition comprises a bio-based polymer and a bio-based wax, wherein the bio-based wax comprises less than about 20% of the bio-based composition. The bio-based composition has a modulus of at least about 0.5 GPa and a modulus of at least about 0.1 mJ / mm, as measured according to ASTM D790-17. 3 The composition of the nonwoven substrate is substantially different from the bio-based composition.

[0011] [Detailed Description of the Invention] The present invention provides a biobased homogeneous composition that can be incorporated into a scoring article. For example, the scoring article can be a wipe or sponge. The biobased homogeneous composition generally comprises a biobased polymer and a biobased wax. When incorporated into a scoring article, the biobased homogeneous composition is fixed onto a first substrate to form a scoring layer, which is then attached to a second substrate with an adhesive. In one embodiment, a scoring article comprising the biobased homogeneous composition is entirely biobased, making it a sustainable product. The present invention enables many opportunities for environmental sustainability, such as through the use of environmentally sustainable raw materials. For example, in one embodiment, the scoring article is at least partially composed of biodegradable, biobased, recyclable, compostable, or recycled materials. The scoring article of the present invention provides these benefits while maintaining sufficient scoring functionality.

[0012] As used herein, a material is "degradable" if it is capable of breaking down upon exposure to environmental factors such as sunlight, heat, water, oxygen, pollutants, microorganisms, insects, and / or animals. Typically, such materials are naturally derived and are typically "biodegradable." As used herein, a "biodegradable" material is one that is broken down by microorganisms or enzymes produced by such microorganisms. As used herein, "biodegradable" refers to a material or product that meets the requirements of ASTM D6400-12(2012), the standard used to determine whether a material or product meets the requirements for being labeled as "compostable in municipal and industrial composting facilities."

[0013] As used herein, a material is "compostable" means that the material can be broken down into natural components in a compost environment. As used herein, "compostable" means that the material breaks down through biological processes during composting, producing carbon dioxide, water, inorganic compounds, and biomass at a rate consistent with other compostable materials and without leaving visible, identifiable, or harmful residues. As used herein, "biodegradable" means a material or product that meets the requirements of ASTM D6400.

[0014] 1 shows a cross-sectional view of a scoring article 100 of the present invention. The scoring article 100 can take any shape without departing from the intended scope of the present invention. The scoring article 100 generally comprises a scoring layer 102 comprising a bio-based homogeneous composition deposited on a first substrate 104. The scoring layer 102 is attached to a second substrate 108 by an adhesive 106.

[0015] Bio-based homogeneous compositions generally include a bio-based polymer and a bio-based wax. The bio-based polymer is the primary component of the bio-based homogeneous composition and must have good adhesion to the first substrate and a minimum hardness for effective scoring. In one embodiment, the bio-based polymer has a Shore D hardness of at least about 50, as measured according to ASTM D2240-15. If the Shore D hardness is less than about 50, the bio-based polymer may be too soft for effective scoring and may easily dent. Therefore, rather than removing deposits from the surface being cleaned, the bio-based homogeneous composition may deform. This may lead to reduced scoring performance and durability of the bio-based homogeneous composition. Examples of suitable bio-based polymers include, but are not limited to, polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, and mixtures thereof.

[0016] The biobased wax functions to enhance lubricity and maintain the viscosity of the biobased homogeneous composition. The biobased wax constitutes less than about 20% of the biobased homogeneous composition, particularly less than about 10% of the biobased homogeneous composition. If the amount of biobased wax in the biobased homogeneous composition is too high, wax separation may occur, which may soften the biobased homogeneous composition and reduce the scoring efficiency of the biobased homogeneous composition. If the amount of biobased wax in the biobased homogeneous composition is too low, the biobased homogeneous composition may not melt and flow easily, making it difficult to deposit on the first substrate. It is important that the melting point of the biobased wax be higher than the application temperature to prevent the biobased wax from melting during use. In one embodiment, the biobased wax has a melting point of at least about 50°C, particularly at least about 60°C. In one embodiment, the biobased wax is hydrogenated. Examples of suitable biobased waxes include, but are not limited to, soybean oil, castor oil, and ethylene bisstearylamide. Particularly suitable examples include hydrogenated castor oil and hydrogenated soybean oil glycerides.

