U.S. patent application number 13/759204 was filed with the patent office on 2013-06-13 for cellulosic biolaminate composite assembly and related methods.
This patent application is currently assigned to Biovation, LLC. The applicant listed for this patent is Biovation, LLC. Invention is credited to Michael J. Riebel, Milton Riebel.
Application Number | 20130149511 13/759204 |
Document ID | / |
Family ID | 44816042 |
Filed Date | 2013-06-13 |
United States Patent
Application |
20130149511 |
Kind Code |
A1 |
Riebel; Michael J. ; et
al. |
June 13, 2013 |
CELLULOSIC BIOLAMINATE COMPOSITE ASSEMBLY AND RELATED METHODS
Abstract
Cellulosic biolaminate assemblies are provided. In one
embodiment, a biolaminate structure is provided comprising a first
cellulosic layer, a second cellulosic layer, and a first bio-based
polymer. The first bio-based polymer impregnates the first
cellulosic layer and the second cellulosic layer. The first
cellulosic layer and the second cellulosic layer are fused
together.
Inventors: |
Riebel; Michael J.;
(Mankato, MN) ; Riebel; Milton; (Mankato,
MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Biovation, LLC; |
Mankato |
MN |
US |
|
|
Assignee: |
Biovation, LLC
Mankato
MN
|
Family ID: |
44816042 |
Appl. No.: |
13/759204 |
Filed: |
February 5, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13182767 |
Jul 14, 2011 |
8389107 |
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13759204 |
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13019060 |
Feb 1, 2011 |
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13182767 |
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12410018 |
Mar 24, 2009 |
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13019060 |
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61038971 |
Mar 24, 2008 |
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61364298 |
Jul 14, 2010 |
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Current U.S.
Class: |
428/211.1 ;
156/306.6; 428/438; 428/480; 428/481; 428/534; 428/535;
428/537.5 |
Current CPC
Class: |
D21H 27/30 20130101;
B32B 27/10 20130101; Y10T 428/31634 20150401; B32B 29/06 20130101;
B32B 7/12 20130101; B32B 23/06 20130101; B32B 27/36 20130101; D21H
27/26 20130101; Y10T 428/31993 20150401; B32B 2262/065 20130101;
B32B 23/14 20130101; B32B 2451/00 20130101; Y10T 428/31982
20150401; Y10T 428/24934 20150115; B32B 29/005 20130101; Y10T
428/24802 20150115; D21H 19/82 20130101; Y10T 428/31978 20150401;
Y10T 428/3179 20150401; B32B 2260/028 20130101; Y10T 428/31786
20150401; B32B 2260/046 20130101 |
Class at
Publication: |
428/211.1 ;
156/306.6; 428/534; 428/481; 428/535; 428/438; 428/480;
428/537.5 |
International
Class: |
B32B 23/06 20060101
B32B023/06; B32B 23/14 20060101 B32B023/14 |
Claims
1. A biolaminate structure, comprising: a first cellulosic layer; a
second cellulosic layer; and a first bio-based polymer that
impregnates the first cellulosic layer and the second cellulosic
layer; wherein the first cellulosic layer and the second cellulosic
layer are fused together.
2. The structure of claim 1, wherein the first bio-based polymer
comprises one of polylactic acid and lactic acid.
3. The structure of claim 1, wherein the biolaminate structure is
suitable for use as a decorative surfacing laminate layer.
4. The structure of claim 1, wherein the biolaminate structure
exhibits substantially no formaldehyde emission and suitable for a
replacement for high pressure laminates.
5. The structure of claim 1, wherein at least one of the first
cellulosic layer and the second cellulosic layer comprises plain
paper, kraft paper, treated paper, wood based paper, recycled
papers, decorative paper, printed paper, fiber reinforced papers,
glass fiber reinforced paper, thin wood veneers, fire retardant
paper, chemically treated paper, ph adjusted papers, or a
combination thereof.
6. The structure of claim 1, further comprising an overlay layer
comprising a thermoset and thermoplastic standard overlay, a
mineral plastic overlay, a bioplastic overlay, or a wear layer
surface overlay.
7. The structure of claim 1, wherein an additive is contacted with
one or more of the layers or the first bio-based polymer.
8. The structure of claim 7, wherein the additive is selected from
the group consisting of drying agents, polymerizing agents,
peroxides and other crosslinking agents, colorants, fire
retardants, impact modifiers, processing aids, lubricants, and pH
modifiers
9. The structure of claim 1, wherein at least one of the first
cellulosic layer and the second cellulosic layer comprises a
biobased paper from a renewable plant fiber selected from the group
of hemp, baggase, wheat straw, and corn stover.
10. The structure of claim 1, further comprising additional
cellulosic layers impregnated with a bio-based polymer to form a
thicker biolaminate structure.
11. The structure of claim 1, further comprising a film layer
comprising polylactic acid, the film layer being reverse printed
with an image, the film layer being provided over the first and
second cellulosic layers.
12. A biolaminate structure, comprising: a first layer comprising a
paper substrate impregnated with a bio-based polymer, the bio-based
polymer being one of polylactic acid and lactic acid; and a second
layer in contact with the first layer; wherein the biolaminate
structure exhibits substantially no formaldehyde emission and
suitable for a replacement for high pressure laminates.
13. The biolaminate structure of claim 12, wherein the second layer
is a paper substrate impregnated with a bio-based polymer.
14. The biolaminate structure of claim 12, wherein the second layer
is a biobased film including a polylactic acid sheet.
15. The biolaminate structure of claim 12, wherein the second layer
is a clear polylactic surface layer.
16. A method for forming a biolaminate structure, the method
comprising: providing a first paper layer; providing a biobased
polymer film layer; providing a second paper layer; and at least
partially saturating the first paper layer and the second paper
layer with a biobased polymer, wherein saturation may be from the
biobased polymer of the biobased polymer film layer or may be from
an additional biobased polymer source; fusing the first paper
layer, the biobased polymer film layer, and the second paper layer
under means of heat and pressure to form the biolaminate
structure.
17. The method of claim 16, wherein fusing is done at a pressure
between about 20 psi and about 1500 psi
18. The method of claim 16, wherein saturating the first paper
layer and the second paper layer comprises submersing the first
paper layer and the second paper layer in a bath of liquid lactic
acid with a low viscosity sufficient to absorb into the saturated
paper layers.
19. The method of claim 16, further comprising drying the saturated
first paper layer and the saturated second paper layer prior to
fusing.
20. The method of claim 19, further comprising texturizing a
surface of the dried, saturated first paper layer.
Description
[0001] This application is a Continuation-in-Part of U.S. patent
application Ser. No. 13/019,060, filed Feb. 1, 2011, entitled
"Biolaminate Composite Assembly and Related Methods," which is a
Continuation of U.S. patent application Ser. No. 12/410,018, filed
Mar. 24, 2009, which claims priority to U.S. Provisional
Application No. 61/038,971, filed Mar. 24, 2008. This application
also claims priority to U.S. Provisional Application No.
61/364,298, filed Jul. 14, 2010. The contents of all
above-mentioned applications are hereby incorporated in their
entirety by reference.
BACKGROUND
[0002] The environmental movement in the United States and abroad
continues to grow into a mainstream concern with growing demand for
environmentally friendlier ("green") products and programs to
remove hazardous materials from the residential and workplace
environment. PVC (polyvinylchloride) and formaldehyde-based
laminate worksurfaces and components are now being removed from
many applications due to their toxic nature. Many businesses and
organizations are taking aggressive action to remove PVC and
formaldehyde-based products from the interior workplace and product
fines.
[0003] The demand continues to grow for "green" products to replace
petrochemical plastics and hazardous polymer. This demand is driven
by environmental awareness and by the architectural and building
communities based on making interior environments healthier.
Materials commonly used in many architectural, institutional, and
commercial applications for vertical and horizontal surfacing
products are primarily derived from PVC and melamine formaldehyde
laminates. With growing concerns over the usage of hazardous PVC
and formaldehyde in interior applications, there is a need for
environmentally friendly alternatives that meet both performance
and economic requirements.
[0004] Formaldehyde has created serious concerns over interior air
quality. Products such as particleboard and high pressure laminates
use substantial amounts of formaldehyde in their resinous makeup.
In many cases, the formaldehyde is not removed completely from the
product and is introduced into interior public or residential
closed spaces and may off-gas for an extended time. Formaldehyde
has been linked to many health problems and is classified as a
known carcinogen. Major corporations have now made public policy
statements that they are to remove PVC and formaldehyde from their
places of work. Japan has put in legislation creating strict
policies inhibiting the usage of PVC and formaldehyde containing
products. Similar legislation has been enacted in Europe.
[0005] PVC has been classified by many groups as a "poison
plastic". Over 7 billion pounds of PVC is discarded every year. The
production of PVC requires the manufacturing of raw chemicals,
including highly polluting chlorine, and cancer-causing vinyl
chloride monomer. Communities surrounding PVC chemical facilities
suffer from serious toxic chemical pollution of their ground water
supply, surface water and air. PVC also requires a large amount of
toxic additives resulting in elevated human exposure to phthalates,
lead, cadmium tin and other toxic chemicals. PVC in interior
applications releases these toxic substances as volatile organic
compounds (VOCs) in buildings. Deadly dioxins and hydrochloric
acids are released when PVC burns or is incinerated.
[0006] The vast majority of vertical or horizontal decorative
surfacing materials are high pressure laminates and thermofoil PVC.
Work surfaces, tables, desktops, and many other work surfaces glue
a thin high pressure laminate (HPL) (typically 0.050 inch thickness
to a wood particleboard adhered with urea formaldehyde glues). Over
the last decade, many kitchen cabinets were produced by cutting a
medium density fiberboard containing phenol formaldehyde glues into
a door shape. A thin PVC sheet or thermofoil was heated and pressed
onto this three dimensional shaped door using a membrane press. The
resultant door was already finished and resistant to water, but
contained high amounts of chlorine. If the cabinets were burned,
the off-gassing may create a deadly hydrochloric acid gas for fire
fighters or people who may not escape the fire.
[0007] Biobased material is seen as an ideal solution in the
architectural, institutional, commercial and even residential
markets. Despite this, few products have entered the market as a
direct replacement for PVC thermofoils used in surfacing and
formaldehyde-based laminates. Biorenewable materials are preferred
over petrochemically derived plastic products. Bioplastics have
been commonly used for various packaging film applications.
Primarily PLA (polylactic acid) has been the most commercially
successful of these bioplastics. PLA is a hard brittle plastic that
is highly mobile or quickly turns into a liquid under open flame
conditions. In addition, PLA may not be easily extruded into
profile shapes due to its high melt index and unique rheology. Most
all of current PLA products are based on creating biodegradability.
As one can appreciate, however, it is not always desirable that
products in long term commercial applications be biodegradable,
even where biorenewability is desired.
[0008] "Green" products have long been desired and are coming into
the mainstream, but in most cases biomaterials or "green" solutions
have come at a high price and typically do not meet the required
performance standards. In some cases, people or companies will pay
slightly more for a "green" product, but in reality, a "green"
product needs to meet performance while being competitive in price.
Being "green" is important, but the ability to supply performance
at a competitive price is important to commercialization of "green"
technologies. It is important that the materials and products
within this environment are not harmful to overall health and
provide a clean, VOC-free environment. PVC and its additives, along
with formaldehyde from laminates and some particleboards, release
harmful VOCs into the work place. These VOCs have been classified
as potential carcinogens, creating a higher risk of cancer.
[0009] Although "green" biodegradable packing materials are moving
the global community towards better environment practices, there
exists a strong market demand for non-biodegradable biorenewable
materials for more permanent applications to replace hazardous or
petrochemically-derived products.
[0010] Methods known in the art for making final laminates include
Low Pressure Laminate (LPL), High Pressure Laminate (HPL) and
Continuous Pressure Laminate (CPL) processes. Low pressure is most
often used with card-board or particle board, whereas high pressure
generally is used with the so-called kraft papers. The sheets or
products resulting from the HPL process are generally not
self-supportive. They are often bonded, with a suitable adhesive or
glue, to a rigid substrate such as particle board or medium density
fiber board (MDF). In a continuous pressure laminate process,
papers may be fed from a role into a continuous belt press.
[0011] Traditional production suffers from drawbacks which are not
easily overcome. One problem is that the laminates made in the high
pressures or continuous process are so hard, that it is difficult
to bend or `post-form` these sheets. At present, post-forming
characteristics are often achieved by either incorporating
expensive modifiers like benzoguanamine or acetoguanamine, or by
making melamine-formaldehyde resins at elevated pressure, allowing
more melamine to react with formaldehyde. The latter process is
relatively expensive, and requires pressure vessels. Yet, it may be
advantageous if, while keeping the abrasion resistance and chemical
resistance properties, the HPL or CPL sheets would be bendable, so
they could be made to cover a substrate not only on one side, but
in one process step. Another drawback of traditional laminates is
the use of formaldehyde, which is known to be a toxic chemical. The
resin used to impregnate traditional paper may be a
formaldehyde-melamine resin. After curing, the laminate may still
release some formaldehyde, which may cause environmental
concerns.
SUMMARY
[0012] Embodiments of the invention relate to a biolaminate
composite assembly, including one or more biolaminate layers, a
non-plastic rigid substrate and an adhesive layer in contact with
the substrate and the one or more biolaminate layers. The substrate
is laminated or formed to the one or more biolaminate layers.
Embodiments also relate to methods of making a biolaminate
composite assembly.
[0013] In one embodiment, a biolaminate structure is provided
comprising a first cellulosic layer, a second cellulosic layer, and
a first bio-based polymer. The first bio-based polymer impregnates
the first cellulosic layer and the second cellulosic layer. The
first cellulosic layer and the second cellulosic layer are fused
together.
[0014] In another embodiment, a biolaminate structure is provided
comprising a first layer and a second layer. The first layer
comprises a paper substrate impregnated with a bio-based polymer,
the bio-based polymer being one of polylactic acid and lactic acid.
The second layer is on contact with the first layer.
[0015] In yet another embodiment, a method for forming a
biolaminate structure is provided. The method includes providing a
first paper layer, providing a biobased polymer film layer, and
providing a second paper layer. The first paper layer and the
second paper layer are at least partially saturated with a biobased
polymer. Saturation may be from the biobased polymer of the
biobased polymer film layer or may be from an additional biobased
polymer source. The method further comprises fusing the first paper
layer, the biobased polymer film layer, and the second paper layer
under means of heat and pressure to form the biolaminate
structure.
