U.S. patent application number 11/192946 was filed with the patent office on 2006-01-05 for polyamide and composition and article including the same.
Invention is credited to Sharf U. Ahmed, Andualem W. Emiru, Steven L. Scholl.
Application Number | 20060003176 11/192946 |
Document ID | / |
Family ID | 29733044 |
Filed Date | 2006-01-05 |
United States Patent
Application |
20060003176 |
Kind Code |
A1 |
Scholl; Steven L. ; et
al. |
January 5, 2006 |
Polyamide and composition and article including the same
Abstract
A polyamide that includes the reaction product of dimer acid
(e.g. a dimer acid including at least 98% by weight dimer),
caprolactam, hexamethylene diamine, sebacic acid, and optionally,
chain terminating agent.
Inventors: |
Scholl; Steven L.; (Cottage
Grove, MN) ; Ahmed; Sharf U.; (Woodbury, MN) ;
Emiru; Andualem W.; (Woodbury, MN) |
Correspondence
Address: |
H.B. FULLER COMPANY
1200 WILLOW LAKE BLVD.
P.O. BOX 64683
ST. PAUL
MN
55164-0683
US
|
Family ID: |
29733044 |
Appl. No.: |
11/192946 |
Filed: |
July 29, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10172389 |
Jun 14, 2002 |
|
|
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11192946 |
Jul 29, 2005 |
|
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Current U.S.
Class: |
428/474.4 ;
528/310 |
Current CPC
Class: |
C08G 69/36 20130101;
C08G 69/48 20130101; C08G 69/34 20130101; C08G 69/02 20130101; Y10T
428/31725 20150401 |
Class at
Publication: |
428/474.4 ;
528/310 |
International
Class: |
C08L 53/00 20060101
C08L053/00; B32B 27/08 20060101 B32B027/08 |
Claims
1. An article comprising a polyamide comprising the reaction
product of dimer acid; caprolactam; hexamethylene diamine; sebacic
acid; and optionally, chain terminating agent, said polyamide
exhibiting a viscosity no greater than 20,000 centipoise at
205.degree. C.
2. The article of claim 1 wherein said polyamide is in a form
selected from the group consisting of film, fibers, nonwoven web,
woven web, and combinations thereof.
3. The article of claim 2, wherein said polyamide is in the form of
a film and said article is in the form of a label comprising said
polyamide film.
4. The article of claim 1 further comprising a substrate, and a
composition comprising said polyamide polymer disposed on said
substrate.
5. The article of claim 4, wherein the substrate comprises
fibers.
6. The article of claim 4, wherein said substrate is porous.
7. The article of claim 4, wherein said article is in the form of a
filter or a label.
8. The article of claim 4, wherein said composition is a hot melt
adhesive composition.
9. An article comprising a polyamide polymer comprising the
reaction product of dimer acid comprising at least 98% by weight
dimer, caprolactam, hexamethylene diamine, dicarboxylic acid, and
optionally, chain terminating agent.
10. The article of claim 9, wherein said dicarboxylic acid
comprises sebacic acid.
11. The article of claim 10, wherein said polyamide polymer is in a
form selected from the group consisting of film, fibers, nonwoven
web, woven web, and combinations thereof.
12. The article of claim 10 further comprising a substrate, and a
composition comprising said polyamide polymer, said composition
being in contact with said substrate.
13. The article of claim 12, wherein the substrate comprises at
least one of a film, fibers, nonwoven web, and woven web.
14. The article of claim 12, wherein the article is in the form of
a filter or a label.
15. The article of claim 13, wherein said composition is a hot melt
adhesive composition.
16. The article claim 12, further comprising ink.
17. The article of claim 16, wherein said composition is in the
form of a coating on said substrate, said ink being in contact with
said coating.
18. The article of claim 12, wherein said substrate is impregnated
with said composition.
19. The article of claim 14, wherein said substrate is selected
from the group consisting of a nonwoven web and a woven web, and
said polyamide polymer comprises the reaction product of from about
15 parts by weight to about 25 parts by weight said dimer acid,
from about 25 parts by weight to about 35 parts by weight epsilon
caprolactam, from about 20 parts by weight to about 25 parts by
weight said sebacic acid, and from about 15 parts by weight to
about 25 parts by weight said hexamethylene diamine.
20. The article of claim 12, wherein said composition comprises a
hot melt adhesive composition and said substrate has a first
surface and a second surface, said first surface is bonded to said
second surface through said hot melt adhesive composition.
21. The article of claim 20, wherein said substrate is porous.
22. The article of claim 20, wherein said substrate comprises
pleats.
23. The article of claim 20, wherein said first surface comprises a
first terminal pleat of said filter and said second surface
comprises a second terminal pleat of said filter.
24. The article of claim 20, wherein said article is in the form of
a fuel filter.
25. The article of claim 20, wherein said hot melt adhesive
composition is capable of maintaining said surfaces of said
substrates bonded together after immersion of said article in motor
oil for a period of seven days at 250.degree. F.
26. The article of claim 9 further comprising: a substrate; and a
hot melt composition comprising said polyamide polymer and a
ultraviolet light stabilizing agent, said hot melt composition
being in contact with said substrate.
