Europaisches Patentamt

© Publication number: 0 379 3 0 5

European Patent Office
A1
Dff ice europeen des brevets

EUROPEAN PATENT APPLICATION

© Application number: 90300312.7 © Int. CIA C09J 4/02, C09J 5/04,

B32B 7/12, C 0 9 J 133/26,
© Date of filing: 11.01.90 C09J 1 1 / 0 0

§> Priority: 17.01.89 US 297873 © Applicant: MINNESOTA MINING AND

MANUFACTURING COMPANY
§) Date of publication of application: 3M Center, P.O. Box 33427
25.07.90 Bulletin 90/30 St. Paul Minnesota 55133-3427(US)

© Designated Contracting States: © Inventor: Muggee, John M., c/o Minnesota

DE FR GB IT Mining and
Manufac. Co., 2501 Hudson Road
P.O. Box 33427, St. Paul Minnesota 55144(US)
Inventor: Zilley, Eric L. c/o Minnesota Mining
and
Manufacturing Company 2501 Hudson Road
P.O. Box 33427 St. Paul Minnesota 55133(US)

© Representative: Baillie, lain Cameron et al

c/o Ladas & Parry Isartorplatz 5
D-8000 MUnchen 2(DE)

© Low odor adhesive compositions.

© A novel, fast-bonding adhesive composition is disclosed having low odor, and when cured, forms adhesive
bonds having high glass transition temperature, Tg, and high shear strength at elevated temperatures. The
composition comprises one or more of acryl- and methacrylamides which have a cyclic group directly attached
to the amide nitrogen or has the amide nitrogen as a member of a cyclic group. The composition further
comprises a polymeric toughener that is dissolved or dispersed in the composition.

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 EP 0 379 305 A1

LOW ODOR ADHESIVE COMPOSITIONS

Field of the Invention

This invention relates to fast-bonding, low-odor adhesive compositions based on substituted ac-
rylamides or methacrylamides and a polymeric toughener. In another aspect, it relates to a process for
5 bonding substrates together using the adhesive compositions. In a further aspect it relates to substrates
bonded together by the adhesive compositions of the invention.

BACKGROUND OF THE INVENTION

70

Second generation acrylic adhesives (SGA's) which are acrylic-based adhesives containing polymeric
tougheners are known in the art. U.S. Patent Nos. 3,890,407; 4,106,971; and 4,112,013 disclose adhesive
systems composed of solutions of chlorosulfonated polyethylene or mixtures of sulfonyl chlorides and
75 chlorinated polymers in polymerizable vinyl (preferably acrylic) monomers which cure to high bond
strengths. U.S. Patent No. 3,994,764 discloses an SGA system derived from a solution of a thermoplastic,
nonreactive polyester- or polyether-based polyurethane resin in an addition polymerizable combination of an
acrylic or methacrylic monomer and a copolymerizable monomer containing at least one free carboxylic
acid group. U.S. Patent No. 4,126,504 discloses the use of a thermoplastic nonreactive elastomer (typically
20 based on at least one of butadiene, neoprene, and their derivatives) dissolved in an addition polymerizable
combination of an acrylic or methacrylic monomer and a copolymerizable monomer containing at least one
free carboxylic group to give a second generation acrylic adhesive. U.S. Patent No. 4,138,449 discloses an
SGA comprising a butadiene/acrylonitrile rubber having an acrylate end group dissolved in an acrylic,
methacrylic, or dimethacrylic ester monomer.
25 European Patent Application 87,304 discloses non-aqueous compositions useful as, or in, low odor
adhesives comprised of a sequential polymer (frequently designated as a core/shell polymer), of at least
25% by weight of an elastomeric stage and 5% by weight of an outermost rigid stage, dispersed (not
dissolved) in an acrylic or methacrylic ester monomer, including blends of such monomers. These
°
monomers (e.g. acryloyloxypropionic acid) have a flash point greater than 95 C, and form a polymer whose
30 glass transition temperature (Tg) falls within the range of 0 to 100° C.
The cited art suffers from one or more of the following deficiencies: first, the common use of lower
molecular weight monomers (i.e., lower esters of acrylic and methacrylic acid, e.g. methyl methacrylate)
results in a noxious odor problem, often in conjunction with undesirable flammability and toxicity char-
acteristics; second, the use of higher molecular weight monomers to avoid odor, flammability, and toxicity
35 problems can have other effects. For example, the higher molecular weight monomer may become a solid,
leading to formulation difficulties. Also, the Tg of a polymer usually decreases as the molecular weight of
the monomer increases, resulting in a loss of performance characteristics in the adhesives. In addition, the
higher molecular weight monomers may not be suitable for dissolving the polymeric tougheners.
U.S. Patent Nos. 4,322,504; 4,308,014; 4,393,237; and 3,658,624 disclose the use of substituted
40 acrylamides and methacrylamides, with and without other functional groups present in the substituents, for
use in resin binders, medical and dental bonding agents, and untoughened adhesives.
U.S. Patent No. 2,658,056 discloses a method of making cyclic amines by the reaction of acrylyl
chloride and methacrylyl chloride.
U.S. Patent No. 4,718,899 discloses water-insolubilized products of N-alkyl- or N-alkylene-substituted
45 (metha)acrylamides used for absorbing and releasing urine.
U.S. Patent No. 3,876,594 discloses copolymers containing N-acryloyl-morpholine, -piperidine, or
-pyrolidine used for filling postoperative cavities.
U.S. Patent No. 4,062,831 discloses N-acrylomorpholine and N-acryloyl piperidine as possible compo-
nents in the preparation of polymers for use as membrane and as packing for chromatography columns.
so Of the above cited art, only U.S. Patent Nos. 3,994,764 and 4,126,504 broadly disclose N-substituted
acrylamides as potential vinyl monomers, although none are exemplified by the patentees. These two
patents, in addition, use tougheners which are soluble and non-reactive with respect to the acrylic
monomers.

