U.S. patent application number 09/915832 was filed with the patent office on 2002-01-17 for method for damping noise, vibration and harshness of a substrate and composition therefor.
Invention is credited to Irvine, Daniel W., Locke, Ralph J..
Application Number | 20020007037 09/915832 |
Document ID | / |
Family ID | 22219517 |
Filed Date | 2002-01-17 |
United States Patent
Application |
20020007037 |
Kind Code |
A1 |
Locke, Ralph J. ; et
al. |
January 17, 2002 |
Method for damping noise, vibration and harshness of a substrate
and composition therefor
Abstract
A material for damping vibration of a substrate that cures
substantially instantaneously upon application in the ambient
environment. The damping material composition comprises a resin
component and an isocyanate component. The resin component includes
a polymer(s) for imparting tensile strength, hardness and
flexibility; an optional chain extender(s) for imparting tensile
strength, weatherability, flexibility, adhesion to specific
substrates, and hardness; and an optional filler for imparting
hardness, flexibility, and specific noise, vibration and harshness
blocking characteristics to the after-application, cured surface.
The isocyanate component of the composition includes an isocyanate
quasi-prepolymer(s) based on a uretonimine modified MDI and a high
molecular weight polyether polyol having an isocyanate equivalent
content of 15.8% and a 2,4'-isomer content of less than about 15%;
and an optional plasticizer(s) for imparting flexibility.
Inventors: |
Locke, Ralph J.; (Ft. Myers,
FL) ; Irvine, Daniel W.; (Traverse City, MI) |
Correspondence
Address: |
YOUNG & BASILE, P.C.
Suite 624
3001 West Big Beaver Road
Troy
MI
48084-3107
US
|
Family ID: |
22219517 |
Appl. No.: |
09/915832 |
Filed: |
July 26, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09915832 |
Jul 26, 2001 |
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09335115 |
Jun 17, 1999 |
|
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|
6291019 |
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60089774 |
Jun 18, 1998 |
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Current U.S.
Class: |
528/76 |
Current CPC
Class: |
C08J 2475/00 20130101;
C08G 18/6685 20130101; C09D 175/02 20130101; C08J 7/043 20200101;
C08G 2350/00 20130101; C08J 7/0427 20200101; C08J 7/046
20200101 |
Class at
Publication: |
528/76 |
International
Class: |
C08G 018/48 |
Claims
What is claimed is:
1. A sprayable, substantially instantaneously curable, vibration
damping liquid composition for application on a substrate, the
liquid composition consisting essentially of: a first component,
consisting essentially of at least one polymer present in an amount
sufficient to impart a predetermined amount of tensile strength,
hardness and flexibility; and a second component, consisting
essentially of at least one isocyanate compound.
2. The vibration damping liquid composition as defined in claim 1
wherein the first component further consists essentially of: at
least one chain extender present in an amount sufficient to impart
a predetermined amount of tensile strength, weatherability,
flexibility, adhesion to specific substrates, and hardness; and at
least one filler present in an amount sufficient to impart a
predetermined amount of hardness, flexibility, and specific
vibration blocking characteristics to the substrate.
3. The vibration damping liquid composition as defined in claim 2
wherein the first component further consists essentially of: a
colorant compound selected from the group consisting of carbon
black, titanium dioxide, iron oxide, organic pigments, dyes, and
mixtures thereof, and a catalyst selected from the group consisting
of tertiary amines, organometallic catalysts, and mixtures
thereof.
4. The vibration damping liquid composition as defined in claim 2
wherein the at least one polymer is selected from the group
consisting of polyoxypropylene diols, polyoxypropylene triols, di-,
tri-, quad- or penta-functional polyester polyols, di-, tri-, quad-
or penta-functional polyether polyols, and mixtures thereof.
5. The vibration damping liquid composition as defined in claim 1
wherein the isocyanate compound consists essentially of isocyanate
quasi-prepolymers based on a uretonimine modified MDI and a high
molecular weight polyether polyol having an isocyanate content of
about 15.8% and a 2,4-isomer content of less than about 10%.
6. The vibration damping liquid composition as defined in claim 1
wherein the second component further consists essentially of at
least one plasticizer present in an amount sufficient to impart a
predetermined amount of flexibility.
7. The vibration damping liquid composition as defined in claim 6
wherein the plasticizer consists essentially of alkylene carbonates
selected from the group consisting of ethylene carbonates,
propylene carbonates, butylene carbonates, dimethyl carbonates, and
mixtures thereof.
8. The vibration damping liquid composition as defined in claim 4
wherein the at least one polymer comprises amine-terminated
polyoxypropylene diols of about 2000 molecular weight; wherein the
at least one chain extender is selected from the group consisting
of dialkyl substituted methylene dianilines, diethyltoluene
diamines, and mixtures thereof, and wherein the at least one filler
is selected from the group consisting of barium sulfate, calcium
carbonate, clay, talc, aluminum silicate, titanium dioxide, nitrile
rubbers, butyl rubbers, synthetic rubbers, chopped fiberglass,
calcium metasilicate, fibers, fumed silica, and mixtures
thereof.
9. The vibration damping liquid composition as defined in claim 8
wherein the first component of the composition further consists
essentially of at least one adhesion promoter, wherein the adhesion
promoter comprises an organosilane compound.
10. A sprayable, substantially instantaneously curable, vibration
damping liquid composition for application on a substrate, the
liquid composition consisting essentially of: a first component,
consisting essentially of: at least one polymer present in an
amount sufficient to impart a predetermined amount of tensile
strength, hardness and flexibility; at least one chain extender
present in an amount sufficient to impart a predetermined amount of
tensile strength, weatherability, flexibility, adhesion to specific
substrates, and hardness; and at least one filler present in an
amount sufficient to impart a predetermined amount of hardness,
flexibility, and specific vibration blocking characteristics to the
substrate; and a second component, consisting essentially of at
least one isocyanate compound.
11. The vibration damping liquid composition as defined in claim 10
wherein the at least one polymer is selected from the group
consisting of polyoxypropylene diols, polyoxypropylene triols, di-,
tri-, quad- or penta-functional polyester polyols, di-, tri-, quad-
or penta-functional polyether polyols, and mixtures thereof.
12. The vibration damping liquid composition as defined in claim 11
wherein the isocyanate compound consists essentially of isocyanate
quasi-prepolymers based on a uretonimine modified MDI and a high
molecular weight polyether polyol having an isocyanate content of
about 15.8% and a 2,4'-isomer content of less than about 10%.
13. The vibration damping liquid composition as defined in claim 12
wherein the second component further consists essentially of at
least one plasticizer present in an amount sufficient to impart a
predetermined amount of flexibility.
