TEPZZ 

6Z¥568B_T
(19)

(11) EP 2 603 568 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C08G 59/42 (2006.01) C08G 59/50 (2006.01)
03.06.2015 Bulletin 2015/23 C08G 59/68 (2006.01) C08G 18/00 (2006.01)
C08L 63/00 (2006.01) C08L 75/00 (2006.01)
(21) Application number: 11739239.9 C09J 163/00 (2006.01)

(22) Date of filing: 19.07.2011 (86) International application number:

PCT/US2011/044414

(87) International publication number:

WO 2012/021258 (16.02.2012 Gazette 2012/07)

(54) EPOXY STRUCTURAL ADHESIVE

EPOXIDSTRUKTURKLEBSTOFF
ADHÉSIF STRUCTUREL EPOXIDÉ

(84) Designated Contracting States: (72) Inventor: KROPP, Michael C.

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Saint Paul, Minnesota 55133-3427 (US)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO
PL PT RO RS SE SI SK SM TR (74) Representative: Vossius & Partner
Patentanwälte Rechtsanwälte mbB
(30) Priority: 10.08.2010 US 372304 P Siebertstrasse 3
81675 München (DE)
(43) Date of publication of application:
19.06.2013 Bulletin 2013/25 (56) References cited:
WO-A1-2008/089410 WO-A1-2010/011705
(73) Proprietor: 3M Innovative Properties Company WO-A1-2010/091072 WO-A2-2010/011714
Saint Paul, MN 55133-3427 (US) WO-A2-2010/039614 US-A- 5 134 216
EP 2 603 568 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 2 603 568 B1

Description

FIELD

5 [0001] The present disclosure relates to two-part epoxy structural adhesives, including low odor, fast reacting, two-
part epoxy structural adhesives that show good adhesion to plastic substrates.

SUMMARY

10 [0002] Briefly, in one aspect, the present disclosure provides an adhesive comprising an epoxy resin component
comprising a first epoxy resin and a second epoxy resin; a first amine curing agent having an equivalent weight of at
least 50 grams per mole of amine equivalents; a second amine curing agent having an equivalent weight of no greater
than 45 grams per mole of amine equivalents; an acetoacetoxy-functionalized compound; a metal salt catalyst; and a
multifunctional acrylate.
15 [0003] In some embodiments, the first epoxy resin has the general formula of

20

wherein, R comprises one or more aliphatic, cycloaliphatic, and/or aromatic hydrocarbon groups, optionally wherein R
further comprises at least one ether linkage between adjacent hydrocarbon groups; and n is an integer greater than 1.
In some embodiments, the first epoxy resin comprises a glycidyl ether of bisphenol-A, bisphenol-F, or novolac.
25 [0004] In some embodiments, the second epoxy resin is a polyurethane-modified epoxy resin. In some embodiments,
the second epoxy resin is an isocyanate-modified epoxy resin. In some embodiments, the epoxy resin component
comprises a third epoxy resin, wherein the third epoxy resin comprises at least one epoxy-based reactive diluent. In
some embodiments, the third epoxy resin shows a high affinity for plastic substrates as determined by swelling or
dissolution of the plastic substrate e.g., polycarbonate (PC) and/or acrylonitrile-butadiene-styrene (ABS), left in contact
30 with the third epoxy resin for less than 6.5 hours.
[0005] In some embodiments, the equivalent weight of the first amine curing agent is at least 55 grams per mole of
amine equivalents. In some embodiments, the equivalent weight of the second amine curing agent is no greater than
40 grams per mole of amine equivalents. In some embodiments, the relative amounts of low equivalent weight amine
curing agent and high equivalent weight amine curing agent are selected such that the low equivalent weight amine
35 curing agent composes at least 25 wt.% of the combined weight of the low and high equivalent weight amine curing
agents, e.g., in some embodiments, the relative amounts of low equivalent weight amine curing agent and high equivalent
weight amine curing agent are selected such that the low equivalent weight amine curing agent composes between 30
and 60 wt.%, inclusive, of the combined weight of the low and high equivalent weight amine curing agents.
[0006] In some embodiments, at least one amine curing agent, in some embodiments, both amine curing agents, have
40 the formula

45

wherein, R1, R2, and R4, are independently selected from hydrogen, a hydrocarbon containing 1 to 15 carbon atoms,
and a polyether containing 1 to 15 carbon atoms; R3 represents a hydrocarbon containing 1 to 15 carbon atoms or a
50 polyether containing 1 to 15 carbon atoms; and n is from 2 to 10, inclusive.
[0007] In some embodiments, the acetoacetoxy-functionalized compound has the general formula:

55

2
 EP 2 603 568 B1

wherein, x is an integer from 1 to 10; Y represents O, S or NH; R6 is selected from the group consisting of linear, branched
and cyclic alkyl groups, aryl groups, alkylaryl groups, polyethers, polyesters, or combinations thereof; wherein R6 is
linked to Y via a carbon atom; and R7 is a linear or branched or cyclic alkyl having 1 to 12 carbon atoms. In some
embodiments, the multifunctional acrylate and the acetoacetoxy-functionalized compound together comprise at least
5 11 wt.% of the adhesive. In some embodiments, the ratio of the multifunctional acrylate to the acetoacetoxy-functionalized
compound ranges from 80 parts by weight multifunctional acrylate:20 parts by weight acetoacetoxy-functionalized com-
pound to 20 parts by weight multifunctional acrylate:80 parts by weight acetoacetoxy-functionalized compound.
[0008] In some embodiments, the metal salt catalyst comprises calcium triflate. In some embodiments, the adhesive
comprises 0.3 to 1.5 wt.% catalyst, based on the total weight of the composition.
10 [0009] In some embodiments, the adhesive further comprises a toughening agent; e.g., a core/shell polymer and/or
a butadiene-nitrile rubber. In some embodiments, the adhesive further comprises an aromatic tertiary amine.
[0010] In some aspects of the present disclosure, the adhesive comprises two components. The first component
comprises the acetoacetoxy-functionalized compound, the multifunctional acrylate, and at least a portion of the epoxy
resin component, and the second component comprises the first amine curing agent, the second amine curing agent,
15 and the metal salt catalyst. In some embodiments, the second component further comprises a portion of the epoxy resin
component. In some embodiments the first component further comprises at least one epoxy diluent.
[0011] In some embodiments, the adhesive comprises at least 16 wt.% of acetoacetoxy-functionalized compound
based on the total weight of the first component.
[0012] In some embodiments, the adhesive has a gel time at 25 °C of no greater than 20 minutes as measured
20 according to the Gel Time Test Method. In some embodiments, when cured at 23 °C, the adhesive has an over-lap
shear value of at least 0.34 MPa after no greater than 30 minutes, according to the Rate of Strength Buildup Test Method.
[0013] In another aspect, the present disclosure provides an adhesive dispenser comprising a first chamber containing
a first component of a two-part adhesive, a second chamber containing a second component of the two-part adhesive,
and a mixing tip, wherein the first and second chambers are coupled to the mixing tip to allow the first component and
25 the second component to flow through the mixing tip. The first component comprises an epoxy resin, a polyurethane-
modified or isocyanate-modified epoxy resin, a multifunctional acrylate, and an acetoacetoxy-functionalized compound,
and, in some embodiments, the first component further comprises at least one epoxy diluent. The second component
comprises a first amine curing agent having an equivalent weight of at least 50 grams per mole of amine equivalents;
a second amine curing agent having an equivalent weight of no greater than 45 grams per mole of amine equivalents;
30 and a metal salt catalyst. In some embodiments, at least one of the first or second components further comprises a
toughening agent; e.g. a core/shell polymer and/or a butadiene-nitrile rubber.
[0014] The above summary of the present disclosure is not intended to describe each embodiment of the present
invention. The details of one or more embodiments of the invention are also set forth in the description below. Other
features, objects, and advantages of the invention will be apparent from the description and from the claims.
35
DETAILED DESCRIPTION