2
 P 0 379 305 Al

UMMARY Or- I Hb IINVbIN I IUIN

None of the above mentioned art discloses the use ot low oaor iN-cycnc group-suDsiuuieu acryiamiue
insoluble
5 or methacrylamide monomers in combination with tougheners, the tougheners preferably being
but dispersable in the substituted monomers, to obtain low odor anaerobic adhesives with properties
comparable to those of the currently available high performance/high odor type anaerobic adhesives.
Briefly, the present invention provides a fast bonding adhesive composition which can be formulated
either as a one or two part system and comprises
o (a) one or more cyclic group-containing acrylamido compounds, selected from acrylamides and
methacrylamides that have a cyclic group attached directly to the amide nitrogen, and acrylamides and
methacrylamides in which the amide nitrogen is a member of a cyclic group;
(b) at least one ethylenically-unsaturated acid that is copolymerizable with (a);
(c) an effective amount of a polymeric toughener; and
'5 (d) at least one of an initiator and activator.
Preferably, the ethylenically-unsaturated acid is present in an amount of 0.01 to 1.25 parts by weight
per part of acrylamido compound.
The composition is useful as a layer on a variety of substrates and it possesses low odor, and when
cured forms adhesive bonds having a high glass transition temperature, Tg, and high shear strength at
w elevated temperatures.
In a preferred embodiment, the composition contains 0.1 to 1.25 parts by weight of the polymeric
toughener comprising one or more of (1) core/shell materials and (2) elastomeric polymers that have a Tg of
30° C or lower and are soluble or dispersable in the acrylamido compound.
As used in the present application:
15 The term "acrylamido" means compounds (monomers, oligomers, and polymers) of substituted
acrylamides and substituted methacrylamides. Hereinafter, the specific nature of the substituents is
described in detail;
"core shell" refers to a particle having a diameter of about 0.1 to 10 micrometers in an unswollen state and
has an elastomeric center and a glassy shell. These particles are well known and are used to improve the
30 impact resistance of polymers;
"low odor" means monomers having less odor than methyl methacrylate monomer as determined by ASTM
D 4339-84.
"dispersable" means that the toughener swells, but does not dissolve in the uncured cyclic group-
containing acrylamido composition.
35 "soluble" means in the range of 0.1 to 1.25 parts by weight of the toughener dissolves in one part of the
uncured cyclic group-containing acrylamido composition.

DETAILED DESCRIPTION OF THE INVENTION

40

The present invention provides a fast-bonding, low odor adhesive composition prepared by mixing in
and/or
any order: one part of one or more copolymerizable N-cyclic group-substituted acrylamides
methacrylamides, 0.01 to 1.25 parts by weight (preferably 0.1 to 0.2 parts by weight) of one or more
45 ethylenically-unsaturated carboxylic and/or phosphoric acids copolymerizable with acrylamides and
methacrylamides; 0.1 to 1.25 parts by weight (preferably 0.2 to 0.5 parts by weight) of one or more
polymeric tougheners; and up to about one part by weight of one or more volatile solvents when necessary
to form a solution or dispersion of the composition.
Cyclic group-containing acrylamido compounds that can be used in the preferred embodiment of the
50 invention have the general formula

O R1
M/
H2C-C-CN
55 X R

wherein
 EP 0 379 305 A1

X is hydrogen, methyl, or halogen; preferably X is hydrogen or methyl;

