JP2013538135A - Biolaminate composite assembly and related methods - Google Patents

Abstract

Embodiments of the present invention relate to a biolaminate composite assembly that includes one or more biolaminate layers, a non-plastic rigid substrate, and an adhesive layer contacting the substrate and the one or more biolaminate layers. The substrate is laminated or molded into one or more biolaminate layers. Embodiments also relate to methods of making a biolaminate composite assembly.
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Description

[Cross-reference to related applications]
This application is a continuation-in-part of US patent application Ser. No. 13 / 019,060, filed Feb. 1, 2011, entitled “Biolaminate Composite Assembly and Related Methods,” which application is incorporated herein by reference. No. 12/410, filed on Mar. 29, 2009, claiming priority based on US Provisional Application No. 61 / 038,971, filed Mar. 24, 2009. It is a continuation application of 018 issue. This application is also related to US Provisional Application No. 61 / 364,298 filed on July 14, 2010 (Attorney Docket No. 222923 / US), US Provisional Application No. filed on July 14, 2010. No. 61 / 364,189 (Attorney Docket No. 222076 / US), US Provisional Application No. 61 / 364,181 filed on July 14, 2010 (Attorney Docket No. 222075 / US), 2010 US Provisional Application No. 61 / 364,345, filed July 14, 2010 (Attorney Docket No. 222919 / US), US Provisional Application No. 61 / 364,366, filed July 14, 2010 No. (Attorney Docket No. 222918 / US), US Provisional Application No. 61 / 364,301 filed on July 14, 2010 (Attorney Docket No. 222925 / US), 2 US Provisional Application No. 61 / 364,193 filed on July 14, 2010 (Attorney Docket No. 222928 / US), and US Provisional Application No. 61/479 filed on April 26, 2011 No. 140 (Attorney Docket No. 222386 / US) to claim priority. The entire contents of these applications are incorporated herein by reference in their entirety.

  The environmental movement, both inside and outside the United States, continues to grow into a major concern with the growing demand for more environmentally friendly ("green") products and programs that remove harmful substances from residential and work environments. There is. Surfaces and components of PVC (polyvinyl chloride) and formaldehyde based laminated materials are currently excluded from many uses due to their toxicity. Many businesses and organizations are taking positive action to remove PVC and formaldehyde based products in the workplace and from product files.

  Such demand continues to grow for "green" products that replace petrochemical-based plastics and harmful polymers. Such demand is being driven by environmental awareness, building groups and building groups based on trying to make the indoor environment more healthy. Materials commonly used in many architectural, corporate and commercial applications for processing horizontal and vertical surfaces are mainly derived from PVC and melamine formaldehyde laminates. In the face of growing concern about the use of harmful PVC and formaldehyde in indoor applications, there is a need for environmentally friendly alternatives that balance their performance with economic needs.

  Formaldehyde has created serious problems for the indoor air environment. Particle boards and high pressure laminates use huge amounts of formaldehyde in their resin finish. In many cases, formaldehyde does not get completely removed from the product, but enters the indoor public space or a closed living space, and off gas may occur for a long time. Formaldehyde is associated with many health problems and is classified as a known carcinogen. Currently, large companies have issued a statement that they will remove PVC and formaldehyde from their workplaces. Japan has put in place strict policies prohibiting the use of products containing PVC and formaldehyde. Similar laws have been enacted in Europe.

  PVC is classified as "toxic plastic" by many organizations. Each year, over 7 billion pounds of PVC are discarded. The production of PVC involves the production of highly toxic chlorine and chemical feedstocks that contain carcinogenic vinyl chloride monomers. In areas around PVC chemical plants, there are serious pollution problems with groundwater supply, surface water and toxic chemicals in the air. Also, although the formation of PVC involves the formation of large amounts of toxic additives, the result is that human exposure to phthalate esters, lead, cadmium tin and other toxic chemicals is increased. Indoor use PVC generates its toxic substances as volatile organic compounds (VOCs) in buildings. When PVC is burned or incinerated, extremely harmful dioxins and hydrochloric acid are generated.

  The majority of decorative vertical or horizontal surfacing materials are high pressure laminates and thermofoil PVC. A thin high-pressure laminate (HPL) (generally 0.050 inch thick for a single wood particle board bonded with urea resin adhesive) on machined surfaces, tables, desks and many other machined surfaces Glue. In the last decade, many kitchen cabinets have been manufactured by cutting medium quality fiberboard containing phenol formaldehyde resin adhesive into a door mold. A thin PVC sheet or thermofoil was heated and the three-dimensional shaped door was pressed using a membrane press. As a result, the door was completed as an off-the-shelf product and was water resistant, but contained a large amount of chlorine. When this cabinet burns, the off-gas can produce hydrochloric acid gas, which can be extremely harmful to firefighters and those who could not escape from the fire.

  Currently, virtually all processed surfaces that are found in commercial, corporate and even residential applications are harmful petrochemical based products. The most commonly used high pressure laminates are commonly used in office desks, tables and counters. They are manufactured using dangerous formaldehyde based materials which still produce an off gas after installation. Although PVC thermofoil is also commonly used, harmful PVCs are causing a number of problems. Although many organizations, businesses, and governments have restricted or even prohibited the use of these materials, few have been found to be effective and superior alternatives to such products. The

  Bio-based materials are considered as an ideal solution in the construction market, enterprise market, commercial market, and even the housing market. Nevertheless, very few biobased materials have come into the market as direct substitutes for PVC thermofoil and formaldehyde based laminates used for surface processing. Biorenewable materials are preferred over petrochemical-based plastic products. In general, bioplastics have been used for various packaging film applications. Initially, PLA (polylactic acid) was the most commercially successful in such bioplastics. PLA is a hard and brittle plastic that is very fluid and liquefies rapidly under direct fire conditions. In addition, PLA is not easily extruded into profile shapes because of its high melt index and unique rheology. Most current PLA products are based on producing biodegradability. However, as is understood, it is not always desirable that a product subjected to long-term commercial use be biodegradable, even if bioregeneration is desired.

PVC is attacked by many global organizations because of its harmful nature and its finish. At present, it is difficult to produce environmentally friendly alternatives to PVC. Another type of petrochemical-based plastic tries to achieve this, but with only a slight improvement on the environmental protection. Bioproducts provide an alternative solution to PVC based on biorenewable materials, and contain no harmful chemicals, plasticizers, additives. Flexible PVC is used in many applications, making its first application a decorative flexible plastic product. Signboards, vinyl wallpaper, upholstery, etc. are some of the most common applications of flexible PVC sheets commonly used for indoor applications. Designers and architects who design furniture in particular care about the indoor air environment and promote the use of environmentally friendly materials. The United States government has also agreed that "bio-preferred" products are good as an environmental solution, and has identified other agricultural material products as bio-preferred for green building applications.

The material for the signage is generally a very flexible PVC loaded with harmful chemical plasticizers. Flexibility is required for banners attached to curved surfaces, allowing operation with large ink jet printing systems. Second, most of the inks used in signage are also solvents that use harmful chemicals that can generate harmful gases during manufacturing and end use.

Profile-wrapped components are usually manufactured using various shapes of foam plastic or wood / aggregate composites that are machined and have a specific shape, and also to meet functional or decorative needs Can be used in thin foil-wrapped surfaces. Profile linear wrapped wood products and components are commonly used in a number of applications, including the following.
Window members Door frame Door members Laminated flooring Architectural woodwork product paneling synthetic deck

  Wood plastic extrusion has been commercialized over the past decade as a wood substitute in exterior applications, primarily decks and window members. Nowadays, they are single color, like wood with a chopped plastic and do not have high aesthetic value. Typically, wood plastic composites use polyethylene, polypropylene or PVC as a bonding plastic to bond such wood to produce such products. In some cases, these composites perform a coextrusion of solid plastic on the outside to form a solid colored skin for UV protection and also hide the chopped portions of wood to make them slightly aesthetically pleasing Satisfy.

  While "green" products have long been desired and are now mainstream, biomaterials or "green" solutions are often expensive and usually do not meet the required performance criteria. In some cases, people and businesses are willing to pay slightly higher for "green" products, but in reality "green" products fulfill their performance while having price advantages There is a need. Being 'green' is important, but in order to commercialize 'green' technology, the ability to deliver performance at competitive prices is important. It is important that the materials and products in this environment are not harmful to overall health and provide a clean, VOC-free environment. PVC and its additives, along with laminate and particle board formaldehyde, emit harmful VOCs to the workplace. These VOCs are classified as potential carcinogens, creating a higher risk of cancer.

  While “green” biodegradable packaging materials are moving the global community to better environmental practices, they can not be biodegraded for more permanent use to replace harmful or petrochemical products There is a strong market demand for biorenewable materials.

  Given the growing concern for the environment and the growing demand for more “green” products, the need for materials to replace harmful and non-renewable petrochemical products quickly stems from renewable resources. did. In addition, there is a market need for current buildings, billboards, decorative sheets, and laminate materials to have high levels of performance and cost advantages.

  For the past decade, bioplastics have become the mainstream of the market, especially for biodegradable plastic applications. The practical use of biopolymers such as PLA and PHA has been limited to film and blow molded bottles, mainly due to market demand and technological limitations on the rheology of these forms of bioplastics. Bioplastics, such as PLA, have unique flow dynamics, lower thermal deformation levels, polarizability, as well as unique properties of rheology.

  Methods known to those skilled in the art for producing the final laminate include the low pressure laminating (LPL) method, the high pressure laminating (HPL) method, and the continuous pressure laminating (CPL) method. The low pressure method is most often used for corrugated paper and particle boards, while the high pressure method is generally used for so-called kraft paper. Sheets and products resulting from the HPL method are generally not self-supportive. They are often adhered to rigid substrates such as particle boards and medium density fiberboard (MDF) with suitable adhesives or glues. In continuous pressure lamination, it is also possible to feed from a roller to a continuous belt press.

  Traditional manufacturing methods have drawbacks that are not easily overcome. One problem is that the laminates produced by the high pressure method and the continuous pressure method are very hard and it is difficult to bend or "reform" these sheets. At present, the "post-formation" feature incorporates expensive polymerization modifiers such as benzoguanamine and acetoguanamine or makes melamine-formaldehyde resin in pressure increase to react more melamine with formaldehyde It is often achieved by The latter method is relatively expensive and also requires a pressure vessel. However, if it is possible to bend the HPL sheet or LPL sheet while maintaining wear resistance and chemical resistance, it is possible not only to cover one side of the substrate, but also in one processing step. It can be advantageous to do so. Another disadvantage of conventional laminates is the use of formaldehyde, known as a toxic chemical. The resin used to penetrate conventional paper can be formaldehyde-melamine resin. After curing, the laminate may still release some formaldehyde, which can be an environmental concern.

  Embodiments of the present invention relate to a biolaminate composite assembly that includes one or more biolaminate layers, a non-plastic rigid substrate, an adhesive layer in contact with the substrate, and one or more biolaminate layers. The substrate is laminated or molded into one or more biolaminate layers. In addition, embodiments of the present invention relate to a method of manufacturing a biolaminate composite assembly.

  In the drawings, although not necessarily drawn to scale, like numerals indicate substantially similar components throughout the several views. Similar symbols with different subscripts indicate different examples of substantially similar components. In general, the drawings show, for illustration purposes, the various embodiments discussed in this document, but not for limitation purposes.

FIG. 1 depicts a cross-sectional view of a biolaminate composite assembly according to some embodiments. FIG. 2 depicts a block flow diagram of a method of manufacturing a biolaminate composite assembly according to some embodiments. FIG. 3 depicts an enlarged view of a biolaminate composite assembly according to some embodiments. FIG. 4 depicts an enlarged view of a biolaminate composite assembly according to some embodiments. FIG. 5 depicts an enlarged view of a biolaminate composite assembly according to some embodiments. FIG. 6 depicts an enlarged view of a biolaminate composite assembly according to some embodiments. FIG. 7 depicts a cross-sectional view of a veneer board biolaminate composite assembly according to some embodiments. FIG. 8 depicts a cross-sectional view of a biolaminate composite assembly including a high performance surface layer according to some embodiments.

  As used herein, "additive" refers to a substance or material included in a biolaminate layer or biolaminate composite assembly that provides a practical or decorative / aesthetic purpose. Examples of practical additives include fire retardants, impact modifiers, antimicrobials, UV stabilizers, processing aids, plasticizers, fillers, mineral particles to obtain hardness, and other standard plastic additives There will be agents or bioplastics additives. Examples of decorative additives would be colorants, fibers, particles, dyes. The additives may serve both practical and decorative purposes. The additives can be incorporated as part of one or more biolaminate layers in a biolaminate composite assembly, or as a separate layer of one or more biolaminate layers.

  As used herein, "adhesive layer" or "adhesive" refers to a material that adheres two or more layers in a biolaminate layer or biolaminate composite assembly. The adhesive includes a glue adhesive. Examples of adhesives include urethane, PVC, PVA, PUR, EVA and other forms of cold pressed or hot pressed laminating adhesives and methods. Generally, biolaminates and laminates are usually adhered to non-plastic or wood / aggregate composite materials by various glue adhesives and laminating processes. In HPL (high pressure laminate), glue adhesives such as synthetic adhesives, PVA, urethane, hot melt, and other forms of adhesives are commonly used. While many of these glue adhesives are useful for embodiments of the present invention, any of the hot pressed or hot rolled, or cold pressed, processes to bond the biolaminate layer to the substrate In the agent system, low VOC containing or VOC free glue adhesives are preferred.

  As used herein, "bioink" refers to non-petroleum based inks. Bio-inks can be produced, for example, from organic materials.

  As used herein, a "biolaminate layer" or "biolaminate" is one or more thin layers in contact with a non-plastic hard substrate, which are materials derived from natural or biological elements. It refers to the one that contains The biolaminate layer may be a multilayer comprising multiple layers. One form of biolaminate is composed of bioplastics or biocopolymers such as PLA (polylactic acid). Biocopolymers comprising PLA and other biopolymers may be used in the present invention to make biolaminates. The biolaminate layer contains one or more than 50% PLA combined with optional additives, colorants, fillers, reinforcing agents, minerals, and other inputs to produce a biolaminate composite assembly It may refer to multiple layers.

  As used herein, "biopolymer" or "bioplastic" refers to a polymer derived from a natural source such as a living organism. The biopolymer may also be a combination of such polymers, eg as a mixture or copolymer. The biopolymer may be a polymer derived from a natural source such as a living organism. For example, the biopolymer may be a saccharide. Polylactic acid (PLA) and polyhydroxyalkanoate (PHA) can be examples of biopolymers. The biopolymer can be derived from, for example, corn or soybean. The biopolymer may be a copolymer or a mixture of one or more biopolymers, such as, for example, a mixture of PLA and PHA. Other forms of biopolymers (and derived from renewable resources) included in embodiments of the present invention are polymers comprising one of the polymers known as polylactic acid (PLA) and polyhydroxyalkanoate (PHA) . PHA polymers are polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-polyhydroxyvalerate copolymer (PHBV), polycaprolactone (PCL) (ie TONE), polyesteramide (ie BAK), Included are modified polyethylene terephthalate (PET) (i.e. BIOMAX), and "aliphatic-aromatic" copolymers (i.e. ECOFLEX and EASTER BIO) mixtures of these materials, and the like.

  As used herein, "contacting" refers to physical, mechanical, chemical, or electrical contact between two or more objects or in close proximity. The contact may be, for example, mixing or dry mixing.

  "Molding" or "shaped" as used herein refers to contacting two or more material layers such that adhesive semi-permanent or permanent adhesion is achieved. Examples of forming refer to thermoforming, vacuum forming, linear forming, profile packaging, or combinations thereof.

  As used herein, "heating" refers to increasing the molecular or kinetic energy of a substance and raising its temperature.

  As used herein, "laminate" or "laminating" refers to contacting two or more material layers with heat and / or pressure to form a single assembly or single multilayer. . Laminating can be accomplished, for example, by using an adhesive between the layers or by thermally fusing without using an adhesive.

  As used herein, "mixture" refers to two or more compositions that are not chemically bonded to one another and can be separated.

  As used herein, "non-biodegradable" refers to materials that are non-biodegradable over a significant period of time. The non-biodegradable substance may be, for example, one that does not substantially decompose after about 5 years, about 10 years, about 20 years, about 30 years.

  As used herein, “non-plastic hard substrate” consists of wood, wood plastic, agrifiber, or mainly consisting of particles, fibers, flakes, threads or layers, which only meet the demand for furniture and other building supplies And a mineral fiber composite panel heat pressed with a small amount of resin to produce a panel having sufficient strength. The non-plastic hard substrate can include some plastics, but in extrusion sheeting and compression sheet forming, it can also include non-plastic materials such as wood or agrifiber plastic composites. The non-plastic hard substrate can be a particle-free VOC-free particle board or MDF (medium quality fiber board), but a rapidly renewable wheat straw or other biofiber or agricultural based fiber is preferred. Other non-plastic hard substrates include metal particle boards, wood particle boards, agrifiber particle boards, veneers, OSB (oriented strand boards), gypsum boards, sheet locks, hardboards (mesonite, etc.) ), Cement or cement board, and other rigid substrates. Non-plastic rigid substrates can include paper-based boards, cellulosic substrates (or other organic fibers), cellulosic paper composites, multi-layer cellulosic glue composites, veneers, bamboo or recycled paper substrates. Examples of agrifurber particle boards include wheat boards such as microstrands manufactured by Environ Biocomposites Inc. Materials such as particle boards, medium density fiberboards, high density fiberboards, veneers, and OSB are often used for synthetic building boards which are good substrates for high pressure lamination. Due to environmental pressures, wood composite boards that were bonded in the past with formaldehyde based resins such as urea adhesive resins and phenolic adhesive resins are now low VOC adhesives or in the form of urethane diisocyanide or methyl diisocyanide or It is replaced by an adhesive without VOC. In the past decade, concerns about wood supply have spurred the development of new fiber boards from more rapid renewable resources, including many agrifibers such as straw, rice straw, and other grain straws .

  As used herein, "PLA" or "polylactic acid" refers to thermoplastic polyester derived from 2-hydroxylactate (lactic acid) or lactide of corn grown in the field. The chemical formula of the subunit is represented by-[O-CH (CH3) -CO]-. The monomer alpha carbon is optically active (L-configuration). Polylactic acid-based polymers generally are D-polylactic acid, L-polylactic acid, D, L-polylactic acid, meso-polylactic acid, and D-polylactic acid, L-polylactic acid, D, L-polylactic acid. It is selected from the group consisting of lactic acid and any combination of meso-polylactic acid. In one embodiment, the polylactic acid based material is mostly PLLA (poly-L-lactic acid). The operable range of the polymer is between about 15,000 and 300,000 molecular weight, but in one embodiment its number average molecular weight is about 140,000.

  As used herein, "thermoforming" refers to molding using heat. Thermoforming involves pressing a film or layer onto a complex three-dimensional shape or two or more substrate surfaces, forming the film, or using a heat and bladder on the film surface of the film formed by the film press. It may include placing a layer. Prior to thermoforming the film or layer on the surface, a heat activated adhesive may be first applied to the three dimensional substrate. Thus, both heat and pressure shape the layer into the shape of the substrate and at the same time activate the adhesive layer.

Detailed Description of the Invention

  The following detailed description includes references to the accompanying drawings, which form the subject matter of the detailed description. The drawings show, by way of illustration, specific embodiments in which the invention can be practiced. These embodiments, also referred to herein as "examples," are described in sufficient detail to enable those skilled in the art to practice the invention. The embodiments can be combined and other embodiments can be utilized, and structural or logical changes can be made without departing from the scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims and their equivalents.

  In this document, the terms "(a)" or "an" are used to include one or more than one, and the term "or" does not specifically indicate otherwise As long as it is used as a non-exclusive "or" pointing. Additionally, it is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation, unless the contrary is specifically stated. Further, all publications, patents, patent documents referred to in this document are incorporated herein by reference in their entirety, each of which is incorporated by reference. In the case of inconsistencies in the use of terms between this document and the aforementioned documents incorporated by reference, it is to be understood that the incorporated reference is an adjunct to this document. In the case of conflicting inconsistencies, use in this document will prevail.

  introduction

  Biolaminate composites are provided. The biolaminate composite is flexible and can be molded in three dimensions. Generally, the biolaminate composite comprises one or more biolaminate layers, of which at least one biolaminate layer comprises polylactic acid. In some embodiments, the at least one biolaminate layer can further comprise a natural wax, such as a soy wax. The one or more biolaminate layers can be molded including three-dimensional molding on a rigid non-plastic substrate to form a biolaminated composite assembly. Embodiments of the present invention are bioplastics, biocopolymers, or biosynthetics, biolaminates and systems derived from assemblies, and providing biobased solutions that replace formaldehyde based laminates and PVC products. Describe. In addition, embodiments of the present invention provide an economically advantageous solution to large scale production.

  Further provided is a biosynthetic substrate. Such biosynthetic substrates may be three dimensional and may have a practical and / or decorative biolaminate surface. Such biosynthetic substrates are particularly useful for profile linear wrap woodworking products (millwork) and components. Biosynthetic substrates can also be designed such that biodegradation is not possible.

  Various embodiments of biolaminates exhibiting different properties are provided. In some embodiments, the at least one biolaminate layer can comprise a plastic and a mineral and is suitable for use as a wear layer. In some embodiments, polyetheretherketone (PEEK) can be used in the surface wear layer. In other embodiments, the two cellulose layers can comprise polylactic acid sandwiched therebetween. In other embodiments, a thermal expansion layer may be provided in the biolaminate composite so that the composite exhibits fire resistant properties.

  Embodiments relate to a product and a method of manufacturing a biolaminate assembly utilizing a resin impregnated or impregnated paper layer, particularly a decorative surface treatment laminate layer. Such layer may comprise at least one cured layer of polylactic acid or lactic acid impregnated paper. The top or surface layer may comprise decorative printing paper or color paper. In another embodiment, a paper impregnated with melamine-formaldehyde resin can be placed on top of a laminate of paper impregnated with phenol-formaldehyde resin and then cured. In general, such biolaminate assemblies can include a first cellulose layer and a second cellulose layer. A first biobased polymer, such as PLA, can be provided between the first cellulose layer and the second cellulose layer. The fusing of the first cellulose layer, the first biobased polymer, and the second cellulose layer causes the cellulose layer to be impregnated into the first biobased polymer substantially to the entire cellulose layer, Good.

  Some embodiments may be formed as a useable biocorrugated system to replace building materials. Corrugation can be provided by molding a corrugated bioplastic core body onto which additional layers can be laminated.

  Some embodiments relate to biolaminates that profile wrap a substrate. Three dimensional substrates are further provided for such wraps.

  In some embodiments, decorative biolaminate composites can be provided. This decorative biolaminate can have natural three dimensional dimensional depth of field compared to PVC thermofoil or high pressure laminate based on the biopolymer translucency, bio It provides similar aesthetics to laminate-specific aesthetics and other surfacing materials. In some embodiments, latex paint layers that provide efficient color matching may be incorporated into the biolaminate for decorative purposes.

  In some embodiments, various shapes of aesthetic multicolor biolaminate assembly are formed from random particles of biopolymer matrix resin and novel biocomposite to create a wider aesthetic and three dimensional appearance obtain. The resulting sheet product has the natural appearance of natural granite and can be used in a wide variety of building applications where high aesthetic value and environmental properties are desired. In that case, even more, the embodiment is 100% biobased which can be substituted for dangerous PVC thermofoil or formaldehyde based high pressure laminate to provide a biologic solution for problematic products.

  In some embodiments, a fire resistant biolaminate composite assembly is provided, such assembly may include a biolaminate layer and a thermal expansion layer, and also has a strong charring and low flame spread characteristics to minimize smoke generation. It can have. The biolaminate layer can include a PLA sublayer and can include a fire protection material. The thermal expansion layer may include a thermal expansion material that expands as a result of being exposed to heat.

  In addition, long-term applications and long-term applications commonly used in indoor applications amid growing incentives for clean air and environmentally friendly products that are derived from rapidly renewable agricultural materials as an option for biologic solutions A design designed for the product is provided.