27. The article of claim 26, wherein said ultraviolet light
stabilizing agent comprises
2,5-thiophenyediylbis(5-tert-butyl-1,3-benzoxazole).
28. The article of claim 26, wherein said dicarboxylic acid is
selected from the group consisting of sebacic acid, dodecanoic
acid, adipic acid, azelaic acid, and combinations thereof.
29. An article in the form of a filter comprising: a porous
substrate; and an adhesive composition disposed on said porous
substrate, said adhesive composition comprising the reaction
product of dimer acid; caprolactam; hexamethylene diamine;
dicarboxylic acid; and optionally, chain terminating agent, said
adhesive composition exhibiting less than 18 mg extractives
residue/in.sup.2 porous substrate when tested according to the
Extraction Test Method using a water extraction media.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 10/172,389 filed Jun. 14, 2002, now U.S. Pat. No. ______,
and incorporated herein.
BACKGROUND
[0002] The invention relates to a polyamide and compositions
including the polyamide.
[0003] Many articles that incorporate an adhesive composition or a
polymeric coating must withstand repeated or prolonged contact with
a variety of liquids. Textile labels, filters used in the
automotive industries, and filters used in purifying water are
examples of articles that are used in applications that involve
water, polar solvents, gasoline or oils.
[0004] Textile labels often include information printed on a piece
of material that has been treated with a hot melt composition. Some
textile labels also include an adhesive composition coated on one
or more surfaces of the material. Textile labels are designed to
permanently retain the printed information and are used in many
forms including, e.g., emblems, patches and labels for laundry
instruction and identification. These labels are applied to
garments and other materials by sewing or heat-sealing and must be
capable of successfully withstanding repeated home laundering,
commercial laundering or dry cleaning conditions and processes.
Although a number of organic solvent-based adhesive compositions
have been developed to aid in maintaining print on textile labels,
the use of organic solvents in industry is disfavored due to the
harmful environmental effects and health and safety concerns
associated with such solvents. Organic solvent-based compositions
are also undesirable because they tend to discolor when exposed to
ultraviolet radiation.
[0005] Many filter applications require the adhesive composition
present on the filter to be insoluble in the liquid being filtered.
If the adhesive composition is soluble in or breaks down in the
presence of the liquid being filtered, the liquid can become
contaminated, which can impair or destroy the integrity and
function of the filter.
SUMMARY
[0006] In one aspect, the invention features a polyamide that
includes the reaction product of dimer acid, caprolactam,
hexamethylene diamine, sebacic acid, and optionally, chain
terminating agent, the polyamide exhibiting a viscosity no greater
than 20,000 centipoise at 205.degree. C. In one embodiment, the
polyamide exhibits a viscosity no greater than 10,000 centipoise at
205.degree. C. In other embodiments, the polyamide exhibits a
viscosity from about 2,000 centipoise to about 10,000 centipoise at
205.degree. C. In another embodiment, the dimer acid comprises at
least 98% by weight dimer. In some embodiments, the polyamide is
free of visible color.
[0007] In one embodiment, the dimer acid comprises dimerized fatty
acids having from 18 to 44 carbon atoms. In some embodiments, the
dimer acid includes 36 carbon atoms. In other embodiments, the
dimer acid is essentially free of fatty acid monomer. In other
embodiments, the dimer acid includes no greater than 0.1% by weight
fatty acid monomer. In some embodiments, the dimer acid includes no
greater than 1% by weight fatty acid trimer.
[0008] In other embodiments, the caprolactam includes epsilon
caprolactam.
[0009] In other embodiments, the polyamide includes the reaction
product of from about 5 parts by weight to about 40 parts by weight
the dimer acid, from about 10 parts by weight to about 60 parts by
weight the caprolactam, and from about 5 parts by weight to about
35 parts by weight the hexamethylene diamine. In some embodiments,
the polyamide includes the reaction product of dimer acid,
caprolactam, hexamethylene diamine, sebacic acid and chain
terminating agent.
[0010] In some embodiments, the chain terminating agent is selected
from the group consisting of stearic acid, hexadecanoic acid and
combinations thereof. In other embodiments, the chain terminating
agent comprises stearic acid. In some embodiments, the amount of
stearic acid is from about 0.1 part by weight to about 3.5 parts by
weight.
[0011] In one embodiment, the amount of the sebacic acid is from
about 5 parts by weight to about 35 parts by weight.
[0012] In other embodiments, the amount of the dimer acid is from
about 15 parts by weight to about 25 parts by weight, the amount of
the caprolactam is from about 15 parts by weight to about 45 parts
by weight, the amount of the sebacic acid is from about 15 parts by
weight to about 30 parts by weight, and the amount of the
hexamethylene diamine is from about 10 parts by weight to about 30
parts by weight. In another embodiment, the amount of the dimer
acid is from about 15 parts by weight to about 25 parts by weight,
the amount of the caprolactam is from about 25 parts by weight to
about 35 parts by weight, the amount of the sebacic acid is from
about 20 parts by weight to about 25 parts by weight, and the
amount of the hexamethylene diamine is from about 15 parts by
weight to about 25 parts by weight.