R' is a mono or poiycyclic monovalent group, the cyclic groups of which are selected from (a) aromatic
carbocyclic and heterocyclic (i.e., containing atoms such as N, O, S, P, and Si) groups having 5 to 18
atoms in the cyclic group and (b) saturated and unsaturated aliphatic carbocyclic and heterocyclic (i.e.,
5 containing atoms such as N, 0, S, P, and Si) groups having 4 to 18 atoms in the cyclic group, R1 being
optionally substituted by groups selected from lower alkyl groups of 1 to 4 carbon atoms, hydroxyl, acyloxy,
alkoxy of 1 to 4 carbon atoms, cyano, halo, phenyl, and benzo groups;
R2 is selected from R\ hydrogen and lower alkyl groups having 1 to 4 carbon atoms or R2 together with R1
is a divalent group, which together with the nitrogen atom to which they are attached form a heterocyclic
70 group having 5 or 6 atoms in the ring that can be substituted by lower alkyl groups of 1 to 4 carbon atoms,
hydroxy, acyloxy, alkoxy of 1 to 4 carbon atoms, cyano, halo, or phenyl group or a divalent group that
forms a di- or tricyclic group having 12 to 18 atoms in the rings, with the proviso that when X is methyl, R2
is hydrogen.
Examples of acryl- and methacrylamides, which are commercially available or can be made by
75 methods well-known in the art, that can be used in the adhesive composition of the invention include:
N-(piperidyl)acrylamide, also known as N-acryloylpiperidine (this compound is named 1-(1 -oxo-2-propenyl)-
piperidine by Chemical Abstracts), N-(4-chloropiperidyl)acrylamide,
N-(1,2-dihydroquinoline)acrylamide,
N-(morpholyl)acrylamide,
20 N-(2,6-dimethylmorpholyl)acrylamide,
N-(thiomorpholyl)acrylamide, N-(pyrrolidyl)acrylamide,
N-(4-phenylphenyl)acrylamide,
N-(4-hydroxyphenyl)acrylamide,
N-(3-methoxyphenyl)acrylamide, N-(4-cyanophenyl)acrylamide,
25 N-(cyclohexyl)acrylamide, N-(cyclopentyl)acryiamide,
N-(norbomyl)acrylamide (also named N-(bicyclo[2.2.1 ]hept-2-yl)acrylamide),
N-(isobomyl)acrylamide, N-methyl-N-phenylacrylamide,
N-cyclohexyl-N-methylacrylamide,
N-n-butyl-N-cyclohexylacrylamide,
30 N-(naphthalenyl)acrylamide,
N-(4-acetylphenyl)acrylamide,
N-(2-pyridinyl)acrylamide,
N-(2-furanylmethyl)acrylamide,
N,N-(dicyclohexyl)acrylamide, N-(phenyl)methacrylamide,
35 N-(norbornyl)methacrylamide, N-(phenyl)acrylamide,
N-(cyclohexyl)methacrylamide, and
N-(isobornyl)methacrylamide.
The preferred acrylamido compounds are N-(piperidyl)acry!amide, N-(morpholyl)acrylamide, N-(2,6-
dimethylmorpholyl)acryIamide, and N-cyclohexyl-N-methylacrylamide. Generally, the glass transition tem-
40 peratures of acryl- and methacrylamides that are useful for the invention are in the range of 125-200° C.

The Polymeric Toughener

45
The polymeric tougheners that may be employed can be divided into two main classes: reactive and
nonreactive. These two categories of reactive and nonreactive tougheners may be further subdivided as
either soluble or dispersable in the acrylic monomer. These classes of polymeric tougheners are well-known
in the art and are commercially available. An example of a reactive toughener would be a toughener having
50 polymerizable ethylenic-unsaturation. The amount of toughener used is determined by the desired effect
upon the performance and properties of the resultant adhesive composition. Such considerations include
the desired application, the desired viscosity, and other requirements peculiar to a given end use.
Examples of reactive, soluble tougheners are elastomeric polymers generally having a Tg below about
30 °C such as the polyurethanes, polyesters, and polyethers capped with acrylate, methacrylate, ac-
55 rylamide, or methacrylamide functionalities, which dissolve in the adhesive mixture. Suitable elastomeric
polymers generally have a molecular weight of about 1,000 to 100,000, preferably 5,000 to 15,000.
Examples of nonreactive, soluble polymeric tougheners are soluble elastomeric polymers including the
polymers derived from 1,3-diolefins such as 1,3-butadiene, isoprene, 2,3-dimethyl-1 ,3-butadiene, and the