  Embodiments of the present invention are faster to process than conventional PVC, are manufactured from rapidly renewable resources and do not emit VOCs to the indoor environment while taking advantage of PVC thermofoil and high pressure laminates. Use unique bioplastics in combination with optional and inexpensive bioadditives that can be sold.

  Embodiments of biolaminate composites generally relate to biolaminate composite assemblies and / or biolaminate surface systems. Such biolaminate surface systems can include bioplastics, biocopolymers, and biolaminate biocomposite systems that are laminated or thermoformed with an adhesive layer or an adhesive layer to a rigid plastic material. The biolaminate system may also include a matching profile extrusion support product obtained by the same composition and the same processing method.

  Thus, the biolaminate composite assembly includes one or more biolaminate layers adhered by being laminated or thermoformed onto a non-plastic rigid substrate. The resulting biolaminate composite assembly is designed for use on desk surfaces, table surfaces, machined surfaces, wallboards, wallpaper, cabinet doors, woodworking products, and other decorative laminates. The biolaminate surface layer contacts or planar laminates various non-plastic rigid substrates by thermoforming for three-dimensional components. The biolaminate layer may comprise one or more layers of biopolymers, biocopolymers, biocomposites, or combinations thereof. The biopolymers and modified biopolymers may comprise predominantly PLA or PHA or mixtures thereof. The biolaminate layer may comprise a biocomposite in which the biocopolymer comprises an additional biopolymer, bioplastic, or petrochemical-based plastic or regenerated plastic. The biolaminate layer may comprise a biocomposite in which the biopolymer is mixed with various fillers, reinforcing agents, functional additives, fire retardants, and other materials that meet the aesthetic or practical needs.

  In some embodiments, the biosurfactant, biolaminate, is integrated with various plastic or plastic fiber composite products to create an environmentally friendly group of linear building components. The goal of this technology is the development of biobased components that quickly replace harmful products and petrochemical products with renewable solutions. These unique substrate shapes are linear molding by profile extrusion processing or final three-dimensional molding. Three-dimensionally shaped shapes are created using similar compositions, but to press three-dimensional shapes such as walkway doors, table surfaces, machined surfaces, fixture members, and cabinet doors etc. Use technology.

  Composite assembly

  Referring to FIG. 1, a cross-sectional view 100 of a biolaminate composite assembly according to some embodiments is shown. The non-plastic hard substrate 106 may be in contact with the adhesive layer 104. The adhesive layer 104 may be in contact with one or more biolaminate layers 102. Non-plastic hard substrate 106 may, for example, be in contact with layer 102. The biolaminate layer 102 may comprise multiple layers.

  Thus, the composite assembly can include one biolaminate layer and one or more other layers. Other multiple layers can also be biolaminate layers. Possible embodiments of these layers are described below. Although these layers can be discussed as layers separate from the biolaminate layer, the components and functionality of these layers are alternatively provided in the biolaminate layer.

  Embodiments of the present invention are most preferably all biopolymers, but forming different biopolymers in multiple layers and / or integrating different petroleum based film layers to obtain different functionalities May also be included. Embodiments of the present invention include other high temperature polymers as top and top layers of thin films made from Teflon, PEEK, PET or combinations thereof to impart higher heat resistance, such as a cooktop.

  Embodiments of the invention range from about 0.001 inches to slightly more than about 0.005 inches of individual film thickness and about 0.001 inches to about final biolaminate film thickness. Also included is a single layer or multiple layers of biopolymer film, which is about 0.125 inches.

  Biolaminate layer

  The at least one biolaminate layer of the biolaminate composite assembly may predominantly comprise biopolymers comprising PLA, PHA, or similar biopolymers.

  Biopolymers, biocopolymers, and biolaminates (or biolaminate layers or biolaminate composite assemblies) can include one or more additives. Suitable additives include one or more dyes, pigments, colorants, hydrolysates, plasticizers, fillers, fillers, preservatives, antioxidants, nucleating agents, antistatic agents, biocides, biocides Fire retardants, heat stabilizers, light stabilizers, electrical conductors, water, oil, lubricants, impact modifiers, coupling agents, crosslinking agents, blowing agents, regenerated plastics, etc., or mixtures thereof. In certain embodiments, additives may tailor the properties of the biolaminate composite assembly to the end use. In one embodiment, the biopolymer can optionally include about 1 to about 20% by weight of an additive. Other additives, synthetic plastics such as polyethylene, polypropylene, EVA, PET, polycarbonate, etc., to enhance performance, and to add recycled content as desired or desired. It may include plastics and other plastics. In one embodiment, the biolaminate layer may comprise 100% biorenewable biopolymer. A binder such as EVA may be added to the biolaminate layer.

  Additives may be present in at least one biolaminate layer, including PLA and similar biopolymers, or may be provided in separate layers in a composite assembly. Such additives may, for example, be practical or decorative. The discussion of such additives present in the biolaminate or provided in separate layers should be made for illustrative purposes only and such discussion applies to other embodiments as well. It should be understood that

  Bioplasticizers, biolubricants, fire retardants, decorative and practical fibers, decorative and practical fillers, colorant systems, and textured surfaces can be bioplastics, biocopolymers, or biolaminate sheets or It may be integrated with a biocomposite (as a biolaminate layer (monolayer, multilayer) or as part of an assembly) that produces an extrudable material that can be formed into a matching profile extrusion member. For example, the biolaminate layer may comprise about 50% to about 95% polylactic acid from corn and other natural materials in combination with bioplasticizer / biolubricant and other additives.

  The biolaminate layer can include a biopolymer such as PLA mixed with a plasticizer to form a flexible biolaminate sheet that can also be printed or reverse printed on a clear flexible laminate surface. Flexible biolaminates can be laminated to sheet locks as a substitute for PVC vinyl wallpaper. In this case, any non-woven material can be coextruded to the back of the flexible biolaminate to add additional strength for such applications. The flexibility of the biolaminate layer is comparable to that of PVC sheets.

  The biolaminate layer of the biolaminate composite assembly may include plasticizers or impact modifiers to produce a more flexible biolaminate or softer surface biolaminate layer. Preferably the plasticizer has a boiling point of at least 150 ° C. Examples of plasticizers that may be used include glycerin, polyglycerol, glycerol, polyethylene glycol, ethylene glycol, propylene glycol, sorbitol, mannitol and their acetates, ethoxylates or propoxylates derivatives, and mixtures thereof Not limited to these. Examples of specific plasticizers that may be used are ethylene diglycol or propylene diglycol, ethylene triglycol or propylene triglycol, polyethylene glycol or polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2,6-hexanetriol, 1 , 3,5-Hexanetriol, neopentylglycol trimethylolpropane, pentaerythritol, sorbitol acetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol dipropoxylate, sorbitol diethoxylate Sorbitol hexaethoxylate, aminosorbitol, trihydroxymethylaminomethane, glucose / PEG, reaction product of ethylene oxide and glucose, trimethylolpropane, monoethoxylate, mannitol monoacetate, mannitol monoethoxylate, butyl glucoside, glucose mono It includes, but is not limited to, ethoxylates, alpha-methyl glucoside, sodium salt of carboxymethyl sorbitol, polyglycerol monoethoxylates and mixtures thereof. The impact modifier can be in the form of a plasticizer or an elastomeric material. Impact modified elastomeric materials include, but are not limited to, EVA, EMA, TPE, metallocene, and other similar forms of elastomers.

  Naturally occurring or biobased plasticizers may also be used such as soya wax, natural wax, glycerin, natural esters, citric acid esters, soya oil, epoxidized or heated soya oil and other similar plasticizers.

  In profile die processing, vegetable oil, glycerin (biodiesel by-product), soy wax and other low-cost to create a combination of biopolymer lubrication and bioplasticization while improving lubricity Other additives such as biomaterials may be added at lower rates. The form of these materials lowers the price of the final product while maintaining an environmentally friendly biocomposition. Also, the form of these materials helps to improve the dispersion of various fire retardants, fillers, and fibers while improving the impact strength of the overall system.

  The incorporation of these powder shapes into a biopolymer matrix that provides better processing parameters and increases flexibility and impact resistance by adding low molecular weight bioplasticizer / lubrication systems to embodiments of the present invention Becomes possible. Examples of plasticizers that can be used in the present invention include (i) phthalic acid, adipic acid, trimellitic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid or acids containing phosphoric acid An ester comprising one or more of the residues and (ii) one or more aliphatic, cycloaliphatic or aromatic alcohol containing alcohol residues comprising up to about 20 carbon atoms. Furthermore, non-limiting examples of alcohol residues of plasticizers are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, stearyl alcohol, lauryl alcohol, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neoi And pentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol. Also, the plasticizer may comprise one or more of benzoate, phthalate, phosphate, isophthalate. In another embodiment, the plasticizer comprises diethylene glycol dibenzoate, herein abbreviated as "DEGDB". Examples of bioplasticizers include hardened vegetable oils, epoxy-group hardened or congregated vegetable oils, vegetable oils, mineral oils, natural waxes, drying oils derived from polylactocaptone, citric acid and others It is not limited to. The combination of the resulting PLA and a plasticizer or bioplasticizer is considered a biocopolymer system. A lower bioplasticizer content can be used to maintain a rigid profile or sheet extrusion member, and a higher bioplasticizer content further provides additional flexibility. Flexible or high impact properties may be required for various product applications.

  All the additive forms of plasticizers made to the biolaminate layer or assembly balance the impact resistance and the more flexible properties of the biolaminate layer so as to be comparable to the performance of PVC film products. Can be helpful. Although various plasticizers may be used for flexible biolamination or impact modification, it may be preferable to use biobased plasticizers to maintain the biobased environmental position of the product. unknown.

  Additives may be added to any layer or membrane of the biolaminate assembly provided herein. In some embodiments, additives may be selected to maintain the degree of transparency. For example, a transparent or translucent coating layer is provided on a decorative veneer board in order to see through the biolaminate layer so that the natural appearance of the veneer board can be seen. Additives may include, but are not limited to, color additives, nucleating agents, petrochemical polymers, or other practical or aesthetic additives. For example, the additive can be less than about 50%, less than about 40%, or less than about 30% of the overall composition of the biolaminate film.

  The petrochemical additives can be in the form of conventional plastics and / or plastic additives in order to give a change in their functionality and performance.

  In some embodiments, fillers including synthetic materials, natural minerals, and biomaterials can be added to the biopolymer of the biolaminate layer. These fillers include biofibers, proteins, starches, vegetable oils, natural fatty acids, and other materials. In general, fibers and minerals help to adjust and process the viscosity of various plastics.

  In some embodiments, the biolaminate layer can include additional elements that add other functionality to the layer. For example, the biolaminate layer can include quartz or other minerals or fibers.

  Cellulose layer

  In some embodiments, a resin impregnated paper substrate or backing layer may be provided as part of or in contact with one or more biolaminate layers of a biolaminate assembly. Such layers may include the form of polylactic acid or other biopolymers to create biobased, environmentally friendly products that replace formaldehyde based high pressure laminates. Embodiments of the present invention may utilize either molten PLA or processed liquid lactic acid impregnated in one or more paper layers. The impregnated paper or paper layer is thermoformed into a decorative or practical laminate. One or more layers can be contacted with heat and / or pressure sufficient to cure or polymerize the resin. In some embodiments, an additional cellulose layer impregnated with the bio-based polymer can be provided to form a thicker biolaminate structure.

  In the first cellulose embodiment, the biolaminate assembly can include a first cellulose layer and a second cellulose layer. A first bio-based polymer such as polylactic acid or lactic acid may be provided between the first cellulose layer and the second cellulose layer. Melting the first cellulose layer, the first biobased polymer, and the second cellulose layer can impregnate the cellulose layer with the first biobased polymer substantially throughout the cellulose layer.

  In the second cellulose embodiment, the biolaminate assembly can include a first layer and a second layer in contact with the first layer. The first layer may be a paper substrate impregnated with a biobased polymer such as polylactic acid or lactic acid. In various embodiments, the second layer can be a paper substrate impregnated with a bio-based polymer such as polylactic acid or lactic acid, a bio-based film comprising a PLA sheet, or a transparent PLA surface layer. The biolaminate assembly is substantially formaldehyde free and may be suitable as a high pressure laminate replacement.

  Embodiments of the present invention include a biolaminate assembly using impregnated paper that is substantially free of formaldehyde emissions. Various other layers may be used as an embodiment using cellulose. For example, decorative layers (including printed layers), overlay layers, wear layers, or other practical layers may be provided. One example of a decorative layer comprises a coating layer, such as a PLA coating layer on which the image is reverse printed. A printed PLA coating layer may then be provided in the biolaminate composite, for example on the first cellulose layer or the second cellulose. Overlaid paper may reasonably be transparent if impregnated and cured. The overlay paper can be transparent as it makes sense when impregnated and cured. A clear polylactic acid or a mixture of bioplastics or bioplastics and petrochemical-based plastics can be melted, or even plain paper impregnated with PLA or LA can be heat-melted to the surface, for example, to provide a good transparent layer . Suitable overlay layers may include thermosetting and thermoplastic standard overlays, mineral plastic overlays, bioplastic overlays, or wear layer surface overlays.

  Thus, various forms of polylactic acid can be infiltrated into paper for the production of biolaminate layers. Additionally, as noted above, the additive may be contacted with polylactic acid. As alternatives to petrochemical-based formaldehyde-based laminates, other bio-resins and bio-based polymers can be used to penetrate paper and can be made into single or multiple layers of laminates. For example, monomers such as polyurethanes, polyesters, biobased resins such as nylon, polyols, organic acids, and other similar biobased resins may be used to penetrate paper for lamination. A new generation of protein polymer chemistry may include zein proteins, soy proteins, and mixtures of other bioresins or bioadhesive materials. Such bio-based adhesive materials or polymers can be used either in the liquid state in the natural state or in a liquid having various viscosities that can be melted by heat, into which the paper penetrates Finally, it is cured to form a single layer structure of the biolaminate into a multilayer structure. Other new biopolymers derived from D-type glucose, such as acrylic acid and 3HP chemical platforms that become acrylic polymers, can provide biobased resins that can be used alone or in combination with other biopolymers such as PLA .

  Currently, wood-derived paper is a major source of paper used in cellulose biolaminate composites. However, any suitable woven cellulose paper or non-woven cellulose paper may be used. Suitable papers are, for example, plain paper, kraft paper, surface-treated paper, wood paper, recycled paper, decorative paper, printing paper, fiber reinforced paper, fiberglass reinforced paper, thin wood veneer, fire resistant paper, chemically treated paper, pH Adjustment paper, or a combination of these. Cellulose paper can be biobased paper taken from renewable plant fibers such as hemp, bagasse, wheat straw and corn stover.

  In one embodiment of a biolaminate comprising a cellulose layer, four laminate layers are provided and completed by melting with textured release paper. The lower layer is a PLA layer, the second layer is a decorative paper, the third layer is a PLA layer, and the fourth layer is a wear layer. Heat and pressure can be used to melt the layer, thereby causing the decorative printing paper to penetrate and impregnate the PLA. If the layer is provided on a substrate such as a wood composite prior to the use of heat and pressure, the heat and pressure act to melt the layer into the wood composite. Textured release paper is provided on top of the wear layer.

  Surface wear layer / high performance layer

  A biolaminate surface layer can be provided having the properties of the wear layer and the properties of the high performance layer. Such biolaminate surface wear layers can include natural fine quartz materials for specific, high resistance surface processing applications while still maintaining a translucent material. In the manufacture of flooring products that provide high levels of abrasion resistance and hardness, various natural and other minerals such as silica (natural quartz), alumina, calcium carbonate may be used. These wear resistant materials can be in the form of mediating particles that can be visually recognized as decorative, functional particles. Such finely divided materials become transparent or translucent in the biocopolymer matrix or in the form of nanosize in the biolaminate layer. Natural minerals can be included on the surface of a multilayer biolaminate layer near the surface of the biolaminate composite assembly, or on a single layer biolaminate layer.

  "Nano quartz" technology can provide high performance and durability of the surface. Natural quartz or natural silica sand of various particle sizes from nano size to larger sizes can be used for decorative applications and can be added to the biolaminate system. In embodiments of the present invention, natural quartz is one of the hardest materials in nature, although other natural minerals may be used. Also, quartz integrated with the biolaminate assembly offers an inexpensive alternative to expensive granite and other surfacing composites in kitchen benches and tables and other areas where higher performance is required. Can be provided. The shapes of these biolaminate layers can be laminated flat or thermoformed to provide a three-dimensional surface treatment for kitchen applications and other forms of countertop applications.

  In an alternative embodiment, the surface wear layer may comprise a polyetheretherketone (PEEK) polymer. PEEK is a biomedical plastic that is widely accepted for medical and other applications. PEEK has been approved by the Food and Drug Administration (FDA) for its food contact and is considered "green". The surface layer of PEEK has excellent properties in the area of improved abrasion resistance, improved mechanical properties, high temperature performance, good electrical insulation, food contact according to FDA regulations, and improved fire resistance. provide.

  PEEK can be produced in either amorphous or semi-crystalline grade. Amorphous grades can be formed at lower temperatures, and also crystallize in these forming and thermofoil operations, resulting in more sophisticated biolaminate surfaces. Thus, the PEEK single-layer biolaminate used for the top wear layer provides excellent performance and ultimately provides a "green" and rapidly renewable solution. Amorphous grades can be shaped by thermoforming and can be flexible in that form. By integrating the moldable biolaminate and the PEEK wear surface layer, its power is maintained in a three-dimensional shape of non-plastic or fiber-plastic composites, which can be used in kitchens, baths, fixtures, food preparation areas, and others. Used for the application used.

  Surface wear layer with a decorative layer or surface wear layer as a hybrid laminate

  In one embodiment, a two-layer biolaminate composite can be provided that includes a surface layer comprising transparent quartz that becomes thermally melted into an opaque biolaminate layer with printing between the layers. In the case of multilayer biolaminate layers, the layers of the biolaminate can be melted by a thermal process under pressure or a separate adhesive or adhesive layer.

  Other embodiments include the use of hybrid biolaminates. A hybrid biolaminate can refer to a biolaminate layer wherein the biolaminate surface layer comprises one or more layers, the top layer can be a plastic different from the first biopolymer base film and the biopolymer that melts. In this case, a biopolymer membrane comprising PLA or other form of biopolymer, biocomposite, or modified biopolymer is extruded onto the first base membrane. The bioplastic base film can generally be white or background color to be suitable for printing. The base film can then be printed using direct ink jet printing or other printing methods. The upper transparent film, which may include polyester, acrylic, or other high performance plastic, is then topped using heat to melt the layer or using a transparent adhesive for hot lamination. It can be laminated. The final hybrid laminate may then have different surface performance to meet a wider range of lamination applications. The hybrid laminate may then be laminated onto a wood composite or aggravated composite for use in the form of a closet, table, workpiece surface, kitchen countertop, or other component.

  In the case of a single-layer PEEK biolaminate, a white colorant may be added, a dye to impregnate the image into the material rather than just floating on the top of the surface to improve the wear of the image. Imaging is performed on the surface using sublimation by. PEEK can be difficult to color and often presents a natural "bronze" color. Dye sublimation may also act on this background color, and computer image manipulation can adjust the non-white background image. Sublimation by dyes uses dyes that are smaller in molecules and pass through the molecular structure of the material rather than pigments. Thus, in contrast to the usual standard printing inks used only on the surface, the image is not scraped off the surface.

  Fiber layer

  The biolaminate layer may comprise a biopolymer mixed with natural fibers such as wheat, rice and similar forms of hydrophilic fibers. Such biolaminate layers, in addition to their organic properties, provide both higher abrasion resistance and improved carbonization promotion in the manufacture of fire retardant laminates and matching profile extruded composites. The fire protection material may be included in any combination with one or more biolaminate layers, adhesive layers, non-plastic rigid substrates or biolaminate composite assemblies.

  A biolaminate layer containing natural fibers or fillers can often be found on high-pressure laminate images that repeat solid surfaces and patterns because of its environmental protection properties and the ability to provide random shapes in a clear or translucent matrix It may be desirable from the fact that it gives a natural appearance to the "artificial" appearance it receives. Natural fiber materials are wheat straw, soybean straw, rice straw, corn stalk, hemp, bagasse, soybean hull, oat hull, corn hull, sunflower hull, paper mill waste, nut shell, cellulose fiber , Paper mill sludge, and other agriculturally produced fibers, but is not limited thereto. Wheat and rice fibers are not as fine filler powder as is commonly done in wood plastic composites, but rather are ground and elongated filaments characteristic of such fibers, but with their shiny surface Therefore it may be preferable. Although natural fibers are preferred, other fibers such as fiber glass, particles, minerals, and fillers may be used where the biocopolymer may impregnate the glass fibers in the process. Other bio-based materials such as seeds, proteins, and starches can be used to extend the natural aesthetic properties of the biolaminate and matching extrusion profiles (such as edge bands and other support members).

  Fire protection layer

  In one embodiment, a fire retardant biolaminate composite assembly is provided which may include a biolaminate layer and a thermal expansion layer and may have good carbonization and low flame diffusion with minimal smoke generation. The biolaminate layer may include a PLA sublayer and may also include a fire protection material. The thermal expansion layer may include a thermal expansion material that expands as a result of being exposed to heat.

  The biolaminate layer may include fire protection materials commonly used in dry fire extinguishers, such as ammonium phosphate used in combination with mica and silica. Such fire protection materials provide good performance in biolaminate composite assemblies due to their pH and low degree of reaction with the biocopolymer system. These provide a high degree of flame suppression and accelerate carbonization. Other fire retardants may be used, but halogen free fire retardants such as alumina trihydrate and magnesium hydroxide are preferred.

  Additional materials such as fire retardant biocopolymers (PLA) that reduce flowability during combustion, improve carbonization that isolates the material from heat during combustion, and provide a high degree of material integrity in maintaining its shape / Bioplasticizer). Examples of carbonization promoters include nanoclays, zinc borate, thermally expandable fire retardants, agricultural powders, wood flour, starch, paper mill waste, synthetic fibers (such as fiberglass and powders), minerals, and other materials Including, but not limited to. Other forms of flow inhibitors, such as polytetrafluoroethylene, may also be used to control drip and act in concert with the carbonization promoter. Other forms of carbonization promoters may help to prevent flow or may provide drip control such as natural rubber or synthetic rubber. Such charring agents also provide additional flexibility and improved impact resistance to biolaminate and matching profile bio solutions.

  The result has very good carbonization and low flame spread with minimal smoke generation as compared to PVC laminates that emit high levels of toxicity and smoke. For small amounts of smoke emissions, the smoke is translucent white or completely invisible.

  In another embodiment, a fire retardant biolaminate composite door surface is provided, which may include a biolaminate layer and a thermal expansion layer, having good carbonization and low flame spread with minimal smoke generation. it can. The biolaminate layer may include a PLA sublayer and may also include a fire protection material. The thermal expansion layer may include a thermal expansion material that expands as a result of being exposed to heat.

  In yet another embodiment, a fire protection biolaminate composite assembly is provided, wherein at least one of the biolaminate layer and the adhesive layer comprises fire protection material, and the biolaminate composite assembly is good at minimizing smoke generation. Can include biolaminate layers and adhesive layers with low carbonization and low flame spread. The biolaminate layer can include a PLA sublayer. The biolaminate layer may be laminated to the substrate by an adhesive layer.

  The fire protection biolaminate composite may be applied in a wrap configuration such that the composite wrap is made on or under flooring, insulation, flooring, drywall, etc.

  Generally, the thermal expansion agent consists of the system's polymer and at least three major additives. An essentially phosphorus-containing additive whose purpose is to form an impermeable semi-solid glass layer composed of polyphosphoric acid during combustion and to activate the process of thermal expansion agent formation. , A second additive containing nitrogen which acts as a blowing agent, and a carbon donor capable of forming an insulating porous carbon layer ("carbonized") between the polymer and the flame. It is a third additive containing carbon.

  The activated fire protection material may comprise an activated fire protection material comprising at least one phosphate nitrogen and / or sulfonate and at least one activator. The activator may comprise a carbonization catalyst and / or a phase transfer catalyst. More specifically, the activated fire protection material comprises at least one nitrogen-containing reactant and at least one nitrogen-forming component capable of forming a nitrogen phosphate component in the presence of at least one carbonized tetraoxaspiro (tetraoxaspiro) catalyst. An activated nitrogen phosphate fire protection material may be included that includes a reaction product with a reactant that includes phosphoric acid.