14. The vibration damping liquid composition as defined in claim 13
wherein the plasticizer consists essentially of alkylene carbonates
selected from the group consisting of ethylene carbonates,
propylene carbonates, butylene carbonates, dimethyl carbonates, and
mixtures thereof.
15. The vibration damping liquid composition as defined in claim 14
wherein the at least one polymer comprises amine-terminated
polyoxypropylene diols of about 2000 molecular weight; wherein the
at least one chain extender is selected from the group consisting
of dialkyl substituted methylene dianilines, diethyltoluene
diamines, and mixtures thereof; and wherein the at least one filler
is selected from the group consisting of barium sulfate, calcium
carbonate, clay, talc, aluminum silicate, titanium dioxide, nitrile
rubbers, butyl rubbers, synthetic rubbers, chopped fiberglass,
calcium metasilicate, fibers, fumed silica, and mixtures
thereof.
16. The vibration damping liquid composition as defined in claim 15
wherein the first component further consists essentially of: a
colorant compound selected from the group consisting of carbon
black, titanium dioxide, iron oxide, organic pigments, dyes, and
mixtures thereof; and a catalyst selected from the group consisting
of tertiary amines, organometallic catalysts, and mixtures
thereof.
17. The vibration damping liquid composition as defined in claim 16
wherein the first component of the composition further consists
essentially of at least one adhesion promoter, wherein the adhesion
promoter comprises epoxy silane compounds.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of co-pending application
U.S. Ser. No. 09/335,115 filed Jun. 17, 1999. This application also
claims the benefit of U.S. Provisional Application Serial No.
60/089,774, filed Jun. 18, 1998.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for damping
vibration of a substrate and a composition therefor, and
especially, although not exclusively to such a method and
composition suitable for use in the automotive industry.
BACKGROUND OF THE INVENTION
[0003] As the automobile has evolved, consumers have become
continually more sophisticated and demanding. As such, they require
many amenities, above and beyond excellent functionality. For
example, in luxury automobiles especially, the consumer expects a
quiet ride. This feature is of such importance that automobile
manufacturers frequently spend millions of dollars on advertising
campaigns inundating the media with what a smooth, quiet and plush
ride their particular automobiles have.
[0004] As such, the automotive industry, as well as the aerospace
industry, railway industry, and the truck and bus industry, has
dedicated considerable research and development money to improving
on a vehicle's noise, vibration and harshness (NVH)
characteristics.
[0005] Many means have been attempted in order to solve the problem
of vibration in a vehicle. One previous method of damping vibration
included the placement of moldings and/or pads in appropriate
areas. However, several drawbacks existed to this method in that
the moldings and/or pads had to be very precisely precut in order
to fit properly. Further, they required time consuming assembly to
properly and securely attach the moldings/pads to the respective
areas. Due to these drawbacks, the moldings and/or pads were nearly
cost prohibitive in many cases.
[0006] Another solution was to spray epoxy or water born plastisols
in liquid form onto (for example, in the automotive industry) a
body in white. These sound damping compositions were sprayed wet
and remained wet until they were cured. However, curing the
plastisol on the body in white required heating. This resulted in
several drawbacks, a few of which are that the plastisol
composition would drip off and could contaminate the paint and/or
E-coat system. Further, this composition could only go on the
automotive body at a particular point in the assembly process,
namely relatively soon before the body was to be put in the oven
for baking (since the plastisol required heat for curing).
[0007] Accordingly, an object of the present invention is to
provide a new and improved method for damping vibration of a
substrate which does not require heating or other specialized
process steps. It is a further object of the present invention to
provide such a method which is simple and cost effective. It is yet
a further object of the present invention to provide such a method
which requires very little time in the assembly process and
advantageously will not contaminate the vehicle paint or E-coat
system. Still further, it is an object of the present invention to
provide such a method which may be used at any point in the
assembly process, eg. at the metal stamping stage up to and
including the body in white stage, and either before or after the
application of primer to the body in white.
[0008] It is also an object of the present invention to provide a
composition which will damp vibration of a substrate, which
composition advantageously cures substantially instantaneously in
an ambient environment. Yet another object of the present invention
is to provide such a composition which does not substantially
release volatile organic materials.
SUMMARY OF THE INVENTION
[0009] The present invention addresses and solves the
problems/drawbacks enumerated above, and encompasses other features
and advantages as well. The present invention comprises a method
for damping vibration of a substrate which comprises the step of
applying a liquid material onto the substrate in an ambient
environment, wherein, after application to the substrate, the
material cures substantially instantaneously in the ambient
environment.
[0010] A damping composition usable therefor comprises two
components. The first component (ie. the resin component) consists
essentially of a polymer and/or a blend of polymers present in an
amount sufficient to impart a predetermined amount of tensile
strength, hardness and flexibility; optionally, a chain extender
and/or a blend of chain extenders present in an amount sufficient
to impart a predetermined amount of tensile strength,
weatherability, flexibility, adhesion to specific substrates, and
hardness; and optionally, a filler and/or blend of fillers present
in an amount sufficient to impart a predetermined amount of
hardness, flexibility, and specific noise, vibration and harshness
blocking characteristics to the after-application, cured
surface.
[0011] The second component (ie. the isocyanate component) of the
composition may consist essentially of isocyanate quasi-prepolymers
based on a uretonimine modified MDI and a high molecular weight
polyether polyol having an isocyanate equivalent content of 15.8%
and a 2,4'-isomer content of less than about 15%. The second
component may optionally also consist essentially of a plasticizer
and/or a blend of plasticizers present in an amount sufficient to
impart a predetermined amount of flexibility.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0012] The method according to the present invention comprises the
step of applying a liquid material onto the substrate in an ambient
environment. It is to be understood that "ambient environment" as
used herein may be the environment wherever the substrate is
located and/or assembled, processed or otherwise manipulated, eg.
an automotive assembly factory, an aeronautical factory, a stamping
plant, etc.; and it is to be further understood that the present
method and composition will achieve the stated objects and
advantages in substantially any such "ambient environment."
However, it is preferred that the ambient temperature range between
about 35.degree. F. (1.7.degree. C.) and about 160.degree. F.
(71.1.degree. C.); it is more preferred that the ambient
temperature range between about 50.degree. F. (10.degree. C.) and
about 120.degree. F. (48.9.degree. C.); and it is most preferred
that the ambient temperature range between about 70.degree. F.
(21.1.degree. C.) and about 95.degree. F. (35.degree. C.). It is
preferred that the ambient pressure range between about 730 mm Hg
and about 800 mm Hg; however, it is more preferred that the ambient
pressure range between about 750 mm Hg and about 780 mm Hg.