4
 BP 0 379 305 A1

like and the copolymers of these monomers with 5 to 40% by weight of a modifying comonomer such as
styrene, acrylonitrile, methyl methacrylate and the like. Natural rubber can also be used. Other examples of
nonreactive, soluble polymeric tougheners are disclosed in U.S. Patent No. 4,126,504.
Examples of reactive, dispersable tougheners are core/shell materials comprised of a crosslinked
5 acrylic elastomeric core and a glassy acrylic-functionalized shell, that disperse rather than dissolve in the
adhesive mixture. Such core/shell materials are disclosed in U.S. Patent Nos. 3,649,337; 3,660,371;
3,689,307; 3,689,308; 3,689,309; 3,697,312; 3,701,679; 3,719,521; 3,719,522 and 3,719,523 which are
incorporated herein by reference. Polymers of butyl acrylate or styrene/butadiene which contain low levels
of cross-linking and are functionalized by capping with acrylates, methacrylates, acrylamides, or
<o methacrylamides are also examples of reactive, dispersable tougheners.
The nonreactive dispersable tougheners are based on either crosslinked elastomeric polymers or
core/shell materials. Nonfunctionalized, lightly crosslinked acrylic or styrene/butadiene rubbers are exam-
ples of the former. Core/shell materials such as those described in European Patent Application No. 87,304
are examples of the latter. In these materials the core is derived from a crosslinked acrylic or butadiene-
f5 based elastomeric polymer and is graft-linked to a thermoplastic shell (e.g. poly(methyl methacrylate)),
which does not contain any activated double bonds. The particular additive selected, and the concentration
level used in the formulation will depend upon the desired end use and processing criteria.

20 The Ethylenically-Unsaturated Acid

Ethylenically-unsaturated acids which can be used in the adhesive composition of the invention are any
such compounds that in water have a pH of 5.0 or less and are soluble in and copolymerizable by free
25 radical initiated polymerization with the acrylamide compounds described above. Preferably, the
ethylenically-unsaturated acids are ethylenically-unsaturated carboxylic acids and ethylenically-unsaturated
acids of phosphorus..Examples of preferred acids include acrylic acid, methacrylic acid, itaconic acid,
maleic acid; half esters of dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, terephthalic
acid, maleic acid, and itaconic acid; and the ethylenically-unsaturated phosphinous, phosphonous,
30 phosphinic, phosphonic, and phosphoric acids such as divinylphosphinous acid [(H2C = CH)2POH], 2-
propenyl phosphonous acid [H2C = CHCH2P(OH)2], di-(2-propenyl)phosphinic acid [(H2C = CHCH2)2P(0)-
OH], 2-acryloyloxyethylphosphonic acid [H2C = CHC(0)OCH2CH2P(0)(OH)2], 2-methacryloyloxyethyl-
phosphonic acid [H2C = C(CH3)C(0)OCH2CH2P(0)(OH)2], 2-methacryloxyethyl phosphoric acid [H2C = C-
(CH3)C(0)OCH2CH2OP(0)(OH)2 and the like.
35

The solvent

It is preferable that no solvent be used in the adhesive composition of the invention. However, by
40 including inert organic solvents, the use of substituted acrylamides or methacrylamides that have a melting
point of above 30 °C can be facilitated in the adhesive composition. Preferably, the solvent has a boiling
point at atmospheric pressure of less than about 200° C, preferably 50 to 100° C, so that the solvent can be
readily volatilized from a coating of the composition. Examples of useful solvents include methanol, ethanol,
isopropanol, 2-methoxyethanol, acetone, methylethylketone, tetrahydrofurane, and the like.

The Initiator/Activator

To achieve fast curing, both an initiator and an activator are generally required. When a two-part system
50 is formulated, one part will contain an initiator and the other part an activator.
The adhesive compositions of the invention can be cured by an initiator that generates free radicals and
is well known and frequently described in. the polymerization art. They include: peroxy compounds, i.e.
organic peroxides, hydroperoxides, peracids, and peresters; and azo compounds, i.e. azobis(isobutyronitrile)
(AIBN). Included among these free-radical initiators are the conventional heat-activated compounds, i.e.
55 benzoyl peroxide, tertiary-butyl perbenzoate, cumene hydroperoxide and AIBN.
It is preferred that the adhesive compositions of the present invention be storage stable and cure at
room temperature. Consequently, they are formulated as two-part systems. The first part (A) contains the
initiators described above. The second part (B) contains an activator which upon mixing with the initiator

