GB2121811A - Solventless two-part adhesive composition - Google Patents
Solventless two-part adhesive composition Download PDFInfo
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- GB2121811A GB2121811A GB08315882A GB8315882A GB2121811A GB 2121811 A GB2121811 A GB 2121811A GB 08315882 A GB08315882 A GB 08315882A GB 8315882 A GB8315882 A GB 8315882A GB 2121811 A GB2121811 A GB 2121811A
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- Prior art keywords
- atwo
- adhesive composition
- radical
- part adhesive
- composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Abstract
A two-part adhesive composition comprises as a first part a polymerizable vinyl-type material and a free-radical initiator and as a second part a polymerizable vinyl-type material and a solventless accelerator system comprising a transition metal salt and optionally an amine co-accelerator. The resin systems of each part are substantially similar in rheology and viscosity to optimize the effectiveness of the adhesive composition.
Description
SPECIFICATION
Solventless two-part adhesive composition
This invention relates to a solventless two-part
adhesive composition.
More particularly, the invention is directed to a
two-part solventless adhesive system characterized
by excellent gap-filling capabilities and rapid curing,
as well as a process forthe adhesive bonding of
surfaces therewith.
Two-partadhesive compositions are well known in
the field of ethylenically unsaturated free-radical cu ring-adhesive systems. Heretofore, these adhesive
compositions have required the use of solvents as carriersfortheirprimeroracceleratorsystems.
Usually the primer is coated on the surface priorto
deposition or contact with the polymerizable part of
the composition. The solvent carrying the primer is usually allowed to evaporate off the surface prior to contact with the polymerizable part. Typical examples
of patents in this field are U.S. Nos. 4,081,308 and 4,052,244, both to M. Skoultchi. These patents present two-part adhesive compositions wherein the first part
is a polymerizable acrylic monomer and the second
part is an accelerator in a solvent carrier. Other U.S.
patents which are two-part adhesive compositions
containing solutions of elastomeric polymers in vinyl
monomers are Nos. 3,810,407, 3,962,372,4,112,013, 4, 1 18,436, 3,994,764,3,832,274 and 4,138,449. These systems, which are used in the manufacture oftough acrylics, also employ solvent carriers forthe accelera tor part of the adhesive composition. Anaerobic compositions have effectively used primers and
accelerators as a means oftreating a surface priorto deposition of the polymerizable portion ofthe adhesive composition. Primers were traditionally kept
separate from the adhesive composition and dis
solved in a solvent carrier, such astrichloroethane and the like.Examples of anaerboic compositions which
use, albeit optionally, solvent solutions of primers for
accelerating cure are U.S. Patents Nos. 2,895,950,
3,043,820 and 3,218,306 among others.
This invention relates to two-part adhesive com
positions which are characterized by rapid cure and excellentcurethrough volume, e.g., gap-filling ability,
on active as well as inactive surfaces. This invention
also relates to a process of bonding surfaces together
whereby the adhesive composition employed is used.
More specifically, this invention relates to an
adhesive composition comprising,
(A) as afirst part a resin system comprising,
(i) at least one polymerizable acrylate or methacry
late material;
(ii) an initiatoroffree-radical polymerization
selected from the group consisting of peroxides,
hydroperoxides, peresters, persalts and peracids;
(iii) optionally a sulfimide; and
(iv) optionally a hydrazine derivative; and
(B) as a second part a resin system comprising,
(i) at least one polymerizable acrylate or methacry
late material;
(ii) a solventless accelerator system comprising a
transition metal salt; and
(iii) optionally an amine co-acceleratorwith said transition metal salt, wherein the two resin systems are substantially matched in viscosity and rheology.
The present invention discloses a two-part composition which is novel in that neither part of the composition contains a solvent carrierforthe accel eration or primer components. Whereas the prior art disclosed the polymerizable portion of an adhesive composition to be contained solely in one part, while the second part comprised a solution of accelerator or primer in an organic solvent, the present invention requires that the polymerizable material, e.g. a vinyltype monomer, be present in both parts of the adhesive composition. According to the invention, both parts ofthe adhesive composition preferably contain similar proportions of a vinyl-type monomer, which cures via a free-radical reaction. The initiators of the free-radical reaction must be kept in one part of the adhesive and the transition metal accelerators kept in the other part.Each part remains stable until admixed with the other, whereupon cure ofthe adhesive composition is effected. It is possible for certain compounds known to accelerate the generation of free-radicals, to be in the same part as the free-radical initiators, without causing stability problems. Sulfimides and hydrazine derivatives can be contained in the part having the initiators. However, transition metal salts and complexes, which are required for this invention, must not be formulated into the same part as the initiators or the hydrazine derivatives.