[0016] Embodiments also relate to a decorative biolaminate layer,
including a clear biopolymer layer, an opaque biopolymer layer and
a decorative print layer. The print layer is positioned between the
clear layer and opaque layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In the drawings, which are not necessarily drawn to scale,
like numerals describe substantially similar components throughout
the several views. Like numerals having different letter suffixes
represent different instances of substantially similar components.
The drawings illustrate generally, by way of example, but not by
way of limitation, various embodiments discussed in the present
document.
[0018] FIG. 1 illustrates a cross-sectional view of a biolaminate
composite assembly, according to some embodiments.
[0019] FIG. 2 illustrates a block flow diagram of a method of
making a biolaminate composite assembly, according to some
embodiments.
[0020] FIG. 3 illustrates an expanded view of a biolaminate
composite assembly, according to some embodiments.
[0021] FIG. 4 illustrates an expanded view of a biolaminate
composite assembly, according to some embodiments.
[0022] FIG. 5 illustrates an expanded view of a biolaminate
composite assembly, according to some embodiments.
[0023] FIG. 6 illustrates an expanded view of a biolaminate
composite assembly, according to some embodiments.
DEFINITIONS
[0024] As used herein, "additive" refers to a material or substance
included in a biolaminate layer or biolaminate composite assembly
that provides a functional purpose or a decorative/aesthetic
purpose. An example of a functional additive would be a Eire
retardant, impact modifier, antimicrobial, UV stabilizer,
processing aid, plasticizer, filler, mineral particle for hardness,
and other forms of standard plastic or bioplastic additives. A
decorative additive would be a colorant, fiber, particle, dye.
Additives may also perform both functional and decorative purposes.
Additives may be implemented as part of one or more biolaminate
layers or as one or more separate layers in a biolaminate composite
assembly.
[0025] As used herein, "adhesive layer" or "adhesive" refers to a
substance that bonds two or more layers in a biolaminate layer or
biolaminate composite assembly. Adhesives may include glues.
Examples of adhesives include urethane, PVC, PVA, PUR, EVA and
other forms of cold press or hot pressed laminating adhesives and
methods. The biolaminate and laminates in general are typically
adhered to a non plastics or wood/agrifiber composite material
using various glues and laminating processes. Glues, such as
contact cement, PVA, urethanes, hot melts and other forms of
adhesives are commonly used in HPL (high pressure lamination).
Although many of these glues may optionally work for embodiments of
the invention, low or no VOC-containing glues are preferable in the
adhesive system that may be either hot pressed, rolled or cold
pressed processes to adhere the biolaminate layer to a
substrate.
[0026] As used herein, "bioink" refers to a non-petroleum based
ink. A bioink may be made of organic material, for example.
[0027] As used herein, "biolaminate layers" or "biolaminate" refers
to one or more thin layers in contact with a non-plastic rigid
substrate, including materials that are derived from natural or
biological components. The biolaminate layer may be a multi-layer,
such as including multiple layers. One form of biolaminate is made
up of a bioplastic or bio-co-polymer, such as PLA (polylactic
acid). A biocopolymer, including PLA and other biopolymers, may be
used within this invention to create a biolaminate. Biolaminate
layers may refer to one or more thin layers including over 50% PLA
in combination with optional additives, colorants, fillers,
reinforcements, minerals, and other inputs to create a biolaminate
composite assembly.
[0028] As used herein, "biopolymer" or "bioplastic" refers to a
polymer derived from a natural source, such as a living organism. A
biopolymer may also be a combination of such polymers, such as in a
mixture or as a copolymer, for example. A biopolymer may be a
polymer derived from a natural source, such as a living organism. A
biopolymer may be a sugar, for example. Polylactic acid (PLA) and
polyhydroxyalkanoate (PHA) may be examples of a biopolymer.
Biopolymers may be derived from corn or soybeans, for example. A
biopolymer may be a co-polymer or a mixture of more than one
biopolymer, such as a mixture of PLA and PHA, for example. Other
forms of biopolymers included within the embodiments of the
invention (and derived from renewable resources) are polymers
including polylactic acid (PLA) and a class of polymers known as
polyhydroxyalkanoates (PHA). PHA polymers include
polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV), and
polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV),
polycaprolactone (PCL) (i.e. TONE), polyesteramides (i.e. BAK), a
modified polyethylene terephthalate (PET) (i.e. BIOMAX), and
"aliphatic-aromatic" copolymers (i.e. ECOFLEX and EASTAR BIO),
mixtures of these materials and the like.
[0029] As used herein, "contacting" refers to physically,
mechanically, chemically or electrically bringing two or more
substances together or within close proximity. Contacting may be
mixing or dry blending, for example.
[0030] As used herein, "forming" or "formed" refers to contacting
two or more layers of material, such that an adherent
semi-permanent or permanent bond is formed. Examples of forming
include thermoforming, vacuum forming, linear forming, profile
wrapping or a combination thereof.
[0031] As used herein, "heating" refers to increasing the molecular
or kinetic energy of a substance, so as to raise its
temperature.
[0032] As used herein, "laminate" or laminating" refers to
contacting two or more layers of material using heat and/or
pressure to form a single assembly or multilayer. Laminating may be
accomplished with the use of an adhesive between the layers or by
thermally fusing without the use of an adhesive, for example.
[0033] As used herein, "mixture" refers to a composition of two or
more substances that are not chemically combined with each other
and are capable of being separated.
[0034] As used herein, "non-biodegradable" refers to a substance
that is non-biodegradable for a significant amount of time. A
non-biodegradable material may not substantially degrade after
about 5 years, after about 10 years, after about 20 years or after
about 30 years, for example.
[0035] As used herein, "non-plastic rigid substrate" refers to
wood, wood plastic, agrifiber, or mineral fiber composite panel
primarily consisting of a particle, fiber, flake, strand or layer
that is thermally pressed with a small amount of resin to produce a
panel of sufficient strength for furniture and other building
products requirements. A non-plastic rigid substrate may include
some plastic, but include non-plastic materials, such as a wood or
agrifiber plastic composite in an extruded or compressed sheet
form. The non plastic rigid substrate may be a VOC-free particle
board or MDF (medium density fiberboard) and preferably derived
from rapidly renewable resources such as wheat straw or other
biofiber or agricultural based fibers. Other non-plastic rigid
substrates may include metal, wood particleboard, agrifiber
particleboard, plywood, OSB (orientated strand board), gypsum
board, sheet rock, hardboard (such as Masonite), cement or cement
board and other rigid substrates. Non-plastic rigid substrates may
include paper-based boards, cellulosic substrates (or other organic
fibers), cellulose paper composites, multilayer cellulose glue
composites, wood veneers, bamboo or recycled paper substrates.
Examples of agrifiber particleboard include wheatboard such as
MicroStrand produced by Environ Biocomposites Inc. Materials such
as particleboard, medium density fiberboard, high density
fiberboard, plywood, and OSB are commonly used composite building
panels that provide a good substrate for high pressure laminates.
Due to environmental pressures many of the wood composite panels
that in the past were glued with formaldehyde based resins, such as
urea form and phenol form, are being replaced with low or no VOC
glues in the forms of urethane or methyl diisocyanide. Over the
past decade, concerns over wood supplies have spurred the
development of new fiber panels from more rapidly renewable
resources including many agrifibers such as wheat straw, rice straw
and other cereal grain straws.
[0036] As used herein "PLA" or "polylactic acid" refers to a
thermoplastic polyester derived from field corn of 2-hydroxy
lactate (lactic acid) or lactide. The formula of the subunit is:
--[O--CH(CH3)-CO]-- The alpha-carbon of the monomer is optically
active (L-configuration). The polylactic acid-based polymer is
typically selected from the group consisting of D-polylactic acid,
L-polylactic acid, D,L-polylactic acid, meso-polylactic acid, and
any combination of D-polylactic acid, L-polylactic acid,
D,L-polylactic acid and meso-polylactic acid. In one embodiment,
the polylactic acid-based material includes predominantly PLLA
(poly-L-Lactic acid). In one embodiment, the number average
molecular weight is about 140,000, although a workable range for
the polymer is between about 15,000 and about 300,000.
[0037] As used herein, "thermoforming" may refer to forming with
the use of heat. Thermoforming may include the step of positioning
a film or layer over the surface of a shaped substrate by means of
a membrane press using heat and a bladder that presses and forms
the film or layer over a complex three dimensional shape or two or
more surfaces of a substrate. A thermally activated adhesive may
initially be applied to the three dimensional substrate prior to
heat forming the thin film or layer onto the surface. Thus the heat
and pressure both form the layer onto the substrate shape and
activate the adhesive layer at the same time.
DETAILED DESCRIPTION
[0038] The following detailed description includes references to
the accompanying drawings, which form a pan of the detailed
description. The drawings show, by way of illustration, specific
embodiments in which the invention may be practiced. These
embodiments, which are also referred to herein as "examples," are
described in enough detail to enable those skilled in the art to
practice the invention. The embodiments may be combined, other
embodiments may be utilized, or structural, and logical changes may
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.
[0039] In this document, the terms "a" or "an" are used to include
one or more than one and the term "or" is used to refer to a
nonexclusive "or" unless otherwise indicated. In addition, it is to
be understood that the phraseology or terminology employed herein,
and not otherwise defined, is for the purpose of description only
and not of limitation. Furthermore, all publications, patents, and
patent documents referred to in this document are incorporated by
reference herein in their entirety, as though individually
incorporated by reference. In the event of inconsistent usages
between this document and those documents so incorporated by
reference, the usage in the incorporated reference should be
considered supplementary to that of this document; for
irreconcilable inconsistencies, the usage in this document
controls.
[0040] Introduction
[0041] A biolaminate composite is provided. The biolaminate
composite is flexible and 3D formable. Generally, the biolaminate
composite comprises one or more biolaminate layers with at least
one of the biolaminate layers compromising polylactic acid. In some
embodiments, the at least one biolaminate layer may further
comprise a natural wax such as soy wax. The one or more biolaminate
layers may be formable over a rigid non-plastic substrate to form a
biolaminate composite assembly. Embodiments of the present
invention describe a biolaminate derived from bioplastic,
biocopolymer or biocomposites products, assemblies, and systems
that provide a biosolution system to replace formaldehyde-based
laminates and PVC products. In addition, embodiments of the
invention provide an economically competitive solution to large
commodity products.
[0042] Various embodiments are provided that exhibit differing
properties. In some embodiments, at least one of the biolaminate
layers may include a plastic and a mineral and be suitable for use
as a wear layer. In other embodiments, two cellulose layers may be
provided with the polylactic acid layer being provided
therebetween. In other embodiments, an intumescent layer may be
provided in the biolaminate composite such that the composite
exhibits fire retardant properties.
[0043] Embodiments relate to a product and methods for making a
biolaminate assembly utilizing a saturated or resin impregnated
paper layer, in particular a decorative surfacing laminate layer.
The layer may include at least one cured layer of a polylactic or
lactic acid saturated paper. The top or surface layer may include a
decorative printed or colored paper. In another example,
melamine-formaldehyde resin impregnated papers may be put on top of
a stack of phenol-formaldehyde resin impregnated papers and
subsequently cured. Generally, such biolaminate assembly may
include a first cellulosic layer and a second cellulosic layer. A
first bio-based polymer, such as PLA, may be provided between the
first cellulosic layer and the second cellulosic layers. Fusing of
the first cellulosic layer, the first bio-based polymer, and the
second cellulosic layer may impregnate the cellulosic layers with
the first bio-based polymer substantially throughout the cellulosic
layers.
[0044] Embodiments of this invention use unique bioplastics in
combination with optional lower cost bioadditives that allow faster
processing than conventional PVC and laminates and allow the
products to be sold competitively with PVC thermofoils and high
pressure laminates while being produced from rapidly renewable
resources and providing no VOC contribution to the interior
environment.
[0045] Generally, embodiments of the biolaminate composite may
relate to a biolaminate composite assembly and/or a biolaminate
surface system. Such biolaminate surface system may comprise a
bioplastic, bio-copolymer, and biocomposite system in the form of a
biolaminate layer that is laminated or thermoformed to a rigid
non-plastic substrate by means of a glue line or adhesive layer.
The biolaminate system also may include matching profile extrusion
support products derived from the same composition and processing
method.
[0046] In some embodiments, a decorative biolaminate composite may
be provided. The decorative biolaminate may have a natural three
dimensional depth of field as compared to PVC thermofoils or high
pressure laminates based on the semitransparent nature of the
biopolymers providing unique aesthetic and similar performance to
that of other surfacing materials.
[0047] Further, a biosolution option is provided that is derived
from rapidly renewable agricultural materials and designed for
longer term applications and products typically used in interior
applications where concerns over clean air and encouragement of
environmentally friendly products are heightened.
[0048] Thus, a biolaminate composite assembly is described
including one or more biolaminate layers that are adhered by means
of laminating or thermoforming onto a non-plastic rigid substrate.
The resultant biolaminate composite assembly is designed to be used
for desktops, tabletops, worksurfaces, wall panels, wall coverings,
cabinet doors, millwork, and other decorative laminated products.
The biolaminate surface layer can be contacted with various
nonplastic substrates by means of thermoforming for three
dimensional components or flat laminated. The biolaminate layer may
include one or more layers of a biopolymer, biocopolymer,
biocomposite materials or a combination thereof. The biopolymer or
modified biopolymer may include primarily a PLA or PHA or blend
thereof. The biolaminate layer may include a biocopolymer wherein
the biocopolymer includes an additional biopolymer or bioplastic or
a petrochemical based plastic or recycled plastic. The biolaminate
layer may include a biocomposite wherein a biopolymer is blended
with various fillers, reinforcement, functional additives, fire
retardants, and other such materials for aesthetic or functional
needs.
[0049] Composite Assembly
[0050] Referring to FIG. 1, a cross-sectional view 100 of a
biolaminate composite assembly is shown, according to some
embodiments. A non-plastic rigid substrate 106 may be in contact
with an adhesive layer 104. The adhesive layer 104 may be in
contact with one or more biolaminate layers 102. The non-plastic
rigid substrate 106 may also be in contact with the layers 102, for
example. A biolaminate layer 102 may include multiple layers.