[0013] In another embodiment, a polyamide described herein has an
acid number of from about 2 to about 40. In other embodiments, a
polyamide described herein has an acid number of from about 8 to
about 15. In some embodiments, a polyamide described herein has an
amine number of from about 2 to about 40. In another embodiment, a
polyamide described herein has an amine number of from about 8 to
about 15. In some embodiments, a polyamide described herein having
a ring and ball softening point of from about 265.degree. F. to
about 310.degree. F.
[0014] In another aspect, the invention features a polyamide that
includes the reaction product of dimer acid comprising at least 98%
by weight dimer, caprolactam, hexamethylene diamine, sebacic acid,
and, optionally, chain terminating agent. In some embodiments, the
amount of the dimer acid is from about 15 parts by weight to about
25 parts by weight, the amount of the caprolactam is from about 15
parts by weight to about 45 parts by weight, the amount of the
sebacic acid is from about 15 parts by weight to about 30 parts by
weight, and the amount of the hexamethylene diamine is from about
10 parts by weight to about 30 parts by weight. In other
embodiments, the amount of the dimer acid is from about 15 parts by
weight to about 25 parts by weight, the amount of the caprolactam
is from about 25 parts by weight to about 35 parts by weight, the
amount of the sebacic acid is from about 20 parts by weight to
about 25 parts by weight, and the amount of the hexamethylene
diamine is from about 15 parts by weight to about 25 parts by
weight.
[0015] In some embodiments, the polyamide exhibits a change in
weight of no greater than 25% after exposure to oil for a period of
seven days at 250.degree. F. In other embodiments, the polyamide
exhibits a change in weight of no greater than 25% after exposure
to a 50/50 glycol/water mixture for a period of seven days at
180.degree. F. In other embodiments, the polyamide exhibits a
change in weight of no greater than 25% after exposure to a diesel
fuel for a period of seven days at 140.degree. F. In other
embodiments, the polyamide exhibits a change in weight of no
greater than 25% after exposure to unleaded gasoline containing 10%
ethanol for a period of seven days at 77.degree. F. In another
embodiment, the polyamide exhibits a Shore A hardness of from about
90 to about 100. In another embodiment, the polyamide exhibits a
change in Shore A hardness of no greater than 15% after exposure to
oil for a period of seven days at 250.degree. F. In other
embodiments, the polyamide exhibits a change in Shore A hardness of
no greater than 15% after exposure to diesel fuel for a period of
seven days at 140.degree. F. In other embodiments, the polyamide
exhibits a change in Shore A hardness of no greater than 15% after
exposure to 50/50 glycol/water mixture for a period of seven days
at 180.degree. F. In other embodiments, the polyamide exhibits a
change in Shore A hardness of no greater than 15% after exposure to
unleaded gasoline containing 10% ethanol for a period of seven days
at 77.degree. F.
[0016] In another aspect, the invention features a hot melt
composition that includes a polyamide polymer comprising the
reaction product of dimer acid comprising at least 98% by weight
dimer, caprolactam, hexamethylene diamine, dicarboxylic acid, and
optionally, chain terminating agent, and ultraviolet light
stabilizing agent. In some embodiments, the ultraviolet light
stabilizing agent includes
2,5-thiophenyediylbis(5-tert-butyl-1,3-benzoxazole). In some
embodiments, the dicarboxylic acid is selected from the group
consisting of sebacic acid, dodecanoic acid, adipic acid, azelaic
acid, and combinations thereof.
[0017] In some aspects, the invention features an article that
includes a hot melt adhesive composition that includes a polyamide
polymer including the reaction product of dimer acid comprising at
least 98% by weight dimer, caprolactam, hexamethylene diamine,
sebacic acid, and optionally, chain terminating agent, and a
substrate having a first surface and a second surface, the first
surface being bonded to the second surface through the hot melt
adhesive composition. In some embodiments, the substrate includes a
filter. In some embodiments, the substrate includes a pleated
filter. In some embodiments, the first surface includes a first
terminal pleat of the filter and the second surface includes a
second terminal pleat of the filter. In some embodiments, the
filter includes a fuel filter.
[0018] In some embodiments, the hot melt adhesive composition is
capable of maintaining the surfaces of the substrate bonded
together after immersion of the article in motor oil for at least
seven days at 250.degree. F. In some embodiments, the surfaces of
the substrate remain bonded together through the adhesive
composition after immersion of the article in diesel fuel for at
least seven days at 140.degree. F.
[0019] In another aspect, the invention features an article that
includes a hot melt adhesive composition that includes a polyamide
polymer including the reaction product of dimer acid, caprolactam,
hexamethylene diamine, sebacic acid, and optionally, chain
terminating agent, the hot melt adhesive composition having a
viscosity of no greater than 20,000 centipoise at 205.degree. C.,
and a substrate having a first surface and a second surface, the
first surface being bonded to the second surface through the hot
melt adhesive composition.
[0020] In one embodiment, the article includes a substrate, and a
composition that includes a polyamide polymer disposed on the
substrate, the polyamide polymer including the reaction product of
dimer acid comprising at least 98% by weight dimer, caprolactam,
hexamethylene diamine, sebacic acid, and optionally, chain
terminating agent. In some embodiments, the substrate is selected
from the group consisting of a nonwoven web and a woven web.
