U.S. patent application number 11/542019 was filed with the patent office on 2008-04-03 for polyester binder for flooring products.
Invention is credited to Fang Qiao, Jeffrey S. Ross, Gary A. Sigel, Dong Tian, Rebecca L. Winey.
Application Number | 20080081882 11/542019 |
Document ID | / |
Family ID | 39261841 |
Filed Date | 2008-04-03 |
United States Patent
Application |
20080081882 |
Kind Code |
A1 |
Tian; Dong ; et al. |
April 3, 2008 |
Polyester binder for flooring products
Abstract
A flooring product is provided comprising at least one layer
including a polymeric binder comprising at least one thermoplastic
polyester resin, wherein the polyester resin comprises at least one
renewable component. A flooring product is also provided that
includes at least one layer comprising filler and at least one
thermoplastic, high molecular weight polyester resin. The flooring
product may also qualify for at least one point under the LEED
System. A composition is also provided that can be melt mixed in
low intensity mixers and processed into flooring layers.
Inventors: |
Tian; Dong; (Lancaster,
PA) ; Sigel; Gary A.; (Millersville, PA) ;
Qiao; Fang; (Lancaster, PA) ; Winey; Rebecca L.;
(Lancaster, PA) ; Ross; Jeffrey S.; (Lancaster,
PA) |
Correspondence
Address: |
Douglas E. Winters;Armstrong World Industries, Inc.
2500 Columbia Avenue, P.O. Box 3001
Lancaster
PA
17604-3001
US
|
Family ID: |
39261841 |
Appl. No.: |
11/542019 |
Filed: |
October 2, 2006 |
Current U.S.
Class: |
525/444 |
Current CPC
Class: |
C08K 5/1515 20130101;
C08L 67/02 20130101; C09D 167/02 20130101; E04F 15/00 20130101;
C08L 2205/025 20130101; C08L 2207/20 20130101; C09D 7/61 20180101;
C08L 67/02 20130101; C08L 2666/18 20130101 |
Class at
Publication: |
525/444 |
International
Class: |
C08L 67/02 20060101
C08L067/02 |
Claims
1. A resilient flooring product comprising a layer, the layer
comprising a polymeric binder, the polymeric binder comprising a
first thermoplastic polyester resin, wherein the polyester resin
comprises a renewable component.
2. The flooring product of claim 1, wherein the polyester resin is
amorphous.
3. The flooring product of claim 1, wherein the polyester resin is
crystalline.
4. The flooring product of claim 1, wherein the polyester resin has
a number average molecular weight of at least 5,000.
5. The flooring product of claim 4, wherein the polyester resin has
a number average molecular weight of at least 10,000.
6. The flooring product of claim 1, wherein the polymeric binder
further comprises a second polyester resin.
7. The flooring product of claim 6, wherein the first polyester
resin is amorphous and the second polyester resin is
crystalline.
8. The flooring product of claim 6, wherein one of the polyester
resins has a number average molecular weight of at least 5,000.
9. The flooring product of claim 8, wherein one of the polyester
resins has a number average molecular weight of at least
10,000.
10. The flooring product of claim 3, wherein the crystalline
polyester resin has a Tm below about 200.degree. C.
11. The flooring product of claim 3, wherein the crystalline
polyester resin has a Tg of about room temperature or below.
12. The flooring product of claim 2, wherein the amorphous
polyester has a Tg of about room temperature.
13. The flooring product of claim 2, wherein the amorphous
polyester has a Tg is between 20.degree. C. and 35.degree. C.
14. The flooring product of claim 6, wherein one of the first and
second polyester resins is amorphous and has a Tg at or below room
temperature and the other polyester resin is amorphous and has a Tg
above room temperature.
15. The flooring product of claim 1, wherein the polyester resin
comprises the co-reaction product of a renewable polyester resin
and a recycle polyester resin.
16. The flooring product of claim 1, wherein the polyester resin
further comprises a recycle component.
17. The flooring product of claim 16, wherein the polyester resin
comprises at least 98% by weight of renewable and recycle
components.
18. The flooring product of claim 1, wherein the layer is a non-PVC
layer.
19. The flooring product of claim 1, wherein the polyester resin
comprises a Biobased Content of at least 5% by weight.
20. The flooring product of claim 1, wherein the polyester resin
comprises an epoxidized natural oil moiety.
21. The flooring product of claim 1, further comprising an
epoxidized natural oil.
22. The flooring product of claim 1, wherein the polyester resin
comprises a carboxylic acid end group.
23. The flooring product of claim 1, wherein the polyester resin
comprises an aromatic diacid component and an aliphatic diacid
component.
24. The flooring product of claim 23, wherein the polyester resin
further comprises a second aromatic diacid component.
25. A resilient flooring product comprising a layer, the layer
comprising filler and a polymeric binder, the polymeric binder
comprising a polyester resin.
26. The flooring product of claim 25, wherein the polyester resin
is amorphous.
27. The flooring product of claim 25, wherein the polyester resin
is crystalline.
28. The flooring product of claim 25, wherein the polyester resin
has a number average molecular weight of at least 5,000.
29. The flooring product of claim 28, wherein the polyester resin
has a number average molecular weight of at least 10,000.
30. The flooring product of claim 25, wherein the polymeric binder
further comprises a second polyester resin.
31. The flooring product of claim 30, wherein the first polyester
resin and the second polyester resin are amorphous.
32. The flooring product of claim 30, wherein the first polyester
resin is amorphous and the second polyester resin is
crystalline.
33. The flooring product of claim 30, wherein one of the polyester
resins has a number average molecular weight of at least 5,000.
34. The flooring product of claim 33, wherein one of the polyester
resins has a number average molecular weight of at least
10,000.
35. The flooring product of claim 30, wherein the crystalline
polyester resin has a Tm below about 200.degree. C.
36. The flooring product of claim 27, wherein the crystalline
polyester resin has a Tg of about room temperature or below.
37. The flooring product of claim 26, wherein the amorphous
polyester has a Tg about room temperature.
38. The flooring product of claim 26, wherein the amorphous
polyester has a Tg is between 20.degree. C. and 35.degree. C.
39. The flooring product of claim 30, wherein one of the first and
second polyester resins is amorphous and has a Tg at or below room
temperature and the other polyester resin is amorphous and has a Tg
above room temperature.
40. The flooring product of claim 25, wherein the polyester resin
comprises the co-reaction product of a renewable polyester resin
and a recycle polyester resin.
41. The flooring product of claim 25, wherein the polyester resin
further comprises a renewable component.
42. The flooring product of claim 25, wherein the polyester resin
further comprises a recycle component.
43. The flooring product of claim 25, wherein the polyester resin
comprises at least 98% by weight of renewable and recycle
components.
44. The flooring product of claim 25, wherein the filler comprises
recycle filler.
45. The flooring product of claim 25, wherein the layer is a
non-PVC layer.
46. The flooring product of claim 25, wherein the polyester resin
has a Biobased Content of at least 5% by weight.
47. The flooring product of claim 25, wherein the polyester resin
comprises an epoxidized natural oil moiety.
48. The flooring product of claim 25, further comprising an
epoxidized natural oil.
49. The flooring product of claim 25, wherein the polyester resin
comprises a carboxylic acid end group.
50. The flooring product of claim 25, wherein the polyester resin
comprises an aromatic diacid component and an aliphatic diacid
component.
51. The flooring product of claim 50, wherein the polyester resin
further comprises a second aromatic diacid component.
52. A resilient flooring product, wherein the flooring product
qualifies for at least one point in the LEED System and comprises a
layer, the layer comprising a polymeric binder, the polymeric
binder comprising a first polyester resin.
53. The flooring product of claim 52, wherein the polyester resin
is amorphous.
54. The flooring product of claim 52, wherein the polyester resin
is crystalline.
55. The flooring product of claim 52, wherein the polyester resin
has a number average molecular weight of at least 5,000.
56. The flooring product of claim 55, wherein the polyester resin
has a number average molecular weight of at least 10,000.
57. The flooring product of claim 52, wherein the polymeric binder
further comprises a second polyester resin.
58. The flooring product of claim 57, wherein the first and second
polyester resins are amorphous.
59. The flooring product of claim 57, wherein the first polyester
resin is amorphous and the second polyester resin is
crystalline.
60. The flooring product of claim 54, wherein the crystalline
polyester resin has a Tm below about 200.degree. C.
61. The flooring product of claim 54, wherein the crystalline
polyester resin has a Tg of about room temperature or below.
62. The flooring product of claim 53, wherein the amorphous
polyester has a Tg around room temperature.
63. The flooring product of claim 53, wherein the amorphous
polyester has a Tg is between about 20.degree. C. and about
35.degree. C.
64. The flooring product of claim 58, wherein one of the first and
second amorphous polyester resin has a Tg at or below room
temperature and the other amorphous polyester resin has a Tg above
room temperature.
65. The flooring product of claim 52, wherein the polyester resin
comprises the co-reaction product of a renewable polyester resin
and a recycle polyester resin.