[0013] After application to the substrate, the liquid material
cures substantially instantaneously on the substrate in the ambient
environment. The curing time of the present invention preferably
ranges between about 15 seconds and about 20 seconds, but can be as
low as 2 seconds or as high as 30 minutes while still within the
scope of the present invention and providing the advantages stated
herein.
[0014] It is to be understood that the substrate may comprise any
suitable substrate, including, but not limited to, metal stampings,
bodies in white either before or after application of primer
coat(s), carbon graphite composites, fiberglass, polycarbonates,
ABS, and any other structural polymeric materials. As used herein,
"body in white" is intended to mean a vehicle body assembled with
all paintable components thereon, but without trim work or any
other components which are not painted.
[0015] It is to be understood that the application step may
comprise any suitable application means such as, for example,
spraying, dipping, brushing, and it may be desired to utilize
suitable hoods, ventilation means, and/or standard paint style
spray booths. It is to be further understood that any of the
application means may be performed either manually and/or
automatically and/or robotically.
[0016] In a preferred embodiment, the application means is a
conventional two component spray system, accommodating the first
component and the second component of the composition of the
present invention. In a more preferred embodiment, the application
means is a high pressure, impingement mix spray system. One such
suitable spray system is commercially available from GUSMER
Corporation, and is described in a technical paper entitled, "The
Processing of Spray Polyurea Elastomer Systems," D. J. Primeaux II
and K. C. Anglin, 34th Annual Polyurethane Technical/Marketing
Conference, Oct. 21-24, 1992, pp. 598-604, which paper is
incorporated herein by reference.
[0017] The method of the present invention renders many advantages,
including, but not limited to, the elimination of a process step,
namely heating in order to cure the applied liquid material. Since
the material to be applied is liquid, it is relatively simple to
apply to the substrate. However, since it cures substantially
instantaneously, virtually none of the applied material comes off
to contaminate paint and/or the E-coat system. Further, since the
applied material does not need any further process steps in order
to cure, it may be applied at any point in the assembly process,
eg. from a metal stamping up to and including the body in white,
either before or after primer has been applied thereto. However, it
may be desirable in the present invention to apply the liquid
material after primer has been applied.
[0018] It is to be understood that the vibration(s) damped by the
method of the present invention may be audible (sound/noise)
vibrations, tactile vibrations, and/or non-tactile vibrations (eg.
"body boom"). However, the method and composition of the present
invention may be especially suitable for damping vibrations within
audible frequencies.
[0019] The composition according to the present invention is
suitable as a noise, vibration and/or harshness damping liquid
material. Broadly speaking, the inventive composition comprises a
first (eg. resin) component and a second (eg. isocyanate)
component. More particularly, the present inventive elastomer
systems may include the reaction product of, for example: an
amine-terminated polyether, or a hydroxy-terminated polyether, or
blends of the two as an active hydrogen containing material; and an
isocyanate compound to produce a polyurea, polyurethane or hybrid
elastomer.
[0020] The first component consists essentially of a polymer and/or
a blend of polymers present in an amount sufficient to impart,
through reaction with an appropriate isocyanate compound (from the
second component of the composition), a predetermined amount of
tensile strength, hardness and flexibility properties that are
required for a given application. These materials represent the
backbone of the composition. It is to be understood that any
suitable polymers may be used. However, in the preferred
embodiment, the polymers are selected from the group consisting of
polyoxypropylene diols, polyoxypropylene triols, polyester polyols
(di, tri, quad, penta, etc. functional), polyether polyols (di,
tri, quad, penta, etc. functional), and mixtures thereof.
[0021] The active amine hydrogen containing materials useful in the
present invention may be chosen from amine-terminated polyethers.
Preferably the amine-terminated polyethers are selected from
aminated diols or triols and, more preferably, may include a blend
of aminated diols and/or triols. More preferably, the
amine-terminated polyethers are selected from mixtures of high
molecular weight polyols, such as mixtures of di- and trifunctional
materials. However, a single high molecular weight aminated polyol
can be used. It is to be understood that high molecular weight
amine-terminated alkylenes and simple alkyl amines are also
included within the scope or this invention, and may be used alone
or in combination with the aforementioned amine-terminated polyols.
In addition, other amine-terminated materials having different
molecular weights or different chemical compositions may be
used.
[0022] Especially preferred are amine-terminated polyethers,
including primary and secondary amine-terminated polyethers of
greater than about 1,500 average molecular weight, having a
functionality of from about 2 to about 6, preferably from about 2
to about 3, and an amine equivalent weight of from about 750 to
about 4,000. Mixtures of amine-terminated polyethers may be used.
In a preferred embodiment, the amine-terminated polyethers have an
average molecular weight of at least about 2,000. These materials
may be made by various methods known in the art.
[0023] The amine-terminated polyethers useful in this invention may
be, for example, polyether resins made from an appropriate
initiator to which lower alkylene oxides, such as ethylene oxide,
propylene oxide, butylene oxide, or mixtures thereof, are added
with the resulting hydroxyl-terminated polyol then being aminated.
Wherein two or more oxides are used, they may be present as random
mixtures or as blocks of one or the other polyether. In the
amination step, it may be highly desirable that the terminal
hydroxyl groups in the polyol be essentially all secondary hydroxyl
groups for ease of amination. The polyols so prepared are then
reductively aminated by known techniques, such as, for example,
those described in U.S. Pat. No. 3,654,370, which is incorporated
herein by reference. Normally, the amination step does not
completely replace all of the hydroxyl groups. However, a majority
of hydroxyl groups are replaced by amine groups. In a preferred
embodiment, the amine-terminated polyether resins useful in this
invention have greater than about 90 percent of their active
hydrogens in the form of amine hydrogens.
[0024] It is to be understood that many high molecular weight
amine-terminated polyethers or simply polyether amines may be used
as the polymer and/or part of the polymer blend in the first
component of the composition of the present invention. Particularly
preferred are the JEFFAMINE.RTM. brand series of polyether amines
available from Huntsman Petrochemical Corporation in Houston, Tex.
This series includes JEFFAMINE.RTM. D-2000 (an amine-terminated
polyoxypropylene diol of 2000 molecular weight), JEFFAMINE.RTM.
D-4000, JEFFAMINE.RTM. T-3000 (an amine-terminated polyoxypropylene
triol of 3000 molecular weight) JEFFAMINE.RTM. T-5000 (an
amine-terminated polyoxypropylene triol of 5000 molecular weight),
JEFFAMINE.RTM. T-403 (an amine-terminated polyoxypropylene triol of
400 molecular weight), and JEFFAMINE.RTM. D-230 (an
amine-terminated polyoxypropylene diol of 230 molecular weight).
These polyetheramines are described with particularity in Huntsman
Corporation's product brochure entitled "The JEFFAMINE.RTM.