[0017] The entire bio-based homogeneous composition is generally homogeneous, as opposed to a liquid containing suspended particles. The bio-based homogeneous composition has an elastic modulus of at least about 0.5 GPa and a modulus of at least about 0.1 mJ / mm 3 The modulus of elasticity is a measure of the stiffness of a material, while the strain energy density is the potential energy stored when the material is deformed. The strain energy density is defined as the area under the stress-strain curve, and stress and strain measurements are performed according to ASTM D790-17 and calculated using Equations 3 and 5, respectively. The modulus of elasticity is calculated using Equation 6 of ASTM D790-17.

[0018] The bio-based homogeneous composition has a wet coefficient of friction of about 0.50 or less, specifically about 0.45 or less, and more specifically about 0.40 or less. If the wet coefficient of friction is too high, the bio-based homogeneous composition will not slide smoothly over the surface being cleaned, but will instead "grab" the surface, even if the surface is clean. The bio-based homogeneous composition has a crystallinity of about 50% or less, specifically about 40% or less, and more specifically about 35% or less. The crystallinity of the bio-based homogeneous composition can affect processability, particularly hot melt processing. The crystallinity should be low to help avoid the formation of "gel" particles in the cooling zones of printing equipment.

[0019] Because the bio-based homogeneous composition is applied to the surface of the first substrate in a molten state, it must be within a specific viscosity range at temperatures typically used in hot melt coatings. The bio-based homogeneous composition has a complex viscosity of at least about 5×10 at 100° C. 1 The complex viscosity at 175°C is approximately 1×10 Pa·s. 5 Pa s, in particular at least about 1 × 10 at 100 °C 2 Pa s and approximately 5×10 at 175°C 4 Pa s, more particularly at least about 1 × 10 3 Pa s and approximately 1×10 at 175°C 4 In one embodiment, the bio-based homogeneous composition is substantially free of tackifiers.

[0020] The bio-based homogeneous composition can be incorporated into the scoring article as part of a scoring layer. The scoring / texturing layer of the present invention is non-brittle and has sufficient hardness even in warm soapy water to prevent deformation due to hand pressure, while still being melt-formable. When the bio-based homogeneous composition is incorporated into the scoring article, the bio-based homogeneous composition is fixed to a first substrate to form the scoring layer. The scoring layer must be sufficiently durable to allow the scoring article to glide on a variety of surfaces. The scoring layer must also be able to adhere to the first substrate. The first substrate must have sufficient cohesive strength through its thickness to prevent premature disintegration of the scoring layer.

[0021] The first substrate has a basis weight of about 50 gsm to about 500 gsm. If the basis weight of the first substrate is less than about 50, unsightly adhesive oozing through the first substrate to the top surface of the scoring article may be observed. If the basis weight of the first substrate is greater than about 500, the first substrate may be too stiff and not flexible enough to conform when actually used to clean a surface. In one embodiment, the first substrate is bio-based. In one embodiment, the first substrate is fibrous. Fibrous substrates are advantageous in terms of conformability / flexibility and are also useful for allowing water to pass through the structure. The first substrate may or may not participate in the scoring action of the scoring article. In one embodiment, the first substrate is a nonwoven or bicomponent nonwoven. In one embodiment, the first substrate is a spunbond bicomponent nonwoven comprising a core and a sheath. The sheath has a melting point low enough to allow for good cohesive strength (i.e., good z-direction strength), but not so low that the sheath melts and hardens when the bio-based homogeneous composition is affixed to the first substrate, e.g., when the bio-based homogeneous composition is hot-melt screen-printed onto the first substrate. The core and sheath may be formed of the same or different compositions, ranging from about a 70 / 30 core / sheath ratio to about a 50 / 50 core / sheath ratio. Examples of first substrates include, but are not limited to, various grades of polylactic acid and polybutylene succinate. However, the first substrate must have a different composition from the bio-based homogeneous composition. This difference in composition prevents the first substrate from melting when the bio-based homogeneous composition is affixed to the first substrate.