[0051] Accordingly, the composite assembly may include a
biolaminate layer and one or more other layers. The one more other
layers may also be biolaminate layers. Some possible embodiments
for these layers are described below. It is to be appreciated that
while these layers may be discussed as separate layers from the
biolaminate layer, the components or functionality of these layers
may alternatively be provided in the biolaminate layer.
[0052] Biolaminate Layer
[0053] At least one biolaminate layer of the biolaminate composite
assembly may include primarily a biopolymer including PLA, PHA or
similar biopolymers. The biopolymer, biocopolymer and biolaminate
(or biolaminate layer or biolaminate composite assembly) may
include one or more additives. Suitable additives include one or
more of a dye, pigment, colorant, hydrolyzing agent, plasticizer,
filler, extender, preservative, antioxidants, nucleating agent,
antistatic agent, biocide, fungicide, fire retardant, heat
stabilizer, light stabilizer, conductive material, water, oil,
lubricant, impact modifier, coupling agent, crosslinking agent,
blowing or foaming agent, reclaimed or recycled plastic, and the
like, or mixtures thereof. In certain embodiments, additives may
tailor properties of the biolaminate composite assembly for end
applications. In one embodiment, the biopolymer may optionally
include about 1 to about 20 wt-% of an additive or additives. Other
additives may include other forms of synthetic plastics or recycled
plastics such as polyethylene, polypropylene, EVA, PET,
polycarbonate, and other plastics to enhance performance and add
recycled content if desired or required. In one embodiment, the
biolaminate layer may comprise 100% biorenewable biopolymer.
Binders may be added to the biolaminate layer, such as EVA.
[0054] Additives may be present in the at least one biolaminate
layer comprising PLA or similar biopolymer or may be provided in a
separate layer within the composite assembly. Such additives may be
functional or decorative, for example. Any discussion of such
additives as present within the biolaminate layer or as provided in
a separate layer is intended for the purposes of illustration only
and it is to be appreciated that such discussion may equally apply
to the other embodiment.
[0055] Bioplasticizers, biolubricants, fire retardants, decorative
and functional fibers, decorative and functional fillers, colorant
systems and surface textures may be integrated into a bioplastic,
biocopolymer, or biocomposite (as part of the biolaminate layer or
layers or assembly) producing an extrudable material that may be
formed into a biolaminate sheet and matching profile extrusion
components. For example, the biolaminate layer may include about
50% to about 95% polylactic acid polymer from corn or other natural
materials in combination with a bioplasticizer/biolubricant and
other additives.
[0056] The biolaminate layer may include a biopolymer such as PLA
blended with plasticizers to form a flexible biolaminate sheet that
also can be printed on the surface or reversed printed on a clear
flexible biolaminate. The flexible biolaminate can be laminated
onto a sheet rock wall as a replacement for PVC vinyl wall
covering. In this case, an optional nonwoven material may be
coextruded onto the backside of the flexible biolaminate to add
additional strength for such application. The flexibility of the
biolaminate layer may be comparable to that of a PVC sheet.
[0057] The biolaminate layer of the biolaminate composite assembly
may also include a plasticizer or impact modifier to produce a more
flexible biolaminate or softer surface biolaminate layer.
Preferably, the plasticizer has a boiling point of at least
150.degree. C. Examples of plasticizers that may be used include,
but are not limited to, glycerine, polyglycerol, glycerol,
polyethylene glycol, ethylene glycol, propylene glycol, sorbitol,
mannitol, and their acetate, ethoxylate, or propoxylate
derivatives, and mixtures thereof. Specific plasticizers that may
be used include, but are not limited to, ethylene or propylene
diglycol, ethylene or propylene triglycol, polyethylene or
polypropylene glycol, 1,2-propandiol, 1,3-propandiol, 1,2-, 1,3-,
1,4-butandiol, 1,5-pentandiol, 1,6-, 1,5-hexandiol, 1,2,6-,
1,3,5-hexantriol, neopentylglycol trimethylolpropane,
pentaerythritol, sorbitol acetate, sorbitol diacetate, sorbitol
monoethoxylate, sorbitol dipropoxylate, sorbitol diethoxylate,
sorbitol hexaethoxylate, aminosorbitol,
trihydroxymethylaminomethane, glucose/PEG, the product of reaction
of ethylene oxide with glucose, trimethylolpropane, monoethoxylate,
mannitol monoacetate, mannitol monoethoxylate, butyl glucoside,
glucose monoethoxylate, alpha-methyl glucoside, the sodium salt of
carboxymethylsorbitol, polyglycerol monoethoxylate and mixtures
thereof. An impact modifier maybe in the form of a plasticizer or
in the form of an elastomer material. Impact modifying elastomeric
materials include, but are not limited to EVA, EMA, TPE, metalecene
and other similar forms of elastomers.
[0058] Natural or biobased plasticizers may be also used including
soybean wax, natural waxes, glycerine, natural esters, citric
esters, soybean oils, epoxified or heat embodied soybean oils and
other similar plasticizers.
[0059] Other additives, such as congregated vegetable oils,
glycerine (by-product of biodiesel production), soybean wax and
other lower cost biomaterials, may be added as an additive in lower
percentages to create a combination of lubricant action and
bioplasticization of the biopolymer, while improving the
lubrication within the profile die process. These forms of material
lower the cost of the end product while maintaining the
environmentally friendly bio-composition. These forms of material
also may assist in improved dispersion of various fire retardants,
fillers, and fibers while improving the impact strength of the
overall system.
[0060] The addition of a low molecular weight
bioplasticizers/lubricant system within the embodiments of the
present invention allow for better loading of these forms of
powders into the biopolymer matrix which provides better processing
parameters and increases flexibility and impact resistance.
Examples of plasticizers which may be used according to the
invention are esters comprising: (i) an acid residue comprising one
or more of: pthhalic acid, adipic acid, trimellitic acid, benzoic
acid, azelaic acid, terephthalic acid, isophthalic acid, butyric
acid, glutaric acid, citric acid or phosphoric acid; and (ii) an
alcohol residue comprising one or more aliphatic, cycloaliphatic,
or aromatic alcohols containing up to about 20 carbon atoms.
Further, non-limiting examples of alcohol residues of the
plasticizer include methanol, ethanol, propanol, isopropanol,
butanol, isobutanol, stearyl alcohol, lauryl alcohol, phenol,
benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene
glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene
glycol. The plasticizer also may comprise one or more benzoates,
phthalates, phosphates, or isophthalates. In another example, the
plasticizer comprises diethylene glycol dibenzoate, abbreviated
herein as "DEGDB". Examples of bioplasticizers include, but not
limited to, hydrogenated vegetable oils, epoxified or congregated
vegetable oils, drying oils derived from vegetable oils, mineral
oils, natural waxes, polylactocaptone, citric acid and others. The
resultant material of a PLA in combination with a plasticizer or
bioplasticizer is considered to be a bio-co-polymer system. Lower
loadings of a bioplasticizer may be used to maintain a rigid
profile or sheet extrusion component and high loadings will further
impart additional flexibility. Flexible or higher impact properties
may be required by the varying product applications.
[0061] All forms of plasticizer additions to the biolaminate layer
or assembly may assist in both impact resistance and in making the
biolaminate layer more flexible in nature to match the performance
of flexible PVC film products. Although various plasticizers may be
used for a flexible biolaminate or for impact modification, it may
be preferred to use a biobased plasticizer to maintain the biobased
environmental position of the product.
[0062] In some embodiments, fillers, including synthetic materials,
natural minerals, and biomaterials, may be added to the biopolymer
of the biolaminate layer. Such fillers include biofibers, proteins,
starches, vegetable oils, natural fatty acids and other materials.
Fibers and minerals typically help in the viscosity and processing
of various plastics.
[0063] In some embodiments, the biolaminate layer may include
further components adding other functionality to the layer. For
example, the biolaminate layer may include quartz or other minerals
and fibers.
[0064] Cellulosic Layers
[0065] In some embodiments, resin impregnated paper substrate or
backer layer may be provided as part of or in contact with the one
or more biolaminate layers of the biolaminate assembly. The layer
may include forms of polylactic acid or other biopolymers to create
a biobased and environmentally friendly alternative to formaldehyde
based high pressure laminates. Embodiments of the invention may
utilize either molten PLA or forms of processed lactic acid liquids
that are impregnated into the one or more layers of paper. The
saturated paper or paper layers may be heat formed into a
decorative or functional laminate. The one or more layers may be
contacted with heat and/or pressure sufficient to cure or
polymerize the resin. In some embodiments, additional cellulosic
layers impregnated with a bio-based polymer may be provided to form
a thicker biolaminate structure.
[0066] In a first cellulosic embodiment, the biolaminate assembly
may include a first cellulosic layer and a second cellulosic layer.
A first bio-based polymer, such as polylactic acid or lactic acid,
may be provided between the first cellulosic layer and the second
cellulosic layers. Fusing of the first cellulosic layer, the first
bio-based polymer, and the second cellulosic layer may impregnate
the cellulosic layers with the first bio-based polymer
substantially throughout the cellulosic layers.
[0067] In a second cellulosic embodiment, the biolaminate assembly
may 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 bio-based polymer such as polylactic acid or lactic acid. In
various embodiments, the second layer may be a paper substrate
impregnated with a bio-based polymer, may be a biobased film
including a PLA sheet, or may be a clear PLA surface layer. The
biolaminate assembly exhibits substantially no formaldehyde
emission and may be suitable for replacement for high pressure
laminates.
[0068] Embodiments of the present invention include biolaminate
assemblies utilizing a saturated paper with substantially no
formaldehyde emission. Various other layers may be provided with
cellulosic embodiments. For example, decorative layers (including
printed layers), overlay layers, wear layers, or other functional
layers may be provided. An example decorative layer comprises a
film layer, such as a PLA film layer, reverse printed with an
image. The printed PLA film layer may then be provided within the
biolaminate composite, such as over the first and second cellulosic
layers. Overlay papers may be reasonably transparent when
impregnated and cured. Either a clear polylactic or bioplastic or
bioplastic/petrochemical plastic blend may be fused onto a
biolaminate layer or a plain paper saturated with PLA or LA may be
thermally fused onto the surface, also providing a good transparent
layer, for example. Suitable overlay layers may include a thermoset
and thermoplastic standard overlay, a mineral plastic overlay, a
bioplastic overlay, or a wear layer surface overlay.
[0069] Accordingly, various forms of polylactic acids may be
saturated into papers for the production of a biolaminate layer.
Further, additives may be contacted with the polylactic acid as
described above. Other bioresins and biobased polymers also may be
used for paper saturating and produced into a single or multilayer
laminate layer as an alternative to petrochemical formaldehyde
based laminates. For example, biobased resins such as
polyurethanes, polyesters, nylong and monomers such as polyols,
organic acids and other similar biobased resins may be used to
saturate papers for laminates. New generations of protein polymer
chemistry also may be included such as Zein proteins, soybean
protein and other bioresin or bioadhesive blends. Such biobased
adhesives or polymers may be used in a liquid form either in their
natural liquid state or by heat melting into various viscosity
liquids in which the paper may be saturated and eventually cured in
a single or multilayer biolaminate structure. Other new biopolymers
derived from dextrose such as 3HP chemical platforms that lead to
acrylic acid and acrylic polymers may also provide a biobased resin
that may be used by itself or in combination with other biopolymers
including PLA and the like.
[0070] Currently, paper from wood may be the primary source of
paper used for a cellulosic biolaminate composite. However, any
suitable woven or nonwoven cellulosic paper may be used. Suitable
papers include, for example, plain paper, kraft paper, treated
paper, wood based paper, recycled papers, decorative paper, printed
paper, fiber reinforced papers, glass fiber reinforced paper, thin
wood veneers, fire retardant paper, chemically treated paper, ph
adjusted papers, or a combination thereof. The cellulosic paper may
be a biobased paper from a renewable plant fiber such as hemp,
baggase, wheat straw, and corn stover
[0071] In one embodiment of a biolaminate including a cellulosic
layer, four laminate layers are provided and fused and topped with
a textured release paper. The bottom 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 may be used
to fuse the layers, thereby saturating and impregnating the
decorative print paper layer with PLA. If provided over a substrate
such as a wood composite substrate before application of heat and
pressure, the heat and pressure operate to fuse the layers into the
wood composite substrate. The textured release paper is provided
over the wear layer.
[0072] Surface Wear Layer
[0073] A biolaminate surface layer may be provided having wear
layer characteristics. Such biolaminate surface wear layer may
include natural fine quartz materials for specific high durability
surfacing applications, while still maintaining a translucent
material. Various natural minerals such as silica (natural quartz),
alumina, calcium carbonate, and other minerals may be used in the
production of flooring products to provide a higher degree of wear
resistance and hardness. These wear resistant materials may be in
the forms of medium particles that may be seen by the eye as
decorative and functional particles. Such fine powder material
becomes clear or semi-translucent in the bio-co-polymer matrix or
in nanosized form within the biolaminate layer. The natural
minerals may be included in a surface layer of a multilayer
biolaminate layer or within a single biolaminate layer positioned
near the surface of a biolaminate composite assembly.
[0074] The "nanoquartz" technology may provide good performance and
durability of the surface. Natural quartz or silica sand in various
particle sizes from nano-sized to larger sizes may be used in
decorative applications and be added to the biolaminate system.
Although, within embodiments of this invention, other natural
minerals may be used, natural quartz is one of the hardest
materials in nature. A biolaminate laminate assembly integrating
quartz may also provide a lower cost option for expensive granite
and other solid surfacing composites for kitchen countertops,
tables, and other higher performance areas. These forms of
biolaminate layers may be either flat laminated or thermoformed
into three dimensional worksurface for kitchen and other forms of
countertop applications.
[0075] Surface Wear Layer with Decorative Layer
[0076] In one embodiment, a two layer biolaminate composite may be
provided including a clear quartz loaded surface layer thermally
fused to an opaque biolaminate layer with printing encapsulated
between the layers. In the case of a multilayer biolaminate layer,
the layers of the biolaminate may be fused together by thermal
processing with pressure or by means of a separate glue line or
adhesive layer.