  Examples of such compositions can be found, for example, in U.S. Patent 6,733,697, U.S. Patent Application 2004/0036061, and U.S. Patent Application 2004/0012004. Examples of fire protection materials are, for example, the products pending under trade mark application CEASEFIRE (Cote-1 Industries, 1542, Jefferson Street, Teaneck, N. J. 07666) and trademarked product INTUMAX (Broadview Technologies, 7-33 Amsterdam St., Newark) , N. J. 07105).

  Decorative layer

  The biolaminate composite assembly is a transparent or translucent biotech that contacts various forms of printing methods and inks or dyes that may be used to use decorative or customized features on the printing layer. It may include a laminate layer. Suitable are lactic acid based inks, also derived from corn, which provide a truly environmentally friendly biolaminate product.

  The biolaminate composite assembly can be a decorative composite that includes a transparent biopolymer layer, an opaque biopolymer layer, and a decorative print layer. The print layer may be disposed between the transparent layer and the opaque layer. Transparent layers can be textured. Layers can be selectively fused.

  The surface layer of the biolaminate composite assembly may be a transparent or translucent film or may be directly printed with the upper layer or outer surface, or selectively liquid coated the upper layer to protect the printing surface and improve the surface properties. It may contain layers. Liquid laminating can be achieved by roll application, rod application (such as Mery rod application), spray application, UV curing application system, and other standard application systems.

  The surface layer of the biolaminate composite assembly may include reverse direct printing, with the print layer between the biolaminate layer and the adhesive layer. This arrangement allows the entire clear biolaminate layer to be a wear layer whose surface can be refinished. In contrast, traditional high pressure laminate layers quickly lose pattern and can not be reconditioned or refinished.

  A decorative pattern may be printed on one or more sides of the biolaminate layer. The pattern may be on the outer surface or the inner surface, and may be visible to the user through the translucent biolaminate layer. Printing may include direct printing, reverse printing, digital printing, dye sublimation rotogravure printing, or other methods. Printing can be performed at any suitable time, such as before molding or lamination, or after molding or lamination. Printing can be done by pressing or laminating on one or more layers followed by subsequent molding or laminating to a substrate. The printed layer may be in contact with the adhesive layer or disposed on the outer surface. A protective transparent layer may be in contact with the printed outer surface. The printing ink can include an ink that can provide sufficient adhesion to the biolaminate layer and maintain adhesion in laminating applications with secondary heating. Certain solvent-based inks may not be able to maintain sufficient adhesion during the hot lamination process. In addition, the type of ink needs to have some flexibility so that it does not break in the thermofoil process or application. UV inks are more environmentally friendly than solvents, are more preferable, but may not have sufficient flexibility and adhesion. A new corn-based ink derived from lactic acid derived from corn is the best from an environmental standpoint and also provides improved adhesion while maintaining flexibility for final use and hot lamination process Most preferred.

  The surface layer of the biolaminate layer is a transparent biolaminate film layer having a top surface texture, and the second sublayer is an opaque (i.e. white) biolaminate film layer, and the printing layer is two. In between the two biopolymer films, the biopolymer film layer may comprise two layers of biopolymer film that is heat melted or laminated with an adhesive. Once a multi-layer decorative laminate is manufactured, it can be laminated onto various non-plastic rigid substrates, such as wood and agrifiber composite panels, in a manner similar to high pressure lamination.

  In one embodiment, multilayer biolaminate composites can be designed to perform specific aesthetic functions. The multi-layer transparent biolaminate layer has a different pattern so that the printed transparent multi-layer biolaminate layer can provide a characteristic three-dimensional depth of field in the image or pattern after heat melting And can be printed in color. Such an aesthetic depth of field is not found in HPL products and PVC products, both opaque materials printed on the surface. Multilayer printed laminates can utilize transparent layer formation with a selective white underlayer that provides high quality and excellent image depth.

  One embodiment of a multilayer biolaminate is a transparent, opaque of PLA, PHA, and other biopolymers, wherein the secondary decorative solid printed film is used on the back or back by a transparent adhesive layer Or light colored film may be included.

  In many embodiments, the decorative layer can include, for example, a printing surface disposed between one or more biolaminate layers or biolaminate layers and an underlayer, surface layer, or substrate or the like. When using PLA, many inks do not have sufficient adhesion to heat melt the layer without the possibility of delamination. Bio-inks such as BioVue, and other lactic acid-based or bio-based inks, are most compatible with the biolaminate shapes described above, in particular the assembly of multiple layers. In such embodiments, at least one layer can be in the form of a PLA film, and the bioink can be efficiently and effectively utilized at any time during the cooling treatment, the post-treatment of heat treatment.

  Other decorative layers may be used for multilayer biolaminate composite assemblies such as decorative paper, decorative fiber sheets, random fibers, and organic materials. In the case of wheat straw, leaves, pine needles and other natural materials, placed between layers of transparent biolaminate, ie "sandwich", to provide translucent architectural products specific to high performance architectural applications "It may be arranged in between.

  Colorant system

  The biolaminate layer in the biolaminate composite assembly may include a colorant system. Colorants include, but are not limited to, pearls, granite particles, solids, dyes, "lights up" additives, vortices, mixtures and other forms of decorative colorant systems. In order to provide the beauty of a solid surface without the need for a printed layer, the color of particles with pigmented minerals, fibers and other forms of distinctive color and distinctive shape are integrated with the biolaminate layer It can be done.

Suitable inorganic colorants include metallic coloring materials, such as those of the type that grind metal oxidants commonly used to color cements and grouts. Such inorganic colorants include red iron oxide (mainly Fe ₂ O ₃ ), iron yellow (Fe ₂ OHO), titanium dioxide (TiO ₂ ), a mixture of iron yellow and titanium dioxide, nickel oxide, manganese dioxide (MnO ₂₎ And metal oxides such as chromium oxide (Cr ₂ O ₃ ); nickel antimony titanium rutile ({Ti, Ni, Sb} O ₂ ), cobalt aluminate spinel (CoAl ₂ O ₄ ), zinc iron chromite spinel, manganese antimony Mixed metal rutile or spinel pigments such as titanium rutile, iron titanium spinel, chromium antimony titanium rutile, copper chromite spinel, chromium iron nickel spinel, and manganese iron spinel; lead chromate; lead phosphate; cobalt phosphate (CO ₃ (PO ₄ ) ₂ ) ; lithium cobalt phosphate (COLiPO _4); manga Ammonium pyrophosphate; magnesium cobalt borate, including alumino sulpho sodium silicate _{(Na 6 Al 6 Si 6 O} 24 S 4), but are not limited to. Suitable organic colorants are lamp black pigment dispersions; xanthan dyes; phthalocyanine dyes such as copper phthalocyanines, polychlorocopper phthalocyanines; quinacridone pigments such as chlorinated quinacridone pigments; dioxazine pigments; anthroquinone dyes; azo naphthalene disulfonic acids etc Dyes; kappa azo dyes; pyrrolopyrrole pigments; and isoindolinone pigments including but not limited to. Such dyes and pigments are available from Mineral Pigments Corp. (Beltsville, Md), Shepherd Color Co. (Cincinnati, Ohio.), Tamms Industries Co. (Itasca, Ill.), Huls America Inc. (Piscataway, N. J.), Ferro Corp. (Cleveland, Ohio), Engelhard Corp. (Iselin, N. J.), BASF Corp. (Parsippany, N. J.) Ciba-Geigy Corp. (Newport, Del.) And Dupont Chemicals (Wilmington, Del.).

  The colorant system may be included as part of the biocomposite layer or as a separate layer in one laminate.

  The colorant may be added to the biocomposite layer in an amount suitable to provide the desired color. In some embodiments, the colorant in the particulate material is less than or equal to about 15% by weight of the biocomposite matrix and less than or equal to about 10% by weight of the biocomposite matrix; The amount is about 5% by weight or less. It is desirable to use a biopolymer carrier as the colorant to maintain the biobased characteristics of the biolaminate. Standard color carriers such as EVA do not contain harmful substances, but it is preferred to use natural polymers as color carriers. Three dimensional appearance by utilizing transparent biopolymers can be achieved in embodiments of the present invention.

  The surface layer of the biolaminate composite assembly may optionally include solid opaque colorants with fibers, fillers, or minerals to add decorative value to the product. Similar to that of thin solid surface materials, the color and texture can be consistent in the product.

  In some embodiments, a latex paint layer may be included in the biolaminate to provide a colorant system. The colored layer may be visible in the clear, translucent, or lightly colored upper layer 102. In addition, transparent or translucent light-colored films are then allowed to "color match" quickly, using standard paint strips from any manufacturer's brand of latex paint. It can be backcoated using a latex paint. This allows the designer to drop in at a local store to select a very specific color. Embodiments allow for the rapid and easy manufacture of accurate color matched biolaminates. The colored layer can also function as an adhesive layer. The colored layer may adhere to the untreated PLA film rather than other untreated petrochemical based films. Colored layers (e.g., latex paints) can have "stretch" properties, which allow the biolaminate to be composite molded without the paint layer cracking or peeling from the biofilm top layer. It can be thermofoiled into shape. The latex can meet the designer's specific color needs, and various modifiers can be added to the paint depending on the decorative or functional needs. The latex may be directly coated on the back with a roll, spray, curtain coat, or other common coating method. The surface can generally be coated on the entire backside and then dried using various methods known to those skilled in the art.

  The latex backside of the film can be laminated onto the non-plastic rigid substrate using the various three-dimensional laminating methods described above, and top planar laminating methods. Latex paints are thermally expandable fire retardants, shield metals, special effect additives, adhesion promoters, performance modifiers, UV initiators, "nightlight" components, magnetic particles, decorative pieces or particles, and paint layers or colorings It may be largely adjusted by other additives compatible with the layer.

  The other form is by taking a latex coated biofilm and laminating it on a backing paper which is first laminated with a back latex coated film by a cooling or heat laminating adhesive and infiltrated 2 Including creating a biolaminate of two layers. This then allows the end user to laminate the biolaminate to various flat and contoured shaped articles similar to that of the pre-finished plywood using standard methods.

  Other forms include mixing transparent or translucent light colored films with plastic pellets that create the films to create highly transparent colors. In this case, the light colored film can be laminated directly to a hard substrate or a real wood veneer as an environmentally friendly coating, and also with the stain effect of a real veneer, bio-friendly to the end user A base pretreated veneer is provided. A clear or lightly colored biofilm can be laminated directly to a wood veneer using transparent or lightly colored laminating adhesive to represent the texture of real wood at the finish of the biofilm.

  Glossy laminate

  Other embodiments include those in which two layers of biofilm are laminated to create a biolaminate layer where the overlying biopolymer film may have a certain level of texture and gloss for high pressure laminating applications . The bottom biofilm may be top printed and an adhesive may be used on the bottom or bottom. The two biolaminate layers can then be melted by heat or a clear adhesive.

  Transparent or translucent film layer

  In some embodiments, a substantially transparent, transparent, translucent film layer can be provided in the biolaminate composite. Suitable transparent or translucent films include polymers derived from renewable resources such as polymers such as polylactic acid (PLA), and a class of polymers known as polyhydroxyalkanoates (PHAs). PHA polymers are polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), copolymers of poly (hydroxybutyrate-hydroxyvalerate) (PHBV), polycaprolactone (PCL) (ie TONE), polysteramide (ie BAK) ), Modified polyethylene terephthalate (PET) (i.e. BIOMAX), and "aliphatic-aromatic" copolymers (i.e. ECOFLEX and EASTAR BIO), mixtures of these materials, and the like. Other forms of biobased polymers or plastics are also cellulose acetate and mixtures thereof.

  Base material

  The biolaminate composite or any layer thereof may be laminated to a substrate. Such substrates may include non-plastics such as medium density fiberboard, particle board, agricultural fiber composites, plywood, gypsum board, wood or aggregate plastic substrates. One suitable substrate is wheat (wheat) board composite, which does not contain rapidly renewable formaldehyde. In addition, generally, non-plastic substrates can be composites of hard wood or agrifiber commonly used in furniture, cupboards, millwork, laminate flooring, furniture and other such applications. it can. In most such applications, flat sheets may be used in which the biolaminate is adhered to the front and back in a balanced configuration. In one embodiment, profile moldings may be used where MDF made of wood or agrifiber can be machined to a woodworking product application to a three dimensional linear shape, and the biolaminate layer is molded on this surface and also laminated It can be done.

  The substrate can be a plastic-blended wood or aggregate that is extruded into its final shape, such as a woodworking product or window frame where the biolaminate is then shaped by heat or an adhesive layer and bonded to the surface. The biolaminate layer in this embodiment can be either practical or decorative.

  In addition, glass panels can be laminated with the biolaminates provided herein to create translucent architectural panel products using transparent laminate tapes obtained from 3M.

  Biocomposite substrate

  In certain embodiments, a substrate can be provided for three-dimensional shaping. Composites of foamed plastic, plastic, or bioplastics can be useful because they can utilize recycled plastic and provide high water resistance and ultimate performance.

  Various substrates can be molded and created using profile extrusion methods to create long continuous linear moldings. In order to reduce the cost and / or weight of linear moldings while maintaining high performance, they can be based on expandable fillers and composite fillers, firstly. Higher water resistance than conventional particle boards and MDF substrates that offer higher value and higher performance by integrating first plastic or bioplastic as binder in the case of biocomposites Is provided. In addition, this also results in the substrate having a higher degree of mold resistance, also with respect to mold resistance, which is a common problem of many wood-based composite substrates.

Regenerated Foam Plastics In the profile extrusion process, various blowing agents can be used to create foam plastic or bioplastic. PVC, PET, PE, PP and other commonly used plastics can be recycled to become parts of foam moldings. PLA, PHA, other bioplastics and regenerated bioplastics can be foamed into the final extruded shape. Where 100% plastic or bioplastics can be foamed, the shape of these materials is water resistant, but may not have sufficient mechanical strength, heat deformability, etc. for many exterior applications. In applications such as laminate flooring, woodworking products and substrates for other applications where mechanical strength is not required, these forms of foamed plastic will be sufficient for a good substrate. In order to create a lightweight extrusion, foamed plastics can generally use chemical blowing agents or blowing agents. In the case of bioplastics, chemical blowing agents and blowing agents can also be used, but other forms of proteins and biofoaming agents can also be used. In the case of bioplastics, it is preferable to extrude bioplastics such as PLA, PHA etc. in a visco-elastic state below their melting point. This keeps the degree of crystallization higher in the final product and provides higher melt strength to maintain the final three-dimensional shape. Generally, treating many biopolymers above their melting point does not have sufficient melt strength to maintain complex profile shapes. Bioplastics such as PLA manufactured by Natureworks generally have a Melt Flow Index (MFI) of 4 or more. Plastics for good profile extrusion, with much higher viscosity and higher melt strength to retain their shape, generally have an MFI of 1 or less. Processing bioplastics above their melting point will have honey-like viscosities with very low ability to retain their shape, while profile extrusion grade plastics with MFI less than 1 are generally In addition, it will have the same viscosity as "play dough" that can maintain its shape during extrusion.

Biocomposites and Composites In general, biocomposites are plastics integrated with the form of cellulose-based materials that can be extruded and molded into various shapes. The addition of these forms of fibers and substances to the plastic increases the mechanical properties and mechanical or thermal stability of the plastic matrix while still maintaining a high degree of water resistance, mold resistance. These forms of material can be processed into three-dimensional components in continuous linear forming by extrusion or can be processed into three-dimensional component substrates by compression molding.

Various forms of wood / plastic composite substrates can be created using wood waste and plastic or waste plastic to form a composite matrix. The various wood sources that can be integrated are wood chips, wood flour, ground wood, and other forms of wood waste products. Various plastics such as PVC, PP, PE, PET etc. can be used as binders and can also be used to improve performance and water resistance.

Biofibers / Plastics In accordance with the present invention, biobased to produce substrates such as wheat straw, rice straw, corn fiber, soybean stock, soy peel, oat peel, corn peel and many other biofiber based materials. Various fibers of can be used. Although synthetic plastics such as PE, PVC, PP, PET may also be used, it is preferred to use bioplastics such as PLA or similar forms of bioplastics. Also, low viscosity binders or biobinders can be used in the extrusion and molding process to allow for flow improvements in the composite matrix biofiber material rich. Biobased binders can include PLA, lactic acid, linseed oil, glycerin, and other forms of biobased binder systems. Optimally, biofibers in combination with biobased binder systems provide truly renewable resource materials. The field of development is the use of lactic acid in combination with a bio-based binder that provides a matrix resin that can be used with various biofibers such as wheat straw, rice straw, seed coat, corn fiber and other forms of agrifiber materials .

Bioplastics / Synthetic Fibers Bioplastics can be extruded into highly resistant forms by viscoelastic processing methods where the processing temperature is below the melting point of the bioplastics. Although it is preferable to add bio-based fibers to create shaped or profile extruded substrates, other synthetic fibers may be integrated to create even higher performance. Fiberglass, carbon fibers, Kevlar fibers, and other types of synthetic fibers may be integrated with the shape of these substrates in either an extrusion or compression molding process. Examples of this system can be PLA or lactic acid matrix biopolymers in combination with various synthetic fibers extruded into various shapes.

Plastic / Bioplastic and Paper Mill Sludge In producing environmentally friendly substrates, recycled paper and paper mill sludge can also be used as reinforcements in combination with bioplastics such as PLA or lactic acid / binder. They can be in the form of solid extrusions or moldings or in the form of foam extrusions.

Extrusion or molding process All the above-mentioned base material composites and foamed plastics are extruded by profile extrusion processing and three-dimensionally molded, or molded into a specially designed mold by compression molding, It can be processed into a three-dimensional shape such as a table surface or a cabinet door.

  Other types of substrates can be extruded and formed into the final shape or machined and formed into the final shape, but in any case to be widely used in architectural applications It is a three-dimensional shape. For example, extruded aluminum or synthetic fiber composites may also be extruded or pultrusion to produce higher performance substrates. In general, both aluminum and pultruded synthetic fibers are extruded using specific processes. Pultrusion is a process that orients the fibers linearly with respect to the extrusion direction in order to maximize the mechanical strength of the extruded member.

  Various substrates can generally be laminated with the biolaminates provided herein to form practical and / or decorative members in both substantially planar or three-dimensional shapes. . In addition, in the three-dimensional member, the member may be formed into a linear shape of a three-dimensionally formed molded article of the member.

  adhesive

  In general, any suitable adhesive may be used, and such adhesives generally include materials that adhere two or more layers in a biolaminate layer or biolaminate composite assembly. The adhesive can include glue adhesive. Examples of adhesives include urethane, PVC, PVA, PUR, EVA and other forms of cold pressed or hot pressed laminating adhesives and methods. Common biolaminates and laminates are usually adhered to non-plastic or wood / aggregate composites by various glue adhesives and laminating processes. Synthetic adhesives, PVA, urethane, hot melt and other forms of adhesives are often used in HPL (high pressure lamination). While many of these glue adhesives are effective for selective use in embodiments of the present invention, hot-press, roll, or cold-press to bond the biolaminate layer to the substrate. In adhesive systems that can be processed, glues with low or no VOC content are preferred.

  Bonding plastic films to foamed plastic or plastic composites with standard methods and adhesives can be difficult. Thus, new forms of aqueous urethane and urethane hot melt adhesives activated by heating make this possible.

Aqueous Urethane The new form of aqueous urethane adhesive is both environmentally friendly and has very good adhesion performance. Other forms of standard laminating adhesives are not effective for plastics and plastic composites, and the degree of adhesion is not adequate. An aqueous urethane used to thermofoil genuine wood composites, such as that sold by Daulbert Corporation, may be used, in which case the aqueous adhesive is sprayed onto the above substrate, or It is rolled. Water is flashed off by air drying or forced heat, but at a sufficiently low temperature so that the adhesive does not polymerize. Thin biofoil or biolaminate can be adhered to the shaped surface by using heat and pressure with a roller or compression system. Heat has two main functions. To soften the biofoil or biolaminate in order to be able to be shaped into a three-dimensional shape and to activate or polymerize the urethane in order to provide strong adhesion. In the test, the temperature required for this is between 100 and 200 degrees Fahrenheit, more preferably between 150 and 180 degrees Fahrenheit. If the temperature is too high, the surface of the biofoil or biolaminate will melt or its textured surface will be lost. If the temperature is too low, the biofoil or biolaminate will not form sufficiently to form into a three dimensional shape or lose its stretchability. Moreover, urethane may not fully harden. In this case, the thickness range of the biofoil or biolaminate is 0.005 to 0.1 inch, more preferably, the thickness range is 0.010 to 0.030 inch. In testing, these forms of biofoil and biolaminate achieve lower processing temperatures and lower heat distortion temperatures that when molded are more "sharp" than conventional petrochemical plastics. I found it to have. In addition, the integration of biofoil or biolaminate with biobased composites or foam substrates provides a 100% biobased solution that meets the needs of new environmental protection markets and government plans for biotaste .

Hot Melt Urethane Urethanes are also solvent free, or 100% solids, requiring heat for liquefaction to have a flow and provide a good adhesive. These forms of hot melt urethane are manufactured by 3M and HB Fuller et al. For many applications. Hot melt urethanes provide strong adhesion to biofoil or biolaminate of bioplastic composites. The heat from the hot melt adhesive also provides improved adhesion to polar natured bioplastics and biofoil or biolaminates used in substrates.

  Composite Assembly Example

  Embodiment of mineral wear layer

  In one embodiment of the biolaminate composite assembly, the top layer can be a biolaminate that includes natural quartz to provide a high wear surface. The second layer can be a white sheet of biolaminate printed on top. In this case, the quartz biolaminate layer can be melted with the lower layer printed by heat and pressure or by a transparent adhesive.

  Embodiments of PEEK wear layer

  Referring to FIG. 7, a cross-sectional view of a biolaminate composite assembly utilizing a high performance surface layer is shown, according to some embodiments. A non-plastic hard substrate 106 may be in contact with the selective adhesive layer 104. Such adhesive layer 104 may be in contact with one or more biolaminate layers 102. Substrate 106 may, for example, be in contact with layer 102. Biolaminate layer 102 may include multiple layers, such as thin films. The high performance layer 702 can be in contact with one or more biolaminate layers. Although specific discussions are made below on PEEK high performance layers, it should be appreciated that alternative high performance layers such as quartz wear layers may be used instead.

  Embodiments of the present invention include the integration of a high performance surface layer 702 in contact with one or more biolaminate layers 102 on the surface side of layer 102. The high performance layer 702 may be a PEEK layer.

  A decorative layer or ink may be disposed between the biolaminate layer 102 and between the smart layer 702. In the case of ink, it can be printed on either the biolaminate 105 or the smart layer 702 to provide aesthetic value. PEEK is a very high performance thermoplastic that has extremely high heat resistance. The heat resistance of various PEEK films or coatings is continuously in excess of 500 degrees Fahrenheit. Other forms of current surface layers have only continuous heat resistance slightly above the boiling point of water (212 degrees Fahrenheit).

  The high performance surface layer 702 can be used in various ways or forms. In one embodiment, layer 702 may be heat melted onto the surface of biolaminate 102. This can also be done using a clear adhesive layer between the biolaminate and the PEEK surface.

  The high performance layer 702 can also be used as a single layer laminate that can be thermofoiled into various shapes.

  While a single layer of PEEK may be used, other forms include the use of PEEK as a surface wear layer in combination with the biolaminate 102.

  Decorative coloring example

  Referring to FIG. 8, a cross-sectional view 800 of a colored biolaminate composite assembly is shown, according to some embodiments. The rigid non-plastic substrate 106 can be in contact with the colored layer 802. Colored layer 802 may be in contact with one or more biolaminate layers 102. The substrate 106 may also contact, for example, the layer 102. Biolaminate layer 102 may include multiple layers, such as thin films. The substrate 106 may, for example, be further in contact with an additional rigid substrate. The assembly may include a selective adhesive layer. The optional underlying layer 804 can, for example, contact the substrate 106 and the colored layer 802.