Although it is not absolutely necessarythat equivalent amounts of polymerizable material be present in both parts, it is recommendedthatthis be the case in orderto facilitate the diffusion ofthe various components in each part (particularly the initiators and accelerators). The rheology of the two parts should be substantially similarto promote the effective intermingling ofthe initiator in one part with the accelerator in the other part, andto effect a uniform cure throughoutthe polymerizable material.
One advantage overthe prior art gained by this invention isthatthe accelerators are more effectively dispersed throughoutthe adhesive composition as a whole, ratherthan merely applying an acceleration solution to the surface of the adhesive. It is believed thatimprovements in curethrough volume and gap-filling capability may be attributed to this.
It is not necessary to pre-mix the two components priorto deposition on a surface. Acoating of one part oftheadhesivecomposition may be placed on one surface and a coating of the other part may be placed on another surface, the two surfaces then being mated together so the respective coatings are in contact with each other.
While anyvinyl-type monomers are usefully em- ployable, the preferred polymerizable materials are the acrylates and methacrylates, which may be monoor polyfunctional.
Controlled cure speeds are possible independently
of substrate surface. Priming of surfaces with accelerating solutions, as in the prior art, is not
necessary. Cure through relatively large bond-line
gaps is now possible in relativelyshorttimes.
In practice, the adhesive composition can be applied
by several methods. The two parts of the adhesive
composition may be applied, one part to one surface, the other part to a second anrface and the two coated surfaces placed in contact with each other; or alternatively, a layer of one part ofthe adhesive composition may be applied to a firstsurface, a layer ofthe other part applied overthe first layer and a second uncoated surface placed in contact with the doubly coated first surface.Another alternative, especially suitable for slip-fitting parts or screw-threaded parts, is to place each part ofthe adhesive composition side by side on a first surface and to place a second surface in contact with the coated first surface, moving the two surfaces relative to each other to thereby mixthetwo parts ofthe adhesive composition. A less preferable alternative is to mix the two parts ofthe adhesive together prior to any deposition onto surfaces. Once the coated parts are placed in contact with each other, the adhesive composition cures at room temperature to a storage bond in a relativelyshorttime.
At least one polymerizable material must be present in each ofthetwo-partsofthis invention,whileany allyl orvinyl-type reactive compound which under goesfree-radical polymerization is effectively useful, monomers of the acrylate and methacrylate ester type are preferred. The polymerizable acrylate and methacrylate ester monomers may be monofunctional, polyfunctional, or a combination of both. Generally, the monomers are exemplified but not limited to those selected from the class consisting of alkyl acrylates, cycloalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, alkoxy acrylates, alkoxy methacrylates, alkylene diacrylates and alkylene dimethacrylates.Among the preferred monofunctional monomers are methyl methacrylate, lauryl methacrylate, 2-ethyl hexyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate and t-butyl methacrylate. The most preferred are those monomers which have high boiling points and low volatility characteristics, including such monomers as tetrahydrofurfuyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The monofunctional monomers mentioned above may generally be represented bytheformula
wherein R1 is H, CH3 or loweralkyl, R2 is H, alkyl, alkoxy, cycloalkyl, oralkylene group.
The effective rangeofthe monofunctional polymerizable acrylate ester monomer to be used in the instant compositions may vary somewhat depending on the specific properties desired, but generally 1 to 90% byweightofthe composition and preferably within the range of 15 to 80% by weight, and most preferably 15 to 40% by weight of the composition. Adjustments within these ranges are easily made within the skill of the art.
Itmay be desirableto add a polyfunctional monomerto the composition as well. When this is done, it generally should be in the range of 1 to 90% by weight of the composition depending on the specific polyfunctional monomer, and preferably 15% to 40% by weightofthe composition. The preferred polyfunc- tionals are dimethacrylates of various glycols. These monomersaredisclosed in U.S.Patent No.3,218,305, and are of the general formula:
wherein R3 is H, C14alkyl or hydroxyalkyl or R5OCH2-; R6 is H, halogen or C1 alkyl; R4 is H, OH or R50--; R5 is CH2 = CRGC=O--; mis an integer, preferably 1 to 8; k is an integer, preferably 1 to 20; andpisOor1.