[0022] The bio-based homogeneous composition may be immobilized on the first substrate as a textured, patterned layer to aid in scoring. In some embodiments, the patterned layer has a pattern, such as pattern 200 in FIG. 2. The bio-based homogeneous composition may be immobilized on the first substrate as a plurality of individual segments. The individual segments may form a pattern or may be randomly distributed on the surface of the first substrate. In one embodiment, the individual segments are a plurality of dots. In one embodiment, the dots have a height of about 0.1 mm to about 5 mm, particularly about 0.2 mm to about 2.5 mm, and more particularly about 0.3 mm to about 1.5 mm. In another embodiment, the scoring layer is immobilized as a thin layer along the entire surface of the first substrate. The bio-based homogeneous composition can be immobilized on the first substrate by any method known to those skilled in the art, such as spraying or screen printing. In one embodiment, the bio-based composition is immobilized on the first substrate by a melt coating process, such as hot melt screen printing, hot melt gravure roll coating, or spray application. In one embodiment, when the bio-based homogeneous composition is screen printed, the bio-based homogeneous composition covers from about 1% to about 100%, particularly from about 10% to about 30%, and more particularly from about 15% to about 20% of the surface of the first substrate. In one embodiment, when the bio-based homogeneous composition is sprayed, the bio-based homogeneous composition covers up to about 80%, particularly up to about 90%, and more particularly up to about 100% of the surface of the first substrate.

[0023] The bio-based homogeneous composition is completely bio-based yet is effective at scoring when used as part of the scoring layer.

[0024] The first substrate and the scoring layer comprising the bio-based homogeneous composition may optionally be secured to a second substrate. The second substrate may provide a better grip for the user and may also provide a second surface for cleaning with the scoring article. Examples of second substrates include, but are not limited to, cellulose or foam sponges, nonwoven fabrics, and the like. In one embodiment, the second substrate is bio-based.

[0025] When the scoring article includes a second substrate, the scoring layer is attached to the second substrate with an adhesive. The adhesive must ensure flexibility of each layer for good conformability. Additionally, the adhesive must not delaminate in hot water. In one embodiment, the adhesive is bio-based. In one embodiment, the adhesive may include, but is not limited to, polyamide. To adhere the scoring layer to the second substrate, the adhesive is first applied by spraying, roll coating, or extrusion to one side of the second substrate, and then the scoring layer is placed on the adhesive-bearing side of the second substrate.

[0026] The scoring article of the present invention is biodegradable. One indicator of biodegradability is disintegration. Disintegration can be measured according to ISO 20200 under thermophilic aerobic composting conditions or ISO 16929 using a vessel with a capacity of 35 L or greater. In one embodiment, the scoring article has at least about 50% disintegration after 8 weeks when measured according to a modified ISO 20200:2015 (tested for 8 weeks instead of 12 weeks). Compostability can be measured according to ISO 20200, which states that a plastic product is considered to have demonstrated satisfactory disintegration in a controlled composting test if, after 12 weeks, no more than 10% of its original dry weight remains when sieved through a 2.0 mm sieve. Biodegradation can also be measured by additional CO2 measurements according to other test methods described in Section 6.3 of ISO 20200.

[0027] Other materials can be added to the scoring article for specific purposes, including, but not limited to, grinding aids, lubricants, wetting agents, surfactants, pigments, dyes, colorants, fillers, fragrances, coupling agents, plasticizers, mild abrasives, abrasive materials, crosslinking agents, antistatic agents, antioxidants, particles, and suspending agents. These materials can be added for functional or aesthetic purposes. For example, dyes, colorants, fragrances, and particles serve aesthetic purposes. Examples of suitable abrasive materials include, but are not limited to, crushed walnut shells, peach kernels, and rice husks. Other suitable abrasive materials include inorganic materials such as iron oxide-based pigments. In one embodiment, the additives are composed of sustainable materials. That is, the additives may be biodegradable, biobased, recyclable, compostable, or made from recycled materials.

