U.S. patent application number 16/705394 was filed with the patent office on 2020-06-11 for bis-primary amines as cross-linkers for the curing of acetoacetylated resin compositions.
This patent application is currently assigned to Eastman Chemical Company. The applicant listed for this patent is Eastman Chemical Company. Invention is credited to Nick Allen Collins, Leslie Shane Moody, Robert Jacks Sharpe.
Application Number | 20200181338 16/705394 |
Document ID | / |
Family ID | 69006074 |
Filed Date | 2020-06-11 |
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United States Patent
Application |
20200181338 |
Kind Code |
A1 |
Collins; Nick Allen ; et
al. |
June 11, 2020 |
BIS-PRIMARY AMINES AS CROSS-LINKERS FOR THE CURING OF
ACETOACETYLATED RESIN COMPOSITIONS
Abstract
This invention provides a composition comprising I. a first
component comprising at least one resin having two or more
functional groups selected from the group consisting of
.beta.-ketoester and malonate functional groups, and II. a second
component having at least one or at least two primary amine
functional groups.
Inventors: |
Collins; Nick Allen; (Fall
Branch, TN) ; Sharpe; Robert Jacks; (Johnson City,
TN) ; Moody; Leslie Shane; (Johnson City,
TN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Eastman Chemical Company |
Kingsport |
TN |
US |
|
|
Assignee: |
Eastman Chemical Company
Kingsport
TN
|
Family ID: |
69006074 |
Appl. No.: |
16/705394 |
Filed: |
December 6, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62777876 |
Dec 11, 2018 |
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62777865 |
Dec 11, 2018 |
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62777871 |
Dec 11, 2018 |
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62900939 |
Sep 16, 2019 |
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62916503 |
Oct 17, 2019 |
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62777880 |
Dec 11, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 2323/06 20130101;
C09D 175/08 20130101; C08G 63/005 20130101; C08K 5/18 20130101;
C08J 5/18 20130101; C09J 167/03 20130101; C08G 63/87 20130101; C09J
167/02 20130101; C09D 167/02 20130101; C08J 7/043 20200101; C08K
5/0066 20130101; C09D 161/20 20130101; C08J 2367/02 20130101; C08K
5/07 20130101; C09J 2461/00 20130101; C08G 63/12 20130101; C08K
3/013 20180101; C09D 7/65 20180101; C09D 167/00 20130101; C08J
2323/12 20130101; C09J 171/00 20130101; C09D 7/20 20180101; C08G
12/00 20130101; C08K 5/3462 20130101; C08J 3/24 20130101; C08K
5/0016 20130101; C08K 5/0025 20130101; C09J 11/08 20130101; C08G
63/914 20130101; C08G 63/916 20130101; C09J 5/00 20130101; C08L
67/03 20130101; C08K 5/005 20130101; C09J 161/20 20130101; C09J
2467/00 20130101 |
International
Class: |
C08J 3/24 20060101
C08J003/24; C08G 63/91 20060101 C08G063/91; C09J 167/02 20060101
C09J167/02; C09D 167/02 20060101 C09D167/02; C09J 5/00 20060101
C09J005/00 |
Claims
1. A composition comprising: I. a first component comprising at
least one amorphous or semi-crystalline polyester or polyether
having two or more functional groups selected from the group
consisting of .beta.-ketoester and malonate functional groups, and
II. a second component having at least one or at least two primary
amine functional groups.
2. The composition of claim 1, wherein said polyester is an
acetoacetate functional polyester comprising the residues of a. a
hydroxyl component comprising: i. a diol in an amount ranging from
60 to 100 mole %, based on the total moles of (i) and (ii) equaling
100 mole %; and ii. a polyol in an amount ranging from 0 to 40 mole
%, based on the total moles of (i) and (ii) equaling 100 mole %; b.
a carboxyl component comprising a polycarboxylic acid compound, a
derivative of polycarboxylic acid compound, or a combination
thereof; and c. an alkyl acetoacetate, a diketene, or a combination
thereof in an amount ranging from about 5 to about 65 weight %,
based on the total weight of (a), (b), and (c) equaling 100 weight
%.
3. The composition of claim 2, wherein the diol component (a)(i) is
selected from the group consisting of 2,2-dimethyl-1,3-propanediol,
2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate,
tricyclodecanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol,
and polyethylene glycol, or mixtures thereof.
4. The composition of claim 2, wherein the polyol component (a)(ii)
is selected from 1,1,1-trimethylol propane,
1,1,1-trimethylolethane, glycerin, sorbitol, and pentaerythritol or
mixtures thereof.
5. The composition of claim 2, wherein said carboxyl component (b)
is selected from the group consisting of adipic acid, isophthalic
acid, dimethyl isophthalate, terephthalic acid, dimethyl
terephthalate, 1,4-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid or
tetrahydrophthalic anhydride, hexahydrophthalic acid or
hexahydrophthalic anhydride, maleic anhydride, succinic anhydride,
phthalic acid, and phthalic anhydride, or mixtures thereof.
6. The composition of claim 1 wherein said alkyl acetoacetate is
selected from t-butyl acetoacetate, methyl acetoacetate, ethyl
acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, and
n-butyl acetoacetate or mixtures thereof.
7. The composition of claim 1 wherein said polyester has a glass
transition temperature (Tg) of about -75.degree. C. to about
50.degree. C.
8. The composition of claim 1 containing essentially no volatile
solvents.
9. The composition of claim 1 comprising one or more organic
solvents.
10. The composition of claim 1 wherein at least one said amine is
selected from aliphatic, cycloaliphatic, aromatic-aliphatic, or
aromatic primary amines.
11. The composition of claim 1 wherein said at least one primary
amine is selected from C1-C20 alkyl or aryl amines or a mixture
thereof.
12. The composition of claim 1 wherein at least one primary amine
is selected from at least one of: ethylenediamine;
diethylenetriamine; triethylenetetramine; tetraethylenepentamine;
2,2,4-trimethylhexamethylenediamine;
2,4,4-trimethylhexamethylenediamine; 1,2-diaminopropane;
1,3-diaminopropane; 2,2-dimethylpropylenediamine;
1,4-diaminobutane; 2-methylpentamethylenediamine;
1,6-hexanediamine; 1,7-diaminoheptane; 1,8-diaminooctane;
1,9-diaminononane; 1,12-diaminododecane;
4-azaheptamethylenediamine;
N,N-bis(3-aminopropyl)butane-1,4-diamine;
N,N-bis(3-aminopropyl)ethylenediamine; 2,4-toluenediamine;
2,6-toluenediamine; 3,3'-iminobispropylamine;
1,2-diaminocyclohexane; 1,3-diaminocyclohexane;
1,4-diamino-2,5-diethylcyclohexane;
1,4-diamino-3,6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane;
1,2-diamino-4-cyclohexylcyclohexane; isophorone diamine;
norbornanediamine; 4,4'-diaminodicyclohexylmethane;
4,4'-diaminodicyclohexylethane; 4,4'-diaminodicyclohexylpropane;
2,2-bis(4-aminocyclohexyl)propane;
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane;
3-amino-1-(4-aminocyclohexyl)propane;
1,3-bis(aminomethyl)cyclohexane;1,4-bis(aminomethyl)cyclohexane;
1-cyclohexyl-3,4-diamino-cyclohexane; m-xylylenediamine and its
hydrogenation products; p-xylylenediamine and its hydrogenation
products; 4,4'-methylenedianiline; 2,4-bis(p-aminobenzyl)aniline;
diethyltoluenediamine; m-phenylenediamine, diphenylethylenediamine,
2,2,4,4-tetramethylcyclobutane-1,3-diamine,
2,2-dimethylpropane-1,3-diamine, 2,3-dimethylbutane-2,3-diamine,
1,2-diaminocyclopentane, 1,2,2-trimethylcyclopentane-1,3-diamine,
1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diamine,
4,4'-methylenebis[2-methylcyclohexanamine], and
polyetheramines.
13. The composition of claim 1 wherein said amine is selected from
the group consisting of triethylenetetramine, 1,6-hexanediamine,
2-methylpentamethylenediamine, isophorone diamine,
4,4'-methylenebis[2-methylcyclohexanamine], and
polyetheramines.
14. The composition of claim 1 wherein the equivalent ratio of the
acetoacetate (AcAc) functionality in the resin to the primary amine
functionality in the composition is from about 0.25 about 4.
15. The composition of claim 1 wherein the composition is prepared
by a process comprising: (a) mixing at least one component having
two or more .beta.-ketoester functional groups, and at least one
component having two or more primary amine functional groups, and
(b) after optional activation, curing the composition at 20.degree.
C. or higher in six days or less, and (c) optionally post-curing
the composition at or above 20.degree. C.
16. A composition according to claim 1 comprising at least one
additive selected from the group consisting of tackifiers,
plasticizers, fillers, pigments, stabilizers, antioxidants, waxes,
adhesion promoters, flame retardants, conductive agents, rheology
modifiers or mixtures thereof.
17. An adhesive, coating, or article of manufacture comprising the
composition of claim 1.
18. An article comprising a cured adhesive composition of claim 1
where the bond is maintained after cure and/or post-cure at
60.degree. C.
19. An article comprising said composition of claim 1 selected from
at least one of the following: an adhesive, a laminate, a tape, a
label, a tag, a radio frequency identification (RFID) tag, a
coating, a sealant, a flexible or non-flexible film, a foam, a
potting compound, a disposable hygiene article, a fiberglass
reinforced plastic, a composite, a compound, an assembly part, a
motor vehicle molded part, a motor vehicle extruded part, a motor
vehicle laminated part, a furniture part, fabric, a woven textile,
a nonwoven, a flexible packaging multilayer; wherein the adhesive
is selected from at least one of the following: automotive interior
adhesive, flexible laminating adhesive, rigid laminating adhesive,
assembly adhesive, labelling adhesive, nonwoven adhesive, tape
adhesive, structural adhesive, hygiene nonwoven construction
adhesive, hygiene elastic attachment adhesive, home repair
adhesive, industrial adhesive, construction adhesive, furniture
adhesive, medical adhesive, contact adhesive, hot melt adhesive,
solvent-based adhesive, packaging adhesive, product assembly
adhesive, woodworking adhesive, flooring adhesive, automotive
assembly adhesive, assembly part adhesive, structural adhesive,
pressure sensitive adhesive, pressure sensitive adhesive tape,
pressure sensitive adhesive label, pressure sensitive adhesive
protective film, laminating adhesive, packaging adhesive, flexible
film adhesive, flexible packaging adhesive, hygiene core integrity
adhesive, hygiene core integrity adhesive, and solvent-based
adhesives; wherein the composite is selected from at least one of a
polyester composite, a glass composite, or a wood-plastic
composite; and wherein said compound is selected from at least one
of an extruded compound, a polyacrylic blended compound, a potting
compound, a rubber compound, a sheet molding compound or a dough
molding compound.
20. The process of applying the adhesive of claim 1 to a substrate
and subsequently laminating to another substrate.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application Nos. 62/777,876, 62/777,865, 62/777,871, 62/777,880 all
filed Dec. 11, 2018; 62/900,939 filed Sep. 16, 2019; and 62/916,503
filed Oct. 17, 2019 under 35 U.S.C. .sctn. 119(e)(1); the entire
contents of the provisional applications are hereby incorporated by
reference.
FIELD OF THE INVENTION
[0002] The present invention relates to polyester compositions
having beta-ketoester group(s) arid primary amines, having improved
properties.
BACKGROUND OF THE INVENTION
[0003] Reactive compositions based on isocyanate crosslinkers are
widely used for coating and adhesive applications. Such systems are
curable at room temperature or low temperatures (e.g.
<100.degree. C.) and are capable of providing the desirable
properties for a variety of applications. However, there have been
increasing concerns associated with the production and the use of
isocyanate compounds and formulations based on isocyanates.
[0004] Compositions based on isocyanate crosslinkers frequently
require reaction with moisture to form the crosslinked composition.
If a solvent-based system is used due to application equipment or
other reasons, it is desirable that trace moisture in the solvent
will not initiate curing or crosslinking of the curable composition
and thus will not reduce the pot life of the curable
composition.
[0005] Commercially, it is desirable that the system does not:
generate by-products during curing that can be detrimental to film
formation or quality, have volatility, cause defects, have adhesion
failure, and/or have unpleasant odor.
[0006] In addition, there is a need in commerce for a system that
has a combination of two or more of the following properties:
isocyanate free, curable at low temperatures, and good adhesion to
substrates typically bonded or coated with isocyanate-containing
systems. It is also desirable to have a curable system that is
applied and cured below about 100.degree. C. while providing
suitable adhesion at service temperatures up to 130.degree. C.
[0007] Further, there is a need in the art for a commercial
adhesive or coating composition that has the desired level of
adhesion to the substrate to which it is applied and that also
adheres to many different substrates.
SUMMARY OF THE INVENTION
[0008] In view of the above commercial shortcomings in the art, the
present disclosure addresses the need for properties in curable
compositions including one or more of the following properties: (1)
a system that cures and that is isocyanate free, (2) curable at low
temperatures (e.g. <100.degree. C.), (3) suitable adhesion at
service temperatures up to 130.degree. C., (4) good adhesion to
substrates typically bonded or coated with isocyanate-containing
systems, (5) no Volatile Components, e.g., Volatile Organic
Components (VOCs), or has low Volatile Components, e.g., VOCs,
released before, during, and/or after curing, (6) does not generate
by-products during curing that can be detrimental to film formation
or bond quality, (7) reduces defects, (8) has more pleasant odor,
less odor, or is odorless, (9) can contain low or no moisture, (10)
can be used with moisture-impermeable substrates such as artificial
leather, (11) under certain conditions, can be a crosslinking
system, (12) can provide more controlled curing, (13) good thermal
stability and/or UV stability, (14) good chemical resistance, (15)
good mechanical properties, for example, tensile strength,
elongation at break, impact strength, and/or Young's modulus, (16)
good aging resistance or stability, (17) can provide improved green
strength, (18) can provide a usable working life for many
applications and/or (19) can provide longer pot life [in some
instances, the pot life can be extended by controlling the reaction
of the components (controlled cure)].
[0009] The compositions of this invention can provide desirable
properties for a variety of applications. In certain embodiments,
the compositions of this invention are suitable for applications in
the adhesives area, for example, automotive adhesives, structural
adhesives, wood adhesives, and laminating adhesives, and
applications in the coatings area, for example, automotive,
industrial maintenance, marine craft, field-applied coatings, and
furniture.
[0010] For the ease of reference but not intending to be limiting
in any way, certain aspects of this disclosure are numbered
consecutively, as follows:
[0011] In aspect 1 of this invention, there is provided a
composition comprising: Component (I) having at least one or at
least two or more functional groups selected from the group
consisting of .beta.-ketoester and malonate functional groups; and
Component (II) having at least one or at least two primary amine
functional groups.
[0012] In aspect 2 of the invention, there is provided the
composition of aspect 1 comprising: (I) a first component
[Component (I)] comprising at least one amorphous or
semi-crystalline polyester or at least one polyether having at
least one or at least two functional groups selected from the group
consisting of .beta.-ketoester and malonate functional groups, and
(II) a second component [Component (II)] comprising at least one or
at least two primary amine functional groups.
[0013] In aspect 3 of this invention, there is provided a
composition of aspects 1 or 2, wherein the polyester is an
acetoacetate functional polyester comprising the residues of
[0014] a. a hydroxyl component comprising: [0015] i. at least one
diol in an amount ranging from 50 to 100 mole %, based on the total
moles of (i) and (ii) equaling 100 mole %; and [0016] ii. at least
one polyol in an amount ranging from 0 to 50 mole %, based on the
total moles of (i) and (ii) equaling 100 mole %;
[0017] b. at least one carboxyl component comprising a
polycarboxylic acid compound, a derivative of a polycarboxylic acid
compound, or a combination thereof; and
[0018] c. at least one compound selected from an alkyl
acetoacetate, a diketene, or a combination thereof.
[0019] In aspect 4 of this invention, there is provided the
composition of aspect 2, wherein the residues of alkyl acetoacetate
or diketene are present in an amount ranging from about 5 to about
50 weight %, or from about 5 to about 40 weight %, or from about 10
to about 30 weight %, based on the total weight percentages of (a),
(b), and (c) equaling 100 weight %.
[0020] In aspect 5 of this invention, there is provided the
composition of aspect 4, wherein the residues of alkyl acetoacetate
or diketene is present in an amount ranging from about 15 to about
30 weight %.
[0021] In aspect 6 of this invention, there is provided a
composition of any one of aspects 3-5, wherein the diol component
(a)(i) is present in an amount ranging from about 35 to about 100,
or from about 30 to about 95, or from about 50 to about 95, or from
about 70 to 90, or from about 85 to about 95 mole % and the polyol
component (a)(ii) is present in an amount ranging from about 0 to
about 65, or from about 5 to about 70, or from about 5 to about 50,
or from about 10 to about 30, or from about 5 to about 15 mole %,
wherein the total mole % of (a)(i) and (a)(ii) equals 100 mole
%.