Examples ofsome preferred glycol dimethacrylates ofthisformula are polyethylene glycol dimethacrylate and dipropylene glycol dimethacrylate, to name a few.
Othersuitable polymerizable acrylate ester monomers which may be employed are described in
U.S. Patent No.4,018,851, having the general for- mula:
wherein R8 is selected from the class consisting of hydrogen, chlorine, and methyl and ethyl radicals; R7 is a bivalent organic radical selected from the group consisting of lower alkylene of 1 -8 carbon atoms, phenylene, and naphthylene; W is a polyisocyanate radical;E isan aromatic, heterocyclicorcycloaliphatic polyol or polyamine radical, preferably a diol, and more preferably a diol ofacycloaliphaticcompound; d is either 1 or 0; i isO when d is 0, and otherwise equal to one less than the number of reactive hydrogen atoms of E; wherein Z is a (i) polymeric or copolymeric grafted alkylene ether polyol radical or (ii) polymeric or copolymeric methylene ether polyol radical; z is an integer equal to the valency of Z; wherein an asterisk indicates a urethane (-NH- CO-O-) or ureide (-NH-CO-NH-) linkage. Z may also be a polymeric orcopolymeric methylene ether polyol radical, giving-a group of polymerizable monomers disclosed in U.S. Patent No.3,993,815.
Monomers generally characterized as polyurethanes or polyureides, as disclosed in U.S.
Patent No.3,425,988 may also be used effectively.
These monomers reformed from the reaction of an organic polyisocyanate and an acrylate ester having an active hydrogen in the non-acrylate portion ofthe ester. These monomers may be represented by the general formula: Iv. (A-X-CO.NH i n B wherein X is--OO- or--RSNN-; R9 is H oraloweralkyl group of 1 to 7 carbon atoms; A is CH2=CR10.CO.; R10 is H or CH3; n is an integerfrom 2to 6 inclusive; and B is a polyvalent substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkyloxy
alkylene, aryloxy-arylene or heterocyclic radical.
Finally, polymerizable urethane-acrylate monom
ers may be employed, which typically have the
general formula: V (CH2=CR11 .CO.O.R13.O.CO.NH)2-R12 wherein R11 is H, CHB, C2H5 or Cl; R12 is C220 alkylene, alkenylene orcycloalkylene radical our a C640 arylene, alkarylene, aralkarylene, alkyloxyalkylene or aryloxy aryleneradicalwhich may be substituted by 1-4 chlonne atoms or by 1-3 amino or mono-ordi-C1.3 alkylamino or C1.3 alkylamino or C1.3 alkoxy groups.
R13 is one ofthe following less one hydrogen atom: (a) a C1-8 hydroxy alkyl or aminoalkyl group, (b) a C1 6 alkylamino-C1.8 alkyl group; or (c) a hydroxyphenyl, an aminophenyl, a hydroxynaphthyl oran aminonaphthyl group which may be further substituted by an alkyl, alkylamino or dialkyiamino group, each alkyl group in thissubpart (c) containing upto 3 carbon atoms. Of these, the preferred compositions contain eithermonomerVI., offormula:
or monomer Vll, offormula:
or both, (PR represents a propylenetriol oligomer residue).
Mixtures of some or all oftheabove polymerizable acrylate estermonomersare also useful.The accelerators of free-radical polymerization ofthe instant compositions are generally used with good results in concentrations of less than 10% by weight, the preferred range being about 0.1% to about 0.75%.
Sulfimides are the preferred group of free-radical accelerators, with the preferred species being 3-oxo2,3 - dihydrobenz[d] isothiazole - 1,1 - dioxide, commonly known as benzoic sulfimide or saccharin.
Tertiary amines may also be employed as accelerators for free-radical production with the preferred amine being N,N -dimethyl - paratoluidine. Acids having a pKa not exceeding 6, as disclosed in U.S.