  The one or more biolaminate layers 102 can include, but is not limited to, clear or translucent polymer forms made from the following polymers. That is, PVC, PET, cellulose acetate, PC, acrylic, polystyrene, ABS, PEEK, Teflon film, or a combination thereof. Polymers and biopolymer films such as PLA, PHA, cellulose acetate, and other rapidly renewable or biobased plastics are preferred to provide a substantially or all "green" product.

  The clear or translucent film (i.e., biolaminate layer 102) can be about 0.001 to about 0.050 inches thick. The top layer of the film layer can be textured to have a specific gloss and texture within the usual range of general laminate surface processing. During the extrusion process, a transparent or translucent film can be produced to give texture and gloss, or of a press process using a hot platen press or a continuous hot roller to provide the correct texture and gloss. Post processing may be done.

  The performance of the final product related to scratches, scratches, and abrasion can be influenced by the type of texture applied to the top layer of the clear or translucent film surface (the top layer of the one or more biolaminate layers 102). The film can be in the form of a sheet or roll. Although embodiments of the present invention may include petrochemical-based and bio-based polymer films, the most preferred method is to use bio-based films to create environmentally friendly products.

  Embodiments of the present invention include the use of a colored layer that contacts the bottom of the biolaminate layer 102, the top of the substrate 106, or the optional underlying layer 804, such as a latex or oil-based paint.

  Embodiments of decorative fused random particles

  In some embodiments, various forms of aesthetic multicolor biolaminate assemblies can be formed from biopolymer matrix resin and novel biocomposite random particles to provide a wide aesthetic and three dimensional appearance. The resulting sheet product has the natural appearance of natural granite and can be used in many architectural applications where high aesthetic value and environmental protection properties are desired.

  The present invention produces products with novel materials and large depth of field. Decorative biocomposite particles are coated unevenly with liquid colorants and waxes (eg, hydrogenated vegetable oils). Biocomposite particles can include, for example, fully impregnated fibers without colorants and / or fully impregnated fibers with colorants. In processing these, flow and visible stratification are created to create different visual effects. Bioplastic matrix resins are even more transparent or translucent. Thus, the final product may have multiple stages of transparency to create a truly three dimensional or natural appearance.

  The present invention can be designed to be manufactured in surface processed material forms to replace formaldehyde based high pressure laminates and PVC thermofoil. In these cases, both products are manufactured in one dimension using printing paper on their surface layer. These types of decorative overlays or laminates are inexpensive but, due to their optical properties, do not have the three dimensional or depth of field of natural products. In addition, the printing process is limited to repeating the handle pattern over one area. In the present invention, the resulting product has a truly random fractal shape that can not be an exact replica of the natural stone with that one piece.

  PLA, when mixed with various microparticles, provides unique properties and unique transparency that can create many decorative and practical products. Biocomposite particles derived from PLA, paper mill sludge, and various other additives may be extruded, but in such extrusion the paper mill sludge is colored in its natural state or colored in the coating process Ru. PLA is biosynthetic but is not truly biodegradable according to official sources and its manufacturers. PLA has surprisingly good stability when exposed to UV light or direct sunlight. Paper mill sludge also has good UV resistance due to the inorganic fillers used in the paper making process. Biocomposite particles consisting of pigmented paper mill sludge and PLA can be extruded into various forms of sheets, bedplates, wallboards, handrails, fences, building members, baseboards, and other decorative and practical applications . Additives can be selectively added to biocomposite particles consisting of PLA / paper mill sludge, such as plasticizers, impact modifiers, heat stabilizers, and fire retardants. Biocomposite particles can be manufactured with PLA and various cellulosic materials for extrusion, but with higher loading, improved performance, and derived from waste streams, paper mills Sludge is preferred.

  Decorative biocomposite particles can be manufactured in various colors, shapes, and sizes. Decorative biocomposite particles can be mixed to have various decorative properties. Decorative biocomposite particles can be used as biocolorant systems for various bioplastics and biopolymer systems. Providing the true performance of solid surface materials by melting different sizes, colors and shapes of biocomposite particles with the matrix bioplastic or biocopolymer and then forming into a sheet or three-dimensional shape While providing a three-dimensional appearing solid surface having a pattern with an appearance similar to granite.

  Cellulose insulation is available, although other decorative fiber systems with similar fiber characteristics are available that provide hydrophilicity to the impregnation and maintain its integrity in order not to form a composite of homogeneous appearance. The body-like bottom, fluffy cellulose can be used as a basis for decorative biocomposite particles. As most composite materials struggle to achieve uniformity, the present invention is based on random particle shape to give the final product decorative biocomposites and biolaminate products aesthetics .

  Additives include random particulate paper mill sludge, broken down into fibers, or randomly shaped agrifibers, and fiber glass. In these materials, it is possible to impregnate hydrogenated soybean oil or natural wax without colorants so that the material can form particles with higher integrity for more optimal aesthetic performance. It is important to have

  Although the invention is based on hydrophilic biocomposite decorative particles, other particles may also be mixed in the decorative system. Reformed PLA particles may be colored by simply painting the outside of the individual particles on one side. As these particles are deformed using heat and pressure, the result has yet another distinctive aesthetic effect. As the material is processed, the clear biopolymer particles can be seen through so that the back printed side of the particles is visible. These bioplastic particle forms can be mixed with biocomposite particles to provide greater aesthetic effect and value. The colored and coated decorative biocomposite particles are mixed with the usually transparent or translucent bioplastic or biocopolymer by an extrusion method. In some cases, the bioplastic or biocopolymer is preblended with a different color than the biocomposite particles.

  Also, the coat of PLA provides other unique features of the final product biocomposite. The coated biocomposite particles generally have a natural fiber color inside and have a colored coat on the outside, a liquid colorant, a wax made of different substances, and the like. Bioparticles coated with this bilayer material have unique thermal properties and provide unique aesthetic potential. The coat is mainly for coloring and is also used to better maintain boundary conditions during hot melt processing. These coatings may include fire retardants, fibers, minerals, fillers, metals, and other additives, due to aesthetic or performance requirements for the final melted biocomposite sheet or molded article. .

  Optical properties using coated biocomposite particles are also unique. As one example, biocomposite particles can be compared to applying a metallic paint to a transparent glass plate. The upper side of the glass plate shows the color of the paint, but at the optical level it is not completely smooth, while the bottom side where the paint-glass interface is visible has different optical properties . Also, the depth of field can be recognized by looking through this interface through the transparent glass plate. When used for coated biocomposite particles, the paint-particle interface is visible rather than the direct surface of the paint.

  The present invention may start from a dyed, transparent or translucent color in the form of polylactic acid, preferably in the form of lignding which provides a transparent interior of biocomposite particles. In addition, PLA can be formulated to contain various multicolored particulates to create a translucent or light diffusing medium to create discrete particles. Once fused, bio-composite particles having different colors, light diffusion properties, shapes, sizes, and various other optical properties, when fused, these particles form a solid surface of this bio-based It has unique optical properties and translucency that provides true depth of field to materials it has. With regard to the value of natural granite in the market, its value is so high that the "depth" of the material is high, ie it can be seen into the granite. Materials with solid surfaces usually do not have this type of depth of field, or the particles float uniformly in the clear resin and appear unnatural when using the clear resin.

  Within the biocomposite particle matrix, the coated particles can have a transparent or translucent interior. To create a translucent interior, various cellulose or mineral particulates are used, although their depth of field varies, but still have a depth of field.

  A paper mill sludge impregnated with the dye can be produced by adding the paper mill sludge which remains unchanged in shape to the aqueous dye often used in clothing.

  Natural colored biocomposite particles use natural colors found around various forms of agricultural materials, industrial by-products, scrap wood, natural wood shavings, minerals, and other three-dimensional shaped colored materials It can also be produced by In this case, these shapes of decorative additives are in the form of microparticles less than about 50% of the diameter of the first biocomposite particles, more preferably to provide good optical aesthetic appeal , The diameter is less than 0.060 inches, and has a three-dimensional random shape. The use of natural colored microparticles avoids the use of chemical based colorants in applications where environmental protection is desirable and desirable.

  The biocomposite biocolorant system with various functions has important effects on the biolaminate and its aesthetic value for producing its support members. While crushed regenerated cellulose is suitable as a starting material to create decorative coated biocomposite particles, other forms of cellulosic material may also be used to provide unique shapes and aesthetic effects. Paper mill sludge, agricultural fibers, and other natural fibers may be used with liquid colorants and hydrogenated vegetable oils or waxes and processed by similar means. This method creates a wide range of biocomposite particle shapes that allow for different aesthetic values and handle designs.

  The resultant comprising decorative composite / wax coated biocomposite particles in a translucent bioplastic or biocopolymer matrix offers a wide range of applications. The main application of the present invention is to make this biocomposite into a thin sheet with a thickness similar to that of high pressure laminates and PVC thermofoil. Generally, the thickness is 0.012 inches to over 0.125 inches, but 0.020 inches to 0.040 inches are more common. The decorative laminate can be textured on its surface while the material is extruded into a sheet by a texture roller. The back of the highly decorative biolaminate can be processed by corona treatment, flame treatment, or other means to enhance the adhesion of the biolaminate to non-plastic substrates.

  There is a need to make the properties of biocomposite particles more elastic in a variety of architectural applications where biocomposites are preferred over petrochemical plastics and harmful plastics. Plasticizers can be added to maintain the translucency of the biocomposite or with the biocomposite particles. Plasticizers such as glycerol, oleic acid, and other fatty acids and natural oils all make PLA biocomposite particles more elastic. In many applications, when providing a green solution, it is preferable to use naturally derived plasticizers obtained by processing plants, but is not limited thereto.

  Decorative biocomposite particles or biocolorant systems may be added to bioplastics in other extrusion and plastic processing applications. As disclosed in the inventor's previous patent application, profile extrusion of PLA can be done by novel processing methods and additives. The resulting stone-like profile is 100% biobased and a corner guard that is desired to replace PVC and other petrochemical-based extrusions with environmentally friendly and highly aesthetic products, It can be used for baseboards, edge bands, partitions, woodworking products, and other building components. Other processes for manufacturing the component are in the form of injection molding, blow molding and other plastic processing.

  Depending on the application, additional performance may be required, for example, depending on the application requiring first grade fire protection materials, such as buildings of schools, hospitals and other facilities and commercial buildings. A fire protection material pack containing ammonium phosphate forms may be added to the PLA or biocomposite particles, which are gently agitated during the extrusion process to create a fire protection biolaminate or matching profile.

  Embodiment of plywood

  Referring to FIG. 7, a cross-sectional view 700 of a veneer-board biolaminate composite assembly according to some embodiments is shown. The veneer substrate 702 may be in contact with the adhesive layer 104. Adhesive layer 104 may be in contact with one or more biolaminate layers 102. The veneer substrate 702 may also contact, for example, the adhesive layer 102. Biolaminate layer 102 may include multiple layers, such as thin films. The veneer substrate 702 may, for example, be further in contact with a rigid substrate.

  The veneer 702 may include a decorative design, texture, or appearance. The biolaminate layer 102 can be, for example, a transparent, translucent or lightly colored film. Instead of the lower layer of the biolaminate layer 102 and the adhesive layer 104, the infiltrated base paper layer can be selectively disposed on the bottom surface of the substrate 702.

  The assembly includes a plywood substrate 702, a transparent, light-colored or translucent biopolymer layer 102 having a selectively textured upper surface, an impregnated base paper layer and a transparent laminating adhesive 104. obtain.

  Generally, wood veneers are manufactured using various veneer processing processes. Several new processes are currently under development to further produce restructured veneers or wood veneers with extremely thin and brittle properties that optimize the yield from wood. These veneers are difficult to finish and process by conventional means. The wood veneer may be real wood or reconstituted wood veneer.

  A base paper, such as a base paper impregnated with Neehan latex, may be used as a composite base. In place of or in addition to the lower adhesive layer 104 and the biolaminate layer 102, an underlayer may be disposed on the top or bottom of the veneer board substrate 702. Instead of a primer layer, rubber, fiber rubber composite sheets, hard substrates, or other composites may be in contact with the veneer board substrate at the bottom or underside of the veneer board.

  The final bio-based veneer assembly including textured top layer of biofilm, wood veneer layer, and substrate is flat laminated or rigid 3D hard substrate on hard substrate Can be used to be three-dimensional (3D) molded. Substrates may include, but are not limited to, substrates of wood composites, agrifiber composites, plastic fiber composites, cement fiber composites, and other forms of composites.

  Bio-based veneers can be laminated to various 3D rigid substrates such as relief panel members for aisle doors and cabinet doors and the like. In this case, the veneer may be polished or sprayed as part of a larger wood assembly requiring a final finishing process. The veneer assembly has a good adhesion function to various types of common wood coatings as compared to most petrochemical-based plastics.

  Plywood assembly laminates to form a wide range of applications including but not limited to cabinets, cabinet doors, walkway doors, furniture doors, furniture, woodworking products, flooring materials, wallpaper, fences, ceiling tiles, and other plywood applications. It can be done.

  Corrugated embodiment

  Embodiments of the present invention also relate to a structural and / or decorative lightweight panel or laminate assembly comprising one or more surface layers or sheets in contact with the extruded bioplastic substrate or core. The adhesive layer may, for example, contact the substrate and the layer. The substrate or core can be highly resistant to moisture attack, and the selective open spaces between the truss elements provide the flexibility to control thermal expansion and contraction. The structural assembly may have a higher stiffness as compared to polyolefins or functional surfaces on which standard hot melt adhesives may be used.

  In one embodiment, more than one metal face sheet can be used, and the core can be a corrugated bioplastic core. The core sheet or body may be formed by continuous plastic extrusion techniques. Diagonal plastic webs or vertical plastic I-beams can be used for truss elements of bio-wave material. Further embodiments include one or more laminate layers of bioplastic corrugated sheet that may be laminated with a glue adhesive. Alternatively, only one sided sheet that can be bonded to one side of the plastic core may be used to enable its use as a veneer or a rounded structure with a curved surface . Further embodiments include face sheets such as, for example, high pressure laminates, rigid plastics, natural fiber reinforced sheets and fiber glass sheets.

  Biocorrugated systems can be used for commercial or residential purposes, as an alternative to moisture-sensitive building materials such as wood, plywood and composites made from either of the two. Embodiments of the present invention provide lightweight, economical, environmentally friendly structures and / or decorative panels that can withstand moisture expansion, weathering, freeze-thaw cycles. Such panels are easy to manufacture and make maximum use of materials in the manufacturing process.

  Embodiments include structural panels having at least one face sheet made of a durable material having high tensile strength and a core material comprised of one or more corrugated layers. The core layer may be laminated to provide spaced apart internal bioplastic truss elements. The core can be contacted with the top sheet with an adhesive.

  Adhesive bonding of the layers that make up the core provides a high strength laminate bond that is extremely resistant to delamination. The core may be bipolar and has high affinity for bonding, lamination and fusion by standard hot melt adhesion methods. The substrates do not require surface treatments for adhesion such as flame treatments, corona treatments, plasma treatments, etc., which can be dangerous and expensive. The bioplastic core body may be highly resistant to moisture attack and the space between the truss elements may provide flexibility to accommodate thermal expansion and contraction. Also, the core can typically have high stiffness with a modulus of elasticity greater than 400,000 psi. The core or substrate may have a stiffness equal to or higher than currently used core materials such as particle boards. In addition, the core can be lighter than competing products and does not emit formaldehyde gas toxic gas.

  The use of a core body made of one or more bioplastics such as PLA, PHA or PHHA provides properties that are unique to the overall assembly or system. The face sheet may be made of metal because the metal has high tensile strength. Plastics, high pressure laminates, fiber reinforced skin may also be used for specific applications.

  The PLA or PHA bioplastics can be extruded as profiles or corrugated articles using processing methods to provide the desired shape or profile. The core may be laminated in the same direction or may comprise single layers or multiple layers of bioplastic corrugated material orthogonal to one another. Two metal face sheets can be bonded to the opposite side of the bioplastic core.

  The entire assembly or system can be manufactured with a thickness of 0.125 inches to over 1 inch even when using two face sheets. Additives may be utilized for bioplastics in the core to provide optimal or customizable properties. The layers of bioplastic core can be laminated using standard hot melt additives and standard laminating methods. The core can be laminated, for example, with all the grooves in the same direction as all the flutes, to obtain maximum linear mechanical strength. Alternatively or subsequently, the corrugated bioplastic sheet may be rotated so that the sheets point in different directions, as well as a cross band of plywood, for additional strength.

  Lamination may utilize an adhesive such as EVA (ethylene vinyl acetate). Other adhesive materials can be, for example, reactive polyester epoxy or polyurethane or various types of latex. Heat and / or pressure may be applied to the adhesive for spray or mist. Because the epoxy tends to be friable, an adhesive or modified epoxy (TS) of polyurethane with greater elasticity may be used when the laminate is bent or processed. Bioplastic cores derived from PLA or PHA provide a unique, hyper-curved or functional surface that does not require pretreatment for surface adhesives such as those required for polyethylene and many petrochemical-based plastics.

  The truss element may comprise an I-beam, "x brace", corrugated or sinusoidal shaped part. By creating space in the truss system, the panel system is less expensive, lighter and more robust than competing products that use separate structural elements.

  When used as part of an outdoor wall construction, structural panels are often required to be heat resistant. By using different non-conductive materials for the core body (i.e. plastic), the panels of the embodiments of the present invention provide high resistance to heat flow through the entire panel. The thermal properties of the panel improve the control of moisture on the wall of the building panel, since it is not necessary to think too much about causing or causing damage to the panel. The panels of embodiments of the present invention are superior to conventional plywood and wood panels for several reasons. Conventional structural panels having a plywood core are more expensive year after year because they absorb water easily, the quality of the material is inferior, and the natural resources of old-age trees are decreasing. Plywood has disadvantages of natural origin such as bumps and cracks and deterioration as an organism. Accumulation of water and exposure to water cause corrosion and decay, and eventually it is consumed by natural deterioration.

  Applications for the panels and systems described above may include metal cabinets, storage systems, pallets, hand wash partitions, architectural panels, blindness, lightweight transportation panels, displays and display panels, curved panels, seats and the like.

  Embodiments of Three-Dimensional Biocomposite Substrates

  In some embodiments, three-dimensional biocomposite substrates can be laminated by the biolaminate described herein. Such three-dimensional biocomposite substrates can be useful for decorative woodworking products, door members, or other architectural linear members.

  For example, the three-dimensional biocomposite substrate can be a linear extruded biocomposite assembly comprising a decorative biofoil and a biocomposite extruded substrate used as a linear component for construction. The biofoil can include a biopolymer, a biocopolymer, a modified biopolymer, or a biocomposite substrate. The biofoil can be made decorative by printing, internal coloring or decorative inclusions. Biofoil can be used by the linear wrap method.

  In other embodiments, the three-dimensional biocomposite substrate can be a linear wrapped biocomposite comprising an extruded substrate. Substrates include petrochemical plastics and agrifibers, petrochemical plastics and wood, petrochemical plastics and paper mill sludge, bioplastics such as PLA, or bioplastics and wood in biocomposites, agrifibers, and papermaking It may be factory sludge. The substrate can be foam or solid and / or can include foam plastic or bioplastic.

  Wallpaper embodiment

  In some embodiments, a biocomposite substrate can be provided as an alternative to flexible vinyl wallpaper, optionally with a biolaminate. Vinyl wallpaper is frequently used in commercial applications due to its washability and toughness. Flexible PVC contains a large amount of phthalic acid plasticizer which is considered to be extremely harmful and releases dangerous volatile substances. The present invention is intended to create PLAs similar to flexible biofilms used for signage applications simply by adding a nonwoven or woven underlayer laminated to the back of the flexible PLA film in the extrusion process. In combination with Halstar plasticizer. When the flexible PLA is extruded, the fabric fiber base layer is compressed and melted on the back side of the visco-elastic flexible PLA film.

  After being cooled and rolled, the flexible base film is printed using bioink derived from lactic acid. Optionally, a clear liquid protective coating may be used. The clear liquid is preferably in the form of lactic acid ink. Other standard coatings can be used, but clear liquid bioink is preferred to maintain 100% of the bio-preferred product. Another option for transparent liquid coatings is other transparent flexible PLA thin films that are heat melted to the surface.

  The addition of plasticizers and, optionally, lubricants makes it much easier to add halogen-free, powder-like, environmentally friendly, fire-retardants such as alumina trihydrate and magnesium hydroxide. I found it. Thus, by adding sufficient fire protection material, high flexibility is maintained while providing a product that can meet Class IE 84 for indoor application code requirements.

  Other additional value-adding steps may include the use of a wallpaper adhesive on the back side to aid in application and to facilitate application.

  In one embodiment, such flexible wallpapers include PLA and biobased inks with Halstar plasticizers and biobased clear ink coatings. In other embodiments, decorative biowallpapers are provided that use biobased inks from lactic acid and other biobinders / additives. In other embodiments, bio-based clear coatings derived from clear lactic acid printing inks may be provided along with selective fire protection materials. In a further embodiment, a biobased flexible wallpaper derived from plasticized lactic acid having a woven or non-woven substrate is provided.

  Method of manufacturing biolaminate composite material

  Referring to FIG. 2, a block flow diagram 200 of a method of manufacturing a biolaminate composite structure according to some embodiments is shown. A non-plastic hard substrate 106 may be formed by one or more biolaminate layers 102 or may be a laminate 202. Forming 202 may include thermoforming, vacuum forming, thermoforming, or a combination thereof. Additives can be introduced before, during, or after shaping 202.

  Referring to FIGS. 3-6, enlarged views (300, 400, 500, 600) of a biolaminate composite assembly according to some embodiments are shown. A substrate 106, such as a rigid non-plastic substrate, may be in contact with the transparent biolaminate layer 302 using the adhesive layer 104 on the first side. The transparent biolaminate layer 302 can, for example, be in contact with the reverse printing layer 304. In some embodiments, they can be joined, for example, by thermal fusion. The second biolaminate layer 102 may contact the second side of the substrate 106, such as by thermoforming or lamination (see FIG. 3).

  The transparent biolaminate layer 406 can be in contact with the direct print layer 404 and then protected, for example, by a transparent protective coating 402 (see FIG. 4). The biolaminate layer may include between them two or more layers such as white biolaminate layer 102, surface biolaminate layer 302, and print layer 502 (see FIG. 5). The surface layer 302 can include, for example, quartz. In other embodiments, a fire protection material can be integrated into the biolaminate layer 602 and then directly printed 502 with a decorative layer. The transparent biolaminate layer 406 may face the outside (see FIG. 6).

  These various steps are described in further detail below.

  Polylactic acid, or PLA, is processed into a packaging film where extrusion is used to produce ultrathin sheets or films, typically 0.003 inches to 0.060 inches thick. PLA is difficult to extrude due to its low extensional viscosity and lack of shape retention ability in the molten state.

  During extrusion, many plastics, such as polyethylene, polypropylene and other shapes of thermoplastics, use melt index as a common measure of viscosity. Usually, the melt flow index (MFI) of extrusion grade of these plastics is between 0.1 and 2 MFI. Such measurements are usually made at 190 degrees Fahrenheit in which the plastic is heated to such levels and the flow or material passes through the orifice in a fixed amount of time. Extrusion grades have extremely high viscosities at processing temperature levels that can maintain their shape for profile extrusion. Materials with higher melt flow index or lower viscosity have problems with profile extrusion and can not maintain their shape. This is also due to having a lower molecular weight than extrusion grade plastics. PLA has a melt index between 4 and 10 and can usually not be below 3 MFI. In addition, PLA has very characteristic thermal properties, with a wider range between Tg or thermal deflection temperature and melting point. Generally, PLA has a melting point near 390-420 degrees Fahrenheit, its recommended processing temperature. Also, PLA has a thermal deflection temperature that is below the thermal deflection temperature of many common plastics and slightly above 110 degrees Fahrenheit. In normal plastic processing, the plastic processing temperature is usually 10 to 20 degrees higher than the Tm or melting point of the plastic. In published data for PLA processing, the processing temperature is usually processed at a temperature higher than 390 ° F., which is the melting point of PLA.