[0022] In aspect 7 of this invention, there is provided a
composition of any one of aspects 3-6, wherein the polyester is an
acetoacetate functional polyester comprising the residues of
[0023] a. a hydroxyl component comprising: [0024] i. at least one
diol in an amount ranging from 85 to 95 mole %, based on the total
moles of (i) and (ii); and [0025] ii. a polyol in an amount ranging
from 5 to 15 mole %, based on the total moles of (i) and (ii);
[0026] b. at least one carboxyl component comprising a
polycarboxylic acid compound, a derivative of polycarboxylic acid
compound, or a combination thereof; and
[0027] c. at least one compound selected from an alkyl
acetoacetate, a diketene, or a combination thereof in an amount
ranging from about 5 to about 50 weight %, based on the total
weight of (a), (b), and (c).
[0028] In aspect 8 of this invention, there is provided a
composition of any one of aspects 3-7, wherein the diol component
(a)(i) is selected from the group consisting of
2,2-dimethyl-1,3-propanediol (neopentyl glycol),
2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate,
2,2,4,4-tetramethylcyclobutane-1,3-diol, tricyclodecanedimethanol,
and polyethylene glycol, or mixtures thereof.
[0029] In aspect 9 of this invention, there is provided a
composition of any of aspects 3-8 wherein diol component (a)(i)
contains only oxygen, carbon, and hydrogen.
[0030] In aspect 10 of this invention, there is provided a
composition of any of aspects 3-9 wherein diol component (a)(i)
does not have any carbonyl groups (--CO--).
[0031] In aspect 11 of this invention, there is provided a
composition of any of aspects 3-10 wherein diol component (a)(i)
does not contain ether groups.
[0032] In aspect 12 of this invention, there is provided a
composition of any one of aspects 3-11, wherein at least one polyol
component (a)(ii) is selected from 1,1,1-trimethylol propane,
1,1,1-trimethylolethane, glycerin, sorbitol, and pentaerythritol or
mixtures thereof.
[0033] In aspect 13 of this invention, there is provided a
composition of any one of aspects 3-12, wherein at least one
carboxyl component (b) or all of carboxyl component (b) is selected
from the group consisting of adipic acid, isophthalic acid (or
dimethyl isophthalate), terephthalic acid,
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
tetrahydrophthalic acid or anhydride, hexahydrophthalic acid or
anhydride, maleic anhydride, succinic anhydride, phthalic acid, and
phthalic anhydride, or mixtures thereof.
[0034] In aspect 14 of this invention, there is provided a
composition of any one of aspects 3-13, wherein said alkyl
acetoacetate is selected from t-butyl acetoacetate, methyl
acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl
acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, t-amyl
acetoacetate, diisopropyl carbinol acetoacetate or mixtures
thereof.
[0035] In aspect 15 of this invention, there is provided a
composition of any one of aspects 1-14, wherein said polyester has
a glass transition temperature (Tg) of about -85.degree. C. to
about 60.degree. C.; or about -85.degree. C. to about 50.degree.
C.; or about to about 40.degree. C.; or about -85.degree. C. to
about 30.degree. C.; or about -85.degree. C. to about 20.degree.
C.; or about -85.degree. C. to about 10.degree. C.; or about
-85.degree. C. to about 0.degree. C.; or about -85.degree. C. to
about -10.degree. C.; or about -85.degree. C. to about -20.degree.
C.; or about -85.degree. C. to about -25.degree. C.; or about
-85.degree. C. to about 30.degree. C.; or about -85.degree. C. to
about 60.degree. C.; or about -85.degree. C. to about 50.degree.
C.; or about -85.degree. C. to about 40.degree. C.; or about
-85.degree. C. to about 30.degree. C.; or about -85.degree. C. to
about 20.degree. C.; or about -85.degree. C. to about 10.degree.
C.; or about -85.degree. C. to about 0.degree. C.; or about
-85.degree. C. to about -10.degree. C.; or about -85.degree. C. to
about -20.degree. C.; or about -85.degree. C. to about -25.degree.
C.; or about -85.degree. C. to about -30.degree. C.; or about to
about 60.degree. C.; or about -70.degree. C. to about 50.degree.
C.; or about -70.degree. C. to about 40.degree. C.; or about
-70.degree. C. to about 30.degree. C.; or about -70.degree. C. to
about 20.degree. C.; or about -70.degree. C. to about 10.degree.
C.; or about -70.degree. C. to about 0.degree. C.; or about
-70.degree. C. to about -10.degree. C.; or about -70.degree. C. to
about -20.degree. C.; or about -70.degree. C. to about -25.degree.
C.; or about -70.degree. C. to about -30.degree. C.; or about
-65.degree. C. to about 60.degree. C.; or about -65.degree. C. to
about 50.degree. C.; or about -65.degree. C. to about 40.degree.
C.; or about -65.degree. C. to about 30.degree. C.; or about
-65.degree. C. to about 25.degree. C.; or about -65.degree. C. to
about 20.degree. C. or about -65.degree. C. to about 10.degree. C.;
or about -65.degree. C. to about 0.degree. C.; or about -65.degree.
C. to about -10.degree. C.; or about -65.degree. C. to about
-20.degree. C.; or about -65.degree. C. to about -25.degree. C.; or
about -65.degree. C. to about -30.degree. C.; or about -45.degree.
C. to about 60.degree. C.; or about -45.degree. C. to about
50.degree. C.; or about -45.degree. C. to about 40.degree. C.; or
about -45.degree. C. to about 30.degree. C.; or about -45.degree.
C. to about 25.degree. C.; or about -45.degree. C. to about
20.degree. C. or about -45.degree. C. to about 10.degree. C.; or
about -45.degree. C. to about 0.degree. C.; or about -45.degree. C.
to about -10.degree. C.; or about -45.degree. C. to about
-20.degree. C.; or about -45.degree. C. to about -25.degree. C.; or
about -45.degree. C. to about -30.degree. C. As used herein, Tg
and/or melting point is determined using a Q2000 differential
scanning calorimeter (DSC) from TA Instruments, New Castle, Del.,
US, at a scan rate of 20.degree. C./min.
[0036] In aspect 16 of this invention, there is provided a
composition of any one of aspects 1-15 wherein said polyester has a
Tg of from about -85.degree. C. to about -10.degree. C.; or about
-70.degree. C. to about 50.degree. C.; or from about -65 to about
40.degree. C.; or from about -65.degree. C. to about 25.degree. C.;
or from about -10.degree. C. to about 50.degree. C.; or from about
-45.degree. C. to about -10.degree. C.; or from about -45.degree.
C. to about -25.degree. C.
[0037] In aspect 17 of this invention, there is provided a
composition of any one of aspects 1-16 which upon curing releases
essentially no volatile organic compounds; or no VOCs; or less than
5 weight %, less than 4 weight %, less than 3 weight %, less than 2
weight %, or less than 1 weight % VOCs; based on the total weight
of the composition.
[0038] In aspect 18 of this invention, there is provided a
composition of any one of aspects 1-17 where the curing agent
comprises an aliphatic, cycloaliphatic, or aromatic, di-, or
poly-amine or mixtures thereof.
[0039] In aspect 19 of this invention, there is provided a
composition of any one of aspects 1-18 wherein the primary amine
can be selected from at least one of: ethylenediamine;
diethylenetriamine; triethylenetetramine (TETA) or isomers thereof;
tetraethylenepentamine or isomers thereof;
2,2,4-trimethylhexamethylenediamine;
2,4,4-trimethylhexamethylenediamine; 1,2-diaminopropane;
1,3-diaminopropane; 2,2-dimethylpropylenediamine;
1,4-diaminobutane; 2-methylpentamethylenediamine (MPMDA);
1,6-hexanediamine; 1,7-diaminoheptane; 1,8-diaminooctane;
1,9-diaminononane; 1,12-diaminododecane;
4-azaheptamethylenediamine;
N,N-bis(3-aminopropyl)butane-1,4-diamine;
N,N-bis(3-aminopropyl)ethylenediamine; 2,4-toluenediarnine;
2,6-toluenediarnine; 3,3'-irninobispropylamine;
1,2-diaminocyclohexane; 1,3-diaminocyclohexane;
1,4-diamino-2,5-diethylcyclohexane;
1,4-diamino-3,6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane;
1,2-diamino-4-cyclohexylcyclohexane; isophorone diamine (IPDA);
norbornanediamine; 4,4'-diaminodicyclohexylmethane;
4,4'-diaminodicyclohexylethane; 4,4'-diaminodicyclohexylpropane;
2,2-bis(4-aminocyclohexyl)propane;
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane;
3-amino-1-(4-aminocyclohexyl)propane;
1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane;
1-cyclohexyl-3,4-diamino-cyclohexane; xylylenediamine and its
hydrogenation products; p-xylylenediamine and its hydrogenation
products; 4,4'-methylenedianiline; 2,4-bis(p-aminobenzyl)aniline;
diethyltoluenediamine; m-phenylenediamine; diphenylethylenediamine;
2,2,4,4-tetramethylcyclobutane-1,3-diamine;
2,2-dimethylpropane-1,3-diamine; 2,3-dimethylbutane-2,3-diamine;
1,2-diaminocyclopentane; 1,2,2-trimethylcyclopentane-1,3-diamine;
1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diamine;
4,4'-methylenebis[2-methylcyclohexanamine] (MACM); and
polyetheramines such as JEFFAMINE.RTM. D-230, D-400, D-2000, and
T-403 amines.
[0040] In aspect 20 of this invention, there is provided a
composition of any of aspects 1-19 wherein the amines can be
employed as their salts, including but not limited to their
carboxylate, phosphate, sulfate, and/or hydrochloride salts. The
salt of the amine can be prepared in situ by addition of the
corresponding acid and amine and/or it can be prepared separately
by prereacting amine and acid.
[0041] In aspect 21 of this invention, there is provided a
composition of any one of aspects 1-20 further comprising an adduct
having two or more .beta.-ketoacetate functional groups selected
from 2-methyl-1,3-propanediol diacetoacetate; neopentyl glycol
diacetoacetate; 2,2,4,4-tetramethylcyclobutane-1,3-diol
diacetoacetate; or trimethylolpropane triacetoacetate.
[0042] In aspect 22 of this invention, there is provided a
composition of any one of aspects 1-21 wherein the equivalent ratio
of the acetoacetate (AcAc) functional group of Component (I) to the
primary amine functional group in the composition [Component (II)]
is from about 0.25 about 4, or from about 0.5 to about 2, or from
about 0.7 to about 1.3, or from about 0.8 to about 1.2.
[0043] In aspect 23 of this invention, there is provided a curable
composition of aspects 1-22 wherein at least one wax or at least
one tackifies is pre-combined with at least one curing agent in
order to provide controlled cure profile (where the curing process
is controlled).
[0044] In aspect 24 of this invention, there is provided a
composition of any one of aspects 1-23 comprising at least one
additive selected from the group consisting of tackifiers,
plasticizers, fillers, pigments, stabilizers, antioxidants,
adhesion promoters, flame retardants, conductive agents, rheology
modifiers and mixtures thereof.
[0045] In aspect 25 of this invention, there is provided a
composition of any one of aspects 1-24 wherein the composition is
prepared by a process comprising: (a) mixing at least one component
having two or more .beta.-ketoester functional groups, and at least
one component having two or more primary amine functional groups,
and (b) after optional activation, curing the composition at
20.degree. C. or higher in six days or less, and (c) optionally,
post-curing the composition at or above 20.degree. C.
[0046] In aspect 26 of this invention, there is provided a
composition of any one of aspect 1-25, wherein the composition is
solventless or solvent free.
[0047] In aspect 27 of this invention, there is provided the
composition of any of aspects 1-26 wherein the composition is
substantially free of solvent or comprises essentially no
solvent.
[0048] In aspect 28 of this invention, there is provided a
composition of any one of aspects 1-25 comprising at least one
solvent.
[0049] In aspect 29 of this invention, there is provided the
composition of aspect 28 wherein the solvent borne composition
comprises organic solvents.
[0050] In aspect 30 of this invention, there is provided a
composition of aspect 29 comprising one or more organic solvents
selected from the group comprising acetone, ethanol, ethyl acetate,
butyl acetate, xylene, methyl amyl ketone, methyl ethyl ketone,
arid toluene.
[0051] In aspect 31 of this invention, there is provided the
composition of any of aspects 28-30 which does not contain solvents
or residues of solvents such as ethylene glycol and/or
ether-containing compounds, for example, dimethyl ether, ethylene
glycol diethyl ether, diethylene glycol dimethyl ether, or
diethylene glycol diethyl ether.
[0052] In aspect 32 of this invention, there is provided the
composition of any of aspects 1-31 wherein the composition can be
water-free, and/or moisture-free, and/or can comprise substantially
no water, and/or can contain essentially no water, or can contain
one of the following weight percentages of water: 0 to 20 weight %,
or 0 to 19 weight %, or 0 to 18 weight %, or 0 to 17 weight %, or 0
to 16 weight %, or 0 to 15 weight %, or 0 to 14 weight %, or 0 to
13 weight %, or 0 to 12 weight %, or 0 to 11 weight %, or 0 to 10
weight %, or 0 to 9 weight %, or 0 to 8 weight %, or 0 to 7 weight
%, or 0 to 6 weight %, or 0 to 5 weight %, or 0 to 4 weight %, or 0
to 3 weight %, or 0 to 2 weight %, or 0 to 1 weight %, or 0.01 to
20 weight %, or 0.01 to 19 weight %, or 0.01 to 18 weight %, or
0.01 to 17 weight %, or 0.01 to 16 weight %, or 0.01 to 15 weight
%, or 0.01 to 14 weight %, or 0.01 to 13 weight %, or 0.01 to 12
weight %, or 0.01 to 11 weight %, or 0.01 to 10 weight %, or 0.01
to 9 weight %, or 0.01 to 8 weight %, or 0.01 to 7 weight %, or
0.01 to 6 weight %, or 0.01 to 5 weight %, or 0.01 to 4 weight %,
or 0.01 to 3 weight %, or 0.01 to 2 weight %, or 0.01 to 1 weight
%, based on the total weight of the composition.
[0053] In aspect 33 of this invention, there is provided the
composition of any of aspects 1-32 wherein the composition is not a
water-borne or a water-dispersible composition.
[0054] In aspect 34 of this invention, there is provided the
composition of any of aspects 1-33 wherein the composition does not
contain: a polyvinyl alcohol, or a polyvinyl polymer, or a poly
vinyl acetate polymer.
[0055] In aspect 35 of this invention, there is provided the
composition of any of aspects 1-34 wherein the composition does not
contain neutralizing agents.
[0056] In aspect 36 of this invention, there is provided the
composition of any of aspects 1-35 wherein the composition of the
invention or the polyester resin of the invention has an acid
number (AN) of 0 to 15, 0 to 10, less than 10, 0 to 5, or less than
5 mg KOH/g with and/or without neutralizing agents.
[0057] In aspect 37, there is provided the composition of any of
aspects 1-36 wherein the acid number of the compositions of the
invention or of the polyester resin of the invention can be from 0
to about 14, or from 0 to about 13, or from 0 to about 12, or from
0 to about 11, or from 0 to about 10, or from 0 to about 9, or from
0 to about 8, or from 0 to about 7, or from 0 to about 6, or from 0
to 5 or from 0 to about 4, or from 0 to about 3, or from 0 to about
2, or from 0 to about 1, or from 0.01 to about 15, or from 0.01 to
about 14, or from 0.01 to about 13, or from 0.01 to about 12, or
from 0.01 to about 11, or from 0.01 to about 10, or from 0.01 to
about 9, or from 0.01 to about 8, or from 0.01 to about 7, or from
0.01 to about 6, or from 0.01 to 5 or from 0.01 to about 4, or from
0.01 to about 3, or from 0.01 to about 2, or from 0.01 to about 1,
or from 0.50 to about 15, or from 0.50 to about 14, or from 0.50 to
about 13, or from 0.50 to about 12, or from 0.50 to about 11, or
from 0.50 to about 10, or from 0.50 to about 9, or from 0.50 to
about 8, or from 0.50 to about 7, or from 0.50 to about 6, or from
0.50 to about 5, or from 0.50 to about 4, or from 0.50 to about 3,
or from 0.50 to about 2, or from 0.50 to about 1.5 mg KOH/g, with
or without addition of neutralizing agents.
[0058] In aspect 38 of this invention, there is provided the
composition of any of aspects 1-37 wherein the composition can have
any one of the acid numbers of aspects 36 or 35, where neutralizing
agents are not added to the composition after the polymerization
reaction. In aspects 35-36, neutralizing agents can be any
neutralizing agent known in the art. In the aspect of the invention
where neutralizing agents are excluded from the scope of this
invention, particularly where added after polymerization,
neutralizing agents can include but are not limited to primary
amines, secondary amines, tertiary amines, and ammonia as well as
any other neutralizing agent known in the art, for example, for
water dispersible or water dispersed microgel compositions.
[0059] In aspect 39 of this invention, there is provided the
composition of any of aspects 1-38 wherein the composition is
prepared by a process comprising: (a) mixing at least one component
having two or more primary amine functional groups, and at least
one ketone, and (b) converting some or all of the amine functional
groups to ketimine groups through reaction with the ketone, and (c)
mixing this product with at least one component having two or more
.beta.-ketoacetate functional groups.
[0060] In aspect 40 of this invention, there is provided the
composition of aspect 39 wherein the composition is prepared by a
process comprising: (a) mixing at least one component having two or
more primary amine functional groups, and at least one ketone, and
(b) converting some or all of the amine functional groups to
ketimine groups through reaction with the ketone, and (c) mixing
this product with at least one component having two or more
.beta.-ketoacetate functional groups, and (d) after optional
activation with heat and/or moisture, curing the composition at
20.degree. C. or higher in six days or less, and (e) optionally,
post-curing the composition at or above 20.degree. C.
[0061] In aspect 41 of this invention, there is provided the
composition of any of aspects 1-38 wherein the composition is
prepared by a process comprising: (a) mixing at least one component
having two or more primary amine functional groups, and at least
one aldehyde, and (b) converting some or all of the amine
functional groups to aldimine groups through reaction with the
aldehyde, and (c) mixing this product with at least one component
having two or more .beta.-ketoester functional groups.
[0062] In aspect 42 of this invention, there is provided the
composition of aspect 41 wherein the composition is prepared by a
process comprising: (a) mixing at least one component having two or
more primary amine functional groups, and at least one aldehyde,
and (b) converting some or all of the amine functional groups to
aldimine groups through reaction with the aldehyde, and (c) mixing
this product with at least one component having two or more
.beta.-ketoester functional groups, and (d) after optional
activation with heat and/or moisture, curing the composition at
20.degree. C. or higher in six days or less, and (e) optionally,
post-curing the composition at or above 20.degree. C.
[0063] In aspect 43, there is provided the composition of any of
aspects 41-42 wherein the composition can contain residues of
aldimine that may be incorporated into the composition during
curing.
[0064] In aspect 44 of this invention, there is provided the
composition of any of aspects 1-43 wherein the polyester resin of
the composition of the invention is not an alkyd polyester resin
and/or is not a polyester resin containing alkyd residues and/or
fatty acid residues.
[0065] In aspect 45 of this invention, there is provided the
composition of any of aspects 1-44 wherein the composition of the
invention is not a thermosetting composition.
[0066] In aspect 46 of this invention, there is provided the
composition of any of aspects 1-45 wherein the composition of this
invention does not contain polysaccharides and/or oxidized
polysaccharides having aldehyde groups.
[0067] In aspect 47 of this invention, acrylates are not blended
with the acetoacetylated polyester resins of any of aspects 1-46 of
the invention.
[0068] In aspect 48 of this invention, acrylates are not included
within the compositions and/or adhesives and/or articles of any of
aspects 1-47 of the invention.
[0069] In aspect 49 of this invention, there is provided the
composition of any of aspects 1-48 wherein the composition is
curable (capable of curing).
[0070] In aspect 50 of this invention, there is provided the
composition of any of aspects 1-49 wherein curing of the
composition occurs.
[0071] In aspect 51 of this invention, there is provided the
composition of any of aspects 1-50 that can be cured at low
temperatures (e.g. <80.degree. C.).
[0072] In aspect 52 of this invention, there is provided the
composition of any of aspects 1-51 that can be cured at room
temperature, or 10.degree. C. to 30.degree. C. or to 130.degree.
C., or 20.degree. C. to 120.degree. C. or 20.degree. C. to
115.degree. C., or 20.degree. C. to 110.degree. C., or 20.degree.
C. to 105.degree. C., or 20.degree. C. to 100.degree. C., or
20.degree. C. to 90.degree. C., or 20.degree. C. to 80.degree. C.,
or 20.degree. C. to 70.degree. C., or 30.degree. C. to 130.degree.
C., or 30.degree. C. to 120.degree. C., or 30.degree. C. to
115.degree. C., or 30.degree. C. to 110.degree. C., or 30.degree.
C. to 105.degree. C., or 30.degree. C. to 100.degree. C., or
30.degree. C. to 90.degree. C., or 30.degree. C. to 80.degree. C.,
or 30.degree. C. to 70.degree. C., or 40.degree. C. to 130.degree.
C., or 40.degree. C. to 120.degree. C., or 40.degree. C. to 115
.degree. C., or 40.degree. C. to 110.degree. C., or 40.degree. C.
to 105.degree. C., or 40.degree. C. to 100.degree. C., or
40.degree. C. to 90.degree. C., or 40.degree. C. to 80.degree. C.,
or 40.degree. C. to 70.degree. C., 80.degree. C. to 130.degree. C.
or 50.degree. C. to 130.degree. C. or 50.degree. C. to 120.degree.
C. or 50.degree. C. to 115.degree. C., or 50.degree. C. to
110.degree. C., or 50.degree. C. to 105.degree. C., or 50.degree.
C. to 100.degree. C., or 50.degree. C. to 90.degree. C., or
50.degree. C. to 80.degree. C., or 60.degree. C. to 130.degree. C.,
60.degree. C. to 120.degree. C., or 60.degree. C. to 115.degree.
C., or 60.degree. C. to 110.degree. C., or 60.degree. C. to
105.degree. C., or 60.degree. C. to 100.degree. C., or 60.degree.
C. to 90.degree. C., or 60.degree. C. to 80.degree. C., or
70.degree. C. to 130 70.degree. C. to 120.degree. C., or 70.degree.
C. to 115.degree. C., or 70.degree. C. to 110.degree. C., or
70.degree. C. to 105.degree. C., or 70.degree. C. to 100.degree. C.
or 60.degree. C. to 90.degree. C., or 70.degree. C. to 80.degree.
C. or 80.degree. C. to 130.degree. C., 80.degree. C. to 120.degree.
C., or 80.degree. C. to 115.degree. C., or 80.degree. C. to
110.degree. C., or 80.degree. C. to 105.degree. C., or 80.degree.
C. to 100.degree. C. or 80.degree. C. to 90.degree. C. or
90.degree. C. to 130.degree. C., 90.degree. C. to 120.degree. C.,
or 90.degree. C. to 115.degree. C., or 90.degree. C. to 110.degree.
C. or 90.degree. C. to 105.degree. C., or 90.degree. C. to
100.degree. C., or 100.degree. C. to 130.degree. C., 100.degree. C.
to 120.degree. C., or 100.degree. C. to 115.degree. C.
[0073] In aspect 53 of this invention, there is provided the
composition of any of aspects 1-52, wherein, after curing, the
compositions of the invention can have service temperatures of up
to 130.degree. C., or up to 120.degree. C., or up to 115.degree.
C., or up to 110.degree. C., or up to 105, or up to 100.degree. C.,
or up to 95.degree. C., or up to 90.degree. C., or up to 85.degree.
C., or up to 80, or up to 75.degree. C.
[0074] In aspect 54 of this invention, there is provided adhesive
compositions of any one of aspects 1-53 that can have a 180 degree
peel strength of at least 2 lb/in, or at least 3 lb/in, or at least
4 lb/in, or at least 5 lb/in as measured according to ISO
8510-2-2006 Part 2 at 5 mm/sec.
[0075] In aspect 55 of this invention, there is provided the
composition of any of aspects 1-54 that can be cured at room
temperature, or 10.degree. C. to 30.degree. C., or 10.degree. C. to
130.degree. C., or 20.degree. C. to 120.degree. C., or 20.degree.
C. to 115.degree. C., or 20.degree. C. to 110.degree. C., or
20.degree. C. to 105.degree. C., or 20.degree. C. to 100.degree.
C., or 20.degree. C. to 90.degree. C., or 20.degree. C. to
80.degree. C., or 20.degree. C. to 70.degree. C., or 30.degree. C.
to 130.degree. C., or 30.degree. C. to 120.degree. C., or
30.degree. C. to 115.degree. C., or 30.degree. C. to 110.degree.
C., or 30.degree. C. to 105.degree. C., or 30.degree. C. to
100.degree. C., or 30.degree. C. to 90.degree. C., or 30.degree. C.
to 80.degree. C., or 30.degree. C. to 70.degree. C., or 40.degree.
C. to 130.degree. C., or 40.degree. C. to 120.degree. C., or
40.degree. C. to 115.degree. C., or to 110.degree. C. or 40.degree.
C. to 105.degree. C., or 40.degree. C. to 100.degree. C., or
40.degree. C. to 90.degree. C., or 40.degree. C. to 80.degree. C.,
or 40.degree. C. to 70.degree. C., 80.degree. C. to 130.degree. C.,
or 50.degree. C. to 130.degree. C., 50.degree. C. to 120.degree.
C., or 50.degree. C. to 115.degree. C., or 50.degree. C. to
110.degree. C., or 50.degree. C. to 105.degree. C., or 50.degree.
C. to 100.degree. C., or 50.degree. C. to 90.degree. C., or
50.degree. C. to 80.degree. C., or 60.degree. C. to 130.degree. C.,
60.degree. C. to 120.degree. C., or 60.degree. C. to 115.degree.
C., or 60.degree. C. to 110.degree. C., or 60.degree. C. to
105.degree. C., or 60.degree. C. to 100.degree. C., or 60.degree.
C. to 90.degree. C., or 60.degree. C. to 80.degree. C., or
70.degree. C. to 130.degree. C., 70.degree. C. to 120.degree. C.,
or 70.degree. C. to 115.degree. C., or 70.degree. C. to 110.degree.
C., or 70.degree. C. to 105.degree. C., or 70.degree. C. to
100.degree. C., or 60.degree. C. to 90.degree. C., or 70.degree. C.
to 80.degree. C. or 80.degree. C. to 130.degree. C., 80.degree. C.
to 120.degree. C., or 80.degree. C. to 115.degree. C., or
80.degree. C. to 110.degree. C., or 80.degree. C. to 105.degree.
C., or 80.degree. C. to 100.degree. C., or 80.degree. C. to
90.degree. C., or 90.degree. C. to 130.degree. C., 90.degree. C. to
120.degree. C., or 90.degree. C. to 115.degree. C., or 90.degree.
C. to 110.degree. C., or 90.degree. C. to 105.degree. C., or
90.degree. C. to 100.degree. C., or 100.degree. C. to 130.degree.
C., 100.degree. C. to 120.degree. C., or 100.degree. C. to
115.degree. C.; and wherein, after curing, the compositions of the
invention can have service temperatures up to 130.degree. C., or up
to 120.degree. C., or up to 115.degree. C., or up to 110.degree.
C., or up to 105.degree. C., or up to 100.degree. C., or up to
95.degree. C., or up to 90.degree. C., or up to 85.degree. C., or
up to 80.degree. C., or up to 75.degree. C.; and optionally, after
service at these temperatures, can maintain a 180 degree peel
strength of at least 2 lb/in, or at least 3 lb/in, or at least 4
lb/in, or at least 5 lb/in as measured according to ISO 8510-2-2006
Part 2 at 5 mm/sec.
[0076] In aspect 56 of this invention, there is provided a
composition of any of aspects 1-55 which is not a water-dispersible
polyester microgel composition.
[0077] In aspect 57 of this invention, there is provided an
adhesive comprising the composition of any one of aspects 1-56.
[0078] In aspect 58 of this invention, there is provided an
adhesive comprising any of the compositions of aspects 1-57 which
can be used in at least one of the following: automotive interior
adhesive, flexible laminating adhesive, rigid laminating adhesive,
assembly adhesive, labelling adhesive, nonwoven adhesive, tape
adhesive, structural adhesive, hygiene nonwoven construction
adhesive, hygiene elastic attachment adhesive, home repair
adhesive, industrial adhesive, construction adhesive, medical
adhesive, contact adhesive, hot melt adhesive, solvent-based
adhesive, packaging adhesive, product assembly adhesive,
woodworking adhesive, flooring adhesive, automotive assembly
adhesive, structural adhesive, pressure sensitive adhesive (PSA),
PSA tape, PSA label, PSA protective film, laminating adhesive,
flexible packaging adhesive, and hygiene core integrity
adhesive.
[0079] In aspect 59 of this invention, there is provided a coating
comprising the composition of any one of aspects 1-58.
[0080] In aspect 60 of this invention, there is provided an article
comprising the composition of any of aspects 1-58.
[0081] In aspect 61 of this invention, there is provided the
article of aspect 60 which is at least one of the following: an
adhesive, a laminate, a tape, a label, a tag, a radio frequency
identification (RFID) tag, a coating, a sealant, a film, a foam, a
disposable hygiene article, a fiberglass reinforced plastic, a
compound, a motor vehicle molded part, a motor vehicle extruded
part, a motor vehicle laminated part, a woven textile, a nonwoven,
a flexible packaging multilayer.
[0082] In aspect 62 of this invention, there is provided an article
of aspects 60 or 61 comprising the cured composition of aspects
1-58 where the bond is maintained after cure and/or post-cure at or
above about 60.degree. C.
[0083] In aspect 63 of this invention, there is provide an article
of aspects any one of 1-59 comprising an additional step of
blending in at least one additive selected from the group
consisting of tackifiers, plasticizers, fillers, pigments,
stabilizers, antioxidants, adhesion promoters, waxes, flame
retardants, conductive agents, rheology modifiers or mixtures
thereof.
[0084] In aspect 64 of this invention, there is provided a
composite comprising the composition of any one of aspects 1-58
where the composite is selected from a polyester composite, a glass
composite, or a wood-plastic composite.
[0085] In aspect 65 of this invention, there is provided at least
one compound comprising any one of aspects 1-58 where the compound
is selected from a polyacrylic blended compound, a potting
compound, a rubber compound, a sheet molding compound (SMC) or a
dough molding compound (DMC).
[0086] Formulations based on such polyesters and amine compounds
are especially suitable for low-temperature curing adhesive
applications without the use of Isocyanates. Chemical and/or
physical protection of the primary amine curing agents can provide
additional control options to influence the cure profile.
Additionally, the novel system does not require moisture, so it can
be used with moisture-impermeable substrates such as artificial
leather.
[0087] Unpredictably, the compositions useful in this invention
have a good combination of properties including but not limited to
good thermal stability, the ability to cure and/or crosslink, good
cure rate, good green strength, good peel strength, and ability to
adhere to various substrates.
DETAILED DESCRIPTION
[0088] The present invention may be understood more readily by
reference to the following detailed description of certain
embodiments of the invention and the working examples. In
accordance with the purpose(s) of this invention, certain
embodiments of the invention are described in the Summary of the
Invention and are further described herein below. Also, other
embodiments of the invention are described herein.
[0089] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties such as molecular weight,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about." Unless indicated to the contrary, the numerical
parameters set forth in the following specification and attached
claims are approximations that may vary depending upon the desired
properties sought to be obtained by the present invention. At the
very least, each numerical parameter should be construed in light
of the number of reported significant digits and by applying
ordinary rounding techniques. Further, the ranges stated in this
disclosure and the claims are intended to include the entire range
specifications and not just the endpoint(s). For example, a range
stated to be 0 to 10 is intended to disclose all whole numbers
between 0 and 10 such as, for example 1, 2, 3, 4, etc., all
fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57,
6.1113, etc., and the endpoints 0 and 10.
[0090] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains certain errors necessarily resulting from the
standard deviation found in its respective testing
measurements.
[0091] As used in the specification and the appended claims, the
singular forms "a," "an" and "the" include their plural referents
unless the context clearly dictates otherwise. For example, a
reference to "a polyester," "a dicarboxylic acid", "a residue" is
synonymous with "at least one" or "one or more" polyesters,
dicarboxylic acids, or residues and is thus intended to refer to
both a single or plurality of polyesters, dicarboxylic acids, or
residues. In addition, references to a composition containing or
including "an" ingredient or "a" polyester is intended to include
other ingredients or other polyesters, respectively, in addition to
the one named. The terms "containing" or "including" are intended
to be synonymous with the term "comprising", meaning that at least
the named compound, element, particle, or method step, etc., is
present in the composition or article or method, but does not
exclude the presence of other compounds, catalysts, materials,
particles, method steps, etc., even if the other such compounds,
material, particles, method steps, etc., have the same function as
what is named, unless expressly excluded in the claims.
[0092] Also, it is to be understood that the mention of one or more
process steps does not preclude the presence of additional process
steps before or after the combined recited steps or intervening
process steps between those steps expressly identified.
[0093] Compositions comprising polyesters having moieties
containing activated methylene or methine groups, such as those of
beta-ketoesters, have properties including but not limited to one
or more of the following properties: (1) cures and is isocyanate
free, (2) is curable at low temperatures (e.g. <100.degree. C.),
(3) has suitable adhesion at service temperatures up to 130.degree.
C., (4) has good adhesion to substrates typically bonded or coated
with isocyanate-containing systems, (5) no Volatile Organic
Components (VOCs) or has low VOCs, (6) does not generate
by-products during curing that can be detrimental to film formation
or quality, (7) reduces defects, (8) has more pleasant odor, less
odor, or is odorless, (9) can contain low or no moisture, (10) can
be used with moisture-impermeable substrates such as artificial
leather, (11) under certain conditions, can be a crosslinking
system, (12) can provide more controlled curing, (13) good thermal
stability, (14) good chemical resistance, (15) good impact
strength, (16) good tensile strength, (17) good aging resistance,
and/or (18) can provide longer pot life.
[0094] In one embodiment, the invention provides a cured
composition.
[0095] In one embodiment, the invention provides a cured
composition that has good thermal stability.
[0096] In one embodiment, the invention provides a cured
composition that has good thermal stability and good peel
strength.
[0097] In one embodiment, the invention provides an adhesive
composition comprising: [0098] I. a first component [Component (I)]
comprising at least one polyester having two or more functional
groups selected from the group consisting of .beta.-ketoester and
malonate functional groups, and [0099] II. a second component
[Component (II)] comprising at least one curing agent having two or
more primary amine functional groups, salts thereof, or mixtures
thereof.
[0100] The beta-ketoester groups are represented by Formula 1,
wherein R is a branched or straight chain, saturated or unsaturated
alkyl, alicyclic, or aromatic group; and R' is a hydrogen or a
branched or straight chain, saturated or unsaturated alkyl,
alicyclic, or aromatic group.
##STR00001##
[0101] In one embodiment, the equivalent ratio of the
.beta.-ketoacetate functional groups in the resin(s) of Component
(I) to the primary amine functionality in the composition (i.e. eq.
of .beta.-ketoacetate/eq. of primary amine) is from about 0.10 to
about 8.0; or from about 0.25 to about 8.0; or from about 0.50 to
about 8.0; or from about 1.0 to about 8.0; or from about 1.5 to
about 8.0; or from about 2.0 to 8.0; or from about 2.5 to about
8.0; or from about 3.0 to about 8.0; or from about 3.5 to about
8.0; or from about 0.10 to about 7.0; or from about 0.25 to about
7.0; or from about 0.50 to about 7.0; or from about 1.0 to about
7.0; or from about 1.5 to about 7.0; or from about 2.0 to about
7.0; or from about 2.5 to about 7.0; or from about 3.0 to about
7.0; or from about 3.5 to about 7.0; or from about 0.10 to about
6.0; or from about 0.25 to about 6.0; or from about 0.50 to about
6.0; or from about 1.0 to about 6.0; or from about 1.5 to about
6.0; or from about 2.0 to about 6.0; or from about 2.5 to about
6.0; or from about 3.0 to about 6.0; or from about 3.5 to about
6.0; or from about 0.10 to about 5.0; or from about 0.25 to about
5.0; or from about 0.50 to about 5.0; or from about 1.0 to about
5.0; or from about 1.5 to about 5.0; or from about 2.0 to 5.0 or
from about 2.5 to about 5.0; or from about 3.0 to about 5.0; or
from about 3.5 to about 5.0; or from about 0.10 to about 4.0; or
from about 0.25 to about 4.0; or from about 0.50 to about 4.0; or
from about 1.0 to about 4.0; or from about 1.5 to about 4.0; or
from about 2.0 to 4.0 or from about 2.5 to about 4.0; or from about
3.0 to about 4.0; from about 0.10 to about 3.0; or from about 0.25
to about 3.0; or from about 0.50 to about 3.0; or from about 1.0 to
about 3.0; or from about 1.5 to about 3.0; or from about 2.0 to
3.0; or from about 0.10 to about 2.0; or from about 0.25 to about
2.0; or from about 0.50 to about 2.0; or from about 0.50 to about
1.5; or from about 0.7 to about 1.3; or from about 0.8 to about
1.2; or from about 1.0 to about 2.0; or from about 1.05 to about
2.0; or from about 1.10 to about 2.0; or from about 1.2 to about
2.0; or from about 1.3 to about 2.0; or from about 1.4 to about
2.0; or from about 1.5 to about 2.0; or from about 0.10 to about
1.0; or from about 0.25 to about 1.0; or from about 0.50 to about
1.0. The equivalent ratio of the .beta.-ketoacetate functional
groups in the resin(s) of Component (I) to the primary amine
functional groups in the composition is defined as the ratio of the
equivalents of .beta.-ketoacetate functional groups or acetoacetate
(AcAc) functional groups in the resin to the equivalents of primary
amine functional groups in the composition. For example, the
equivalents of the AcAc functional group in a sample of 100 g AcAc
polyester with AcAc number of 120 mgKOH/g can be calculated by the
formula: equivalents of AcAc polyester=100.times.120/56100=0.21;
whereas the equivalents of the amine functional group in a sample
of 0.10 moles of a diamine is equal to 0.10.times.2=0.20. Thus, the
equivalent ratio is equal to 0.21/0.20=1.05.
[0102] In one embodiment, the equivalent ratio of the
.beta.-ketoacetate functionality in the polyester to the primary
amine functionality in the composition (i.e. eq. of
.beta.-ketoacetate/eq. of primary amine) is from about 0.25 to
about 4.0; or from about 0.50 to about 4.0; or from about 0.25 to
about 3.0; or from about 0.50 to about 3.0; or from about 0.25 to
about 2.0; or from about 0.50 to about 2.0; or from about 0.50 to
about 1.5; or from about 0.7 to about 1.3; or from about 0.8 to
about 1.2.
[0103] The polyesters useful in the invention can contain two or
more beta-ketoester groups, represented by Formula 2, wherein Z is
a polyester residue, R is an alkyl group, R' is hydrogen or an
alkyl group, and n represents the average number of beta-ketoester
groups per polymer chain and is an average of at least 2. In one
aspect, the beta-ketoester group is acetoacetate (AcAc), and the
polyester is an acetoacetate-functional polyester.
##STR00002##
[0104] The acetoacetate-functional polyester may be prepared by
reacting a polyester resin containing hydroxyl groups, for example,
a polyester having a hydroxyl number of at least 5 mg KOH/g,
desirably about 30 to 200 mg KOH/g, with diketene or a compound
having the beta-ketoacetate moiety such as t-butylacetoacetate
(tBAA). Various methods for the preparation of acetoacetylated
polyester coating resins have been described by Witzeman et al. in
the Journal of Coatings Technology, Vol. 62, No. 789, pp. 101-112
(1990). A reaction mixture can include from about 50 to 95, 60 to
90, 65 to 85, or 70 to 80 weight % of the polyester resin and from
about 5 to 50, 10 to 40, 15 to 35, or 20 to 30 weight % of the
compound having a beta-ketoacetate moiety or a diketene; these can
be reacted together, wherein the weight percentages are based on
the total weight of the polyester resin and the compound having the
beta-ketoacetate moiety equaling 100 weight %.
[0105] In one embodiment, the curing agent [Component (II)] is a
small molecule or an adduct having one or more primary amine
functional groups or two or more primary amine functional groups.
Examples of amines useful in this invention include but are not
limited to at least one of ethylenediamine; diethylenetriamine;
triethylenetetramine (TETA) or isomers thereof;
tetraethylenepentamine or isomers thereof;
2,2,4-trimethylhexamethylenediamine;
2,4,4-trimethylhexamethylenediamine; 1,2-diaminopropane;
1,3-diaminopropane; 2,2-dimethylpropylenediamine;
1,4-diaminobutane; 2-methylpentamethylenediamine (MPMDA);
1,6-hexanediamine; 1,7-diaminaheptane; 1,8-diaminooctane;
1,9-diaminononane; 2-diaminododecane; 4-azaheptamethylenediamine;
N,N-bis(3-aminopropyl)butane-1,4-diamine;
N,N-bis(3-aminopropyl)ethylenediamine; 2,4-toluenediamine;
2,6-toluenediamine; 3,3'-iminobispropylamine;
1,2-diaminocyclohexane; 1,3-diaminocyclohexane;
1,4-diamino-2,5-diethylcyclohexane;
1,4-diamino-3,6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane;
1,2-diamino-4-cyclohexylcyclohexane; isophorone diamine (IPDA);
norbornanediamine; 4,4'-diaminodicyclohexylmethane;
4,4'-diaminodicyclohexylethane; 4,4'-diaminodicyclohexylpropane;
2,2-bis(4-aminocyclohexyl)propane;
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane;
3-amino-1-(4-aminocyclohexyl)propane;
1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane;
1-cyclohexyl-3,4-diamino-cyclohexane; xylylenediamine and its
hydrogenation products; p-xylylenediamine and its hydrogenation
products; 4,4'-methylenedianiline; 2,4-bis(p-aminobenzyl)aniline;
diethyltoluenediamine; m-phenylenediamine; diphenylethylenediamine;
2,2,4,4-tetramethylcyclobutane-1,3-diamine;
2,2-dimethylpropane-1,3-diamine; 2,3-dimethylbutane-2,3-diamine;
1,2-diaminocyclopentane; 1,2,2-trimethylcyclopentane-1,3-diamine;
1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diamine;
4,4'-methylenebis[2-methylcyclohexanamine] (MACM); and
polyetheramines such as JEFFAMINE.RTM. D-230, 0-400, 0-2000, and
T-403 amines.
[0106] The amine compounds may be chemically blocked to improve
storage stability and/or extend the open time for application of
the curable composition of the invention. The amine may be reacted
with a ketone such as acetone to form a ketimine. The amine may be
reacted with an aldehyde such as isobutyraldehyde to form an
aldimine. The resulting blocked amine may be de-blocked by changing
the pH or heating or moisture.
[0107] In this invention, "curing" means to develop at least one
strength property and/or increase in the average molecular weight
(either Mn or Mw) of the composition(s) of the invention, for
example, an adhesive composition or a coating composition, by
chemical reaction. "Curing agent" means a substance or mixture of
substances that reacts with resin during a curing reaction. "Curing
temperature" means the temperature to which at least one
composition(s) of the invention or an article of manufacture
containing at least one composition(s) of the invention is
subjected to cure the composition. "Curing time" means the period
of time for curing of the composition(s) of the invention to occur,
whether or not they cure at room temperature, and whether or not
they are subjected to application of thermal energy; radiation,
e.g., microwave, ultraviolet, or infrared radiation; ultrasonic
waves; pressure; moisture; or other sources of activation; or any
other variables. "Curable" means capable of curing.
[0108] In another embodiment, the acetoacetate functional polyester
comprises the reaction product (or residues) of (a) from about 50
to about 95 weight percent of a hydroxyl functional polyester and
(b) from about 5 to about 50 weight percent of an alkyl
acetoacetate or diketene, wherein the weight percentages are based
on the total weight of (a) and (b) equaling 100 weight %.
[0109] In one embodiment, the polyester (hydroxyl functional) can
be present in the amount of from 50 to 95 weight %, or from 60 to
90 weight %, or from 65 to 85 weight %, or from 70 to 80 weight %;
and the alkyl acetoacetate or diketene can be present in the amount
of 5 to 50 weight %, or from 10 to 40 weight %, or from 15 to 35
weight %, or from 20 to 30 weight %, respectively, wherein the
weight percentages are based on the total weight of (a) and (b)
equaling 100 weight %.
[0110] The hydroxyl number of the hydroxyl functional polyester
resin used to make the curable acetoacetate functional polyester
resin can be within a range of from 0 to 300 mg KOH/g. Suitable
ranges of hydroxyl number can include from 0 to 300, or from 10 to
300, or from 30 to 300, or from 50 to 300, or from 60 to 300, or
from 80 to 300, or from 100 to 300, or from 120 to 300, or from 140
to 300, or from 160 to 300, or from 180 to 300, or greater than 0
to 250, or from 10 to 250, or from 30 to 250, or from 50 to 250, or
from 60 to 250, or from 80 to 250, or from 100 to 250, or from 120
to 250, or from 140 to 250, or from 160 to 250, or from 180 to 250,
or greater than 0 to 240, or from 10 to 240, or from 30 to 240, or
from 50 to 240, or from 60 to 240, or from 80 to 240, or from 100
to 240, or from 120 to 240, or from 140 to 240, or from 160 to 240,
or from 180 to 240, or greater than 0 to 220, or from 10 to 220, or
from 30 to 220, or from 50 to 220, or from 60 to 220, or from 80 to
220, or from 100 to 220, or from 120 to 220, or from 140 to 220, or
from 160 to 220, or from 180 to 220 or greater than 0 to 200, or
from 10 to 200, or from 30 to 200, or from 50 to 200, or from 60 to
200, or from 80 to 200, or from 100 to 200, or from 120 to 200, or
from 140 to 200, or from 160 to 200, or from 180 to 200 or greater
than 0 to 180, or from 10 to 180, or from 30 to 180, or from 50 to
180, or from 60 to 180, or from 80 to 180, or from 100 to 180, or
from 120 to 180, or from 140 to 180, or from 160 to 180, or from 0
to 160, or from 10 to 160, or from 30 to 160, or from 50 to 160, or
from 60 to 160, or from 80 to 160, or from 100 to 160, or from 120
to 160, or from 140 to 160 or from 0 to 150, or from 10 to 150, or
from 30 to 150, or from 50 to 150, or from 60 to 150, or from 70 to
150, or from 80 to 150, or from 100 to 150, or from 120 to 150, or
from 130 to 150 mg KOH/g.
[0111] In one embodiment, the hydroxyl number of the hydroxyl
functional polyester resin is desirably at least 5, or at least 30,
or at least 50, or at least 80, or from 30 to 200; or from 50 to
150 mg KOH/g.
[0112] In one embodiment, the composition of the invention or the
polyester resin of the invention has an acid number of 0 to 15, or
0 to 10, or less than 10, or 0 to 5, or less than 5 mg KOH/g, with
and/or without neutralizing agents being added to the
composition.
[0113] In one embodiment, the compositions of the invention or of
the polyester resin of the invention can have acid numbers from 0
to about 14, or from 0 to about 13, or from 0 to about 12, or from
0 to about 11, or from 0 to about 10, or from 0 to about 9, or from
0 to about 8, or from 0 to about 7, or from 0 to about 6, or from 0
to about 5, or from 0 to about 4, or from 0 to about 3, or from 0
to about 2, or from 0 to about 1, or from 0.01 to about 15, or from
0.01 to about 14, or from 0.01 to about 13, or from 0.01 to about
12, or from 0.01 to about 11, or from 0.01 to about 10, or from
0.01 to about 9, or from 0.01 to about 8, or from 0.01 to about 7,
or from 0.01 to about 6, or from 0.01 to about 5, or from 0.01 to
about 4, or from 0.01 to about 3, or from 0.01 to about 2, or from
0.01 to about 1, or from 0.50 to about 15, or from 0.50 to about
14, or from 0.50 to about 13, or from 0.50 to about 12, or from
0.50 to about 11, or from 0.50 to about 10, or from 0.50 to about
9, or from 0.50 to about 8, or from 0.50 to about 7, or from 0.50
to about 6, or from 0.50 to 5 or from 0.50 to about 4, or from 0.50
to about 3, or from 0.50 to about 2, or from 0.50 to about 1.5 mg
KOH/g, with or without addition of neutralizing agents.
[0114] In one embodiment of this invention, the composition can
have any one of the acid numbers in the previous paragraph, where
neutralizing agents are not added to the composition after the
polymerization reaction. Neutralizing agents can any neutralizing
agent known in the art. In the embodiment of the invention where
neutralizing agents are excluded from the scope of this invention,
particularly where added after polymerization, neutralizing agents
can include but are not limited to primary amines, secondary
amines, tertiary amines, and ammonia as well as any other
neutralizing agent known in the art, for example, for water
dispersible or water dispersed microgel compositions.
[0115] In one embodiment of the invention, there are provided
compositions wherein the composition can contain residues of amine,
formed from the use of at least one primary amine, that may be
incorporated into the composition during curing. The primary amines
or amine salts useful in this invention can be used as curing
agents for the reaction of the p-ketoacetate (AcAc) group of
Component (I) and not as a neutralizing agent.
[0116] The acid number as referred to herein was measured by using
a procedure based on ASTM D7253-16 entitled "Standard Test Method
for Polyurethane Raw Materials: Determination of Acidity as Acid
Number for Poly ether Polyols," and hydroxyl number was measured
using a procedure based on ASTM E222-17 entitled "Standard Test
Methods for Hydroxyl Groups Using Acetic Anhydride."
[0117] The glass transition temperature (Tg) of the
acetoacetate-functional polyester of the present invention can be
from about -85.degree. C. to about 150.degree. C.; or from
-85.degree. C. to 130.degree. C.; or from -85 to 120.degree. C.; or
from -85.degree. C. to 110.degree. C.; or from -85.degree. C. to
100.degree. C.; or from -85.degree. C. to 80.degree. C.; or from
-85.degree. C. to about 60.degree. C.; or about -85.degree. C. to
about 50.degree. C.; or about -85.degree. C. to about 40.degree.
C.; or about -85.degree. C. to about 30.degree. C.; or about
-85.degree. C. to about 20.degree. C.; or about -85.degree. C. to
about 10.degree. C.; or about -85.degree. C. to about 0.degree. C.;
or about -85.degree. C. to about -10.degree. C.; or about
-85.degree. C. to about -20.degree. C.; or about -85.degree. C. to
about -25.degree. C.; or about -85.degree. C. to about 30.degree.
C. about -85.degree. C. to about 60.degree. C.; or about
-85.degree. C. to about 50.degree. C.; or about -85.degree. C. to
about 40.degree. C.; or about -85.degree. C. to about 30.degree.
C.; or about -85.degree. C. to about 20.degree. C.; or about
-85.degree. C. to about 10.degree. C.; or about -85.degree. C. to
about 0.degree. C.; or about -85.degree. C. to about -10.degree.
C.; or about -85.degree. C. to about -20.degree. C.; or about
-85.degree. C. to about -25.degree. C.; or about -85.degree. C. to
about -30.degree. C.; or about -70.degree. C. to about 60.degree.
C.; or about -70.degree. C. to about 50.degree. C.; or about
-70.degree. C. to about 40.degree. C.; or about -70.degree. C. to
about 30.degree. C.; or about -70.degree. C. to about 20.degree.
C.; or about -70.degree. C. to about 10.degree. C.; or about
-70.degree. C. to about 0.degree. C.; or about -70.degree. C. to
about -10.degree. C.; or about -70.degree. C. to about -20.degree.
C.; or about -70.degree. C. to about -25.degree. C.; or about
-70.degree. C. to about -30.degree. C.; or about -65.degree. C. to
about 60.degree. C.; or about -65.degree. C. to about 50.degree.
C.; or about -65.degree. C. to about 40.degree. C.; or about
-65.degree. C. to about 30.degree. C.; or about -65.degree. C. to
about 25.degree. C.; or about -65.degree. C. to about 20.degree.
C.; or about -65.degree. C. to about 10.degree. C.; or about
-65.degree. C. to about 0.degree. C.; or about -65.degree. C. to
about -10.degree. C.; or about -65.degree. C. to about -20.degree.
C.; or about -65.degree. C. to about -25.degree. C.; or about
-65.degree. C. to about -30.degree. C.; or about -45.degree. C. to
about 60.degree. C.; or about -45.degree. C. to about 50.degree.
C.; or about -45.degree. C. to about 40.degree. C.; or about
-45.degree. C. to about 30.degree. C.; or about -45.degree. C. to
about 25.degree. C.; or about -45.degree. C. to about 20.degree.
C.; or about -45.degree. C. to about 10.degree. C.; or about
-45.degree. C. to about 0.degree. C.; or about -45.degree. C. to
about -10.degree. C.; or about -45.degree. C. to about -20.degree.
C.; or about -45.degree. C. to about -25.degree. C.; or about
-45.degree. C. to about -30.degree. C.
[0118] In certain embodiments, the glass transition temperature
(Tg) of the acetoacetate-functional polyester of the present
invention can be from about -85.degree. C. to about -10.degree. C.;
or from about -70.degree. C. to about 50.degree. C.; or from about
-65.degree. C. to about 40.degree. C.; or from about -65.degree. C.
to about 25.degree. C.; or from about -10.degree. C. to about
50.degree. C.; or from about -45.degree. C. to about -10.degree.
C.; or from about -45.degree. C. to about -25.degree. C.
[0119] The number average molecular weight (Mn) of the acetoacetate
functional polyester useful in the present invention may be from
500 to 100,000; or from 700 to 50,000; or from 700 to 40,000; or
from 700 to 30,000; or from 700 to 25,000; or from 700 to 20,000;
or from 700 to 15,000; or from 700 to 10,000; or from 700 to 9,000;
or from 700 to 8,000; or from 700 to 7,000; or from 1000 to 6,000;
or from 700 to 5,000; or from 700 to 4,000; or from 700 to 3500; or
from 1,000 to 50,000; or from 1,000 to 40,000; or from 1,000 to
30,000; or from 1,000 to 25,000; or from 1,000 to 20,000; or from
1000 to 15,000; or from 1000 to 10,000; or from 1000 to 9,000; or
from 1000 to 8,000; or from 1000 to 7,000; or from 1000 to 6,000;
or from 1000 to 5,000; or from 1000 to 4,000; or from 1500 to
4,000; or from 1500 to 3,500; or from 1500 to 3,000; or from 1500
to 2500; or from 1200 to 3500 g/mole. The polyester may be linear
or branched. The Mn is measured by gel permeation chromatography
(GPO) using polystyrene equivalent molecular weight.
[0120] The hydroxyl functional polyester that is used to prepare
acetoacetate polyester useful in the invention can be synthesized
by reacting a hydroxyl compound, for example, a diol or triol, with
a carboxyl compound, for example, a dicarboxylic acid. Examples of
hydroxyl compounds include diols such as
2,2,4,4-tetraalkylcyclobutane-1,3-diol (TACO),
2,2-dimethyl-1,3-propanediol (neopentyl glycol),
1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,
hydroxypivalyl hydroxypivalate, tricyclodecanedimethanol,
2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol,
2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol,
1,4-benzenedimethanol, hydrogenated bisphenol A, ethylene glycol,
propylene glycol, diethylene glycol, dipropylene glycol,
triethylene glycol, tetraethylene glycol, polyethylene glycol, and
polyols such as 1,1,1-trimethylol propane, 1,1,1-trimethylolethane,
glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol,
sorbitol, and the like.
[0121] In one embodiment, the diol can be
2,2,4,4-tetraalkylcyclobutane-1,3-diol (TACD). Examples of TACD
include 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD),
2,2,4,4-tetraethylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-propylcyclobutane-1,3-diol, and
2,2,4,4-tetra-n-butylcyclobutane-1,3-diol. In one embodiment, the
TACO can be TMCD.
[0122] The carboxyl compound may be a polycarboxylic acid compound,
a derivative of polycarboxylic acid compound, or a combination
thereof. Suitable polycarboxylic acid compounds include compounds
having at least two carboxylic acid groups. In one aspect, the
polycarboxylic acid compound comprises a dicarboxylic acid compound
having two carboxylic acid groups, derivatives thereof, or
combinations thereof, capable of forming an ester linkage with a
polyhydroxyl component. For example, a polyester can be synthesized
by using a polyhydroxyl compound and a derivative of a dicarboxylic
acid such as, for example, dimethyl ester or other dialkyl esters
of the diacid, or diacid chloride or other diacid halides, or acid
anhydride. In another aspect, the polycarboxylic acid compound
comprises a tricarboxylic acid or anhydride, for example,
trimellitic acid or trimellitic anhydride.
[0123] Examples of dicarboxylic acids that may be used include
aliphatic dicarboxylic acids, alicyclic dicarboxylic acids,
aromatic dicarboxylic acids, derivatives of each, or mixtures of
two or more of these acids. Thus, suitable dicarboxylic acids
include, but are not limited to, isophthalic acid (or dimethyl
isophthalate), terephthalic acid (or dimethyl terephthalate),
phthalic acid, phthalic anhydride, 1,4-cyclohexane-dicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic
anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic
anhydride, dodecanedioic acid, sebacic acid, azelaic acid, maleic
acid or anhydride, fumaric acid, succinic anhydride, succinic acid,
adipic acid, 2,6-naphthalenedicarboxylic acid, glutaric acid,
itaconic acid, hexahydrophthalic acid or anhydride and their
derivatives, diglycolic acid, 2,5-norbornanedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid,
diphenic acid, 4,4'-oxydibenzoic acid, 4,4'-sulfonyldibenzoic acid,
and mixtures thereof.
[0124] In one embodiment, where the hydroxyl component of the
polyester comprises at least one diol and at least one polyol, the
mole % of the diol component can be 60 to 100, 80 to 97, or 85 to
95 mole % based on the mole percentages of the diol and polyol
equaling 100 mole % of the hydroxyl component, and the mole % of
the polyol component of the hydroxyl component of the polyester can
be 0 to 40, 3 to 20, or 5 to 15 mole %, based on the mole
percentages of the diol and polyol equaling 100 mole % of the
hydroxyl component.
[0125] Preferably, the diol of the hydroxyl component of the
polyester comprises one or more selected from the group consisting
of 2,2-dimethyl-1,3-propanediol (neopentyl glycol),
2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate,
2,2,4,4-tetramethylcyclobutane-1,3-diol, tricyclodecanedimethanol,
and polyethylene glycol.
[0126] In one embodiment of this invention, there is provided a
composition wherein diol component (a)(i) of the polyester contains
only oxygen, carbon, and hydrogen.
[0127] In one embodiment of this invention, there is provided a
composition wherein diol component (a)(i) of the polyester does not
have any carbonyl groups (--CO--).
[0128] In one embodiment of this invention, there is provided a
composition wherein diol component (a)(i) of the polyester does not
contain ether groups.
[0129] In one embodiment, the polyol component (a)(ii) of the
hydroxyl component of the polyester is selected from at least one
of 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin,
pentaerythritol or sorbitol.
[0130] In one embodiment, the carboxyl component of the polyester
comprises one or more carboxylic acids and/or anhydrides selected
from the group consisting of isophthalic acid (or dimethyl
isophthalate), terephthalic acid (or dimethyl terephthalate),
phthalic acid, phthalic anhydride, 1,4-cyclohexane-dicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, adipic acid,
2,6-naphthalene-dicarboxylic acid, 1,4-naphthalenedicarboxylic
acid' 2,5-naphthalenedicarboxylic acid' hexahydrophthalic acid or
anhydride, tetrahydrophthalic acid or anhydride, trimellitic
anhydride, maleic acid or anhydride, fumaric acid, succinic
anhydride, and succinic acid. In one embodiment, the carboxyl
compound is selected from the group consisting of adipic acid,
isophthalic acid (or dimethyl isophthalate),
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
hexahydrophthalic acid or anhydride, maleic anhydride, succinic
anhydride, phthalic acid, and phthalic anhydride.
[0131] In one embodiment, at least one semi-crystalline polyester
resin can be used. In one embodiment, the semi-crystalline
polyester resin can possess enough crystalline character to give
the material a sharp melting point rather than slowly softening
when heated. The semi-crystalline polyester resin can be a solid,
or a waxy or a semi-solid material at room temperature with a
melting point, for example, from 10 to 100.degree. C., or for
example, from 15 to 75.degree. C., or for example, from 25 to
65.degree. C.
[0132] The glass transition temperature (Tg) of the
semi-crystalline polyester of the invention can be from -70 to
20.degree. C., or from -60 to 0.degree. C., or from -50 to
-20.degree. C.,
[0133] The polyester resin can have a number average molecular
weight (Mn) from 1000-5000 viol, preferably 1500-4000 viol.
[0134] In one embodiment, the invention may comprise at least one
polyether glycol functionalized with acetoacetate groups instead of
or in addition to a polyester functionalized with acetoacetate
groups.
[0135] Suitable polyethers include unsubstituted poly(alkylene
glycol)s having alkylene chains of 1 to 3 carbon atoms, substituted
or unsubstituted poly(alkylene glycol)s having alkylene chains of
at least 4 carbon atoms and preferably less than 10 carbon
atoms.
[0136] In one embodiment, the equivalent ratio of the acetoacetate
(AcAc) functionality of the polyether glycol to the primary amine
functionality in the composition is from 0.25 to 4, or from 0.5 to
2.0, or from 0.7 to 1.5.
[0137] Suitable polyethers may be branched to increase their
functionality. For example, glycerol or sucrose may be included to
increase branching, such as in propoxylated glycerol and
propoxylated sucrose. The compositions of the invention can
comprise residues of at least one polyol component selected from
1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerin,
sorbitol, and pentaerythritol or mixtures thereof. Triisocyanates
and aliphatic or aromatic glycols may be used to increase branching
as well. The poly(alkylene glycol)s can be obtained by methods well
known in the art. Examples of poly(alkylene glycol)s include
poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene
glycol), poly(pentamethylene glycol), poly(hexamethylene glycol),
poly(heptamethylene glycol), and poly(octamethylene glycol).
Preferred poly(alkylene glycol)s include poly(ethylene glycol),
poly(propylene glycol) and poly(tetramethylene glycol). Almost any
number of repeating units may be used; however poly(alkylene
glycol)s having number average molecular weights in the range of
about 500 to 5,000 are preferred. Suitable poly(alkylene glycol)s
may have a variety of suitable end groups, including, but not
limited to hydroxyl, epoxy, methyl and the like. Preferred end
groups are methyl and hydroxyl.
[0138] In one embodiment of the invention, there are provided
compositions comprising blends of at least one acetoacetylated
polyether resin and/or at least one acetoacetylated polyester resin
and optionally, other polymers.
[0139] The amount of the polyether in the present invention may
vary, so long as the final composition can be formed into the
desired article. In one embodiment, Component (I) can contain 100%
by weight acetoacetylated polyether, 0 to 100% by weight
acetoacetylated polyether, or 20 to 80% by weight acetoacetylated
polyether; or 35 to 65% by weight acetoacetylated polyether, based
on the total weight percentage of Component (I) comprising 100
weight %. The remaining weight percentages can be any polymer, for
example, polyester, acetoacetylated polyester or polycarbonate.
[0140] In one embodiment of the invention, there are provided
compositions comprising from 100% or less, or 0.01 to 100%, or 0.01
to 80%, or 0.01 to 65%, or 0.01 to 25%, or 20 to 100%, or 20 to
80%, or 20 to 65%, or 5 to 25'%, or 20 to 80%, or 30 to 100%, or 30
to 80%, or 30 to 65%, or 40 to 100%, or 40 to 80%, or 40 to 65%, or
35 to 65%, or 35 to 54%, or 50 to 100%, or 50 to 80%, or 50 to
100%, or 50 to 80%, or 60 to 100%, or 60 to 80% by weight of
acetoacetylated polyesters of the invention wherein the remaining
weight percentages of the resin in Component (I) can be any polymer
or copolymer, for example, polyethers, polyurethanes, or
polycarbonates, (acetoacetylated or not), based on the total weight
percentage of Component (I) equaling 100 weight %.
[0141] Polyalkylene oxides such as polypropylene oxides and
ethylene oxides may also be used, such as linear polyethylene
oxide), linear poly(propylene oxide), linear copolymers of
polyethylene oxide) and poly(propylene oxide), linear
poly(1,3-trimethylene oxide), and linear poly(1,4-tetramethylene
oxide). Poly(alkylene glycol) copolymers of various glycol units
may also be used in the present invention. The copolymers may be
alternating, random, segmented, block, graft, or branched.
[0142] Examples of poly(alkylene glycol) copolymers include
polyethylene glycol)-ran-polypropylene glycol), poly(ethylene
glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)
and polypropylene glycol)-block-poly(ethylene
glycol)-block-poly(propylene glycol). A more specific example is a
block copolymer in which a polypropylene glycol) initiated with a
polyhydric alcohol is endcapped with ethylene oxide to convert some
or the majority of the secondary hydroxyls to primary hydroxyls.
The polyether condensation product may be prepared using methods
known in the art. For example, a polyether condensation product may
be formed by reacting polyethylene glycol with tetramethyl
cyclopentane-1,2,3,4-tetracarboxylate. This is a general method
that may be used to prepare other polyether condensation products
useful in the invention.
[0143] The condensation product of the polyethers can be produced
by reacting at least one core molecule having more than one
carboxylic add group with a sufficient amount of at least one
polyether terminated with hydroxy groups to produce an esterified
polyether with an average of more than two hydroxy end groups.
Suitable core molecules include, but are not limited to oxalic add,
malonic add, succinic add, glutaric add, adipic add,
hexahydrophthalic add or anhydride, benzenedicarboxylic add,
benzenetricarboxylic add, benzenetetracarboxylic add,
cyclohexanetricarboxylic add, cyclopentanetetracarboxylic add,
adamantanetetracarboxylic add, biphenyltetracarboxylic add,
benzophenonetetracarboxylic acid, propanetricarboxylic add,
butanetetracarboxylic add, and mixtures thereof.
[0144] In addition to poly(alkylene glycol)s, polyethers comprising
polymeric ethers derived from cyclic ether monomers can be used.
For example, poly(2,3-dihydrofurandiyl), prepared by cationic
polymerization of 2,3-dihydrofuran, can be incorporated into an
oxygen scavenging composition in the same fashion as the
above-mentioned poly(alkylene glycol)s.
[0145] Examples of the alkyl acetoacetate useful in the invention
include t-butyl acetoacetate, methyl acetoacetate, ethyl
acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate,
n-butyl acetoacetate, isobutyl acetoacetate, t-amyl acetoacetate,
diisopropyl carbinol acetoacetate, and the like or mixtures
thereof.
[0146] In one embodiment, the composition of the invention can
contain blends with other polymers, including but not limited to
blends of polyether resin(s) and polyester resin(s), or blends of
AcAc polyether resins and AcAc polyester resin(s).
[0147] In one embodiment, any composition of the invention can be
curable (capable of curing). In one embodiment, any composition
useful in the invention can be cured. In one embodiment, the
compositions of the invention can be cured at low temperatures
(e.g. <100.degree. C.). In one embodiment, the compositions of
the invention can be cured at room temperature, or 10.degree. C. to
130, or 10.degree. C. to 30.degree. C., or 20.degree. C. to
120.degree. C., or 80.degree. C. to 130.degree. C., or 50.degree.
C. to 130.degree. C., or 50.degree. C. to 120.degree. C., or
50.degree. C. to 115.degree. C., or 50.degree. C. to 110.degree. C.
or 50.degree. C. to 105.degree. C., or 50.degree. C. to 100.degree.
C., or 50.degree. C. to 90.degree. C., or 50.degree. C. to
80.degree. C., or 60.degree. C. to 130.degree. C., or 60.degree. C.
to 120 or 60.degree. C. to 115.degree. C., or 60.degree. C. to
110.degree. C., or 60.degree. C. to 105.degree. C., or 60.degree.
C. to 100.degree. C., or 60.degree. C. to 90.degree. C., or
60.degree. C. to 80.degree. C., or 70.degree. C. to 130.degree. C.,
or 70.degree. C. to 120.degree. C., or 70.degree. C. to 115.degree.
C., or 70.degree. C. to 110.degree. C., or 70.degree. C. to
105.degree. C., or 70 to 100.degree. C., or 60.degree. C. to
90.degree. C., or 70.degree. C. to 80.degree. C. or 80.degree. C.
to 130.degree. C., or 80.degree. C. to 120.degree. C., or
80.degree. C. to 115.degree. C. or 80.degree. C. to 110.degree. C.,
or 80.degree. C. to 105.degree. C., or 80.degree. C. to 100.degree.
C., or 80.degree. C. to 90.degree. C., or 90.degree. C. to
130.degree. C., or 90.degree. C. to 120.degree. C., or 90.degree.
C. to 115.degree. C., or 90.degree. C. to 110.degree. C., or
90.degree. C. to 105.degree. C., or 90.degree. C. to 100.degree.
C., or 100.degree. C. to 130.degree. C., or 100.degree. C. to
120.degree. C., or 100.degree. C. to 115.degree. C.
[0148] In another embodiment, after curing, the compositions of the
invention can maintain suitable adhesion or bond strength at
service temperatures up to 130.degree. C., or up to 120.degree. C.,
or up to 115.degree. C., or up to 110.degree. C., or up to
105.degree. C., or up to 100.degree. C., or up to 95.degree. C., or
up to 90.degree. C., or up to 85.degree. C., or up to 80.degree.
C., or up to 75.degree. C. In certain embodiments, "suitable
adhesion or bond strength" can include but is not limited to the
composition having a 180 degree peel strength of at least 2 lb/in,
or at least 3 lb/in, or at least 4 lb/in, or at least 5 lb/in as
measured according to ISO 8510-2-2006 Part 2 at 5 mm/sec.
[0149] In order to extend the pot life of the curable adhesive of
the invention, the amine curing agent [Component (II)] may be
temporarily blocked. For example, a carboxylic acid, such as
benzoic acid, acetic acid, formic acid, or cyanoacetic acid, can
also be added to the composition to chemically block the amine and
subsequently deblock by heating. Such techniques for blocking and
deblocking amines have been disclosed in "Delayed (Latent)
Catalysis in Coatings" Werner J. Blank, Kurt Dietliker, Tunja Jung,
Caroline Lordelot, Antoine Carroy
(www.researchgate.net/publication/228420884). The addition of mild
buffering agents such as weak acids can influence the cure rate,
thermal stability and polymer performance. Solid catalysts may be
particularly suited to chemical blocking, as only the outer surface
of a solid particle need be blocked. "Pot life" herein means period
of time during which a multi-part composition can be used after
mixing the components.
[0150] In one embodiment of the invention, there are provided
compositions useful in the invention that are capable of curing,
being curable, having been cured, or having reached a gelation
point. At the gelation point, a loose network of crosslinks are
formed across the material and the gel or gelation point can be
measured as either (1) the point when the storage modulus (G') and
the loss modulus (G'') cross, or (2) when the tan delta is
independent of frequency, each method by rotational rheometry using
a Discovery Hybrid Rheometer 3 (DHR), T.A. Instruments.
[0151] As used herein, storage modulus is a measure of elastic
response of a material. It measures the stored energy. Loss modulus
is a measure of viscous response of a material. It measures the
energy dissipated as heat. Tan delta, a measure of damping, is the
ratio of loss modulus to the storage modulus, G''/G'. These
properties can be used to evaluate compositions for stability at
storage and spray conditions, gelation process, and thermal
stability.
[0152] In one embodiment of the invention, there are provided
compositions having a gelation point, or that cures, at or above
25.degree. C. as measured by a Discovery Hybrid Rheometer (DHR),
T.A. Instruments.
[0153] "Pot life" herein means the period of time during which a
multi-part composition can be used after mixing the components.
"Working life" means the time period that a composition is
available to be applied to at least one substrate and to be capable
of forming a bond.
[0154] Pot life measurements can include various methods such as:
(1) the time from the initial viscosity (when components have been
all combined) to the time of doubling of viscosity; (2) reaching a
particular viscosity value above which the composition can no
longer be used in a given application or application method; (3)
reaching a viscosity so high that the curable composition can no
longer be molded or applied to a substrate, depending on the
particular application and its requirements; or (4) for
solvent-based compositions, reaching a viscosity of 24 seconds
using a #2 Zahn cup following ASTM Method D4212 at room
temperature.
[0155] The curing agents (amines) may be released for reaction in a
controlled manner through a physical protecting mechanism or
protecting layer, for example, a coated or blended component that
releases the curing agent upon heating, to improve storage
stability, and/or extend the pot life or open time for application
of the curable composition of the invention, and/or enable rapid
formation of initial "green strength" while preventing full cure
until "activated" or "de-protected." This may also be called a
controlled cure profile. Solid curing agents can be particularly
suited for physical protection, as only the outer surface of a
particle usually has to be coated. The protecting layer could
include materials such as waxes, tackifier resins, or rosin ester
tackifier resins, including but not limited to Permalyn.TM. 6110,
Permalyn.TM. 6110M, Permalyn.TM. 5095, Kristalex.TM. 3070, or
Foralyn.TM. 90 (Eastman Chemical Company). Physical protecting and
chemical blocking mechanisms may be combined to improve protection
and/or to control the cure profile of the inventive curable
compositions by activating, or de-protecting, under varying
conditions. In one embodiment, tackifier resins can be used. In one
embodiment, waxes can used. In another embodiment, a combination of
tackifier resins and/or waxes can be used.
[0156] In addition to adjusting the cure profile of the composition
through the physical blocking of the curing agent, the wax(es)
and/or tackifier resin(s) may reduce the overall viscosity of the
adhesive, reduce application temperature, and improve application
and uniformity.
[0157] Any conventionally known wax, which is suitable for use in
formulating adhesives, can be used in the practice of the
invention. Suitable waxes can include, for example,
microcrystalline wax, paraffin wax, waxes produced by
Fischer-Tropsch processes, functionalized waxes (maleated,
fumerated, silanated, or wax with functional groups etc.),
polyolefin waxes, petroleum waxes, polypropylene waxes,
polyethylene waxes, ethylene vinyl acetate waxes, and vegetable
waxes.
[0158] Non-limiting examples of commercially available waxes that
can be suitable for this invention include A-C.TM. 9 and A-C.TM.
810, available from Honeywell International Inc. Morristown, N.J.,
US; POLYWAX.TM. 400, 850, 1000, and 3000 from Baker Hughes Inc.,
Sugar Land, Tex., US; Licocene.TM. PE4201 from Clariant
International LTD, Muttenz, Switzerland; Epolene.TM. N-15,
Epolene.TM. C-10, Epolene.TM. C-17 and Epolene.TM. C-18 from
Westlake Polymers, LLC, Houston, Tex., US; Sasolwax.TM. 3279
microcrystalline wax from Sasol Chemical Industries Limited, South
Africa; and microcrystalline wax Be Square.TM. 195 (Baker
Hughes).
[0159] In various embodiments, adhesives comprising the curable
compositions of the inventions can comprise at least 1, 2, 5, 8, or
10 and/or not more than 40, 30, 25, 20, or 15 weight percent of at
least one wax based on the total weight of the final composition
equaling 100 weight %. Moreover, said adhesives can comprise in the
range of 1 to 40, 5 to 30, 8 to 25, or 10 to 20 weight percent of
at least one wax.
[0160] Furthermore, a functionalized wax may react with the curable
composition, reducing the amount of material that may potentially
migrate from the adhesive or coating. Suitable functionalized waxes
include but are not limited to Honeywell A-C.TM. 596; Clariant
Licocene.TM. MA6252 and Licocene.TM. MA6452; and Westlake
Epolene.TM. E-43.
[0161] In addition to physically protecting curing agents
[Component (II)], tackifying resins (tackifiers) may be added to
the curable compositions of the invention to modify the adhesive or
coating properties, including but not limited to the viscosity,
wetting behavior, adhesion, particularly to low energy surfaces,
and viscoelastic behavior of the finished adhesive or coating
composition. The tackifier resin selected may vary depending on the
exact curable composition and the balance of properties needed in
an application, such as peel strength, shear strength, and tack.
These properties are important to adhesive compositions and the
best advantages are achieved where the overall balance of these
properties, both initially and over time in different environmental
conditions, have been optimized.
[0162] Tackifier resins that may be present in the adhesive
compositions include, without limitation, cycloaliphatic
hydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon
resins, aromatically modified C5 resins (commercially available as
Piccotac.TM. resins, Eastman Chemical Company, Tenn., US), C9
hydrocarbon resins (commercially available as Picco.TM. resins,
Eastman), pure monomer resins, e.g. copolymers of styrene with
alpha-methyl styrene, vinyl toluene, para-methyl styrene, indene,
and methyl indene (commercially available as Kristalex.TM. resins,
Eastman), dicyclopentadiene (DCPD) resins, dicyclopentadiene
based/containing resins, cyclopentadiene based/containing resins,
terpene resins (commercially available as Sylvares.TM. resins, AZ
Chem Holdings, LP, Jacksonville, Fla., US), terpene phenolic
resins, terpene styrene resins, esters of rosin (commercially
available as Permalyn resins, Eastman), esters of modified rosins,
liquid resins of fully or partially hydrogenated rosins, fully or
partially hydrogenated rosin esters (commercially available as
Foral.TM. E and Foralyn.TM. resins, Eastman), fully or partially
hydrogenated modified rosin resins, fully or partially hydrogenated
rosin alcohols, fully or partially hydrogenated C5 resins, fully or
partially hydrogenated C5/C9 resins, fully or partially
hydrogenated DCPD resins (commercially available as Escorez.RTM.
5000-series resin, ExxonMobil Chemical Company, Tex., US), fully or
partially hydrogenated dicyclopentadiene based/containing resins,
fully or partially hydrogenated cyclopentadiene based/containing
resins, fully or partially hydrogenated aromatically modified C5
resins, fully or partially hydrogenated C9 resins (commercially
available as Regalite.TM. resins, Eastman), fully or partially
hydrogenated pure monomer resins (e.g., copolymers or styrene with
alpha-methyl styrene, vinyl toluene, para-methyl styrene, indene,
and methyl indene) (commercially available as Regalrez.TM. resins,
Eastman), fully or partially hydrogenated C5/cycloaliphatic resins
(commercially available as Eastotac.TM. resins, Eastman), fully or
partially hydrogenated C5/cycloaliphatic/styrene/C9 resins, fully
or partially hydrogenated cycloaliphatic resins, and/or mixtures
thereof.
[0163] The adhesive composition may be useful as a "warm" melt
adhesive for those applications where hot melt adhesives are
currently employed and applied by techniques known to those skilled
in the art. The melting point and/or ring and ball softening point
(RBSP) of one or more tackifier resins in the curable composition
can be selected to suit the intended end use for the adhesive
curable composition, where RBSP is measured by ASTM 06493-11
"Standard Test Methods for Softening Point of Hydrocarbon Resins
and Rosin Based Resins by Automated Ring-and-Ball Apparatus." In
various embodiments, the tackifier resin has a RBSP from
-10.degree. C. to 160.degree. C. In some embodiments, the tackifier
resin has an acid number in the range of 0 to 170, 0 to 30, 0 to
25, or 0 to 11 mg KOH/g. In some embodiments, tackifier resins with
zero or low acid numbers are preferred to reduce interference with
the amine crosslinker. In some embodiments, tackifier resins can
have moderate or high acid numbers, for example, where the primary
amine is buffered.
[0164] In other embodiments, tackifier resins with RBSP above the
expected application temperature and with acid numbers of about 5
to about 10, or of about 11 to about 22, or of about 145 to about
165 mg KOH/g, can be added in order to act as a base scavenger at
high temperatures and improve thermal stability of the cured
composition as well as to provide improved adhesion. Non-limiting
examples of tackifier resins that may be used include Poly-Pale.TM.
(AN 155, RBSP 103.degree. C.), Dymerex.TM. (AN 145, RBSP
144.degree. C.), Foral.TM. AX-E (AN 165, RBSP 8.degree. C.),
Permalyn.TM. 6110 (AN 13, RBSP 103.degree. C.), and Foralyn.TM. 90
(AN 8, RBSP 82.degree. C.) (Eastman).
[0165] In various embodiments, the adhesives can comprise at least
1, 2, 5, 8, or 10 and/or not more than 40, 30, 25, 20, or 15 weight
percent of at least one tackifying resin based on the total weight
of the composition. Moreover, the adhesives can comprise in the
range of 2 to 40, 5 to 30, 8 to 25, or 10 to 20 weight percent of
at least one tackifying resin based on the total weight of the
composition.
[0166] In another embodiment, the curable adhesive composition of
the present invention further comprises one or more adducts having
two or more .beta.-ketoacetate functional groups such as, for
example, 2-methyl-1,3-propanediol diacetoacetate; neopentyl glycol
diacetoacetate; 2,2,4,4-tetramethylcyclobutane-1,3-diol
diacetoacetate; or trimethylolpropane triacetoacetate; or any
isomers thereof, or mixtures thereof. The adducts can function as
reactive diluents to reduce the viscosity of the adhesive
formulations, especially those of solventless formulations for
extending their pot lives. The adducts can also modify the
functionality of the .beta.-ketoacetate functional groups available
for curing agents.
[0167] The curable adhesive composition of the invention is capable
of reacting at higher temperature (above ambient temperature) with
more control of shelf life in the presence of a protected curing
agent. In this so-called 1K system, the present invention allows
the mixing of the two components (AcAc resin and amine curing
agent); the resin and the curing agent may not react when the
curing agent is protected. The protected composition can be mixed
and stored until the mixture is ready to be used and is activated
(de-protected.)
[0168] The manner and order of protection of the curing agent(s)
(amine) can be used to control the cure profile of the curable
composition of the invention in both 1K and 2K systems.
[0169] The curable adhesive composition of the invention may be a
1K system with extended shelf life, and a controlled cure profile
that provides desired green strength and is also capable of curing
at higher temperature. For example, the curable adhesive
composition of the invention may comprise a portion of a physically
protected amine curing agent that is de-protected (activated) at
40.degree. C. and a portion of a physically protected amine curing
agent that is de-protected at 60.degree. C. In this example 1K
system, the present invention allows the mixing of the two
components (resin and amine curing agent) and storage until the
mixture is ready to be used. The inventive composition is activated
in stages, with first de-protection at 40.degree. C. to allow a
first stage of curing and formation of green strength, which is
desired to hold assembled substrates in position, followed by
second stage de-protection at 60.degree. C. to allow further cure
of the composition.
[0170] The cure profile of the curable composition may also be
controlled by a combination of chemical and/or physical protection
strategies and with selection of curing agent(s). For example, the
curable composition may comprise two curing agents with different
reactivity that are protected by the same or different physical
mechanism. The protection provides extended shelf life and/or pot
life, and after activation/de-protection at the indicated
condition(s), for example, the curing agent that provides faster
reaction speed may provide a desired level of green strength, and
the curing agent that provides lower reaction speed may provide the
final level of cure and bond strength. In this manner, the
formulator can obtain a desirable, superior balance of composition
properties for a particular application method, substrate choice,
and/or end use requirement.
[0171] The curable adhesive composition of the invention can
include chemical and/or physical protection of the curing agent
(amine). Upon de-protection/de-activation, the protecting agent can
then be released allowing the composition(s) of the invention to
achieve improvement in green bond strength and/or final adhesion
bond strength as measured, for example, by 180 degree peel
adhesion. Non-limiting examples of such materials can include
functionalized waxes, tackifier resins, rosin acid tackifier
resins, and rosin ester tackifier resins.
[0172] The curable composition of the invention may be essentially
solvent free, solvent-less or solvent-based. In one embodiment, the
solvent-based composition of the invention comprises an organic
solvent. Suitable organic solvents include acetone, ethanol, ethyl
acetate, butyl acetate, xylene, ketones (for example, methyl amyl
ketone and methyl ethyl ketone), 2-butoxyethanol,
ethyl-3-ethoxypropionate, toluene, butanol, cyclopentanone,
cyclohexanone, and other volatile inert solvents typically used in
adhesives. In one embodiment, the solvents useful in the invention
are acetone, ethanol, ethyl acetate, butyl acetate, xylene, methyl
amyl ketone, methyl ethyl ketone, and toluene.
[0173] The amount of solvents (excluding water) can range from 0%
to 80%, 5% to 70%, 10% to 70%, 15% to 70%, 20% to 70%, 25% to 70%,
20% to 70%, 0% to 60%, 5% to 60%, 10% to 60%, 15% to 60%, 20% to
60%, 25% to 60%, 20% to 60%, 0% to 50%, 5% to 55%, 10% to 55%, 15%
to 55%, 20% to 55%, 25% to 55%, 20% to 55%, 25% to 55%, 30% to 55%,
5% to 50%, 10% to 50%, 15% to 50%, 20% to 50%, 25% to 50%, 20% to
50%, 25% to 50%, 30% to 50%, 0% to 40%, 5% to 40%, 10% to 40%, 15%
to 40%, 20% to 40%, 25% to 40%, 0% to 30%, 5% to 35%, 10% to 35%,
15% to 35%, 20% to 35%, or 25% to 35% by weight based on the total
weight of the composition equaling 100 weight %. In one embodiment,
the amount of solvents (excluding water) can range from 25 to 50,
or 25 to 55, or 25 to 60% by weight based on the total weight of
the composition equaling 100 weight %. The percentage by weight of
solids (based on the total weight of the composition equaling 100
weight %) is the remainder of the weight % of the composition that
does not comprise solvent(s). Therefore, the percentage by weight
of solids based on the total weight of the composition equaling 100
weight % would be, for example, 20% to 100%, 30% to 95%, 30% to
90%, 30% to 85%, 30% to 80%, 30% to 75%, 30% to 70%, 40% to 100%,
40% to 95%, 40% to 90%, 40% to 85%, 40% to 80%, 40% to 75%, 40% to
70%, 50% to 100%, 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%,
50% to 75%, 50% to 70%, 50% to 65%, 50% to 60%, 55% to 100%, 55% to
95%, 55% to 90%, 55% to 85%, 55% to 80%, 55% to 75%, 55% to 70%,
55% to 65%, 60% to 100%, 60% to 95%, 60% to 90%, 60% to 85%, 60% to
80%, 60% to 75%, 60% to 70%, etc.
[0174] In one embodiment of this invention, the curable composition
of this invention does not contain solvents or residues of solvents
such as ethylene glycol and/or ether-containing compounds, for
example, dimethyl ether, ethylene glycol diethyl ether, diethylene
glycol dimethyl ether, or diethylene glycol diethyl ether.
[0175] In one embodiment of this invention, the curable composition
of the invention can be water-free, and/or moisture-free, and/or
can comprise substantially no water, and/or can contain essentially
no water, or can contain one of the following percentages of water:
0 to 20 weight %, 0 to 19 weight %, 0 to 18 weight %, 0 to 17
weight %, 0 to 16 weight %, 0 to 15 weight %, 0 to 14 weight %, 0
to 13 weight %, 0 to 12 weight %, 0 to 11 weight %, 0 to 10 weight
%, 0 to 9 weight %, 0 to 8 weight %, 0 to 7 weight %, 0 to 6 weight
%, 0 to 5 weight %, 0 to 4 weight %, 0 to 3 weight %, 0 to 2 weight
%, 0 to 1 weight %, 0.01 to 20 weight %, 0.01 to 19 weight %, 0.01
to 18 weight %, 0.01 to 17 weight %, 0.01 to 16 weight %, 0.01 to
15 weight %, 0.01 to 14 weight %, 0.01 to 13 weight %, 0.01 to 12
weight %, 0.01 to 11 weight %, 0.01 to 10 weight %, 0.01 to 9
weight %, 0.01 to 8 weight %, 0.01 to 7 weight %, 0.01 to 6 weight
%, 0.01 to 5 weight %, 0.01 to 4 weight %, 0.01 to 3 weight %, 0.01
to 2 weight %, or 0.01 to 1 weight %, based on the total weight of
the composition.
[0176] In one embodiment of this invention, the composition of this
invention is not a water-borne or a water-dispersible
composition.
[0177] In one embodiment of the invention, the composition of the
invention does not contain: a polyvinyl alcohol, or a polyvinyl
polymer, or a poly vinyl acetate polymer.
[0178] In one embodiment of this invention, the polyester resin of
the composition of the invention is not an alkyd polyester resin
and/or is not a polyester resin containing alkyd and/or fatty acid
residues.
[0179] In one embodiment of this invention, the composition of the
invention can be or, alternatively, is not a thermosetting
composition.
[0180] In one embodiment of this invention, the composition of this
invention does not contain polysaccharides and/or oxidized
polysaccharides having aldehyde groups.
[0181] The compositions of the invention can comprise at least one
additive selected from the group consisting of tackifiers,
plasticizers, fillers, pigments, stabilizers, antioxidants,
adhesion promoters, flame retardants, conductive agents, rheology
modifiers and mixtures thereof and the process of preparing the
curable compositions of the invention may comprise an additional
step of blending in one or more of these additives.
[0182] In various embodiments, the compositions of the invention
can comprise at least 0.1, 0.5, 1, 2, or 3 and/or not more than 5
weight percent of at least one antioxidant, based on the total
weight of the composition equaling 100 weight %.
[0183] One or more fillers, such as but not limited to, talc,
carbon black, calcium carbonate, titanium oxide and zinc oxide, may
be incorporated into the curable compositions of the invention. In
various embodiments, the adhesives of the invention can comprise at
least 1, 5, 10, 20, 30, or 40 and/or not more than 80, 70, 60, 55,
50 or 45 weight percent of at least one filler, based on the total
weight of the compositions equaling 100 weight %. Moreover, the
adhesives of the invention can comprise in the range of 1 to 80, 5
to 70, 10 to 60, 20 to 55, 30 to 50, or 40 to 45 weight percent of
at least one filler, based on the total weight of the compositions
equaling 100 weight %.
[0184] Further, in some embodiments, the composition of the
invention may exclude one or more additives typically found in
conventional compositions. For example, in some cases, the adhesive
formed using the compositions of the invention can be used as a
pressure sensitive adhesive (e.g., tapes and labels) and nonwoven
adhesive applications without addition of oils or plasticizers that
can possibly volatilize, migrate, or be extracted. For example, in
some cases, adhesive compositions of the present invention can
include not more than about 2, not more than about 1.5, not more
than about 1, not more than about 0.5, not more than about 0.25,
not more than about 0.1, or not more than about 0.05 weight percent
of one or more oils or plasticizers, based on the total weight of
the adhesive composition equaling 100 weight %.
[0185] In some cases, the adhesive composition may be a liquid
composition in water or solvent, applied to a surface and dried or
permitted to dry, while, in other embodiments, the composition may
be at or near 100 percent solids. In some embodiments, essentially
no volatile organic compounds (VOCs) or no VOCs are released during
the cure process. In certain embodiments, VOCs can be present in
the adhesive compositions of the present invention in the amount
less than 5 weight %, less than 4 weight %, less than 3 weight %,
less than 2 weight %, or less than 1 weight % VOCs, based on the
total weight of the composition.
[0186] The adhesive composition of the present invention may be
prepared according to any suitable method, techniques and
equipment. For example, the components of the adhesive composition
may be blended in a mixer, an extruder, an aluminum can, and/or at
the point of application, e.g. a head mixing system. In some cases,
the components of the adhesive composition may be blended,
optionally with a solvent, to form a mixture, which can then be
cast onto a backing or other substrate and dried or cured or
partially cured to form an article comprising the curable
composition.
[0187] Furthermore, the adhesive composition may be shaped into a
desired form, such as a tape or sheet, by an appropriate technique
including casting, extrusion, or roll coating techniques (gravure,
reverse roll, etc.). Alternatively, the composition may be applied
to a substrate using conventional adhesive application equipment
recognized in the art, e.g. curtain coating, slot-die coating,
wire-wound rod coating, gravure coating, roll coating, knife
coating, hot or "warm" melt coating. The adhesive composition may
be applied as either a continuous or discontinuous coating or film
or layer or sprayed through different nozzle and/or head
configurations at different speeds using typical application
equipment. The application may be followed by drying or heat
treatment.
[0188] In one embodiment, there is provided a process for preparing
a flexible film laminate comprising: (1) applying at least one of
Components (I)-(II) of the compositions useful in the invention to
the surface of a first substrate, (2) applying the remaining
component(s) of said Components on the surface of a second
substrate, (3) combining said substrates and then curing said
combined components, thus forming a cured composition.
[0189] In another embodiment, the curable adhesive of the present
invention is a laminating adhesive for flexible packaging. The
curing temperature for such an adhesive is desirably a low
temperature ranging from room temperature to about 80.degree.
C.
[0190] After formulation, the curable adhesive can be applied to a
substrate and subsequently laminated to another substrate. Suitable
substrates include but are not limited to textile, fabric, mesh,
film, poly(acrylonitrile butadiene styrene) (ABS), polypropylene
(PP), glass-filled PP, talc-filled PP, impact-modified PP,
polycarbonate (PC), PC-ABS, biaxially oriented polypropylene
(BOPP), thermoplastic polyolefin (TPO) compounds, pigmented TPO
compounds, filled TPO compounds, rubber-modified TPO compounds,
paper, glass, plastic, metal, PVC (polyvinyl chloride),
PET(polyethylene terephthalate), modified PET such as PETG (PET
modified with 1,4-cyclohexanedimethanol) and PCTG, Mylar.TM.
plastic, aluminum, leather, synthetic leather, nonwoven materials,
foams, painted surfaces, printed surfaces, thermosets,
thermoplastics, polymer films such as polyethylene, polypropylene,
oriented polyethylene, oriented polypropylene; metallized plastic
films; aluminum foil; wood; metals such as aluminum, steel or
galvanized sheeting; glass; urethane elastomers; primed (painted)
substrates, and laminates, blends or coated substrates comprising
at least one of these materials. Any of these substrates may be
untreated, corona treated, chemically treated, plasma treated,
flame treated, rubber-modified, impact-modified, filled with e.g.
talc or glass, pigmented with e.g. carbon black, chromium oxide or
titanium oxide, or otherwise modified as known by those skilled in
the art to provide improved properties to the substrate.
[0191] The curable adhesive can be coated onto a substrate using
techniques known in the art, for example, by spraying, draw-down,
roll-coating, brushing, nozzle dispensing, printing, etc. arid
subsequently laminated to another substrate manually or by a
roll-to-roll laminating machine. The coating and laminating process
may be done at room temperature or elevated temperatures. The
laminated films may be cured at room temperature or elevated
temperatures. In various embodiments, the curable mixture of the
present invention can cure at 20.degree. C. in various amounts of
time. In one embodiment, the curable mixture of the present
invention can cure at 20.degree. C. or higher in six days or
less.
[0192] In some embodiments, the pot life of the curable mixture can
be 5 minutes or more; or 10 minutes or more; or 25 minutes or more.
Independently, in some embodiments, pot life can be 7 days or less;
or 1 day or less; or 8 hours or less; or 2 hours or less; or 30
minutes or less.
[0193] In certain embodiments of the invention, the compositions of
the invention can be prepared by a process comprising: (a) mixing
at least one component having two or more .beta.-ketoester
functional groups, and at least one component having two or more
primary amine functional groups, and (b) after optional activation,
curing the composition at 20.degree. C. or higher, for example, in
six days or less, and (c) optionally, post-curing the composition
at or above 20.degree. C.
[0194] In certain embodiments of the invention, the compositions of
the invention can be prepared by a process comprising: (a) mixing
at least one component having two or more .beta.-ketoester
functional groups, and at least one component having two or more
primary amine functional groups, and (b) after optional activation,
curing the composition at or above 20.degree. C., or above
35.degree. C., or above 50.degree. C., or above 55.degree. C., or
above 70.degree. C., or above 80.degree. C., or above 100.degree.
C., or from 20.degree. C. to 180.degree. C., or from 50.degree. C.
to 180.degree. C., or from 50.degree. C. to 80.degree. C. in any
time known to one of ordinary skill in the art, for example, in six
days or less, and (c) optionally, post-curing the composition at or
above 20.degree. C., or above 35.degree. C., or above 55.degree.
C., or above 70.degree. C., or above 80.degree. C., or above
100.degree. C., or from 20.degree. C. to 110.degree. C., or from
50.degree. C. to 110.degree. C.
[0195] In some embodiments, the curable composition of this
invention can be cured after optional activation, for example, to
de-protect a component, at temperatures above 20.degree. C., or
above 35.degree. C., or above 50.degree. C., or above 55.degree.
C., or above 70.degree. C., or above 80.degree. C., or above
100.degree. C. and can then be post-cured at a higher
temperature(s) above 20.degree. C., or above 35.degree. C., or
above 55.degree. C., or above 70.degree. C., or above 80.degree.
C., or above 100.degree. C.
[0196] In some embodiments, the curable composition can be
partially cured before being applied to a substrate, used in a
laminate, molded or otherwise incorporated into an article.
[0197] In this invention, Brookfield viscosity can be measured
using a Brookfield viscometer as described in ASTM D3236 "Apparent
Viscosity of Hot Melt Adhesives and Coating Materials." Viscosity
measurements are reported in centipoise (cP) units. In various
embodiments, the curable compositions of the invention, for
example, adhesive compositions, can exhibit a Brookfield viscosity
in the range of 5 to 300,000 cP, or 300 to 200,000 cP, or 300 to
150,000 cP, or 300 to 100,000 cP, or 500 to 200,000 cP, or 500 to
150,000 cP, or 500 to 100,000 cP, or 500 to 90,000 cP, or 500 to
80,000 cP, or 500 to 50,000 cP, or 500 to 45,000 cP, or 500 to
40,000 cP, or 500 to 35,000 cP, or 500 to 30,000 cP, or 500 to
25,000 cP, or 500 to 20,000 cP, or 500 to 15,000 cP, or 500 to
10,000 cP, or 500 to 8,000 cP, or 500 to 5,000 cP, or 500 to 3,000
cP, or 1000 to 100,000 cP, or 1000 to 90,000 cP, or 1000 to 80,000
cP, or 1000 to 50,000 cP, or 1000 to 45,000 cP, or 1000 to 40,000
cP, or 1000 to 35,000 cP, or 1000 to 30,000 cP, or 1000 to 25,000
cP, or 1000 to 20,000 cP, or 1000 to 15,000 cP, or 1000 to 10,000
cP, or 1000 to less than 10,000 cP, or 1000 to 8,000 cP or 1000 to
5,000 cP, or 1000 to 3,000, or 5000 to 90,000 cP, or 5000 to 80,000
cP, or 5000 to 50,000 cP, or 5000 to 45,000 cP, or 5000 to 40,000
cP, or 5000 to 35,000 cP, or 5000 to 30,000 cP, or 5000 to 25,000
cP, or 5000 to 20,000 cP, or 5000 to 15,000 cP, or 5000 to 10,000
cP, or 5000 to less than 10,000 cP, or 5000 to 8,000 cP, or 10,000
to 90,000 cP, or 10,000 to 80,000 cP, or 10,000 to 50,000 cP, or
10,000 to 45,000 cP, or 10,000 to 40,000 cP, or 10,000 to 35,000
cP, or 15,000 to 90,000 cP, or 15,000 to 80,000 cP, or 15,000 to
50,000 cP, or 15,000 to 45,000 cP, or 15,000 to 40,000 cP, or
15,000 to 35,000 cP, or 20,000 to 90,000 cP, or 20,000 to 80,000
cP, or 20,000 to 50,000 cP, or 20,000 to 45,000 cP, or 20,000 to
40,000 cP, or 20,000 to 35,000 cP, or 25,000 to 90,000 cP, or
25,000 to 80,000 cP, or 25,000 to 50,000 cP, or 25,000 to 45,000
cP, or 25,000 to 40,000 cP, or 25,000 to 35,000, or 1 to 500 cP at
application temperature. In certain embodiments, application
temperature can be at 45.degree. C. or less.
[0198] In other embodiments, the curable adhesive compositions may
exhibit a ring and ball softening point in the range of -10 to
180.degree. C.
[0199] In various embodiments, the curable adhesive compositions
can have a peel strength in a 180 degree peel test of at least 2
lb/in or at least 5 lb/in as measured according to ISO 8510-2-2006
Part 2 at 5 mm/sec.
[0200] In various embodiments, the curable adhesive compositions
can be applied in the range of about 0.5 gsm to about 200 gsm
(gsm=grams per square meter). In embodiments where the curable
composition will be used to bond substrates to each other, the
add-on rate used will be suitable for generating laminates or
composites with desired bond strength. The curable composition can
be applied to one or both substrates before the substrates are
brought into contact to form a composite, laminate or article. The
article so formed may be optionally contacted with additional
substrates, additional curable compositions, adhesives, and/or may
be subjected to applied pressure and/or applied heat, in any order
or combination without limitation.
[0201] The invention also provides a process for curing the curable
mixture comprising the step of: contacting at least one
AcAc-functionalized resin with at least one multifunctional amine,
wherein said curable mixture is capable of curing after optional
activation at 20.degree. C. in six days or less.
[0202] In various embodiments of the present invention, the curable
composition can be utilized as an adhesive and can comprise at
least one resin having two or more beta-ketoester groups, and at
least one curing agent having two or more primary amine functional
groups. Optionally, the curable adhesive composition can further
comprise at least one tackifier resin, and/or at least one wax
and/or at least one antioxidant.
[0203] The compositions of this invention can provide desirable
properties for a variety of applications. In certain embodiments,
the compositions of this invention are suitable for applications in
the adhesives area, for example, automotive adhesives, structural
adhesives, wood adhesives, and laminating adhesives, and
applications in the coatings area, for example, automotive,
industrial maintenance, marine craft, field-applied coatings, and
furniture.
[0204] The curable compositions of the present invention can be
used in a variety of adhesive compositions, including, but not
limited to, automotive interior assembly adhesives, flexible
laminating adhesives, rigid laminating adhesives, assembly
adhesives, labelling adhesives, nonwoven adhesives, tape adhesives,
pressure sensitive adhesives, structural adhesives, hygiene
construction adhesives, hygiene elastic attachment adhesives, home
repair adhesives, pressure sensitive adhesives, industrial
adhesives, construction adhesives, medical adhesives, contact
adhesives, hot melt adhesives, or solvent-based adhesives.
[0205] In one embodiment of the invention, there is provided a
composition that is used at, or above, or near its glass transition
temperature.
[0206] In one embodiment of the invention, there are provided cured
compositions wherein AT is the difference between the temperature
at use and the glass transition temperature (Tg) of the cured
composition, and AT is from -30 to 60.degree. C. or from -30 to
10.degree. C.
[0207] In some embodiments, such as pressure sensitive adhesives,
the curable compositions of the present invention can be
characterized by adhesive strength by 180-degree peel test e.g.
according to PSTC-101 or ISO 8510-2-2006 Part 2 at 5 mm/sec,
cohesive strength and/or temperature resistance by static shear
hold power testing (room temperature or elevated temperature, e.g.,
40.degree. C. or 70.degree. C.) by PSTC-107 and/or by shear
adhesion failure temperature (SAFT) by PSTC-17.
[0208] In some embodiments, the curable compositions of the present
invention can be characterized by lap shear testing: ASTM
D3163-01(2014) Standard Test Method for Determining Strength of
Adhesively Bonded Rigid Plastic Lap-Shear Joints in Shear by
Tension Loading. Impact strength can also be measured any method
known in the art, for example, by pendulum or ball drop impact
tests.
[0209] In some embodiments, the curable compositions of the present
invention can be used in flexible packaging and characterized by
tests such as DIN ISO 53357 Internal Adhesion, DIN ISO 55529 Sealed
Seam Strength, DIN 53357 Bonding Adhesion, DIN 53504 Elongation at
Tear and Tearing Tension, ASTM D1003 Transparency of film, ASTM
D2578 Wetting Tension of Film Surface, ASTM F1249 Water Vapor
Transmission Rate, ASTM F2622 or D3985 Oxygen Transmission Rate,
and/or T-peel by ASTM F904-16 "Standard Test Method for Comparison
of Bond Strength or Ply Adhesion of Similar Laminates Made from
Flexible Materials."
[0210] The inventive compositions can exhibit improved heat
resistance and/or improved adhesion over time, particularly after
heat aging, as evidenced by tests such as elevated temperature
aging of the adhered articles comprising the inventive
compositions, followed by lap shear testing, by fiber tear testing,
by peel testing, by peel adhesion failure temperature (PAFT)
testing, by shear adhesion failure temperature (SAFT) testing,
and/or by shear hold power testing at elevated temperatures such as
40.degree. C., 60.degree. C. 70.degree. C., 85.degree. C.,
95.degree. C., 105.degree. C., or 120.degree. C. The adhered
articles comprising the compositions of the invention can also
exhibit improved humidity resistance as evidenced, for example, by
aging at 95 to 100% relative humidity at 40.degree. C. for 24 to
144 hours followed by any of the above listed adhesion and cohesion
tests at room temperature and/or at elevated temperature.
[0211] An article comprising the curable compositions of the
invention may be an adhesive, a laminate, a tape, a label, a tag, a
radio frequency identification (RAD) tag, a coating, a sealant, a
film, a foam, a disposable hygiene article, a polyester composite,
a glass composite, a fiberglass reinforced plastic, a wood-plastic
composite, an extruded compound, a polyacrylic blended compound, a
potting compound, a rubber compound, a motor vehicle molded part, a
motor vehicle extruded part, a motor vehicle laminated part, a
sheet molding compound (SMC) or dough molding compound (DMC), a
woven textile, a nonwoven textile, a flexible packaging
multilayer.
[0212] In one embodiment, there is provided a process wherein the
composition of the invention is prepared by a process comprising:
(a) mixing a first component comprising at least one resin having
two or more functional groups selected from the group consisting of
.beta.-ketoester and malonate functional groups, and a second
component comprising at least one curing agent having at least two
primary functional groups, salts thereof, or mixtures thereof and
(b) curing the composition after optional activation between
20.degree. C. and 60.degree. C. in six days or less, and (c)
optionally, post-curing the composition below 60.degree. C.
[0213] The curable adhesive composition may be prepared by a
process comprising: (a) mixing a first component comprising at
least one resin having two or more functional groups selected from
the group consisting of .beta.-ketoester and malonate functional
groups, and a second component comprising at least one curing agent
having at least two primary amine functional groups, salts thereof,
or mixtures thereof and (b) after optional activation, curing the
composition at 20.degree. C. or higher in six days or less, and (c)
optionally post-curing the composition at or above 20.degree.
C.
[0214] In one embodiment, articles are provided comprising the
above cured compositions where the bond is maintained after cure
and/or post-cure at 60.degree. C.
[0215] The following examples further illustrate how the polyesters
useful in the invention can be made and evaluated, and how the
curable compositions useful in this invention can be made and
evaluated and are intended to be purely exemplary of the invention
and are not intended to limit the scope thereof. Unless indicated
otherwise, parts are parts by weight, temperature is in degrees C.
(Celsius) or is at room temperature, and pressure is at or near
atmospheric.
EXAMPLES
[0216] In the Examples herein, analysis of the acetoacetate (AcAc)
number of the resin employs a potentiometric titration method based
on the titration of the proton in the AcAc group with a strong
base, tetrabutylammonium hydroxide solution (TBAOH) in methanol.
The titration was conducted on a titrator (904 Titrando, Metrohm
AG, US) equipped with Tiamo software and a pH electrode
(DG116-solvent, Mettler Toledo, US) as sensing probe. Depending on
the expected AcAc number of the sample, 0.05 to 0.5 grams sample
was weighted to a titration cell and stirred to dissolve in 35 mL
pyridine at room temperature. The sample solution was titrated to
the endpoint at pH around 16, which was determined by Tiamo
software or manually. The AcAc number, reported as mg KOH/g sample,
was calculated from the volume of TBAOH used at the titration
endpoint, its normality, and weight of sample.
Example 1. Synthesis of Acetoacetate Functional Polyester 1 (AcAc
Polyester 1 or AcAc Resin 1)
Hydroxyl Functional Polyester 1:
[0217] A 2-L kettle with a four-neck lid was equipped with a
mechanical stirrer, a thermocouple, a heated partial condenser
(115.degree. C.), a Dean-Stark trap, and a chilled condenser
(15.degree. C.). To the flask were charged neopentyl glycol (NPG)
(178.6 g), 2-methyl-1,3-propanediol (MPDiol) (154.6 g),
trimethylolpropane (TMP) (131.5 g), adipic acid (AD) (511.5 g), and
the acid catalyst, Fascat-4100 (Arkema Inc.) (0.98 g). The reaction
was allowed to react under nitrogen at 170.degree. C. for one hour,
at 200.degree. C. for one hour, and at 230.degree. C. for about 3
hours to yield a clear, viscous mixture. A total of 126 g of the
distillate was collected in the Dean-Stark trap. The resulting
mixture was allowed to cool to 120.degree. C. for the reaction with
t-butyl acetoacetate below. Acid number: <1.0 mg KOH/g; hydroxyl
number: 165.5 mg KOH/g; glass transition temperature (Tg):
-49.6.degree. C.; number average molecular weight (Mn): 2050
g/mole; weight average molecular weight (Mw): 5921 g/mole.
Acetoacetate Functional Polyester 1:
[0218] The next synthesis was aimed to convert hydroxyl number of
150 mg KOH/g of the above hydroxyl functional polyester (1) to
acetoacetate number of 150 mg KOH/g. To the above
hydroxyl-functional polyester 1 (850g) was added t-butyl
acetoacetate (359 g). The mixture was gradually heated and allowed
to react at 120.degree. C. for 20 minutes and at 140.degree. C. for
two hours. A total of 14 4 g of the condensate (t-butanol) was
collected in the Dean-Stark adapter. The resulting viscous resin
was allowed to cool and subsequently collected. Glass transition
temperature (Tg): -51.degree. C.; number average molecular weight
(Mn): 1804 g/mole; weight average molecular weight (Mw): 5790
g/mole; AcAc number 127 mgKOH/g.
Example 2. Synthesis of Acetoacetate Functional Polyester 2 (AcAc
Polyester 2 or AcAc Resin 2)
Acetoacetate Functional Polyester 2:
[0219] To the above hydroxyl-functional polyester 1 (912g) was
added t-butyl acetoacetate (321 g). The mixture was gradually
heated and allowed to react at 120.degree. C. for 20 minutes and at
140.degree. C. for two hours. The condensate (t-butanol) was
collected in the Dean-Stark adapter. The resulting viscous resin
was allowed to cool and subsequently collected. Glass transition
temperature (Tg): -51.degree. C.; number average molecular weight
(Mn): 1771 g/mole; weight average molecular weight (Mw): 5848
g/mole; AcAc number 107 mgKOH/g.
TABLE-US-00001 TABLE 1 Abbreviations of amines used. Name CAS #
Other names IPDA 2855-13-2 5-Amino-1,3,3-
trimethylcyclohexanemethanamine; isophorone diamine MPMDA
15520-10-2 2-Methyl-1,5-pentanediamine;
2-methylpentamethylenediamine MACM 6864-37-5
4,4'-Methylenebis[2-methylcyclohexan- amine] TETA 112-24-3
Triethylenetetramine Epicure 940 25620-58-0
2,2,4(2,4,4)-Trimethyl-1,6-hexanediamine Jeffamine 39423-51-3
Amine-terminated polypropylene glycol T-403 trimethylolpropane
ether 1,3-CHBMA 2579-20-6 1,3-Cyclohexanebis(methylamine);
1,3-bis(aminomethyl)cyclohexane Curing agent amount is given as
equivalents (moles amine functional groups to moles AcAc functional
groups in resin). E.g., 1.0 equiv means that there is one mole of
amine functional groups in the composition per mole AcAc functional
groups in the resin.
Examples 3-20: Demonstration of Cure Using Various Diamine Curing
Agents
[0220] In Examples 3-20, the AcAc Polyester 1 or 2 was mixed in a
vial with an amine curing agent, as described in Table 2. The
samples were observed to see if the compositions thickened, how
long they were of low enough viscosity to be workable/stirrable,
and if they cured. As can be seen in Table 2, all compositions in
which 1.0 equivalent of amine curing agent was added cured
(Examples 3-6, 10-17). Most thickened quickly, and some were not
workable after 2-4 minutes, indicating that rapid curing was taking
place. Compositions with less than one equivalent of amine curing
agent (Examples 7, 8, 18, 19; 0.33-0.8 equiv curing agent) also
cured. However, when the amount of curing agent was reduced further
to 0.25 equivalents (Examples 9, 20), compositions did not cure,
even after 3-4 days.
[0221] Examples 17-19 show that for the same resin and curing
agent, as the amount of curing agent is reduced from 1.0 to 0.5 to
0.33 equivalents, the time that the composition remains workable
increased from less than 3.5 minutes, to less than 6 minutes, to
more than 12 minutes. Thus, the amount of curing agent added can be
used to modify the time that the composition is workable, while
still resulting in a cured composition.
TABLE-US-00002 TABLE 2 Curable compositions comprising AcAc resins
and amine curing agents. Exam- AcAc Amine ple # Resin curing agent
Observation 3 1 IPDA Thickened. Still workable after 3 minutes.
(1.0 equiv) Cured within 24 h. 4 1 MPMDA Not workable after 2
minutes. Cured. (1.0 equiv) 5 1 MACM Thickened. Still workable
after 3 minutes. (1.0 equiv) Cured within 24 h. 6 1 TETA Not
workable after 2 minutes. Cured. (1.0 equiv) 7 1 Epikure 940 Gelled
fast. Not workable after 3 minutes. (0.8 equiv) Cured. 8 1 Epikure
940 Thickened. Still workable after 3 minutes. (0.65 equiv) Cured
in less than 3 days. 9 1 Epikure 940 Thickened. Still workable
after 3 minutes. (0.25 equiv) Was not cured after 3 days. 10 1
Jeffamine Thickened. Still workable after 3 minutes. T-403 Cured in
less than 3 days. (1.0 equiv) 11 2 IPDA Thin after 4 minutes. Cured
within 24 h. (1.0 equiv) 12 2 MPMDA Workable after 5 minutes. Set
up after 10 (1.0 equiv) minutes. Cured. 13 2 MACM Thin after 5
minutes. Cured within 24 h. (1.0 equiv) 14 2 Epikure 940 Thin after
8 minutes. Cured within 24 h. (1.0 equiv) 15 2 Jeffamine Thin after
9 minutes. Cured after 3 hours. T-403 (1.0 equiv) 16 2 1,3-CHBMA
Not workable after 6 minutes. Cured. (1.0 equiv) 17 2 TETA Not
workable after 3.5 minutes. Cured. (1.0 equiv) 18 2 TETA Not
workable after 6 minutes. Cured. (0.5 equiv) 19 2 TETA Still
workable after 12 minutes. Cured (0.33 equiv) within 24 h. 20 2
TETA Still workable after 10 minutes. After 4 (0.25 equiv) days
still gooey, not cured.
Examples 21-23: Peel Strength of Cured Compositions and Thermal
Stability
[0222] Compositions were prepared by mixing AcAc Polyester 1 with
an amine curing agent as described in Table 3. To prepare
laminates, a 10 mil drawdown bar was used to form a film (target
thickness: 4 mil) of the composition on solid substrates (Trinseo
Magnum 3325 ABS, from Standard Plaque Inc., Melvindale, Mich.,
1''.times.6''.times.0.125''). A mesh fabric (Teflon-coated 3-mesh
spacer fabric, T5977-0370-1480-01T1, obtained from Mueller
Textiles) was placed over the composition, and a handheld roller
was rolled over the sample twice to laminate the sample. The
samples were cured at ambient conditions for 7 days. Peel testing
was done either after 7 days cure or after an additional 7 day
post-cure at 80.degree. C.
[0223] The samples were tested for 180-degree peel strength
following ISO 8510-2-2006 Part 2 at 5 mm/s (12 inch/minute)
crosshead displacement rate using either an MTS Criterion Universal
Tensile Tester model C43-104E, 500 Newton load cell (MTS Systems
Corporation, Eden Prairie, Minn., US) or an Instron Model 4201. A
minimum of three samples of each composition were tested and the
average and standard deviation reported.
[0224] Examples 21-23 show that laminates with the curable
compositions can be useful as adhesives, and some have peel
strengths greater than 15 N/25 mm (Examples 21-22). Additionally,
the peel strength did not change significantly after ageing at
80.degree. C. for 7 days, indicating that the compositions are
thermally stable at these temperatures. The desired level of peel
strength can be achieved by using different curing agents.
TABLE-US-00003 TABLE 3 180 degree peel strength of cured
compositions. Peel strength Peel strength after 7 day after 7 day
RT cure + Example AcAc Amine curing RT cure 7 days at 80.degree. C.
# Resin agent (N/25 mm) (N/25 mm) 21 1 IPDA 17.9 (1.7) 21.7 (2.8)
(1.0 equiv) 22 1 MACM 25.8 (2.5) 20.3 (3.1) (1.0 equiv) 23 1
Jeffamine 6.4 (0.4) 8.1 (1.3) T-403 (1.0 equiv)
[0225] The invention has been described in detail with reference to
the embodiments described herein, but it will be understood that
variations and modifications can be effected within the scope of
the invention.
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