Patent No.4,1 80,640 to Melody, are also useful as accelerators. Hydrazine derivatives ofthe type disclosed in U.S. Patent No. 4,321,349 to R. Rich, herein incorporated by reference, are found to be very effective in the instant compositions. The preferred hydras'we is 1 - acetyl - 2 - phenyl hydrazine. The hydrazines useful generally have the formula R17-NH-NH-CO-R18 wherein R'7 and R18 may be the same or different and are C1 6 straight and branched chain alkyl radicals, C1.4 acyl radicals and C1.4 aryl radicals.The hydrazines if present, are in amounts sufficientto accelerate the polymerization at room temperature.Transition metal accelerators are preferably a salt or complex of copper, nickel, cobalt or ion. Examples of these accelerators preferred are copper octoate, copper naphthenate, copper ethylhexanoate and copperacetylacetonate, among others. It is prefer able thatthetransition metal accelerator is soluble in the polymerizable material. The transition metal accelerator must be kept in the part of the adhesive composition which does not contain the free-radical initiator orthe hydrazine derivative.The relative part of the adhesive composition contains the transition metal accelerator in a proportion effectiveforcuring the adhesive composition when the two parts are placed in close contact with each other, or mixed.
Preferably the proportion is effective for curing a mixture of substantially equal amounts (volumes) of the two parts.
Initiators may be of the organic peroxy or hydroperoxytype; perester or peracid type; or persalt.
Especially useful are the perester and peroxide type, among which t-butyl perbenzoate, t-butyl peroctoate and cumene hydroperoxide are preferred. The initiators are usually employed in amounts of about 0.1 % to about 10% by weight of the composition.
Useful free-radical initiators also include those that can be decomposed by the action of heat to produce free radicals. They also include other redox polymerization catlaysts or any compound capable of generating free radicals. Such compounds can easily be selected from those skilled in the art. For a more detailed discussion, see U.S. Patent Nos. 3,043,820, 3,691,438,3,616,640 and 3,832,274.
Inhibitors and chelators, well recognized in the art for imparting stabilityto polymerizable compositions, are optional but recommended. Those inhibitors useful in the present composition are usually selected from the group consisting of hydro quinones, benzoquinones, naphthoquinones, phe- nanthraquinones, anthraquinones, and substituted compounds of any of these. Additionally, various phenols can be employed as inhibitors, the preferred one being 2,6 - di -tert- butyl -4-methyl phenol.
Among the chelators which may be optionally present in the adhesive composition arethe betadiketones and the salt of ethylenediaminetetra acetic acid (EDTA). Both the inhibitors and chelators may be effectively employed in levels of 0.1 to 1 by byweight, without adversely affecting the speed of cure of the polymerizable adhesive composition. Cross-linking agents, optionally present in amounts from zero to 10% by weight of the composition, include such compounds as copolymerizable dimethacrylate.
The amount ofthickness, viscosity orthixotropy desired can be varied in accordance with the particu lar application required. Thickeners, plasticizers, diluents and various other agents common to the art can be employed in any reasonable mannerto produce the desired characteristics.
The invention will be appreciated further from the examples to follow, which are not meant in anyway to restrict the effective scope of the invention.
Example 1
A composition of the present invention was formulated using the following ingredients. All percent weights (% wt.) in these examples are based on the weight ofthe respective part ofthe adhesive composition.
FirstPart %wit.
urethane-acrylate block resin(1) 36.31 hydroxyethyl methacrylate 58.45 cumene hydroperoxide 0.94 f-acetyl-2-phenyl hydrazine 0.47 benzoic sulfimide 0.42 acryiicacid 2.00 chelator 1.04
'100
SecondPart %wot.
urethane-acrylate block resin(') 28.00 hydroxyethyl methacrylate 69.70 copper octoate 2.00 chelator 0.30
100
(1) See U.S. Patent Nos. 4,309,526 and 4,295,409.
A linear bead ofthefirst partwas dispensed on a cylindrical ceramic magnetic surface. A bead of equal size ofthe second part was dispensed on top ofthe first part and a cadmium plated surface was mated with the ceramic surface so thatthe surfaces were in close contact with each other, and the adhesive parts were co-mingled.
The adhesive composition fixtured at room temperature is about twenty (20) seconds. The bond between the surfaces was tested for tensile shear strength and was found to have cured to a strong bond within a shorttime.
The same test, using the above composition was conducted using a zinc plated surface in place ofthe cadmium plated surface, with similar results obtained.