[0028] The present invention is further described in the following examples, which are illustrative only and are not intended to be limiting, as numerous modifications and variations within the scope of the invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are by weight. [Table 1-1] [Table 1-2]

[0029] [Example] [Base material] Four substrates were prepared according to the general method disclosed in U.S. Pat. No. 3,802,817 (Matsuki et al.). The fiber-forming material was melted in an extruder and pumped into an extrusion head with a regular (e.g., linear) array of orifices. Filaments of the fiber-forming solution were extruded from the extrusion head and passed through an air-filled space into a drawing machine. The filaments had a core / sheath structure. This structure is maintained because of the existence of a boundary between the two layers (core and sheath), even when the core and sheath are composed of the same material. A quenching air stream was blown onto the extruded filaments, which reduced their temperature and allowed them to partially solidify.

[0030] After passing through the drawer, the filaments were deposited onto a generally flat collector surface and collected as a mass of fibers or web.

[0031] The collector was generally porous, with a gas removal (vacuum) device located underneath to aid in the deposition of the fibers onto the collector (the porosity of the collector, e.g., relatively small porosity, does not alter the fact that the collector is generally flat, as described above).

[0032] The sheath / core type filament is extruded at 200°C-230°C, followed by quenching air at 10°C and 23 m 3 The nonwoven web was formed by drawing at an air flow rate of 100 / min. The web speed was adjusted to obtain the desired basis weight. The resulting web had a basis weight of 45 to 150 grams per square meter (gsm). When the core and sheath were of different compositions, i.e., bicomponent, the core to sheath ratio was approximately 50 / 50 or approximately 70 / 30, as shown below.

[0033] Base material 1: A 45gsm spunbond nonwoven fabric with a core and sheath made of PLA6102D.

[0034] Base material 2: 100, 125, and 150 gsm PLA6202D spunbond nonwoven fabrics with 2% pigment concentrate (made from a 2:1 blend of brown and white masterbatches) were calendered between two heated rolls at 104°C, 3 meters per minute (m / min), and a nip pressure of 90,000 N / m. One of the calender rolls was smooth, and the other had a pattern that contacted 17% of the treated area.

[0035] Base material 3: A 100 gsm spunbond bicomponent nonwoven fabric with a core of PLA6202D and a sheath of PBS FZ71 (PTT MCC Bioche, Thailand) in a core / sheath ratio of approximately 70 / 30, calendered in the same way as Substrate 2.

[0036] Base material 4: A 100 gsm spunbond bicomponent nonwoven having a core of PLA6100D and a sheath of PLA6302D in a core / sheath ratio of approximately 70 / 30, spunbonded and calendered similarly to Substrate 2.

[0037] Bio-based Compositions [Examples 1 to 16 (EX1 to EX16) and Comparative Examples 1 to 10 (CE1 to CE10)] Examples 1-6 and Comparative Examples 2-6 were compounded using a Coperion (Stuttgart, Germany) 18mm co-rotating twin-screw extruder at 160-195°C and 7-14 kg / hr. Examples 10-21 were compounded using a Berstorff 25mm co-rotating twin-screw extruder at 190-220°C and 7.5 kg / hr. The selected compositions were printed onto the above substrates using a custom-built hot melt screen printer (Telstar Engineering, Burnsville, MN, USA), except for Comparative Example 1, which was printed as supplied by the supplier and manually as described below. Comparative Examples 8-14 and Examples 7-12 were not printed. The printing temperature and web speed were adjusted to achieve optimal dot appearance. Unless otherwise noted, the hot melt printing temperature was typically 160-190°C and the web speed was 3-30 m / min. Where noted, circular dots (typically 1.5-2.0 mm in diameter and approximately 0.3-2.0 mm in height) were printed onto the substrate with the composition.

[0038] Comparative example 1 (CE1): HJ-2000 was used as is. An array of flat-topped dots spaced 5 mm apart was produced on Substrate 1 by melting the HJ-2000 composition onto the substrate using a perforated metal plate as a stencil. The excess was scraped off with a heated putty knife before removing the stencil.