[0015] Structural adhesives are useful in many bonding applications. For example, structural adhesives may be used
to replace or augment conventional joining techniques such as welding or the use of mechanical fasteners such as nuts
40 and bolts, screws, rivets, and the like.
[0016] Generally, structural adhesives may be divided into two broad categories: one-part adhesives and two-part
adhesives. With a one-part adhesive, a single composition comprises all the materials necessary to obtain a final cured
adhesive. Such adhesives are typically applied to the substrates to be bonded and exposed to elevated temperatures
(e.g., temperatures greater than 50 °C) to cure the adhesive.
45 [0017] In contrast, two-part adhesives comprise two components. The first component, typically referred to as the
"base resin component," comprises the curable resin, e.g., a curable epoxy resin. The second component, typically
referred to as the "accelerator component," comprises the curing agent(s) and catalysts. Various other additives may
be included in one or both components.
[0018] Generally, the two components of a two-part adhesive are mixed prior to being applied to the substrates to be
50 bonded. After mixing, the two-part adhesive gels, reaches a desired handling strength, and ultimately achieves a desired
final strength. Some two-part adhesives must be exposed to elevated temperatures to cure, or at least to cure within a
desired time. However, it may be desirable to provide structural adhesives that do not require heat to cure (e.g., room
temperature curable adhesives), yet still provide high performance in peel, shear, and impact resistance.
[0019] As used herein, "gel time" refers to the time required for the mixed components to reach the gel point. As used
55 herein, the "gel point" is the point where the mixture’s storage modulus exceeds its loss modulus.
[0020] "Handling strength" refers to the ability of the adhesive to cure to the point where the bonded parts can be
handled in subsequent operations without destroying the bond. The required handling strength varies by application. As
used herein, "initial cure time" refers to the time required for the mixed components to reach an overlap shear adhesion

3
 EP 2 603 568 B1

of 0.34 MPa (50 psi); which is a typical handling strength target. Generally, the initial cure time correlates with the gel
time; i.e., shorter gel times typically indicate adhesives with shorter initial cure times.
[0021] Generally, the bond strength (e.g., peel strength, overlap shear strength, or impact strength) of a structural
adhesive continues to build well after the initial cure time. For example, it may take hours or even days for the adhesive
5 to reach its ultimate strength.
[0022] Exemplary two-part structural adhesives include those based on acrylic, polyurethane, and epoxy chemistries.
Epoxy-based, two-part structural adhesives typically offer high performance in peel strength and shear strength, even
at elevated temperatures. Common curatives are typically amine- or mercapto-functional materials, and many variations
of these compounds are available for epoxy curing. However, most amine-cured room temperature curing epoxy-based
10 adhesives are relatively slow curing and can take several hours to reach handling strength. Catalysts, typically tertiary
amines, phenol functional resins, and some metal salts can accelerate these cures. Still, the initial cure time at room
temperature for epoxy adhesives is typically much longer than the initial cure time for acrylic adhesives.
[0023] Another difficulty with epoxy resins is their limited adhesion to certain substrates, particularly plastic substrates.
Typically plastics are bonded using acrylic adhesives, but acrylics can have a strong odor, and the cure is inhibited by
15 oxygen, which leads to inhibited cure on porous substrates.
[0024] There remains a need for an epoxy adhesive that cures rapidly and provides high adhesive strength to engi-
neering thermoplastics. In some embodiments, the present disclosure provides fast curing, room temperature curable,
two-part epoxy adhesives. In some embodiments, such adhesives can provide rapid handling strength while maintaining
excellent adhesion properties to plastics. In some embodiments, these adhesives provide room temperature gel times
20 and handling strength times of less than 30 minutes in adhesive bond thicknesses of up to 0.5 millimeters (20 mils). In
some embodiments, the adhesive is low odor, and is free of mercaptan functionality, which can be desirable in certain
applications.
[0025] Generally, the adhesives of the present disclosure comprise an epoxy resin component, a high equivalent
weight amine curing agent, a low equivalent weight amine curing agent, an acetoacetoxy-functionalized compound, a
25 metal salt catalyst, and a multifunctional acrylate. The epoxy resin component comprises a first epoxy resin and a second
epoxy resin, wherein the second epoxy resin is a polyurethane-modified or isocyanate-modified epoxy resin. In some
embodiments, the epoxy resin component may comprise additional epoxy resins. In some embodiments, the epoxy resin
component further comprises a third epoxy resin, wherein the third epoxy resin comprises at least one epoxy-based
reactive diluent.
30 [0026] First Epoxy Resins. Exemplary epoxy resins that are useful as first epoxy resins in the compositions of the
present disclosure are of the glycidyl ether type. Useful resins include those having the general Formula (I):

35

wherein

40 R comprises one or more aliphatic, cycloaliphatic, and/or aromatic hydrocarbon groups, optionally wherein R further
comprises at least one ether linkage between adjacent hydrocarbon groups; and
n is an integer greater than 1.

[0027] Generally, n is the number of glycidyl ether groups and must be greater than 1 for at least one of the first epoxy
45 resins of Formula I present in the adhesive. In some embodiments, n is 2 to 4, inclusive.
[0028] Exemplary first epoxy resins include glycidyl ethers of bisphenol A, bisphenol F, and novolac resins as well as
glycidyl ethers of aliphatic or cycloaliphatic diols. Examples of commercially available glycidyl ethers include diglyci-
dylethers of bisphenol A (e.g. those available under the trade names EPON 828, EPON 1001, EPON 1310 and EPON
1510 from Hexion Specialty Chemicals GmbH, Rosbach, Germany, those available under the trade name D.E.R. from
50 Dow Chemical Co. (e.g., D.E.R. 331, 332, and 334), those available under the trade name EPICLON from Dainippon
Ink and Chemicals, Inc. (e.g., EPICLON 840 and 850) and those available under the trade name YL-980 from Japan
Epoxy Resins Co., Ltd.); diglycidyl ethers of bisphenol F (e.g. those available under the trade name EPICLON from
Dainippon Ink and Chemicals, Inc. (e.g., EPICLON 830)); polyglycidyl ethers of novolac resins (e.g., novolac epoxy
resins, such as those available under the trade name D.E.N. from Dow Chemical Co. (e.g., D.E.N. 425, 431, and 438));
55 and flame retardant epoxy resins (e.g., D.E.R. 580, a brominated bisphenol type epoxy resin available from Dow Chemical
Co.). In some embodiments, aromatic glycidyl ethers, such as those prepared by reacting a dihydric phenol with an
excess of epichlorohydrin, may be preferred.
[0029] In some embodiments, the first epoxy resin has a molecular weight of at least 170, e.g., at least 200 g/mole.

4
 EP 2 603 568 B1

In some embodiments, the first epoxy resin has a molecular weight of no greater than 10,000, e.g., no greater than 3,000
g/mol. In some embodiments, the epoxy equivalent weight of the first epoxy resin is at least 50, in some embodiments,
at least 100 g/mole of epoxy equivalents. In some embodiments, the epoxy equivalent weight of the first epoxy resin is
no greater than 500, in some embodiments, no greater than 400 g/mole of epoxy equivalents
5 [0030] As used herein, the phrase "total weight of the composition" refers to the combined weight of both components,
i.e., the base resin component and the accelerator component.
[0031] Second epoxy resins. Generally, the second epoxy resin is selected from the group consisting of Polyurethane-
Modified Epoxy Resins, Isocyanate-Modified Epoxy Resins, and combinations thereof. Isocyanate modified epoxy resins
can have oxazolidine functionality if the isocyanate reacts directly with the epoxy, or ureido functionality if the isocyanate
10 reacts with secondary hydroxyl groups present in the epoxy molecule. Examples of isocyanate- or polyurethane-modified
epoxy resins useful as second epoxy resins in the compositions of the present disclosure include those available under
the trade names, EPU-17T-6, EP-78-11, and EPU-1761, available from Adeka Co., those under the trade name, DER
6508, from Dow Chemical Co., and those under the trade name, AER 4152, available from Asahi Denka. The present
inventors have discovered that, within the compositions of the present disclosure, polyurethane- and/or isocyanate-
15 modified epoxies generally improve adhesion to plastics such as ABS and polyvinyl chloride (PVC).
[0032] Generally, the epoxy resin component may comprise additional epoxy resins, including, but not limited to, two
or more first epoxy resins and/or two or more second epoxy resins. In some embodiments, the epoxy resins component
comprises a third epoxy resin, wherein the third epoxy resin comprises at least one epoxy-based reactive diluent.
[0033] Epoxy-based Reactive Diluent. Epoxy-based reactive diluents, including mono-epoxy compounds and di/poly-
20 functional epoxy compounds, may be added to, e.g., reduce viscosity and improve wetting. The presence of the epoxide
group(s) allows the reactive diluent to participate, with the other epoxy resin components and curing agents, in polym-
erization and crosslinking, thus allowing the diluent to be co-reacted into the resultant crosslinked network. Suitable
diluents can have at least one reactive terminal end portion and, preferably, a saturated or unsaturated cyclic backbone.
Exemplary reactive terminal ether portions include glycidyl ether. Commercially available epoxy-based reactive diluents
25 useful in the present disclosure as third epoxy resins include purified p-t-butyl glycidylphenol (available under the trade
name, EP 509S, from Adeka, Co.), 1,4-butanediol diglycidyl ether (available under the trade name, ERISYS GE21, from
CVC; and available under the trade name, RD-2, from Ciba Product Corp.), hexanediol diglycidyl ether (available under
the trade name, YED 216, from Japan Epoxy Resins, Ltd.), divinylbenzene dioxide, allocimene dioxide, monovinyl
cyclohexane oxide, epoxypentyl ethers, epoxidized cyclohexenyl compounds, limonene diepoxide, bis(2,3-epoxy-2-
30 methyl propyl)ether, 2,3-epoxy-2-methyl propyl ethers of alkylene glycols, 1,2-bis(epoxyalkyl)cyclobutanes, glycidyl gly-
cidate, 3,4-epoxyhexahydrobenzyl glycidyl ether, glycidyl ethers of C7 to C9 alcohols, oxymethyl-1,3-diozalane glycidyl
ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, and octylene oxide.
[0034] In some embodiments, the epoxy-based reactive diluent shows a high affinity for one or more plastic substrates
as determined by swelling or dissolution of the plastic substrate left in contact with the epoxy-based reactive diluent for
35 6.5 hours or less. In some embodiments, the epoxy-based reactive diluent shows a high affinity for one or more plastic
substrates as determined by swelling or dissolution of the plastic substrate left in contact with the epoxy-based reactive
diluent for an amount of time between about 5 hours and about 6.5 hours. Exemplary plastic substrates include PC,
ABS, polyamides, polyesters, polyurethanes and/or combinations thereof. In some embodiments, the addition of the
epoxy-based reactive diluent may improve the bond strength of the adhesive to certain plastic substrates.
40 [0035] In some embodiments, the compositions of the present disclosure comprise at least 20 wt.%, e.g., at least 25
wt.%, or even at least 30 wt.% of the epoxy resin component, based on the total weight of the composition. In some
embodiments, the compositions of the present disclosure comprise no greater than 90 wt.%, e.g., no greater than 75
wt.%, or even no greater than 60 wt.% of the epoxy component resin, based on the total weight of the composition.
[0036] Amine Curing Agents. Suitable curing agents are compounds which are capable of cross-linking the epoxy
45 resin. Typically, these agents are primary and/or secondary amines. The amines may be aliphatic, cycloaliphatic, or
aromatic. In some embodiments, useful amine curing agents include those having the general Formula (II)

50

wherein
55
R1, R2, and R4, are independently selected from hydrogen, a hydrocarbon containing 1 to 15 carbon atoms, and a
polyether containing up to 15 carbon atoms;
R3 represents a hydrocarbon containing 1 to 15 carbon atoms or a polyether containing up to 15 carbon atoms; and

5
 EP 2 603 568 B1

n is from 2 to 10, inclusive.

[0037] The adhesives of the present disclosure comprise at least two amine curing agents. One amine curing agent
is a low equivalent weight amine curing agent, i.e., an amine curing agent having an amine equivalent weight of no
5 greater than 45 grams per mole of amine equivalents. In some embodiments, the low equivalent weight amine curing
agent has an amine equivalent weight of no greater than 40, or even no greater than 35 grams per mole of amine
equivalents. In some embodiments, two or more low equivalent weight amine curing agents may be used.
[0038] The second amine curing agent is a high equivalent weight amine curing agent, i.e., an amine curing agent
having an amine equivalent weight of at least 50 grams per mole of equivalents. In some embodiments, the high equivalent
10 weight amine curing agent has an amine equivalent weight of at least 55 grams per mole of amine equivalents. In some
embodiments, two or more high equivalent weight amine curing agents may be used.
[0039] Exemplary amine curing agents include ethylene amine, ethylene diamine, diethylene diamine, propylene di-
amine, hexamethylene diamine, 2-methyl-1,5-pentamethylene-diamine, triethylene tetramine, tetraethylene pentamine
("TEPA"), hexaethylene heptamine, and the like. Commercially available amine curing agents include those available
15 from Air Products and Chemicals, Inc. under the trade name ANCAMINE.
[0040] In some embodiments, at least one of the amine curing agents is a polyether amine having one or more amine
moieties, including those polyether amines that can be derived from polypropylene oxide or polyethylene oxide. Suitable
polyether amines that can be used include those available from Huntsman under the trade name JEFFAMINE, and from
Air Products and Chemicals, Inc. under the trade name ANCAMINE.
20 [0041] In some embodiments, the relative amounts of the low and high equivalent weight amine curing agents are
selected such that the low equivalent weight amine curing agent(s) compose at least 25 wt.%, in some embodiments,
at least 30 wt.%, at least 40 wt.%, or even at least 50 wt.%, of the combined weight of the low and high equivalent weight
amine curing agents. In some embodiments, the low equivalent weight amine curing agent(s) compose between 30 and
70 wt.%, in some embodiments, between 30 and 60 wt.%, or even between 30 and 50 wt.% of the combined weight of
25 the low and high equivalent weight amine curing agents.
[0042] Unless otherwise indicated, all ranges expressed herein are inclusive, i.e., all ranges include the end points of
the range. Thus, for example, a range of 30 to 70 wt.% includes 30 wt.%, 70 wt.% and all values in between (e.g., 30.1
wt.%, 40 wt.%, and 69.9 wt.%).
[0043] Acetoacetoxy-functionalized compound. The acetoacetoxy-functionalized compound is a material comprising
30 at least one acetoacetoxy group, preferably in a terminal position. Such compounds include acetoacetoxy group(s)
bearing hydrocarbons, such as linear, branched and cyclic alkyl groups, aryl groups, alkylaryl groups, as well as poly-
ethers, polyesters, or combinations thereof.
[0044] Generally, the acetoacetoxy-functionalized compound is a monomer or relatively low molecular weight oligomer.
In some embodiments, the oligomer comprises no greater than 20 repeat units, in some embodiments, no greater than
35 10, or even no greater than 5 repeat units. In some embodiments, the acetoacetoxy-functionalized oligomer has a
molecular weight of no greater than 10,000 g/mol, e.g., no greater than 4,000, no greater than 3000, or even no greater
than 1000 g/mol. In some embodiments, the acetoacetoxy-functionalized compound has a molecular weight of at least
100 g/mol, e.g., at least 150, or even at least 200 g/mol.
[0045] In some embodiments, the acetoacetoxy-functionalized compound has the general Formula (III):
40

45

In Formula (III)

x is an integer from 1 to 10 (e.g., an integer from 1 to 3);

50
Y represents O, S or NH; and

R7 is a linear or branched or cyclic alkyl having 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, butyl, sec-butyl,
tert-butyl, and the like).
55
[0046] In Formula (III), R6 is selected from the group consisting of polyoxy groups, polyester -alkyls, -aryls, and
-alkylaryls, and linear, branched, saturated, and unsaturated alkyl-, aryl-, and alkylaryl- groups; wherein R6 is linked to
Y via a carbon atom.

6
 EP 2 603 568 B1

[0047] Generally, R6 may be linear or branched. In some embodiments, R6 comprises from 2 to 20 carbon atoms,
e.g., from 2 to 10 carbon atoms. In some embodiments, R6 may contain from 2 to 20 oxygen atoms, e.g., from 2 to 10
oxygen atoms.
[0048] Acetoacetoxy-functionalized compounds are commercially available, for example, as K-FLEX XM-B301 from
5 King Industries.
[0049] The compositions of the present disclosure comprise at least 16 wt.% acetoacetoxy-functionalized compound,
based on the total weight of the composition. In some embodiments, the composition comprises at least 17 wt.%, or
even at least 18 wt.% acetoacetoxy-functionalized compound, based on the total weight of the composition. In some
embodiments, the composition comprises no greater than 30 wt.%, e.g., no greater than 25 wt.%, or even no greater
10 than 20 wt.% acetoacetoxy-functionalized compound, based on the total weight of the composition.
[0050] Metal Salt Catalyst. Suitable metal salt catalysts include the group I metal, group II metal, and lanthanoid salts.
In some embodiments, the group I metal cation is lithium. In some embodiments, the group II metal cation is calcium or
magnesium. Generally, the anion is selected from nitrates, iodides, thiocyanates, triflates, alkoxides, perchlorates, and
sulfonates, including their hydrates. In some embodiments, the anion is a nitrate or a triflate. In some embodiments, the
15 metal salt catalyst may be selected from the group consisting of lanthanum nitrate, lanthanum triflate, lithium iodide,
lithium nitrate, calcium nitrate, calcium triflate, and their corresponding hydrates.
[0051] In general, a catalytic amount of salt is employed. In some embodiments, the composition will comprise at least
0.1, e.g., at least 0.5, or even at least 0.8 wt.% catalyst based on the total weight of the composition. In some embodiments,
the composition will comprise no greater than 2 wt.%, e.g., no greater than 1.5 wt.%, or even no greater than 1.1 wt.%
20 catalyst based on the total weight of the composition In some embodiments, the composition comprises 0.2 to 2 wt.%,
e.g., 0.3 to 1.5 wt.% , or even 0.8 to 1.1 wt.% catalyst based on the total weight of the composition.
[0052] Multifunctional Acrylates. Multifunctional acrylates include compounds comprising two or more acrylate func-
tional groups. The acrylates will react with amines in the accelerator component of a two-part epoxy system via the
Michael reaction, which is a more rapid reaction than that of the epoxy with the amine. Exemplary multifunctional acrylates
25 useful for shortening the gel time include hexanediol diacrylate; pentaerythritol pentaacrylate; blends of multifunctional
acrylic resins available under the trade name MCURE, from Sartomer; and trimethylol propane triacrylate (TMPTA),
available, in various levels blended with bisphenol A epoxy resins, under the trade name, EPON 8111, from Hexion.
[0053] In some embodiments, the multifunctional acrylate and the acetoacetoxy-functionalized compound together
comprise at least 11 wt.% of the adhesive. In some embodiments, the ratio of the multifunctional acrylate to the ace-
30 toacetoxy-functionalized compound ranges from 80 parts by weight multifunctional acrylate:20 parts by weight acetoac-
etoxy-functionalized compound to 20 parts by weight multifunctional acrylate:80 parts by weight acetoacetoxy-function-
alized compound.
[0054] In some embodiments, the adhesive compositions of the present disclosure can be used in bonding applications
that require fast cure times and good adhesion to plastic substrates such as PC, ABS, polyamides, polyesters, poly-
35 urethanes, and combinations thereof.
[0055] The adhesive compositions of the present disclosure may contain any of a wide variety of additional, optional,
components. Exemplary, non-limiting, optional additives include the following.
[0056] Toughening agents. Toughening agents are polymers capable of increasing the toughness of cured epoxy
resins. The toughness can be measured by the peel strength of the cured compositions. Typical toughening agents
40 include core/shell polymers, butadiene-nitrile rubbers, and acrylic polymers and copolymers.
[0057] In some embodiments, the toughening agent is a core/shell polymer. In some embodiments, the core may be
an elastomer, e.g., an elastomer having a glass transition temperature lower than 0 °C. In some embodiments, the core
comprises a butadiene polymer or copolymer (e.g., a butadiene-styrene copolymer), an acrylonitrile polymer or copol-
ymer, an acrylate polymer or copolymer, or combinations thereof. In some embodiments, the polymers or copolymers
45 of the core may be cross-linked.
[0058] Generally, the shell comprises one or more polymers grafted on to the core. In some embodiments, the shell
polymer has a high glass transition temperature, i.e. a glass transition temperature greater than 26 °C. The glass transition
temperature may be determined by dynamic mechanical thermo analysis (DMTA) ("Polymer Chemistry, The Basic
Concepts, Paul C. Hiemenz, Marcel Dekker 1984).
50 [0059] Exemplary core/shell polymers and their preparation are described in, e.g., U.S. Patent No. 4,778,851. Com-
mercially available core/shell polymers include, e.g., PARALOID EXL 2600 from Rohm & Haas Company, Philadelphia,
USA, and KANE ACE MX120 from Kaneka, Belgium.
[0060] In some embodiments, the core/shell polymer has an average particle size of at least 10 nm, e.g., at least 150
nm. In some embodiments, the core/shell polymer has an average particle size of no greater than 1,000 nm, e.g., no
55 greater than 500 nm.
[0061] In some embodiments, the core/shell polymer may be present in an amount of at least 5 wt.%., e.g., at least 7
wt.%, based on the weight of the total composition. In some embodiments, the core/shell polymer may be present in an
amount no greater than 50 wt.%, e.g., no greater than 30 wt.%, e.g., no greater than 15 wt.% , based on the weight of

7
 EP 2 603 568 B1

the total composition.

[0062] In some embodiments, the composition may also comprise a secondary catalyst. Exemplary secondary catalysts
include imidazoles, imidazole-salts, and imidazolines. Aromatic tertiary amines may also be used as secondary curatives,
including those having the structure of Formula (IV):
5

10

wherein; R8 is H or an alkyl group; R9, R10, and R11 are, independently, hydrogen or CHNR12R13, wherein at least
15 one of R9, R10, and R11 is CHNR12R13; and R12 and R13 are, independently, alkyl groups. In some embodiments,
the alkyl groups of R8, R12, and/or R13 are methyl or ethyl groups. One, exemplary secondary curative is tris-
2,4,6-(dimethylaminomethyl)phenol, commercially available as ANCAMINE K54 from Air Products Chemicals.
[0063] Other additives may include adhesion promoters, corrosion inhibitors and rheology controlling agents. Exem-
plary additives include silica-gels, calcium silicates, phosphates, molybdates, fumed silica, clays such as bentonite or
20 wollastonite, organo-clays, aluminium-trihydrates, hollow-glass-microspheres; hollow-polymeric microspheres, silane
coupling agents, and calcium-carbonate.
[0064] Pigments may include inorganic or organic pigments including ferric oxide, brick dust, carbon black, titanium
oxide and the like.

25 Examples

Test Methods

[0065] Gel Time Test Method. Gel times were measured at 25 °C with an ARES LS2 rheometer (TA Instruments),
30 using a parallel plate configuration with 25 mm diameter plates and a 0.5 mm gap. Measurements were made in dynamic
mode at 1 Hz, starting at 5% strain. The autotension and autostrain settings were used to control the gap and torque
during the measurement. After applying samples directly to the bottom plate, the gap was set and the test was started
within 30 seconds. The time to reach the crossover point, i.e., the point where the storage modulus (G’) value became
greater than the loss modulus (G") value, was reported as the gel time.
35 [0066] Overlap Shear Adhesion Test Method. Test panels measuring 2.5 cm wide by 10.2 cm long (1 inch by 4 inches)
of several different materials were used to evaluate overlap shear adhesion. The bonding surfaces of the panels were
cleaned by lightly abrading them using a 3M SCOTCH-BRITE No. 86 scouring pad (green colored), followed by an
isopropyl alcohol wipe to remove any loose debris. A bead of adhesive was then dispensed along one end of a test
panel, about 6.4 mm (0.25 inch) from the end. The panels were joined together face to face along their length to provide
40 an overlap bond area measuring approximately 1.3 cm long and 2.5 cm wide (0.5 inch by 1 inch). A uniform bond line
thickness was provided by sprinkling a small amount of 0.2 mm (0.008 inch) diameter solid glass beads on the adhesive
before joining the two test panels together. The bonded test panel samples were allowed to dwell at 23 °C (room
temperature) for at least 48 hours to ensure full cure of the adhesive. The samples were tested at 22 °C for peak overlap
shear strength at a separation rate of 2.5 mm/minute (0.1 inch/minute). The reported values represent the average of
45 three samples.
[0067] Rate of Strength Buildup Test Method. Six aluminum test panels measuring 10.2 cm long by 2.5 cm wide by
1.6 mm thick ((4 inches by 1 inch by 0.063 inch) were cleaned and bonded as described above in the Overlap Shear
Adhesion Test Method with the following modification. Spacer beads having a diameter of between 0.08 and 0.13 mm
(0.003 and 0.005 inches) were used to control the bond line thickness. The bonded test panels were held at room
50 temperature (23 °C) and evaluated for overlap shear strength at periodic intervals from the time the bonds were made.
[0068] Materials. The inventive compositions are comprised of a first epoxy resin (component a1) and a second epoxy
resin (component a2); a first amine curing agent having an equivalent weight of at least 50 grams per mole of amine
equivalents (component b); a second amine curing agent having an equivalent weight of no greater than 45 grams per
mole of amine equivalents (component c); an acetoacetoxy-functionalized compound (component d); a metal salt catalyst
55 (component e); and a multifunctional acrylate (component f). Some embodiments of the inventive compositions may
also comprise a third epoxy resin (component a3), wherein the third epoxy resin comprises at least one epoxy-based
reactive diluent. Some compositions may also comprise other additives (component other). The materials used in the
examples as components a1-other are summarized in Table 1.

8
 EP 2 603 568 B1

Table 1: Materials.
Component Material Description Source

5 KANE-ACE MX-257 37 wt.% core/shell rubber dispersed in bisphenol

("MX-257") A epoxy Kaneka Texas Corp
KANE-ACE MX-267 37 wt.% core/shell rubber dispersed in bisphenol
("MX-267") F epoxy Kaneka Texas Corp
a1
10 bisphenol A epoxy (average ew = 186), electronic Japan Epoxy Resins,
YL 980 grade Ltd.
EPON 834 bisphenol A epoxy (average ew = 255) Hexion, Columbus, OH
EPON 828 bisphenol A epoxy (average ew = 189) Hexion, Columbus, OH
15 Asahi Kasai Chemicals,
a2
AER 4152 isocyanate modified epoxy Tokyo, Japan
EP 509S p-t-butyl glycidylphenol, distilled grade Adeka, Tokyo, Japan
a3 CVC Chemical,
20 ERISYS GE21 1,4 butanediol diglycidyl ether Moorestown, NJ
diethylene glycol di(aminopropyl) ether (average Air Products, Allentown,
b
ANCAMINE 1922A ew = 55) PA
Air Products, Allentown,
c
25 ANCAMINE 2678 proprietary diamine (average ew = 30) PA
acetoacetate ("AcAc") functional reactive diluent King Industries,
d
XM B301 (average ew = 190) Norwalk, CT
calcium trifluoromethanesulfonate (i.e., calcium
e
30
CaOTf triflate) 3M Co., St Paul, MN
proprietary blend of multifunctional acrylates
MCURE 201 (average ew = 100) Sartomer, Exton, PA
f
proprietary blend of multifunctional acrylates
MCURE 300 (average ew = 116) Sartomer, Exton, PA
35
Dow Corning Co.,
Z-6040 glycidoxy propyltrimethoxy silane Midland, MI
BASF, Ludwigshafen,
ASP 600 hydrous aluminosilicate DE
40
SYLOTHIX 52 polyethylene/silica fibers EP Minerals, Reno, NV
Unimin, New Canaan,
MINEX 7, 4, or 10 alumina silicate CT
Other
45 epoxy-modified, carboxyl-terminated, butadiene- CVC Chemical,
HYPOX RF 1341 nitrile rubber Moorestown, NJ
KELPOXY epoxy-modified, carboxyl-terminated, butadiene-
G293-100 nitrile rubber Reichhold

50
Air Products, Allentown,
K-54 2,4,6-tri(dimethylaminomethyl)phenol PA
R805 octylsilane treated fumed silica Evonik, Essen, DE
* ew = equivalent weight in grams per mole of equivalents.
55
[0069] Base Component Preparation Method. Using the compositions summarized in Table 2, all materials were
weighed into plastic cups that varied in size depending on the batch size. The materials were mixed at room temperature
in a DAC 600 FVZ SPEEDMIXER (Hauschild Engineering, Hamm, Germany) for one to two minutes at 2350-3000 rpm

9
 EP 2 603 568 B1

to prepare the base component.

Table 2: Base Component Compositions (reported in wt. %).

I.D. B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 REF-B
5
MX-257 34.2 32.6 33.2 33.5 34.5 --- --- --- --- --- 33.2 26.8
MX-267 --- --- --- --- --- 28.2 27.8 28.8 26.8 31.0 --- ---
a1 YL 980 --- --- 16.2 --- --- --- --- --- --- 15.8 --- 30.0
10 EPON 828 --- --- --- --- --- --- --- --- --- --- --- 10.6
EPON 834 --- --- --- --- --- --- --- --- 13.7 --- --- ---
a2 AER 4152 16.7 --- 16.2 16.4 16.9 14.4 14.1 14.6 --- 15.8 16.2 ---
509S 16.7 15.9 --- 16.3 16.9 --- --- --- --- --- 16.2 ---
15 a3
ERISYS GE21 --- --- --- --- --- 14.4 14.1 14.6 13.7 --- --- ---
b --- --- --- --- --- --- --- --- --- --- --- --- ---
c --- --- --- --- --- --- --- --- --- --- --- --- ---
20 d XM B301 13.2 12.6 12.8 25.9 --- 10.5 20.7 --- 10.0 11.5 8.4 22.8
e --- --- --- --- --- --- --- --- --- --- --- --- ---
f MCURE 201 13.2 12.6 12.8 --- 26.7 10.5 --- 21.4 10.0 11.5 17.2 ---
Z-6040 1.0 1.0 1.0 1.0 1.1 0.9 0.9 0.9 0.9 0.9 1.0 0.7
25
ASP 600 3.5 8 6.3 5.4 2.6 --- --- --- --- ---- 5.8 ---
Other SYLOTH IX 52 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.0 ---
MINEX 4 or 7 --- --- --- --- --- 19.6 20.9 18.1 23.5 12.0 --- 8.2
30
R805 --- --- --- --- --- --- --- --- --- --- --- 0.9

[0070] Accelerator Component Preparation Method. Accelerator components were prepared according to the com-
positions summarized in Table 3. The ACAMINE 1922A, and 2678 amines were weighed into a 0.5 liter can. This mixture
35 was stirred at 350 rpm with an overhead stir motor and impellor blade under a nitrogen stream while heated to 71 °C
on a hot plate. The epoxy resins were added in multiple charges via a syringe at approximately 30 g per addition. The
exotherm that occurred after each epoxy resin addition was allowed to subside such that the temperature of the mixture
returned to 71 °C. Additional epoxy resin was added when the temperature had returned to 71 °C. This process was
repeated until the desired amount of epoxy resin had been added. The temperature of amine/epoxy mixture was then
40 raised to 82 °C, the CaOTf was added, and the mixing speed was increased to 750 rpm. After 30 minutes, the temperature
was reduced to 71 °C. Upon reaching this temperature, the ANCAMINE K-54 was added, and the accelerator composition
was stirred for an additional 5-10 minutes. If any fillers were used in the accelerator composition, these materials were
added and mixed in using the DAC 600 FVZ SPEEDMIXER as described above for the base resins.

45 Table 3: Accelerator Component Compositions (reported in wt. %).

I.D. A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 REF-A
a1 EPON 828 5.6 6.1 5.8 5.7 5.4 5.3 5.2 4.9 5.7 12.6
a2 --- --- --- --- --- --- --- --- --- --- ---
50
a3 --- --- --- --- --- --- --- --- --- --- ---
b ANCAMINE 1922A 49.1 54.2 51.6 50.8 47.6 55.0 53.8 50.8 50.7 32.5
c ANCAMINE 2678 7.3 8.0 7.6 7.5 7.0 8.4 8.2 7.8 7.5 21.7

55 d --- --- --- --- --- --- --- --- --- --- ---
e CaOTf 2.3 2.6 2.4 2.4 2.3 2.5 2.5 2.3 2.4 2.8
f --- --- --- --- --- --- --- --- --- --- ---

10
 EP 2 603 568 B1

(continued)

I.D. A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 REF-A
HYPOX RF 1341 or
5 17.0 18.8 17.9 17.6 16.5 22.5 22.1 20.8 17.6 21.8
KELPOXY G293-100
K-54 5.7 6.3 6.0 5.9 5.6 5.1 5.0 4.7 4.8 3.6

Other ASP 600 11.4 2.4 7.0 8.4 14.0 --- --- --- 7.2 ---

10 SYLOTHIX 52 1.6 1.6 1.6 1.6 1.6 1.2 1.4 1.4 4.0 ---
MINEX 4 or 7 --- --- --- --- --- --- 1.8 8.4 --- 4.0
R805 --- --- --- --- --- --- --- --- --- 1.0

15 [0071] Resin/Substrate Affinity. Plastic coupons measuring 10.2 by 2.5 by 0.3 cm were cleaned with isopropyl alcohol.
The plastic coupon substrate materials are defined in Table 4. A small amount of epoxy-based reactive diluent was
placed onto the surface of each plastic coupon, 76-127 micrometer (3-5 mil) spacer beads were sprinkled onto the
diluent, and an 18mm diameter microscope slide coverslip was placed onto the diluent and pressed against the substrate.
The resin was left in contact with the plastic coupon for 5 to 6.5 hours. The coverslip was then removed, and the coupon
20 was wiped with isopropyl alcohol and visually inspected. A ’pass’ was recorded when the resin clearly dissolved or
swelled the plastic coupon, either leaving an indentation or raised bump on the substrate. A ’fail’ was recorded if there
was no mark or only slight hazing of the substrate, with no evidence of dissolution or swelling. The results are shown in
Table 5.

25 Table 4: Substrate Materials.

I.D. Material Description Source
PC1 LEXAN polycarbonate resin thermoplastic SABIC
PC2 EMERGE 8600 Dow Chemical Co.
30
ABS ABS NATURAL acrylonitrile-butadiene-styrene Plastic Intl, Eden Prairie, MN
PC/ABS CYCOLOY 6600 Acrylonitrile-butadiene-styrene and polycarbonate plastic SABIC

35
Table 5: Substrate Affinity of Epoxy-Based Reactive Diluent.
Epoxy-Based Reactive Solubility Parameter (Diluent) Viscosity
Diluent (J/cm) (cps) PC1 PC2 ABS PC/ABS
EP 509S 20.03 25 Fail Fail Fail Pass
40
ERISYS GE21 19.56 15 Pass Pass Pass Pass

[0072] Two-Part Dispenser. The base resin and the accelerator components were degassed under vacuum at room
temperature while mixing. The materials were then loaded into 2:1 DUO-PAK syringes (available from Wilcorp Corpo-
45
ration). The ratio was 2 parts by weight base component to 1 part by weight accelerator component, yielding a 2:1 ratio
of epoxy equivalents to amine equivalents. Samples were degassed by placing the syringes in an oven at 70 °C for 15
to 20 minutes. After being removed from the oven and allowed to cool to room temperature, resin was dispensed until
a bubble free, even flow from both sides of the cartridge was observed. A static mixing tip was then attached to the outlet
of the syringe and used to dispense the adhesives for curing and bonding.
50
[0073] Experiment 1: Examples 1-2 (EX-1 and EX-2), Comparative Examples 1-3 (CE-1 through CE-3).
[0074] Various combinations of the base epoxy and amine accelerators were placed into Duo-Pak syringes. These
were tested for gel point using the ARES rheometer. The same adhesives were used to prepare overlap shear samples
for testing on PC2 and PC/ABS substrates. The results are shown in Table 6.

55

11
 5

55
50
45
40
35
30
25
20
15
10
Table 6
Overlap Shear (MPa)
Ex. Base (2 pbw) Accel. (1 pbw) a1 a2 a3 b c d e f Other Gel Time (min)
PC2 PC/ABS
EX-1 B-1 A-1 24.7 11.1 11.1 16.4 2.4 8.8 0.8 8.8 15.9 12.7 3.6 SF
EX-2 B-3 A-3 34.8 10.8 --- 17.2 2.5 8.5 0.8 8.5 16.9 13.4 SF SF
CE-1 B-2 A-2 23.7 --- 10.6 18.1 2.7 8.4 0.9 8.4 27.2 14.2 3.3 5.0
CE-2 B-4 A-4 24.2 10.9 10.9 16.9 2.5 17.3 0.8 --- 16.5 12.5 3.5 4.6
CE-3 B-5 A-5 24.8 11.3 11.3 15.9 2.3 --- 0.8 17.8 15.8 28.9 SF 6.1
SF = substrate failure

12
EP 2 603 568 B1
 EP 2 603 568 B1

[0075] Table 6 shows the accelerating effect the combination of the acetoacetoxy functionalized compound (AcAc),
CaOTf, and amine functionality on the gel time for the amine cured epoxy adhesive. This shows that using the multi-
functional acrylate without the AcAc component results in the slowest gel time. Table 6 also shows that adhesion to
plastics is diminished in samples without the polyurethane epoxy or the multifunctional acrylate. Comparative Example
5 3 (CE-3) illustrates that good adhesion to plastics can be obtained without the AcAc component, but the gel time is
increased. Example 1 (EX-1) illustrates that diluents can be used, especially if they show a strong affinity for the plastic
being bonded (see Table 5, above).
[0076] Experiment 2: Example 3 (EX-3), Comparative Examples 4-6 (CE-4 through CE-6), and Reference Example
1 (REF-1).
10 [0077] Bonding can be more challenging on certain plastic substrates, for example, on pure ABS and PC1. In such
cases, it is beneficial to add the epoxy-based reactive diluent to achieve better bonding. Various combinations of the
base epoxy and amine accelerators were tested for gel point using the ARES rheometer and to prepare overlap shear
samples on PC1 and pure ABS. The results are shown in Table 7. A comparison of the gel times of the compositions
shown in Table 6 (EX-1, EX-2, and CE-1) with the gel times of the compositions shown in Table 7 (EX-3, CE-6, and
15 REF-1) shows that a greater total amount of AcAc and acrylate in the compositions of table 6 results in faster gel times.
When lower amounts of amine are used, the corresponding gel time is longer.

20

25

30

35

40

45

50

55

13
 5

55
50
45
40
35
30
25
20
15
10
Table 7
Overlap Shear (MPa)
Ex. Base (2 pbw) Accel (1 pbw) a1 a2 a3 b c d e f Othe r Gel Time (min)
PC1 ABS
EX-3 B-6 A-6 20. 6 9.6 9.6 18. 3 2.8 7.0 0.8 7.0 38.3 22.8 6.0 6.3
CE-4 B-7 A-6 20. 3 9.4 9.4 1.8 3 2.8 13. 8 0.8 --- 25.2 20.8 4.7 5.5
CE-5 B-8 A-7 20. 9 9.7 9.7 17. 9 2.7 --- 0.8 14. 3 24.0 26.1 4.9 5.4
CE-6 B-9 A-6 28. 8 --- 9.1 18. 3 2.8 6.7 0.8 6.7 26.8 23.4 6.3 3.5
REF-1 B-10 A-8 26. 1 10. 5 --- 16. 9 2.6 7.7 0.8 7.7 27.7 25.3 3.5 2.8

14
EP 2 603 568 B1
 EP 2 603 568 B1

Experiment 3: Example 4 (EX-4) and Reference Example 2 (REF-2).

[0078] The gel time of EX-4 was tested by dispensing 10g of material into a plastic Petri dish from a 2:1 cartridge with
a static mixing tip. A wooden dowel was used to occasionally stir the material to determine when it had gelled. As shown
5 in Table 8, the sample gelled in 7 minutes.
[0079] REF-2 (a fast-cure epoxy adhesive available under the trade name DP 405 from 3M) and EX-4 were used to
prepare overlap shear tests on PC2 and PC/ABS substrates.

10

15

20

25

30

35

40

45

50

55

15
 5

55
50
45
40
35
30
25
20
15
10
Table 8
Overlap Shear (MPa)
Ex. Base (2 pbw) Accel. (1 pbw) a1 a2 a3 b c d e f Other
PC2 PC/ABS
EX-4 B-11 A-9 24.1 10.8 10.8 16.9 2.5 5.6 0.8 11.5 17.0 9.23 (SF) 9.36 (SF)
REF-2 REF-B REF-A 49.2 --- --- 10.8 7.2 15.2 0.9 --- 16.7 2.90 3.43
SF = Substrate Failure

16
EP 2 603 568 B1
 EP 2 603 568 B1

[0080] Six 10.2 by 2.5 cm aluminum coupons were bonded with the adhesives of EX-4 using a 1.3 cm overlap and
76-127 micrometer (3-5 mil) spacer beads to control the bond line thickness. The overlap shear strength was measured
at periodic intervals from the time the bonds were made according to the Rate of Strength Buildup Test Method. The
results of the Rate of Strength Buildup Test are shown in Table 9.
5
Table 9: Rate of strength build-up.
Time (min) Shear Strength (MPa)
10 0.007
10 15 0.02
20 0.29
25 0.3
30 0.34
15

[0081] Table 9 shows that, in some embodiments, adhesive compositions of the present disclosure can achieve a
handling strength in overlap shear of about 0.3 MPA in 20 minutes, and 0.34 MPa in 30 minutes.
[0082] Additional Properties. To determine tip life, EX-4 was also dispensed from the cartridge at 5 and 10 minutes
20 following initial dispensing. The material was able to be dispensed successfully, without plugging the tip, after 10 minutes
from initial dispensing.

Claims
25

1. An adhesive comprising:

(a) an epoxy resin component comprising:

30 (a1) a first epoxy resin, and

(a2) a second epoxy resin, wherein the second epoxy resin is selected from the group consisting of a
polyurethane-modified epoxy resin, an isocyanate-modified epoxy resin, and combinations thereof;

(b) a first amine curing agent having an amine equivalent weight of at least 50 grams per mole of amine
35 equivalents;
(c) a second amine curing agent having an amine equivalent weight of no greater than 45 grams per mole of
amine equivalents;
(d) an acetoacetoxy-functionalized compound;
(e) a metal salt catalyst; and
40 (f) a multifunctional acrylate.

2. The adhesive of claim 1, wherein the epoxy resin component further comprises:

(a3) a third epoxy resin, wherein the third epoxy resin comprises at least one epoxy-based reactive diluent.
45

3. The adhesive according to claim 2, wherein the third epoxy resin shows a high affinity for one or more plastic
substrates selected from the group comprising polycarbonate, acrylonitrile-butadiene-styrene, or combinations there-
of, as determined by swelling or dissolution of the plastic substrate left in contact with the third epoxy resin for an
amount of time equal to or less than 6.5 hours.
50

4. The adhesive according to any of the preceding claims, wherein the amount of the multifunctional acrylate and the
acetoacetoxy-functionalized compound together comprises at least 11 wt.% of the adhesive.

5. The adhesive according to any of the preceding claims, wherein the ratio of the multifunctional acrylate to the
55 acetoacetoxy-functionalized compound ranges from 80 parts by weight multifunctional acrylate:20 parts by weight
acetoacetoxy-functionalized compound to 20 parts by weight multifunctional acrylate:80 parts by weight acetoace-
toxy-functionalized compound

17
 EP 2 603 568 B1

6. The adhesive according to any one of the preceding claims, wherein the amine equivalent weight of the first amine
curing agent is at least 55 grams per mole of amine equivalents and wherein the amine equivalent weight of the
second amine curing agent is no greater than 40 grams per mole of amine equivalents.

5 7. The adhesive according to any one of the preceding claims, wherein the first epoxy resin comprises a glycidyl ether
of bisphenol-A, bisphenol-F, or novolac.

8. The adhesive according to any one of the preceding claims, wherein at least one of the amine curing agents has
the general formula
10

15

wherein,

20 R1, R2, and R4, are independently selected from hydrogen, a hydrocarbon containing 1 to 15 carbon atoms,
and a polyether containing 1 to 15 carbon atoms;
R3 represents a hydrocarbon containing 1 to 1 carbon atoms or a polyether containing 1 to 15 carbon atoms; and
n is from 1 to 10, inclusive.

25 9. The adhesive according to any one of the preceding claims, wherein the relative amounts of low equivalent weight
amine curing agent and high equivalent weight amine curing agent are selected such that the low equivalent weight
amine curing agent comprises at least 25 wt.% of the combined weight of the low and high equivalent weight amine
curing agents.

30 10. The adhesive according to any one of the preceding claims, wherein the relative amounts of low equivalent weight
amine curing agent and high equivalent weight amine curing agent are selected such that the low equivalent weight
amine curing agent comprises between 30 and 60 wt.%, inclusive, of the combined weight of the low and high
equivalent weight amine curing agents.

35 11. The adhesive according to any one of the preceding claims, wherein the acetoacetoxy-functionalized compound
has the general formula of:

40

wherein,
45
x is an integer from 1 to 10;
Y represents O, S or NH;
R6 is selected from the group consisting of polyoxy groups, polyester -alkyls, -aryls, and -alkylaryls, and linear,
branched, saturated, and unsaturated alkyl-, aryl-, and alkylaryl- groups; wherein R6 is linked to Y via a carbon
50 atom; and
R7 is a linear or branched or cyclic alkyl having 1 to 12 carbon atoms.

12. The adhesive according to any one of the preceding claims, wherein the metal salt catalyst comprises calcium triflate.

55 13. The adhesive according to any one of the preceding claims, wherein the adhesive comprises 0.3 to 1.5 wt.% catalyst,
based on the total weight of the composition.

14. The adhesive according to any one of the preceding claims, wherein the adhesive comprises two components,

18
 EP 2 603 568 B1

wherein:

(a) the fist component comprises:

5 (i) the acetoacetoxy-functionalized compound,

(ii) the multifunctionalized acrylate, and
(iii) at least a portion of the epoxy resin component; and

(b) the second component comprises:

10
(i) the first amine curing agent,
(ii) the second amine curing agent, and
(iii) the metal salt catalyst.

15 15. An adhesive dispenser comprising a first chamber containing a first component of a two-part adhesive, a second
chamber containing a second component of the two-part adhesive, and a mixing tip, wherein the first and second
chambers are coupled to the mixing tip to allow the first component and the second component to flow through the
mixing tip; and wherein the first component comprises an epoxy resin, a polyurethane-modified or isocyanate-
modified epoxy resin, a multifunctional acrylate, and an acetoacetoxy-functionalized compound, and the second
20 component comprises a first amine curing agent having an amine equivalent weight of at least 50 grams per mole
of amine equivalents; a second amine curing agent having an amine equivalent weight of no greater than 45 grams
per mole of amine equivalents, and a metal salt catalyst.

25 Patentansprüche

1. Klebstoff, umfassend:

(a) einen Epoxidharz-Bestandteil, umfassend:

30
(a1) ein erstes Epoxidharz und
(a2) ein zweites Epoxidharz, wobei das zweite Epoxidharz ausgewählt ist aus der Gruppe bestehend aus
einem polyurethan-modifizierten Epoxidharz, einem isocyanatmodifizierten Epoxidharz und Kombinationen
davon,
35
(b) ein erstes Aminhärtungsmittel mit einer Aminäquivalentmasse von mindestens 50 Gramm pro Mol Aminä-
quivalente,
(c) ein zweites Aminhärtungsmittel mit einer Aminäquivalentmasse von nicht mehr als 45 Gramm pro Mol
Aminäquivalente,
40 (d) eine acetoacetoxy-funktionalisierte Verbindung,
(e) einen Metallsalz-Katalysator und
(f) ein multifunktionelles Acrylat.

2. Klebstoff nach Anspruch 1, wobei der Epoxidharz-Bestandteil ferner umfasst:

45
(a3) ein drittes Epoxidharz, wobei das dritte Epoxidharz mindestens ein epoxidbasiertes reaktives Verdün-
nungsmittel umfasst.

3. Klebstoff nach Anspruch 2, wobei das dritte Epoxidharz eine hohe Affinität für ein oder mehrere Kunststoffsubstrate
50 zeigt, ausgewählt aus der Gruppe umfassend Polycarbonat, Acrylnitrilbutadienstyrol oder Kombinationen davon,
gemäß Bestimmung durch Quellen oder Auflösung des Kunststoffsubstrats, welches mit dem dritten Epoxidharz
für eine Dauer in Kontakt gelassen wird, die gleich oder geringer als 6,5 Stunden ist.

4. Klebstoff nach einem der vorstehenden Ansprüche, wobei die Menge des multifunktionellen Acrylats und der ace-
55 toacetoxy-funktionalisierten Verbindung zusammen mindestens 11 Gew.-% des Klebstoffs umfasst.

5. Klebstoff nach einem der vorstehenden Ansprüche, wobei das Verhältnis des multifunktionellen Acrylats zu der
acetoacetoxy-funktionalisierten Verbindung im Bereich von 80 Gewichtsteilen multifunktionelles Acrylat: 20 Ge-

19
 EP 2 603 568 B1

wichtsteilen acetoacetoxy-funktionalisierte Verbindung bis 20 Gewichtsteilen multifunktionelles Acrylat: 80 Ge-

wichtsteilen acetoacetoxy-funktionalisierte Verbindung liegt.

6. Klebstoff nach einem der vorstehenden Ansprüche, wobei die Aminäquivalentmasse des ersten Aminhärtungsmittels
5 mindestens 55 Gramm pro Mol Aminäquivalente beträgt und wobei die Aminäquivalentmasse des zweiten Amin-
härtungsmittels nicht mehr als 40 Gramm pro Mol Aminäquivalente beträgt.

7. Klebstoff nach einem der vorstehenden Ansprüche, wobei das erste Epoxidharz einen Glycidylether von Bisphenol-
A, Bisphenol-F oder Novolac umfasst.
10
8. Klebstoff nach einem der vorstehenden Ansprüche, wobei mindestens eines der Aminhärtungsmittel die allgemeine
Formel

15

20
aufweist, worin

R1, R2 und R4 unabhängig ausgewählt sind aus Wasserstoff, einem Kohlenwasserstoff mit 1 bis 15 Kohlen-
stoffatomen und einem Polyether mit 1 bis 15 Kohlenstoffatomen,
25 R3 einen Kohlenwasserstoff mit 1 bis 1 Kohlenstoffatomen oder einen Polyether mit 1 bis 15 Kohlenstoffatomen
darstellt und
n 1 bis einschließlich 10 ist.

9. Klebstoff nach einem der vorstehenden Ansprüche, wobei die relativen Mengen von Aminhärtungsmittel mit niedriger
30 Äquivalentmasse und Aminhärtungsmittel mit hoher Äquivalentmasse so ausgewählt sind, dass das Aminhärtungs-
mittel mit niedriger Äquivalentmasse mindestens 25 Gew.-% des kombinierten Gewichts der Aminhärtungsmittel
mit niedriger und hoher Äquivalentmasse umfasst.

10. Klebstoff nach einem der vorstehenden Ansprüche, wobei die relativen Mengen von Aminhärtungsmittel mit niedriger
35 Äquivalentmasse und Aminhärtungsmittel mit hoher Äquivalentmasse so ausgewählt sind, dass das Aminhärtungs-
mittel mit niedriger Äquivalentmasse zwischen einschließlich 30 und einschließlich 60 Gew.-% des kombinierten
Gewichts der Aminhärtungsmittel mit niedriger und hoher Äquivalentmasse umfasst.

11. Klebstoff nach einem der vorstehenden Ansprüche, wobei die acetoacetoxy-funktionalisierte Verbindung die fol-
40 gende allgemeine Formel besitzt:

45

worin

50 X eine ganze Zahl von 1 bis 10 ist,

Y für O, S oder NH steht,
R6 ausgewählt ist aus der Gruppe bestehend aus Polyoxygruppen, Polyesteralkylen, -arylen und -alkylarylen
und linearen, verzweigten, gesättigten und ungesättigten Alkyl-, Aryl- und Alkylarylgruppen, wobei R6 mit Y
über ein Kohlenstoffatom verbunden ist, und
55 R7 ein lineares oder verzweigtes oder cyclisches Alkyl mit 1 bis 12 Kohlenstoffatomen ist.

12. Klebstoff nach einem der vorstehenden Ansprüche, wobei der Metallsalz-Katalysator Calciumtriflat umfasst.

20
 EP 2 603 568 B1

13. Klebstoff nach einem der vorstehenden Ansprüche, wobei der Klebstoff zu 0,3 bis 1,5 Gew.-% Katalysator, basierend
auf dem Gesamtgewicht der Zusammensetzung, umfasst.

14. Klebstoff nach einem der vorstehenden Ansprüche, wobei der Klebstoff zwei Bestandteile umfasst, wobei:
5
(a) der erste Bestandteil Folgendes umfasst:

(i) die acetoacetoxy-funktionalisierte Verbindung,

(ii) das multifunktionalisierte Acrylat und
10 (iii) wenigstens einen Teil des Epoxidharz-Bestandteils, und

(b) der zweite Bestandteil Folgendes umfasst:

(i) das erste Aminhärtungsmittel,

15 (ii) das zweite Aminhärtungsmittel und
(iii) den Metallsalz-Katalysator.

15. Klebstoffspender, umfassend eine erste Kammer, die einen ersten Bestandteil eines zweiteiligen Klebstoffs enthält,
eine zweite Kammer, die einen zweiten Bestandteil des zweiteiligen Klebstoffs enthält, und eine Mischspitze, wobei
20 die erste und die zweite Kammer mit der Mischspitze verbunden sind, damit der erste Bestandteil und der zweite
Bestandteil durch die Mischspitze hindurchfließen können, und wobei der erste Bestandteil ein Epoxidharz, ein
polyurethan-modifiziertes oder isocyanat-modifiziertes Epoxidharz, ein multifunktionelles Acrylat und eine acetoa-
cetoxy-funktionalisierte Verbindung umfasst und der zweite Bestandteil ein erstes Aminhärtungsmittel mit einer
Aminäquivalentmasse von mindestens 50 Gramm pro Mol Aminäquivalente, ein zweites Aminhärtungsmittel mit
25 einer Aminäquivalentmasse von nicht mehr als 45 Gramm pro Mol Aminäquivalente und einen Metallsalz-Katalysator
umfasst.

Revendications
30
1. Adhésif comprenant :

(a) un composant résine époxy comprenant :

35 (a1) une première résine époxy, et

(a2) une deuxième résine époxy, dans lequel la deuxième résine époxy est choisie dans le groupe constitué
d’une résine époxy à modification polyuréthane, une résine époxy à modification isocyanate et leurs
combinaisons ;

40 (b) un premier agent de durcissement amine possédant un poids équivalent d’amine d’au moins 50 grammes
par mole d’équivalents amine ;
(c) un deuxième agent de durcissement amine possédant un poids équivalent d’amine de pas plus de 45
grammes par mole d’équivalents amine ;
(d) un composé fonctionnalisé acétoacétoxy ;
45 (e) un catalyseur à sel métallique ; et
(f) un acrylate multifonctionnel.

2. Adhésif selon la revendication 1, dans lequel le composant résine époxy comprend en outre :

50 (a3) une troisième résine époxy, dans lequel la troisième résine époxy comprend au moins un diluant réactif à
base d’époxy.

3. Adhésif selon la revendication 2, dans lequel la troisième résine époxy présente une forte affinité pour un ou plusieurs
substrats en plastique choisis parmi le groupe comprenant polycarbonate, acrylonitrile-butadiène-styrène ou leurs
55 combinaisons, telle que déterminée par gonflement ou dissolution du substrat en plastique laissé en contact avec
la troisième résine époxy pendant un laps de temps égal ou inférieur à 6,5 heures.

4. Adhésif selon l’une quelconque des revendications précédentes, dans lequel la quantité de l’acrylate multifonctionnel

21
 EP 2 603 568 B1

et du composé fonctionnalisé acétoacétoxy constitue conjointement au moins 11 % en poids de l’adhésif.

5. Adhésif selon l’une quelconque des revendications précédentes, dans lequel le rapport de l’acrylate multifonctionnel
sur le composé fonctionnalisé acétoacétoxy va de 80 parties en poids d’acrylate multifonctionnel:20 parties en poids
5 de composé fonctionnalisé acétoacétoxy à 20 parties en poids d’acrylate multifonctionnel:80 parties en poids de
composé fonctionnalisé acétoacétoxy.

6. Adhésif selon l’une quelconque des revendications précédentes, dans lequel le poids équivalent d’amine du premier
agent de durcissement amine est d’au moins 55 grammes par mole d’équivalents amine et dans lequel le poids
10 équivalent d’amine du deuxième agent de durcissement amine n’est pas plus de 40 grammes par mole d’équivalents
amine.

7. Adhésif selon l’une quelconque des revendications précédentes, dans lequel la première résine époxy comprend
un éther glycidylique de bisphénol-A, bisphénol-F ou novolac.
15
8. Adhésif selon l’une quelconque des revendications précédentes, dans lequel au moins l’un des agents de durcis-
sement amine est de formule générale

20

25 dans laquelle,

R1, R2 et R4 sont indépendamment choisis parmi l’hydrogène, un hydrocarbure contenant 1 à 15 atomes de

carbone et un polyéther contenant 1 à 15 atomes de carbone ;
R3 représente un hydrocarbure contenant 1 à 1 atome de carbone ou un polyéther contenant 1 à 15 atomes
30 de carbone ; et
n va de 1 à 10, inclus.

9. Adhésif selon l’une quelconque des revendications précédentes, dans lequel les quantités relatives d’agent de
durcissement amine à faible poids équivalent et d’agent de durcissement amine à poids équivalent élevé sont
35 choisies de telle sorte que l’agent de durcissement amine à faible poids équivalent comprend au moins 25 % en
poids du poids combiné des agents de durcissement amine à poids équivalents bas et élevé.

10. Adhésif selon l’une quelconque des revendications précédentes, dans lequel les quantités relatives d’agent de
durcissement amine à faible poids équivalent et d’agent de durcissement amine à poids équivalent élevé sont
40 choisies de telle sorte que l’agent de durcissement amine à faible poids équivalent comprend entre 30 et 60 % en
poids, inclus, du poids combiné des agents de durcissement amine à poids équivalents bas et élevé.

11. Adhésif selon l’une quelconque des revendications précédentes, dans lequel le composé fonctionnalisé acétoacé-
toxy est de formule générale suivante :
45

50
dans laquelle,

X est un nombre entier allant de 1 à 10 ;

Y représente O, S ou NH ;
55 R6 est choisi dans le groupe constitué de groupes polyoxy, polyester -alkyles, - aryles et -alkylaryles, et groupes
alkyle-, aryle- et alkylaryle- linéaires, ramifiés, saturés et insaturés ; où R6 est lié à Y par l’intermédiaire d’un
atome de carbone ; et
R7 est un alkyle cyclique linéaire ou ramifié possédant 1 à 12 atomes de carbone.

22
 EP 2 603 568 B1

12. Adhésif selon l’une quelconque des revendications précédentes, dans lequel le catalyseur à sel métallique comprend
du triflate de calcium.

13. Adhésif selon l’une quelconque des revendications précédentes, où l’adhésif comprend 0,3 à 1,5 % en poids de
5 catalyseur, sur base du poids total de la composition.

14. Adhésif selon l’une quelconque des revendications précédentes, où l’adhésif comprend deux composants, dans
lequel :

10 (a) le premier composant comprend :

(i) le composé fonctionnalisé acétoacétoxy,

(ii) l’acrylate multifonctionnalisé et
(iii) au moins une partie du composant résine époxy ; et
15
(b) le deuxième composant comprend :

(i) le premier agent de durcissement amine,

(ii) le deuxième agent de durcissement amine et
20 (iii) le catalyseur à sel métallique.

15. Distributeur d’adhésif comprenant une première chambre contenant un premier composant d’un adhésif en deux
parties, une deuxième chambre contenant un deuxième composant de l’adhésif en deux parties et un embout de
mélange, dans lequel les première et deuxième chambres sont couplées à l’embout de mélange pour permettre au
25 premier composant et au deuxième composant de s’écouler à travers l’embout de mélange ; et dans lequel le
premier composant comprend une résine époxy, une résine époxy à modification polyuréthane ou à modification
isocyanate, un acrylate multifonctionnel et un composé fonctionnalisé acétoacétoxy et le deuxième composant
comprend un premier agent de durcissement amine possédant un poids équivalent d’amine d’au moins 50 grammes
par mole d’équivalents amine ; un deuxième agent de durcissement amine possédant un poids équivalent d’amine
30 de pas plus de 45 grammes par mole d’équivalents amine et un catalyseur à sel métallique.

35

40

45

50

55

23
 EP 2 603 568 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 4778851 A [0059]

Non-patent literature cited in the description

• PAUL C. HIEMENZ. Polymer Chemistry, The Basic

Concepts. Marcel Dekker, 1984 [0058]

24