Example 2
A composition ofthe instant invention was formula lated using the ingredients of Example 1, except the concentration of the transition metal in the second partwasvaried.Tablel below showstensile shear strengths (kg/cm2/psi) atvarious bondline gaps, as a function of curing time, for several transition metal concentrations. The control is an organic chlorinated solution of a transition metal salt (copper octoate) and an amine. The control represents a typical primer solution which is used to coat surfaces, especially inactive surfaces such as cadmium, prior to deposition ofthe polymerizable portion of the first part of the instant invention.
This example demonstrates that the compositions of the instant invention exhibit excellent cure speed, tensile shear strength and gap curing capability. At gaps between the lap shears of 0.254 mm and 0.508 mm (10 mils and 20 mils),the control sample demonstrated onlyweakfixture strength, while the instant composition showed excel lent strength at these bondline gaps.
TABLE I
2% Copper 4% Copper 8% Copper l Octoate Octoate Octoate (1)Control (2)Bondline Gap/Cure time kg/cm2 (Psi) kg/cm2 (Psi) kg/cm2 (Psi) kg/cm2 (Psi)
0/60 secs. 6.33 (90) 11.25 (160) 20.39 (290) 70.31 (l000) 0/120 secs. 35.86 (510) 42.19 (600) 45.70 (650) 84.37 (1200)
0/300 secs. 62.28 (900) 91.40 (1300) 85.78 (1220) 101.25 (1440)
0/24 hrs. 133.59 (1900) 140.62 (2000) 130.07 (1850) 130.78 (1860) 0.254 mm (10 mils)/30 mins. 74.53 (1060) 101.25. (1440) 116.71 (1660) Fixture only 0.508 mm (20 mils)/30 mins. 59.06 (840) 119.53 (1700) 88.59 (1260) Very weak
Fixture (1) 3.5% copper octoate, 0.5% amine and 95% chlorinated solvent. The control primer was
used to coat the lapshear surfaces prior to deposition of first part of the adhesive
composition of Example 1.
(2) All lapshear specimens were sand-blasted mild steel.
Claims (22)
1. Atwo-part adhesive composition comprising,
(A) as a first part a resin system comprising
(i) at least one polymerizable acrylate or methacrylate material;
(ii) an initiatoroffree-radical polymerization selected from the group consisting of peroxides, hydroperoxides, peresters, persalts and peracids;
(iii) optionally a sulfimide; and
(iv) optionally a hydrazine derivative; and
(B) as a second part a resin system comprising,
(i) at least one polymerizable acrylate ar methacrylate material;
(ii) a solventless acceleratorsystem comprising a transition metal salt; and
(iii) optionally an amineco-acceleratorwith said transition metal salt, wherein the two resin system are substantially matched in viscosity and rheology.
2. Atwo-part adhesive composition as claimed in
Claim 1,wherein the polymerizable material of either or both parts is a monofunctional monomer and corresponds to the formula
wherein R1 is H, CH3 or lower alkyl, R2 is H, alkyl,
alkoxy, cycloalkyl or alkylenyl group.
3. Atwo-partadhesivecompositionasclaimed in Claim 2 wherein, the monofunctional monomer is
hydroxypropyl methacrylate.
4. Atwo-partadhesivecomposition as claimed in
Claim 2 wherein the monofunctional monomer is hydroxyethyl methacrylate.
5. Atwo-part adhesive composition as claimed in
Claim 2 wherein, the monofunctional monomer is tetrahydrofurfuryl methacrylate.
6. Atwo-part adhesive composition as claimed in
Claim 1 wherein the polymerizable material of either or both parts is a polyfunctional monomer and corresponds to the formula
wherein R3 is H, CIA alkyl or hydroxyalkyl or
RSOCWT-; R6is H, halogen or CIA alkyl; R4 is H, OH or R5O-; R5 is CH2=CR6C=O; m is an integer, from 1 to
8; k is an integerfrom 1 to 20; and p is O orl.
7. Atwo-part adhesive composition as claimed in
Claim 6 wherein the polyfunctional monomer is
polyethylene glycol dimethacrylate.
8. Atwo-partadhesivecomposition as claimed in Claim 6 wherein the polyfunctional monomer is tetraethylene glycol dimethylacrylate.
9. Atwo-partadhesive composition as claimed in
Claim 6 wherein the polyfunctional monomer is triethylene glycol dimethacrylate.
10. A two-part adhesive composition as claimed in Claim 6 wherein the polyfunctional monomer is dipropyleneglycol dimethacrylate.