[0039] Example 1 (EX1): A 60 / 40 blend of HJ-2000 and CaCO3 was compounded and then printed onto a substrate 2 in a pattern of dots 200 as shown in Figure 2.

[0040] Comparative Example 2 (CE2): A blend of 95% PLA4060D / PLA6252D / R8010 / citric acid / CaCO3 (ratio of 30 / 50 / 10 / 2 / 8) and 5% yellow masterbatch was formulated and printed on substrate 2 in a dot pattern as shown in Figure 2 .

[0041] Example 2 (EX2): A blend of PLA6252D / HJ2000 / MP-80 / CaCO3 was formulated in a ratio of 60 / 10 / 10 / 20. This composition required temperatures of up to 190°C and line speeds of up to 45 m / min when printed on Substrate 2, as shown in Figure 2.

[0042] Example 3 (EX3) and Example 4 (EX4): A blend of PBS FZ71 and MP-80 was formulated in a 90 / 10 ratio and printed in a dot pattern as shown in Figure 2 onto Substrate 2 and Substrate 3, respectively, to form EX3 and EX4.

[0043] Comparative Example 3 (CE3) and Comparative Example 4 (CE4): A blend of PBS FZ71 / MP-80 / citric acid was formulated in a ratio of 70 / 28 / 2 and printed in a dot pattern as shown in Figure 2 onto Substrate 2 and Substrate 3, respectively, to form CE3 and CE4.

[0044] Example 5 (EX5) and Example 6 (EX6): A blend of PBS FZ71 / MP-80 / citric acid was formulated in a ratio of 80 / 18 / 2 and printed on substrate 2 and substrate 3, respectively, in a dot pattern as shown in Figure 2 to form EX5 and EX6.

[0045] Example 7 (EX7): A blend of PLA6361 / MP-80 was formulated in a 90 / 10 ratio and printed onto substrate 4 in a dot pattern as shown in FIG.

[0046] Example 8 (EX8): A blend of PLA6361 / MP-80 was compounded in a 95 / 5 ratio and printed onto substrate 4 in a dot pattern as shown in FIG.

[0047] Example 9 (EX9): PLA6361 (100%) was used as a control and no dot array or pattern was printed.

[0048] Example 10 (EX10): A blend of 94.5 wt% PLA6361, 5 wt% ethylene bis(stearylamide) wax, and 0.5 wt% brown masterbatch was formulated and printed as a dot array on Substrate 4. The dot array, spaced 5 mm apart, was printed using the hot melt screen printer described above.

[0049] Examples 11 to 16 (EX11 to EX16) and Comparative Examples 5 to 10 (CE5 to CE10): Ecovio or Ecoflex polyester resin was blended with soy wax according to the composition defined in Table 2. [Table 2]

[0050] [Scrubbing items] Examples 17 to 21 (EX17 to EX21) and Comparative Example 11 (CE11) Various adhesives were applied to one side of cellulose sponges of different thicknesses by melt extrusion or roll coating, and then the unprinted side of the printed substrate was brought into contact with the adhesive-coated cellulose and pressed by hand or between rubber rolls to form a laminated scrubbing sponge structure. Alternatively, the adhesive was first applied to the unprinted side of the printed substrate, and then the adhesive-coated side was brought into contact with the cellulose sponge and pressure was applied to form a laminated structure.

[0051] Comparative example 11 (CE11): Technomelt 6240 adhesive was extruded onto cellulose sponge and sponge cloth of various thicknesses using a Coperion ZSX18 co-rotating twin screw extruder operating at approximately 250°C, at a coating weight of 80 g / m 2 Then, the composition was pressed onto the substrate 2 on which the composition described in Comparative Examples 3 and 4 had been printed, and laminated thereon.

[0052] Example 17 (EX17): Technomelt 6240 adhesive was extruded onto cellulose sponge and sponge cloth of various thicknesses using a Coperion ZSX18 co-rotating twin screw extruder operating at approximately 250°C, at a coating weight of 80 g / m 2 Then, the composition was pressed onto the substrate 3 on which the composition described in Examples 5 and 6 had been printed and laminated.