[0077] Fibrous Layer
[0078] The biolaminate layer may include a biopolymer blended with
natural fibers such as wheat, rice, and other similar forms of
hydrophilic fibers. This, in addition to its organic nature,
provides both higher degrees of wear resistance and improves char
promotion in creating fire rated laminates and matching profile
extrusion components. A fire retardant may be included in one or
more biolaminate layers, in the adhesive layer, in the non-plastic
rigid substrate or any combination with a biolaminate composite
assembly.
[0079] A biolaminate layer including natural fibers or fillers may
be desired due to their environmentally nature and for the fact
that they provide a random geometry within the clear or
semitransparent matrix yielding a natural look compared to an
ordered "man-made" appearance commonly found in solid surface or
repeating pattern high pressure laminate images. Natural fiber
materials may include, but are not limited to: wheat straw, soybean
straw, rice straw, corn stalks, hemp, baggase, soybean hulls, oat
hulls, corn hulls, sunflower hulls, paper mill waste, nut shells,
cellulosic fiber, paper mill sludge, and other agriculturally
produced fibers. Wheat and rice fiber may be preferred for their
shiny surfaces wherein these types of fiber are uniquely ground
into long narrow strands and not into a fine filler powder as
typically done in wood plastic composites. Although natural fibers
may be preferred, other fibers, particles, minerals and fillers may
be used, such as fiber glass wherein the bio-co-polymer may also
impregnate the glass fibers within this process. Other forms of
biobased materials may be used, such as seeds, proteins and
starches, to expand the natural aesthetic nature of the biolaminate
and matching extrusion profiles (such as edgebanding and other
support components).
[0080] Fire Retardant Layer
[0081] The biolaminate layer may include fire retardants commonly
used in dry fire extinguishers, such as ammonia phosphorus in
combination with mica and silica. Such fire retardants provide good
performance in a biolaminate composite assembly due to their pH and
lack of reactivity with a bio-co-polymer system. These provide a
high degree of flame suppression and induces char. Other fire
retardants may be used, preferably non-halogenated retardants
including alumina thyrate and magnesium hydroxides.
[0082] Additional materials may be added to the fire retardant
bio-co-polymer (PLA/bioplasticizer) that reduces liquid mobility
during burning, improving charring that insulates the material from
heat during burning, and provides a higher degree of material
integrity during burning as to hold its shape. Examples of
additional char promoters include, but are not limited to:
nanoclay, zinc borate, intumescent fire retardants, agricultural
flour, wood flour, starch, paper mill waste, synthetic fibers (such
as fiberglass or powders), minerals, and other materials. Other
forms of drip suppressants, such as polytetrafluoroethylene, may
also be used to reduce liquid mobility and be synergistic with the
char promoters. Other forms of char promoters also may assist in
stopping the liquid mobility or provide drip suppression, such as
natural or synthetic rubbers. Such char promoters also provide
additional flexibility or improved impact resistance for the
biolaminate or matching profile biosolutions.
[0083] The resultant material has a very good char and low flame
spread with very minimal smoke generation as compared to the high
smoke producing PVC laminates that also are highly toxic. In
regards to small amount of smoke generated, the smoke is
semitransparent white or not seen at all.
[0084] Decorative Layer
[0085] The surface layer of a biolaminate composite assembly may
include a clear or semitransparent biolaminate layer in contact
with a printed layer wherein various forms of printing methods and
inks or dyes can be used to apply a decorative or customized
feature on the printed layer. A suitable is a lactic acid based ink
also derived from corn to provide a truly environmental biolaminate
product.
[0086] The biolaminate composite assembly may be a decorative
composite, including a clear biopolymer layer, an opaque biopolymer
layer; and a decorative print layer. The print layer may be
positioned between the clear layer and opaque layer. The clear
layer may be textured. The layers may be optionally fused
together.
[0087] The surface layer of a biolaminate composite assembly may
include a clear or semitransparent film or layer that is direct
printed on the top or outer surface and optionally liquid coated
over the top to protect the printed surface and for improved
surface characteristics. Liquid laminating may be accomplished by
roll coating, rod coating (such as Mery rod coating), spray
coating, UV cured coating systems and other standard coating
systems.
[0088] The surface layer of the biolaminate composite assembly may
include reverse direct printing wherein the print layer is
positioned between the biolaminate and adhesive layer. This
positioning allows the entire biolaminate clear layer to be a wear
layer that can be refinished. In contrast, traditional high
pressure laminate layers quickly wear through the pattern and can
not be refurbished or refinished.
[0089] A decorative pattern may be printed on one or more sides of
a biolaminate layer. The pattern may be on an outer surface or may
be on an inner surface and visible to a user through a translucent
biolaminate layer. Printing may include direct printing, reverse
printing, digital printing, dye sublimation rotor gravure or other
methods. Printing may occur at any suitable time, including before
forming or laminating or after forming or laminating. Printing may
be performed on one or more layers, pressed or laminated together,
before the subsequent forming or laminating to a substrate. The
printed layer may be in contact with the adhesive layer or may be
on an outer surface. A protective, clear layer may be further
contacted to an outer printed surface. Printing inks may include
inks that provide sufficient adhesion to the biolaminate layer and
can maintain adhesion in secondary heat laminating applications.
Certain solvent based inks may not maintain sufficient adhesion
during hot laminating processes. In addition the ink type needs to
have some degree of flexibility as not to crack during hot
thermofoiling processes and applications. UV inks are more
environmentally friendly than solvent and are more preferred, but
may not have sufficient flexibility or adhesion. New corn based
inks derived from forms of lactic acid from corn are most preferred
as to maintain the best environmental position and also provides
improved adhesion while maintaining flexibility for such final
applications and hot laminating processes.
[0090] The surface layer of the biolaminate layer may include two
layers of biopolymer films wherein the top layer is a clear
biolaminate film layer with a top surface texture and the second
bottom layer is an opaque (i.e., white) biolaminate film layer with
a print layer between the two biopolymer film layers in which the
biopolymer film layers are thermally fused together or laminated by
means of an adhesive. Once the multilayer decorative laminate is
produced, it can be laminated in a manner similar to that of high
pressure laminates onto various non-plastic rigid substrates
including wood or agrifiber composite panels.
[0091] Colorant System
[0092] The biolaminate layer or layers within the biolaminate
composite assembly may include a colorant system. Colorants
include, but are not limited to: pearls, particle granites, solids,
dyes, "glow in the dark" additives, swirls, blends and other forms
of decorative colorant systems. Colored minerals, fibers, and other
forms of unique color and unique geometry particles may be
integrated with the color into the biolaminate layer to provide
solid surface aesthetics without requiring a printing layer.
[0093] Suitable inorganic colorants include metal-based coloring
materials, such as ground metal oxide colorants of the type
commonly used to color cement and grout. Such inorganic colorants
include, but are not limited to: metal oxides such as red iron
oxide (primarily Fe.sub.2O.sub.3), yellow iron oxide (Fe.sub.2OHO),
titanium dioxide (TiO.sub.2), yellow iron oxide/titanium dioxide
mixture, nickel oxide, manganese dioxide (MnO.sub.2), and chromium
(III) oxide (Cr.sub.2O.sub.3); mixed metal rutile or spinel
pigments such as nickel antimony titanium rutile
({Ti,Ni,Sb}O.sub.2), cobalt aluminate spinel (CoAl.sub.2O.sub.4),
zinc iron chromite spinel, manganese antimony titanium rutile, iron
titanium spinel, chrome antimony titanium ruffle, copper chromite
spinel, chrome iron nickel spinel, and manganese ferrite spinel;
lead chromate; cobalt phosphate (CO.sub.3(PO.sub.4).sub.2); cobalt
lithium phosphate (CO.sub.3(PO.sub.4); manganese ammonium
pyrophosphate; cobalt magnesium borate; and sodium alumino
sulfosilicate (Na.sub.6Al.sub.6Si.sub.6O.sub.24S.sub.4). Suitable
organic colorants include, but are not limited to: carbon black
such as lampblack pigment dispersion; xanthene dyes; phthalocyanine
dyes such as copper phthalocyanine and polychloro copper
phthalocyanine; quinacridone pigments including chlorinated
quinacridone pigments; dioxazine pigments; anthroquinone dyes; azo
dyes such as azo naphthalenedisulfonic acid dyes; copper azo dyes;
pyrrolopyrrol pigments; and isoindolinone pigments. Such dyes and
pigments are commercially available from Mineral Pigments Corp.
(Beltsville, Md.), Shephard 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.).
[0094] The colorant may be added to the biocomposite layer in an
amount suitable to provide the desired color. In some embodiments,
the colorant is present in the particulate material in an amount no
greater than about 15% by weight of the biocomposite matrix, in an
amount no greater than about 10%, or in an amount no greater than
about 5%. Preferably, colorants use biopolymer carriers to maintain
the biobased characteristics of the biolaminates. Although standard
color carriers, such as EVA, do not contain hazardous materials, it
is preferred to use natural polymers as color carriers. A three
dimensional appearance due to utilizing a clear biopolymer may be
achieved within the embodiments of the present invention.
[0095] The surface layer of a biolaminate composite assembly may
include a solid opaque colorant with optional fibers, fillers, or
minerals to add decorative value to the product. The color and
texture may be consistent throughout the product similar to that of
a thin solid surface material.
[0096] Example Composite Assemblies
[0097] In one example of a biolaminate composite assembly, the top
layer may be a biolaminate loaded with natural quartz to provide a
high wear surface. The second layer may be a top printed white
sheet of biolaminate. In this case, the quartz biolaminate layer
may be fused together with the printed bottom layer by means of
heat and pressure or by means of a clear adhesive.
[0098] In one embodiment, a multiple layer biolaminate composite
may be designed for unique aesthetic function. Multiple clear
layers of the biolaminate may be printed with differing patterns
and colors so that after multilayers of printed clear biolaminates
are fused together, they provide a unique three dimensional depth
of field in the image or pattern. Such an aesthetic depth of field
is not found in HPL or PVC products, which are typically both
opaque materials with printing on the surface. The multilayer
printed biolaminate may utilize clear layering with an optional
white back layer that provides for high quality and excellent image
depth.
[0099] Substrates
[0100] The biolaminate composite or any layer thereof may be
laminated to a substrate. Such substrate may include non plastic
substrates such as medium density fiberboard, particle board,
agricultural fiber composites, plywood, gypsum wall board, wood or
agrifiber plastic substrates and the like. Ond suitable substrate
is a formaldehyde free wheatboard composite that is rapidly
renewable. Further non plastic substrate may typically be a rigid
wood or agrifiber composite commonly used for furniture, cabinet,
millwork, laminate flooring, store fixture and other such
applications. In most of these types of applications a fiat sheet
may be used in which the biolaminate may be adhered to the surface
and backside for balanced construction. In one embodiment, forms of
profiles may be used in which MDF made from either wood or
agrifiber can be machined into a three dimensional linear shape for
millwork applications and the biolaminate layer may be formed and
laminated onto this surface
[0101] A substrate may also be a wood or agrifiber mixed with
plastic that is extruded into a final shape such as a millwork or
window profile in which the biolaminate may then be formed and
adhered to the surface by means of heat and a glue fine. The
biolaminate layer in this embodiment may be either functional or
decorative.
[0102] Methods of Making the Biolaminate Composite
[0103] Referring to FIG. 2, a block flow diagram 200 of a method of
making a biolaminate composite structure is shown, according to
some embodiments. A non-plastic rigid substrate 106 may be formed
or laminated 202 with one or more biolaminate layers 102. Forming
202 may include thermoforming, vacuum forming, thermoforming or a
combination thereof. Additives may be introduced before, during or
after forming 202.
[0104] Referring to FIGS. 3-6, an expanded view (300, 400, 500,
600) of a biolaminate composite assembly is shown, according to
some embodiments. A substrate 106, such as a rigid non-plastic
substrate, may be contacted with a clear biolaminate layer 302
utilizing an adhesive layer 104 on a first side. The clear
biolaminate layer 302 may be in contact with a reverse print layer
304, for example. They may be joined by fusing for example. On a
second side of the substrate 106, a second biolaminate layer 102
may be contacted, such as by thermoforming or lamination (see FIG.
3).
[0105] A clear biolaminate layer 406 may be contacted with a direct
print layer 404 and then protected on an outer surface by a clear
protective coating 402, for example (see FIG. 4). A biolaminate
layer may include two or more layers, such as a white biolaminate
layer 102, a surface biolaminate layer 302 and a print layer 502 in
between (see FIG. 5). The surface layer 302 may be loaded with
quartz, for example. In another embodiment, a fire retardant may be
integrated in a biolaminate layer 602, then direct printed 502 with
a decorative layer. A clear biolaminate layer 406 may face an outer
surface (see FIG. 6).
[0106] Various of these steps will be described in more detail
below.
[0107] PLA used in the biolaminate layer may be processed above its
melting point in extrusion film processing. The PLA used in the
biolaminate may also be processed below its melting point in its
viscoelastic state and maintain a higher degree of crystallinity in
the biolaminate layer. For example, see U.S. patent application
Ser. No. 11/934,508, filed Nov. 2, 2007, the disclosure of which is
herein incorporated in its entirety. According to the embodiments
of the invention, the extrusion process for producing the
biolaminate layer may be performed at a temperature significantly
lower than the melting point and keeps the PLA in its crystalline
state and processes the PLA in its viscoelastic state. In one
example, both a flat sheet can be produced, or a matching three
dimensional profile such as a matching edgebanding or millwork
piece.
[0108] U.S. patent application Ser. No. 11/934,508 teaches that PLA
in combination with an EVA type or synthetic form of binder allows
PLA to be processed below its melting point. In addition, this
teaches that fire retardants may be added. In embodiments disclosed
herein, the combination of the binder and highly polar PLA makes it
difficult to load fire retardant to the required level to reach a
class I rating without the material becoming extremely brittle and
not meeting the requirements of PVC applications. Although this
technique works well for producing a high tolerance profile shape,
the addition of EVA is not necessary in these embodiments. Other
forms of additives, along with processing at temperatures below the
melting point of PLA, may achieve a similar result. Accordingly,
embodiments of the invention use various forms of a
bioplasticizer/biolubrication system to replace the binder in the
above mentioned reference. In addition, the embodiments also show
that by increasing shear rate and maintaining a lower processing
temperature than the melting point of PLA, a high tolerance profile
extrusion can be produced.