[0021] In other embodiments, the article is a label. In some
embodiments, the label includes ink. In another embodiment, the
composition is in the form of a coating on the substrate of the
label and the ink is disposed on the coating. In other embodiments,
the substrate of the label is impregnated with the composition. In
another embodiment, the ink is in the form of information. In one
embodiment, the substrate of the label is selected from the group
consisting of a nonwoven web and a woven web, and the polyamide
polymer includes the reaction product of from about 15 parts by
weight to about 25 parts by weight the dimer acid, from about 25
parts by weight to about 35 parts by weight epsilon caprolactam,
from about 20 parts by weight to about 25 parts by weight the
sebacic acid, and from about 15 parts by weight to about 25 parts
by weight the hexamethylene diamine.
[0022] In another embodiment the article is a filter. In another
embodiment, the invention features a filter that includes a porous
substrate, and an adhesive composition disposed on said porous
substrate, the adhesive composition including the reaction product
of dimer acid, caprolactam, hexamethylene diamine, dicarboxylic
acid, and optionally, chain terminating agent, the adhesive
composition exhibiting less than 18 mg extractives residue/in.sup.2
porous substrate when tested according to the Extraction Test
Method using a water extraction media.
[0023] In one aspect, the invention features a fiber that includes
a polyamide described herein.
[0024] In another aspect, the invention features a nonwoven web
that includes a polyamide described herein. In one embodiment, the
nonwoven web includes fibers that include a polyamide described
herein.
[0025] In other aspects, the invention features a film that
includes a polyamide described herein.
[0026] The invention features a polyamide that is well suited to
textile applications. The polyamide can be formulated to be clear
and colorless and to exhibit good ultraviolet light stability. The
polyamide can also be formulated to exhibit good stability when
exposed to heat and water, e.g., can be wash resistant. The
polyamide can also be formulated to be printable, i.e., capable of
receiving and retaining ink.
[0027] Use of the polyamide in place of organic solvent-based
compositions can also provide processing free of the harmful
environmental effects associated with the organic solvents of
organic solvent-based compositions.
[0028] Other features of the invention will be apparent from the
following description of the preferred embodiments thereof, and
from the claims.
DETAILED DESCRIPTION
[0029] The polyamide exhibits hot melt adhesive properties, i.e.,
is nontacky at room temperature, is tacky when heated, and exhibits
adhesive bond strength. The polyamide also is nonblocking and can
be wound upon itself to form a roll without sticking to itself. The
polyamide can be formulated to be stable in heat and water and
preferably passes Food and Drug Administration (FDA) Test Method
FDA-175-300 for repeated use (21 CFR 175.300 FDA Water and Heptane
Extraction Testing, Feb. 20, 2002).
[0030] The polyamide can be formulated with components such as
ultraviolet light (UV) stabilizers to exhibit UV stability.
[0031] The polyamide also exhibits good resistance to chemicals
such as oil and gas. One method of determining chemical resistance
includes measuring the change in weight and the change in Shore A
hardness of the compound before and after exposure to the chemical.
Preferably the polyamide exhibits a change in weight of no greater
than 25%, preferably no greater than 20%, more preferably no
greater than 10%, most preferably 0% after immersion in oil for a
period of seven days at 250.degree. F., after immersion in 50/50
glycol/water mixture for a period of seven days at 180.degree. F.,
diesel fuel for a period of seven days at 140.degree. F., or
unleaded gasoline containing 10% ethanol for a period of seven days
at 77.degree. F.
[0032] The polyamide also preferably exhibits a Shore A hardness of
from about 96 to about 100 and a change in Shore A hardness of no
greater than 15%, preferably no greater than 10%, more preferably
0% after immersion in oil for a period of seven days at 250.degree.
F., after immersion in 50/50 glycol/water mixture for a period of
seven days at 180.degree. F., after immersion in diesel fuel for a
period of seven days at 140.degree. F., or after immersion in
unleaded gasoline containing 10% ethanol for a period of seven days
at 77.degree. F.
[0033] The polyamide is prepared by reacting dimer acid,
caprolactam, hexamethylene diamine, dicarboxylic acid, and,
optionally, a chain terminating agent. The resulting polyamide
preferably exhibits a viscosity of from about 2000 centipoise (cps)
to about 40,000 cps, more preferably from about 4000 cps to about
20,000 cps, most preferably from about 4,000 to about 10,000 cps at
400.degree. F. and has an acid number from about 2 to about 40,
more preferably from about 10 to about 20, most preferably from
about 8 to about 15. Alternately, the polyamide can be amine
terminated and have an amine number from about 2 to about 40, more
preferably from about 10 to about 20, most preferably from about 8
to about 15. The polyamide exhibits a ring and ball softening point
of from about 250.degree. F. to about 350.degree. F., more
preferably from about 265.degree. F. to about 310.degree. F.
[0034] Suitable dimer acids include, e.g., fatty acid hydrogenated
dimers having alkyl groups that include from 18 to 44 carbon atoms.
Preferred dimer acids are pure, i.e., the components present in the
dimer acid other than dimer, e.g., monomer and trimer, are present
in an amount of less than 2%, more preferably less than 1%, most
preferably less than 0.5% by weight based on the weight of the
dimer acid. Preferably the dimer acid is at least 98% by weight
dimer, more preferably at least 98.5% by weight. One useful
commercially available dimer acid is available under the trade
designation Pripol 1009 from Unichema (New Castle, Del.) and
includes a mixture of hydrogenated dimerized fatty acids having 36
carbon atoms and includes greater than 98.5% dimer, no greater than
0.1% monomer and no greater than 2.0% trimer.
[0035] The amount of dimer acid present in the reaction mixture is
preferably from about 5 parts by weight to about 40 parts by
weight, more preferably from about 10 parts by weight to about 30
parts by weight, most preferably from about 15 parts by weight to
about 25 parts by weight.
[0036] Epsilon caprolactam is the preferred caprolactam.
Caprolactam is preferably present in the reaction mixture in an
amount of from about 10 parts by weight to about 60 parts by
weight, more preferably from about 15 parts by weight to about 45
parts by weight, most preferably from about 25 parts by weight to
about 35 parts by weight.
[0037] Suitable dicarboxylic acids have an alkyl group that
includes 6, 8, 10 or 12 carbon atoms. Examples of suitable
dicarboxylic acids include sebacic acid, dodecanedioic acid,
azelaic acid, adipic acid and combinations thereof. Preferably the
dicarboxylic acid is sebacic acid. The amount of dicarboxylic acid
present in the reaction mixture is from about 5 parts by weight to
about 35 parts by weight, preferably from about 15 parts by weight
to about 30 parts by weight, more preferably from about 20 parts by
weight to about 25 parts by weight.
[0038] The amount of hexamethylene diamine present in the reaction
mixture is from 5 parts by weight to about 35 parts by weight,
preferably from about 10 parts by weight to about 30 parts by
weight, more preferably from about 15 parts by weight to about 25
parts by weight.
[0039] The reaction mixture may optionally include a chain
terminator. Useful chain terminators include, e.g., stearic acid,
hexadecanoic acid, monoamines including, e.g., benzyl amine,
hexylamine, octadecylamine, and monoamines commercially available
under the ARMEEN 18D trade designation from Akzo Nobel Chemicals
Inc., (McCook, Ill.), and combinations thereof. The amount of chain
terminator, when present in the reaction mixture, preferably is
present in an amount of no greater than 5 parts by weight, and can
be present in an amount from about 0.1 parts by weight to about 3.5
parts by weight, and from about 1 part by weight to about 3.5 parts
by weight.
[0040] The polyamide is preferably prepared by condensation
reaction.
[0041] The composition can include a catalyst to speed the rate of
reaction of the formation of the polyamide. An example of a
suitable catalyst is hypophosphoric acid, sodium benzene
phosphonate, sodium benzene phosphinate and combinations
thereof.
[0042] The polyamide can be used neat as a 100% solids hot melt
composition or formulated with other components to form various hot
melt compositions including, e.g., hot melt pressure sensitive
adhesives. Other components that can be combined with the polyamide
include, e.g., thermoplastic polymers, tackifiers, plasticizers,
antioxidants (e.g., Irganox 1098, 1010 and 1076), coloring agents
including, e.g., pigment (e.g., titanium dioxide, calcium carbonate
clay, talc, terra alba, bentonite, barium sulfate, zinc oxide,
silica, alumina, cellulose powder, starch particles, phthalocyanine
pigment synthetic resin powders, and combinations thereof), UV
stabilizers, corrosion inhibitors, and combinations thereof.
[0043] Suitable tackifying agents include, e.g., rosin derivatives
including wood rosin, tall oil, tall oil derivatives,
pentaerythritol esters of tall oil, gum rosin, rosin ester resins,
natural and synthetic terpenes, and aliphatic tackifying resins
(e.g., hydrogenated C.sub.9 resins, branched and unbranched C.sub.5
resins and mixtures thereof) and mixed aromatic-aliphatic
tackifying resins (e.g., styrenated terpene resins, styrenated
C.sub.5 resins and mixtures thereof) and mixtures thereof.
[0044] Useful plasticizers preferably have aromatic character and a
softening point of at least 60.degree. C. Other useful plasticizers
include aromatic carboxylic acid esters of polyfunctional alcohol
having from 1 to 10 hydroxyl groups. Suitable polyfunctional
alcohols include, e.g., compounds having at least two hydroxyl
groups and at least two carbon atoms including, e.g., ethylene
glycol, propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol,
glycerine, glucose, fructose, sucrose, mannitol, trimethylol
ethane, 1,4-cyclohexane dimethanol, pentaerythritol,
2,2-dimethyl-1,3-propane diols, 2-hydroxy
methyl-2-methyl-1,3propane diol and neopentyl glycol. Aromatic
acids that can be used with the polyfunctional alcohols to form
ester plasticizers include, e.g., aromatic carboxylic acids
(preferably having one aromatic group and at least one carboxyl
function) examples of which include benzoic acid, naphthanoic acid,
4-mehtyl benzoic acid and 1,4-cyclohexane dimethanol dibenzoate.
Examples of suitable plasticizers include benzoates, phthalates,
polyols, liquid polyesters (preferably liquid polyesters having a
molecular weight less than about 1500) and combinations
thereof.
