U.S. patent application number 13/863319 was filed with the patent office on 2013-09-05 for uv/eb curable biobased coating for flooring application.
This patent application is currently assigned to ARMSTRONG WORLD INDUSTRIES, INC.. The applicant listed for this patent is ARMSTRONG WORLD INDUSTRIES, INC.. Invention is credited to Mary Kate BOGGIANO, Larry W. LEININGER, Jeffrey S. ROSS, Dong TIAN.
Application Number | 20130230729 13/863319 |
Document ID | / |
Family ID | 41255317 |
Filed Date | 2013-09-05 |
United States Patent
Application |
20130230729 |
Kind Code |
A1 |
TIAN; Dong ; et al. |
September 5, 2013 |
UV/EB CURABLE BIOBASED COATING FOR FLOORING APPLICATION
Abstract
A coating composition and a floor product are disclosed. The
coating composition has a biobased component that includes urethane
acrylate, vinyl ether, or polyester acrylate. The coating
composition includes at least about 5% by weight of renewable
and/or biobased component. The coating composition is radiation
curable, formed by acrylating a biobased polyol acrylate, and
reacting the biobased polyol acrylate with polyisocyanate to form a
biobased resin. The floor product includes a cellulosic substrate
and a biobased coating applied to the cellulosic substrate.
Inventors: |
TIAN; Dong; (Lancaster,
PA) ; ROSS; Jeffrey S.; (Lancaster, PA) ;
LEININGER; Larry W.; (Akron, PA) ; BOGGIANO; Mary
Kate; (Stevens, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ARMSTRONG WORLD INDUSTRIES, INC. |
Lancaster |
PA |
US |
|
|
Assignee: |
ARMSTRONG WORLD INDUSTRIES,
INC.
Lancaster
PA
|
Family ID: |
41255317 |
Appl. No.: |
13/863319 |
Filed: |
April 15, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12432845 |
Apr 30, 2009 |
8420710 |
|
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13863319 |
|
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61125918 |
Apr 30, 2008 |
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Current U.S.
Class: |
428/425.1 ;
428/481; 428/532; 522/21; 522/25 |
Current CPC
Class: |
C09D 133/08 20130101;
C08G 18/758 20130101; C08G 18/68 20130101; Y10T 428/31591 20150401;
C09D 175/16 20130101; C09D 133/14 20130101; Y10T 428/3179 20150401;
C09D 129/10 20130101; C08G 18/36 20130101; C09D 167/07 20130101;
C09D 133/02 20130101; Y10T 428/31971 20150401; C09D 175/14
20130101 |
Class at
Publication: |
428/425.1 ;
522/21; 522/25; 428/481; 428/532 |
International
Class: |
C09D 129/10 20060101
C09D129/10; C09D 175/14 20060101 C09D175/14; C09D 133/08 20060101
C09D133/08 |
Claims
1. A coating, comprising: a biobased component including urethane
acrylate, vinyl ether, or polyester acrylate; wherein the biobased
component is blended with a coating formula, the coating formula
including an initiator; wherein the coating includes at least about
5% by weight of renewable or biobased content.
2. The coating of claim 1, wherein the coating formula includes
epoxy resin.
3. The coating of claim 1, wherein the biobased component includes
an epoxidized oil.
4. The coating of claim 1, wherein the biobased component includes
a biobased diol.
5. The coating of claim 1, wherein the biobased component includes
a biobased diacid.
6. The coating of claim 1, wherein the biobased component includes
acrylic acid.
7. The coating of claim 1, wherein the biobased component includes
diisocyanate or triisocyanate.
8. The coating of claim 1, wherein the biobased component includes
a biobased polyol acrylate.
9. The coating of claim 1, wherein the coating includes at least
about 30% by weight of renewable or biobased content.
10. The coating of claim 1, wherein the coating includes at least
about 40% by weight of renewable or biobased content.
11. The coating of claim 1, wherein the initiator is a cationic
type initiator.
12. The coating of claim 1, wherein the coating qualifies for at
least one point under the LEED rating system.
13. The coating of claim 1, wherein the coating is a radiation
curable coating.
14. The coating of claim 1, wherein the coating is positioned on a
flooring.