[0109] When processing the PLA at a specific temperature range, in
which the PLA is in an "elastic state" similar to a rubber, the PLA
stays in its amorphous state and acts similar to that of various
other elastomeric materials. Also in this state, the material is
less susceptible to moisture and shear. In fact, in processing it
was found that higher shear levels when the PLA is in this
elastomeric state provides advantages in profile extrusion and with
the addition of various additives. PLA has a melting point of
approximately 390.degree. F. The embodiments of this invention
teach that with sufficient shear, PLA may be processed at a
temperature far lower than its melting point. In this embodiment,
the profile extrusion process ranges from about 280 to about
340.degree. F., and more preferably between about 300 to about
320.degree. F. With the addition of high loadings of fillers,
higher temperatures may be used, but preferably below the melting
point of the PLA.
[0110] Biolubricants assist in this low temperature viscoelastic
process, such as natural waxes, lignants or plasticizers.
Preferably, the wax or plasticizers are based on biobased
materials. Embodiments of the present invention describe a two
component composition processed below its melting point into a
profile extrusion continuous shape using a PLA and a plasticizer or
biolubricant may create complex shaped profiles of high
tolerance.
[0111] At these processing conditions, it may be possible to blend
in various additives, fillers, and reinforcement materials in
liquid or solid forms in addition adding various other polymeric
additives to develop a wider range of end performance qualities for
various non-biodegradable profile extrusion applications. The PLA
also may be foamed using celuka die systems and a foaming or
biofoaming agent to produce light weight profile extrusions. Other
fillers maybe added to the solid or foamed profile shape, including
wood fiber, wood flour, paper millsludge, agrifibers, cereal
straws, minerals, fiberglass fibers, starch, proteins, and other
forms of fillers or reinforcement. The resultant bioprofile may be
colored throughout to match the biolaminate composite assemblies or
printed using the same patterns as other biolaminates. This
provides the ability to create a full solution for buildings,
offices and commercial building as to allow for aesthetic matching
of environmental components in architectural design.
[0112] The addition of fillers, either synthetic, natural minerals
or biomaterials, may be added to the biopolymer in the elastomeric
state. The addition of these materials in the biopolymer
elastomeric state allows for processing using much higher shear
rates, provides improved dispersion and provides less brittleness
in the biopolymer by staying below its melting point and minimizing
crystallization of the biopolymer.
[0113] As noted, the biolaminate layer or layers within the
biolaminate composite assembly may include a colorant system.
Colorants may be added directly into the biolaminate layer by
mixing colorants with the biocopolymer and/or by coloring the
fibers by means of dying or other coloring processes to provide
single and multicolored high aesthetic biolaminates and matching
profiles.
[0114] A biolaminate layer using primarily PLA with optional
additives may be sheet extruded to meet the requirements of PVC or
HPL decorative surfacing products. The extruded sheet of
biolaminate may be processed either above the melting point to
achieve a clear amorphous biolaminate or below the melting point in
its viscoelastic state to increase its crystallinity. The extruded
biolaminate may be extruded in thicknesses ranging from 0.002'' to
0.3'' and more preferably between 0.005'' to 0.030'' and most
preferred between 0.010'' to 0.025''. The hot extruded biolaminate
clear sheet may then be processed through various rollers for both
cooling purposes and to imprint a texture on the surface and
backside of the biolaminate. The top surface texture may range from
a smooth high gloss to a highly textured flat surface. For
worksurface, tables, and most cabinet door applications a gloss
level between 10-30 degrees gloss may be preferred as not to show
scratching and reduce light reflection. The backside of the
biolaminate can also match the topside texture, but it is preferred
to have a low flat gloss as to promote adhesion in laminating. Even
though the biolaminate material may be clear, the addition of the
same or different textures on both sides may make the biolaminate
semitransparent and hard to see through.
[0115] After the clear biolaminate has been extruded, it may be
optionally used in this form as a clear film finishing over raw
wood or agrifiber composites as a direct replacement for liquid
finishing providing a VOC environmental and high performance finish
for such products.
[0116] In some embodiments, the semitransparent biolaminate may be
direct printed on the topside, reverse printed on the backside or
printed within layers of the biolaminate using various printing
methods or inks (as discussed earlier). Methods of printing
include, but are not limited to inkjet, rotor gravure,
flexographic, dye sublimation process, direct UV inject printing,
screen printing using standard or UV inks, and other means of
printing. A bioink may be utilized in the printing process. One
method for printing may be to heat either the ink or the substrate
prior and after printing to maximize adhesion of the printing inks.
In some cases, a primer layer may be utilized between the
biolaminate surface and the printing layer to improve adhesion of
these layers.
[0117] A printing process may be used to print a single layer clear
biolaminate in which the print is reversed printed on the back side
which may be a flat texture. The printing process wets out the flat
surface and increases the clarity of the biolaminate. Heat
laminating the biolaminate increases its amorphous nature. This may
cause the biolaminate to become more clear, resulting in a higher
quality of print. Because the printing is on the back side of the
clear biolaminate, the biolaminate provides a thicker wear layer
than PVC products that are typically printed on the surface with
minimal or no protective layers to protect the aesthetic print
layer.
[0118] Various printing inks can be used including solvent, UV
cured, silkscreen ink and other forms of ink as long as there is
appropriate adhesion and the ability to have some stretch for
thermofoiling applications. In some test cases, certain inks are
too rigid and may crack or loose adhesion in laminating processes.
One suitable ink is a biobased ink (i.e, bioink) such as the type
produced by Mubio for Mutoh Valuejet digital printing systems to
provide a 100% biobased product including the ink layers.
[0119] In one embodiment, a thin PLA film less than about 0.010'',
less than about 0.005'', may be reverse direct printed using wide
format digital printers or other means of printing. A recycled
mineral fiber composite including fiberized mineral and a biobased
binder with a heavy surface texture may be prepared by cutting to
size and a heat activated adhesive may be applied to the top and
side surfaces. The image on the PLA film may be of a pattern,
photo, signage or typically any form of computer generated artwork.
The composite may be placed in a thermofoiling machine along with
the printed film over the surface. The PLA film may be only heated
to about 140.degree. F. and held for a few seconds. At typical
thermofoiling temperatures, this film may sag and create holes
during vacuum processing. A vacuum may then be applied under the
warm film and it may then completely conforms to the rough
stonelike texture of the mineral fiber composite. The resultant
"ecoart" may be highly wear resistant due to the fact that the
print layer is below the clear film layer. The end product also
results in an approximate 30% biocontent and a 60% recycled content
with the balance of 10% a natural clay.
[0120] The biolaminate layer may include one or more layers of the
extruded biolaminate material. In producing a multilayer, a heat
laminating process may be used to form the layers together into the
biolaminate surface layer. Each layer may be the same, may be
similar, or may have specific and different functions. Multiple
layers of biolaminate may be fused together by heat and pressure in
which the material is slightly below the melting point of the
biopolymer using hot press systems and reasonable pressures around
50 PSI. Other means of fusing two layers of biolaminate may be used
including adhesive double side tapes, heat activated adhesives,
solvent bonding, and other methods. Fused together they form a
multilayer functional biolaminate that then can be laminated or
thermoformedonto a non plastic substrate to form a biolaminate
composite assembly.
[0121] The biolaminate composite or any layer thereof may be
laminated onto a non plastic substrate. Optionally, a paper, non
woven mat, woven mat or other forms of backer may be positioned on
the back of the biolaminate surface prior to laminating onto a
nonplastic rigid substrate. Various fabricators may use simple
water based PVA glues in the field for good adhesion of the
biolaminate to the non plastic rigid substrates. In addition, this
may provide additional functional performance of the biolaminate
layer.
[0122] In some embodiments, heat activated adhesives may be used
for contacting the biolaminate. This may be useful for simple cold
press adhesives, such as PVA, that require that the laminate
underside absorb water and create a bond without heat. The
biolaminate of these embodiments may be completely waterproof on
both sides, for example. Thus by the usage of heat processing in
laminating the "polar" nature of the PLA is increased and creates a
high degree of bond strength required for specific applications.
Another suitable method of laminating may be in a hot pressure
laminating process using a heat activated or heat cured
adhesion.
[0123] Laminating may include flat laminating or three dimensional
laminating processes. Flat lamination is used currently with high
pressure laminates to adhere the laminate onto a wood or agrifiber
composite substrate. Flat laminating is based on the application of
an adhesive or glue layer onto either the substrate or laminate
then using pressure to laminate together. Flat laminating may use
many types of glues and processes including both hot press, cold
press or pressure sensitive systems. Hot laminating system may
allow for improved adhesion between the biolaminate and the
substrate.
[0124] Thermofoil laminating or thermoforming is commonly used for
three dimensional laminating in which a non plastic substrate is
machined into a three dimensional part such as a table top,
worksurface, cabinet door or the like. A water based urethane
adhesive may be sprayed onto the substrate. By means of heat and
pressure using a vacuum or membrane press, the biolaminate layer
may be formed to the substrate and simultaneously the adhesive may
be heat activated to cure,
[0125] Profile wrapping is similar to that of thermoforming (i.e.,
thermofoiling) but is done using linear processing equipment to
create millwork, windows, and other linear components. In this
embodiment, the substrate may either be machined from a wood or
agrifiber composite into a linear millwork shape. This may also be
accomplished by extruding a shape from a natural fiber or mineral
with a plastic as to eliminate the machining and reducing the waste
from machining. Using a profile wrapping machine, typically, a hot
melt contact adhesive may be applied hot to the substrate or
biolaminate then pressed using a series of small rollers to form
the biolaminate layer onto the linear substrate.
[0126] In standard laminate worksurfaces, an edgebanding is
required. A biopolymer, such as PLA processed below its melting
point and in its viscoelastic state similar to producing the
biolaminate, may be used to produce profiles such as shaped
edgebanding and other support components. Either a tee molding that
is mechanically attached to the non-plastic rigid substrate or a
flat profile edgebanding that is glued is described within these
embodiments. Matching bioedgebanding may be produced using the same
biopolymer or biocopolymer system and process to allow for matching
aesthetics and performance. In addition, a matching linear profile
wrapped millwork product may be produced using the biolaminate
surface layer laminated onto a wood, agrifiber or plastic fiber
composite extrusion to create an aesthetic matching green system
for an entire office or building solution.
[0127] Other means of creating a matching edgebanding or matching
millworkprofile may be accomplished using pro file extrusion
methods of a composite substrate in a continuous linear shape such
as millwork. The biolaminate layer may be laminated using a linear
wrapping process and a hot melt adhesive to create a myriad of
environmental millwork as a replacement for PVC foamed or PVC
wrapped millwork.
[0128] High pressure laminates typically come with supporting
products such as edgebanding in the form of slit laminate or
profile extruded linear shapes. In the embodiments of the
invention, the biolaminate layer may be slit or cut into strips to
be used as matching edgebanding. The "slit" or cut biolaminate
layer may then laminated to the edge of the substrate by means
typically of a hot melt adhesive with slight pressure. The
biolaminate layer edgebanding may then trimmed. The biolaminate
surface layer edgebanding may also be printed or extruded with
solid colors and patterns.
[0129] The embodiments of the present invention use a novel method
and optional compositions to maintain crystallinity of a PLA or
other biopolymer through processing and maintain this in the end
profile extrusion or sheet components. Embodiments utilize higher
shear, which is not recommended by the manufacture of PLA products,
and very low processing temperatures typically below that of
320.degree. F. or 300.degree. F. to process the material in its
elastomeric state well below its melting point and recommended
processing point of 380.degree. F. to 420.degree. F. where the
material converts to a fully amorphous material. Conventional
processes provide a cloudy extruded component versus a clear and
more brittle packaging material.
[0130] At this processing temperature, the material may be fully
crystallized, but below the temperature and processing parameters
to create a full amorphous material. The resultant materials may be
cloudy, but have a significantly higher flexibility while still
maintaining a high degree of mechanical performance.
[0131] By maintaining a crystalline state or partial crystalline
state by the process within embodiments of this invention,
stickiness of the polymer may be greatly reduced and advantageous
properties may be retained for products that may replace PVC in
profile and extrusion applications. Also, within the processing
parameters of the embodiments of the present invention, the
material may have a different rheology and melt index that may
allow processing into extruded three dimensional shapes.
[0132] Additives may also assist in these embodiments and still
maintain the crystalline state of the PLA or PLA admixtures.
Nanomaterials, fillers, fibers, proteins, starch, wood flour, wood
fibers papermill waste and other materials may increase the
nucleation of the PLA and affect the crystalline states to the
material. By processing well below the melting point and through
the usage of high shear it may be possible to maintain a less
brittle state of the PLA and be able to more closely match the
desired properties of PVC products and applications requirements.
Other nucleating agents, fillers, fibers and materials have been
tested with positive results using this novel process
methodology.
[0133] Method for Making a Cellulosic Biolaminate Composite
Assembly
[0134] Embodiments relate to a product and method for making a
biolaminate assembly utilizing a non saturated paper and layers of
extruded biopolymer dry films that once a stack of the nonsaturated
papers and biopolymer films are subjected to heat, pressure, and
moisture, the biopolymer film changes viscosity as to allow
saturation and impregnation of the paper and fuses multiple layers
together into a monolithic composite structure. This structure may
be used for either decorative surfacing, such as by use as a
decorative surfacing laminate layer, or structural composite
applications. Embodiments relate to a product and methods for
making a biolaminate assembly utilizing a saturated or resin
impregnated paper layer, in particular a decorative surfacing
laminate layer. Embodiments of the present invention include
biolaminate assemblies utilizing a saturated paper with
substantially no formaldehyde emission. Such embodiments may be
used as replacements for high pressure laminates. Another
embodiment utilizes standard methods to work with existing form
formaldehyde based laminate production processes. A further
embodiment may be to improve post forming characteristics without
the need of applying pressure during resin production, or expensive
modifiers.
[0135] Generally, the method may comprise providing a first paper
layer, providing a biobased polymer film layer, and providing a
second paper layer. The first paper layer and the second paper
layer may be at least partially saturated with a biobased polymer,
such as from the biobased polymer of the biobased polymer film
layer and/or from an additional biobased polymer source. The first
paper layer, the biobased polymer film layer, and the second paper
layer may be fused under means of heat and pressure to form the
biolaminate structure. Fusing may be done at a pressure between
about 20 psi and about 1500 psi, for example. In some embodiments,
the biolaminate layer, such as a PLA biopolymer, can be in a dry
extruded film form.