5
 EP 0 379 305 A1

contained in part A enters into an oxidation-reduction reaction with the initiator to generate the free radicals
that cure the adhesive.
Activators that can be used consist of tertiary amines, amine/aldehyde (or ketone) condensates,
mercapto compounds, or transition metal compounds. Examples of useful tertiary amines are: N,N-
5 dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, or N,N-diisopropyl-p-
toluidine. Examples of mercapto compounds are: 2-mercaptobenzimidazole, allylthiourea, and ethylene
thiourea. Examples of useful amine/aldehyde condensates are: aniline/butyraldehyde,
butylamine/benzaldehyde, and butylamine/benzil. Examples of transition metal compounds are: copper
naphthenate, iron naphthenate; cobalt naphthenate, nickel naphthenate, manganese naphthenate; copper
70 octanoate; iron hexanonate, iron propionate; copper oxide, manganese oxide, vanadium oxide, molybdenum
dioxide; and vanadium oxide (acetylacetonateh, and molybdenum oxide (acetylacetonate)2.
The preferred activator for the present invention is the condensation product of an alpha-hydroxy ketone
and a primary amine in combination with a salt containing one or more transition metals selected from the
group consisting of vanadium, molybdenum, cobalt, iron, and copper as described in detail in applicants co-
75 pending application Serial No. 07/297,886.
Various adjuvants can be added to the adhesive composition to alter or even improve the characteris-
tics of cured or uncured adhesive composition. These are known in the art and include viscosity modifiers,
stabilizers, fillers, pigments, dyes, fibers, glass or plastic microbeads or bubbles, plasticizers, antioxidants,
etc., or components which provide enhanced properties at elevated temperatures such as epoxies and
20 maleimides. Depending on the desired function of the additive, from traces to 100% or more by weight of
the additive may be used in the composition.
The adhesive compositions of the present invention can be formulated using a primer system wherein
the primer consists of a volatile liquid carrier medium containing the activator component of the initiator
system. The solution or dispersion of the activator then can be applied by brushing, spraying, dipping, or
25 the like upon at least one of the surfaces to be bonded, and the solvent allowed to evaporate leaving a
deposit of the activator on the surface.
The amount of activator to be applied to a given surface should be no more than necessary to obtain
efficient acceleration of the bonding operation. Excess activator on one or more of the bonding surfaces can
interfere with the bond mechanism between the adherend and adhesive composition, thereby adversely
30 affecting the strength of the final bond. Further, when the amount of activator exceeds about 5 percent by
weight of the adhesive composition used, typically little, if any, addition increase in speed of the cure is
noted. Generally, an amount of activator equal to between about 0.05 and 1.0 percent by weight of adhesive
composition is adequate. Typically, satisfactory results are obtained with a single application of a thin film of
activator to the surface or surfaces to be bonded.
35 When the activator has been applied to the surface and the solvent, if any, has been allowed to
subsequently evaporate, the bonding operation can proceed in the normal manner. The adhesive can be
applied either to the surface which has been treated with the activator or the appropriate mating surface.
Customarily, as with most bonding operations, a thin film of adhesive is most desirable. The two mating
surfaces are then placed in abutting relationship, and, preferably, a moderate compressive force is applied
40 to produce a relatively thin layer of adhesive spread substantially evenly between the two surfaces.
Typically, a thickness of adhesive between the surfaces in the range of about 0.0254 and 0.127 mm is
desirable. However, activators of the present invention may be used to accelerate cure of bonds having
bond thicknesses outside this range if desired.
Alternatively, the adhesive can be formulated as a latent two-part adhesive composition in kit form, in
45 which one part is the adhesive formulation containing the free radical source and the second part is the
same formulation but with the activator present in place of the free radical source. The two parts are then
mixed together just prior to application to one or both surfaces, followed by an immediate joining of the
surfaces.
Various modifications and alterations of this invention will become apparent to those skilled in the art
50 without departing from the scope and spirit of this invention, and it should be understood that this invention
is not to be unduly limited to the illustrative embodiments set forth herein.
In the examples below, samples were evaluated by the tests described below. These are exemplary of
adhesive performance. Different absolute values will be obtained with other adherends and test methods.

55
A. T-Peel Test

ASTM Standard method of Test for PEEL RESISTANCE OF ADHESIVES (T-PEEL TEST) Designation

6
 =P 0 379 305 A1

D1876-72d was used following the recommended procedure with the following modifications.
1) Adherends were 1010 cold rolled steel sheet 0.81 mm thick cut to a width of 2.5 cm and a length
of 20 cm;
2) Adherends were methylethylketone wiped, Scotch-BriteTM (3M, St. Paul, MN) abraded and acetone
5 wiped;
3) Adhesive composition was applied as subsequently indicated to about 15 cm x 2.5 cm area of the
adherends which were then clamped together;
4) Bonds were allowed to cure for at least 48 hours at 20-25° C.