[0053] Example 18 (EX18): HY288 was extruded onto Substrate 4, which had been printed with the composition described in Example 7, using a Coperion ZSX18 co-rotating twin screw extruder operating at approximately 110°C, at a coating weight of 150 g / m 2 The coated substrate was immediately pressed onto sponges and sponge cloths of various thicknesses in a dry and wet state.

[0054] Example 19 (EX19): HY288 was extruded onto Substrate 4, which had been printed with the composition described in Example 7, using a Coperion ZSX18 co-rotating twin screw extruder operating at approximately 115°C, at a coating weight of 215 g / m 2 The coated substrate was immediately pressed onto sponges and sponge cloths of various thicknesses in a dry and wet state.

[0055] Example 20 (EX20): HY288 was roll coated onto 15 mm thick cellulose and sponge cloth using a Model 775 hot melt SPR S / T laminator (Black Bros. Co., Mendota, Illinois, USA) operating at an adhesive temperature of approximately 180°C. Substrate 4, printed with the composition described in Example 7, was then applied to the coated cellulose and held under pressure until the adhesive cured. The coating weight was 172 g / m 2 ~366g / m 2 It was.

[0056] Example 21 (EX21): 3M Adhesive 3789 was roll coated onto 15 mm thick cellulose using a Model 775 Hot Melt SPR S / T Laminator (Black Bros. Co., Mendota, Illinois, USA) operating at an adhesive temperature of approximately 180°C. Substrate 4, printed with the composition described in Example 7, was then applied to the coated cellulose and held under pressure until the adhesive cured. The coating weight was 172 g / m 2 ~366g / m 2 It was.

[0057] [Test method] In-sink test: A sink was filled with 2-6 liters of tap water at 45°C and approximately 3g of liquid dish detergent (Dawn, P&G, Cincinnati, Ohio, USA) was added. The scrubbing sponge structures were used to clean lightly soiled ceramic or plastic dishes for a total of approximately 5-10 minutes, then rinsed with warm water. The sponges were visually evaluated for substrate wear, dot removal, and delamination between the printed substrate and the cellulose sponge. The scrubbing sponges were allowed to air dry and then the test was repeated multiple times or until failure was observed.

[0058] In-sink testing confirmed that in Comparative Example 11 and Example 17, the adhesive softened in hot water, causing separation of the printed substrate and cellulose. In Examples 18 and 21, adhesive peeling occurred after 1 to 6 uses. In Examples 19 and 20, the adhesive bonded well and no peeling was observed even after several uses in the sink test, but the minimum adhesive application amount in Example 20 caused peeling on the first use.

[0059] Hardness, friction and 3-point bending tests: Test samples were melted in a Blue M gravity convection laboratory oven (Thermal Product Solutions, White Deer, PA, USA) operating at temperatures between 275°F and 375°F and then poured into aluminum pans or silicone molds to produce plates, slabs, or wafers 1.5 mm to 1 cm thick, depending on the requirements for hardness, friction, and three-point bend tests described below.

[0060] Hardness Test: The durometer hardness of a 0.5 to 1 cm thick sample of each dot composition was measured using a Shore D hardness tester according to the method of ASTM D2240-15.

[0061] Wet dynamic friction coefficient: Wet kinetic coefficient of friction (WDCOF) was measured on 1.5-4 mm thick flat plates using a BOT3000E digital tribometer (Regan Scientific Instruments) equipped with a styrene butadiene rubber sensor according to the method of ANSI B101.3-2012, with four scans per sample, and four measurements per scan. Dry static COF was measured without liquid on the surface, according to the instrument manufacturer's instructions. Shore D hardness and coefficient of friction results are shown in Table 3. [Table 3]

[0062] For Comparative Examples 2, 3, and 4, the durometer values ​​are given as a range because the samples frequently broke during the durometer test.