Polyoxyalkyleneamines." The JEFFAMINES are amine-terminated
polyoxypropylenes, the "D" designates a diamine, the "T" designates
a triamine, and the number extension designates the molecular
weight.
[0025] It is to be understood that the term "high molecular weight"
is intended to include polyether amines having a molecular weight
of at least about 1000. For the diamines, a suitable molecular
weight may range between about 1000 and about 4000. For the
triamines, a suitable molecular weight may range between about 2000
and about 6000.
[0026] Other polymer materials suitable for use in the first
component of the composition of the present invention include the
following. VORANOL 230-660 triol is a polyether polyol commercially
available from Dow Chemical Company in Midland, Michigan. VORANOL
230-660 has an average molecular weight of 250; a typical hydroxyl
number of 660; a functionality of 3; an average hydroxyl content of
20.0%; and a maximum water content of 0.05%. VORANOL 220-056 diol
is a polyether polyol commercially available from Dow Chemical
Company in Midland, Mich. VORANOL 220-056 has an average molecular
weight of 2000; a typical hydroxyl number of 56; a functionality of
2.0; an average hydroxyl content of 1.70%; and a maximum water
content of 0.06%. Ethylene glycol may successfully be used, as may
polypropylene glycol (PPG) having an average molecular weight of
about 2000. One suitable PPG-2000 product is commercially available
from Huntsman Corporation under the tradename JEFFOX.RTM. PPG-2000.
POLY-G 55-173 is a polyether diol commercially available from
Lyondell Chemical in Newtown Square, Pa. More specifically, POLY-G
55-173 is a hydroxyl terminated poly(oxyalkylene) polyol.
THANOL.RTM. SF-5505 is a 5500 molecular weight polyether triol
containing approximately 80% primary hydroxyl groups, and is
commercially available from Lyondell Chemical in Newtown Square,
Pa. 1,4-Butane diol may also be used; and one such suitable
compound is commercially available from Lyondell Chemical under the
tradename 1,4-BDO. BASF in Mount Olive, N.J. also supplies a
suitable 1,4-Butane diol.
[0027] It is to be understood that the polymer(s) of the first
component of the composition of the present invention may be
present in any amount sufficient to achieve desired degrees of the
characteristics mentioned hereinabove. These compounds contribute
to the amount of cross link density imparted to the composition, as
well as to the amount of rigidity or softness imparted to the
composition. However, in the preferred embodiment, these may
comprise between about 0 wt % and about 100 wt. % of the first
component of the composition. More preferably, these range between
about 20 wt % and about 80 wt. % of the first component of the
composition. In a preferred embodiment, the polymer or a blend of
the polymers may be present in an amount ranging between about 40
wt % and about 80 wt. % of the first component of the
composition.
[0028] The first component of the composition of the present
invention may further optionally comprise a chain extender and/or a
blend of chain extenders present in an amount sufficient to impart
a predetermined amount of tensile strength, weatherability,
flexibility, adhesion to specific substrates, and hardness to the
overall system. The chain extender(s) may also adjust the reaction
rates of the overall system. Suitable chain extenders are selected
from the group consisting of dialkyl substituted methylene
dianiline, diethyltoluene diamine, substituted toluene diamines,
and mixtures thereof. Other suitable chain extenders may include
amine terminated aliphatic chain extenders selected from (but not
limited to) the group consisting of cyclohexane diamine, isophorone
diamine, and mixtures thereof Other suitable chain extenders may
include low molecular weight glycol type chain extenders, such as
for example, 1,4-butane diol.
[0029] It is to be understood that any suitable chain extenders may
be used in the present invention. In the preferred embodiment,
DETDA (diethyltoluene diamine) is used. One such suitable material
is sold under the tradename ETHACURE.RTM. 100, which is a
diethyltoluene diamine chain extender commercially available from
Albemarle Corporation located in Baton Rouge, La. Another suitable
material is sold under the tradename ETHACURE.RTM. 300, which is a
di(methylthio) toluenediamine chain extender, also commercially
available from Albemarle Corporation located in Baton Rouge,
La.
[0030] Another preferred chain extender is UNILINK.RTM. 4200, which
is a dialkyl substituted methylene dianiline chain extender
commercially available from UOP Chemical Company located in Des
Plaines, Ill. It has been discovered in the present invention that
the addition of this dialkyl substituted methylene dianiline chain
extender to the DETDA provides advantageous and desirable increases
in tensile strength and flexibility while extending the system cure
times. This liquid secondary diamine based on methylene dianiline
is discussed in the technical paper entitled, "The Versatility of
UOP UNILINK and CLEARLINK Diamines in Polyurethane and Polyurea
Systems," David W. House, Ray V. Scott and John E. Wetherall, UTECH
Asia 1996 Conference papers, 16 pages (the substance of which is
also published by the same authors under the title, "The
Versatility of Secondary Diamines in Polyurethane and Polyurea
Systems," available from UOP Chemical Company located in Des
Plaines, Ill., pp. 1-13), which paper is incorporated herein by
reference. Another preferred chain extender is UNILINK.RTM. 4100,
which is a dialkyl substituted diaminobenzene chain extender
commercially available from UOP Chemical Company located in Des
Plaines, Ill. Another available chain extender is UNILINK 4300 (a
blend derived from UNILINK 4100 and UNLINK 4200), also from
UOP.
[0031] Further suitable chain extenders include AMP 95, AMP 75 and
AMP REGULAR, commercially available from Angus Chemicals located in
Buffalo Grove, Ill. These are difunctional products, having a
primary amine end group and a primary hydroxyl end group. These
impart extended cure times to the system, resulting in a slower
cure time, eg. between about 60 seconds and about 240 seconds.
[0032] It is to be understood that the chain extenders may be
present in any desired amounts sufficient to impart the
predetermined characteristics described hereinabove. In the
preferred embodiment, the chain extenders are present in an amount
ranging between about 0 wt. % and about 60 wt. %; more preferably
in an amount ranging between about 5 wt. % and about 50 wt. %, and
even more preferably in an amount ranging between about 20 wt. %
and about 30 wt. % of the first component of the composition.
[0033] The first component of the composition of the present
invention may further optionally consist essentially of a filler
and/or blend of fillers present in an amount sufficient to impart a
predetermined amount of hardness, flexibility, and specific noise,
vibration and harshness blocking characteristics to the
after-application, cured surface. In the past, the use of
filler(s)/filler systems in conventional polyurea amine (PUA) spray
systems had generally been considered bad practice and thus avoided
due in part to undesirable wear of metal components inside the
spray equipment used. However, it has been fortuitously and
unexpectedly discovered that wear on metal components inside the
spray equipment may successfully be minimized, if desired and/or
necessary. Without being bound to any theory, it is believed that
this undesirable wear is minimized if the filler has an acceptably
low hardness value and/or an acceptably small particle size.