[0136] Various of these steps will now be described in more
detail.
[0137] Any suitable woven or nonwoven cellulosic paper may be used.
Suitable papers include, for example, plain paper, kraft paper,
treated paper, wood based paper, recycled papers, decorative paper,
printed paper, fiber reinforced papers, glass fiber reinforced
paper, thin wood veneers, fire retardant paper, chemically treated
paper, ph adjusted papers, or a combination thereof. The cellulosic
paper may be a biobased paper from a renewable plant fiber such as
hemp, baggase, wheat straw, and corn stover.
[0138] Various methods for impregnating the cellulosic layers with
a biopolymer may be used. These include composite pressing a stack
of at least one non-saturated paper and at least one biopolymer
film, direct applying molten biopolymer to non-saturated paper, and
saturating the cellulosic papers with a liquid biopolymer.
[0139] In composite pressing of a stack of at least one
non-saturated paper and at least one biopolymer film, the stack is
processed under heat and pressure conditions within a hot press.
Temperatures can range from 310 F to 400 F, but not limited to, and
pressure ranging from 20 psi to 1500 psi. Residual moisture content
of the paper and paper chemistry will have an effect on the time
required to fully saturate and impregnate the papers within the
press system and effects the dynamic rheology of the biopolymer.
This method removes the current process wherein papers are required
to be saturated prior to the composite pressing process.
[0140] In embodiments using direct application of molten
biopolymer, for example molten PLA, the molten PLA may be direct
applied using roll coating. Various additives can be blended into
either the paper or into the molten PLA prior to coating
applications to enhance properties or processing speeds. Various
papers layers are placed through a hot melt roll coating machine in
which PLA in molten liquid form is directly applied to the paper
and ran through chilled rollers. The coated paper layers are then
stacked into the desired amount of layers and placed under heat and
pressure in a composite press. Temperatures range from 310 F to 400
F and pressures between 20 psi to 1500 psi as to saturate,
impregnate and fuse layers together as to create a monolithic
structural composite structure.
[0141] In embodiments using liquid biopolymer, woven or nonwoven
cellulosic paper or various forms of biobased fiber papers may be
saturated with a liquid form of PLA or LA. The paper may then be
submersed in a bath of liquid LA with a low viscosity sufficient to
absorb into the paper. Lactic acid is the precursor to polylactic
acid and may be in a low viscosity for in that absorbs into the
paper.
[0142] The LA saturated paper may then be dried using heat, air or
other drying methods commonly used in drying saturated papers. In
some embodiments, the surface of the dried, saturated first paper
layer may be texturized. Core layers of saturated paper may be
plain papers. Surface layer or layers may be in the form of a
preprinted pattern, color or image printed by standard means of
printing including but not limited to wide format UV digital
printing.
[0143] Additives may be contacted with the paper or resin, one or
more of drying agents, polymerizing agents, peroxides and other
crosslinking agents, colorants, ETC and fire retardants.
[0144] Once the LA saturated paper is dried, one or more layers may
be placed onto a textured paper, metal or composite platen. The
platen may impart a texture onto the surface of the final laminate
and also provides a uniform cooling process while the laminate is
curing and cooling.
[0145] In one embodiment, a printed LA saturated paper may be
placed on top. The single or stacked layers of LA saturated papers
may be then thermally fused into a solid laminate sheet.
Temperature range from about 120.degree. F. to over about
300.degree. F. until the LA is fully impregnated into the fibers,
layers may be fused or the desired polymerization had occurred.
[0146] Thermofusing may be done using a hot platen press with
pressure ranging from 20 psi to over 1000 psi depending on the
final desired specific gravity or hardness of the biolaminate. In
another embodiment, a hot roll press may be used to heat and fuse
the layers into a solid laminate.
[0147] A single layer of paper may also be saturated and cured
using the lactic acid polymer that may be used as a backer layer.
In this case, the saturated paper may be produced, then may be
thermally fused or adhered to a thin biobased film including a
polylactic acid sheet with a color backcoat or digital imaged to
produce a decorative laminate. The saturated LA paper provides for
a paperback surface that may be easily laminated onto various rigid
substrates including particleboard, MDF, agrifiber composites,
mineral fiber composites and other types of thin or thick rigid
composite structures, thus providing a waterproof and decorative
surface option that is completely formaldehyde free.
[0148] Another embodiment includes laminating a clear polylactic
surface layer and the LA saturated paper to impart a high degree of
stain, chemical and wear resistance. In addition, this biobased
wear layer may be refurbished with similar processes used in
petrochemical polymer solid surface materials. Accordingly, in some
embodiments, an overlay layer comprising a thermoset and
thermoplastic standard overlay, a mineral plastic overlay, a
bioplastic overlay, or a wear layer surface overlay may be
provided.
[0149] Another method for curing the liquid LA resin saturated
paper may be-through the-usage of Ebeam or UV cured technology in
which photoinitiator is added to the LA resin prior to the paper
saturating process. The saturated LA resin paper may then be placed
under an Ebeam or UV light to final cure the material.
[0150] Uses
[0151] The biolaminate composite assembly can be made into table
tops, desk tops, cabinet doors, cabinet boxes, shelving, millwork,
wall panels, laminated flooring, countertops, worksurfaces, exhibit
panels, office dividers, bathroom dividers, laminate flooring and
other areas may use the system of the biolaminate in combination
with a non-plastic substrate and adhesive layer to create a truly
"green" solution for the growing demand for more environmentally
friendly products.
[0152] A biolaminate composite assembly may be made into various
forms of cabinet doors that are based on flat laminating,
thermofoiled three dimensional, or integrating profile wrapping
components and combining all of these together to create various
designs of cabinet or passage way doors.
[0153] A biolaminate composite assembly may be formed as ecoart and
may comprise a heavily textured mineral composite. Various heavily
textured mineral composites may be commonly used for ceiling tile
applications. Ceiling tiles of various heavy surface textures and
composition may be used. Ceiling tiles may typically be fire
retardant and thus the above imaged tile or panel meets such
specifications.
[0154] The biolaminate surface layer can also be plasticized to a
high degree using various normal or preferably biobased
plasticizers to create a more flexible biolaminate surface layer
that can be produced as a wall covering that is adhered onto wall
board as a high performance wall covering that may replace PVC
vinyl wall coverings. In this embodiment, a secondary non woven
cloth may be laminated onto the backside of the biolaminate layer
to provide improved performance while maintaining flexibility. The
biolaminate layer that is highly plasticized as above, may also be
used as a replacement for flexible PVC media for printing.
[0155] A biolaminate composite assembly utilizing a PLA
biocopolymer biolaminate based on a plasticizer or processing aid
additive and the addition of a "nanoquartz" additive to the
biolaminate surface layer provides for a high degree of wear and
temperature resistance sufficient to be used in countertop
applications. Currently food grade surfaces consist primarily of
HDPE and stainless steel. Stainless is expensive and HDPE may trap
food or liquids in scratches or cuts within the surface. The
"nanoquartz" technology may provide good performance and durability
of the surface. A biolaminate laminate assembly integrating quartz
may also provide a lower cost option for expensive granite and
other solid surfacing composites for kitchen countertops, tables,
and other higher performance areas. These forms of biolaminate
layers may be either flat laminated or thermoformed into three
dimensional worksurface for kitchen and other forms of countertop
applications.
[0156] Currently, PLA is very difficult to extrude into profile
shapes due to its poor melt stability, high melt index, and other
factors. Embodiments of this invention describe a method to extrude
PLA or other biopolymer into shapes and compositions that assure
that the material will not degrade in various longer term
commercial profile extruded applications and products. Secondly,
embodiments of the inventions describe methods of processing that
provide high quality profiles and material compositions that may
directly compete with or replace current hazardous plastics such as
PVC in architectural, commercial and industrial markets. The
profile extruded PLA or PLA biocomposite can be used as a substrate
for the biolaminate surface layer or be colored to match the
biolaminate. This biolaminate composite system of merging an
environmentally friendly substrate with a biolaminate derived from
rapidly renewable resources provides a true environmental solution
for future worksurfaces and other applications where HPL or PVC
thermofoil components are commonly used.
EXAMPLES
Example 1
[0157] PLA pellets were placed into an extruder with temperatures
settings 20.degree. F. above the melting point at 420.degree. F.
which is also recommended by Natureworks for processing
temperature. The material poured out of the die like honey sticking
to the die. The temperature was dropped to 310.degree. F., over
80.degree. F. lower than its melting point. The RPM was increased
to add shear input to the material. The resultant shape held its
complex shape with minimal distortion.
Example 2
[0158] PLA pellets were placed into an extruder using a sheet die
with processing temperatures of 380 to 420.degree. F. and a clear
sheet was produced. The sheet was brittle and easily cracked when
bent. The resultant sheet was flat laminated onto a wood
particleboard using a heat activated glue under heat and pressure
using a hot press with temperature of 150.degree. F. and pressures
under 50 PSI. The material showed very good adhesion to the
substrate.
[0159] The same sheet as above was laminated using a cold
laminating method commonly used for HPL using a PVA and cold press
laminating method. The PLA biolaminate sheet did not have any
adhesion to the substrate and was easily pulled away.
[0160] PLA pellets were placed into a open twinscrew extruded and
processing, temperatures were lowered to 320.degree. F. and
material pulled out of the extruder through the vent before the die
section.
[0161] PLA was placed into an extruder and processed at
temperatures below 330.degree. F. well below the melting point
using a sheet die. The resultant film was cloudy but had very good
melt strength. After cooling it was very apparent that the material
was more flexible and had better properties. The thickness of the
biolaminate was 0.015''
[0162] The resultant sheet from above was hot laminated onto an
agrifiber substrate comprising of wheatstraw using a heat activated
glue and pressure. The resultant bond strength was very good and in
adhesion tests fiber was being pulled away from the particleboard
sticking to the biolaminate showing that the adhesive bond was
better than the internal bond of the wheat particleboard.
[0163] The resultant sheet of biolamiante was then placed into a
membrane press with a machined three dimensional substrate wherein
the substrate had a heat activated uretane preapplied. A
temperature of 160.degree. F. with less than 50 PSI was applied for
over two minutes. A comparison test using a PVC film of 0.012''
with a chemical solvent primer to improve adhesion was also
membrane pressed using the same substrate, glue and method. The
forming of the biolaminate showed equal stretching and forming
ability as compared to the PVC. Both the PVC and biolaminate
samples were tested in regards to adhesion and were equal in bond
strength even with the biolaminate not having a chemical primer to
promote adhesion.
[0164] The biolaminate film was reversed printed using a solvent
inkjet system. The initial ink bond seemed to be sufficient by
means of cross hatching the surface and performing a tape peal
test. The reversed printed biolaminate was then thermofoiled using
heat and pressure in combination with the heat activated urethane
adhesive wherein the ink layer was in contact with the laminating
adhesive layer and substrate. After processing, a peal test was
done. The ink separated from the biolaminate film not having
sufficient bond strength. A second test was done wherein the
surface of the biolaminate was treated with a solvent chemical
before printing. Although improvements were seen in adhesion, it
was not sufficient for this application.
[0165] A clear biolaminate was direct top printed and coated with a
clear liquid topcoat of urethane. The topprinted biolaminate was
hot laminated onto a substrate. The bond between the clear
biolaminate and substrate was sufficient were fiber tear out was
seen on the substrate.
[0166] A UV cured screen printing ink was applied to the backside
of the clear biolaminate or reversed printed. The biolaminate was
thermofoiled using heat and pressure with a urethane heat activated
adhesive with the printed side in contact with the adhesive and
substrate layer. The adhesion was significantly improved over the
standard solvent ink printing process with fiber tear-out of the
substrate.
[0167] Two three dimensional cabinet door was machined out of
medium density fiberboard in the shape of a classic raised panel
cabinet door. The first door was processed in a membrane press and
standard heat activated thermofoil process using a PVC thermofoil
of 0.010''. Press time was 2.5 minutes with 50 PSI at a temperature
of 170.degree. F. The second door was processed to the same methods
only using a biolaminate surface layer to replace the PVC film. The
resultant forming process was surprisingly the same with the same
stretching and forming nature of the PVC. Although the PVC had a
primer to promote adhesion on the backside and our biolaminate did
not, we seen very similar adhesion to the substrates as measured by
peal testing. The pull down on the edge of the cabinet door due to
the forming process also was the same between the PVC and
biolaminate.
[0168] A PVC film and biolaminate surface layer were thermoformed
onto a three dimensional cabinet door shaped substrate using the
same urethane adhesive. Both the PVC and biolaminate were subjected
to independent testing according to high pressure laminate
standards (NEMA LD3). The resultant data shows that the biolaminate
had improved stain resistance, improved tabor wear resistance, and
improved mar resistance than the standard PVC decorative surfacing
product.
[0169] A piece of WilsonArt standard grade high pressure laminate
was laminated to a wood particleboard substrate using a contact
adhesive. The biolaminate sheet was also laminated to the same wood
particleboard using the same contact adhesive and subjected to
independent testing in accordance with NEMA LD3 requirements. In
this test the biolaminate had over 5 times the impact strength,
improved stain resistance, over 2 times the scratch resistance, and
other performance improvements.
[0170] Different results after secondary heat test was done to
evaluate the change in state of the PLA as it was subjected to
multiple heat histories. The PLA film produced at a temperature
below its melting point in its viscoelastic state at 340.degree. F.
was produced in a 0.010'' thickness film. The film was reversed
printing using a UV cured ink system and a direct printing inkjet
system. The samples were broken into two groups and group I samples
were tested for impact, hardness, and scratch resistance. The
second group of samples were hot laminated using a membrane press
and a thermally activated urethane for 2.5 minutes at a temperature
of 170.degree. F. until the glue was cured. These second group of
samples were tested directly against the first group. The second
group showed a harder surface with improved scratch resistance, but
lower impact resistance.
[0171] A wood bioplastic profile extrusion was produced at a
temperature between 310 to 320.degree. F. with about 20% loading of
wood fiber creating a linear shaped piece of millwork. The
biolaminate surface layer was heated with a heat activated adhesive
applied to the backside of the biolaminate surface layer and
compared to PVC films processing using the same method. The
biolaminate surface layer had very similar adhesion and formed
surprisingly similar to that of the PVC film.