15. The coating of claim 14, wherein the flooring includes a
cellulosic substrate and the coating is positioned on the
coating.
16. A radiation curable flooring coating, comprising: a biobased
component comprising renewable and/or biobased materials; wherein
the radiation curable flooring coating is formed by acrylating a
biobased polyol acrylate; and reacting the biobased polyol acrylate
with diisocyanate or triisocyanate to form a biobased resin;
wherein the biobased resin is blended into a radiation curable
biobased coating formulation including at least one initiator.
17. The radiation curable flooring coating of claim 16, wherein the
biobased polyol acrylate is directly blended into the radiation
curable biobased coating formulation; wherein the radiation curable
biobased coating formulation includes at least one initiator.
18. The radiation curable flooring coating of claim 16, wherein the
biobased polyol acrylate is directly blended into the radiation
curable biobased coating formulation; wherein the radiation curable
biobased coating formulation includes at least one epoxy resin or
vinyl ether; wherein the radiation curable biobased coating
formulation includes at least one initiator.
19. The radiation curable flooring coating of claim 16, wherein the
initiator includes a cationic type photo initiator.
20. A floor, comprising: a cellulosic substrate; and a coating
applied to the cellulosic substrate, the coating comprising a
biobased component including urethane acrylate, vinyl ether, or
polyester acrylate; wherein the biobased component is blended with
a coating formula, the coating formula including an initiator;
wherein the coating includes at least about 5% by weight of
renewable or biobased content.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Nonprovisional
patent application Ser. No. 12/432,845 filed Apr. 30, 2009, and
also claims priority to U.S. Pat. No. 8,420,710 issued on Apr. 16,
2013 and Provisional Application No. 61/125,918, filed Apr. 30,
2008, which are hereby incorporated by reference in their
entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to biobased coatings for
flooring applications, and more particularly to an ultraviolet
(UV)/electron beam (EB) curable biobased coating for flooring
applications.
BACKGROUND OF THE INVENTION
[0003] Radiation curable coatings, such as UV/EB curable coatings,
are applied to various types of substrates to enhance their
durability and finish. The radiation curable coatings are typically
resin based mixtures of oligomers or monomers that are cured or
cross-linked after being applied to the substrate by radiation
curing. The radiation curing polymerizes the resins to produce a
high or low gloss coating having superior abrasion and chemical
resistance properties. The radiation curable coatings of this type
are often referred to as topcoats or wear layers and are used, for
example, in a wide variety of flooring applications, such as on
linoleum, hardwood, laminate, cork, bamboo, resilient sheet, and
tile flooring.
[0004] The above-described radiation curable coatings are made from
fossil fuels, such as petroleum and coal. Because the use of fossil
fuels negatively impacts the environment, new radiation curable
coatings need to be developed which are derived from recycled
materials or renewable resources, such as biobased materials.
Recycled materials are materials that have been recovered or
otherwise diverted from the solid waste stream, either during the
manufacturing process (pre-consumer), or after consumer use
(post-consumer). Recycled materials therefore include
post-industrial, as well as, post-consumer materials. Biobased
materials are organic materials containing an amount of non-fossil
carbon sourced from biomass, such as plants, agricultural crops,
wood waste, animal waste, fats, and oils. The biobased materials
formed from biomass processes therefore have a different
radioactive C14 signature than those produced from fossil fuels.
Because the biobased materials are organic materials containing an
amount of non-fossil carbon sourced from biomass, the biobased
materials may not necessarily be derived 100% from biomass. A test
has therefore been established for determining the amount of
biobased content in the biobased material. Generally, the amount of
biobased content in the biobased material is the amount of biobased
carbon in the material or product as a fraction weight (mass) or
percentage weight (mass) of total organic carbon in the material or
product.
[0005] The calculation of the amount of biobased content in the
material or product is important for ascertaining whether the
material or product, when used in commercial construction, would
qualify for Leadership in Energy and Environmental Design (LEED)
certification. The US Green Building Council has established a LEED
rating system which sets forth scientifically based criteria for
obtaining LEED certification based on a point system. As shown in
Table 1, under the LEED rating system, for new construction 1 point
is granted for at least 5% wt of the total of post-consumer
materials and 1/2 post-industrial materials. A second point is
granted for at least 10% wt of the total of post-consumer materials
and 1/2 post-industrial materials. An additional point is granted
for at least 5% wt of rapidly renewable building materials and
products. For existing building 1 point is granted for at least 10%
wt post-consumer materials. A second point is granted for at least
20% wt of post-industrial materials. An additional point is granted
for at least 50% wt of rapidly renewable materials. Thus, flooring
products meeting the LEED criteria can be used to obtain points for
LEED certification.
TABLE-US-00001 TABLE 1 LEED Rating System Rating LEED--Version 2.1
Rating LEED--Version 2.0 System New Construction System Existing
Building MR Credit =5% wt of post- MR Credit =10% wt of post- 4.1
consumer materials + 1/2 2.1 consumer materials 1 Point
post-industrial materials 1 Point MR Credit =10% wt of post- MR
Credit =20% wt of post- 4.2 consumer materials + 1/2 2.1 industrial
materials 1 Point post-industrial materials 1 Point MR Credit =5%
wt of rapidly MR Credit =50% wt of rapidly 6 renewable building 2.5
renewable materials 1 Point materials and products 1 Point
[0006] Because there has been renewed market interest in giving
preference to "greener" flooring products based upon the LEED
rating system, there remains a need to develop "greener" flooring
products based upon existing product structures/processes and
available renewable materials. The key to this approach is to
integrate rapidly renewable materials, such as biobased materials,
into the radiation curable coatings, such as those used in flooring
applications, to reduce reliance on limited resources such as
fossil fuels.
[0007] A radiation curable biobased coating for flooring
applications having at least about 5% by weight of renewable or
biobased content would be desirable in the art.
BRIEF DESCRIPTION OF THE INVENTION
[0008] In an exemplary embodiment, a coating having a biobased
component including acrylate, vinyl ether, or polyester acrylate,
where the biobased component is blended with a coating formula, the
coating formula includes an initiator and the coating includes at
least about 5% by weight of renewable or biobased content.
[0009] In another exemplary embodiment, a radiation curable
flooring coating having a biobased component including renewable
and/or biobased materials, where the radiation curable coating is
formed by acrylating a biobased polyol acrylate and reacting the
polyol acrylate with diisocyanate or triisocyanate to form a
biobased resin.
[0010] In another exemplary embodiment, a floor comprising a
cellulosic substrate and a coating applied to the cellulosic
substrate, the coating having a biobased component including
urethane acrylate, vinyl ether, or polyester acrylate where the
biobased component is blended with a coating formula, including an
initiator, and the coating includes at least about 5% by weight of
renewable or biobased content.
[0011] Other features and advantages of the present invention will
be apparent from the following more detailed description of the
preferred embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Provided is a UV/EB curable biobased coating for a flooring
application. The biobased component includes a urethane acrylate, a
vinyl ether, or a polyester acrylate. The biobased component is
blended with a coating formula where the coating formula includes
an initiator and the coating includes at least about 5% by weight
of renewable and/or biobased content.
[0013] The radiation curable floor coating has a biobased component
that includes renewable and/or biobased materials. The radiation
curable floor coating is formed by acrylating a biobased polyol
acrylate and reacting the biobased polyol acrylate with
diisocyanate or triisocyanate to form a biobased resin where the
biobased resin has at least one initiator, the initiator includes a
cationic type photo initiator.
[0014] In one embodiment, the biobased polyol acrylate is directly
blended into the radiation curable biobased coating formulation
comprising the at least one initiator to form the radiation curable
biobased coating. In another embodiment, the biobased polyol is
directly blended into a radiation curable biobased coating
formulation comprising at least one epoxy resin or vinyl ether and
at least one initiator, which may be, for example, a cationic type
photoinitiator, to form the radiation curable biobased coating.
[0015] The biobased polyol may be made from various diacids or
diols, which are derived from renewable and/or biobased material.
The biobased polyol is-derived from renewable and/or biobased
materials and contains a weight percentage of renewable materials
or biobased content of at least about 5%, preferably at least about
75%, and more preferably at least about 95%. The biobased polyol
may be derived, for example, from plant oils extracted from plant
seeds, such as castor oil, linseed oil, soy oil, tall oil (pine
oil), tung oil, vernonia oil, lesquerella oil (bladderpod oil),
cashew shell oil, or other plant oils rich in unsaturated fatty
acids. The plant oils include triglycerides generally comprised of
esters formed from glycerol and saturated and unsaturated fatty
acids. A typical structure of a triglyceride unsaturated fat
contains three fatty acids esterified to three hydroxyl groups of
glycerol. The triglycerides are converted to individual saturated
fatty acids, unsaturated fatty acids, and glycerol by acid or base
catalyzed transesterification. Examples of some of the acid
components in various plant oils are listed in Table 2.
TABLE-US-00002 TABLE 2 Plant Oil Acids Plant Oil Acid Castor Oil
Ricinoleic Linseed Oil Linolenic, Linoleic, Oleic Soy Oil Palmitic,
Linoleic, Oleic Tall Oil (Pine Oil) Palmitic, Linoleic, Oleic Tung
Oil Eleaostearic Vernonia Oil Vernolic Lesquerella Oil (Bladderpod
Oil) Lesquerolic, Oleic, Linoleic Cashew Shell Oil Cardanol
[0016] The unsaturated fatty acids are of particular, interest as
precursor chemicals for polyol synthesis because they have the
functionality for satisfactory derivitization. Specifically, the
unsaturated fatty acids contain functional groups, such as
olefinic, hydroxyl, and epoxy, on a long carbon chain. For example,
castor oil and lesquerella oil (bladderod oil) have a pendent
hydroxyl group, and vernonia oil has a natural epoxy group. Thus,
the unsaturated fatty acids include several chemical functions that
facilitate polymer synthesis, such as unsaturated carbon chains,
hydroxyl groups, ester linkages, and epoxy functions. As a result,
the unsaturated fatty acids of the plant oils enable direct
radiation cross-linking or chemical modifications toward polyol
synthesis. Because many biobased polyols made from plant oils are
commercially available, and the method of forming biobased polyols
from plant oils is well known in the art, further description of
the biobased polyols, made from plant oils has been omitted.
[0017] Alternatively, the biobased polyol may be a biobased
polyester polyol or biobased polyester-ether polyol. The biobased
polyester polyols and the biobased polyester-ether polyols may be
made, for example, from biobased diols and biobased diacids derived
from renewable resources, such as corn, sugar cane, vegetable oil,
and the like. The biobased diol may be selected from the group
consisting, for example, of 1,3 propanediol, 1,4 butanediol,
propylene glycol, glycerol, and combinations thereof. The biobased
diacid may be selected from the group consisting, for example, of
sebacic acid, furnaric acid, succinic acid, tumaric acid, malic
acid, dicarboxylic acid, citric acid, azelaic acid, lactic acid,
and any combination thereof. Additional additives include
surfactant, defoamer, organic and/or inorganic flatting agents,
abrasion fillers, texture particles, and the like.
[0018] Table 3A shows some examples of some biobased polyester
polyol formulations. Reaction of the diacid with the diol produces
the biobased polyester polyol by condensation, with water as a
by-product. For example, the biobased polyester polyol may be
prepared according to the procedure set forth in Examples 1-4 of
U.S. Pat. No. 5,543,232, which is hereby incorporated by reference
in its entirety. Because the method of preparing polyester polyols
is well known in the art, further description thereof has been
omitted.
TABLE-US-00003 TABLE 3A Biobased Polyester Polyol Formulations EX-1
EX-2 EX-3 EX-4 EX-5 EX-6 EX-7 EX-8 Ingredient Amt (g) Amt (g) Amt
(g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Sebacic 639.18 648.31
663.10 672.94 0 0 0 0 Acid Succinic 0 0 0 0 539.50 551.69 557.92
570.97 Acid 1,3 360.72 291.48 336.80 264.57 460.40 360.65 441.99
338.32 Propanediol Glycerine 0 60.10 0 62.39 0 87.56 0 90.81 Fascat
4100 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Wt % 99.99 99.99 99.99
99.99 99.99 99.99 99.99 99.99 Renewable Materials Wt % 99.99 99.99
99.99 99.99 99.99 99.99 99.99 99.99 Biobased Content
[0019] The biobased polyester polyol may also be made by ring
opening polymerization of lactone, lactide, and glycolide in the
presence of a biobased diol or triol, such as 1,3 propanediol, 1,4
butanediol, glycerol, and combinations thereof, as initiator and a
ring-opening polymerization catalyst. Table 3B shows some examples
of some biobased polyester polyol formulations made by ring opening
polymerization. These biobased polyester polyols may be prepared
according to the procedure set forth in U.S. Pat. No. 6,916,547,
which is hereby incorporated by reference in its entirety. For
example, these biobased polyester polyols may be prepared by
charging lactone/lactide monomer(s) and Bio-PDO into a 1 liter
glass reactor equipped with anchor stirrer, temperature probe,
nitrogen sparge tube and air condenser, and stirring at 175 rpm
with 0.4 SCFH nitrogen sparge. The polymerization catalyst stannous
2-ethyl hexanoate is then charged. The nitrogen sparge is continued
for 10 minutes. The nitrogen charge is then maintained, and the
reactants are heated to 130 degrees Celsius over 30 minutes. The
nitrogen sparge is then maintained at 130 degrees Celsius for 6-14
hours until the reaction is complete. The batch is then cooled to
30 degrees Celsius and discharged.
TABLE-US-00004 TABLE 3B Biobased Polyester Polyol Formulations EX-9
EX-10 EX-11 Ingredient Amt (g) Amt (g) Amt (g) Caprolactone 500.00
0 250.00 Lactide 0 550.00 250.00 1,3-Propanediol 154.36 134.47
138.30 Stannous 2-ethyl hexanoate 0.0654 0.0684 0.0388 Wt %
Renewable Materials 23.59 99.99 60.83 Wt % Biobased Content 19.21
99.99 54.91
[0020] The biobased polyol may also be a biobased polyether polyol.
The biobased diol may be selected from the group consisting, for
example, of 1,3 propanediol and 1,4 butanediol, propylene glycol,
glycerol, and combinations thereof. Examples of biobased polyether
polyols include poly(trimethylene ether glycol) and
poly(tetramethylene ether glycol). One commercially available
poly(trimethylene ether glycol) is CERENOL manufactured by E.I. du
Pont de Nemours and Company of Wilmington, Del. CERENOL is made 1,3
propanediol originating from corn sugar via aerobic fermentation.
The biobased content of poly(trimethylene ether glycol) made from
polycondensation of 1,3 propanediol originating from corn sugar via
aerobic fermentation is about 100%.
[0021] Additionally, the biobased polyol may be derived, for
example, from vegetable oils, corn, oats, cellulose, starch, sugar,
sugar alcohols, such as xylitol, sorbitol, maltitol, sucrose,
glycol, glycerol, erythritol, arabitol, rebitol, mannitol, isomalt
laetitol, fructose, or polysaccharides or monosaccharides
originated from cellulose, starches, or sugars. It will be
appreciated by those skilled in the art that other renewable and/or
biobased materials containing primary and secondary hydroxyl groups
could also be used as the biobased polyol, because such renewable
and/or biobased materials are capable of acylated, as described
herein, to form the radiation curable biobased coating of the
present invention.
[0022] The biobased polyol is partially or fully acrylated to form
a biobased polyol acrylate. Because the biobased polyol acrylate is
derived from renewable and/or biobased materials, the biobased
polyol acrylate contains a weight percentage of renewable materials
of at least about 5%, preferably at least about 50%, and more
preferably at least about 70%. The biobased polyol acrylate may be
formed, for example, by reacting the biobased polyol with acrylic
acid. Table 4 shows some examples of some biobased polyol acrylate
formulations using the biobased polyols made from castor oil
(Polycin D-290; Polycin M-280; Polycin D-265; Polycin D-140), and
soy oil (Soyol R2-052-F; Soyol R3-1710-F).
TABLE-US-00005 TABLE 4 Biobased Polyol Acrylate Formulations EX-12
EX-13 EX-14 EX-15 EX-16 EX-17 EX-18 Ingredient Amt (g) Amt (g) Amt
(g) Amt (g) Amt (g) Amt (g) Amt (g) Polycin D-290 800.00 0 0 800.00
0 0 0 Polycin M-280 0 500.00 0 0 0 0 0 Polycin D-265 0 0 450.00 0 0
0 0 Polycin D-140 0 0 0 0 800.00 0 0 Soyol R2-052-F 0 0 0 0 0
800.00 0 Soyol R3-1710-F 0 0 0 0 0 0 800.00 Acrylic Acid 328.29
108.00 91.07 179.07 86.40 33.38 104.73 p-toluene 5.40 3.38 3.04
5.40 5.40 5.40 5.40 sulfonic acid Hydroquinone 0.12 0.08 0.07 0.12
0.12 0.12 0.12 Monomethyl ether 0.12 0.08 0.07 0.12 0.12 0.12 0.12
hydroquinone (p-methoxyphenol) 0.62 0.39 0.35 0.62 0.62 0.62 0.62
Phosphorous Acid n-heptane 200 ml 182.75 0 0 0 0 0 Toluene 0 0
130.06 200 ml 200 ml 200 ml 200 ml N-methyl- 0 0 0 0 0 0 0
diethanolamine Reaction 100-105.degree. C. 100-105.degree. C.
110-112.degree. C. 110-112.degree. C. 110-112.degree. C.
110-112.degree. C. 110-112.degree. C. Temperature Wt % Renewable
70.51 81.71 82.53 81.19 89.62 95.28 87.82 Materials
[0023] A method for acrylating the biobased polyol using the
formulation in Table 4, EX-14 will now be described. A 1.0 liter
jacketed glass reaction flask is prepared for toluene reflux and
water separation. The flask is sparged with about 0.5 standard
cubic feet per hour of dry air and about 1.5 standard cubic feet
per hour nitrogen blend. An anchor stirrer is activated at about
200 rpm. The polycin D-265, hydroquinone, monomethyl ether
hydroquinone (p-methoxyphenol), and phosphorous acid are charged.
The reactants are then heated to about 60 degrees Celsius. The
acrylic acid and p-toluene sulfonic acid are charged. The p-toluene
sulfonic acid is allowed to dissolve. The toluene is charged. The
jacket of the glass reaction flask is heated to and maintained at a
temperature of about 125 degrees Celsius. The reactants temperature
is controlled at about 116-119 degrees Celsius by regulating the
amount of the toluene. The toluene is refluxed back to the
reactants and the reaction water is separated. The reaction water
is then collected and measured. The conditions are maintained until
the reaction water ceases. The jacket of the glass reaction flask
is then reset to about 100 degrees Celsius, and a vacuum
distillation is prepared to remove the toluene. When the reactants
temperature reaches about 100 degrees Celsius, the blanket of dry
air and nitrogen blend is slowly turned off and a vacuumed is
slowly applied. The vacuum is continued at 26'' Hg until the
toluene distillation ceases. The batch is then cooled and
discharged.
[0024] The biobased polyol acrylate is then reacted with
di-isocyanates or tri-isocyanates or reacted with di-isocyanates or
tri-isocyanates and UV/EB moieties to form a biobased resin, such
as a biobased urethane acrylate or a biobased polyester acrylate.
Because the biobased resin is derived from renewable and/or
biobased materials, the biobased resin contains a weight percentage
of renewable materials of at least about 5%, preferably at least
about 50%, and more preferably at least about 65%. The biobased
resin comprises a mixture of crosslinkable monomers and oligomers
having reactive groups capable of providing the ability to
polymerize upon exposure to radiation, such as UV/EB radiation.
Table 5 shows some examples of some biobased resin formulations
using the biobased polyol acrylates from Table 4.
TABLE-US-00006 TABLE 5 Biobased Resin Formulations EX-19 EX-20
EX-21 Ingredient Amt (g) Amt (g) Amt (g) EX-14 600.00 0 459.85
EX-18 0 600.00 0 Desmodur W 132.48 23.60 101.53 Silwet L-7200 1.89
0 1.45 Iragacure 184 5.49 0 4.21 Benzophenone 21.97 0 16.84 Wt %
Renewable Materials 65.00 84.49 65.00
[0025] A method for reacting the biobased polyol acrylate to
produce the biobased resin using the formulation in Table 5, EX-21
will now be described. EX-14 from Table 4 is charged to a 1.0 liter
jacketed glass reaction flask. An anchor stirrer is activated at
about 200 rpm, and EX-14 is heated to about 35 degrees Celsius. The
flask is blanketed with about 1.1 standard cubic feet per hour of
dry air for about 30 minutes. EX-14 is heated to about 50 degrees
Celsius. The blanket of dry air is adjusted to about 0.45 standard
cubic feet per hour. Desmodur W is charged in one third increments
(about 33.84 g) and exotherm is observed with each addition. The
reactants are maintained at a temperature of about 85 degrees
Celsius over about a 2 hour period. The reactants are then held at
a temperature of about 85 degrees Celsius, and infrared is used to
monitor the decline in the numerically controlled oscillator (NCO)
peak. When the NCO peak is gone, the batch is cooled to about 60
degrees Celsius. The Silwet L-7200, Irgacure 184, and benzophenone
are then charged and mixed for about 30 minutes until all
dissolved. The batch is then cooled and discharged.
[0026] The biobased resin is then blended, for example, with an
initiator, surfactant, and other additives, such as acrylate
reactive diluents, defoamer, matting agent, abrasion agent, and
texture particles, to form the radiation curable biobased coating.
The acrylate reactive diluents may include, for example,
(meth)acrylic acid, isobornyl(meth)acrylate,
isodecyl(meth)acrylate, hexanediol di(meth)acrylate, N-vinyl
formamide, tetraethylene glycol(meth)acrylate, tripropylene
glycol(meth)acrylate, neopentyl glycol di(meth)acrylate,
ethoxylated neopentyl glycol di(meth)acrylate, propoxylated
neopentyl glycol di(meth)acrylate, trimhethylol propan
tri(meth)acrylate, ethoxylated trimethylol propan
tri(meth)acrylate, propoxylated trimethylol propan
tri(meth)acrylate, ethoxylated or propoxylated tripropylene glycol
di(meth)acrylate, pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, tris(2-hydroxy
ethyl)isocyanurate tri(meth)acrylate, and combinations thereof. The
initiator may be any chemical capable of initiating, assisting, or
catalyzing the polymerization and/or cross-linking of the biobased
resin. The initiator may be, for example, a photoinitiator or
photosensitizer that allows the biobased coating to cure when
exposed to UV/EB radiation. The initiators may be chosen to
increase curing rate and sensitivity to specific wavelengths of
UV/EB radiation. The concentration of the initiator is the amount
necessary to provide satisfactory curing for the biobased resin in
the coating mixture.
[0027] Table 6A shows some examples of some radiation curable
biobased coating formulations using the biobased resins from Table
5 based on a free radical curing mechanism. Because the radiation
curable biobased coating is derived from renewable and/or biobased
materials, the radiation curable biobased coating contains a weight
percentage of renewable materials of at least about 5%, preferably
at least about 30%, and more preferably at least about 40%.
TABLE-US-00007 TABLE 6A Radiation Curable Biobased Coating
Formulations EX-22 EX-23 EX-24 EX-25 Ingredient Amt (g) Amt (g) Amt
(g) Amt (g) EX-21 50.00 50.00 50.00 50.00 SR-3010 28.13 20.00 12.50
6.00 Silwet L-7200 0.07 0.05 0.03 0.02 Irgacure 184 0.21 0.15 0.09
0.05 Benzophenone 0.84 0.60 0.38 0.18 Wt % Renewable 41.01 45.91
51.59 57.78 Materials
[0028] In another embodiment, the biobased polyol acrylate is
directly blended into a radiation curable biobased coating
formulation similar to the radiation curable biobased coating
formulations in Table 6A to form the radiation curable biobased
coating. The biobased polyol acrylate may be, for example, any of
the biobased polyol acrylates from Table 4, and the biobased polyol
acrylate would be substituted for EX-21 in Table 6A.
[0029] In a further embodiment, the biobased polyol is directly
blended into a radiation curable biobased coating formulation
comprising at least one epoxy resin or vinyl ether and at least one
initiator, which may be, for example, a cationic type
photoinitiator, to form the radiation curable biobased coating. The
biobased polyol may be, for example, any of the biobased polyols
from Tables 3A-3B or combinations thereof. The epoxide resins may
include, for example,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
bis-(3,4-epoxycyclohexyl)adipate, 3-ethyl-3-hydroxy-methyl-oxetane,
1,4-butanedial diglycidyl ether, 1,6 hexanediol diglycidyl ether,
ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl
ether, polyglycol diglycidyl ether, propoxylated glycerin
triglycidyl ether, monoglycidyl ester of neodecanoic acid,
epoxidized soy, epoxidized linseed oil, epoxidized polybutadiene
resins, or combinations thereof. The vinyl ether resins may
include, for example, 1,4-butanediol divinyl ether,
diethyleneglycol divinyl ether, triethyleneglycol divinyl ether,
N-vinyl caprolactam, N-vinylformamide, N-vinyl pyrrolidone, n-butyl
vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether,
dodecyl vinyl ether, octadecyl vinyl ether, trimethylolpropane
diallyl ether, allyl pentaerythritol, trimethylolpropane
monoallylether, or combinations thereof. The initiator may be, for
example, a cationic photoinitiator and a photosensitizer, such as
triarylsulfonium hexafluoroantimonate salts, triarylsulfonium
hexafluorophosphate salts,
bis(4-methylphenyl)-hexafluorophosphate-(1)-iodonium, isopropyl
thioxanthone, 1-chloro-4-propoxy-thioxanthone,
2,4-diethylthioxanthone, 2-chlorothioxanthone, camphorquinone.
[0030] Table 6B shows some examples of some radiation curable
biobased coating formulations using the biobased polyols from Table
3A based on cationic curing mechanism.
TABLE-US-00008 TABLE 6B Radiation Curable Biobased Coating
Formulations Ingredient EX-26 EX-27 Chemical Name Function Amt (g)
Amt (g) EX-5 resin 12.5 12.5 3,4-epoxy cyclohexyl methyl-3,4 resin
50 50 epoxy cyclohexane carboxylate Silwet L-7200 surfactant 0.156
0.156 Isopropylthioxanthone photosensitizer 0.313 0 2,4-diethyl
thioxanthone photosensitizer 0 0.313
Arylsulfoniumhexafluoro-phosphate photoinitiator 3.75 3.75 Gasil
UV70C flatting agent 5.3375 5.3375 Wt % Renewable Materials 17.35
17.35 Wt % Biobased Content 13.32 13.31
[0031] The radiation curable biobased coating is then applied to a
surface of a substrate and is cured or cross-linked by radiation
curing to form a topcoat or wear layer thereon. The substrate may
be made, for example, from a variety of materials, such as wood,
ceramic, plastic, or metal. Additionally, the substrate may be, for
example, a substrate of a flooring application, such as linoleum,
hardwood, laminate, cork, bamboo, resilient sheet, or tile. The
radiation curable biobased coating may be radiation cured, for
example, with UV/EB radiation. For example, standard high pressure
mercury vapor type UV lamps with wavelengths of about 1800-4000
Angstrom units can be used to cure the radiation curable biobased
coating, as well as UV lamps containing additives to enhance
specific UV regimes. The radiation curable biobased coating is
exposed to the UV lamps at about 0.5-2.5 joules per centimeter
squared at about 0.3-1.2 watts megawatts per centimeter squared. It
will be appreciated by those skilled in the art, however, that the
length and intensity of the exposure to the radiation may vary
depending oh the thickness and composition of the radiation curable
biobased coating and the desired finish, e.g., gloss level.
Additionally, the radiation curable biobased coating may be cured
in air or nitrogen depending upon the composition of the radiation
curable biobased coating and the desired finish.
[0032] The foregoing illustrates some of the possibilities for
practicing the invention. Many other embodiments are possible
within the scope and spirit of the invention. It is, therefore,
intended that the foregoing description be regarded as illustrative
rather than limiting, and that the scope of the invention is given
by the appended claims together with their full range of
equivalents.
[0033] While the invention has been described with reference to a
preferred embodiment, it will be understood by those skilled in the
art that various changes may be made and equivalents may be
substituted for elements thereof without departing from the scope
of the invention. In addition, many modifications may be made to
adapt a particular situation or material to the teachings of the
invention without departing from the essential scope thereof.
Therefore, it is intended that the invention not be limited to the
particular embodiment disclosed as the best mode contemplated for
carrying out this invention, but that the invention will include
all embodiments falling within the scope of the appended
claims.
* * * * *