  The PLA used in the biolaminate layer provided herein can be processed at temperatures above the melting point in extrusion film processing. Also, the PLA used in the biolaminate can be processed below the melting point of its viscoelastic state and can maintain higher crystallinity in the biolaminate layer. See, for example, US Patent Application Serial No. 11/934/508, filed November 2, 2007, the entire contents of that application being incorporated herein. According to an embodiment of the invention, the extrusion process for producing the biolaminate layer can be performed at a temperature sufficiently below the melting point, keeping the PLA in its crystalline state and the PLA in its viscoelastic state. Process. In one embodiment, three-dimensional profile alignment may be produced, such as flat sheet and edge banding and piece alignment of woodworking products.

  US patent application Ser. No. 11/934/508 teaches that PLA in combination with EVA-type and synthetic-type binders can be processed below the melting point of PLA. In addition, this teaches that fire retardants can be added. In the embodiments disclosed herein, the combination of binder and highly polar PLA includes fire protection materials up to the required level to reach Class I rates without the presence of materials that are extremely brittle and do not meet the requirements of PVC applications. It will be difficult. Although this technique is useful for producing highly resistant profile shapes, the addition of EVA is not necessary in these embodiments. Other forms of additives may achieve similar results when processed at temperatures below the melting point of PLA. Thus, embodiments of the present invention use various forms of bioplasticizer / biolubricant to replace the above-referenced binders. In addition, the embodiments also show that by increasing the shear rate and maintaining the processing temperature below the melting point of PLA, profiled extrusions with high tolerance can be produced.

  When PLA is processed at a particular temperature range where it is in an "elastic state" similar to rubber, it remains in the amorphous state and has an effect similar to that of various other elastomeric materials. In this state, the material is also less susceptible to humidity and misalignment. In fact, it has been found that it is advantageous to add various additives in profile extrusion if the shear rate at which PLA is in such an elastomeric state is higher during processing. PLA has a melting point of about 390 degrees Fahrenheit. Embodiments of the present invention teach that PLA can be processed at temperatures well below its melting point if there is sufficient shear rate. In this embodiment, the profile extrusion process is performed at about 280 to about 340 degrees Fahrenheit, more preferably about 300 to about 320 degrees Fahrenheit. Higher temperatures can be used by adding more fillers, but preferably below the melting point of PLA.

  Biolubricants such as natural waxes, lignans or plasticizers play an auxiliary role in this low temperature viscoelastic process. Waxes and plasticizers are preferably biobased materials. An embodiment of the present invention is that two component compositions that are processed into continuous profiles of profile extrusion using PLA and a plasticizer or biolubricant are processed at a temperature lower than their melting point and are highly resistant It will be described that profiles of composite shapes can be produced.

  In these processing conditions, in addition to adding various other polymer additives, in order to develop a product with broader final performance quality for various non-biodegradable profiled articles applications It is possible to mix various additives of liquid and solid, fillers and reinforcing agents. The PLA can be made into foam using a celuka die system, a blowing agent or a biofoaming agent to produce lightweight profile extrusions. Wood fibers, wood chips, paper mill sludge, agrifibers, wheat straws, minerals, fiber glass fibers, starches, proteins and other forms of fillers or reinforcing agents etc. may be added to the solid or foam profile shape . The resulting bioprofile may be generally tinted to match the print with the same pattern as the biolaminate composite and other biolaminates. This creates the ability to create an overall solution for buildings, offices, and commercial buildings to enable the aesthetic harmonization of environmental elements in architectural design.

  Fillers such as synthetics, natural minerals, or biomaterials may be added to the biopolymer in elastomeric form. The addition of these materials to the elastomeric state of the biopolymer allows it to stay below its melting point and minimize the crystallization of the biopolymer, allowing processing with much higher shear rates, and dispersibility It improves and the brittleness of the biopolymer is improved.

  As mentioned above, the biolaminate layer in the biolaminate composite assembly may include a colorant system. Coloring agents color the fibers by dyeing or other coloring methods by mixing with the biocopolymer and / or to provide a matching (consistent) profile with a single color and multi-color high aesthetic biolaminate May be added directly to the biolaminate layer.

  Biolaminate layers having PLA-based selective additives and selective additives may be sheet extruded to meet the requirements of PVC or HPL decorative surface products. The extruded sheet of the biolaminate may be treated above the melting point to obtain a clear non-crystalline biolaminate of the biolaminate, or above the melting point in the viscoelastic state to increase its crystallinity. It may be processed below. The biolaminate being extruded may be extruded with a thickness of 0.002 inches to 0.3 inches, but is more preferably 0.005 inches to 0.030 inches, 0.010 inches to 0.025 inches. Most preferably. The heat-extruded clear sheet of the biolaminate can then be treated with various rollers for both cooling and the purpose of texturing the front and back of the biolaminate. Top surface texturing can range from smooth high gloss levels to highly textured planes. For counter, table, and many cabinet door applications, a gloss level of 10 to 30 degrees is preferred so that scratches are not noticeable or light reflection is reduced. The back side of the biolaminate can be matched to the texture on the top side, but is preferably a low gloss flat surface to enhance adhesion during lamination. Although the biolaminate material can be transparent, adding the same or different textures on both sides can make the biolaminate translucent and difficult to see through.

  After the clear biolaminate is extruded, the biolaminate is a transparent to wood or agrifiber composite that provides a VOC-friendly, high-performance finish to the product, directly replacing liquid finishing. It can be used selectively in the same shape as a finish with a film.

  In some embodiments, the translucent biolaminate is directly printed on the top side, reverse printed on the back side, or in layers of the biolaminate using various printing methods and inks (discussed above) It can be printed. Printing methods include, but are not limited to, ink jet, rotor gravure, flexographic printing, dye sublimation methods, direct UV ink jet printing, screen printing with standardized ink or UV ink, and printing by other methods. Bio-ink can be utilized in the printing process. In order to maximize the adhesion of the printing ink, it is possible to heat the ink or the substrate before and after printing as one method of printing. In some cases, a first layer can be used between the biolaminate surface and the printing layer to improve the adhesion of such layers.

  The printing process can be used to print a single layer clear biolaminate, the printing being reverse printed on the back side which may be flat texture. The printing process wets the flat surface and increases the clarity of the biolaminate. Laminating the biolaminate by heating enhances its non-crystallinity. This may make the biolaminate more transparent and may result in higher quality printing. Because the printing is on the back of a clear biolaminate, the biolaminate has a thicker wear layer compared to the PVC product printed on the surface, and only the minimal layer to protect the aesthetic print layer Have no or no layer for protection.

  Various printing inks may be used, including solvents, UV curing, silk screen inks, and other forms of ink, as long as they have adequate adhesion and some stretch for thermofoil applications. In some test patterns, certain inks are too hard to break or lose adhesion during the lamination process. One suitable ink is a biobased ink (ie, bioink) such as Mubio for a Mutoh Valuejet digital printing system that provides a 100% biobased product that includes an ink layer.

  Printing on biofoil can be achieved by any of the above methods using direct, reverse or sandwich methods for biofoil to give the final product high design. Integration with digital printing also enables a large number of customized products. In many cases, printing can be directly printed on white biofoil with a clear protective liquid coating.

  In one embodiment, thin PLA films less than 0.010 inches and less than 0.005 inches can be directly printed in reverse by digital printers of various formats or other printing means. A well-textured, regenerated mineral fiber composite containing fiber-degraded minerals and bio-based binders is prepared by cutting to a suitable size, and a thermally activated adhesive It can be used on the top and side. The image of the PLA film can be in the form of a pattern, a photo, a symbol, or any artwork that is typically generated by a computer. The composite can be placed on a thermofoil machine with the printing film on its surface. The PLA film can be held for several seconds with heating up to about 140 degrees Fahrenheit. At normal thermofoil temperatures, such films may sag and holes may open during vacuum processing. The vacuum treatment can then be done under a warm film, which will then exhibit the texture of a hard stone-like mineral fiber composite. The resulting "Eco-art" can have high abrasion resistance due to the fact that the print layer is under the transparent film layer. The final product eventually has a bio content of about 30%, a content of regenerant of about 60%, and a natural clay content of 10% in balance.

  The biolaminate layer may comprise one or more layers of extruded biolaminate material. In fabricating multilayers, thermal lamination methods may be used to form the layers into a biolaminate surface layer. Each layer may be the same, similar, or may have certain, different functions. The multilayers of the biolaminate can be melted by heat and pressure, but in such melting, with a heat press system and a reasonable pressure of about 50 psi, the material has a melting point slightly lower than that of the biopolymer There is. Other means of fusing the two layers of the biolaminate may be used, such as adhesive double sided tape, heat activated adhesives, solvent bonding and other methods. When fused, these layers form a multilayer functional biolaminate such that it can be laminated or thermofoiled to a non-plastic substrate to form a biolaminated composite assembly.

  An optional layer of biolaminate composite or biolaminate composite may be laminated on a non-plastic substrate. Optionally, a paper, non-woven mat, woven mat or other form of substrate can be placed on the back of the biolaminate surface before being laminated to a non-plastic rigid substrate. Various manufacturers can use simple aqueous PVA glue adhesives of the art to firmly bond the biolaminate to non-plastic hard substrates. In addition, this may impart additional functionality of the biolaminate layer.

  In some embodiments, a heat activated adhesive may be used to adhere the biolaminate. This can be useful for cold press adhesives, such as PVA, which require the laminate on the bottom to absorb water and be able to bond without heat. The biolaminates of these embodiments are, for example, completely waterproof on both sides. In this way, heat treatment during lamination increases the "polarity" of the PLA and results in a high degree of adhesion required for specific applications. Another suitable method of laminating would be to use an adhesive that is heat activated or heat cured in a high pressure laminating process.

  The laminate may comprise a planar laminate or a three dimensional laminating process. Flat laminates are currently used in high pressure laminates to bond the laminate to wood or agrifiber composite substrates. A planar laminate is one that is then laminated together using pressure, based on the use of an adhesive or glue adhesive layer for the substrate or laminate. Planar laminates can use many types of glue adhesives and processing methods such as both hot and cold presses or pressure sensitive systems. In a hot laminating system, an improved adhesive can be placed between the biolaminate and the substrate.

  In order to produce multilayer biolaminate surfaces, usually multilayers of PLA film are used, and alternatively PET, acrylic, polycarbonate, PEEK, or other high performance plastics may be used as the surface wear layer. In some cases, PLA itself may be used as the upper wear layer. Hot melt may be utilized to bond all these layers into a multilayer single sheet biolaminate and produce a uniform sheet. Adhesives may be used to bond the layers, but hot melt may alternatively be used to facilitate performance in the hot lamination post-treatment of the biolaminate laminated to the substrate. Roll lamination, in which two hot rollers heat the material and "pinning" the layer into a uniform molten sheet, can also be one of the processing methods. Other methods such as hot pressing may be used, but hot roll laminating is preferred because of the continuous processing method and its ease of control.

  Thermofoil lamination or thermoforming is often used in three-dimensional laminates where non-plastic substrates are machined into three-dimensional parts such as table surfaces, work surfaces, cabinet doors and the like. An aqueous urethane adhesive can be sprayed onto the substrate surface. The heat and pressure using a vacuum press or a membrane press allow the biolaminate layer to be formed into a substrate, while the adhesive is activated and cured by heating.

  Profile wrapping is similar to thermoforming (i.e. thermofoil) but is performed using linear processing equipment to produce woodworking products, windows and other linear components. In this embodiment, the substrate is machined from wood or agrifiber composites to a linear woodworking product shape. In order to eliminate mechanical processing and reduce mechanical waste, profile wraps can also be made by shape extrusion from natural fibers or minerals and plastics. Typically, when using profile lapping machines, hot melt adhesive is used hot on the substrate or biolaminate, and then pressed using a series of small rollers onto the linear substrate Form a biolaminate layer.

  Linear wrap can be used to apply thin films on wood machined substrates. Usually, all these films are made of PVC. Because of the growing concern for the use of PVC and its negative impact on the environment, the present invention provides a truly green option for windows, door members, floorboards, woodwork products, and other linear building components. The biolaminate or biofoil defined in the previous patent application is manufactured in the form of a decorative film with a thickness of 0.010 inch or less. The film is cut and has an appropriate roll width. The various environmentally friendly substrates defined below are extruded into their final form. These can take various forms, from foams to solids, and are usually in the form of a composite matrix. Using a linear lapping machine, a hot melt adhesive, usually urethane, is used in the melted state and rolled on the substrate. Before hot melt, the glue adhesive can cool a series of rollers and can be pressured using a biofoil to form it into a surface. In some cases, the biofoil can be preheated to soften the material so that it can be formed into a composite article. The final part is a linear component that can be used in many buildings and components.

  For standard laminated surfaces, edge bands are required. Biopolymers, such as PLA, processed at temperatures below the melting point and in the visco-elastic state are similar to the production of biolaminates to produce profiles such as molded edge bands and other support components It can be used. In this embodiment, a tee molding or glued flat profile edge band mechanically attached to a non-plastic hard substrate is described. Bioedge banding can be done using the same biopolymer or biocopolymer system to provide harmonious beauty and performance. In addition, harmonized linear profile wrapped woodwork products can be extruded into wood, agrifurber or plastic fiber composites to create an aesthetically harmonized green system for solutions throughout the office or building Can be manufactured using a biolaminate surface layer laminated to

  Other means for performing edge banding or woodworking product profile alignment may be achieved using composite substrate profile extrusion in a continuous linear configuration, such as woodworking products. The biolaminate layer can be laminated using linear wrap processing methods and hot melt adhesives to create many environmentally friendly woodworking products as an alternative to PVC foam woodworking products and PVC wrapped woodworking products .

  Typically, high pressure laminates involve support products such as slit laminate shaped or profile extruded linear shaped edge bands. In embodiments of the present invention, the biolaminate layer may be scored or cut into strips for use as edge banding. The "cut" or cut biolaminate layer can then be laminated to the edge of the substrate with a hot melt adhesive, usually with a slight pressure. The biolaminate layer edge band may then be trimmed. Biolaminated surface layer edge bands can be printed or extruded in solid color and pattern.

  Some embodiments of the present invention maintain the crystallinity of PLA or other biopolymers throughout processing, and novel methods to maintain such crystallinity in final extrudates and sheet members. And the selective composition. Embodiments process at higher shear rates not recommended for the production of PLA products, and at extremely low processing temperatures, usually less than 320 or 300 degrees Fahrenheit. It treats materials in the elastomeric state at temperatures well below the melting point of the material, and also at 380-400 degrees Fahrenheit, which is the recommended processing temperature when the material turns completely into an amorphous state. In order to Conventional processing methods provide turbid pushers or clear, more fragile packaging materials.

  At this processing temperature, the material can be completely crystallized, but to create a completely non-crystalline material, it will be below this temperature and processing parameters. The result can be turbid, but can have sufficiently high flexibility while maintaining a high degree of mechanical performance.

  By maintaining the crystalline or partially crystalline state by the method of treatment in embodiments of the present invention, the viscosity of the polymer can be significantly reduced and advantageous properties for the profile application and products that can be substituted for extrusion applications can be maintained. Also, at the processing parameters of embodiments of the present invention, the material may have different rheology and melt index that allow for processing of the extruded three-dimensional article.

  Additives may play an auxiliary role in these embodiments and still maintain the crystalline state of PLA or a mixture of PLAs. Nanomaterials, fillers, fibers, proteins, starches, wood flour, wood fiber waste from mills, and other materials increase the nucleation of PLA crystal nuclei and affect the crystalline state of the material. By treating at temperatures well below the melting point and using high shear rates, it will be possible to keep the PLA in a non-breaking condition, which will better meet the requirements for the desired properties and applications of the PVC product. Testing of other crystal nucleating agents, fillers, fibers, and materials has been found to produce positive results using this novel processing method.

  The sheet biocomposites can be reheated and post-formed into various molded articles for use as sinks or other three-dimensional post-formed products. This processing method can be achieved by conventional vacuum forming or simply placing the sheet in a mold after overheating it.

  Molding can be done using biocomposite particles, using inexpensive molding metals, but this processing method does not require pressure to mold. Due to the reduction of air holes in the melt process, the biocomposite particles are placed in a mold with two sides containing extra material in the "sprure" which supplies additional material. In the case of moldings such as sinks where larger scale molding is required, the bulk density of the biocomposite particles is increased due to the smaller biocomposite particles, thereby maintaining the granite-like appearance The range of flow is narrowed.

  Method of manufacturing cellulose biolaminate composite assembly

  Embodiments relate to a biolaminate assembly product utilizing a layer of non-penetrable paper and a dry film of extruded biopolymer, and a method of manufacturing the same, wherein the non-penetrable paper and the biopolymer film are heated once and then added. Pressed and placed in water, the biopolymer film changes its viscosity, allowing it to penetrate the paper, impregnate, and melt the multilayers into one composite. This structure may be used in decorative surface applications or structural composite applications such as use as decorative surface laminate layers. Embodiments relate to biolaminate assembly products and methods of making the same using a paper layer that has been impregnated or resin impregnated, in particular a decorative surface laminate layer. Embodiments of the present invention include a biolaminate assembly using a permeable paper that is substantially free of formaldehyde emissions. Such embodiments may be used as an alternative to high pressure laminates. Other embodiments use standard methods in conjunction with existing forms of formaldehyde based laminate manufacturing methods. A further embodiment would be to improve the molding characteristics without the need to use pressure during resin manufacture or to use expensive modifiers.

  In general, such methods may include providing a first paper layer, providing a bio-based polymer film layer, and providing a second paper layer. The first and second paper layers can be at least partially penetrated into the biobased polymer derived from the biobased polymer film layer and / or the additional biobased polymer source. The first paper layer, the biobased polymer film layer, and the second paper layer can be melted under the means of heat and pressure to form a biolaminate structure. Melting can be done, for example, between about 20 and about 1500 psi. In some embodiments, biolaminate layers such as PLA biopolymers can be dry extruded film molded articles.

  These various steps are described in more detail.

  Any suitable, woven or non-woven cellulose paper may be used. Suitable paper is, for example, plain paper, kraft paper, surface-treated paper, wood paper, recycled paper, decorative paper, printing paper, fiber reinforced paper, fiberglass reinforced paper, thin wood veneer, fire resistant paper, chemically treated paper, pH Adjustment paper, or a combination of these. Cellulose paper can be biobased paper taken from renewable plant fibers such as hemp, bagasse, wheat straw and corn stover.

  Various methods may be used to impregnate the cellulose layer with the biopolymer. These include composite pressing of a bundle of at least one impermeable paper and at least one biopolymer film, direct application of the melted biopolymer to the impermeable paper, and impregnating the cellulose paper with liquid biopolymer .

  In composite pressing of a bundle of at least one impermeable paper and at least one biopolymer film, the bundle is treated under the conditions of heat and pressure in a hot press. Temperatures may range from, but not limited to, 310-400 degrees Fahrenheit, and pressures may range from 20-1500 psi. The remaining moisture content of the paper and the chemistry of the paper will affect the time required to fully penetrate and impregnate the paper in the press system and will also affect the dynamic rheology of the biopolymer. This method eliminates the current need for the paper to be infiltrated prior to composite pressing.

  In embodiments where the melted biopolymer is applied directly, such as, for example, melted PLA, the melted PLA can be applied directly using roll coating. Various additives may be mixed into the paper or molten PLA prior to coating applications to enhance properties or processing rates. The various paper layers are placed on a hot melt roll coating machine, and molten liquid PLA is applied directly to the paper and rolled between cooled rollers. The coated paper layer is then bundled to the desired amount of layer and placed under heat and pressure in a composite press. The temperature for infiltrating, impregnating and melting the layer is from 310 to 400 degrees Fahrenheit and the pressure is from 20 to 1500 psi in order to create a series of structural composite structures.

  In embodiments using a liquid biopolymer, woven or non-woven cellulose paper or various forms of biofiber paper may be impregnated with liquid PLA or LA. The paper can then be immersed in a low viscosity liquid LA bath that is sufficiently impregnated with the paper. Lactic acid is a precursor of polylactic acid and can be of low viscosity to impregnate into paper.

  The LA penetration paper can then be dried using heat, air, or other drying methods commonly used to dry the penetration paper. In some embodiments, the dried and permeated first paper layer can be textured. The core layer of the penetration paper may be plain paper. The surface layer may be in the form of a pattern, color or image pre-printed by standard printing means, including but not limited to extensive UV digital printing.

  The additives may be contacted with paper or resin, one or more desiccants, polymerizers, peroxides and other crosslinkers, colorants, etc., and fire retardants.

  Once the LA permeable paper has dried, one or more layers can be placed on the textured paper, metal or composite platen. The platen can texture the final product laminate and also provide uniform cooling while the laminate is curing and cooling.

  In one embodiment, the printed LA permeable paper can be placed on top. The single layer or bundle of layers of LA permeable paper can then be heat melted and formed into a solid laminate sheet. The temperature ranges from about 120 to 300 degrees Fahrenheit until the LA is sufficiently penetrated into the fiber, the layer is dissolved, or the desired polymerization occurs.

  Hot melting may be performed using a hot platen press, until the pressure range exceeds 20-1000 psi, depending on the desired specific gravity or hardness of the final product biolaminate. In other embodiments, a hot roll press may be used to heat and melt the layer into a solid laminate.

  A single layer of paper can also penetrate and cure using lactic acid polymers that can be used as an underlayer. In this case, the penetration paper is manufactured and can then be heat fused or adhered to a thin bio-based film, such as a polylactic acid sheet with a colored backcoat, to create a decorative laminate, or digital Can be imaged. Penetrated LA paper provides a paper cover that can be easily laminated to various rigid substrates such as particle board, MDF, agrifiber composites, mineral fiber composites, and other types of thin or thick rigid composite structures And this provides a waterproof, decorative cover option that is totally formaldehyde free.

  Another embodiment involves laminating a transparent polylactic acid surface layer with a LA-permeable paper to provide a very stain resistant property and a high degree of chemical resistance, abrasion resistance. In addition, this biobased wear layer can be repaired with the same processing methods as used for petrochemical-based polymer solid surface materials. Thus, in some embodiments, an overlay layer can be provided that includes thermosetting and thermoplastic standard overlays, mineral plastic overlays, bioplastic overlays, or wear layer surface overlays.

  Other methods for curing liquid LA resin impregnated paper can be made by the use of electron beam or UV curing techniques where a photoinitiator is added to the LA resin prior to impregnating the paper. The LA resin impregnated paper is then placed under electron beam or UV light for final curing of the material.

  Method of producing decorative fused random particle / bio composites

  Usually, PLA has a melting point close to the recommended processing temperature of 390-420 degrees Fahrenheit. Also, PLA has a thermal deflection temperature of 110 degrees Fahrenheit, which is lower than the thermal deflection temperature of many common plastics. Processing temperatures in the art are below the melting point Tm of the biopolymer. It is recommended by its manufacturer that PLA be processed above 390 degrees Fahrenheit. At 390 ° F., the material is too viscous to maintain individual particle areas. Processing methods in the art are based on a thermal deflection temperature range in which the particles soften to an elastomeric state that allows deformation with minimal energy conditions without melt flow interfering with the particle area. Generally, for coated PLA or PLA based biocomposite particles, it is preferred that the temperature be 350 degrees Fahrenheit just prior to 200 degrees Fahrenheit.

  At thermal deflection temperatures, ie, between the glass transition temperature and the melting point, PLA particles can be easily deformed with minimal pressure, a minimal energy state from mere gravity or a matrix that does not melt PLA. This is used in the present invention to melt polar biocomposite particles comprising PLA matrix resin into a random and fractal shape resembling natural granite. In this invention, the matrix resin can be a biocopolymer using PLA in combination with hydrogenated soy oil or natural wax. Waxes provide lubricity, plasticity, and coupling of biocomposite particles. The biocopolymer can be 99% PLA and 1% hydrogenated soybean oil, and both can be included between this ratio and a 50:50 ratio.

  Individual biocomposite particles can be manufactured using a wide range of different fillers, fibers, decorative materials, colorants, and other smaller particle forms within the biocomposite matrix. This gives the individual particles the appearance of having three dimensions or depth of field. In general, it is preferred that these biocomposite particles not have a uniform shape, ie, have a shape similar to that of broken glass or shell-like broken pieces.

  Decorative biocomposite particles can be manufactured by two main methods, which can create many aesthetic and geometric particle shapes. The biocomposite particles can be formed by grinding it into a flocculent fiber matrix utilizing recycled paper. This is similar to that of cellulose insulation which is used to be able to add fire protection to fluff cellulose and which is suitable in practice.