'0
B. Overlap Shear Test

ASTM Standard Method of Test for STRENGTH PROPERTIES OF ADHESIVES IN SHEAR BY

TENSION LOADING METAL-TO-METAL Designation D1 002-72 was used with the following modifications:
rs The overlap shear strength of the adhesive compositions were measured on test strips of aluminum and
steel. The steel strips were prepared as described above with the exception that the strips were 10 cm in
length instead of 20 cm. The aluminum test strips consisted of conversion coated 2024 T-3 clad aluminum
strips 1.6 mm thick x 2.5 cm wide x 10 cm long. The chemical conversion coating consisted of: 1) soaking
the strips for 10 minutes in an alkaline degreaser (Oakite 164 available from Oakite Products, Inc., Berkeley
>o Heights, NJ 07922) followed by a 2 minute tap water rinse; 2) immersing the strips for 10 minutes in a
chromic acid solution (30 parts de-ionized water, 10 parts 98% sulfuric acid, and 2 parts sodium
dichromate) followed by a 2 minute tap water rinse, and 3) baking the strips for 5 minutes at 65° C. The test
strips were coated with adhesive by the method described in Example 1.

EXAMPLE 1

In amounts shown in Table I below, adhesive compositions were prepared by nana mixing in sample
30 Nos. 1, 2, and 3, N-(piperidyl)acrylamide (NAP); Sample Nos. 4 and 5, N-(morpholyl)acrylamide (NAM);
Sample Nos. 6 and 7, N-(2,6-dimethylmorpholyl)acrylamide (NADM) with methacrylic acid (MAA), and
cumene hydroperoxide (CHPO). The core/shell toughener KMTM 653 (Rohm & Haas) was added in Sample
Nos. 1, 4, 6 and 7; and the core/shell toughener MetablenTM C223 (M&T Chemical Co.) was added in
Sample Nos. 2, 3, and 5 in the amounts shown in parts by weight in TABLE I. The tougheners used were
35 comprised of a crosslinked butadiene-styrene rubber core and a glassy poly(methylmethacrylate) shell.

TABLE I

Adhesive Composition
Sample NAP NAM NADM MAA CHPO C223 KM653
1 65 - - 10 0.5 - 25
2 60 - - 10 1.0 30
3 50 - - 10 1.0 40
45 4 65 - 10 0.5 - 25
5 - 70 10 1.0 30
6 - - 65 10 0.5 - 25
7 - - 50 10 0.5 - 40

The adhesive composition was coated in a 75 micometers thick layer onto 1.5 cm ot one ena ot a
cleaned strip and about a 2 micrometers thick layer of primer disclosed in Assignee's copending
application, FN 40,466 USA 1A, USSN 07/297,886, filed the same date as this application was coated onto
55 1.5 cm of one end of a second cleaned strip. The two strips were then assembled together so that the
coated areas were in contact and the bonds formed allowed to cure at about 20 °C for two days. T-Peel
strength and Overlap Shear strength were then measured for each construction. The data obtained is shown
in Table II.

7
 EP 0 379 305 A1

TABLE II

Overlap shear strength (MPa) T-Peel strength (N/25

mm)
Adhesive -40° C 20° C 82° C 121 °C -40° C 20° C
No.
1 nt(c) 16.5 12.0 10.2 4.5 93
2 17.3 17.9 11.3 10.6 4.5 142
3 19.0 15.7 8.1 7.9 4.5 196
4 nt 16.2 13.4 7.7 9.0 187
5 nt 15.7 14.6 nt 4.5 111-222
6 nt 14.3 8.6 nt nt 31
7 nt 13.6 nt nt nt nt
8(a) nt 15.8 10.6 nt 4.5 165
9(b) 9.0 15.2 10.4 nt 89 160
(a) Comparative composition (low odor methacrylate) comprising a copolymer of 40
parts tetrahydrofurfuryl methacrylate: 10 parts hydroxyethyl methacrylates: 10 parts
methacrylic acid: 40 parts Metable tm C223 toughener
(b) Comparative composition using KonishiTM AG1 a high odor structural adhesive
,
system composed of both primer and adhesive (by Konishi, Osaka, Japan)
(c) Not tested

The adhesive compositions, Sample Nos. 1-7 were of low odor while comparative Sample No. 8 was
more odorous than Samples 1-7 and Sample No. 9 was highly odorous because of its lower alkyl ester
methacrylate content. It is seen from Table II, that the adhesive compositions of the invention provide good
low and elevated temperature overlap shear strength and good 20° C T-Peel strength.

EXAMPLE 2

Adhesive compositions of the invention, Sample Nos. 2, 3, 4 and 7 of Example 1 and comparative
compositions Sample Nos. 8 and 9 of Example 1, were coated onto steel strips, assembled together, and
the adhesive cured as described in Example 1. After each cured assembly was immersed in water at 50° C
for one week, the Overlap Shear strengths were measured. The results are recorded in Table III.
The same compositions evaluated above were coated onto etched 2024 T3 clad aluminum strips (1.6
mm thick, 2.5 cm x 10.0 cm) and cured as described in Example 1. After each cured assembly was
immersed in water at 50° C for one week, the Overlap Shear strengths were then measured. The results are
recorded in Table III.

8
 =P 0 379 305 A1

fABLE III

Adhesive no. Initial 20° C Overlap shear (MPa) after 1 % Change

on steel overlap shear week in water at 50 C
(MPa)
2 17.9 15.3 -14
3 15.7 15.7 0
4 16.2 0 -100
7 13.6 0 -100
8(a) 15.8 13.0 -17
9(b) 20.1 16.8 -17
On
Aluminum
2 15.6 15.6 0
3 15.7 15.3 -2
4 14.1 0.8 -95
7 10.3 9.4 -9
9(b) 30.5 30.1 -1

(a)&(b) are as defined in TABLE II.

From TABLE III it can be observed that adhesive compositions of Sample Nos. 2 and 3 of the invention
comprising N-(piperidyl)acrylamide maintained excellent overlap shear strength after one week in water at
50 °C when used to adhere both steel and aluminum strips as did the adhesive of Sample No. 7,
comprising N-(2,6-dimethylmorpholyl)acrylamide, on aluminum.

EXAMPLE 3

Adhesive compositions of the invention, Sample Nos. 1, 2, 3 and 4 and comparative compositions of
Sample Nos. 9, 10, 11 were coated onto "as-received" (i.e., not cleaned) plastic strips in place of steel
strips which were assembled, and cured as described in Example 1. The Overlap Shear strength was
measured on each construction and the results recorded in Table IV.

9
 =P 0 379 305 A1

fABLE IV

Overlap Shear (MPa)

Adhesive ABS (d) PVC (e) PS (,) LEX<9> FRP (h)
No.
1 6.2* 4.7* 5.0* 5.4* 4.1*
2 3.2 5.8 3.3 3.9 3.5
3 2.5 4.3 3.4 2.9 3.5
4 5.3 2.6 3.7 2.7 3.4
9<a> 2.2 2.3 nt(i) nt 3.3
10(b) 6.8* 4.6* nt nt 2.2
11<c> 4.7 3.8* nt nt 3.3
la) comparative composition: using Konishi AG1 , a structural adhesive system
(by Konishi, Japan)
(b) comparative composition: using Konishi AG2, a structural adhesive system
(Konishi, Japan)
(c) composition: using Konishi AG3, structural adhesive system (Konishi, Japan)
(d> poly(acrylonitrile: butadiene: styrene)
(e> poly(vinylchloride)
(,) polystyrene
(9) LexanTM (a polycarbonate from Bisphenol A and Phosgene)
(h) fiber reinforced plastic (from unsaturated polyester, styrene and fiberglass)
(i> not tested
*substrate failed during test

It can be seen in Table IV that the adhesive compositions of the invention provide excellent bonds on a
variety of plastic substrates.
Various modifications and alterations of this invention will become apparent to those skilled in the art
without departing from the scope and spirit of this invention, and it should be understood that this invention
is not to be unduly limited to the illustrative embodiments set forth herein.

Claims

1. A low odor adhesive composition comprising:

a) at least one acrylamido compound selected from the group consisting of N-substituted ac-
rylamides and methacrylamides that have a cyclic group directly attached to the amide nitrogen and
acrylamides and methacrylamides in which the amide nitrogen is a member of a cyclic group;
b) at least one ethylenically-unsaturated acid that is copolymerizable with said acrylamido compound;
c) an effective amount of polymeric toughener; and
d) an effective amount of at least one of an initiator and an activator.
2. The composition of claim 1 wherein said acrylamido compound has the formula

0 R1

H2OC-CN^
X

wherein
X is hydrogen, methyl, or halogen;
R1 is a mono or polycyclic monovalent group, the cyclic groups of which are selected from (a) aromatic
carbocyclic and heterocyclic N, 0, S, P and Si-containing groups having 5 to 18 atoms in the cyclic group
and (b) saturated and unsaturated aliphatic carbocyclic and heterocyclic N, 0, S, P, and Si-containing
groups having 4 or 18 atoms in the cyclic group, R' being optionally substituted by groups selected from