66. The flooring product of claim 52, wherein the polyester resin
comprises a renewable component.
67. The flooring product of claim 52, wherein the polyester resin
comprises a recycle component.
68. The flooring product of claim 52, wherein the polyester resin
comprises a renewable and a recycle component.
69. The flooring product of claim 68, wherein the polyester resin
comprises at least 98% by weight of renewable and recycle
components.
70. The flooring product of claim 52, wherein the layer further
comprises recycle filler.
71. The flooring product of claim 52, wherein the layer is a
non-PVC layer.
72. The flooring product of claim 52, wherein the polyester resin
has a Biobased Content of at least 5% by weight.
73. The flooring product of claim 52, wherein the polyester resin
comprises an epoxidized natural oil moiety.
74. The flooring product of claim 52, further comprising an
epoxidized natural oil.
75. The flooring product of claim 52, wherein the polyester resin
comprises a carboxylic acid end group.
76. A resilient floor tile having a PCT structure comprising a
polymeric binder, the polymeric binder comprising a polyester
resin.
77. The floor tile of claim 76, wherein the polyester resin is
amorphous.
78. The floor tile of claim 76, wherein the polyester resin is
crystalline.
79. The floor tile of claim 76, wherein the polyester resin has a
number average molecular weight of at least 5,000.
80. The floor tile of claim 79, wherein the polyester resin has a
number average molecular weight of at least 10,000.
81. The floor tile of claim 76, wherein the polymeric binder
further comprises a second polyester resin.
82. The floor tile of claim 81, wherein the first polyester resin
and the second polyester resin are amorphous.
83. The floor tile of claim 81, wherein one of the first and second
polyester resins is amorphous and the other polyester resin is
crystalline.
84. The floor tile of claim 78, wherein the crystalline polyester
resin has a Tm below about 200.degree. C.
85. The floor tile of claim 78, wherein the crystalline polyester
resin has a Tg of about room temperature or below.
86. The floor tile of claim 77, wherein the amorphous polyester has
a Tg about room temperature.
87. The floor tile of claim 77, wherein the amorphous polyester has
a Tg is between 20.degree. C. and 35.degree. C.
88. The floor tile of claim 81, wherein one of the first and second
polyester resins is amorphous and has a Tg at or below room
temperature and the other polyester resin is amorphous and has a Tg
above room temperature.
89. The floor tile of claim 76, wherein the polyester resin
comprises the co-reaction product of a renewable polyester resin
and a recycle polyester resin.
90. The floor tile of claim 76, wherein the polyester resin further
comprises a renewable component.
91. The floor tile of claim 76, wherein the polyester resin further
comprises a recycle component.
92. The floor tile of claim 76, wherein the polyester resin
comprises at least 98% by weight of renewable and recycle
components.
93. The floor tile of claim 76, wherein the floor tile further
comprises recycle filler.
94. The floor tile of claim 76, wherein the floor tile is a non-PVC
floor tile.
95. The floor tile of claim 76, wherein the floor tile qualifies
for at least one point in the LEED System.
96. The floor tile of claim 76, wherein the polymeric binder
comprises less than about 20% by weight of the floor tile.
97. The floor tile of claim 76, wherein the polyester resin has a
Biobased Content of at least 5% by weight.
98. The floor tile of claim 76, wherein the polyester resin
comprises an epoxidized natural oil moiety.
99. The floor tile of claim 76, further comprising an epoxidized
natural oil.
100. The floor tile of claim 76, wherein the polyester resin
comprises a carboxylic acid end group.
101. The floor tile of claim 76, wherein the polyester resin
comprises an aromatic diacid component and an aliphatic diacid
component.
102. The floor tile of claim 101, wherein the polyester resin
further comprises a second aromatic diacid component.
103. A composition including filler and a polymeric binder, the
binder comprising a first polyester resin, wherein the composition
is capable of being melt mixed in a low intensity mixer and
processed into a flooring layer.
104. The composition of claim 103, wherein the composition further
comprises an acid functionalized polymer resin.
105. The composition of claim 104, wherein the acid functionalized
polymer resin comprises less than about 60 weight percent of the
binder resin in the composition.
106. The composition of claim 103, wherein the filler comprises
recycle filler material.
107. The composition of claim 103, wherein the polyester resin is
amorphous.
108. The composition of claim 103, wherein the polyester resin is
crystalline.
109. The composition of claim 103, wherein the polyester resin has
a number average molecular weight of at least 5,000.
110. The composition of claim 109, wherein the polyester resin has
a number average molecular weight of at least 10,000.
111. The composition of claim 103, wherein the polymeric binder
comprises a second polyester resin.
112. The composition of claim 111, wherein the first and second
polyester resins are amorphous.
113. The composition of claim 111, wherein the first polyester
resin is amorphous and the second polyester resin is
crystalline.
114. The composition of claim 108, wherein the crystalline
polyester resin has a Tm below about 200.degree. C.
115. The composition of claim 108, wherein the crystalline
polyester resin has a Tg of about room temperature or below.
116. The composition of claim 107, wherein the amorphous polyester
has a Tg of about room temperature.
117. The composition of claim 107, wherein the amorphous polyester
has a Tg is between 20.degree. C. and 35.degree. C.
118. The composition of claim 112, wherein one of the first and
second amorphous polyester resins has a Tg at or below room
temperature and the other amorphous polyester resin has a Tg above
room temperature.
119. The composition of claim 103, wherein the polyester comprises
the co-reaction product of a renewable polyester resin and a
recycle polyester resin.
120. The composition of claim 103, wherein the polyester resin
comprises a renewable component.
121. The composition of claim 103, wherein the polyester resin
comprises a recycle component.
122. The composition of claim 103, wherein the polyester resin
comprises a renewable component and a recycle component.
123. The composition of claim 122, wherein the polyester resin
comprises at least 98% by weight of renewable and recycle
components.
124. The composition of claim 103, wherein the polyester resin has
a Biobased Content of at least 5% by weight.
125. The composition of claim 103, wherein the polyester resin
comprises an epoxidized natural oil moiety.
126. The composition of claim 103, further comprising an epoxidized
natural oil.
127. The composition of claim 103, wherein the polyester resin
comprises a carboxylic acid end group.
Description
FIELD OF THE INVENTION
[0001] The present invention relates generally to the field of
floor products. More particularly, the present invention relates to
floor products having a layer including a polyester resin binder
and the composition used to make the polyester resin binder layer.
As used herein a polyester resin is a polycondensation product of
polycarboxylic acids or esters with polyhydroxy alcohols, and are
generally hydroxy-terminated, acid terminated or end-cap
terminated, i.e. capped with a less reactive moiety.
BACKGROUND OF THE INVENTION
[0002] The development of resilient flooring products (i.e.
non-textile) based on polymers besides polyvinyl chloride (PVC) has
been an objective for a long time. For example, acrylic polymers
have been disclosed as a binder for flooring products. U.S. Pat.
No. 3,575,785 discloses a flooring product comprising poly alkyl
methacrylate binder. World Patent Application WO 1994/9415014A1
discloses a floor tile having a binder comprising ethylene
butylacrylate copolymer. WO 94/21721 discloses flooring having a
wear layer comprised of plasticized acrylic polymers.
[0003] Ethylene vinyl acetate (EVA) co-polymers have also been
disclosed as a binder for flooring products. For example, U.S. Pat.
No. 5,244,942 discloses flooring having an EVA binder and filler.
The composition may also contain polypropylene or
ethylene-propylene diene monomer (EPDM) polymers as additives. U.S.
Pat. Nos. 5,928,754; 6,380,296; 5,407,617; 4,614,556; and EP
0,721,829B1 disclose the use of EVA as a binder in flooring
products. U.S. Pat. No. 5,276,082 discloses the use of
silane-grafted EVA as a flooring binder.
[0004] Functionalized polyolefins such as ethylene acrylic acid
co-polymers and their partially neutralized counterparts (ionomers)
have also been disclosed as a binder for flooring products. For
example, U.S. Pat. No. 4,083,824 discloses a non-vinyl flooring
composition comprising (1) a copoly block acrylate comprising at
least two C.sub.1 to C.sub.8 linear or branched alkyl acrylates of
Mw from about 100,000 to about 300,000 and further characterized by
at least two glass transition temperatures, one being above
25.degree. C., the other being below 25.degree. C.; and (2) a
random ionic copolymer comprising ethylene and 2.5% to 25% by
weight acrylic acid or methacrylic acid partially neutralized by a
monovalent or polyvalent metal ion, said ionic copolymer having a
melt index of 0.1 to 1000 grams per minute.
[0005] U.S. Pat. No. 5,391,612 discloses a flooring product
comprising ethylene acrylic acid (EAA) or ethylene methacrylic acid
(EMA) copolymers as binders for flooring products.
[0006] US Patent Application No. 2005/0048277 discloses a non-vinyl
flooring including a binder having a terpolymer comprising
ethylene, methyl acrylate and acrylic acid and a copolymer
comprising ethylene and methacrylic acid. The non-vinyl flooring
may be either a resilient non-vinyl floor tile or a resilient
non-vinyl sheet flooring comprising the non-vinyl terpolymer and a
copolymer.
