Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-03-12
2003-10-14
Zalukaeva, Tatyana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S171000, C526S196000, C526S198000, C526S229000, C526S230000, C526S236000, C526S204000, C526S217000, C526S090000, C526S093000
Reexamination Certificate
active
06632908
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to (meth)acrylate based polymerizable compositions and adhesive systems. The polymerizable compositions and adhesive systems also include an organometallic compound and a peroxide compound. The inventive polymerizable compositions and adhesive systems are particularly well suited to bonding applications which involve at least one low energy bonding surface, for example, polyolefin, polyethylene, and polypropylene surfaces.
2. Brief Description of Related Technology
Low energy surfaces such as polyolefins, i.e, polyethylene, polypropylene, polybutene, polyisoprene, and copolymers thereof, are well known to be difficult to bond to each other and to other surfaces using adhesive bonding technology since they have few active bonding sites available at the free surfaces. Low energy surfaces are defined as those having surface energies less than 45 mN/m, more typically less than 40 mN/m, or less than 35 mN/m.
It is known to enhance the bonding of low energy bonding surfaces by surface pre-treatments such as flame treatments, plasma treatments, oxidation, sputter etching, corona discharge, or primer treatments with a high surface energy material. Such treatments disrupt the bonds at the surface of the low energy material providing sites which are reactive and which can participate in bonding reactions with adhesive materials. However, such surface pre-treatments are usually undesirable, they add costs, they are not particularly reproducible in their results, and the effect of the pre-treatments wears off with time so the pre-treated surfaces must be re-treated if they are not bonded within a reasonable period of time. These pre-treatments are also not generally suited for the consumer market.
The patent literature reports one and two-part bonding compositions which often times contain a very reactive boron compound as an initiator. For instance, PCT International Patent Application WO 99/64528 refers to a polymerizable composition for bonding low energy surface substrates comprising a monomer blend and an organoborane aerobic initiator. U.S. Pat. No. 5,990,036 to Deviny refers to an initiator system for polymerizing acrylic monomers comprising organoborane-anine complexes and a decomplexer. U.S. Pat. No. 5,935,711 to Pocius et al. refers to an organoborane amine complex initiator system, which organoborane amine complex initiator system further contains an aziridine functional material and an acid functional compound as a decomplexer. U.S. Pat. No. 6,329,442 to Sugita refers to an organic boron compound and an acidic compound with the addition of a hexaarylbiimidazole compound as a polymerization initiator for fiber reinforced resins. PCT International Patent Application WO 01/44311 refers to an amine organoborane complex as a polymerization initiator for one or more free radical polymerizable monomers, oligomers or polymers; a separate decomplexer may be needed depending upon the temperature of the composition.
Other initiator systems found in the patent literature include U.S. Pat. No. 4,460,719 to Danville which refers to polyester-based adhesive compositions using peroxides as hardeners for automotive body repair applications. U.S. Pat. Nos. 4,536,546 and 4,942,201 to Briggs and Briggs et al., respectively, refer to an adhesive composition, which uses a peroxy compound with catalyst activators such as aldehyde-amine condensation products, and organic sulfonyl chlorides. Transition metal compounds may be added as promoters. U.S. Pat. No. 4,581,427 to Dunn et al. teaches an adhesive composition comprising a cure system of benzoyl peroxide, ferrocene and a tertiary aromatic amine. U.S. Pat. No. 4,533,446 to Conway et al. teaches a one part UV activated anaerobic adhesive composition. U.S. Pat. No. 4,525,232 to Rooney et al. teaches an initiator system comprising a peroxy compound, ferrocene, and an acid, wherein vinyl ether monomers are added as inhibitors. U.S. Pat. No. 4,076,742 to Berlin et al. refers to an initiator system including benzoyl peroxide combined with ferrocene for an anaerobic composition wherein the polymerizable oligomer is at least one oligocarbonateacrylate. U.S. Pat. No. 3,753,927 to Kracklauer refers to the peroxide induced cure of polyester resins employing a promoter system having a ferrocenyl compound and a member selected from various phosphorus compounds, an ascorbic acid compound, a stannous salt or soap, and an ammonium or alkali metal hydrogen sulfite.
Notwithstanding the state of the technology, it would be desirable to provide another alternative to the end user seeking to bond low energy surfaces without the need for surface pre-treatments, which is a (meth)acrylate-based composition.
SUMMARY OF THE INVENTION
The present invention, in a first aspect, provides a (meth)acrylate composition, which includes:
a (meth)acrylate component;
a first initiator system for initiating polymerization of the (meth)acrylate component including
an organometallic compound; and
a peroxy compound; and
a second initiator system for initiating polymerization of the (meth)acrylate component including
an aziridine functionalized compound; and
a compound having an acid functional group.
In another aspect, the present invention is directed to a (meth)acrylate composition in a two-part system including:
a first part including a (meth)acrylate component, an organometallic compound, and an aziridine functionalized compound; and
a second part including a (meth)acrylate component, a peroxy compound, and a compound having an acid functional group.
In yet another aspect, the present invention is directed to an initiator system for (meth)acrylate based adhesive compositions useful in bonding low energy surfaces. The initiator system includes:
an organometallic compound represented by Formula VI:
where
the dashed line optionally represents one or more bonds to form a five or six membered ring system;
M
e
is a transition metal;
R
10
and R
11
are same or different and each is a member selected from hydrogen, a straight or branched chain alkyl group having from about 1 to about 8 carbon atoms, acetyl, vinyl, allyl, hydroxyl, carboxyl, —(CH
2
)
b
COOR
12
, and —(CH
2
)
b
OH;
where
R
12
is a straight or branched chain alkyl group having from about 1 to about 8 carbon atoms, hydrogen, lithium, sodium or —(CH
2
)
b
—OR
13
;
b is 1 to 8;
R
13
is a straight or branched chain alkyl group having from about 1 to about 8 carbon atoms or —(CH
2
)
b
N
+
(CH
3
)
3
X
−
; and
X is a halogen, ClO
4
−
, or BF
4
−
;
Y is hydrogen, halogen, cyano, an alkoxy group having about 1 to about 4 carbon atoms, acetyl, hydroxyl, nitro, a trialkylamine, a triarylamine, a trialkylphosphine, or tosyl;
z is 0 up to an available valence of M
e
;
x is 1 or 2;
a and a′ are same or different and each is 1 or 2;
c and c′ are same or different and each is 1 to 5 with the proviso that if a or a′ is 1, then c and c′ are each not greater than 4, and if a or a′ is 2, then c and c′ are each not greater than 5; and
A and A′ are same or different and each is carbon or nitrogen; and
a peroxy compound selected from organic peroxides, organic hydroperoxides, peresters, peracids, or mixtures thereof.
Preferably, the initiator system of the current aspect of the present invention further includes a second initiator system including an aziridine functionalized compound and a compound having an acid functional group. It may also further include a polymerizable (meth)acrylate component.
In still yet another aspect, the present invention is directed to a kit useful for bonding substrates, at least one of which includes a low free energy surface to be bonded, including:
a first part including
a (meth)acrylate component;
a metallocene compound; and
an aziridine functionalized compound; and
a second part, separate from the first part, including
a (meth)acrylate component;
a peroxy compound; and
a compound having an acid functional group,
where upon mixing contents of the first part and
Bauman Steven C.
Henkel Loctite Corporation
Zalukaeva Tatyana
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