[0034] It is to be understood that any fillers, filler systems,
reinforcing filler systems, or the like may be used in the present
invention, as desired, as long as such materials are suitable for
use in the present invention as described herein. Some suitable
fillers may include, but are not limited to, barium sulfate,
calcium carbonate, clay, talc, aluminum silicate, titanium dioxide,
nitrile rubber, butyl rubber, synthetic rubbers (eg. styrene
butadiene rubber (SBR) crumb rubber), chopped fiberglass,
Wollastonite (calcium metasilicate), KEVLAR (commercially available
from E.I. du Pont de Nemours Company), any suitable fibrous filler,
fumed silica (also can be used as a thixotrope), and mixtures
thereof
[0035] Barium sulfate is commercially available from many sources,
one of which is Hitox Corp. in Corpus Christi, Tex. under the
tradename BARTEX 10.
[0036] A suitable synthetic crumb rubber is commercially available
under the tradename 1006 CRUMB from Ameripol Synpol Corp. in Akron,
Ohio. Some properties of the 1006 CRUMB include the following. 1006
CRUMB is a light-colored polymer and is in free flowing crumb form
which eliminates the need for milling, cutting or grinding. The
crumb particles retain the porous nature of the coagulated rubber
and can be dissolved in a solvent faster than milled or pelletized
bale rubber. The crumb size, retained on 1/4" screen is 1.0% max;
and less than 16 mesh is 28.0% max.
[0037] One suitable fumed silica is commercially available under
the tradename CAB-O-SWL M-5 UNTREATED FUMED SILICA from Cabot
Corporation in Billerica, Mass. The CAB-O-SWL M-5 has a pH (4%
slurry) of 3.7-4.3; a 325 mesh residue (44 microns) of 0.02 max %;
a specific gravity of 2.2 g/cm.sup.3; an assay (% SiO.sub.2)
greater than 99.8; and an average particle (aggregate) length of
0.2-0.3 microns.
[0038] The fillers may increase impact resistance and tensile
strength. These compounds may also be used in the composition to
modify hardness, flexibility and to provide specific noise and
vibration blocking characteristics.
[0039] In the preferred embodiment, these filler(s) may range
between about 0 wt. % and about 40 wt. %, more preferably may range
between about 5 wt. % and about 25 wt. %, and even more preferably
may range between about 15 wt. % and about 20 wt. % of the first
component of the composition. In one preferred embodiment, the
filler, eg. calcium carbonate, may comprise about 10.0 wt. % of the
first component of the composition. In an alternate preferred
embodiment, the filler, eg. barium sulfate, may comprise about 20
wt. % of the first component of the composition.
[0040] The first component of the composition of the present
invention may further optionally consist essentially of any
suitable colorants, pigments, or the like, as desired. Some
non-limitative examples of such materials are selected from the
group consisting of carbon black, titanium dioxide, iron oxide (a
suitable iron oxide is commercially available under the tradename
RED OXIDE from Harcros Chemicals, Inc. in Kansas City, Kans.),
organic pigments and dyes, and mixtures thereof These compounds are
used primarily to impart a specific color to the composition.
However, in some instances, carbon black and titanium dioxide, for
example, may also affect the hardness of the system.
[0041] The first component of the composition may further
optionally consist essentially of a catalyst and/or a blend of
catalysts. These compounds are used to either increase or decrease
the inherent reaction rate of the resin:isocyanate system. In
systems where two or more polymers and chain extenders are used,
the catalyst(s) may also be used to promote a specific reaction
order.
[0042] Suitable catalysts are tertiary amines selected from the
group consisting of triethylamine, tributylamine,
N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine,
N,N,N',N'-tetramethylethylene diamine, and mixtures thereof Other
suitable catalysts are organometallic catalysts selected from the
group consisting of organic tin catalysts such as tin-(II) salts of
carboxylic acids (eg. tin-(II)-laurate), dialkyl tin salts of
carboxylic acids (eg. dibutyltindilaurate), and mixtures thereof.
It is to be understood that the organometallic catalysts may be
used alone or in combination with tertiary amines.
[0043] Other catalysts which would be suitable are known to those
skilled in the art. See, for example, Carl Hanser Verlag, Kunstoff
Handbuch, Volume VII, published by Vieweg and Hochtlen, Munich,
Germany, pp. 96-102 (1966), which is incorporated herein by
reference.
[0044] If catalyst(s) are used, it is preferred that it/they be
present in an amount ranging between about 0.001 wt % and about 10
wt % (based on the resin component); and more preferably between
about 0.05 wt % and about 1 wt % (based on the resin
component).
[0045] Water may be used as a blowing agent in the foaming of the
polyurea elastomer of the present invention. More specifically, it
is believed that the water reacts with the isocyanate employed in
the second component to produce an amine and carbon dioxide. The
CO.sub.2 liberated in the foregoing reaction is what "blows" the
foam. This is described more fully in U.S. Pat. No. 5,153,232
(mentioned hereinbelow). Blowing catalysts, such as those described
below, are employed to promote or enhance the reaction.
[0046] The amount of water used in the first component of the
system, based on total weight of the first component, typically
ranges from about 1 wt. % to about 8 wt. %. Preferably, the amount
of water ranges from about 1 to about 4 wt. %. The catalysts used
to promote the reaction described above are ones known to those
skilled in the art. Particularly preferred are tertiary amine
catalysts. Some suitable catalysts are 2,2'-dimorpholinediethyl
ether, N,N,N'-trimethyl-N'-hydroxyethyl-bisamino- ethyl ether, and
mixtures thereof Another suitable catalyst is commercially
available under the tradename NIAX CATALYST A-1 from OSi
Specialties, Inc. in Danbury, Conn. This is a tertiary amine/glycol
mixture which is a clear, colorless liquid having an amine odor; is
completely soluble in water; has a boiling point (at 760 mm Hg) of
190.degree. C. (374.degree. F.); and a density of 0.902. NIAX
CATALYST A-1 imparts a faster blowing and cure time to the
system.
[0047] A cell stabilizer or surfactant may optionally be added to
the first component to provide cell stabilization. Particular foam
stabilizers are those described in U.S. Pat. No. 4,907,705, which
is incorporated herein by reference. These surfactants are
generally polysiloxane polyether block copolymers. Generally, the
surfactant is employed in an amount of between about 0.5 wt. % and
about 2.5 wt. % (based on the first component), and more preferably
between about 0.5 wt. % and about 0.75 wt. % (based on the first
component). When the cell stabilizer/surfactant is introduced into
the first component of the composition of the present invention, a
substantially closed cell polyurea foamed elastomer is formed. The
water or blowing agent is added to produce a foamed system with
approximately a 25-35 pound per cubic foot density.