11. Atwo-partadhesive composition as claimed in Claim 1,wherein the polymerizable material of either or both parts is a polymerizable acrylate ester monomer represented bytheformula:
wherein R8 is selected from the class consisting of hydrogen chlorine, and methyl and ethyl radicals; R7 is a bivalent organic radical selected from the group consisting of lower alkylene of 1-8 carbon atoms, phenylene, and naphthylene; W is a polyisocyanate radical;E is an aromatic, heterocyclic orcycloalipha- tic polyol or polyamine radical, a diol of a cycloaliphatic compound, d is either 1 or 0; i is when d is 0, and otherwise equal to one less than the number of reactive hydrogen atoms of E; wherein Z is a (i) polymeric or copolymeric grafted alkylene ether polyol radical or(ii) polymeric or copolymeric methylene ether polyol radical; z is an integer equal to the valency of Z; wherein an asterisk indicates a urethane (-NH-CO-O-) or ureide (-NH-CO- NH-) linkage; Z may also be a polymeric or copolymermethyleneetherpolyol radical; or IV. (A-X-Co.NH ) n B wherein X is- or-R9N-; R9 is H or a lower alkyl group of 1 to 7 carbon atoms;A is CH2=CR1 .CO.O; R10 is H, or CH3; n is an integerfrom 2 to 6 inclusive; and B is a polyvalent substituted or unsubstituted alkyl, alkyl, cycloalkyl, aryl, aralkyl, alkyloxyalkylene, aryloxy-arylene or heterocyclic radical.
12. Atwo-part adhesive composition as claimed in Claim 1, wherein the polymerizable material of either or both parts is a polymerizable acrylate ester monomer represented bytheformula:
V. (CB2=CR11.Co.O.R13 .O.CO.NH i2 R12 wherein R11 is H, CH3, C2H5orC1; R'2 is a C220 alkylene, alkenylene orcycloalkylene radical ora C640 arylene, alkarylene, aralkarylene, alkoxyalkylene or aryloxyarylene radical which may be substituted by 1-4 chlorine atoms or by 1-3 amino or mono-ordi-C1.3 alkylamino or Ca 3 alkoxy groups, R13 is one of the following less one hydrogen atoms: (a) a C, 8 hydroxy alkyl oraminoalkyl group, (b) a C, 6 alkylamino-C1.8 alkyl group; or (c) a hydroxyphenyl, an amino-phenyl, a hydroxynaphthyl oran aminonaphthyl group which may be further substituted by an alkyl, alkylamino or dialkylamino group, each alkyl group in this subpart (c) containing up to about 3 carbon atoms.
13. Atwo part-adhesivecomposition asclaimed in Claim 1, wherein the polymerizable material of either or both parts is a polymerizable acrylate ester monomerwhich has the formula:
where PR represents a propylene triol oligomer residue.
14. Atwo-part adhesive composition as claimed in any of Claims 1 to 13 wherein in thefirst partofthe composition the initiator of free-radical poiymerization is cumene hydroperoxide.
15. Atwo-part adhesive composition as claimed in anyofClaims 1 to 13wherein inthefirstpartofthe composition the initiator of free-radical polymeriza tion ist-butyl perbenzoate.
16. Atwo-part adhesive composition as claimed in anyofClaims 1 to 13 wherein inthefirstpartofthe composition the initiator of free radical polymerization is t-butyl peroctoate.
17. A two-part adhesive composition as claimed in any of Claims 1 to 16whereinthetransition metal salt is selected from the group consisting of copper naphthenate, copper ethyihexanoate and copper acetylacetonate.
18. Atwo-partadhesive composition as claimed in any of claims 1 to 17 wherein the amine coaccelerator ofthe second part is a tertiary aromatic amine.
19. Atwo-part adhesive composition as claimed in anyofclaims 1 to 18whereinthesulphimideinthe first part is saccharin or a derivative thereof.
20. Atwo-part adhesive composition as claimed in any of Claims 1 to 19 wherein the hydrazine derivative ofthefirst part is oftheformula R'7--NHH-NNH--CO-R'8 wherein R17 and R18 may be the same or different and are C1 6 straight and branched chain alkyl radicals,
C14 acyl radicals and C14 aryl radicals.