  The cellulosic material is coated by spraying colorant onto the fiber during mixing. The fibers quickly absorb moisture in the paint or colorant, and the loosened fibers create individual particles. In the coating process, various forms of sprayable paint are used which coat the outside of these particles. The particles are dried to a very low moisture content, typically less than 0.5%. In the present invention, various liquid coloring system forms may be used, such as acrylic aqueous colorants, oil-based paints, latex paints, or vegetable oil-based paints. It is preferred to use aqueous or natural oil based paints to maintain the environmental protection of the product. Natural colorants can also be used in liquid carriers.

  In a secondary processing method, a hydrogenated vegetable oil such as hydrogenated soybean oil is melted and sprayed onto the colored particles. This further strengthens the fiber and results in individual particles. The particles are cooled and classified by size and color. Other forms of natural waxes may also be used in addition to or instead of hydrogenated soybean oil. Natural waxes include, but are not limited to beeswax, vegetable oil waxes, synthetic waxes, and other similar materials. Natural waxes have two main functions: to coat the cellulose coated particles so colored as to be free of moisture again and to impregnate the fibers more firmly. In addition, in a further step, the biopolymer as part of the wax or hydrogenated oil acts as a biolubricant / bioplasticizer / biocoupling agent for the final product and the resulting biolaminate product Be "donated" to The particles can be sized prior to application using standard screening methods. The particle groups of each size may be coated with a unique color, and then the full size and the full color may be remixed to form a biocomposite particle blend.

  Generally, random shapes of biocomposite particles, including cellulose, colorants, and hydrogenated vegetable oils, can be produced in various sizes or shapes, depending on the liquid to solid ratio of the decorative biocomposite particles. In some cases, using a low ratio of liquid colorant to cellulose fiber may result in many of the recycled paper not being coated. Thus, the final product has a multicolored decorative appearance.

  The coating process with liquid colorants and the secondary process of coating with wax or hydrogenated vegetable oil make the material of very low bulk density available for use in feeding the extruder. Feeding ordinary newsprint paper into an extruder can be extremely difficult due to its fluffy nature. In one example, when low disintegrating cellulose (10% by weight) is synthesized with 90% by weight bioplastic pellets, 10% by weight cellulose means about 15 times the pellet volume. Furthermore, the mashed cellulose has no flow and creates additional problems in processing. Fully cured vegetable oils or waxes may also be used to fully impregnate the fibers. To achieve this, between 1% and 50% by weight of liquid wax can be added to the pigmented coated cellulose. This amount not only impregnates the hydrophilic fibers, but also pushes some of the fibers from the fibers into a narrow volume during the synthetic processing provided to the matrix bioresin system.

  This method allows cellulose to have a higher bulk density than conventional bulk processing can handle from conventional bulk density. The resulting biocomposite decorative particles range in size usually from 0.1 inches to over 0.75 inches, and have the appearance of loosely shaped, randomly shaped fibers rather than uniform particles. Have.

  Coated decorative and colored biocomposite particles comprising a coloring agent and a hydrogenated vegetable oil or wax are not uniform in shape and do not mix completely. In this state, the colorant / wax is dominated by the coating ratio rather than the completely mixed state.

  The decorative biocomposite particles or biocolorant system is then subjected to an extrusion process at a level of 1% to 30% with the bioplastic or biopolymer material. In the extrusion process, heating is performed to mix the materials. In this process it is preferred to minimize mixing, shear rate, and heating in order to maintain the random fractal beauty without homogenizing the mixture. Various bioplastics or biocopolymers such as polylactic acid, PHA and other natural bioplastics provide good matrix resin, and their transparency provides additional depth of field with regard to the beauty of the final product .

  The material is heated until all of the biocomposite particles melt. Because the polarity of PLA in biocomposite particles is high and the colorant may usually contain various additives and modifiers, the particles melt and form a characteristic boundary at the particle interface. As the material melts, these boundary conditions are mixed and unshaped to create high aesthetic value.

  The wax provider plays a role in the extrusion process. In the extrusion process, when the bio-coloring agent is compressed and heated, the wax melts before the bioplastic softens or melts. This impregnates the hydrophilic fibers and provides extra melted wax to the PLA. This process also keeps the temperature below the melting point of PLA and in a visco-elastic state, as the liquid wax is "kneaded" into the elastic PLA. The provision of wax provides bio-lubrication, bio-plasticization, bio-binding of colored bio composite particles and also provides specific flow dynamics that enhance the aesthetics of the product in addition to aiding mechanical properties of the final product Do.

  In extrusion processing using decorative and practical biocomposite particles, low shear rate processing may be useful to reduce the breakdown of the fine particles into a homogeneous form of the mixture. By maintaining fine particles using low shear rates and processing temperatures below the melting point of PLA, the aesthetic value of the material can be maintained.

  In the extrusion of PLA biocomposite particles, it is important to maintain the temperature below the melting point of PLA and to process in an elastomeric state above the thermal deflection temperature. This also makes it possible to prevent PLA from becoming crystalline and maintain its amorphous nature. PLA is usually processed at temperatures well above 390 degrees Fahrenheit to crystallize PLA and produce a clear film for packaging. However, in the industry, it is important to operate at a temperature of approximately 280-360 degrees Fahrenheit, well below this temperature range. In addition, by treating the PLA biocomposite particles with the fine particles at this temperature and in the elastomeric state, it is possible to obtain an extrusion or profile during the extrusion process.

  Method of manufacturing plywood laminate

  The plywood substrate can be in contact with the adhesive layer. The adhesive layer may be in contact with one or more biolaminate layers. Also, plywood substrates may be in contact with one or more biolaminate layers. The biolaminate layer can comprise multiple layers, such as thin films. The plywood substrate may, for example, be further in contact with the rigid substrate.

  The layer is laminated with two clear adhesive layers, using a continuous roll press or platen press, so that wood can be seen through the textured film layer of the upper biopolymer (biolaminate layer as a film) It can be done. The adhesive can be a cold set, hot melt, or heat activated adhesive system used for laminating, but it is desirable that it be transparent so that the appearance of a real wood veneer board can be seen. Preferably, a biobased adhesion system is used to complete the 100% biobased veneer product.

  Other embodiments include a light colored biolaminate layer (thin film) to omit the wood stain liquid dyeing process. Many wood veneers are difficult to dye due to the formation of wood species. The film can be tinted by mixing the clear color light tint directly into the film or coating the back with a clear color paint by standard plastic mixing techniques.

  Another embodiment is to back print additional wood grain patterns to enhance the value of cheap veneers that can mimic more expensive wood grades. Biofilm layers (thin biopolymer films or biolaminate layers) can also be laminated to the wood veneer board 702 using different methods to create different beauty. One method involves the use of a thermofoil machine in combination with a heat activated adhesive system and a thin biofilm top layer. Thereby, the biofilm tightly coats the texture of the wood veneer to highlight the wood grain pattern of the natural eye. Biofilms, wood veneers, and other methods of laminating substrates use various heated planar platen treatments with smooth or textured sheets to provide a surface texture unique to the veneer substrate. There is something to do.

  Biofilms generally have lower molding points than conventional petrochemical-based polymers. This enables the formation of three-dimensional laminates and complex contoured shapes of bioveneboard at lower temperatures. For this reason, the quality of the wood veneer is maintained, and furthermore, the wood veneer is not discolored by excessive heat in the three-dimensional laminating process.

  For example, a biopolymer film such as PLA can be extruded into a film that gives downstream texture a specific texture and gloss to enhance the appearance of wood veneers or to meet specific surface performance requirements. Films can be produced, for example, in large sheet or roll format.

  The biolaminate top layer can be a continuous film or sheet product having a thickness greater than about 0.001 inch to about 0.050 inch. The upper layer may also include surface textures that provide specific beauty and practical specifications.

  Non-biodegradable and / or softened biopolymer profile

  Polylactic acid is classified as a biodegradable or biocompostable polymer derived from corn lactic acid. The first applications are environmentally friendly packaging applications and fiber applications that promote biodegradability. When processing PLA, PLA is processed at a temperature above its melting point which converts it to an amorphous clear plastic. At this point, the material is fragile and degradable under certain conditions.

  In some embodiments, no binder may be used during PLA processing, and PLA crystal profiles with high tolerance may be produced. The use of a visco-elastic processing method that is processed at a temperature lower than the melting point of PLA or modified PLA at extremely low shear rates maintains high melt strength that is sufficiently resistant to profile extrusion and produces tough "unbroken" parts. In this process, it is preferred that there be some form of "lubricant" such as a biobased such as a natural wax or an oil. Second, although synthetic lubricants may also be used, it is preferred that biobased lubricants be used to maintain the highest biobased content in the product. Lubricants are also masters of certain colors found in plastic colorants that maintain the high crystallinity and melt strength required for this process and product, with a sufficiently low input of share heat. Also seen in batch (materbatch). Colorants or nucleation agents also have a positive effect on maintaining a high degree of crystallinity in PLA or modified PLA extrusion. Colorants affect plasticizers, potential crystal nucleation, and lubricants.

  By adding a bioplasticizer such as Lapol or Halstar, biobased soft touch materials can be produced to a high degree. By maintaining PLA with lubricating oil in combination with the viscoelastic processing method, hard profile portions with high degree of crystallinity and toughness that can not be biodegraded can be produced. These nonbiodegradable moieties are particularly useful as biocomposite substrates.

  By using the viscoelastic processing method, Halstar's bio-plasticizer, polylactic acid can be processed to make an alternative to vinyl upholstery material. The viscoelastic treatment method also improves the toughness required for upholstery and provides an environmental protection solution for plasticized PVC vinyl.

  In this form of the product, the printed layer of bioink may be sandwiched between two flexible PLA layers, the upper layer of which is transparent, but does not require printing. In many cases, colorants for coloring the first film may be used to match up with various vinyl or leather materials. Skin texture may be embossed on the surface.

  Nanocellulosic materials can also be added to the flexible PLA blend to increase the strength of the upholstery material.

  By using the viscoelastic processing method with Halstar's bioplasticizer to process polylactic acid, a "soft" and flexible thick sheet of polylactic acid is produced, which sheet can be used as an edge band for soft touch Cuts can be made so that it can be cut into pieces.

  By using Halstar's plasticizer and visco-elastic processing method, the resulting polylactic acid sheet can be softened. Impact resistance is also affected by this. By plasticizing the material without a completely soft touch, the impact resistance of the polylactic acid sheet may be higher and exceed the impact resistance of PVC.

  Method for producing biocomposite material

  Polylactic acid is a common bioplastic currently used for food packaging. Polylactic acid is a very hard and fragile plastic and is not suitable for replacing flexible PVC film or sheet applications. PLA is in a visco-elastic state at a temperature below the melting point using the methods described herein to maintain a high degree of crystallinity and to facilitate treatment with the bioplasticizer. It is processed. Generally, current approaches to PLA additives have focused on impact modification to reduce brittleness, but have sufficient effect to create the flexibility required for such applications. Not. New forms of plasticizers, such as Halstar's plasticizers, may be mixed with polylactic acid to the extent that the polylactic acid is sufficiently soft to meet the flexibility or durometer required for this application. Viscoelastic processing methods improve processing and maintain the toughness of the final product. Typically, the amount of plasticizer ranges from 10 to 50%, and more preferably about 30 to 40% relative to PLA in our viscoelastic processing method. The result has a durometer similar to that of flexible PVC.

  Thus, in some embodiments, it may be useful to have the bioplasticizer proportion be relatively high, ranging from 10% to 50%. Such high proportions are particularly useful in producing three-dimensional biocomposite substrates. Powdered PVC is mixed with the liquid plasticizer in a proportion of about 30% to produce flexible PVC. This still maintains the powder that can flow into the extruder in a one-step process. In contrast, PLA is usually manufactured in pellet form, and it is difficult to uniformly mix such pellets and liquid in a standard extrusion line. By extruding at a point below the melting point of PLA, treating the PLA in a visco-elastic state maintains a high degree of crystallinity and facilitates better mixing with the plasticizer. In addition, the extruded PLA is generally improved in its toughness. In some embodiments, the processing method may use a two-step screw extrusion system in which a liquid plasticizer is added to the pellet. The second option is described below.

  By using a jet mill manufactured by CCE Technologies, it is possible to maintain a sufficiently low temperature so that the PLA is not affected and the material dissolves or agglomerates. Conventional mechanical milling operations on plastics such as PLA induce a large kinetic energy input that causes the material to melt or flocculate, resulting in inability to produce a uniform powder or clogging the mill.

  Fines can be produced by a jet mill using cold compressed air. In addition, various minerals may be added to the PLA in a jet milling process that can add milling media not only to aid milling but also to add functional value to the final product. The addition of minerals or mineral mixtures such as quartz, calcium carbonate, clays, or other minerals in a proportion of more than 1% and less than 50% greatly improves the jet milling process and makes the particles more uniform and finer PLA particles You can get Along with chemically treated cellulose fibers, other mixtures and mineral sources of minerals such as paper mill sludge of toilet paper mills already containing high grade minerals such as clay and calcium carbonate may be used. This adds the functionality of a flexible product line.

  Various methods of PLA processing for biolaminate formation may be applied in PLA processing methods for forming biocomposite substrates, such as three-dimensional biocomposite substrates. In some embodiments, such biocomposite substrates are conventional double screw or single screw extrusion systems that heat plastics, bioplastics, or resin binders to flow such materials into a forming die system. It can be extruded using Some applications include molding of siding, woodworking products, door members, window members and other forms of linear members. The substrate can be placed on a linear foil wrap machine that applies a biolaminate, such as a biofoil, to the surface of the biocomposite substrate upon heating to form the biolaminate on the surface of the biocomposite substrate after cooling. In addition, this system typically uses a hot melt adhesive such as urethane to pressure the biofoil to shape the surface.

  The flexible sheet is extruded using a single screw or double screw extrusion system, where a plasticizer is added to the PLA pellets and treated at 300-360 degrees Fahrenheit well below the melting point of 390 degrees Fahrenheit of PLA. As a result, in the final product film, a very high degree of crystallinity is maintained and the toughness is improved. The thickness of the film is 2 mm to 30 mm or more depending on the application. The flexible film is cooled and rolled.

  The film can then be printed with newly developed corn, soy, and cotton derived biobased printing inks. Since the corn part of the printing ink is based on lactic acid, the affinity of lactic acid for polylactic acid is very good. When tested on PVC using this lactic acid ink, its adhesion was limited. The biobased inks currently marketed by VuTek, EFI Bioink, MUtoh etc. are all compounds of lactic acid with other bioadditives and biobased binders.

  use

  Biolaminate composite assembly, table surface, desk surface, cabinet door, cabinet box, shelf material, woodworking product, wall board, laminate flooring, counter, processing surface, display panel, office partition, bathroom partition, laminate flooring And other areas are biolaminate systems in combination with non-plastic substrates and adhesive layers to create a truly "green" solution that meets the growing demand for more environmentally friendly products. Can be used.

  Biolaminate composite assemblies can be manufactured into flat laminates, thermofoil three-dimensional, or various forms of cabinet doors based on integral profile wrap members, and all these combined into various designs of cabinets and walkway doors .

  The biolaminate composite assembly may be formed as an eco-art and may include mineral composites that are well textured. Various mineral composites that are well textured can generally be used for ceiling tile applications. Ceiling tiles and compositions with various surface texture treatments can be used. Ceiling tiles can usually be used for fire protection materials, so that the above tiles and panels can meet these specifications.

  Various conventional plasticizers, preferably, to create a more flexible biolaminate surface layer, which may be manufactured as a wallpaper adhering to a wallboard, as a biolaminate surface layer may also be substituted as a PVC vinyl wallpaper. It can be plasticized to a high degree using biobased plasticizers. In this embodiment, a secondary non-woven can be laminated to the back of the biolaminate layer to improve performance while maintaining flexibility. The above highly plasticized biolaminate layer can also be used as a substitute for flexible PVC print media.

  The biolaminate composite assembly uses PLA biocopolymer biolaminates based on plasticizers or processing aids and adding "nano quartz" additives to the biolaminate surface layer is sufficient for use in counter applications Wear resistance, temperature resistance is provided. Currently, food grade surfaces are primarily composed of HDPE and stainless steel. Stainless steel is expensive, and HDPE has the possibility that food and liquid may get into scratches and cuts on the surface. "Nano-quartz" technology can improve surface performance and durability. Also, the biolaminated laminate assembly integrated with quartz offers a low cost option as an alternative to expensive granite and other solid surface processing composites. Here, solid surfacing composites are used for kitchen counter surfaces, tables, and other areas where higher performance is required. These biolaminate layer forms may be formed by planar lamination or thermoforming into a three-dimensional processed surface that is used in the form of kitchen or other counter applications.

  Decoratively fused random particle biocomposites are useful for kitchen or commercial counters, processed surfaces, flooring, flooring, wall tiles, pelvic, forehead worth of commercial applications, solid in other commercial applications The materials of the present invention may be used as a direct substitute for surface processing or other forms of decorative material applications. In addition, the high UV stability of PLA allows it to be used in outdoor applications such as billboards, building panels, tables and other applications.

  Three-dimensional biocomposite substrates can be used for various purposes. The general industry includes profiles that replace commercial baseboards, soft touch edge bands, door crossbars incorporating both hard and soft modified PLAs, corner beads for seat locks, and other PVCs. Other specific examples of three-dimensional biocomposites include a three-dimensional composite molding table integrated with biofoil, a counter combining biocomposite and biolaminate, and an integrated biocomposite and biofoil. Bio-based woodworking products, waterproof flooring integrating bio-composite and bio-laminate, three-dimensional cabinet door integrating bio-composite and bio-foil, bio-composite and bio-laminate (FR) A three-dimensional walkway door that integrates the three-dimensional desktop / surface processing product that integrates the biocomposite and the biolaminate, a window member that integrates the hybrid composite and the biofoil having high UV resistance, , Siding part integrated with foamed plastic or bio composite and bio-foil with high UV resistance Including the.

Flexible Sheet Products and Signs In some embodiments, the biocomposite substrates provided herein are, for example, as an alternative to flexible decorative PVC products used, and also to signs, wallpapers, and chairs. It can be used as an alternative to flexible decorative plastic products such as upholstery materials. Additionally, biocomposite substrates can be printed with biobased ink to provide flexible, green, decorative signs. In such embodiments, a flexible PLA sign may be molded comprising a flexible polylactic acid film using a bio-based plasticizer that combines with lactic acid based printing ink to produce a flexible film.

  PLA is a biopolymer used for packaging but is not truly biodegradable and can be composted under very specific compositional processes. In fact, PLA is a very good outdoor surface processing solution compared to petrochemical-based polymers because it is UV resistant, waterproof, highly stain resistant. The biolaminate of the embodiment of the present invention enables surface processing of a decorative layer that can be laminated to a structure, and provides a member or product with high aesthetics and utility.

  Currently, PLA is extremely difficult to extrude into profile molding due to its poor melt stability, high melt index, and other factors. Embodiments of the present invention describe methods of extruding PLA or other biopolymers, and compositions that ensure that the material does not degrade in various commercial profile extrusion applications and products over a longer period of time. Second, embodiments of the present invention are directed to processing methods that provide high quality profiles and material compositions that can directly compete or replace current harmful plastics such as PVC in the architectural, commercial, and industrial markets. Describe. Profile extruded PLA or PLA biocomposites can be used as a substrate for biolaminate surface layers or can be colored to match up with biolaminates. This biolaminate composite system, combining environmentally friendly substrates and biolaminates derived from rapidly renewable resources, is a future processed surface and other commonly used HPL or PVC thermofoil members. Provide a true environmental solution for your application.

  Example

Example 1
The PLA pellets were placed in an extruder and the temperature was set 20 degrees Fahrenheit above the melting point 420 degrees Fahrenheit as recommended for the processing temperature Natureworks. The substance was expelled from the die (mold) as honey adhering to the die. The temperature was lowered to 310 degrees Fahrenheit, which is more than 80 degrees Fahrenheit below the melting point. The rotational speed (RPM per revolution) was increased to add an input element to the material, the shear rate. The resulting molded article maintained its composite shape with minimal distortion.

Example 2
The PLA pellets were placed in an extruder using a sheet die at a processing temperature of 380-420 ° F. to produce a clear sheet. The sheet was fragile, and when it was bent it immediately got wrinkles. The resulting sheet was flat laminated to wood particle board under heat at 150 degrees Fahrenheit and 50 psi pressure using a heat activated glue adhesive. The material showed very good adhesion to the substrate.

  The same sheet as above was laminated by the cold laminating method generally used in HPL using PVA and cold press laminating method. The PLA biolaminate sheet did not adhere to the substrate and peeled off immediately.

  The PLA pellets were placed in an open two-stage screw extruder, the processing temperature was lowered to 320 ° F., and the material removed from the extruder was aired in front of a die section.

  The PLA was placed in an extruder and processed using a sheet die at a process temperature of less than 330 degrees Fahrenheit well below the melting point. The resulting film was cloudy but had very high melt strength. After cooling, the material is obviously more flexible and has better properties. The thickness of the biolaminate was 0.015 inches.

  The resulting sheet was hot-laminated to the agrifiber substrate containing wheat straw by use of a heat activated glue adhesive and pressure. As a result, the adhesion strength is very good and in the adhesion test the fiber was pulled away from the particle board sticking to the biolaminate, which means the adhesion is better than the internal bond of the particle board of wheat Show that.

  The resulting biolaminate sheet was placed in a membrane press with a machined three-dimensional substrate, which had previously been coated with a urethane that was activated by heating. A pressure of less than 50 psi was applied at 160 ° F. for just over 2 minutes. A similar substrate, glue adhesive, and method were used to perform a membrane press in a comparative example test using a 0.012 inch thick PVC film primed with a chemical solvent to improve adhesion. . The biolaminate molded article showed stretchability and moldability similar to PVC. When the PVC and biolaminate samples are subjected to adhesion tests, they should have adhesive strength comparable to that of PVC, even without using chemical primers to improve the adhesion of the biolaminate samples. I understand.

  The biolaminate film was reverse printed using a solvent ink jet system. Initial ink adhesion appeared to be sufficient from cross hatch and tape peel tests on the surface. The reverse printed biolaminate was then subjected to a heated and pressed thermofoil in combination with a heat activated urethane adhesive. The ink layer is in contact with the laminated adhesive layer and the substrate. After treatment, a peel test was performed. The ink separated from the biolaminate film did not have sufficient adhesive strength. The surface of the biolaminate was treated with a chemical solvent prior to printing and a second test was performed. An improvement in adhesion was observed but was insufficient for this application.

  A clear biolaminate was direct top printed and coated with a clear liquid urethane topcoat. The top printed biolaminate was hot laminated to the substrate. The adhesion between the clear biolaminate and the substrate was sufficient and was seen after the fibers were torn off on the substrate.

  UV curable screen printing ink is used on the back of the clear biolaminate or reverse printed. Using a urethane adhesive activated by heating, the printed side was brought into contact with the adhesive layer and the substrate layer, and heat and pressure were used to thermofoil the biolaminate. After the fibers were torn off on the substrate, the adhesion was significantly improved over the standard solvent ink printing process.

  Two three dimensional cabinet doors were machined from medium quality fiberboard and molded into a classic raised panel cabinet door. The first door was processed with a 0.010 inch thick PVC thermofoil with a membrane press and a standard heat activated thermofoil treatment. At a pressure of 50 psi, the temperature was 170 ° F., and the press time was 2.5 minutes. The second door was processed in the same manner except that a biolaminate surface layer was used instead of the PVC film. The results of the molding process surprisingly had the same stretchability and moldability as PVC. In PVC, a primer was used on the back to improve adhesion whereas in the case of biolaminate, no paint was used, but the adhesion to a very similar substrate from the peel test It was observed. The pull-down properties of the edge portion of the cabinet door were also the same between PVC and biolaminate due to the above molding process.

  The same urethane adhesive as above was used to thermoform the PVC film and the biolaminate surface layer to a substrate in the form of a three dimensional cabinet door. Both PVC and biolaminate were subjected to independent testing according to the high pressure laminate standard (NEMALD 3). The data results showed that the biolaminate improved in stain resistance, table abrasion resistance, scratch resistance over standard PVC decorative surfacing products.