[0048] The first component of the composition may further
optionally consist essentially of an adhesion promoter and/or a
blend of adhesion promoters. These compounds may be used to promote
the adhesion of the inventive spray system to a specific type of
substrate. In a preferred embodiment, adhesion to untreated,
E-Coated or painted metal may be greatly improved by the addition
of between about 0 pbw (parts by weight) and about 0.25 pbw of an
organosilane compound, preferably between about 0.05 pbw and about
0.25 pbw of an organosilane compound; and more preferably between
about 0.01 pbw and about 0.15 pbw of an organosilane compound such
as, for example, epoxy silane compounds, to the first component of
the composition.
[0049] One such suitable adhesion promoting material is
commercially available under the tradename SILQUEST A-1 87 SILANE
from OSi Specialties, Inc. in Danbury, Conn. This is a
gamma-glycidoxypropyl-trime- thoxysilane which is a clear, pale
liquid having an ester odor; reacts slowly in water; has a boiling
point (at 760 mm Hg) of 290.degree. C. (554.degree. F.); and a
density of 1.069.
[0050] Other examples of suitable adhesion promoters include amino
alkoxy silanes and vinyl alkoxy silanes, such as those described in
U.S. Pat. No. 5,731,397, which is incorporated herein by
reference.
[0051] The second component of the composition of the present
invention may consist essentially of isocyanates. It is to be
understood that any suitable isocyanates may be used. Both aromatic
and aliphatic isocyanates can be used in the present invention. The
aliphatic isocyanates employed in the present invention are those
known to one skilled in the polyurea elastomer art. Thus, for
instance, the aliphatic isocyanates may be of the type described in
U.S. Pat. No. 5,162,388, which is incorporated herein by reference.
Accordingly, they are typically aliphatic diisocyanates and, more
particularly, are the bifunctional monomer of the tetraalkyl xylene
diisocyanate, such as the tetramethyl xylene diisocyanate, or the
trimerized or the biuret form of an aliphatic diisocyanate, such as
hexamethylene diisocyanate. Also, cylcohexane diisocyanate and
isophorone diisocyanate are considered preferred aliphatic
isocyanates. Other useful aliphatic polyisocyanates are described
in U.S. Pat. No. 4,705,814, which is incorporated herein by
reference. It is to be understood that the aforementioned
isocyanates may be used alone or in combination.
[0052] A wide variety of aromatic polyisocyanates may also be
utilized to produce the polyurea elastomer of the present
invention. Typical aromatic polyisocyanates include p-phenylene
diisocyanate, polymethylene polyphenyl-isocyanate, 2,6-toluene
diisocyanate, 2,4-toluene diisocyanate,
naphthalene-1,4-diisocyanate, bis-(4-isocyanatophenyl)-meth- ane,
and bis-(3-methyl-4-isocyanatophenyl)methane. Other aromatic
isocyanates used in the practice of this invention are
methylene-bridged polyphenyl polyisocyanate mixtures, which have
functionalities of from about 2 to about 4. These aromatic
isocyanates are described in the literature and in many patents,
for example, U.S. Pat. Nos. 2,683,730; 2,950,263; 3,012,008;
3,344,162; and 3,362,979, all of which are incorporated herein by
reference.
[0053] Usually methylene-bridged polyphenyl polyisocyanate mixtures
contain from about 20 wt % to about 100 wt % methylene diphenyl
diisocyanate isomers, with the remainder being polymethylene
polyphenyl diisocyanate having higher fuinctionalities and higher
molecular weights. Typical of these are polyphenyl polyisocyanate
mixtures containing from about 20 wt % to about 100 wt %
diphenyldiisocyanate isomers, of which from about 20 wt % to about
95 wt % thereof is the 4,4'-isomer, with the remainder being
polymethylene polyphenyl polyisocyanates of higher molecular weight
and functionality that have an average functionality of from about
2.1 to about 3.5. These isocyanate mixtures are known, commercially
available materials, and may be prepared by the process described
in U.S. Pat. No. 3,362,979.
[0054] By far the most preferred aromatic polyisocyanate is
methylene bis(4-phenylisocyanate) or "MDI." Pure MDI,
quasi-prepolymers of MDI, and modified pure MDI, etc., are useful.
Materials of this type may be used to prepare suitable elastomers.
Since pure MDI is a solid and, thus, inconvenient to use, liquid
products based on MDI are also disclosed as suitable for use in the
present invention. For example, U.S. Pat. No. 3,394,164, which is
incorporated herein by reference, describes a liquid MDI product.
More generally, uretonimine modified pure MDI is also included.
This product is made by heating pure distilled MDI in the presence
of a catalyst. Examples of commercial materials of this type are
ISONATE.RTM. 125M (pure MDI), ISONATE.RTM. 2143L (a liquid
uretonimine-modified methylenediisocyanate product), RUBINATE.RTM.
1680 (a liquid uretonimine-modified methylenediisocyanate product),
RUBINATE.RTM. 1209, RUBINATE.RTM. 9009 (an aromatic isocyanate
quasi-prepolymer), RUBINATE.RTM. 9015 (an aromatic isocyanate
quasi-prepolymer), and RUBINATE.RTM. M ("liquid" MDI's). The
ISONATE.RTM. products are available from Dow Chemical Co. in
Midland, Mich., and the RUBINATE.RTM. products are available from
ICI Polyurethanes located in West Deppford, N.J. Preferably, the
amount of isocyanate used to produce the present polyurea
elastomers is equal to or greater than the stoichiometric amount
based on the active hydrogen ingredients in the formulation.
[0055] It is understood that the term "isocyanate" also includes
quasi-prepolymers of isocyanates with active hydrogen-containing
materials. The active hydrogen-containing materials used to prepare
a prepolymer can include a polyol or a high molecular weight
amine-terminated polyether, also described herein as amine
terminated alkylenes, or a combination of these materials. The
amine-terminated polyethers useful in preparing quasi-prepolymers
of isocyanates include the same amine-terminated polyethers
described hereinabove as amine-terminated materials for producing
polyureas.
[0056] The polyols useful in preparing a quasi-prepolymer include
polyether polyols, polyester diols, triols, etc., having an
equivalent weight of at least 500, and preferably of at least about
1,000 to about 5,000. Those polyether polyols based on trihydric
initiators of about 4,000 molecular weight and above are especially
preferred. The polyethers may be prepared from ethylene oxide,
propylene oxide, butylene oxide or a mixture of propylene oxide,
butylene oxide and/or ethylene oxide. Other high molecular weight
polyols that may be useful in this invention are polyesters of
hydroxyl-terminated rubbers, e.g., hydroxyl terminated
polybutadiene. Quasi-prepolymers prepared from hydroxyl-terminated
polyols and isocyanates are generally reserved for use with
aromatic polyurea elastomer systems.