[0172] A 3M contact adhesive used for laminate was sprayed on the
back side of the biolaminate surface layer and onto a flat wheat
board agrifiber substrate. After a minute to flash off any
volatiles, the materials were laminated together using pressure
from a roller system. A second sample of PVC decorative film was
also used on a second sample. The biolaminate had an improved
adhesion.
Example 3
[0173] A soybean wax was added to the PLA at 5% and extruded
through a profile die. The temperature was dropped to 290.degree.
F. and the material was a smooth high integrity shaped with good
melt strength sufficient to hold a profile shape. Shear was
increased and the shape was improved and smoothness of surface was
also improved. The hot shaped article was pulled onto a conveyor
belt with no changes in shape from the die.
Example 4
[0174] PLA and a hydrogenated soybean wax supplied from ADM was
compounded into a biocopolymer of a flexible nature with ratios of
PLA to Soy of 95:5. The resultant compound was then re-compounded
with various powdered non halogenated fire retardants at various
levels. Mag Hydrox, Alumina Tryhydrate, and ammonium phosphate were
all added from levels of 10% to 50%. A strong reaction took place
with the MH and ATH materials that created difficulty in mixing and
would form layers within the material. The Amon phos material
blended well and formed a more homogenous and more flexible
material based on various loadings.
Example 5
[0175] PLA was compounded at a temperature below its melting point
and within its viscoelastic state around 310.degree. F. Glycerol
was added at various levels from 1 to 20%. The resultant material
was a homogenous flexible materials. A second test was done wherein
PLA was heated over its melting point of 400.degree. F. The same
levels of glycerine were added. The glycerine was highly volatile
and released significant smoke due to breakdown and created a non
homogenous material and was difficult to compound into a homogenous
material.
[0176] Wheat straw strands of an average length of 3/4'' and less
than 0.020'' in width were compounded with PLA and a soybean wax
wherein the PLA to soybean wax was at a ratio of 95/5.5% and 10%
addition of the wheat strands were compounded with the biocopolymer
at a temperature within the viscoelastic state of the biocopolymer
of 310.degree. F. The material was homogenous, did not smell, and
had good impact resistance. A second test was done using the same
materials where the process was taken above the required melting
point of the PLA of 400.degree. F. The fibers did not interact with
the biocopolymer well and significant browning and cellulosic
degradation was seen. In addition the material showed signs of
burning and clearly had a very negative smell.
[0177] PLA and EVA were compounded at a temperature of 310.degree.
F. A sample of biodac (papermill sludge particles) were colored by
simply dying the particles and dried. The biodac was compounded at
20% with the biocopolymer at a temperature of 310.degree. F. The
resultant material had a unique aesthetics and was a tough high
impact material. A second process was done using the same materials
at a processing temperature above the melting point of the PLA. The
resultant material showed signs of degradation and burning. The
resultant material was highly brittle with minimal impact
strength.
Example 6
[0178] PLA was placed in pan and put into an oven at a temperature
over 400.degree. F. Five samples pans were placed into the oven
with PLA. An addition of 10% of plasticizers was placed in each
pan. Plasticizers and lubricants were glycerine, wax, citric acid,
vegetable oil, zinc stearate. After the PLA was molten the
materials were mixed. During the heating virtually all of the
plasticizers lubricants started smoking heavily with significant
smell and starting to boil or degrade. The materials could not be
mixed together. The same test was done only at a temperature of
300.degree. F. over 80.degree. F. below the melting point of the
PLA. The plasticizers did not smoke, boil or degrade and were able
to be mixed into a more homogenous material. Zinc stearate was the
worst of these materials with the soybean wax being the easiest to
blend.
Example 7
[0179] PLA and biofiber functional colorant system will be meter
directly into the single screw sheet line wherein a high level of
dispersion with low and medium shear input is required. Processing
temperatures were set well below the melting point of the PLA which
is over 380.degree. F. In this test the heating sections where set
at 310.degree. F. to 315.degree. F. at the die exit. The material
was not sticky and had sufficient melt index to create a profile.
The material was not clear as processing PLA at or above its
melting point, but semitransparent maintaining its crystalline
nature and had more flexibility and impact resistance. Cooling roll
temperature we evaluated between 80.degree. F. to over 200.degree.
F. We found that the material cooled significantly quicker due to
the lower processing temperatures and required heating the
rollers.
Example 8
[0180] PLA 2002 from Natureworks in pelleted form was compounded
with 5% SWL-1, a congregated soybean wax products from ADM.
Compounding was performed in a Brabender twin screw at a
temperature of 300.degree. F. over 80.degree. F. below the melting
point of the PLA. The material came out of a round die holding a
good solid shape and was cooled. The material was a very opaque
milk white color and the resultant material was able to be bent
without breaking with a similar feel and performance t that of
polyethylene.
[0181] A second compounding run was done increasing the amount of
SWL-1 to 10% with 90% PLA. The material was lower in viscosity and
processing temperature was decreased until the material held its
round shape. Again the material was very opaque and white.
[0182] A third compound was done adding screened wheat fiber
wherein a water based colorant was sprayed on the wheat fiber then
dried. The colorized wheat fiber was compounded with 90% PLA, 5%
SW1 and 5% colorized wheatfiber. To our surprise, the material was
clear to semitransparent with a deep three dimensional look with
randomized color fibers. The clearer PLA/SW was slightly tinted to
the color of the wheat, but still maintained a transparent depth.
The material was not as brittle as neat PLA and actually was
similar in flexibility as our first run of 95% PLA and 5% SW1.
Example 9
[0183] PLA was compounded with 10% SW1 and 10% ground sunflower
hulls in which the ground hulls were screened to remove the fines
below 30 mesh. The resultant material was extruded into a sheet and
a texture was imprinted on the hot material. After cooling the
material showed a random flow decorative pattern. The material was
placed in water and we observed the water beaded up on the surface
of the material.
Example 10
[0184] PLA was compounded with a standard magnizume hydroxide fire
retardant and extruded into a test bar. The test bar was very
brittle and could be easily snapped by hand with minimal pressure.
A second compound was done where 10% SW1 was added. The resultant
material had good impact and could be bent.
Example 11
[0185] Wheat fiber was compounded with SW1 at a 50%/50% ratio at a
temperature of 300.degree. F. and mixed. The resultant material was
cooled then granulated into small particles. The compound of wheat
and SW1 was then dry blended with PLA pellets and compounded at
310.degree. F. producing a flat test bar.
Example 12
[0186] Soy Wax SW1 was melted at a temperature of 300.degree. F. in
a 100 gm batch. An equal weight of wheat fiber was added and mixed.
The soywax quickly impregnated the wheat fiber and left the fiber
in a free flowing state. The impregnated fiber was lain out in the
mat and pressed. Water was dripped on the top of the mat in which
the water completely beaded up on the fibrous mat.
[0187] From this it was determined that roughly a 50/50 ration of
soywax to fiber based on a specific bulk density and fiber geometry
would fully impregnate the fibers. The admixture of 50/50
soywax/fiber was added at a 10% ration with PLA and compounded. The
wax on the outside of the fibers where blended with the PLA and
provided for a compatible interface. Only a small amount of wax was
mixed into the clear PLA. The soywax at room temperature is an
opaque white material. The resultant PLA and SW/impregnated fiber
was still clear to semi transparent.
Example 13
[0188] A separate experiment took just the soywax at 5% and PLA at
95% and compounded the two together using a Brabender compounders.
In this test the resultant material was opaque and milky white
color. Thus we see that the addition of fiber allowed impregnation
of the molten soywax prior to the PLA reaching a appropriate
viscoelastic state to allow merging of the soywax/PLA system due to
the transparency of the final biocomposite matrix.
Example 14
Sugar Beet Pulp & Sunflower Hulls
[0189] Ground sugar beet pulp and sunflower hulls were taken from a
regional agricultural processing plant and gently ground or broken
into fibers. The materials were screened with the resulting
material in a range from 30 mesh to 4 mesh. The particles of
sunflowers where a linear geometry wherein the sugar beet pulp were
more of a uniform size, but random shape. A dye used in clothing
was used to soak the fibrous particles then dried to fix the
colorant. The two colored fibers where metered at a 10% rate with
10% soywax and 80% PLA into a brabender compounding system. As soon
as the material hit the hot screw feed section the soywax melted
and started to wet out the fibers even before entering the barrel
section while the PLA was still in its hard state. Compounding
temperatures where maintained well below the melting point of the
PLA (PLA melting point at 390.degree. F.) wherein the processing
temperature was 90.degree. F. below the melting point at
300.degree. F. The resultant material was a uniform mixture that
was not brittle and had a unique three dimensional nature. The exit
of the compounder was shaped into a high tolerance rod. The exiting
material held is shape with a high degree of tolerance.
Example 15
[0190] BioDac
[0191] A sample of BioDac was purchased from GranTek Corporation in
Wisconsin which is a form of waste papermill sludge that has been
compressed and dried forming small spherical balls with a mesh size
of between 15-30 mesh. The BioDac was colored using a water based
colorant and multiple colorized batches were produced. The colored
biodac was compounded at a 20% level with 10% SW and 70% PLA.
Compounding was done using a Brabender twin screw at a processing
temperature of 310.degree. F. The resultant material was then
reheated and pressed into a composite sheet. The material very
closely represented a solid surface looking material. Samples were
submitted into a water bath for 24 hours and was water proof with
no uptake of water measured.
Example 16
[0192] PLA was compounded with long fiber glass at levels of 2% to
over 30% at a temperature below the melting point of the PLA
(315.degree. F.). A second test was done using the same ratios at a
temperature above the melting point (400.degree. F.). A second test
was done wherein 5 and 10% addition of soybean wax was added.
Example 17
[0193] A biolaminate sheet comprising of PLA and soybean wax that
was processed below the melting point of the PLA was taken and
reheated at 200.degree. F. A MDF substrate was formed into a shaped
article and an adhesive was applied. The hot biolaminate was pushed
and formed onto the substrate and allowed to cool. The resultant
material showed a high level of adhesion and very good impact
resistance.
Example 18
[0194] A piece of WilsonArt high pressure laminate was adhered onto
a particleboard substrate using recommended adhesives. The
biolaminate of a similar thickness was adhered to a matching
particleboard using the same methods and adhesives. A hammer was
dropped from 5 feet onto both samples wherein the edge of the
hammer head impacted the samples. The HPL showed signs of cracking
at the edge of the impact hit. The biolaminate showed no signs of
impact at all.
Example 19
[0195] a piece of an agrifiber composite produced from wheatstraw
were cut into 3 samples. The first sample was stained with a common
wood stain to a dark cherry color. The wheat stain was very dark
and "blotchy" covering and hiding most of the natural fiber
appearance. A biolaminate surface was extruded in which one was a
clear and the second run included a transparent dye colorant. The
biolaminate sample containing a dye was then laminated using a
clear adhesive onto the second non stained wheatboard sample. The
clear biolaminate was printed using a transparent UV cured ink on
the backside then also laminated to the third piece of wheatboard.
In looking over the appearance of the three samples, the wood stain
piece was no visually acceptable and did not show the desired
wheatboard texture. The agrifiber clearly stained very different
than a natural wood. The second sample with the dye extruded into
the biolaminate surface clearly was the same overall dark cherry
color, but the pattern of the wheatboard was very clearly defined.
The look was also very deep due to the optics of the dye containing
biolaminate layer. The UV transparent printing was near the
appearance to the dyed biolaminate with similar color and optics
still showing the individual fiber nature of the wheatboard and
providing a good stained color. Another similar test was done using
real wood. Both the integrated dye and the transparent printed
biolaminates maintained a better aesthetics of the wood grain than
the liquid staining process and provided a single processing step
to finish the wood as compared to the two step process of staining
and finishing typically done using wood.
Example 20
[0196] A plain kraft paper, then an biopolmer PLA extruded film
(0.005'') is placed on top of the kraft. A second kraft is place on
the top so that the PLA film is "sandwitched" between the
unsaturated kraft paper. This alternating stack can be repeated to
create thicker structures. The two layers of haft with the
biopolymer film between is then placed into a heated press at 350
degrees F. and pressure over 20 PSI and more preferable between 150
to 500 psi. Two stacked layers were prepared.
[0197] The first stack of alternating layers were placed in a press
for 1 minute and removed. In breaking the final composite, the
paper was not fully saturated or impregnated in which dry sections
of paper were found. In addition the composite could be torn apart
due to the low internal bond of the unsaturated papers.
[0198] The second stack of alternating layers were placed in the
same press and same temperature extending the press time to 8
minutes. Once the composite was cooled, the layers were fully
saturated and could not be torn. In cutting various layers with a
knife, the kraft paper had darken due to the saturation of the PLA
through the kraft also showing on the opposite side.
[0199] Both pieces were cut and sanded on their edges and inspected
using a microscope. The first sample with the 1 minute cycle showed
where the PLA was partically impregnating and saturating through
the kraft, but not completely through whereas the second sample
with the longer press time was completely saturating the paper
layers.
[0200] Both pieces were also subjected to water emersion. The first
sample pressed for 1 minute had very high absorption and swelling
due to the non saturated kraft paper. The second sample look
virtually water proof without swelling or surface roughness.
Example 21
[0201] A second film using standard acrylic (0.005) was done
replacing the PLA in which the Acyrlic film was between two layer
of kraft paper. The stack was placed in a press under the same
conditions above and for the full 8 minutes. The sample was removed
and cooled. The material has no saturation and barely stuck the two
layers together. The samples were easily pulled apart and had no
strength nor stiffness.
[0202] To further illustrate, the following embodiments are here
described:
[0203] 1. A biolaminate composite assembly, comprising: [0204] one
or more biolaminate layers; [0205] a non-plastic rigid substrate;
and [0206] an adhesive layer, in contact with the substrate and the
one or more biolaminate layers; [0207] wherein the one or more
biolaminate layers is laminated to the substrate.
[0208] 2. The biolaminate composite assembly of embodiment 1,
wherein laminated comprises flat laminated.
[0209] 3. The biolaminate composite assembly of embodiment 1,
wherein a single biolaminate layer contacts a single side of the
non-plastic rigid substrate.