21. Atwo-part adhesive composition substantially as described with particular reference to either of the examples.
22. A method of bonding using a two-part adhe sive composition comprising,
(1) coating one part of the two-part adhesive onto afirstsurface: (2) coating the other part ofthe two-part adhesive onto a second surface;
(3) placing the two surfaces in contactwith each other at the area coated by each respective part of the
adhesive composition, whereinthetwo-part adhesive composition is as
defined in any of claims 1 to 21.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38649182A | 1982-06-09 | 1982-06-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8315882D0 GB8315882D0 (en) | 1983-07-13 |
| GB2121811A true GB2121811A (en) | 1984-01-04 |
Family
ID=23525807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08315882A Withdrawn GB2121811A (en) | 1982-06-09 | 1983-06-09 | Solventless two-part adhesive composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS594667A (en) |
| AU (1) | AU1549383A (en) |
| DE (1) | DE3320918A1 (en) |
| FR (1) | FR2528440A1 (en) |
| GB (1) | GB2121811A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232226A2 (en) * | 1986-02-07 | 1987-08-12 | Ciba-Geigy Ag | Two-component adhesives based on acrylate containing vanadium-phosphites |
| GB2196012A (en) * | 1986-09-11 | 1988-04-20 | Loctite Ltd | Acrylic adhesive composition |
| EP0659859A1 (en) * | 1993-12-20 | 1995-06-28 | National Starch and Chemical Investment Holding Corporation | Structural acrylic adhesives |
| WO1996023036A1 (en) * | 1995-01-24 | 1996-08-01 | Henkel Kommanditgesellschaft Auf Aktien | Aerobically hardenable adhesive |
| WO1999048833A2 (en) * | 1998-03-24 | 1999-09-30 | Bpb Plc | Ready made cementitious composition |
| US8119754B2 (en) | 2007-06-08 | 2012-02-21 | Henkel Corporation | Room temperature curing adhesive composition having high temperature properties |
| GB2497114A (en) * | 2011-12-01 | 2013-06-05 | Spinnaker Int Ltd | Anaerobic adhesive compositions |
| US9707312B2 (en) | 2012-05-16 | 2017-07-18 | Heraeus Medical Gmbh | Paste-like bone cement |
| WO2019157264A1 (en) * | 2018-02-09 | 2019-08-15 | 3M Innovative Properties Company | Primer-initiated cure of structural adhesive film |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60219276A (en) * | 1984-04-14 | 1985-11-01 | Toagosei Chem Ind Co Ltd | Acrylic adhesive composition |
| JPS62100566A (en) * | 1985-10-28 | 1987-05-11 | Keinosuke Isono | Adhesive composition |
| JPS62124172A (en) * | 1985-11-22 | 1987-06-05 | Keinosuke Isono | Adhesive composition |
| DE4012720A1 (en) * | 1990-04-21 | 1991-10-24 | Heraeus Kulzer Gmbh | ADHESIVE FOR CONNECTING MOLDED PARTS MADE OF POLYCARBONATE PLASTICS |
| US5426166A (en) * | 1994-01-26 | 1995-06-20 | Caschem, Inc. | Urethane adhesive compositions |
| ATE447596T1 (en) * | 2004-03-09 | 2009-11-15 | Henkel Corp | THERMALLY CONDUCTIVE TWO-COMPONENT ADHESIVE COMPOSITION |
| JP4745905B2 (en) * | 2006-07-21 | 2011-08-10 | 大倉工業株式会社 | Two-component acrylic adhesive for inorganic materials for civil engineering and construction |
| WO2023210718A1 (en) * | 2022-04-28 | 2023-11-02 | 東亞合成株式会社 | Primer composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104458A (en) * | 1977-01-07 | 1978-08-01 | Gaf Corporation | Multifunctional acrylate N-vinylamide anaerobic adhesive composition |
| GB1595085A (en) * | 1976-11-08 | 1981-08-05 | Loctite Ireland Ltd | Curable acrylate ester compositions containing hydrazine accelerators and acid co-accelerators |
| US4331795A (en) * | 1979-07-23 | 1982-05-25 | Denki Kagaku Kogyo Kabushiki Kaisha | Two liquid type adhesive composition comprising a cobalt salt cure accelerator in one portion and a hydroperoxide with an aromatic amine and/or a pyridine derivative cure accelerator in the second portion |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842467B1 (en) * | 1970-12-04 | 1973-12-12 | ||