[0057] These same polyols may also be employed as the active
hydrogen containing material for preparation of the elastomer
system. The polyols may also be blended with the amine-terminated
resins described previously.
[0058] The ratio of equivalents of isocyanate groups in the
polyisocyanate to the active hydrogens, preferably amine hydrogens,
is in the range of about 0.95:1 to about 2.00:1; with about 1.00:1
to about 1.50:1 being preferred; and about 1.05:1 to about 1.30:1
being most preferred. This ratio is sometimes referred to as the
isocyanate INDEX and is expressed as a percentage of excess
isocyanate. The isocyanate INDEX compares the total isocyanate with
the total active hydrogen in the reactant compounds.
[0059] In the present invention, a preferred isocyanate is an
isocyanate quasi-prepolymer based on a uretonimine modified
methylene diisocyanate (MDI) and a high molecular weight polyether
polyol having an isocyanate content of about 15.8% and a
2,4'-isomer content of less than about 10%. One such suitable
isocyanate quasi-prepolymer is RUBINATE.RTM. 9009, mentioned
hereinabove. Other suitable isocyanate compounds include the
following. MONDUR.RTM. ML, which is a liquid uretonimine-modified
methylenediisocyanate product, is commercially available from Bayer
Corporation in Pittsburgh, Pa. MONDUR.RTM. 1437, also commercially
available from Bayer, is an aromatic isocyanate quasi-prepolymer.
VESTANAT.RTM. IPDI is an isophorone diisocyanate commercially
available from Creanova Spezialchemie GmbH, a Hutls Group Co. in
Marl, Germany. m-TMXDI.RTM. is an M-tetramethylxylene diisocyanate
commercially available from Cytec Industries in West Paterson,
N.J.
[0060] The second component of the composition of the present
invention may also optionally consist essentially of a plasticizer
and/or a blend of plasticizers. It is to be understood that any
suitable plasticizer(s) may be used in conjunction with the present
invention. U.S. Pat. No. 5,442,034, which is incorporated herein by
reference, teaches that alkylene carbonates may be incorporated in
the isocyanate quasi-prepolymer for improved mixing characteristics
of the polyurea elastomer system. The preferred alkylene carbonates
include ethylene carbonate, propylene carbonate, butylene carbonate
and dimethyl carbonate, or mixtures thereof. In the preferred
embodiment, JEFFSOL.TM. PC is used, which is a propylene carbonate
commercially available from Huntsman Petrochemical Corporation
located in Houston, Tex.
[0061] It is to be understood that the plasticizer may be present
in an amount sufficient to impart a predetermined amount of
flexibility and improved mixing characteristics. In the preferred
embodiment, this plasticizer ranges between about 0 wt. % and about
40 wt. %; and more preferably ranges between about 5 wt. % and
about 30 wt. % of the second component of the composition. In a
more preferred embodiment, this plasticizer comprises between about
5.0% and about 10% of the second component of the composition.
[0062] The amine terminated polyethers, isocyanates, and chain
extenders that may be used in accordance with the present invention
are those known in the polyurea art as described in U.S. Pat. Nos.
4,891,086; 5,013,813; 5,082,917; 5,153,232; 5,162,388; 5,171,819;
5,189,075; 5,218,005; 5,266,671; 5,317,076; and 5,442,034, all of
which are incorporated herein by reference.
[0063] The compositions of the present invention may be easily
applied in liquid form by any suitable application means onto a
substrate, such means including, but not limited to spraying,
dipping, and/or brushing. Although these compositions
advantageously do not substantially emit volatile organic
materials, it may be desirable to utilize suitable hoods,
ventilation means, and/or standard paint style spray booths. It is
to be further understood that any of the application means may be
performed either manually and/or automatically and/or
robotically.
[0064] In a preferred embodiment, the application means is a
conventional two component spray system, accommodating the first
component and the second component of the composition of the
present invention. In a more preferred embodiment, the application
means is a high pressure, impingement mix spray system. One such
suitable spray system is commercially available from GUSMER
Corporation, as described hereinabove. The first and second
components are delivered from separate chambers of a proportioning
unit and are impacted or impinged upon each other to effectuate and
initiate mixing of the components. This forms the elastomer system,
which is then coated onto the desired substrate via a spray
gun.
[0065] Heretofore, traditional spray polyurea amine (PUA) systems
have been used primarily as a protective coating membrane, and have
been more suited toward a field applied application rather than an
in-house application. As such, traditional PUA systems had not been
used in, for example, the automotive industry, as a noise,
vibration and/or harshness damping liquid material. It is believed
that the reasons for this are several. The PUA chemistry is an
art/field quite diverse from industries seeking to improve upon NVH
characteristics. Further, these industries have believed that,
unless moldings and/or pads were used, a thermosetting system cured
in E-Coat ovens was the only effective way to achieve necessary
and/or desired NVH properties (however, the present inventive
disclosure has shown the contrary). However, as mentioned above,
liquid systems that rely on the E-Coat ovens to effect a cure are
prone to causing contamination in the E-Coat dip tanks; and the
moldings/pads have the drawbacks mentioned above.
[0066] It is believed that a further reason why traditional spray
polyurea systems had not heretofore been used for NVH attenuation
is the relative high cost (as compared to traditional materials
used for NVH attenuation) of the traditional spray polyurea amine
raw materials. As such, manufacturers may have believed (if spray
polyurea systems had come to their attention at all) that the use
of such polyurea spray systems was cost prohibitive. However, it
has been unexpectedly and fortuitously discovered that this may
simply be a "perceived" higher cost. Due to the many advantages of
the process and composition of the present invention (eg. no
heating or other specialized process steps required; very little
time required in the assembly process; substantially no
contamination of the vehicle paint or E-coat system; and may be
used at any point in the assembly or pre-assembly process), the
manufacturer may not spend any more with the process of the present
invention than with conventionally used NVH attenuating
materials/processes. In fact, due to the many enumerated
advantages, the manufacturer may actually save money with the
process of the present invention than with conventionally used NVH
attenuating materials/processes.
[0067] It is further believed that the use of one or more of the
fillers mentioned hereinabove which may effectively block NVH
transmission, taken in conjunction with the above-enumerated
advantages, may bring the perceived higher cost of the inventive
PUA raw materials down, while at the same time providing the same
or better NVH attenuation than do materials traditionally used for
NVH attenuation (eg. moldings and/or pads; sprayed epoxy or water
born plastisols in liquid form; and the like).