[0063] 3-point bending test: The average strain at break, strain energy density, and modulus of elasticity were evaluated using wafers measuring approximately 15 cm x 21 mm x 3.5 mm by three-point bending tests according to ASTM D790-17. The strain energy density was calculated as the area under the stress-strain curve from zero strain to the point of specimen breakage or 2% strain, whichever occurred first. If the specimen did not break, the strain at break and strain energy density could not be measured, but the strain and strain energy density at the end of the test were calculated and used as the lower limit of the fracture properties (indicated by the symbol ">"). The modulus of elasticity was calculated as the tangent modulus, as defined in Section 12.5.1, Equation 6 of ASTM D790-17, from the slope of the tangent to the initial linear portion of the load-deflection curve. [Table 4]

[0064] Melting behavior: The melting behavior of the dot compositions was measured using an ARES G2 rheometer. The complex viscosities (η*) (unit: Pa·s (Pascal-seconds)) at various temperatures are listed in Table 5. [Table 5]

[0065] Crystallinity: The crystallinity of some compositions was measured using a Discovery 2500 differential scanning calorimeter (DSC2A-00883 / RCS) system by the heating-cooling-heating method in temperature modulation mode. The crystallinity (%) was calculated based on the heat of fusion ΔH of the composition. f,DSC is the heat of fusion of a completely crystalline polymer, ΔH f,P (e.g., 91 J / g for PLA) and the mass fraction X of the polymer in the composition P The results are shown in Table 6.

number

[0066] Ecoflex Batch AB1 is 40% PBAT (60% CaCO3), and Ecovio F2341 is 25% filler (CaCO3 and talc) and 75% polymer (55% PBAT / 45% PLA). In calculating the crystalline weight percent, the theoretical 100% crystalline enthalpies of fusion for PLA and PBAT were taken as 91 J / g and 114 J / g, respectively.

[0067] Biodegradability test: Examples 22 to 25 (EX22 to EX25) Samples were prepared on Substrate 4 printed with the composition described in EX7, with the material and adhesive weight parameters defined in Table 7, except for a control consisting of approximately 15 mm thick cellulose sponge laminated with a non-biodegradable material (3M Scrub Dots, obtained from 3M Company, St. Paul, Minnesota, USA). All samples and controls were rinsed several times to remove preservatives from the cellulose before testing began. [Table 7]

[0068] Disintegration was measured using ISO 20200 with the following modifications: the C / N ratio and pH of the compost inoculum were not measured, the volatile solids content was not measured before and after the test, a ventilated oven was used instead of a circulating oven, pine shavings (0-3 mm) were used instead of sawdust, water was added periodically to replace water evaporating from the container, and only one replicate test was performed per material ID. Composting was performed in five 5-liter containers with aeration according to the method described in Section 6 of ISO 20200. Mature compost inoculum was obtained from SET, Inc., Rosemount, Minnesota, in August 2020 and stored at 40°F until the start of the test. After the test, each container was dried at 58°C for 10 days to obtain a dry equilibrium mass. The weight of each container was then measured, and the loss of solids was calculated compared to the mass at the start of the test. Samples were then sieved through 9.5 mm, 4.75 mm, and 2 mm sieves. The collected material was dried at 105°C for 18 hours to remove moisture. The mass collected on each sieve was recorded, and the degree of disintegration was calculated by dividing the mass of material passing through each sieve size by the original sample mass. Samples degraded up to 99% (measured on a 9.5 mm sieve) over the 8-week test period (see Table 8). [Table 8]

[0069] Testing the effectiveness of cleaning items: Testing of cleaning effectiveness of articles was performed generally similarly to the method described in U.S. Patent No. 5,626,512 (Palaikis et al.). A food-soil mixture consisting of 120 g milk, 60 g cheddar cheese, 120 g hamburger, 120 g tomato juice, 120 g cherry juice, 20 g flour, 100 g granulated sugar, and one egg was applied to a stainless steel disc. The coated panel was baked in an oven at 230°C for one hour. This application and curing process was repeated three times to form a uniform coating on the disc surface. The disc was then attached to the lower turntable of a Schiefer abrasion tester, modified to hold the disc. A 2.26 kg (5 lb) head was used as the pressure load. The sample was saturated with water, centered and secured on the upper turntable, and tested wet, lubricating the disc at a rate of one drop of water per second. The test ended when the coated disc was cleaned by scrubbing or after 5,500 cycles, whichever came first. Three replicates were performed for each sample, and the average number of cycles required to clean each panel was recorded (Table 9). The control was 3M Scrub Dots obtained from 3M Company (St. Paul, MN, USA). [Table 9] As shown in Table 9, Examples 7 and 8 performed better than the control.

[0070] While specific embodiments of the present invention have been shown and described, it should be understood that these are but examples of the many specific configurations that can be devised to apply the principles of the present invention. In light of these principles, those skilled in the art will be able to devise numerous and varied configurations without departing from the spirit and scope of the present invention. Accordingly, the scope of the present invention should not be limited to the configurations described herein, but should be defined only by the language of the claims and their equivalents.

Claims

1. 1. A bio-based homogeneous composition comprising: a bio-based polymer; a bio-based wax comprising less than about 20% of said bio-based homogeneous composition; Including, The bio-based composition has an elastic modulus of at least about 0.5 GPa and a modulus of elasticity of at least about 0.1 mJ / mm ３ The bio-based homogeneous composition has a strain energy density of

2. 10. The bio-based homogeneous composition of claim 1, wherein the bio-based polymer is selected from polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, and mixtures thereof.

3. 10. The bio-based homogeneous composition of claim 1, wherein the bio-based homogeneous composition is substantially free of tackifiers.

4. 10. The bio-based homogeneous composition of claim 1, wherein the bio-based polymer has a Shore D hardness of at least about 50 when measured according to ASTM D2240-15.

5. 10. The bio-based homogeneous composition of claim 1, wherein the bio-based homogeneous composition has a wet coefficient of friction of about 0.40 or less.

6. 10. The bio-based homogeneous composition of claim 1, wherein said bio-based homogeneous composition has a crystallinity of about 50% or less.

7. The bio-based homogeneous composition has a complex viscosity at 100°C of at least about 5 x 10 １ Pa s and a complex viscosity at 175°C of about 1 x 10 ５ 10. The bio-based homogeneous composition of claim 1, wherein the viscosity is less than Pa·s.

8. A scoring article, a nonwoven substrate; a bio-based composition secured to the nonwoven substrate, Bio-based polymers, and bio-based waxes comprising less than about 20% of said bio-based composition a bio-based composition comprising Including, The bio-based composition has an elastic modulus of at least about 0.5 GPa and a modulus of at least about 0.1 mJ / mm when measured according to ASTM D790-17. ３ and has a strain energy density of The scoring article, wherein the composition of the nonwoven substrate is substantially different from the bio-based composition.

9. 10. The scoring article of claim 8, wherein the bio-based composition is secured to the nonwoven substrate by a hot melt coating process.

10. 10. The scoring article of claim 8, wherein the bio-based composition is secured to the nonwoven substrate in a plurality of discrete segments.

11. The scoring article of claim 10, wherein the bio-based composition is fixed in a pattern.

12. 9. The scoring article of claim 8, wherein the substrate is fixed to a cellulose or foam sponge.

13. 10. The scoring article of claim 8, wherein the scoring article has a disintegration of at least about 50% when measured according to ISO 20200:2015 for 8 weeks.

14. 9. The scoring article of claim 8, wherein the bio-based polymer is selected from polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, and mixtures thereof.

15. 10. The scoring article of claim 8, wherein the bio-based composition is substantially free of tackifiers.

16. 9. The scoring article of claim 8, wherein the bio-based polymer has a Shore D hardness of at least about 50 when measured according to ASTM D2240-15.

17. 10. The scoring article of claim 8, wherein the bio-based composition has a wet coefficient of friction of about 0.50 or less.

18. 10. The scoring article of claim 8, wherein the bio-based composition has a crystallinity of about 50% or less.

19. The bio-based composition has a complex viscosity at 100°C of at least about 5 x 10 １ Pa s and a complex viscosity at 175°C of about 1 x 10 ５ 9. The scoring article of claim 8, having a viscosity of less than Pa.s.

20. 9. The scoring article of claim 8, wherein the bio-based wax is one of soybean oil, castor oil, and ethylene bisstearylamide.

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