[0045] Useful UV stabilizers impart ultraviolet light resistance to
the polyamide and preferably inhibit or prevent visible yellowing
of the polyamide and compositions formulated with the polyamide.
Examples of suitable UV stabilizers include
2,5-thiophenyediylbis(5-tert-butyl-1,3-benzoxazole);
bis-(1-Octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate;
2-(2H-Benzotirazol-2-yl)-4,6-bis(1-methyl-1-phenylether)phenol;
2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dymethylethil)-4-methylphenol;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;
2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol;
dimethyl succinate polymer with
4-hydroxy-2,2,6,6-tetramethyl-1-piperdineethanol;
bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate;
1,3,5-triazine-2,4,6-triamine,N,N'''-[1,2-ethanediylbis[[[4,6-bis[butyl(1-
,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-p-
ropanediyl]]-bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperid-
inyl); poly[[6-[1.1.3.3-tetramethyl
butyl)amino]-s-triazine-2,4-diyl][[2,2,6,6-tetramethyl-4-piperidyl)
imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]];
1,6-hexanediamine,
N,N'-bis(2,2,6,6,-tetramethyl-4-piperidinyl)-polymer
with-2,4,6-trichloro-1,3,5-triazine, reaction products with
N-butyl-1-butanamine and
N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.
[0046] Suitable UV stabilizers are commercially available under the
TINUVIN series of trade designations including, e.g., TINUVIN 123,
234, 326, 328, 622 and 770, and CHIMASSORB 119, 944 and 202 all
available from Ciba Specialty Chemicals (Tarrytown, N.Y.), blends
of light stabilizers available under the TINUVIN series of trade
designations including, e.g., TINUVIN 111, 123 S, 492, 494, 783,
791, and C 353, under the IRGASTAB series of trade designations
including, e.g., IRGASTAB FS 210, FS 410, FS 811 and FS 812,
FIBERSTAB L 112 and UVITEX OB
2,5-thiophenyediylbis(5-tert-butyl-1,3-benzoxazole) all from Ciba
Specialty Chemicals.
[0047] The polyamide and compositions formulated therewith are
useful in a variety of applications including, e.g., coatings
(e.g., continuous and discontinuous coatings), adhesives, sealants
(e.g., heat sealants), films and laminates (e.g., for textile
lamination) and can be formed into various articles including,
e.g., fibers, filaments, woven and nonwoven webs, films, composites
and combinations thereof. Films including the polyamide are useful
in processes such as laminating and printing.
[0048] The polyamide can be applied in its various forms to a
variety of substrates including, e.g., woven and nowoven webs,
fibers, filaments, filters, textiles, honeycomb structures,
components of footwear and films (e.g., polymer and cellulose). The
polyamide is well suited for use as a coating on woven and nonwoven
labels used in textile and clothing industries, and as an adhesive
for bonding substrates together including, e.g., the pleats (e.g.,
terminal pleats) of a filter including, e.g., air filters, water
filters, oil filters, fuel filters and filters used in engines
including, e.g., vehicle engines (e.g., automobiles, trucks,
tractors, farm equipment and agricultural equipment) and industrial
filters including industrial filters exposed to various
chemicals.
[0049] The invention will now be described further by way of the
following examples. All parts, ratios, percents and amounts stated
in the Examples are by weight unless otherwise specified.
EXAMPLES
Test Procedures Test procedures used in the examples include the
following.
Method of Determining Viscosity
[0050] Viscosity of a sample is determined using a Model DVII+
Brookfield Viscometer (Brookfield Engineering Laboratories, Inc.,
Stoughton, Mass.) according to the following procedure. A number 27
spindle attached to the viscometer and placed in a 10.5 g sample
that is kept heated at 400.degree. F. (205.degree. C.). The spindle
is rotated at 20 rotations per minute (rpm) for 20 minutes. After
20 minutes a reading is taken and recorded in centipoise.
Method of Determining Ring and Ball Softening Point
[0051] Ring and ball softening point is determined according to
ASTM Test Method ASTM E 28-99 Standard Test Methods for Softening
Point of Resins Derived from Naveal Stores by Ring and Ball
Apparatus (Dec. 10, 1999) in which kaydol oil (i.e., white mineral
oil) is used instead of glycerin.
Method of Determining Acid Number
[0052] Acid number is determined by placing a 2 g sample of
polyamide into a 250 mL glass Erlenmeyer flask, and then adding 100
ml of 50:50 isopropyl alcohol/toluene and a stirring bar to the
flask. The sample is refluxed with a water-cooled condenser on a
stirring/hot plate until the sample is completely dissolved. If the
sample has not dissolved after 30 minutes of refluxing use it as
is. The solution is then allowed to cool to room temperature. 1 ml
of phenolphthalein indicator is added to the solution. The flask is
then stirred while titrating to a pink end point using standardized
0.1 N alcoholic potassium hydroxide. The endpoint should persist
for five minutes. The volume of potassium hydroxide required to
reach the endpoint is recorded in milliliters.
[0053] A blank of 100 ml 50:50 isopropyl alcohol/toluene is placed
in a glass Erlenmeyer flask, 1 ml of phenolphthalein indicator is
added to the solution, and the mixture is then titrated using
standardized 0.1 N alcoholic potassium to a pink endpoint. The
volume of potassium hydroxide required to reach the endpoint is
recorded in milliliters.
[0054] The acid number is then calculated according to the
following equation: Acid .times. .times. Number = ( A .times. N
.times. 56.1 ) w ##EQU1## where A=milliliters of potassium
hydroxide titrated (sample-blank), N=normality of the alcoholic
potassium hydroxide solution and w=grams of sample. Method of
Determining Amine Number
[0055] Amine number is determined by placing a 2 g sample of
polyamide into a 250 mL glass Erlenmeyer flask. 100 ml of 50:50
isopropyl alcohol/distilled water solution is added to the flask.
The sample is refluxed with a water-cooled condenser on a stirring
hot plate until the sample is completely dissolved. The solution is
then allowed to cool slightly but remains warm during the
titration. 5 ml of bromocresol green indicator is added to the
solution. The flask is then shaken or stirred while titrating to a
yellow end point using standardized 0.100 N hydrochloric acid.
[0056] The amine number is then calculated according to the
following equation: Amine .times. .times. Number = ( A .times. N
.times. 56.1 ) w ##EQU2## where A=milliliters of hydrochloric acid
titrated, N=normality of the hydrochloric acid solution and w=grams
of sample. Method of Determining Shore A Hardness
[0057] Shore A hardness is determined by measuring the durometer of
a 1.40 in.times.1.25 in.times.0.15 in sample using a Model No. 306L
Type A Shore A durometer conforming to ASTM 2240-75 (Pacific
Transducer Corp., Los Angeles, Calif.).
UV Stability
[0058] The stability of the polyamide in the presence of
ultraviolet light is determined according to Canadian General
Standard Board Test Method 12.8. A film of sample is placed in a
Canadian Fog Chamber and exposed to ultraviolet light generated by
a Sylvania R-S1 100 watt spit lamp #H44GS-100 for a period of seven
days at 140.degree. F.
[0059] The sample is removed from the chamber and observed for
color. If there is no visible yellowing or browning, the sample is
deemed to be UV stable.
Hydrolytic Stability
[0060] A film of sample is immersed in a 140.degree. F. water bath
and left in the water bath for seven days. After seven days the
sample is removed and observed to determine if any degradation,
e.g., solvation, has occurred. If the sample is intact, the sample
is deemed to be hydrolytically stable. If the sample has degraded,
e.g., at least partially dissolved, the sample is not
hydrolytically stable.
Heat Stability
[0061] Heat stability is determined according to ASTM-D-4499-95
(Re-Approved 2000) entitled, "Heat Stability of Hot-Melt
Adhesives." The initial viscosity of a portion of the sample is
measured and recorded along with the color of the sample. The
sample is then placed in a thermosel and the thermosel is placed in
an oven that has been preheated to 400.degree. F. The viscosity of
the sample is measured at four hour intervals over a period of 24
hours and recorded. The sample is also observed for color and signs
of degradation including the presence of charring or gelling. The
observations are recorded.
[0062] A sample that is free of or has negligible degradation,
yellowing and browning after 24 hours, and that does not exhibit a
change in viscosity of more than 75% from its initial viscosity
value is reported as heat stable.
Chemical Resistance
[0063] The Shore A hardness of a 1.40 in.times.1.25 in.times.0.15
in sample is measured according to the above-described method and
recorded.
[0064] The weight of the sample is then measured. The sample is
placed in a glass jar. From 30 g to 35 g of the test fluid is added
to the jar. The immersed sample is then exposed to heat for a
period of 7 days. The samples are then cooled to room temperature,
held at room temperature for 24 hours, removed from the test fluid
and wiped drying using a soft absorbent paper towel. The dried
samples are then weighed and the Shore A hardness is measured.
[0065] A sample is given a pass rating if there is no greater than
a 25% change in weight and durometer as measured from the original
values obtained on the sample to the values obtained on the sample
after exposure to the chemical and conditions specified.
[0066] A sample is given a fail rating if there is greater than a
25% change in weight or durometer as measured from the original
values obtained on the sample to the values obtained on the sample
after exposure to the chemical and conditions specified.
Extraction Test Method
[0067] A sample composition is prepared in the form of a 4
in.times.6 in film. Seven film samples are used in each test for a
total area of 168 in.sup.2. The samples are tested according to 21
CFR 175.300 FDA (Food and Drug Administration) Water and Heptane
Extraction Testing (Feb. 20, 2002) with the following exceptions:
the test specimen is a film of composition as opposed to an article
on which the composition has been coated, a two liter glass beaker
is used as the extraction vessel, and the extractives residue is
calculated in parts per million (ppm) based on 2000 g (i.e., the
total weight of the extraction media in the extraction vessel).
[0068] The seven film samples are immersed in two liters of
extraction media. When water is the extraction media, the water is
maintained at 212.degree. F. and the samples remain in the water
for 30 minutes. When heptane is the extraction media, the heptane
is maintained at 120.degree. F. and the samples remain in the
heptane for 30 minutes.
[0069] The samples are then removed from the vessel, the extraction
media is concentrated to approximately 100 mL, transferred to a
weighing dish, dried down, and the residue is weighed.
[0070] The amount of extracted residue from the seven film samples
is recorded in mg. The residue extracted per square inch of sample
is then calculated and reported in mg/in.sup.2.
[0071] A specimen receives a pass rating for a coating intended for
repeated use if the extractives residue is less than 18
mg/in.sup.2.
[0072] If the extractives residue exceeds 18 mg/in.sup.2, a
chloroform extraction is performed in which 50 ml of chloroform is
added to the residue (at room temperature, i.e., about 72.degree.
F.) and then the chloroform/residue mixture is filtered. This
chloroform extraction step is repeated one more time. The
chloroform extract is collected in a pre-weighed dish, evaporated,
and weighed. The amount of residue resulting from the chloroform
extraction is recorded in mg and the amount of extractives residue
is calculated and reported in mg/in.sup.2.
[0073] The sample passes the criteria under 21 CFR 175.300 FDA for
repeated use if the residue from the chloroform extraction is less
than 18 mg/in.sup.2.
EXAMPLE 1
[0074] The polyamide polymer was prepared by combining 19.99 g
PRIPOL 1009 dimer acid (Uniqema Corp., New Castle, Del.), 22.26 g
sebacic acid, 3.2 g stearic acid, 30.38 g epsilon caprolactam, 23.3
g 70% hexamethylene diamine and 0.04 g 50% hypophosphoric acid in a
four neck reaction kettle. The kettle was kept at a temperature of
from 120.degree. F. to 140.degree. F. with its valve closed to
react the acid and the amine. After five minutes the vessel was
placed under nitrogen gas and the mixture was heated at 265.degree.
F. to 285.degree. F. until the first batch of water started to come
out of the vessel. The temperature was then slowly increased to a
temperature of 500.degree. F. to 520.degree. F. After most of the
water had been removed from the composition, the reaction was held
at 500.degree. F. to 520.degree. F. for 1-2 hours under vacuum. The
vacuum was released by introducing nitrogen gas into the reaction
kettle 0.73 g IRGANOX 1010 antioxidant (Ciba Specialty Chemicals
Corp, Tarrytown, N.Y.), and 0.10 g UVITEX OB ultraviolet light
stabilizer (Ciba Specialty Chemicals) were then added to the kettle
and mixed at 475.degree. F. to 500.degree. F. for 30 minutes.
Vacuum was pulled on the kettle for an additional 30 minutes at
450.degree. F. to 475.degree. F. The product was then maintained
under nitrogen as it was drained into an appropriate container.
[0075] The composition had a ring and ball softening point of
290.degree. F., a viscosity of 5,300 cps (5300 mpas-sec) at
400.degree. F., an acid number of 10.7 and an amine number of
0.1.
[0076] The resulting composition was then tested for UV stability,
heat stability and hydroscopic stability. The composition exhibited
a viscosity of change of less than 10% after 24 hours at
400.degree. F. No visible discoloration or degradation was
observed. The composition did not dissolve when tested according to
the hydrolytic stability test. The composition exhibited UV
stability, heat stability and hydrolytic stability.
[0077] The polyamide of Example 1 was tested according to the
chemical resistance test method. The samples were weighed and the
Shore A hardness was measured before and after exposing the samples
to the test fluids and conditions set forth in Table 1. The results
are set forth in Table 1. TABLE-US-00001 TABLE 1 % Change % Weight
in Shore A Sample Temperature Test Fluid Weight (g) Weight (g)
Shore A Shore A change Hardness 1 250.degree. F. Diesel Oil.sup.1
3.6 3.6 100 100 0 Pass 0 Pass 2 250.degree. F. Oil.sup.2 4.2 4.2 97
100 0 Pass 3 Pass 3 180.degree. F. 50/50 Ethylene 4.3 4.6 98 98 6.9
Pass 0 Pass Glycol/water.sup.3 3 180.degree. F. 50/50 propylene 3.8
4.6 97 95 21.0 Pass 2 Pass glycol/water.sup.4 5 140.degree. F.
Diesel Fuel.sup.5 3.5 3.5 99 99 0 Pass 0 Pass 6 77.degree. F.
Unleaded 4.1 4.8 98 85 17 Pass 13.2 Pass gasoline and at least 10%
ethanol 7 140.degree. F. Unleaded 3.8 5.1 98 85 34.2 Fail 13.2 Pass
gasoline and at least 10% ethanol .sup.1= Premium Blue diesel oil
.sup.2= Hy-Tran plus MS1207 oil .sup.3= 50/50 mixture by weight of
polyethylene glycol and water. .sup.4= A 50/50 mixture by weight of
polypropylene glycol and water. .sup.5= Winter formulated diesel
fuel.
[0078] Portions of the composition of Example 1 was formed into a
film and tested according to the Extraction Test Method. The
results are reported in Table 2. TABLE-US-00002 TABLE 2 Pass or
Fail Extraction Extractives Extractives 21 CFR 175.300 Media (mg)
(mg/in.sup.2) for Repeated Use Water 514 3.1 Pass Chloroform 257
1.5 Pass Heptane 21.6 0.026 Pass
[0079] Other embodiments are within the claims.
* * * * *