[0210] 4. The biolaminate composite assembly of embodiment 1,
wherein two or more biolaminate layers contact two or more sides of
the non-plastic rigid substrate.
[0211] 5. The biolaminate composite structure of embodiment 2,
wherein flat laminated comprises hot pressed, cold pressed, nip
rolled, sheet form, full panel form, custom cut, or some
combination thereof.
[0212] 6. The biolaminate composite assembly of embodiment 1,
wherein the adhesive comprises a glue line.
[0213] 7. The biolaminate composite assembly of embodiment 1,
wherein the adhesive layer comprises a heat activated adhesive.
[0214] 8. The biolaminate composite assembly of embodiment 1,
wherein the adhesive layer comprises a contact adhesive.
[0215] 9. The biolaminate composite assembly of embodiment 1,
wherein the adhesive layer comprises a cold press adhesive.
[0216] 10. The biolaminate composite assembly of embodiment 9,
wherein the adhesive layer comprises a pressure sensitive tape.
[0217] 11. The biolaminate composite assembly of embodiment 1,
wherein the substrate comprises a composite matrix.
[0218] 12. The biolaminate composite assembly of embodiment 1,
wherein the substrate comprises wood composite, MDF, HDF, plywood,
OSB, wood particleboard, wood plastic composite, agrifiber plastic
composite, agrifiber particleboard, agrifiber composite, gypsum
board, sheet rock, hardboard, metal, glass, cement, cement board,
cellulosic substrates, cellulose paper composites, multilayer
cellulose glue composites, wood veneers, bamboo, recycled paper
substrates or a combination thereof.
[0219] 13. The biolaminate composite assembly of embodiment 1,
wherein the substrate comprises substrates that are derived from
agrifibers using a formaldehyde free matrix resin.
[0220] 14. The biolaminate composite assembly of embodiment 1,
wherein biolaminate composite assembly comprises work surfaces,
shelving, millwork, laminated flooring, countertops, tabletops,
furniture components, store fixtures, dividers, wall coverings,
cabinet coverings, cabinet doors, passageway doors or combinations
thereof.
[0221] 15. The biolaminate composite, assembly of embodiment 1,
wherein the one or more biolaminate layers comprises a thickness of
about 0.005 to about 0.25''.
[0222] 16. A biolaminate composite assembly of embodiment 15,
wherein two or more of the one or more biolaminate surface layers
are thermally fused together by heat fusion or an adhesive.
[0223] 17. The biolaminate composite assembly of embodiment 1,
wherein the biolaminate composite assembly comprises a thickness of
about 0.050'' to about 1.5''.
[0224] 18. The biolaminate composite assembly of embodiment 1,
wherein one or more biolaminate layers comprise PLA, PHA or a
combination thereof.
[0225] 19. The biolaminate composite assembly of embodiment 1,
wherein one or more biolaminate layers comprise bioplastics,
biopolymers, modified biopolymer, biocomposite or a combination
thereof.
[0226] 20. A biolaminate composite assembly of embodiment 19,
wherein bioplastic, biopolymer, modified biopolymer, and a
biocomposite comprises polylactic acid base material.
[0227] 21. The biolaminate composite assembly of embodiment 1,
wherein one or more biolaminate layers comprise a modified PLA in
combination with one or more of a plastic, bioplastic, additive or
bioadditives.
[0228] 22. The biolaminate composite assembly of embodiment 1,
wherein one or more biolaminate layers comprise a modified PLA in
combination with one or more of a filler, fiber or colorant.
[0229] 23. The biolaminate composite assembly of embodiment 1,
further comprising one or more print layers.
[0230] 24. The biolaminate composite assembly of embodiment 23,
wherein the print layers are positioned on a top surface of the one
or more biolaminate layers, a bottom surface of the one or more
biolaminate layers or in between the one or more biolaminate
layers.
[0231] 25. The biolaminate composite assembly of embodiment 1,
wherein the one or more biolaminate layers further comprise
bioplasticizers, biolubricants or both.
[0232] 26. The biolaminate composite assembly of embodiment 25,
wherein bioplasticizers comprise citric esters, esters, lactic
acid, and other forms of biobased plasticizer.
[0233] 27. The biolaminate composite assembly of embodiment 25,
wherein biolubricants comprise natural waxes, lignants or a
combination thereof.
[0234] 28. The biolaminate composite assembly of embodiment 1,
wherein the one or biolaminate layers comprise a flexibility
comparable to that of a flexible PVC layer.
[0235] 29. The biolaminate composite assembly of embodiment 1,
further comprising one or more decorative additives.
[0236] 30. The biolaminate composite assembly of embodiment 29,
wherein the one or more decorative additives include a colorant,
texture, decorative particles, decorative flakes or natural
impregnated fibers.
[0237] 31. The biolaminate composite assembly of embodiment 30
wherein the colorant allows for a natural depth of field providing
a three dimensional aesthetic value.
[0238] 32. The biolaminate composite assembly of embodiment 1,
further comprising functional additives.
[0239] 33. The biolaminate composite assembly of embodiment 32,
wherein the functional additives include EVA, FR, natural quartz,
bioplasticizers, biolubricants, minerals, natural fibers, synthetic
fibers, impact modifiers, antimicrobial, conductive fillers, or a
combination thereof.
[0240] 34. The biolaminate composite assembly of embodiment 1,
wherein the one or more biolaminate layers comprise a rolled or
pressed textured surface.
[0241] 35. The biolaminate composite assembly of embodiment 1,
furthering comprising a non-plastic rigid substrate in contact with
a second side of the one or more biolaminate layers.
[0242] 36. The biolaminate composite assembly of embodiment 1,
further comprising a bioplastic edgebanding.
[0243] 37. The biolaminate composite assembly of embodiment 1,
wherein the one or more biolaminate layers comprise
edgebanding.
[0244] 38. The biolaminate composite assembly of embodiment 1,
wherein the non-plastic rigid substrate comprises biobased
edgebanding and biolaminate surfaces.
[0245] 39. The biolaminate composite assembly of embodiment 38,
wherein both the one or more biolaminate layers and edgebanding
comprise PLA, modified PLA or both.
[0246] 40. The biolaminate composite assembly of embodiment 1,
wherein the lamination is done using a hot press process, roll
lamination, cold press process, or utilizing contact adhesives.
[0247] 41. The biolaminate composite assembly of embodiment 1,
further comprising a fire retardant.
[0248] 42. The biolaminate composite assembly of embodiment 1,
wherein the one or more biolaminate layers further comprise natural
minerals.
[0249] 43. The biolaminate composite assembly of embodiment 1,
wherein the biolaminate composite structure comprises a three
dimensional appearance.
[0250] 44. A biolaminate composite assembly, comprising: [0251] one
or more biolaminate layers; [0252] a three-dimensional non-plastic
rigid substrate; and [0253] an adhesive layer, in contact with the
substrate and the one or more biolaminate layers; [0254] wherein
the one or more biolaminate layers is thermoformed to two or more
surfaces of the substrate.
[0255] 45. The biolaminate composite assembly of embodiment 44,
wherein thermoforming is permanent.
[0256] 46. The biolaminate composite assembly of embodiment 44,
wherein thermoformed comprises vacuum forming, linear forming or a
combination thereof.
[0257] 47. The biolaminate composite assembly of embodiment 44,
wherein the adhesive layer comprises a glue fine.
[0258] 48. The biolaminate composite assembly of embodiment 44,
wherein the substrate comprises a composite matrix.
[0259] 49. The biolaminate composite assembly of embodiment 44,
wherein the substrate comprises wood composite, MDF, HDF, plywood,
OSB, wood particleboard, wood plastic composite, agrifiber plastic
composite, agrifiber particleboard, agrifiber composite, gypsum
board, sheet rock, hardboard, metal, glass, cement, cement board,
cellulosic substrates, cellulose paper composites, multilayer
cellulose glue composites, wood veneers, bamboo, recycled paper
substrates or a combination thereof.
[0260] 50. The biolaminate composite assembly of embodiment 44,
wherein the substrate comprises substrates that are derived from
agrifibers using a formaldehyde free matrix resin.
[0261] 51. The biolaminate composite assembly of embodiment 44,
wherein biolaminate composite assembly comprises work surfaces,
shelving, millwork, flooring, countertops, tables, dividers, wall
coverings, cabinet coverings, cabinet doors, store fixture
components, passageway doors or combinations thereof.
[0262] 52. The biolaminate composite assembly of embodiment 44,
wherein the one or more biolaminate layers comprises a thickness of
about 0.005 to about 0.25''.
[0263] 53. The biolaminate composite assembly of embodiment 44,
wherein the biolaminate composite assembly comprises a thickness of
about 0.030'' to about 1.5''.
[0264] 54. The biolaminate composite assembly of embodiment 44,
wherein one or more biolaminate layers comprises PLA, PHA and other
bioplastics/biopolymers.
[0265] 55. The biolaminate composite assembly of embodiment 44,
further comprising bioplasticizers and biolubricants.
[0266] 56. The biolaminate composite assembly of embodiment 44,
further comprising one or more decorative additives.
[0267] 57. The biolaminate composite assembly of embodiment 56,
wherein the one or more decorative additives include a colorant,
texture, decorative particles, decorative flakes or natural
impregnated fibers.
[0268] 58. The biolaminate composite assembly of embodiment 57
wherein the colorant allows for a natural depth of field providing
a three dimensional aesthetic value.
[0269] 59. The biolaminate composite assembly of embodiment 44,
further comprising functional additives.
[0270] 60. The biolaminate composite assembly of embodiment 59,
wherein the functional additives include EVA, FR, natural quartz,
bioplasticizers, biolubricants, minerals, fibers, synthetic fibers
or a combination thereof.
[0271] 61. The biolaminate composite assembly of embodiment 44,
wherein the biolaminate composite structure comprises a rolled or
pressed textured surface.
[0272] 62. The biolaminate composite assembly of embodiment 44,
furthering comprising a non-plastic rigid substrate in contact with
a second side of the one or more biolaminate layers.
[0273] 63. The biolaminate composite assembly of embodiment 44,
further comprising a fire retardant.
[0274] 64. The biolaminate composite assembly of embodiment 44,
further comprising natural minerals.
[0275] 65. The biolaminate composite assembly of embodiment 64,
wherein natural minerals comprise minerals meeting high wear
resistant HPL standards.
[0276] 66. The biolaminate composite assembly of embodiment 44,
wherein the biolaminate composite structure comprises a three
dimensional appearance.
[0277] 67. A method for making a biolaminate composite assembly,
comprising: [0278] laminating one or more biolaminate layers to a
non-plastic rigid substrate.
[0279] 68. The method of embodiment 67, further comprising reverse
printing on the one or more biolaminate layers.
[0280] 69. The method of embodiment 67, wherein the one or more
biolaminate layers is clear or transparent.
[0281] 70. The method of embodiment 67, further comprising direct
printing to the one or more biolaminate layers.
[0282] 71. The method of embodiment 67, further comprising
multilayer printing to the one or more biolaminate layers:
[0283] 72. The method of embodiment 67, further comprising printing
a decorative print layer between two or more of the biolaminate
layers.
[0284] 73. The method of embodiment 72, further comprising
thermally fusing two or more biolaminate layers together.
[0285] 74. The method of embodiment 67, further comprising printing
a decorative layer to the one or more biolaminate layers.
[0286] 75. The method of embodiment 74, wherein printing comprises
offset printing, inkjet printing, screen printing or flexographic
printing.
[0287] 76. The method of embodiment 74, wherein printing utilizes a
bioink.
[0288] 77. The method of embodiment 67, further comprising applying
a clear liquid coating to the one or more biolaminate layers.
[0289] 78. The method of embodiment 77, wherein applying comprises
spraying, rolling, offset printing, or rod coating method.
[0290] 79. The method of embodiment 67, wherein the one or more
biolaminate layers comprises a clear top layer, a decorative
interior layer and an opaque layer, each layer thermally fused to
the adjacent layer.
[0291] 80. The method of embodiment 70, further comprising applying
a clear coating on an outer surface of the printed one or more
biolaminate layers.
[0292] 81. A method for making a biolaminate composite assembly,
comprising: [0293] thermoforming one or more biolaminate layers to
a non-plastic rigid substrate.
[0294] 82. The method of embodiment 81, wherein forming comprises
thermoforming, vacuum forming, thermoforming or a combination
thereof.
[0295] 83. The method of embodiment 81, further comprising reverse
printing on the one or more biolaminate layers.
[0296] 84. The method of embodiment 81, wherein the one or more
biolaminate layers is clear or transparent.
[0297] 85. The method of embodiment 81, further comprising direct
printing to the one or more biolaminate layers.
[0298] 86. The method of embodiment 81, further comprising
multilayer printing to the one or more biolaminate layers.
[0299] 87. The method of embodiment 81, further comprising printing
a decorative print layer between two or more of the biolaminate
layers.
[0300] 88. The method of embodiment 87, further comprising
thermally fusing two or more biolaminate layers together.
[0301] 89. The method of embodiment 88, further comprising printing
a decorative layer to the one or more biolaminate layers.
[0302] 90. The method of embodiment 89, wherein printing comprises
offset printing, inkjet printing, screen printing or flexographic
printing.
[0303] 91. The method of embodiment 89, wherein printing utilizes a
bioink.
[0304] 92. The method of embodiment 81, further comprising applying
a clear liquid coating to the one or more biolaminate layers.
[0305] 93. The method of embodiment 92, wherein applying comprises
spraying, rolling, offset printing, or rod coating method
[0306] 94. The method of embodiment 81, wherein the one or more
biolaminate layers comprises a clear top layer, a decorative
interior layer and an opaque inner layer, each layer thermally
fused to the adjacent layer.
[0307] 95. The method of embodiment 85, further comprising applying
a clear coating on an outer surface of the printed one or more
biolaminate layers.
[0308] 96. A decorative biolaminate layer, comprising: [0309] a
clear biopolymer layer; [0310] an opaque biopolymer layer; and
[0311] a decorative print layer; [0312] wherein the print layer is
positioned between the clear layer and opaque layer.
[0313] 97. he decorative biolaminate layer of embodiment 96,
wherein the clear biopolymer layer is textured.
[0314] 98. The decorative biolaminate layer of embodiment 96,
wherein positioned comprises fused.
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