  A piece of high pressure laminate of WilsonArt Standard Great was laminated to a wood particle board substrate using an adhesive adhesive. The biolaminate sheet was also laminated to a similar wood particle board substrate using a similar adhesive adhesive and tested independently in accordance with the NEMALD 3 requirements standard. In this test, the biolaminate had an impact strength of more than 5 times, an improvement in stain resistance, a scratch resistance of more than 2 times, and an improvement in other performances.

  In order to subject PLA to a number of thermal histories and to evaluate its state change, different results after secondary heating tests were examined. A film produced in the visco-elastic state at 340 degrees Fahrenheit below the melting point resulted in a 0.010 inch thick film. The films were reverse printed using a UV curing ink system and a direct printing ink jet system. The samples were divided into two groups and in group I the samples were tested for impact, hardness, scratch resistance. In Group II, the samples were hot-laminated using a membrane press and heat activated urethane for 2.5 minutes at a temperature of 170 ° F. until the glue adhesive was cured. The Group II samples were tested in direct comparison with the Group I samples. Group II showed a harder surface with improved scratch resistance, but the impact resistance was lower than group I.

  A wood bioplastic profile extrusion containing approximately 20% wood fibers was performed at 310 ° F. to 320 ° F. to obtain a piece of linear shaped woodworking product. A thermally activated adhesive on the biolaminate surface layer was used on the back of the biolaminate surface layer and compared to a PVC film treated using the same method. The biolaminate surface layer had a formability that was surprisingly similar to the adhesion that was very similar to that of PVC film.

  The 3M adhesive adhesive used for lamination was sprayed onto the back of the biolaminate layer and the planar wheat board agriferr substrate. One minute after removing the volatiles, the material was also laminated using the pressure of the roller system. A second sample of PVC decorative film was also used for the second sample. The biolaminate has improved adhesion.

Example 3
5% of soya wax was added to PLA and extruded with profile die. As the temperature was lowered to 290 ° F., a material with sufficient melt strength to maintain profile molding was molded with a smooth and strong integrity. When the shear rate was increased, the formability was improved and the surface smoothness was also improved. The thermoformed article was placed on a conveyor belt without changing the shape from the die.

Example 4
PLA and hardened soya wax (provided by ADM) were compounded into a flexible biocopolymer at a ratio of PLA 95, soya wax 5. The resulting formulation was reblended with various powdered non-halogenated fire retardants. Magnesium hydroxide, alumina trihydrate and ammonium phosphate were all added at a rate of 10% to 50%. With magnesium hydroxide and alumina trihydrate material, a strong reaction occurred, mixing became difficult, and a layer formed in the material. Ammonium phosphate mixed well and formed a more uniform and more flexible material contained with various things.

Example 5
PLA was formulated in a visco-elastic state at about 310 degrees Fahrenheit below the melting point. Glycerol was added at various rates ranging from 1% to 20%. The resulting material was a homogeneous flexible material. A second test was conducted by heating the PLA to a melting point of 400 degrees Fahrenheit. A similar amount of glycerin was added. Glycerin is highly volatile, and generates a lot of smoke due to decomposition, creating a heterogeneous substance which is difficult to mix and create a homogeneous substance.

  Add 95.5% PLA, 0.5% soya wax to PLA and soy wax and add 10% straw strand to a straw strand with an average length of 3/4 inch and a width less than 0.020 inch The biocopolymer was blended with the biocopolymer at 310 ° F. in the visco-elastic state. The material was uniform, odorless and had good impact resistance. The second test was conducted at a processing temperature higher than 400 degrees Fahrenheit, which is the melting point of PLA required using similar materials. The interaction between the fiber and the biocopolymer was small and severe browning and cellulose degradation were observed. In addition, the material showed signs of burning and gave off a very bad odor.

  PLA and EVA were blended at 310 degrees Fahrenheit. A sample of Bioduck (paper mill sludge particles) was colored by simply dyeing and drying the particles. 20% Bioduck was blended with the biocopolymer at 310 degrees Fahrenheit. The product was a strong, high impact resistant material with a unique aesthetics. A second treatment was performed at a processing temperature above the melting point of PLA using similar materials. The result showed signs of deterioration and combustion. The resulting material had minimal impact strength and was very fragile.

Example 6
The PLA was placed in a dish and placed in an oven at a temperature above 400 degrees Fahrenheit. A dish containing 5 samples of PLA was placed in the oven. 10% of the additive was added to each dish. Plasticizers and lubricants are glycerin, waxes, citric acid, vegetable oils, zinc stearate. After the PLA melted, the ingredients were blended. During heating, almost all plasticizers and lubricants started to smoke badly and boiled or decomposed with a strong odor. It was not possible to mix the ingredients. A similar test was conducted except that the conditions were a temperature of 300 degrees Fahrenheit lower than the melting point of PLA by 80 degrees Fahrenheit. The plasticizer did not smoke, boil or decompose, and mixed to obtain a more homogeneous material. Of these materials, zinc stearate was the worst and soya wax was the easiest to mix.

Example 7
PLA and biofiber functional colorants were measured directly in a single-step screw sheet line where high dispersibility was required, with the introduction of moderate and low shear rates. The processing temperature was set to a temperature well below 380 ° F., the melting point of PLA. In this test, the heating section was set at 310 ° F. to 315 ° F. at the exit of the die. The material was not sticky and had sufficient melt index to produce a profile. The material was not as transparent as when PLA was processed at temperatures above its melting point, but was semi-transparent maintaining crystallinity and had better flexibility and impact resistance. The chill roll temperature was estimated to be between 80 degrees Fahrenheit and over 200 degrees Fahrenheit. It has been found that the material is cooled much faster due to the lower processing temperature and the required heating of the rollers.

Example 8
Natureworks PLA 2002 in pellet form was blended with ADM's soy wax product, 5% SWL-1. The blending was performed using a Brabender double screw at 300 degrees Fahrenheit, which is 80 degrees Fahrenheit below the melting point of PLA. The material exited the circular die maintaining a good solid shape and was then cooled. This material was very opaque and milky white and did not crack when bent similar to the feel and performance of polyethylene.

  A second blending operation was performed with the SWL-1 dose increased to 10% for 90% PLA. The material was lowered in processing temperature until the viscosity decreased and the material remained circular. Again, this material was very opaque and white.

  The wheat fiber was sprayed with an aqueous colorant, dried and screened wheat fiber was added to make a third formulation. Colored wheat fibers were compounded at a ratio of 90% PLA, 5% SW1 and 5% colored wheat fibers. Surprisingly, the material was clear to translucent and had a deep three-dimensional appearance with randomly colored fibers. The more transparent PLA / SW, although slightly tinted to wheat color, still maintained the depth of transparency. The material was not as fragile as smooth PLA, and its flexibility was similar to the first 95% PLA and 5% SW1.

Example 9
PLA was formulated with 10% SW1 and 10% ground sunflower hulls, but the ground hulls were screened to remove fines less than 30 mesh. The resultant was extruded into a sheet and imprinted with texture to the hot material. After cooling, the material exhibited a decorative pattern with random flow. When the substance was put into water, it was observed that water was attached to the substance like beads.

Example 10
The PLA was blended with standard magnesium hydroxide fire retardant and extruded into bars for testing. The test bars were very fragile and could be broken down with only minimal manual pressure. A second formulation was made with the addition of 10% SW1. The resultant has good impact resistance and can be bent.

Example 11
Wheat fibers were blended with SW1 at a temperature of 300 degrees Fahrenheit at a ratio of 50% to 50%. The resultant was cooled and then granulated into small particles. The wheat and SW1 blend was then dry blended with PLA pellets and blended at 310 ° F. to obtain a planar test bar.

Example 12
Soy wax SW1 was melted in 100 gm batches at 300 degrees Fahrenheit. The same weight of wheat fiber was added and mixed. The soy wax quickly impregnated the wheat fibers and allowed the fibers to free flow. The impregnated fibers were drawn into a mat and pressed. When water was allowed to drip onto the mat, the water completely beaded and adhered to the fiber mat.

  From this, it was found that incorporating soy wax into the fiber at a ratio of approximately 50 to 50 based on the specific bulk density and the shape of the fiber fully impregnated the fiber. A 50:50 mixture of soya wax and fiber was added to 10% PLA and blended. The wax on the outside of the fiber mixed with the PLA to provide a compatible interface. Very little wax mixed with the clear PLA. Room temperature soy wax is an opaque white material. The resulting PLA and SW impregnated fibers were still clear to translucent.

Example 13
Separate experiments were performed using the two with the Brabender blender using 5% soy wax and 95% PLA. In this test, the result was opaque and milky. Thus, with the addition of the fiber, the melted soy wax is impregnated prior to the PLA, and the transparency of the final biocomposite matrix will reach an appropriate visco-elastic state to fuse the soy wax and PLA system I found that.

Example 14
Sugar beet derived pulp and sunflower hulls Pulverized sugar beet derived pulp and sunflower hulls were harvested from a local agricultural processing plant and gently ground into fibers. The resultant was screened in the range of 30 mesh to 4 mesh. The sunflower particles were linear in shape, and the sugar beet pulp had a more uniform size than the sunflower but was random in shape. In order to dip the fibrous particles, the dye used for the coating was used and then dried to fix the colorant. Two colored fibers were placed in the Brabender blend system with 10% soy wax and 80% PLA, measuring 10%. As soon as the material reaches the hot screw feed section, the soy wax melts and begins to wet the fibers, even before the PLA enters the barrel section where it is still in a rigid state. The compounding temperature was maintained at 300 ° F., which is 90 ° F. lower than the melting point of PLA, and was maintained sufficiently lower than the melting point of PLA (the melting point of PLA is 390 ° F.). The resulting product was a uniform mixture that was not fragile and had a unique three-dimensionality. The exit of the compounder was a highly resistant rod shape. The existing material was highly resistant and maintained shape.

Example 15
A Bioduck sample was purchased from GranTek Corporation of Wisconsin, a compressed and dried form of paper mill sludge that forms small spheres with a Bioduck mesh size between 15 mesh and 30 mesh. The Bioduck was colored with an aqueous colorant to make a multi-colored colored batch. Colored Bioduck was compounded at a blending ratio of 20% to 10% SW and 70% PLA. Compounding was performed at a processing temperature of 310 ° F. using a Bramender two-stage screw. The resultant was then reheated and pressed into a composite sheet. This material was very similar to the material with the appearance of a solid surface. The samples were placed in a water bath for 24 hours and the water absorption was not measured and was waterproof.

Example 16
PLA was blended with long fiber glass at a temperature (315 degrees Fahrenheit) below the melting point of PLA at a rate of 2% to over 30%. A second test was conducted at a similar ratio above the melting point (400 degrees Fahrenheit). A second test was performed with the addition of 5% to 10% soy wax.

Example 17
The biolaminated sheet containing PLA and soya wax processed at a temperature below the melting point of PLA was removed and reheated to 200 ° F. The MDF substrate was molded to produce a molded article and an adhesive was applied. The hot biolaminate was extruded into a substrate and allowed to cool. The resulting material exhibited high adhesion and very good impact resistance.

Example 18
One piece of Wilson Art high pressure laminate was bonded to the particle board substrate using the recommended adhesive. Biolaminates of similar thickness were adhered to matching particle boards using similar methods and similar adhesives. The hammer was dropped from a height of 5 feet with both of the samples in a manner such that the hammerhead hit the sample. The high pressure laminate showed signs of cracking at the end of the impact. The biolaminate showed no signs of impact.

Example 19
One piece of agrifiber composite made from straw was cut into three samples. The first sample was colored deep cherry with common wood colorants. Wheat colorants are very dark in color, "red" coatings, and hide the appearance of most natural fibers. A clear biolaminate surface was extruded, but one was clear and in the second run it contained a clear stain colorant. The dye-containing biolaminate sample was then laminated to a second uncolored wheat board sample using a clear adhesive. A clear UV-curable ink was used on the back to print a clear biolaminate, which was then similarly laminated to a third piece of wheat board. Looking at the three samples, the wood colorant pieces were not visually acceptable and did not exhibit the desired wheat board texture. Clear dyed agrifibers were different from natural wood. The second sample, in which the dye was extruded onto the biolaminate surface, was apparently totally dark cherry in color, but the pattern on the wheat board was very clear. The appearance was also very deep due to the optical effect of the biolaminate layer containing the dye. In the case of UV transparency printing, the appearance was similar to a biolaminate dyed to a similar color. The samples of the UV clear print also showed the fiber properties of the individual wheat board also with optical effect and showed a well dyed color. Similar tests were conducted separately using real wood. Integrated dyeing and clear printing biolaminates have a better aesthetic appearance than wood dyeing processes compared to liquid dyeing processes, and two processes are commonly used when using wood, dyeing and final processing In contrast to this, it provided the finishing of the wood in a single treatment process.

Example 20
Transparent or translucent polymer films of polylactic acid were extruded using standard extrusion equipment and methods. The downstream cooler was adjusted to include a texture roller to provide a consistent "crystal texture" and "gloss" similar to that of a conventional high pressure laminate (12 degrees). Biofilm thickness ranged from 0.005 to 0.040 inches during the extrusion run. The film was not post processed. The back side of the film was coated with an aqueous latex paint in a simple roller method and then allowed to dry for 4 hours.

  The back-faced plastic laminate was then bonded directly to the three-dimensional substrate in a thermofoil process using an aqueous heat activated adhesive. Hard substrates included MDF, particle boards, agrifiber boards, gypsum boards, mineral fiber bonded boards, hardboards, cement fiber boards, wood plastic composite boards, and other rigid substrates.

  A simple peel test was performed in which the biolaminate surface was scored and pulled from the substrate. The film remained on the latex coated film, leaving fibers of the MDF substrate after being torn off and showed very good adhesion.

Example 21
PET film was obtained from a standard extruder vendor. The film was coated with latex paint and allowed to dry. The back printed PET film was then hot laminated with the thermoforming process described above. The adhesion of PET was extremely poor, and the PET and latex paint layers did not separate, and as seen in Example 20, no MDF fibers remained on the back.

Example 22
A modified latex paint to which a thermally expandable powdery fire retardant was added was added. The paint was then applied to the back of a roll textured clear PLA film and allowed to dry. The FR coated film was then laminated by thermoforming to a MDF rigid substrate. The laminated part was then heated to an open flame. The PLA surface did not smoke at all and disappeared, and the thermally expandable latex was exposed and started to expand, creating a fire barrier. After 15 minutes of direct flame, the sample was removed and the thermally expandable latex coat was also removed. The biolaminate protected the wood-based MDF from an open flame, and the MDF samples showed no signs of burns or burns.

Example 23
An extruded film of PLA was produced with a thickness of 0.010 inches. During the extrusion process, textured rollers gave the film texture and gloss. Direct digital images were printed on the back of the film using various format digital printing systems. In this example, the printed pattern covered less than 50% of the back surface to allow the inside to be seen through. In this example, a pattern of a golden "comber's web" was printed.

  The colored latex paint was applied to the upper layer of the back side printing layer by rolling, spraying or other common coating method of latex paint.

  The biolaminate assembly was then placed on a thermofoil machine with a machined substrate sprayed with an adhesive that was activated by aqueous heating on the substrate surface. The biolaminate was then heated and vacuum and / or pressure was applied to align the biolaminate to the substrate. Furthermore, the adhesive was activated by heating. In this test, the latex paint layer improved adhesion with an additional heating step.

  The resulting surface member exhibited high aesthetics with multi-colored images, with the back latex color becoming a patterned field color.

Example 24
Biolaminates comprising PLA, PHA, or cellulose acetate and clear or translucent forms were backcoated with various commercial paints. The preferred method is to use a house latex paint that is applied to the back of the clear biolaminate film. The transparent film then provides a protective layer for laminating applications, simple use of the latex paint can provide sufficient adhesion, and the processing needs of the market designer's color needs are met . Films for "reverse printing" were either thermoformed into three dimensions using methods similar to those described above, or were laminated with an adhesive layer to a permeable paper (generally a latex and / or acrylic impregnated paper).

Example 25
One example is a 0.010 inch thick PLA transparent film whose top surface is textured to have a constant gloss and texture. The back of the film was coated using a spray, brush or roller method using standard indoor house latex paint. The solid color biolaminate sheet was then laminated to a three-dimensional, pre-heat activated water based adhesive and heat sprayed substrate of MDF, particle board, or agrifiber composite. Three-dimensional forming is a standard thermofoil process that typically utilizes pressure and / or vacuum to pull the biolaminate sheet to conform to the specific three-dimensional shape of the substrate and to permanently bond the biolaminate to the substrate. It was done by the method.

Example 26
Another example is a 0.005 inch thick clear film of PLA textured on the top surface and having a constant gloss and texture. The back of the film was applied using standard latex paint. The base paper impregnated with a 0.010 inch thick latex was then adhered to the back of the biolaminate assembly by an adhesive layer. The adhesive layer can include a heat activated, pressure sensitive, chemically bonded, or heat / pressure activated system. To make an alternative decorative panel to be a cabinet, storage furniture, table finish surface, shelf, and other building components, the resulting 0.015 inch thick biolaminate with latex infiltrated substrate should be made of wood particles. It was laminated to other planar substrates such as boards, MDF, and agrifiber composites.

Example 27
Another example is a 0.010 inch thick clear, with the surface textured to meet constant gloss and texture, and a direct digital image with a simple pattern printed on the back of the film. PLA extruded film. Thereafter, the latex paint was applied to the back printing side. The top surface then showed both the color of the print and the color of the latex paint in the background. The biolaminate is then laminated directly to a rigid substrate and subsequently to a permeable paper that is subsequently laminated to a rigid substrate, or using a thermofoiling process, a heat activated process and an adhesive And three-dimensionally formed.

Example 28
Another example is textured to meet constant gloss and texture, with a 0.010 inch thick clear film with the back of the film digitally imaged and / or coated with a latex paint or other solid paint coat It is a PLA extruded film. The biolaminate was then selectively laminated to a thin penetration paper. The biolaminate strip was then laminated to the three dimensional linear shape composite by the linear wrap process. The three-dimensional linear shaped composite is a real wood, wood, paper mill sludge, or agrifiber composite, foamed plastic, or metal extrusion. The biolaminate strip was then laminated to the three dimensional linear shaped composite by an adhesive layer. The adhesive layer can be a hot melt adhesive, a chemically reactive adhesive, or any other form of adhesive commonly used in linear wraps. The resulting biolaminate layer extrusion can be used for outdoor or indoor needs such as, but not limited to, window frames, woodworking products, siding, flooring pieces, hollows, decorative profiles, and other three-dimensional linear moldings. Due to the absence of hydrocarbons contained in petrochemical based products, biopolymers have high UV resistance and provide excellent natural UV resistance to outdoor products.

Example 29
The straw and plastic binder were pressed and formed into three dimensions with a ratio of about 50 to 50, respectively. The molded composite was placed in a mold press and pressed at 500 psi. The heat activated waterborne urethane was sprayed onto the molded surface before the press was completely cooled. The surface was fabricated using a membrane press into a 0.010 inch thick decorative biofoil printed with corn / soybean ink. The membrane press was set at 160 degrees Fahrenheit and pressurized for 2 minutes (about 30 psi). The resulting product has a very good adhesion of biofoil to biosubstrate and is uniformly shaped on a three dimensional surface.

Example 30
A mixture of paper mill sludge and PLA was extruded at a temperature below the melting point of PLA (320 ° F.) into the shape of a common woodworking product. Here, it is assumed that 20% of paper mill sludge is added to PLA. The molded article was then coated with a hot melt urethane adhesive and immediately subjected to a linear wrap system using a 0.010 inch thick biofoil. The biofoil was preheated with warm air. With a lap machine, pressure was applied using a separate roller to form a warm biofoil and formed into a piece of finished woodworking product. Cooling the biofoil showed very good adhesion to the substrate.

Example 31
Foamed PVC plastic in the form of a linear woodworking product baseboard was coated with aqueous urethane and air dried for 30 minutes. A 0.010 inch thick decorative biofoil was placed on the surface and placed in the oven. The biofoil softened, did not deform the PVC but softened the biofoil, and the biofoil was molded around the foamed PVC piece at a temperature (190 ° F.) that activated the adhesive. As a result, the part had very good adhesion in the peel test and was correctly molded into the shape of the woodworking product.

Example 32
PLAs with random particle shapes ranging in particle size from 1/8 inch to less than 0.1 inch, regrind from bottles produced by blow molding, were divided into two groups. The surface of one particle group was sprayed with metallic copper paint and the second group was sprayed with black paint. The bioplastic particles were then mixed. The mixture of multicolored particles was then placed in a sheet mold and forced into an oven at 370 ° F. for 1 hour. The material was then cooled to room temperature and removed from the mold. The resultant was melted in the absence of air holes, but maintained particle boundary conditions for individual particles and biocomposite particles. Also, for each particle, deformation occurred in an elastic state where the color coat was "cracked" to give a new aesthetic appearance.

Example 33
Paper mill sludge (Bioduck), a "ball" shaped material, was mixed with the addition of the aqueous colorant. The colorant coated the paper mill sludge unevenly, as the ratio of cellulose and clay was different for each individual particle. This resulted in a multicolored mixture. The pure PLA was extruded on a Brabender extruder while adding 20% polychromatic paper mill sludge. Low shear rates and heat below the melting point of PLA were used to maintain the individual ball structure of the paper mill sludge. The resultant was ground to a random shape by a standard knife grinder system in the plastics industry. The biocomposite particles were placed in a sheet mold, heated to 390 ° F. and cooled. The result again had a distinctive grain boundary, and the fine pores in the surface were like natural granite. A small ball of paper mill sludge was completely coated and its surface was a microlayer of PLA biopolymer. When this material was put in water, it showed waterproofness with a hard surface.

Example 34
The metallic copper paint was sprayed onto regrind PLA coated on top and sides of the particles. The material was placed in a sheet mold and heated at 380 ° F. for 1 hour. The material was cooled using cold water. The particles were deformed to separate the particles into a solid with sharp boundaries between particles. The coat of each particle was "cracked" and space was created in each particle, and a clear PLA was seen. Thereby, an optical pattern like a two-step metal foil was obtained.

Example 35
The PLA was extruded with the paper mill sludge coated with powdered fire protection material prior to extrusion. The resulting biocomposite particles are extruded and ground into a non-uniform state of random shaped particles, including powder fire retardants and paper mill sludge visible in the biocomposite particles and "vortex" visible in the biocomposite particles. The The particles were placed in a mold and heated to 390 degrees Fahrenheit. The resultant was then subjected to fire by a torch. The torch was exposed to fire for 1 minute and then the torch was removed. The material did not show any signs of liquid flow, and the flame spontaneously disappeared in less than 15 seconds.

Example 36
Alumina, the particles of which are about 30 mesh, was coated with an aqueous colorant. The alumina was extruded and mixed with PLA at a very low shear rate below the melting point of PLA so that the particles did not mix or break down completely. The resultant was ground with a knife grinder to random sizes and shapes. Two separate batches of biocomposite particles of different colors were produced. The bicolor biocomposite particles were dry mixed. One batch was placed in a hot press mold press and the other in an oven. The material placed in the press formed a sheet, but a flow mark was observed, and uneven melting was observed. The temperature for both tests was 350 degrees Fahrenheit. The material in the sheet mold was deformed only by gravity and became solid, but the individual particles were more clear and exhibited a near granite appearance. The material had a very good burning characteristic that once the flame was applied and after 1 minute the flame was removed, the fire would spontaneously disappear in 15 to 20 seconds. When a heavy, pointed object was placed on the alumina biocomposite surface and dragged as a pure biocomposite, the alumina also provided a harder and more scratch resistant surface.

Example 37
After pushing the PLA into the rod, the die was turned into a flat bar. The surface of the material was painted while the hot PLA was exiting the extruder. The material was then ground into particles of random shape. The material was placed in a sheet mold and an oven. The result was that the coat on one side was deformed, but the uncoated side showed a depth and transparency in the deformed shape, which was significantly different from the other biocomposites.

Example 38
The PLA was extruded with multicolored coated paper mill sludge and formed into 1/8 inch extruded sheets. The material had a uniform particle distribution and was surprisingly similar to the solid surface of artificial marble (Corian). This material was clearly consistent with the standard artificial marble color, not a random particle shape like other biocomposites or natural stone.