[0007] U.S. Pat. Nos. 5,728,476; 5,753,767; 5,798,413; 6,921,791;
and EP 0,848,037; and WO Application 2004/069920A1 also disclose
the use of acid functionalized or ionomer polymers as binders in
flooring product.
[0008] Polyolefin materials have also been disclosed as binders for
flooring products. Recent advances in metallocene catalysts have
provided new polyolefin materials of interest. Polyolefin binders
are disclosed in the following patents: U.S. Pat. Nos. 6,103,803;
6,254,956; 6,356,658; 6,224,804; 5,763,501; 6,287,706; 6,017,586;
5,945,472; 6,187,424; 6,214,924; 5,700,865; 6,617,008; 5,997,782;
5,928,754; 5,824,727; and EP 0,861,951B1.
[0009] Aromatic esters and some low molecular weight polyesters
have been traditionally used as plasticizers for PVC. U.S. Pat. No.
4,595,626 discloses unsaturated, cross-linkable unsaturated
polyesters resins as flooring binders. The end group analysis
molecular weight of the polyester is between 600 and 3600. The
composition also comprises reactive monomer diluent.
[0010] PCT Application WO 95/17568 discloses a wear surface for
flooring comprising a thermoset polyester resin and an epoxy or
carboxyl-functional acrylic resin and a cross-linking agent.
Additionally, U.S. Pat. No. 6,911,263 discloses a wear surface for
flooring comprising a composite of PET (polyethylene terephthalate)
clear film and a sol gel type surface coating.
[0011] Most recently, interest in polylactic acid based polyesters
(PLA) has increased since the polymer can be obtained from natural
resources and bio-processes. This has given rise to a large number
of patents based upon these materials and other alpha-hydroxy acid
based polyesters. Due to the polymer structure, these PLA
polyesters require the use of plasticizers or other polymer
additives for processing and to produce products having acceptable
properties. For example, see U.S. Pat. Nos. 6,869,985 and
7,029,750, and US Patent Application No. 2005/0136259 which
disclose compositions comprising PLA as a binder component for
flooring.
[0012] Although there is a still controversy over the manufacture,
use, and disposal of polyvinyl chloride, only recently have
commercial efforts been made to develop materials and polymers from
renewable resources. For example, DuPont's new Sorona fiber
comprises a polyester made from terephthalic acid and Bio-produced
1,3-propanediol.
[0013] Recently, the US Green Building Council has established the
LEED (Leadership in Energy and Environmental Design) system for
scoring points for new commercial construction (Table 1). Under the
LEED system, flooring can be used to obtain points if it contains
10% by weight or more of post-industrial recycle material.
TABLE-US-00001 TABLE 1 LEED System For New Commercial Construction
Rating LEED-NC Rating LEED-EB System Version 2.1 System Version 2.0
MR Credit 5% wt = (post- MR Credit 2.1 10% 4.1 consumer + 1/2 post-
1 Point (Post-Consumer 1 Point industrial) materials), or MR Credit
10% wt = (post- 20% 4.2 consumer + 1/2 post- (Post-Industrial 1
Point industrial) materials) MR Credit 6 5% wt = (rapidly MR Credit
2.5 50% 1 Point renewable building 1 Point (Rapidly materials and
renewable products) materials) NC: New Construction; EB: Existing
Building; Minimum % wt for each point. The % for both NC and EB is
weight percent. For NC 1 point is granted for at least 5% wt of the
total of post-consumer and 1/2 post-industrial. A second point is
granted for at least 10% wt of the total of post-consumer and 1/2
post-industrial. An additional point is granted for at least 5% wt
of rapidly renewable building materials and products. For EB 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.
[0014] There has been renewed market interest in giving preference
to "greener" flooring products based upon this LEED System. The use
of renewable materials is of high interest.
[0015] There continues to be a need for flooring products having a
polymeric binder that comprises components obtained from renewable
resources. Additionally, there is a need for such a new binder
system to be compatible with existing processes and equipment
currently utilized for vinyl flooring manufacturing.
SUMMARY OF THE INVENTION
[0016] The resilient flooring product of the present invention has
at least one layer including a polymeric binder comprising
thermoplastic, polyester resin, wherein the polyester comprises at
least one renewable component. As used in this disclosure,
"thermoplastic" means a polymer that softens when exposed to heat
and returns to its original condition when cooled to room
temperature, whereas "thermoset" means a polymer that solidifies or
sets irreversibly when heated. Thermoset is usually associated with
a cross-linking reaction of the molecular constituents induced by
heat or radiation.
[0017] In some embodiments, the thermoplastic, polyester resin has
a number average molecular weight (Mn) of at least 5,000 and in
other embodiments the polyester resins have a molecular weight (Mn)
of at least 10,000.
[0018] The polyester may be biodegradable, and/or may contain
renewable components. In one embodiment, the polyester comprises at
least 50% by weight renewable components. In another embodiment,
the polyester comprises greater than 80% by weight renewable
components. In another embodiment, the polyester comprises recycle
components. In yet another embodiment, the polyester comprises
essentially 100% renewable and recycle components.
[0019] The polyesters may comprise aliphatic diacid and aliphatic
diol components. In one embodiment, these components come from
renewable sources. In other embodiments, the polyester can comprise
aromatic diacids and aliphatic diol components. In other
embodiments, the polyester can comprise aliphatic diacids, aromatic
diacid, and aliphatic diol components. The polyesters can be
amorphous or crystalline in nature. In one embodiment the polyester
is amorphous having a Tg at about room temperature. In other
embodiments, the polyester may be crystalline and have a Tg at or
below about 25.degree. C. and a melt temperature (Tm) above about
25.degree. C. In some embodiments, the Tm is above about 25.degree.
C. but below about 200.degree. C. In yet another embodiment, the
polyester may comprise branching.
[0020] In another embodiment, the polyester comprises the
co-reaction product of a aliphatic polyester comprising renewable
components and a recycle polyester resin. In some embodiments, the
recycle polyester resin is aromatic based and includes polyethylene
terephthlate, polybutylene terephthlate, and polypropylene
terephthlate.
[0021] In another embodiment, a flooring product is provided having
at least one layer including filler and a polymeric binder
comprising at least one polyester resin
[0022] In another embodiment, a flooring product is provided that
qualifies for at least one point in the LEED System and has at
least one layer including a polymeric binder comprising a high
molecular weight polyester resin.
[0023] In another embodiment, a floor tile having a VCT type
structure where a thermoplastic polyester resin is substituted for
the PVC. In other embodiments, the floor tile comprises renewable
components, and/or recycle components. In one such embodiment, the
polyester resin comprises the co-reaction product of a renewable
polyester resin and a recycle polyester resin. The floor tile may
also qualify for at least one point in the LEED System.
[0024] In another embodiment, a composition is provided having
filler and a polymeric binder comprising at least one
thermoplastic, high molecular weight polyester resin, wherein the
composition may be melt mixed in a low intensity mixer and
processed into a flooring layer.
DETAILED DESCRIPTION OF THE INVENTION
[0025] This invention provides a flooring product having at least
one layer including a polymeric binder comprising thermoplastic
polyester resin, wherein the polyester resin comprises at least one
renewable component. The flooring product can comprise sheet or
tile product structures. At least one layer in these structures may
be solid or foamed, and filled or unfilled. In some embodiments, at
least one layer comprises a transparent wear layer or wear layer
component. Another example is similar to a vinyl composition tile
(VCT), as described by ASTM Specification 1066-04. As used herein a
polyester composition tile (PCT) is similar to a VCT except a
polyester resin is substituted for the PVC. While the present
invention is intended for use in such type tile, the invention is
also directed to various other types of flooring, including tile
type products such as Type III solid vinyl tile, surface applied
tile, and to various sheet flooring products, wherein a polyester
resin is substituted for the PVC. In one embodiment, at least one
layer may comprise consolidated chips/particles having a binder
comprising thermoplastic polyester resin. In another embodiment, at
least one layer may be a homogeneous, melt processed layer having a
binder comprising thermoplastic polyester resin. In yet another
embodiment, the flooring product comprises renewable and recycle
components that qualify the product for at least one point under
the LEED System.
[0026] Unless at least one layer is transparent, it typically
comprises a filler in addition to the polymeric binder. Limestone,
talc, or other minerals are utilized as filler in flooring.
Interest in using recycle materials as fillers has increased due to
"green" issues. Such recycle filler materials include those
obtained from wood or plants. These include pecan shells, wood
flour, saw dust, walnut shells, rice hulls, corn cob grit, and
others. Additionally, ground shells from animals such as clams and
coral are renewable inorganic fillers. Such renewable fillers
contain biobased carbon in the form of carbonates. These can be
considered post-industrial or renewable materials.
[0027] Mineral fillers generated from post-industrial processes
include limestone, quartz, ceramic powders, glass, fly ash, and
concrete powder.
[0028] Recycle thermoset resin based fillers can also be employed.
For example, powders produced by grinding thermoset polyester
materials, such as products made from bulk molding compounds (BMC)
or sheet molding compounds (SMC) can be post-industrial, as well as
post-consumer materials. Another thermoset material of interest is
recycled fillers made from Urea Formaldehyde thermoset resins.
Depending upon the source, these materials can also be
post-industrial or post-consumer. Another example includes ground,
cured (cross-linked) rubber materials such as used in tires. These
rubbers materials can be based on natural or synthetic rubbers,
polyurethanes, or other well known thermoset rubber
compositions.
[0029] Additionally, recycled thermoplastic resin based materials
may be employed as fillers if they are incompatible with the
polyester binder. For example, polyethylene (PE), polypropylene,
polyamide, polyester, polystyrene, polycarbonate, acrylonitrile
butadiene styrene, and thermoplastic rubbers maybe incompatible
with the high molecular weight polyester binder. Such materials, if
added as particulate will essentially function as fillers in these
compositions. If the recycled thermoplastic resin is compatible
with the binder, it may function as a binder and not as a filler in
the composition. DuPont "Sarrona" Bio-PDO based carpet fiber may be
recycled and would be a filler or binder depending upon
compatibility with the binder. Compatibility may be dependent upon
the processing conditions employed. Depending upon the source,
these materials can be post-industrial or post-consumer.
[0030] In one embodiment, the thermoplastic, polyester resin is
high molecular weight and has a number average molecular weight
(Mn) of at least 5,000 and in some embodiments the polyester resins
have a molecular weight (Mn) of at least 10,000. The polyesters may
be biodegradable, and/or may contain renewable components. In one
embodiment, the polyester comprises at least 50% by weight
renewable components. In another embodiment, the polyester
comprises greater than 80% by weight renewable components. In yet
another embodiment, the polyester comprises essentially 100%
renewable and recycle components.
[0031] In one embodiment, the polyester resin may comprise
aliphatic diacid and aliphatic diol components. Although a wide
range of aliphatic diacids and aliphatic diols may be used, these
components may come from renewable sources. Renewable aliphatic
diacid and aliphatic diol components may include but are not
limited to Bio-PDO (1,3-propanediol), 1,4-butanediol, sebacic acid,
succinic acid, adipic acid, azelaic acid, glycerin, and citric
acid. These materials may also be modified by reaction with
epoxidized soybean, epoxidized linseed oil, or other natural
oils.
[0032] The polyesters may be pre-reacted with epoxidized natural
oils, or the reaction can occur during the melt processing into
flooring layers. Such reaction during melt processing is a type of
dynamic vulcanization. Dynamic vulcanization is the process of
intimate melt mixing of two or more reactive components, such as an
acid-terminated polyester and epoxidized natural oil, and the
reaction occurs between at least two of these components during the
melt mixing.
[0033] Other diacid and diol components from renewable resources
will become available as the need for renewable materials continues
to grow. The diol components may also include diols which are
branched or hindered to limit crystallinity in the final polyester
binder. These can include neopentyl glycol, glycerin, and
others.
[0034] Renewable components based on plants, animals, or biomass
processes have a different radioactive C.sup.14 signature than
those produced from petroleum. These renewable, biobased materials
have carbon that comes from contemporary (non-fossil) biological
sources. A more detailed description of biobased materials is
described in a paper by Ramani Narayan, "Biobased &
Biodegradable Polymer Materials: Rationale, Drivers, and Technology
Exemplars", presented at American Chemical Society Symposium, San
Diego 2005; American Chemical Society Publication #939, June 2006.
The Biobased Content is defined as the amount of biobased carbon in
the material or product as fraction weight (mass) or percent weight
(mass) of the total organic carbon in the material or product. ASTM
D6866 (2005) describes a test method for determining Biobased
Content. Theoretical Biobased Content was calculated for the
resultant polyester resins in Table 2 and Table 3.
[0035] In one embodiment, the Biobased Content is at least 20% by
weight. In another embodiment, the Biobased content is at least 50%
by weight. In still another embodiment, the Biobased content is at
least 75% by weight. The higher the Biobased Content the "greener"
the product. The Biobased Content may be at least 25% by weight or
at least 10% by weight or at least 5% by weight, particularly when
the polyester resin is a blend of two or more resins.
[0036] In another embodiment, the thermoplastic polyester resin can
comprise aromatic diacid components and aliphatic diol components.
The aromatic acid components may include but are not limited to
phthalic acid (anhydride), isophthalic, or terephthalic acids. In
some cases an amount of trimellitic anhydride can also be used.
[0037] In another embodiment, the thermoplastic polyester resin may
comprise aliphatic diacid and aromatic diacid components reacted
with various aliphatic diols.
[0038] The thermoplastic polyester resin may also be branched. For
example, utilizing aliphatic alcohols that have more than two
functional groups, such as glycerin, or aromatic acids having more
than two functional groups such as trimellitic anhydride may be
used to produce branched polyesters.
[0039] Although, the above diacid components are described, it is
understood that their simple diesters such as from methanol or
ethanol can be used to prepare the thermoplastic polyester resin
via known transesterification techniques.
[0040] Depending upon the diacid and diol selected, the polyester
resin can be amorphous or crystalline/semi-crystalline materials.
In one embodiment, the polyester resin is amorphous. Table 2 shows
some examples of amorphous polyester resins of the invention and
their % by weight renewable components.
TABLE-US-00002 TABLE 2 Compositions of Amorphous Polyesters With
Renewable Content EX-1 EX-2 EX-3 EX-4 EX-5 EX-6 Ingredient Amt (g)
Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) 1,3-Propanediol 367.60
380.88 381.80 372.21 370.19 357.64 Isophthalic acid 545.99 232.94
233.50 292.68 291.08 218.72 Phthalic anhydride 85.90 385.69 208.18
260.94 259.52 195.01 Adipic acid 0 0 176.03 0 0 0 Azelaic acid 0 0
0 73.66 0 0 Sebacic acid 0 0 0 0 78.71 228.13 Dibutytin bis-lauryl
0.50 0.50 0.50 0.50 0.50 0.50 mercaptide Biobased Content wt % 27
27 47 34 36 53 Wt % Renewable Content of 37 38 56 45 45 59 starting
material Tg Differential Scanning 25.degree. C. 3.degree. C.
-22.degree. C. -9.degree. C. -10.degree. C. 29.degree. C.
Calorimetry (DSC)
[0041] In another embodiment, the polyester resin is crystalline
and comprises a Tg below about 25.degree. C. and a crystalline
melting temperature Tm greater than about 25.degree. C. In yet
another embodiment, the polyester resin has a Tg at or below about
25.degree. C. and a Tm between about 25.degree. C. and about
200.degree. C. Table 3 shows some examples of polyester resins
having a Tg at or below about 25.degree. C. and Tm above about
25.degree. C. Tg and Tm were determined by standard Differential
Scanning Calorimetry (DSC) techniques. The polyester compositions
include modifying essentially 100% renewable aliphatic polyester
resin by the addition of an amount of aromatic diacid, such as
terephthalic acid, to help control crystalline regions and Tm.
Example 3 describes tile flooring comprising blends of polyester
resins, including a commercially available polyester resin, Ecoflex
FBX7011, sold by BASF Plastics. Ecoflex FBX7011 is a high molecular
weight, biodegradable, aliphatic-aromatic copolyester based on
butanediol, adipic acid, and terephthalic acid exhibiting a Tg of
about -25.degree. C. and a Tm of about 115.degree. C.
[0042] The blend of polyester resins allow processing in low
intensity mixers typically used for VCT Tile manufacturing. Also, a
desired Tg can be obtained by blending two or more polyester
resins.
TABLE-US-00003 TABLE 3 Compositions of Crystalline Polyesters With
Renewable Content EX-7 EX-8 EX-9 EX-10 EX-11 EX-12 EX-13 Ingredient
Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Glycerin 25
24 Phthalic anhydride 62 67 387 1,3-Propanediol 510 238 138 258 241
228 334 Trimellitic anhydride 122 Sebacic acid 1130 281 538
Isophthalic acid 765 Terephthalic acid 232 231 394 425 110
1,6-Hexanediol 156 T-20 Catalyst 3.8 1.8 1.5 1.5 1.5 1.8 0.5 Tg
.degree. C. -21 -35 7 25 22 -41 2 Tm .degree. C. 122 125 135 197 77
40 141 Wt % Renewable 88 69 18 34 32 85 33 Content of starting
material Biobased Content wt % 85 67 13 27 26 87 27
[0043] The polyester resin may be prepared by several known
methods. One method involves esterification of a diacid and a diol
components at elevated temperature. Typically, an excess of diol is
employed (see Procedure 1A). After the acid functional groups have
essentially reacted, a high vacuum is applied and excess diol is
stripped off during transesterification, thereby increasing
molecular weight. In some embodiments, 1,3-PDO is the diol of
choice to build high molecular weight in this step of the
process.
[0044] We have also found that polyester resin can be made by
esterification of a diacid and diol at elevated temperature using
an excess of diacid (See Procedure 1B). After all the hydroxyl
groups are reacted, a high vacuum is applied to build molecular
weight. The mechanism by which high molecular weight is achieved is
not clear. Table 4 shows some examples of polyester resins
comprising renewable components and the number average molecular
weights obtained from the processes of Procedure 1.
[0045] Another method for obtaining high molecular weight polyester
resin involves the co-reaction of a renewable polyester resin with
recycle polyester resin such as PET (polyethylene terephthalate),
PBT (polybutylene terephthalate), PPT (polypropylene terephthalate)
or other polyester resins. In these co-reactions, an aliphatic
polyester resin comprising renewable ingredients was first prepared
as described in Procedure 1. The recycle polyester resin was then
mixed with the aliphatic polyester resin and transesterification
between the two polyesters was accomplished at high temperature and
preferably under high vacuum. In one embodiment, the polyester
resin co-reaction product had a Tm at or below about 150.degree. C.
that allowed processing with in low intensity mixers. It is obvious
that these transesterification reactions may be carried out on
virgin PET, PPT or PBT resin if desired.
TABLE-US-00004 TABLE 4 High Molecular Weight Polyester Compositions
Having Renewable Content Ingredient EX-14 EX-7 EX-12 EX-15 EX-16
EX-17 EX-18 Glycerin 25 24 1.53 1.53 Phthalic anhydride 159 133 4
91 1,3-Propanediol 212 510 228 199 38 44 310 Trimellitic anhydride
Sebacic acid 84 1130 538 155 40 51 87 Isophthalic acid 416 347 508
Terephthalic acid 232 110 50 42 Neopentyl glycol 124 2 Cyclohexane
161 dimethanol 1,6-Hexanediol 9 T-20 Catalyst 5 3.8 1.8 5 0.4 0.4 5
Molecular Weight, Mn 16,900 15,900 10,400 8,000 8,490 7,530
7,000
[0046] Molecular weight of the polyester resins were determined by
Gel Permeation Chromatography (GPC) using the following procedure.
The polyester resin was dissolved into tetrahydrofuran (THF),
quantitatively diluting to .about.30 mg/ml and filtering with a
0.45 micron filter. Two drops of toluene were added to each sample
solution as an internal flow rate marker.
[0047] Samples soluble in THF were run by the following conditions.
GPC analysis was run on the TriSec instrument using a four column
bank of columns with pore sizes: 10.sup.6, 2 mixed D PLGel and 500
Angstroms. Three injections were made for the sample and
calibration standards for statistical purposes. Universal
Calibration (UC) GPC was used to determine MW. UC is a GPC
technique that combines Refractive Index (RI) detection
(conventional GPC) with Intrinsic Viscometry (IV) detection.
Advantages of UC over conventional GPC are:
[0048] 1. MW is absolute (not relative only to standards).
[0049] 2. Yields information about branching of molecules.
The mobile phase for the THF soluble samples was THF at 1.0 ml/min.
The data was processed using the Viscotek OmniSec UC software. The
instrument is calibrated using a series of polystyrene narrow
standards. To verify calibration, secondary standards were run.
They include a 250,000 MW polystyrene broad standard, and a 90,000
MW PVC resin. The calculated molecular weight averages are defined
as follows:
M n = ( Area i ) ( Area i ) / ( M i ) ##EQU00001## M w = [ ( Area i
) .times. ( M i ) ] ( Area i ) ##EQU00001.2## M z = [ ( Area i ) 2
.times. ( M i ) ] [ ( Area i ) .times. ( M i ) ] ##EQU00001.3##
Area i = The area of the i th slice of polymer distribution
##EQU00001.4## M i = The molecular weight of the i th slice of
polymer distribution ##EQU00001.5## Polydispersity ( Pd ) = a
number value used to described the molecular weight distribution
and is obtained by Mw Mn ##EQU00001.6##
[0050] Highly crystalline or some high molecular weight samples
insoluble in THF were dissolved in a 50/50 (wt.) mixture of
tetrachloroethylene (TTCE)/phenol. The column set is 10.sup.4 and
500 Angstrom 50 cm Jordi columns. The mobile phase was 50/50 (wt.)
mixture of TTCE/phenol at 0.3 ml/min. flow rate. The slower flow
rate is due to the greater back pressure of the solvent system on
the columns. The data was processed using the Viscotek UC OmniSec
software.
[0051] Since MW data must be compared from one column set to the
other, standards and selected samples were run on both column sets
in THF for comparison. A calibration curve was made for each column
set. There is good agreement of the standards between the two
sets.
[0052] Flooring products having at least one layer comprising
thermoplastic polyester resin binder may be manufactured by
processing methods known in the art, including but not limited to
calendering, extruding, casting, consolidating, and laminating. In
one embodiment, a formulation comprising the polyester resin binder
was melt mixed using low intensity "dough type" mixers
traditionally utilized in the manufacturing of VCT tile (See
Example 3). In another embodiment, the temperature of the melt
mixing in the low intensity "dough type" mixers was in the range
typically used in the manufacture of PVC based VCT Tile. In yet
another embodiment, the formulation comprising the polyester resin
binder was melt mixed using traditional extruder type mixers,
including Farrell type mixers. These may be processed at higher
temperatures than typically utilized in "dough type" mixers for the
preparation of PVC based VCT Tile. Varied techniques may be
utilized to form these melt mixed formulations into layers of
flooring products. In one embodiment, the melt mixed formulation
comprising the polyester resin binder was calendered into a layer.
In another embodiment, the melt mixed formulation may be processed
into chips or particles. Various techniques for consolidating these
chips or particles into flooring layers are well known in the art.
In another embodiment, the melt mixed formulation may be extruded
into a flooring layer.
Procedure 1 Procedure for Preparation of High Molecular Weight
Polyesters from Diacids and Diols
[0053] 1A: This describes the general procedure utilized to make
thermoplastic, high molecular weight polyesters from diacids and
diols. A desired polyester formulation was developed based upon
mole equivalent weight of the diacid and diol functional groups. An
excess of diol of the most volatile diol component of the
formulation was employed in the formulation. In one embodiment,
1,3-propanediol was the excess diol of choice. The diacid and diol
ingredients were added into a stainless steel vessel of a RC1
automated reactor (Mettler-Toledo Inc, 1900 Polaris Parkway,
Columbus, Ohio), stirred and heated under a continuous flow of
pure, dry nitrogen. Typically, the ingredients were heated to
200.degree. C. for 2 hours and temperature increased to 230.degree.
C. for an additional 4 to 6 hours until essentially all acid end
groups were reacted and theoretical amount of water removed.
Subsequently, the nitrogen was stopped and a high vacuum was
applied. The mixture was heat and stirred under high vacuum for an
additional 4 or more hours at 230.degree. C. to 300.degree. C. In
some cases the temperature of the transesterification step was
increased to 250.degree. C. or higher. Depending upon the
experiment, a vacuum in the range of 5 mm of mercury was utilized.
Subsequently, the polymer was allowed to cool to 150.degree. C. to
200.degree. C. and physically removed from the reactor under a flow
of nitrogen and allowed to cool to room temperature.
[0054] It is understood that removal of the volatile diol component
during transesterification leads to high molecular weight. High
molecular weight may be obtained faster if higher vacuum is
utilized (below 1 mm of mercury). It is also known that as the melt
viscosity increases due to increased molecular weight, the removal
of diol becomes more difficult. The increase in molecular weight
can become diffusion dependent because of the high viscosity of the
molten polyester. This means that the released volatile diol from
the transesterification reaction reacts back into the polymer
before it can diffuse out of the melt, and be removed. Renewing the
surface of the melt can facilitate the loss of diol and increase
molecular weight. The polyesters obtained by this procedure
generally have terminal hydroxyl end groups.
[0055] Although, diacid components are described above, it is
understood that their simple diesters such as from methanol or
ethanol can be used to prepare the thermoplastic polyester resin
via known transesterification techniques. The polyesters from this
procedure generally have ester terminated end groups.
[0056] 1B: The same general procedure as in 1A is employed. A
desired polyester formulation was developed based upon mole
equivalent weight of the diacid and diol functional groups. An
excess of about 0.01 to 0.5 mole excess of diacid was typically
employed in the formulation. The ingredients were mixed and heated
as in 1A above, except that the temperature was generally held
below 200.degree. C. to keep acid/anhydride from being removed
until all hydroxyl groups were reacted. Subsequently, a high vacuum
was applied as in 1A and the mixture heated to between 230.degree.
C. and 280.degree. C. and stirred as in Procedure 1A. The resultant
high molecular weight polyester was removed from the reactor and
cooled as in 1A.
[0057] The mechanism of achieving high molecular weight is not
clear. In some formulations containing phthalic anhydride, the
phthalic anhydride was identified as being removed from the
mixture. Using a nitrogen sparge below the surface of the molten
polyester during the vacuum step also helped produce high molecular
weight polyesters. The polyesters obtained by this procedure
generally have terminal acid end groups.
[0058] Tables 5A to 5E provide examples of polyester resins having
renewable components made according to the procedure of Procedure
1.
TABLE-US-00005 TABLE 5A Raw Material EX-19 EX-20 EX-21 EX-22 EX-23
EX-24 Ingredient Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g)
1,3- 380.88 383.65 378.15 382.15 384.72 375.80 Propanediol
Isophthalic acid 232.94 167.59 297.34 210.34 164.70 206.85 Phthalic
385.69 448.26 324.01 348.28 272.71 342.49 anhydride Trimellitic
0.00 0.00 0.00 0.00 0.00 0.00 anhydride Adipic acid 0 0 0 58.73
177.38 0.00 Azelaic acid 0 0 0 0 0 74.37 T-20 0.50 0.50 0.50 0.50
0.50 0.50 Tg (.degree. C.) -1.degree. C. -5.degree. C. 22.degree.
C. -11.degree. C. -23.degree. C. 4.degree. C.
TABLE-US-00006 TABLE 5B Raw Material EX-25 EX-26 EX-27 EX-28
Ingredient Amt (g) Amt (g) Amt (g) Amt (g) 1,3-Propanediol 366.04
373.73 360.20 261.06 Neopentyl glycol 0 0 0 112.82 Isophthalic acid
156.70 205.71 154.20 294.12 Phthalic 259.46 340.60 255.33 112.38
anhydride Azelaic acid 217 0 0 0 Sebacic acid 0 79.47 229.77 219.12
T-20 0.50 0.50 0.50 0.50 Tg (.degree. C.) -12.degree. C.
-12.degree. C. -29.degree. C. -21.degree. C.
TABLE-US-00007 TABLE 5C Raw Material EX-29 EX-30 EX-31 EX-32 EX-33
Ingredient Amt (g) Amt(g) Amt (g) Amt(g) Amt (g) 1,3-Propanediol
481.32 247.27 449.21 410.46 303.48 Isophthalic acid 0 0 0 0 696.01
Phthalic anhydride 198.83 481.53 211.15 639.45 0 Trimellitic
anhydride 319.35 270.70 339.15 449.34 0 T-20 0.50 0.50 0.50 0.50
0.50 Tg (.degree. C.) 25.degree. C. -22.degree. C. -11.degree. C.
21.degree. C. 35.degree. C.* *May be partially crystalline
TABLE-US-00008 TABLE 5D Raw Material EX-34 EX-35 EX-36 EX-37 EX-38
EX-39 Ingredient Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g)
1,3- 311.32 147.21 210.67 86.45 344.66 161.58 Propanediol Neopentyl
201.45 123.55 276.04 0 223.72 glycol Isophthalic acid 475.99 450.16
460.15 440.6 385.09 361.07 Phthalic 212.19 200.68 205.12 196.41
269.76 252.93 anhydride T-20 0.50 0.50 0.50 0.50 0.50 0.66 Tg
(.degree. C.) 32.degree. C. 35.degree. C. 41.degree. C. 42.degree.
C. 46.degree. C. 56.degree. C.
TABLE-US-00009 TABLE 5E EX-40 EX-41 Ingredient Amt (g) Amt (g)
1,3-Propanediol 211.61 200.93 Neopentyl glycol 124.10 0
1,4-Cyclohexanedimethanol 0 163.15 Isophthalic acid 415.99 394.98
Phthalic anhydride 158.95 150.92 Sebacic acid 84.37 80.10 T-20
10.00 9.90 Tg(.degree. C.) 26.degree. C. 34.degree. C.
EXAMPLE 2
Preparation of High Molecular Weight Polyesters by Co-Reaction with
Recycle Crystalline Polyesters
[0059] The following formulation was processed as per Procedure 1
to prepare the aliphatic polyester Ex-42 comprising 100% renewable
components and a Biobased Content of 100%.
TABLE-US-00010 EX-42 Amt (g) 1,4-Butanediol 400.5 Sebacic acid 600
T-20 Catalyst 0.4
[0060] The aliphatic polyester Ex-42 was mixed with clear PET
bottle recycle resin obtained from Nicos Polymers & Grinding of
Nazareth, Pa., and catalyst added as listed below.
TABLE-US-00011 EX-43 Amt (g) PET recycle bottle 100 EX-42 100 T-20
Catalyst 0.13
[0061] The mixture was heated and stirred under nitrogen at
265.degree. C. for a period of about 3 hours, and a high vacuum
applied as in Procedure 1 for an additional 3 hours at 265.degree.
C. Subsequently, the resultant polyester having 50% by weight
renewable content and 50% by weight recycle content was shown to
have a molecular weight Mn of 17,200 with a Tg of -9.degree. C. and
a Tm of 114.degree. C. Molecular weight Mn of the starting PET
recycle bottle resin was determined by GPC techniques described
above and found to be 14,000. A sample of PET film obtained from
Nicos Polymers & Grinding was also analyzed by GPC and
molecular weight Mn determined to be 17,300.
EXAMPLE 3
Preparation of Vinyl Composition Type Tile Having a Binder
Comprising Thermoplastic, High Molecular Weight Polyester Resin
[0062] This is an example of PCT tile flooring product prepared
with a binder comprising a thermoplastic, high molecular weight
polyester resin. Traditionally, VCT tile manufacturing processes
have utilized low intensity "dough" type heated mixers to
compound/melt mix the tile formulation which is subsequently
calendered into a layer. Higher intensity mixers such as extruders
or Farrell type mixers may also be employed, and these high
intensity mixers may also be heated to higher temperatures to
compound the tile formulation.
[0063] The following PCT tile formulations Table 6B-D, comprising
amorphous, polyester resins GPa02176--of Table 5C and 5D, were
mixed using a low intensity Baker Perkins heated mixer. The
ingredients were added to the mixer which was heated to 325.degree.
F. The formulations were mixed and heated for approximately 7-11
minutes on average in the Baker Perkins mixer to a drop temperature
of approximately 280.degree. F. Depending upon the formulation,
mixing time varied between 7-28 minutes and drop temperature varied
between approximately 270.degree. F. and 290.degree. F. (See Table
6B-D).
[0064] The hot, mixed formulations were then dropped into the nip
of a two roll calender. The rolls of the calendar were set at
different temperatures--one roll hotter than the other. Typically,
the hot roll was set at about 290.degree. F. and the cold roll set
at about 250.degree. F. The nip opening between the calendar mill
rolls were set to provide a final sheet thickness of about 125
mils. The processability of the formulations were evaluated using
the key described in Table 6A.
TABLE-US-00012 TABLE 6A Key for Baker Perkins and Mill Evaluations
Mix Appearance 1. very soft, wet, flowable mix 2. tough mix, dough
like 3. soft mix, small beads 4. dry mix with some clumps 5. very
dry powdery mix, no clumps 6. unmelted pellets/polyester Sheet
Appearance 1. soft flexible sheet 2. smooth sheet 3. cracks in
sheet and/or voids 4. ragged edges, uneven sheet thickness, wavy 5.
lots of folds from being taken off with the blade Sheet Hot
Strength 1. falls apart when removed from roll, powder 2. falls
apart when removed from roll, small pieces or partial sheet 3. full
sheet which falls apart under sheet weight 4. no stretch under
sheet weight 5. slight stretch under sheet weight 6. sheet shrinks
when pulled off the mill Roll Tack 1. sticks to a roll, all can't
be removed with the blade 2. sticks to a roll, removed with the
blade but not cleanly (chatter marks) 3. sticks to a roll, removed
cleanly with the blade 4. material split between two rolls 5.
material does not stick to either roll Roll Residue 1. a lot 2. a
little 3. none Self Feeding 1. yes 2. marginal 3. no
[0065] As can be seen from a formulation and processing datasheet
Tables 6B-6D, the formulation based upon high molecular weight
polyesters processed very similar to a standard PVC formulations.
Formulations of Tables 6B-6D are based on blends of Armstrong
amorphous polyesters of Tables 5C-5D with Ecoflex FBX7011 polyester
sold by BASF. Ecoflex FBX7011 is a high molecular weight,
biodegradable, aliphatic-aromatic copolyester based on butanediol,
adipic acid, and terephthalic acid exhibiting a Tg of about
-25.degree. C. and a Tm of about 115.degree. C. The tiles exhibited
acceptable physical properties, with a significant improvement in
breaking load strength.
[0066] It is important to note that formulations based only on
Ecoflex FBX7011 in pellet form could not be adequately mixed in the
low intensity mixer. There was not enough heat transfer and shear
within the mix to breakdown the pellet form of the Ecoflex 7011.
The addition of the amorphous polyester resin changed the physical
nature of the mix allowing the Ecoflex 7011 to be incorporated.
[0067] Tile and sheet formulations may also contain other
ingredients such as processing aids, tackifiers, hydrophobic
agents, stabilizers, colorants and other known additives. Of
particular interest, the tile formulations may also contain up to
30% by weight of one or more additional polymers and sheet
formulations may also contain up to 50% by weight of one or more
additional polymers. These additional polymers may assist in
processing in low intensity mixers, and also may assist in
achieving improved physical properties. These polymers may consist
of acid functionalized polymers including EAA, EMA, and partially
neutralized versions thereof (ionomers), Surlyn, or other
(methacrylic) acrylic acid, or maleic acid (anhydride) copolymers
to obtain desired process and physical properties.
[0068] The use of recycle fillers in these formulations also allows
for the flooring product having at least one layer comprising the
high molecular weight polyester binder to achieve at least one
point within the LEED System.
TABLE-US-00013 TABLE 6B EX-44 EX-45 EX-46 EX-47 EX-48 Ingredient
Trade Name Supplier Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) ESO
Flexol EPO Dow 7.6 14.32 6.13 11.55 6.13 Filler Global stone 229
PenRoc 926.2 926.2 924.74 924.74 924.74 (Limestone) Pigment Kronos
2220 Kronos 6.6 6.6 6.6 6.6 6.6 (TiO2) Aromatic Ecoflex FBX7011
BASF 83.6 83.6 101.2 101.2 101.2 Polyester Aromatic EX-30 Armstrong
76 69.28 61.33 55.91 0 Polyester Aromatic EX-32 Armstrong 0 0 0 0
61.33 Polyester Total 1100 1100 1100 1100 1100 Wt % Binder 0.15
0.15 0.15 0.15 0.15 Wt % Filled 0.85 0.85 0.85 0.85 0.85 Mixer Temp
.degree. F. 324 324 324 324 324 Batch Time (min) 12 11 9 9 7 Mix
Drop Temp 275 272 278 279 280 .degree. F. East Roll Temp 290 290
290 290 290 .degree. F. West Roll Temp 250 250 250 250 250 .degree.
F. Gap Setting 2.1 2.1 2.1 2.1 2.1 Sheet Thickness 125 125 125 125
125 Mix Appearance 2 3 2 3 2 3 2 3 2 3 Sheet 2 2 2 4 2 3 Appearance
Sheet Hot 4 4 5 5 5 Strength Roll Tack 2 3 3 2 3 3 3 Roll Residue 2
2 2 2 2 Self Feeding 1 1 1 1 1
TABLE-US-00014 TABLE 6C EX-49 EX-50 EX-51 EX-52 Ingredient Trade
Name Supplier Amt (g) Amt (g) Amt (g) Amt (g) ESO Flexol EPO Dow
11.55 0 0 Filler Global stone 229 PenRoc 924.74 923.77 926.2 924.74
(Limestone) Pigment Kronos 2220 Kronos 6.6 6.6 6.6 6.6 (TiO2)
Aromatic Ecoflex FBX7011 BASF 101.2 127.22 83.6 101.2 Polyester
Aromatic EX-32 Armstrong 55.91 0 0 0 Polyester Aromatic EX-33
Armstrong 0 42.41 83.6 67.47 Polyester Total 1100 1100 1100 1100 Wt
% Binder 0.15 0.15 0.15 0.15 Wt % Filled 0.85 0.85 0.85 0.85 Mixer
Temp .degree. F. 324 324 321 324 Batch Time (min) 15 15 15 10 Mix
Drop Temp .degree. F. 283 279 279 278 East Roll Set Pressure 78 78
78 78 psi West Roll Set Pressure 26 26 26 26 psi East Roll Temp
.degree. F. 290 290 290 290 West Roll Temp .degree. F. 250 250 250
250 Gap Setting 2.1 2.1 2.1 2.0 Sheet Thickness 125 125 125 125 Mix
Appearance 2 2 2 2 Sheet Appearance 2 2 2 2 Sheet Hot Strength 5 5
5 4 Roll Tack 3 3 3 3 Roll Residue 2 2 2 2 Self Feeding 2 2 2 2
TABLE-US-00015 TABLE 6D EX-54 EX-53 Amt EX-55 EX-56 EX-57
Ingredient Trade Name Supplier Amt (g) (g) Amt (g) Amt (g) Amt (g)
Filler (Limestone) Global stone 229 PenRoc 961.08 926.20 924.74
926.20 924.74 Pigment (TiO2) Kronos 2220 Kronos 6.60 6.60 6.60 6.60
6.60 Aromatic Ecoflex FBX7011 BASF 79.39 83.60 101.20 83.60 101.20
Polyester Aromatic EX-34 Armstrong 52.93 0.00 0.00 0.00 0.00
Polyester Aromatic EX-35 Armstrong 0.00 83.60 67.47 0.00 0.00
Polyester Aromatic EX-36 Armstrong 0.00 0.00 0.00 83.60 0.00
Polyester Aromatic Ex-37 Armstrong 0.00 0.00 0.00 0.00 67.47
Polyester Total 1100 1100 1100 1100 1100 Wt % Binder 0.12 0.15 0.15
0.15 0.15 Wt % Filled 0.88 0.85 0.85 0.85 0.85 Mixer Temp .degree.
F. 324 324.00 324.00 324.00 324 Batch Time (min) 28 12 11 13 8 Mix
Drop Temp .degree. F. 288 274 272 278 288 East Roll Set 78 78 78 78
78 Pressure psi West Roll Set 26 26 26 26 26 Pressure psi East Roll
Temp .degree. F. 290 290 290 290 290 West Roll Temp .degree. F. 250
250 250 250 250 Gap Setting 2.1 2.1 2.1 2.1 2.0 Sheet Appearance 2
2 2 2 2 Mix Appearance 3 2 3 2 3 2 3 2 3 Sheet Thickness 124 124
122 124 124 Sheet Hot Strength 5 4 4 4 5 Roll Tack 3 3 3 3 3 Roll
Residue 2 2 2 2 2 Self Feeding 1 1 2 2 1
EXAMPLE 4
Preparation of Vinyl Composition Type Tile Having a Binder
Comprising Thermoplastic, High Molecular Weight Polyester Resin
[0069] High molecular weight polyester of the composition in table
5E was prepared as per Procedure 1. The high molecular weight
polyester was formulated into a PCT tile formulation and processed
as in Example 3. The datasheet Table 7 describes the conditions
used to make the tile. The tile exhibited acceptable physical
properties, with a significant improvement in breaking load
strength.
TABLE-US-00016 TABLE 7 EX-58 EX-59 Ingredient Trade Name Supplier
Amt (g) Amt (g) Filler (Limestone) Global stone 229 PenRoc 880.00
880.00 Pigment (TiO2) Kronos 2220 Kronos 6.00 6.00 Polyester EX-40
Armstrong 114.00 0 Polyester EX-41 Armstrong 0 114.00 Total 1000.00
1000.00 Wt % Binder 11.40% 11.40% Wt % Filled 88.60% 88.60% Mixer
Temp .degree. F. 326 327 Batch Time (min) 30 20 Mix Drop Temp
.degree. F. 284 278 East Roll Set 77 72 Pressure psi West Roll Set
30 30 Pressure psi East Roll Temp .degree. F. 292 290 West Roll
Temp .degree. F. 252 248 Gap Setting 2.1 2.0 Sheet Appearance 2 2
Mix Appearance 2.3 2.3 Sheet Thickness 124 121 Sheet Hot Strength 4
4 Roll Tack 3 3 Roll Residue 3 3 Self Feeding 1 1
EXAMPLE 5
Examples of Polyesters Made by Transesterification Between High
Molecular Weight Aliphatic, Renewable Polyesters and Recycle
Polyester Resin
[0070] High molecular weight polyesters comprising the compositions
of Table 8A were made according to Procedure 1.
TABLE-US-00017 TABLE 8A T-20 Azelaic Acid 1,4-Butanediol Sebacic
Acid Amt Total Amt (g) Amt (g) Amt (g) (g) Amt (g) EX-60 511 489
0.4 1000 EX-61 582 417.6 0.4 1000 EX-62 400.5 600 0.4 1001 EX-63
471.2 528 0.4 1000 Ex-42 674 325.74 0.5 1000 Ex-64 354 529 0.4
883
[0071] The polyesters of Table 8A, were each mixed with recycle PET
bottle resin obtained from Nicos Polymers & Grinding of
Nazareth, Pa., and 0.1% T-20 catalyst added and transesterification
conducted as per Example 2. In some examples, transesterification
was also carried out on PBT resin Celanex 1600A obtained from
Ticona (formerly Hoechst Celanese Corp.), Summit, N.J. Table 8B
shows some of the resultant polyester co-reaction products and
their Tm. It is obvious that these transesterification reactions
may be carried out on virgin PET or PBT type resin.
TABLE-US-00018 TABLE 8B Mid- Polyester melt range point PE ID used
Recycled (deg C.) mp Transesterification in Transesterification
Bottle PBT PB Ecoflex PB trans (Tm) Rxn # Rxn PET Celanex Azelate
FBX7011 Sebacate product .degree. C. Nicos 255 259 256 Scrap PET
EX-65 EX-60 70 30 138 154 145 EX-66 EX-61 50 50 84.5 104.8 94.9
EX-67 EX-61 70 30 140 159 146 EX-68 EX-62 50 50 99 126 102.9 EX-69
EX-62 70 30 155 170 160 EX-70 EX-63 50 50 101 125 109 EX-71 EX-63
70 30 149 156 151 EX-72 EX-42 50 50 100 111 105 EX-73 EX-42 70 30
133 141 136 EX-74 EX-64 50 50 92 106 97 EX-75 EX-65 70 30 110 170
140 EX-76 EX-60 75 75 135 141 137 EX-77 EX-64 75 75 145 166 156
EX-78 EX-63 180 120 79 153 87 EX-79 EX-42 180 120 73 108 79 EX-80
Ecoflex 180 120 122 158 137 FXB7011
[0072] The melting points listed in Table 8B were determined using
an "Optimelt" automated unit. Higher Tm co-reacted polyesters may
be produced by using less aliphatic polyester than described in the
Table 8B above.
EXAMPLE 6
PCT Tile Compositions Comprising High Molecular Weight Polyester
Binders of Example 5
[0073] Formulations based on the polyester reaction products of
Table 8B were developed to allow processing in low shear Baker
Perkins heated mixers and VCT type calendaring processing. The
formulations in Table 8C and Table 8D include EAA (ethylene acrylic
acid copolymer) and an acrylic processing aid. The use of EAA not
only effect processing in the Baker Perkins and through the
calendar, but the polymer also imparts stiffness and some improved
properties.
TABLE-US-00019 TABLE 8C EX-81 EX-82 EX-83 EX-84 EX-85 Ingredient
Trade Name Supplier Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Filler
Global stone 229 PenRoc 479.9 479.9 479.9 479.9 479.9 (Limestone)
Pigment Kronos 2220 Kronos 3.4 3.4 3.4 3.4 3.4 (TiO2) Polyester
EX-66 Armstrong 65.0 Polyester EX-68 Armstrong 65.0 Polyester EX-70
Armstrong 65.0 Polyester EX-72 Armstrong 65.0 Polyester EX-74
Armstrong 65.0 EAA Primacor 1410 Dow 13 6.5 13 13 13 Acrylic
Plasti-strength 530 Arkema 10 10 10 10 Total 548.3 548.3 548.3
548.3 548.3 Wt % Binder Wt % Filled Mixer Temp .degree. F. 326 325
326 326 326 Batch Time (min) 11 5 5 5 Mix Drop Temp .degree. F. 284
292 284 278 278 East Roll Temp .degree. F. 295 293 287 278 278 West
Roll Temp .degree. F. 293 277 236 200 225 Gap Setting 0.71 6, 7 0.7
0.7 0.7 Sheet Appearance 2 2, 1 2 2 2 Mix Appearance 5 5 5 5 5
Sheet Thickness 75 80 55 65 75 80 75 80 75 80 Sheet Hot Strength 5
5 5 5 5 Roll Tack 3 2 3 3 3 Roll Residue 2 2 2 2 2 Self Feeding 2 2
1 1 1
TABLE-US-00020 TABLE 8D EX-86 EX-87 EX-88 Ingredient Trade Name
Supplier Amt(g) Amt(g) Amt(g) Filler (Limestone) Global stone 229
PenRoc 959.8 959.8 959.8 Pigment (TiO2) Kronos 2220 Kronos 6.8 6.8
6.8 Polyester EX-78 Armstrong 130.0 0.0 Polyester EX-79 Armstrong
130.0 Polyester EX-68 Armstrong 130.0 EAA Primacor 1410 Dow 26 26
52 Acrylic Plasti-strength 530 Arkema 20 20 40 Total 1142.6 1142.6
1188.6 Wt % Binder Wt % Filled Mixer Temp .degree. F. 325 327 327
Batch Time (min) 26 30 -- Mix Drop Temp .degree. F. 278 278 -- East
Roll Temp .degree. F. 225 232 297 West Roll Temp .degree. F. 225
235 292 Gap Setting 2 2 6.2, 4.2 Sheet Appearance 2 2 2 Mix
Appearance 3 4, 3 3, 2 Sheet Thickness 120 123 128 125 134 Sheet
Hot Strength 5 5 5 Roll Tack 3, 2 3, 2 3, 2 Roll Residue 2 2 2 Self
Feeding 1 1 1
EXAMPLE 7
PCT Tile Comprising High Molecular Weight Polyester Binder and
Processing Additives
[0074] A high molecular weight polyester comprising the composition
in Table 9A was prepared as per Procedure 1.
TABLE-US-00021 TABLE 9A Ex-89 Ingredient Supplier Function Amt (g)
Phthalic Anhydride acid 495 Trimellitic Anhydride acid 47.6
Neopenyl Glycol diol 347.9 1,6 hexanediol diol 109.6 T-20 Air
Products catalyst 0.4 Total 1000.5
[0075] PCT tile formulations based on the polyester of Table 9A
were developed to allow processing in low shear Baker Perkins
heated mixers and VCT type calendaring processing. The formulations
in Table 9B include EAA (ethylene acrylic acid copolymer) and an
acrylic processing aid. The use of EAA not only effect processing
in the Baker Perkins and through the calendar, but the polymer also
imparts stiffness and some improved properties.
TABLE-US-00022 TABLE 9B Ex-90 Ex-91 Ex-92 Ingredient Trade Name
Supplier Amt (g) Amt (g) Amt (g) Filler (Limestone) Global stone
229 PenRoc 768.0 768.0 768.0 Filler (Limestone) Emerys DB04 192.0
192.0 192.0 Pigment (TiO2) Kronos 2220 Kronos 6.8 6.8 6.8 Polyester
EX-63 Armstrong 100 80.0 65.0 Ecoflex FBX7011 30 50 65 EAA Primacor
1410 Dow 26 26 26 Acrylic Plasti-strength 530 Arkema 20 20 20 Total
1142.8 1142.8 1142.8 Mixer Temp .degree. F. 327 327 327 Batch Time
(min) 12 14 12 Mix Drop Temp .degree. F. 272 271 277 East Roll Temp
.degree. F. 243 241 241 West Roll Temp .degree. F. 237 235 235 Gap
Setting 2 2 2 Sheet Appearance 2 2 2 Mix Appearance 4 4 4 Sheet
Thickness 130 128 130 128 130 Sheet Hot Strength 4 4 4 Roll Tack 3,
2 3, 2 3, 2 Roll Residue 2 2 2 Self Feeding 1 1 1
[0076] The use of different sized limestone filler yields better
processibility and improved performance.
EXAMPLE 8
PCT Tile Comprising High Molecular Weight Polyester and Processing
Additives
[0077] A high molecular weight polyester comprising the composition
Table 10A was prepared according to Procedure 1.
TABLE-US-00023 TABLE 10A EX-93 Ingredient Amt (g) Sebacic acid
279.11 Terephthalic acid 343.83 Phthalic anhydride 25.55
1,3-Propanediol 262.55 Glycerin 10.59 1,6 Hexanediol 61.16
Neopentyl glycol 10.76 T-20 2.99 Total 996.54 Tg -16.degree. C. Tm
113.degree. C.
[0078] PCT tile formulations based on the high molecular weight
polyester of Table 10A were developed to allow processing in low
shear Baker Perkins heated mixers and VCT type calendaring
processing as per Example 3. The formulation datasheets in Table
10B include the use of a hydrocarbon tackifier, epoxidized soybean
oil and Surlyn ionomer additives. Surlyn ionomer may not only
effect processing in the Baker Perkins and through the calendar
rolls, but Surlyn may also impart some improved properties to the
finished tile. In cases where ESO or other epoxidized oils are also
used in combination with acid functionalized polymers, these may
react with each other (dynamic cross-linking) during processing of
the formulation at elevated temperature.
TABLE-US-00024 TABLE 10B EX-94 EX-95 EX-96 Ingredient Trade Name
Supplier Amt (g) Amt (g) Amt (g) Pigment 348 Kronos 2220 Kronos 5.5
5.5 5.5 Limestone 229 Marble Hill 40X0 JMHuber Corp 908.0 1008.0
958.0 Polyester EX-93 Armstrong 168.0 168.0 168.0 Copal rosin Copal
Ornya Peralta GmbH 15.0 ESO 10.0 15.0 15.0 Ethylene-methacrylic
Surlyn 8920 Du Pont 20.0 acid copolymer, partial metal salt Total
1106.5 1196.5 1166.5 Mixer Temp .degree. F. 324 324 324 Batch Time
(min) 13 13 13 Mix Drop Temp .degree. F. 282 284 284 East Roll Temp
.degree. F. 280 280 288 West Roll Temp .degree. F. 255 255 255 Gap
Setting 2.2 2.2 2 Sheet Appearance 1 2 1 2 2, 1 Mix Appearance 2/3
2/3 2/3 Sheet Thickness 0.125 0.124 0.125 Sheet Hot Strength 5 5 5
Roll Tack 3 3 3 Roll Residue 2 2 3 Self Feeding 2 2 1
* * * * *