10
 P 0 379 305 Al

Dwer alkyl groups of 1 to 4 carbon atoms, hydroxyl, acyloxy, aiKoxy or i to ^ caraon aiomt., uyduu, naiu,
ihenyl, and benzo groups;
\2 is selected from FT, hydrogen, or lower alkyl groups having 1 to 4 carbon atoms; or Ft2 together with Ft1
s a divalent group, R3, which together with the nitrogen to which it is attached forms a heterocyclic group
laving 5 to 6 atoms in the ring that may be substituted by lower alkyl groups of 1 to 4 carbon atoms,
lydroxyl, halo, or phenyl group or by a divalent group that forms a di- or tricyclic group, with the proviso
hat when X is methyl, R2 is hydrogen.
3. The adhesive composition according to claims 1 and 2 wherein said polymeric toughener comprises
it least one of:
a) core/shell materials,
b) elastomeric polymers that have a Tg of 30° C or more and that are dispersible in said acrylamido
;ompound, and
c) elastomeric polymers that have a Tg of 30° C or more and that are soluble and reactive in said
acrylamido compound.
4. The adhesive composition according to claims 1 to 3 wherein said polymeric toughener is present in
an amount in the range of 0.1 to 1.25 parts by weight per part of acrylamido compound.
5. The adhesive composition according to claims 1 to 4 wherein said ethylenically-unsaturated acid is
Dresent in an amount in the range of 0.01 to 1.25 parts by weight per part of acrylamido compound.
6. The composition of claims 1 to 5 wherein the acrylamides are selected from the group consisting of
M-(piperidyl)acrylamide, N-(morpholy!)acrylamide, N-(2,6-dimethylmorpholyl)acrylamide, N-(pyrrolidyl)-
acrylamide, and N-cyclohexyl-N-methylacrylamide.
7. The composition of claims 1 to 6 wherein the ethylenically-unsaturated acids are selected from the
acids of phos-
group consisting of ethylenically-unsaturated carboxylic acids and ethylenically-unsaturated
3-horus.
8. The composition according to claims 1 to 7 wherein said activator composition comprises the
condensation product of an alpha-hydroxy ketone and a primary amine.
9. A laminated structure comprising two or more substrates bonded together by the composition of
claims 1 to 8.
10. A process of bonding together a first and second substrate comprising the steps:
a) applying to at least one of said substrates a coating comprising an adhesive composition
comprising a mixture of:
1) at least one acrylamido compound selected from the group consisting of N-substituted acrylamides and
methacrylamides that have a cyclic group directly attached to the amide nitrogen and acrylamides and
methacrylamides in which the amide nitrogen is a member of a cyclic group;
2) at least one ethylenically-unsaturated acid that is copolymerizable with said acrylamido compound;
3) an effective amount of polymeric toughener; and
4) an effective amount of a free radical initiator; and
b) applying to said second substrate a coating comprising an activator composition;
c) placing said coated substrates in an abutting relationship so as to form contact between said
coatings, optionally under compressive pressure, until said adhesive composition polymerizes thereby
bonding said substrates together.
11. A kit for preparing a latently curable adhesive composition according to claims 1 to 8 having
component parts capable of being mixed when the composition is to be applied, said kit comprising:
in one part an adhesive composition comprising:
a) at least one acrylamido compound selected from the group consisting of N-substituted acrylamides and
methacrylamides that have a cyclic group directly attached to the amide nitrogen and acrylamides and
methacrylamides in which the amide nitrogen is a member of a cyclic group;
b) at least one ethylenically-unsaturated acid that is copolymerizable with said acrylamido compound;
c) an effective amount of polymeric toughener; and
d) an effective amount of an initiator; and
in a second part an adhesive composition comprising:
a) at least one acrylamido compound selected from the group consisting of N-substituted ac-
and
rylamides and methacrylamides that have a cyclic group directly attached to the amide nitrogen
acrylamides and methacrylamides in which the amide nitrogen is a member of a cyclic group;
b) at least one ethylenically-unsaturated acid that is copolymerizable with said acrylamido compound;
c) an effective amount of polymeric toughener; and
d) an effective amount of an activator.
 European Patent Application number
J : EUROPEAN SEARCH R E P O R T
Dffice

DOCUMENTS CONSIDERED TO BE RELEVANT EP 9 0 3 0 0 3 1 2 . 7

Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE
Category of relevant passages to claim APPLICATION (Int CP)

D,Y US - A - 3 658 6 2 4 1,10, C 09 J 4/02

(LEES) 11 C 09 J 5/04
* Claims 1,8,11 * B 32 B 7/12
C 09 J 133/26
D,Y EP - Al - 0 087 3 0 4 1,3,4, C 09 J 11/00
(ROHM AND HAAS COMPANY) 9
* Claims 1,3-5,9,14,15 *

EP Al - 0 128 7 3 1 1,7,9
(MINNESOTA MINING AND MANU-
FACTURING COMPANY)
* Claims 1 - 3 , 7 , 1 1 *

TECHNICAL FlfcLUS
SEARCHED (Int CI*)

C 09 J
B 32 B
C 08 L

The present search report has been drawn up for all claims
Place of search Date of completion of tne search txaminer
VIENNA 26-03-1990 BOHM
CATEGORY OF CITED DOCUMENTS T: theory or principle underlying the invention
E: earlier patent document, but published on, or
X: particularly relevant if taken alone after the filing date
Y: particularly relevant if combined with another D: document cited in the application
document of the same category L: document cited for other reasons
A. technological background
0: non-written disclosure &: member of the same patent family, corresponding
P: intermediate document document