[0068] The present invention has successfully and advantageously
improved upon PUA technology, and, in the preferred embodiment, has
combined this with a robotic application and with improved spray
equipment capable of producing tight, well defined spray patterns
to produce substrates having adequate and/or improved NVH
characteristics (as compared to materials traditionally used for
NVH attenuation).
[0069] To further illustrate the present invention, the following
examples are given. It is to be understood that these examples are
provided for illustrative purposes and are not to be construed as
limiting the scope of the present invention.
EXAMPLE I
[0070] A composition according to the present invention was made in
the following manner. The following compounds in the stated weight
percentages were admixed to form the first component:
1 JEFFAMINE D-2000 SILQUEST A-187 58.4 pbw 0.8 pbw TITANIUM DIOXIDE
ETHACURE 100 1.0 pbw 21.9 pbw BARIUM SULFATE 19.7 pbw
[0071] The resultant composition was a liquid material under
ambient conditions and had a viscosity suitable for spraying
processes.
[0072] The second component of the composition of the present
invention comprised a liquid isocyanate composition comprised of 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and had a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE II
[0073] A composition as prepared in Example I was placed in a
suitable two component spraying device, the first component being
placed in a first suitable vessel, and the second component being
placed in a second suitable vessel. An automotive body in white is
sprayed with the two component liquid composition. After
application, the applied liquid composition cures on the body in a
time interval between about 15 seconds and 20 seconds. After
curing, the composition leaves a substantially smooth finish on the
body in white. The automotive body in white having the cured
composition thereon exhibits enhanced damping of noise, vibration
and harshness, including vibrations both within and outside of the
audible frequencies.
EXAMPLE III
[0074] A composition as prepared in Example I is placed in a
suitable two component spraying device, the first component being
placed in a first suitable vessel, and the second component being
placed in a second suitable vessel. A metal stamping is sprayed
with the two component liquid composition. After application, the
applied liquid composition cures on the stamping in a time interval
between about 15 seconds and 20 seconds. After curing, the
composition leaves a substantially smooth finish on the metal
stamping. The metal stamping exhibits enhanced damping of noise,
vibration and harshness, including vibrations both within and
outside of the audible frequencies.
EXAMPLE IV
[0075] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
2 JEFFAMINE D-2000 ETHACURE 100 70 pbw 30 pbw
[0076] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0077] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE V
[0078] A composition according to the present invention was made in
the following manner. The following compounds in the stated weight
percentages were admixed to form the first component:
3 Weight % JEFFAMINE D-2000 48.0 JEFFAMINE T-5000 25.0 ETHACURE 100
25.2 Titanium Dioxide 1.0 SILQUEST A-187 0.8 100.0
[0079] The resultant composition was a liquid material under
ambient conditions and had a viscosity suitable for spraying
processes.
[0080] The second component of the composition of the present
invention comprised a liquid isocyanate composition comprised of 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and had a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE VI
[0081] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
4 Weight % JEFFAMINE D-2000 20.5 JEFFAMINE T-5000 22.0 ETHACURE 100
24.5 UNILINK 4200 12.2 Calcium Carbonate 20.0 SILQUEST A-187 0.8
100.0
[0082] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0083] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE VII
[0084] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
5 Weight % JEFFAMINE D-2000 30.0 VORANOL 230-660 25.0 ETHACURE 100
43.2 Titanium Dioxide 1.0 SILQUEST A-187 0.8 100.0
[0085] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0086] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 100
wt. % RUBINATE 9009, and has a viscosity under ambient conditions
suitable for spraying processes.
EXAMPLE VIII
[0087] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
6 Weight % JEFFAMINE D-2000 53.2 ETHACURE 300 25.0 SBR Crumb Rubber
5.0 Barium Sulfate 15.0 Titanium Dioxide 1.0 SILQUEST A-187 0.8
100.0
[0088] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0089] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE IX
[0090] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
7 Weight % JEFFAMINE D-2000 40.0 JEFFAMINE T-5000 15.8 UNILINK 4300
25.2 Barium Sulfate 18.0 NIAX A-1 1.0 100.0
[0091] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0092] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 100
wt. % RUBINATE 9009, and has a viscosity under ambient conditions
suitable for spraying processes.
EXAMPLE X
[0093] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
8 Weight % JEFFAMINE T-5000 62.0 Ethylene Glycol 10.0 PPG 2000 15.2
Barium Sulfate 12.0 SILQUEST A-187 0.8 100.0
[0094] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0095] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 100
wt. % RUBINATE M, and has a viscosity under ambient conditions
suitable for spraying processes.
EXAMPLE XI
[0096] A composition according to the present invention was made in
the following manner. The following compounds in the stated weight
percentages were admixed to form the first component:
9 Weight % JEFFAMINE D-2000 55.0 ETHACURE 100 23.2 Barium Sulfate
15.0 Fumed Silica 5.0 Titanium Dioxide 1.0 SILQUEST A-187 0.8
100.0
[0097] The resultant composition was a liquid material under
ambient conditions and had a viscosity suitable for spraying
processes.
[0098] The second component of the composition of the present
invention comprised a liquid isocyanate composition comprised of 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and had a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE XII
[0099] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
10 Weight % JEFFAMINE D-2000 69.2 ETHACURE 100 30.0 SILQUEST A-187
0.8 100.0
[0100] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0101] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE XIII
[0102] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
11 Weight % JEFFAMINE D-2000 57.0 OLIN POLY G 55-173 12.9 ETHACURE
300 15.0 Water 0.3 Barium Sulfate 10.0 Titanium Dioxide 1.0 Red
Oxide 3.0 SILQUEST A-187 0.8 100.0
[0103] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0104] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
EXAMPLE XIV
[0105] A composition according to the present invention is made in
the following manner. The following compounds in the stated weight
percentages are admixed to form the first component of the
composition of the present invention.
12 pbw JEFFAMINE D-2000 20.5 JEFFAMINE T-5000 22.0 ETHACURE 100
24.5 UNILINK 4200 12.5 CALCIUM CARBONATE 19.5
[0106] The resultant composition is a liquid material under ambient
conditions and has a viscosity suitable for spraying processes.
[0107] The second component of the composition of the present
invention comprises a liquid isocyanate composition comprising 95
wt. % RUBINATE 9009 and 5.0 wt. % JEFFSOL PC, and has a viscosity
under ambient conditions suitable for spraying processes.
[0108] While preferred embodiments of the invention have been
described in detail, it will be apparent to those skilled in the
art that the disclosed embodiments may be modified. Therefore, the
foregoing description is to be considered exemplary rather than
limiting, and the true scope of the invention is that defined in
the following claims.
* * * * *