Example 39
The PLA was ground to fines or powder, mixed with silica particles ranging from 1/16 inch to less than 0.05 inch, and placed in an oven at 390 degrees Fahrenheit. First, the bottom of the mold was heated, and the flow layer on the bottom of the mold was PLA only. After 1 hour, the mold was cooled. The material had an exceptional surface and was very hard. The second operation was repeated under similar conditions except that the silica sand was sprayed with a colorant. Additional tests were conducted with the proportion of silica being 10%, 30%, 50%, 80%. At rates greater than 10%, the material required a diamond saw to cut. Further experiments were carried out by increasing the particle size and using particles of different sizes of silica and other minerals.

Example 40
The PLA was mixed using a ceramic powder used in a clear coat for hardwood flooring at a rate of 10%. The resultant was ground to random particles and coated. The biocomposite particles were transparent to translucent and colored for coating. After hot melting in the oven at a temperature below the melting point of PLA, the material was cooled and sanded. The material was hard enough to sand, with marked improvements in scratch and abrasion resistance.

Example 41
Cellulose waste paper was mixed with the dye to be taken and water. The fiber was then dried. Colored fibers were blended with PLA in low proportions to give the material a translucent and random "fiber" character. The material was ground into discrete random particles. A second batch was made using cellulose of different colors. The two colors of the biocomposite particles were mixed and heat melted to produce a material with a solid surface.

Example 42
These were blended using PLA and coated paper mill sludge to produce biocomposite particles, which were extruded to produce molded articles. Molded articles were ground with a plastic grinder into discrete random shaped biocomposite particles. At 320 degrees Fahrenheit (70 degrees Fahrenheit below the melting point of PLA), a low shear rate extruder was used to extrude the profile of the shaped object for edge band applications. The material had a three-dimensional appearance, and no colorant was required to give the overall color appearance of the material. The paper mill sludge particles were clearly visible in the translucent matrix and had an appearance similar to that of the material with a solid surface.

Example 43
Biocomposite particles were produced using PLA and corn hull distilled syrup using a two-step screw compounding system. The hull was in its original size and shape. The material was ground into biocomposite particles. The particles were extruded into a shaped configuration using a standard two-screw extruder with a processing temperature of 300 degrees Fahrenheit (90 degrees below the melting point). The resulting product had satisfactory aesthetics derived from the soft fibrous texture and the random shape of the corn hull fibers. The aesthetic appearance is partly due to the fact that the material surrounding the fibers is translucent rather than transparent.

Example 44
Biocomposite particles were made using PLA and a soy wax bio-plasticizer derived from soy oil. Multicolored coated paper mill sludge was formulated with PLA and a bioplasticizer to produce soft, but translucent, elastomeric biocomposite particles. These particles were placed in a sheet mold and placed in an oven to heat melt at 300 ° F. to solidify, but still individual grain boundaries were still visible. The material was flexible and had good slip resistance.

Example 45
The cellulose insulation was added to the mixture while the liquid colorant was sprayed onto the material. The bulk density of the material increased quickly. The volume of substance was halved and the same weight of liquid colorant was added. The material was then allowed to dry. The material was then coated with 20% of melted liquid soy wax derived from hydrogenated vegetable oil and then cooled. The resulting colored biocomposite particles were coated but not complete and some fibers remained in their natural color. The material was then compounded at 320 ° F., 10% colored biocomposite particles, and 90% of a mixture of PLA and soy wax biocopolymer. The resultant was formed into a sheet or biolaminate sample. Inhomogeneous materials exhibited discrete grain boundaries and had multiple depths of field. The material had a flow and discrete particle boundaries and was surprisingly similar to natural granite.

Example 46
PLA was blended at a temperature below the melting point (310 degrees Fahrenheit) with 5% polysoy hydrogenated soy bean oil with ADM to obtain a flexible white biocopolymer similar in character and appearance to polyethylene. The biocopolymer was compounded and cut into pellets. Second, a fluffy form of ground cellulose insulation paper was mixed while adding the aqueous paint. Fluffy cellulose was converted to smaller particles with reasonable integrity. The particles were allowed to dry. The biocopolymer and colored composite particles were mixed at a ratio of 85% biocopolymer, 15% colored cellulose particles and extruded at a low shear rate below the melting point of PLA (310 ° F.). The result is that the appearance of the individual particles is maintained without mixing into the homogeneous mixture, and the one with extremely high similarity to natural three-dimensional granite is obtained.

Example 47
Crushed random shaped particles of clear PLA were coated with metal paint. The particles were placed in molds and melted by heating them to a temperature below the melting point of PLA, which causes the particles to become elastomeric and deform due to the low thermal deflection temperature of the material. The material was cooled. Initially, it can be seen that the coated surface of the particles deforms on its surface and the material is almost opaque. When the surface layer, at least the coating layer, was removed by sanding, when the transparent particle was opened, only the interface between the back surface of the particle and the paint and the transparent PLA was visible. By polishing the surface, the material became very clear and only the back of each individual coated biocomposite or PLA particle was visible. This provides very specific optical properties as compared to other solid surface processed materials with very good depth of field. By having a random shape in the particle matrix with a clear coat, different reflection angles were also seen in each particle due to its unique shape. Thus, all particles provided unique light properties.

Example 48
Normal Kraft paper followed by biopolymer PLA extruded film (0.005 inch) was placed on top of the Kraft paper. A second kraft paper was placed on top, so that the PLA film was "sandwiched" in non-penetrating kraft paper. This alternate stacking can be repeated to create a thicker structure. The two layers of kraft paper with the biopolymer film sandwiched therebetween were then placed in a heat press and processed at 350 degrees Fahrenheit and 20 psi and more preferably 150 to 500 psi. Thus two layers were prepared.

  The first stack of alternating layers was removed in a similar press for 1 minute. When breaking up the final composite, there was a dry portion of the paper and the paper was not completely penetrated or impregnated. In addition, the composite could be broken due to the low internal bond of the non-penetrable paper.

  A second stack of alternating layers was placed in the same press at the same temperature, extending the press time to 8 minutes. Once the composite was cooled, the bed was completely penetrated and did not break. Kraft paper darkened due to the penetration of PLA into kraft paper when cutting various layers with a knife, which was also true on the other side.

  Both pieces were cut and the edges sanded and examined using a microscope. The first sample with a 1 minute cycle shows that the PLA was partially impregnated and penetrated the kraft paper but did not penetrate completely, while the second was subjected to a longer press time Of the sample showed complete penetration of the paper layer.

  Both pieces were immersed in water. The first sample pressed for 1 minute had very high water absorbency and swelling because it was impermeable kraft paper. The second sample was nearly waterproof with no expansion or surface roughness.

Example 49
A second film was obtained using standard acrylic (0.005) replacing PLA, with an acrylic film between two layers of kraft paper. The laminate was put into the press using fully for 8 minutes under the same conditions as above. The sample was removed and cooled. The material was not permeable and barely adhered to the two layers. The sample pulled off easily and had neither strength nor stiffness.

  To further illustrate, the following embodiments are described herein.

1.
With one or more biolaminate layers;
Non-plastic hard base material;
An adhesive layer contacting the substrate and the one or more biolaminate layers;
A biolaminate composite assembly, comprising: one or more biolaminate layers laminated to the substrate.

2.
The biolaminate composite assembly of claim 1, wherein the laminate comprises a planar laminate.

3.
The biolaminate composite assembly of embodiment 1, wherein a biolaminate monolayer is in contact with one side of the non-plastic hard substrate.

4.
The biolaminate composite assembly according to embodiment 1, wherein two or more biolaminate layers are in contact with two or more sides of the non-plastic hard substrate.

5.
The biolaminate composite structure of embodiment 2, wherein the planar laminate comprises hot press, cold press, nip roll, sheet forming, full panel forming, custom cut, or a combination thereof.

6.
The biolaminate composite assembly according to claim 1, wherein the adhesive comprises an adhesive layer.

7.
The biolaminate composite assembly of claim 1, wherein the adhesive layer comprises a heat activated adhesive.

8.
The biolaminate composite assembly of claim 1, wherein the adhesive layer comprises an adhesive adhesive.

9.
The biolaminate composite assembly of embodiment 1, wherein the adhesive layer comprises a cold press adhesive.

10.
10. The biolaminate composite assembly according to embodiment 9, wherein the adhesive layer comprises a pressure sensitive tape.

11.
The biolaminate composite assembly according to embodiment 1, wherein the substrate comprises a composite matrix.

12.
The base material is wood composite material, MDF, HDF, plywood, OSB, wood particle board, wood plastic composite material, agrifiber plastic composite material, agri fiber particle board, agrifiber composite material, gypsum board, sheet lock, The bio described in embodiment 1, comprising hardboard, metal, glass, cement, cement board, cellulose substrate, cellulose paper composite, multi-layer cellulose adhesive composite, veneer, bamboo, recycled paper substrate, or a combination thereof Laminated composite assembly.

13.
The biolaminate composite assembly of embodiment 1, wherein the substrate comprises a substrate derived from agrifiber using a matrix resin that does not contain formaldehyde.

14.
The biolaminate composite assembly comprises a machined surface, cupboard, woodworking product, laminate flooring, counter, table surface, furniture parts, furniture parts, furniture, partitions, wallpaper, cabinet cover, cabinet door, walkway door or a combination of these. The biolaminate composite assembly according to 1.

15.
The biolaminate composite assembly according to claim 1, wherein the one or more biolaminate layers have a thickness of about 0.005 to about 0.25 inches.

16.
16. The biolaminate composite assembly of claim 15, wherein two or more of the one or more biolaminate surface layers are heat fused by a heat fuse or an adhesive.

17.
The biolaminate composite assembly of claim 1, wherein the biolaminate composite assembly has a thickness of about 0.050 to about 1.5 inches.

18.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers comprise PLA, PHA, or a combination thereof.

19.
The biolaminate composite assembly according to embodiment 1, wherein the one or more biolaminate layers comprise bioplastics, biopolymers, modified biopolymers, biocomposites, or combinations thereof.

20.
20. The biolaminate composite assembly according to embodiment 19, wherein the bioplastic, biopolymer, modified biopolymer, and biocomposite comprises a polylactic acid based material.

21.
The biolaminate composite assembly according to embodiment 1, wherein the one or more biolaminate layers comprise modified PLA in combination with one or more plastics, bioplastics, additives or bioadditives.

22.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers comprise modified PLA in combination with one or more fillers, fibers, or colorants.

23.
The biolaminate composite assembly according to claim 1, further comprising one or more printing layers.

24.
24. The embodiment according to embodiment 23, wherein the print layer is disposed between the top layer of the one or more biolaminate layers, the bottom layer of the one or more biolaminate layers, or the one or more biolaminate layers Biolaminate composite assembly as described.

25.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers further comprise a bioplasticizer, a biolubricant, or both.

26.
26. The biolaminate composite assembly of embodiment 25, wherein the bioplasticizer comprises citric acid ester, ester, lactic acid, and other forms of biobased plasticizer.

27.
26. The biolaminate composite assembly according to embodiment 25, wherein the biolubricant comprises natural wax, lignan, or a combination thereof.

28.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers have a flexibility corresponding to a flexible PVC layer.

29.
The biolaminate composite assembly according to embodiment 1, further comprising one or more decorative additives.

30.
30. The biolaminate composite assembly according to embodiment 29, wherein the one or more decorative additives comprise colorants, textures, decorative particles, decorative flakes, or naturally impregnated fibers.

31.
31. The biolaminate composite assembly according to embodiment 30, wherein the colorant has a natural depth of field with three dimensional aesthetic value.

32.
The biolaminate composite assembly according to embodiment 1, further comprising a functional additive.

33.
Said functional additive comprises EVA, FR, natural quartz, bioplasticizer, biolubricant, mineral, natural fiber, synthetic fiber, impact modifier, antibacterial agent, conductive filler, or a combination thereof The biolaminate composite assembly of Form 32.

34.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers have a rolled or pressed texture surface.

35.
The biolaminate composite assembly of embodiment 1, comprising a non-plastic hard substrate in contact with the second side of the one or more biolaminate layers.

36.
The biolaminate composite assembly according to embodiment 1, further comprising a bioplastic edge band.

37.
The biolaminate composite assembly according to embodiment 1, wherein the one or more biolaminate layers comprise edge bands.

38.
The biolaminate composite assembly of claim 1, wherein the non-plastic hard substrate comprises a bio-based edge band and a biolaminate surface.

39.
40. The biolaminate composite assembly according to embodiment 38, wherein both the one or more biolaminate layers and edge bands comprise PLA, modified PLA, or both.

40.
The biolaminate composite assembly according to embodiment 1, wherein the lamination is performed by using a hot pressing method, roll lamination, cold pressing method, or adhesive adhesive.

41.
The biolaminate composite assembly according to embodiment 1, further comprising a fire protection material.

42.
The biolaminate composite assembly of embodiment 1, wherein the one or more biolaminate layers further comprise a natural mineral.

43.
The biolaminate composite assembly according to embodiment 1, wherein the biolaminate composite structure has a three-dimensional appearance.

44.
With one or more biolaminate layers;
Three-dimensional non-plastic hard substrate;
An adhesive layer in contact with the substrate and the one or more biolaminate layers;
A biolaminate composite assembly comprising: one or more biolaminate layers thermoformed on two or more surfaces of the substrate.

45.
Embodiment 45. The biolaminate composite assembly according to embodiment 44, wherein the thermoforming is permanent.

46.
45. The biolaminate composite assembly according to embodiment 44, wherein said thermoforming comprises vacuum forming, linear forming, or a combination thereof.

47.
Embodiment 45. The biolaminate composite assembly according to embodiment 44, wherein the adhesive layer comprises an adhesive layer.

48.
51. The biolaminate composite assembly according to embodiment 44, wherein the substrate comprises a composite matrix

49.
The base material is wood composite material, MDF, HDF, plywood, OSB, wood particle board, wood plastic composite material, agrifiber plastic composite material, agri fiber particle board, agrifiber composite material, gypsum board, sheet lock, 45. The bio according to embodiment 44 comprising hardboard, metal, glass, cement, cement board, cellulose substrate, cellulose paper composite, multi-layer cellulose adhesive composite, veneer, bamboo, recycled paper substrate, or a combination thereof. Laminated composite assembly

50.
45. The biolaminate composite assembly according to embodiment 44, wherein the substrate comprises a substrate derived from agrifiber using a matrix resin free of formaldehyde.

51.
Embodiment 45. The embodiment according to embodiment 44, wherein said biolaminate composite assembly comprises a processed surface, cupboard, woodworking product, flooring, counter, table surface, partition, wallpaper, cabinet cover, cabinet door, furniture, walkway door or combinations thereof. Biolaminate composite assembly.

52.
45. The biolaminate composite assembly according to embodiment 44, wherein the one or more biolaminate layers have a thickness of about 0.005 to about 0.25 inches.

53.
45. The biolaminate composite assembly according to embodiment 44, wherein the biolaminate composite assembly has a thickness of about 0.030 to about 1.5 inches.

54.
45. The biolaminate composite assembly of embodiment 44, wherein the one or more biolaminate layers comprise PLA, PHA, and other bioplastics / biopolymers.

55.
45. The biolaminate composite assembly according to embodiment 44, further comprising a bioplasticizer and a biolubricant.

56.
Embodiment 45. The biolaminate composite assembly according to embodiment 44, further comprising one or more decorative additives.

57.
57. The biolaminate composite assembly according to embodiment 56, wherein the one or more decorative additives comprise colorants, textures, decorative particles, decorative flakes, or naturally impregnated fibers.

58.
58. The biolaminate composite assembly according to embodiment 57, wherein the colorant has a natural depth of field with three-dimensional aesthetic value.

59.
45. The biolaminate composite assembly according to embodiment 44, further comprising a functional additive.

60.
60. The biolaminate composite assembly according to embodiment 59, wherein the functional additive comprises EVA, FR, natural quartz, bioplasticizer, biolubricant, mineral, natural fiber, synthetic fiber, or a combination thereof.

61.
The biolaminate composite assembly of embodiment 44, wherein the biolaminate composite structure has a rolled or pressed texture surface.

62.
Embodiment 45. The biolaminate composite assembly according to embodiment 44, further comprising a non-plastic hard substrate in contact with the second side of the one or more biolaminate layers.

63.
The biolaminate composite assembly of embodiment 44, further comprising a fire protection material.

64.
The biolaminate composite assembly according to embodiment 44, further comprising a natural mineral.

65.
67. The biolaminate composite assembly of embodiment 64, wherein the natural mineral comprises a mineral that meets high abrasion resistant HPL criteria.

66.
The biolaminate composite assembly of embodiment 44, wherein the biolaminate composite structure has a three-dimensional appearance.

67.
A method of making a biolaminate composite assembly, comprising laminating one or more biolaminate layers to a non-plastic hard substrate.

68.
Embodiment 68. The method of embodiment 67, further comprising reverse printing on the one or more biolaminate layers.

69.
Embodiment 68. The method of embodiment 67 wherein the one or more biolaminate layers are transparent or translucent.

70.
Embodiment 68. The method of embodiment 67, further comprising direct printing on the one or more biolaminate layers.

71.
Embodiment 68. The method of embodiment 67, further comprising multilayer printing on the one or more biolaminate layers.

72.
Embodiment 68. The method of embodiment 67 further comprising a decorative print layer between the two or more biolaminate layers.

73.
Embodiment 73. The method according to embodiment 72, further comprising heat melting the two or more biolaminate layers.

74.
Embodiment 68. The method of embodiment 67, further comprising printing a decorative print layer on the one or more biolaminates.

75.
75. The method of embodiment 74, wherein printing comprises offset printing, ink jet printing, screen printing, or flexographic printing.

76.
Embodiment 75. The method according to embodiment 74, wherein the printing uses bioink.

77.
Embodiment 68. The method of embodiment 67, further comprising applying a clear liquid coat to the one or more biolaminate layers.

78.
78. The method according to embodiment 77, wherein said application comprises spray, roll, offset printing, or rod coat printing.

79.
68. The method of embodiment 67, wherein the one or more biolaminate layers comprise a transparent top layer, a decorative inner layer, and an opaque layer, wherein each layer is heat melted with an adjacent layer.

80.
Embodiment 71. The method according to embodiment 70, further comprising applying a clear coat to the outer surface of the printed one or more biolaminate layers.

81.
A method of making a biolaminate composite assembly comprising thermoforming one or more biolaminate layers onto a non-plastic hard substrate.

82.
The method of embodiment 81, wherein the forming comprises thermoforming, vacuum forming, thermoforming or a combination thereof.

83.
Embodiment 82. The method of embodiment 81 further comprising reverse printing on the one or more biolaminate layers.

84.
Embodiment 81. The method according to embodiment 81, wherein the one or more biolaminate layers are transparent or translucent.

85.
The method according to embodiment 81, further comprising direct printing on the one or more biolaminate layers.

86.
Embodiment 81. The method of embodiment 81, further comprising multilayer printing on the one or more biolaminate layers.

87.
The method of embodiment 81, further comprising printing a decorative print layer between the two or more biolaminate layers.

88.
The method according to embodiment 87, further comprising heat melting the two or more biolaminate layers.

89.
89. The method of embodiment 88, further comprising printing a decorative print layer on the one or more biolaminates.

90.
90. The method of embodiment 89, wherein the printing comprises offset printing, ink jet printing, screen printing, or flexographic printing.

91.
90. The method of embodiment 89, wherein the printing uses bioink.

92.
Embodiment 82. The method according to embodiment 81, further comprising applying a clear liquid coat to the one or more biolaminate layers.

93.
Embodiment 93. The method according to embodiment 92, wherein said applying comprises spraying, rolling, offset printing, or rod coating.

94.
The method according to embodiment 81, wherein the one or more biolaminate layers comprise a transparent top layer, a decorative inner layer, and an opaque inner layer, each layer being heat melted with an adjacent layer.

95.
86. The method of embodiment 85, further comprising applying a clear coat to the outer surface of the printed one or more biolaminate layers.

96.
A transparent biopolymer layer;
Opaque biopolymer layer;
With decorative printing layers;
A decorative biolaminate layer, comprising: the print layer is disposed between the transparent layer and the opaque layer.

97.
97. The decorative biolaminate layer of embodiment 96, wherein the biopolymer layer is textured.

98.
97. The decorative biolaminate layer of embodiment 96, wherein the arrangement comprises melting.

Claims (24)

With one or more biolaminate layers;
With rigid non-plastic base materials;
A colored layer disposed between the one or more biolaminate layers and the substrate;
Including
A biolaminate composite assembly wherein the one or more biolaminate layers are laminated to the substrate.   The biolaminate composite assembly according to claim 1, further comprising an adhesive layer in contact with at least one of the substrate, the colored layer, and the one or more biolaminate layers.   The biolaminate composite assembly according to claim 1, wherein two or more biolaminate layers are in contact with two or more sides of the substrate.   The biolaminate composite assembly comprises a machined surface, cupboard, woodworking product, laminate flooring, counter, table surface, furniture component, furniture, partition, wallpaper, cabinet cover, cabinet door, walkway door or a combination thereof. The biolaminate composite assembly according to 1.   The biolaminate composite assembly of claim 1, wherein the one or more biolaminate layers comprise PLA, PHA, or a combination thereof.   The biolaminate composite assembly of claim 1, further comprising an underlayer.   The biolaminate composite assembly according to claim 1, wherein the underlayer is disposed between the colored layer and the substrate.   The biolaminate composite assembly according to claim 1, wherein the colored layer comprises a latex paint.   The biolaminate composite assembly according to claim 1, wherein the one or more biolaminate layers are transparent or translucent. With one or more thin biolaminate films;
With rigid non-plastic base materials;
A colored layer disposed between the substrate and the one or more biolaminate films;
An underlayer disposed between the substrate and the colored layer;
Including
A decorative biolaminate assembly wherein the one or more biolaminate films are laminated to the substrate.   A decorative biolaminate assembly comprising decorative biocomposite particles dispersed on or within a biopolymer matrix, wherein the decorative biocomposite particles comprise hairy fiber particles.   The decorative biolaminate assembly of claim 11, wherein the biopolymer matrix comprises a cellulose layer.   The decorative biolaminate assembly of claim 11, further comprising a layer of hardened vegetable oil on the decorative biocomposite particles.   12. The decorative biolaminate assembly of claim 11, wherein the decorative biocomposite particles are coated. With one or more biolaminate layers;
With high performance surface layer:
A substrate;
An adhesive layer contacting the substrate and the one or more biolaminate layers;
Including
A biolaminate composite assembly, wherein the one or more biolaminate layers are laminated to the substrate. With decorative biolaminates;
Biocomposite extruded substrates;
A linear extrusion biocomposite assembly, comprising: the decorative biolaminate being provided on the biocomposite extrusion substrate. With one or more biolaminate layers;
Plywood base material;
An adhesive layer in contact with the substrate and the one or more biolaminate layers;
Including
A biolaminate composite assembly, wherein the one or more biolaminate layers are laminated to the substrate.   18. The biolaminate composite assembly of claim 17, wherein the two or more biolaminate layers are in contact with two or more sides of a plywood substrate.   18. The biolaminate composite assembly of claim 17, wherein the substrate comprises wood or wood composites.   The biolaminate composite assembly comprises a machined surface, cupboard, woodworking product, laminate flooring, counter, table surface, furniture component, furniture, partition, wallpaper, cabinet cover, cabinet door, walkway door or a combination thereof. 17. The biolaminate composite assembly according to 17.   18. The biolaminate composite assembly according to claim 17, wherein the one or more biolaminate layers comprise PLA, PHA, or a combination thereof. With one or more thin biolaminate films;
Plywood base material;
A transparent adhesive layer in contact with the substrate and the one or more biolaminate films;
An underlayer disposed on the bottom surface of the plywood substrate;
Including
A decorative veneer biolaminate assembly in which the one or more biolaminate films are laminated to the substrate.   23. The assembly of claim 22, wherein the primer layer comprises a permeable paper, a rubber sheet, or a synthetic rubber sheet. A biolaminate panel assembly for a structure comprising one or more bioplastic layers laminated to form one or more surface sheets of a substrate core and in contact with one or more bioplastic layers.