| JPS5516018A (en) * | 1978-07-19 | 1980-02-04 | Denki Kagaku Kogyo Kk | Acrylate curing composition |
-
1983
- 1983-06-04 JP JP10012883A patent/JPS594667A/en active Pending
- 1983-06-08 AU AU15493/83A patent/AU1549383A/en not_active Abandoned
- 1983-06-09 FR FR8309566A patent/FR2528440A1/en active Pending
- 1983-06-09 GB GB08315882A patent/GB2121811A/en not_active Withdrawn
- 1983-06-09 DE DE19833320918 patent/DE3320918A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1595085A (en) * | 1976-11-08 | 1981-08-05 | Loctite Ireland Ltd | Curable acrylate ester compositions containing hydrazine accelerators and acid co-accelerators |
| US4104458A (en) * | 1977-01-07 | 1978-08-01 | Gaf Corporation | Multifunctional acrylate N-vinylamide anaerobic adhesive composition |
| US4158647A (en) * | 1977-01-07 | 1979-06-19 | Gaf Corporation | Multifunctional acrylate n-vinylamide anaerobic adhesive compositions |
| GB1595089A (en) * | 1977-01-07 | 1981-08-05 | Gaf Corp | Multifunctional acrylate or a-substituted acrylate/n-vinylamide anaerobic adhesive composition |
| US4331795A (en) * | 1979-07-23 | 1982-05-25 | Denki Kagaku Kogyo Kabushiki Kaisha | Two liquid type adhesive composition comprising a cobalt salt cure accelerator in one portion and a hydroperoxide with an aromatic amine and/or a pyridine derivative cure accelerator in the second portion |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232226A2 (en) * | 1986-02-07 | 1987-08-12 | Ciba-Geigy Ag | Two-component adhesives based on acrylate containing vanadium-phosphites |
| EP0232226A3 (en) * | 1986-02-07 | 1989-04-12 | Ciba-Geigy Ag | Two-component adhesives based on acrylate containing vanadium-phosphites |
| GB2196012A (en) * | 1986-09-11 | 1988-04-20 | Loctite Ltd | Acrylic adhesive composition |
| EP0659859A1 (en) * | 1993-12-20 | 1995-06-28 | National Starch and Chemical Investment Holding Corporation | Structural acrylic adhesives |
| WO1996023036A1 (en) * | 1995-01-24 | 1996-08-01 | Henkel Kommanditgesellschaft Auf Aktien | Aerobically hardenable adhesive |
| US6096842A (en) * | 1995-01-24 | 2000-08-01 | Henkel Kommanditgesellschaft Auf Aktien | Aerobically curable adhesive |
| WO1999048833A2 (en) * | 1998-03-24 | 1999-09-30 | Bpb Plc | Ready made cementitious composition |
| WO1999048833A3 (en) * | 1998-03-24 | 1999-11-11 | Bpb Plc | Ready made cementitious composition |
| US8119754B2 (en) | 2007-06-08 | 2012-02-21 | Henkel Corporation | Room temperature curing adhesive composition having high temperature properties |
| GB2497114A (en) * | 2011-12-01 | 2013-06-05 | Spinnaker Int Ltd | Anaerobic adhesive compositions |
| GB2497114B (en) * | 2011-12-01 | 2015-02-18 | Spinnaker Int Ltd | Adhesive composition |
| US9707312B2 (en) | 2012-05-16 | 2017-07-18 | Heraeus Medical Gmbh | Paste-like bone cement |
| WO2019157264A1 (en) * | 2018-02-09 | 2019-08-15 | 3M Innovative Properties Company | Primer-initiated cure of structural adhesive film |
| WO2019157265A1 (en) * | 2018-02-09 | 2019-08-15 | 3M Innovative Properties Company | Primer-initiated cure of structural adhesive film |
| CN111699230A (en) * | 2018-02-09 | 2020-09-22 | 3M创新有限公司 | Primer initiated structural adhesive film curing |
| CN111699231A (en) * | 2018-02-09 | 2020-09-22 | 3M创新有限公司 | Primer initiated structural adhesive film curing |
| CN111699230B (en) * | 2018-02-09 | 2022-08-16 | 3M创新有限公司 | Primer initiated structural adhesive film curing |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8315882D0 (en) | 1983-07-13 |
| DE3320918A1 (en) | 1983-12-15 |
| AU1549383A (en) | 1983-12-15 |
| JPS594667A (en) | 1984-01-11 |
| FR2528440A1 (en) | 1983-12-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |