CA1207944A - Fast curing phosphate modified anaerobic composition - Google Patents
Fast curing phosphate modified anaerobic compositionInfo
- Publication number
- CA1207944A CA1207944A CA000385830A CA385830A CA1207944A CA 1207944 A CA1207944 A CA 1207944A CA 000385830 A CA000385830 A CA 000385830A CA 385830 A CA385830 A CA 385830A CA 1207944 A CA1207944 A CA 1207944A
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- carbon atoms
- sealant composition
- anaerobic adhesive
- weight
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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
FAST CURING PHOSPHATE MODIFIED ANAEROBIC COMPOSITION
ABSTRACT
Cure time of anaerobic adhesive compositions containing organophosphate esters is markedly reduced by the incorporation into such adhesives of certain tertiary amines.
ABSTRACT
Cure time of anaerobic adhesive compositions containing organophosphate esters is markedly reduced by the incorporation into such adhesives of certain tertiary amines.
Description
~0~7~
FAST CURING PHOSPHATE MODIFIED ANAEROBIC COMPOSITION
.
Field of the Invention The present invention relates to polymerizable compositions. More particularly, the invention relates to anaerobic adhesive and sealant compositions, especially such compositions containing organophosphate esters.
Background of the Invention .
Anaerobic adhesive and sealant compositions are well-known compositions of matter. Typically, anaerobic adhesive and sealant compositions comprise precatalyzed polymerizable materials, including monomers, polymers and mixtures of monomers and polymers, which cure by a polymerization mechanism which is inhibited by oxygen. Such anaerobic compositions remain in the unpoiymerized state as long as adequate contact with oxygen is maintained and cure spontaneously to a solid state upon the exclusion of oxygen. Anaerobic adhesive and sealant compositions are especially useful for locking threaded assemblies, sealing porous and flanged assemblies, strenthening cylindrical assemblies and structural bonding.
From the initial development of anaerobic compositions that could be shipped and stored and cured within a matter of hours after application to metal parts, sign;ficant research and development efforts have been, and are still being, expended on improving performance characteristics of anaerobic materials. A meritorious development in the field of anaerobic adhesives was the discovery of Saito, U.S.A. Patent 4,044,044, that the addition of certain organophosphorus esters to anaerobic adhesive and sealant compositions significantly increased the adhesive strength of anaerobic compositions. While effective in improving adhesion, the ; addition of organophosphorus esters is accompanied by a significant jncrease in the time required for cure and, additionally, requires curing .
, ~ ~ 12[)'79~
temperatures in excess of 100C. These negative side effects are highly detrimental to commercial use of an otherwise desirable development.
It has now been discovered that the time required for curing anaerobic adhesive and sealant compositions containing organophosphorus esters corresponding to the general formula O ~' CH2 = C - C - O - ~ - P - OH;
Il I
R O H
wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8, preferably 1 to 4, carbon atoms, and CH2-CH-; A is selected from the group -R20- and -(R30)n7 wherein R2 is an aliphatic or cycloaliphatic alkylene group containing from 1 to 9, preferably 2 to 6, carbon atoms; R3 is an alkylene group having from 1 to 7, preferably 2 to 4, carbon atoms; and n is an integer from 2 to 10, is unexpectedly signi~icantly reduced by incorporating therein certain hereinafter described tertiary amines. In addition to the significant reduction in the time required for curing, the inclusion of the tertiary amines of this invention also significantly reduces the cure temperature. The present discovery is particularly surprising in view of ; the fact that, although tertiary amines are known accelerating agents for anaerobic adhesive and sealant compositions, only the particular tertiary amines employed herein are effective to accelerate anaerobic adhesives and sealant composit;ons containing the herein described organophosphorus esters.
More particularly, the present invention provides anaerobic adhesive and sealant compositions containing an anaerobically polymerizable material having at least one -terminal ethylenically unsaturated group; a polymerization initiator for said anaerobically polymerizable material;
at least one mono-organic ester of phosphoric acid and at least one tertiary dialkylaryl amine.
The invention encompasses the composition as a whole, as described above, as well as two-part anaerobic adhesive and sealant compositions wherein the anaerobically polymerizable ethylenically unsaturated material, polymerization initiator and mono-organic ester of phosphoric acid are used as a first part and the tertiary amine is used as a second part and also such two-part anaeroblc compositions wherein the .
I.Z~ 49t (~
anaerobically polymerizable ethylenically unsaturated material, polymerization initiator and tertiary amine are used as a first part and the mono-organic ester of phosphoric acid as a second part. In the case of either two-part mode, the second part most commonly is used as a surface primer prior to the application of the first part, although the second part can be admixed with the first part immediately prior to use if so desired.
Substantially any of the known anaerobically polymerizable materials may be employed in the practice of this invention. Typically, anaerobic polymerizable materials range in consistency from a water-like liquid to a light-weight grease; are stable in the presence of oxygen; polymerize in the absence of oxygen through a free radical mechanism initiated by a peroxy compound; can be monomer or polymer or mixtures of either or bot~l monomers and polymers; and have as a characteristic feature at least one, preferably at least two, terminal ethylenically unsaturated group or groups. Of particular utility are polymerizable polyacrylate (having a' least two acrylic or substituted acrylic moneties) monomers and polymers. Monoacrylate esters can also be used, especially if the nonacrylate portion of the ester c`ontains a hydroxyl or amino group, or other reactive substitute which serves as a site for potential crosslinking.
Representative of suitable anaerobically polymerizable materials which can be employed in the practice of the in~ention are the following non-limiting materials: -(I) Polyacrylates comprising the reaction products of at least two mols of acrylic and substituted acrylic acids with appropriate alcohols having at least two hydroxyl groups, such as di-, tri-, and tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di(pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di(chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, tetramethylene glycol diacrylate, neopentyl glycol diacrylate and trimethylopropane triacrylate.
~II) Polyacrylates comprising the reaction product of at least two mols of acrylic and substituted acrylic acids with di- and tri-alky101amines.
99~
(III) The reaction products of acrylic and substituted acrylic acids with hydroxyl-containing saturated polyesters obtained by condensation o~
alipatic and aromatic acids, such as adipic acid, sebacic acid, dimeric fatty acid, phthalic acid, isophthalic acid, and terephthalic acid with an excess of one or more polyols having at least two hydroxy groups, such as glycerol, trimethylol propane, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and polyethylene glycol.
(IV) Monoesters of acrylic and substituted acrylic acids, that is, esters containing a single acrylate or substituted acrylate group, especially such esters wherein the nonacrylate moiety possesses a single polar group selected from the group consisting of labile hydrogen, heterocyclic ring, hydroxy, amino, cyano and halogen polar groups.
Representative monoesters include cyc10hexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxyethyl lS methacrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethyl acryla-te and chloroethyl methacrylate.
(V) The reaction products of an excess of acrylic and substituted acrylic esters contain;ng an active hydrogen in the nonacrylate moiety of such esters with organic polyisocyanates, including isocyanate-functional /}
prepolymers. Preferably, the active hydrogen is the hydrogen of a hydroxy, primary amine or secondary amine. Typical acrylic and substituted acrylic esters include, without limitation, hydroxyethyl methacrylate, cyanoethyl acrylate, t-butylaminoethyl methacrylate and glycidyl methacrylate. Typical polyisocyanates include, without limitation, toluene diisocyanate, 4,4'-diphenyl diisocyanate, ; di-anisidine diisocyanate, cyclohexylene diisocyanate9 2-chloropropane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diethyl ether diisocyanate, 3-(dimethylamino) - pentane diisocyanate, isophorone diisocyanate, tetrachlorophenylene diisocyanate -1,4 and trans-vinylene diisocyanate. Other useful polyisocyanates are the isocyanate-functional-prepolymers obtained by reacting an excess of at least one polyisocyanate, such as those described above, with polyamines containing terminal primary and secondary amine groups or polyhydric alcohol such as glycerol, 1,2,6-hexane triol, 1,5-pentane diol, ethylene glycol, polyethylene glycol, trimethylol propane, polyethers and hydroxy-functional polyesters.
.
_ 4 _ ~ J ~, ~07~4 (VI) Reaction products of acrylic and substituted acrylic acids with epoxy compounds and hydroxy-functional polycarbonates. For d complete discussion of anaerobically polymerizable materials, including monomeric and polymeric materials, reference is made to U.S.A. Patents Nos. 2,895,950; 3,041,322; 3,043,820; 3,046,262; 3,203,941; 3,218,305;
3,300,547; 3,425,98~; 3,457,212; 3,625,930; 4,007,323; 4,018,851;
4,107,38G; and French Patent No. 1~581,361.
Naturally, anaerobically polymerizable materials can be used in combination. Many of such anaerobically polymerizable materials, especially of the polyrneric type, are quite viscous and are - advantageously mixed with lower viscosity anaerobically polymerizable materials.
Substantially all of the known polymerization initiators which have been employed with anaerobic adhesive and sealant compositions can be utilized in the practice of this invention. Among the more widely used are organic peroxides, especially hydroperoxides derived from hydrocarbons having up to 18 carbon atoms and peroxides having a half-life period of 10 hours at a temperature in the range of 80C to 140C, with organic hydroperoxides being currently preferred.
Representative organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauroyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl perbenzoate, di-t-butyl-diperoxyphthalate, 2,5-dimethyl
FAST CURING PHOSPHATE MODIFIED ANAEROBIC COMPOSITION
.
Field of the Invention The present invention relates to polymerizable compositions. More particularly, the invention relates to anaerobic adhesive and sealant compositions, especially such compositions containing organophosphate esters.
Background of the Invention .
Anaerobic adhesive and sealant compositions are well-known compositions of matter. Typically, anaerobic adhesive and sealant compositions comprise precatalyzed polymerizable materials, including monomers, polymers and mixtures of monomers and polymers, which cure by a polymerization mechanism which is inhibited by oxygen. Such anaerobic compositions remain in the unpoiymerized state as long as adequate contact with oxygen is maintained and cure spontaneously to a solid state upon the exclusion of oxygen. Anaerobic adhesive and sealant compositions are especially useful for locking threaded assemblies, sealing porous and flanged assemblies, strenthening cylindrical assemblies and structural bonding.
From the initial development of anaerobic compositions that could be shipped and stored and cured within a matter of hours after application to metal parts, sign;ficant research and development efforts have been, and are still being, expended on improving performance characteristics of anaerobic materials. A meritorious development in the field of anaerobic adhesives was the discovery of Saito, U.S.A. Patent 4,044,044, that the addition of certain organophosphorus esters to anaerobic adhesive and sealant compositions significantly increased the adhesive strength of anaerobic compositions. While effective in improving adhesion, the ; addition of organophosphorus esters is accompanied by a significant jncrease in the time required for cure and, additionally, requires curing .
, ~ ~ 12[)'79~
temperatures in excess of 100C. These negative side effects are highly detrimental to commercial use of an otherwise desirable development.
It has now been discovered that the time required for curing anaerobic adhesive and sealant compositions containing organophosphorus esters corresponding to the general formula O ~' CH2 = C - C - O - ~ - P - OH;
Il I
R O H
wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8, preferably 1 to 4, carbon atoms, and CH2-CH-; A is selected from the group -R20- and -(R30)n7 wherein R2 is an aliphatic or cycloaliphatic alkylene group containing from 1 to 9, preferably 2 to 6, carbon atoms; R3 is an alkylene group having from 1 to 7, preferably 2 to 4, carbon atoms; and n is an integer from 2 to 10, is unexpectedly signi~icantly reduced by incorporating therein certain hereinafter described tertiary amines. In addition to the significant reduction in the time required for curing, the inclusion of the tertiary amines of this invention also significantly reduces the cure temperature. The present discovery is particularly surprising in view of ; the fact that, although tertiary amines are known accelerating agents for anaerobic adhesive and sealant compositions, only the particular tertiary amines employed herein are effective to accelerate anaerobic adhesives and sealant composit;ons containing the herein described organophosphorus esters.
More particularly, the present invention provides anaerobic adhesive and sealant compositions containing an anaerobically polymerizable material having at least one -terminal ethylenically unsaturated group; a polymerization initiator for said anaerobically polymerizable material;
at least one mono-organic ester of phosphoric acid and at least one tertiary dialkylaryl amine.
The invention encompasses the composition as a whole, as described above, as well as two-part anaerobic adhesive and sealant compositions wherein the anaerobically polymerizable ethylenically unsaturated material, polymerization initiator and mono-organic ester of phosphoric acid are used as a first part and the tertiary amine is used as a second part and also such two-part anaeroblc compositions wherein the .
I.Z~ 49t (~
anaerobically polymerizable ethylenically unsaturated material, polymerization initiator and tertiary amine are used as a first part and the mono-organic ester of phosphoric acid as a second part. In the case of either two-part mode, the second part most commonly is used as a surface primer prior to the application of the first part, although the second part can be admixed with the first part immediately prior to use if so desired.
Substantially any of the known anaerobically polymerizable materials may be employed in the practice of this invention. Typically, anaerobic polymerizable materials range in consistency from a water-like liquid to a light-weight grease; are stable in the presence of oxygen; polymerize in the absence of oxygen through a free radical mechanism initiated by a peroxy compound; can be monomer or polymer or mixtures of either or bot~l monomers and polymers; and have as a characteristic feature at least one, preferably at least two, terminal ethylenically unsaturated group or groups. Of particular utility are polymerizable polyacrylate (having a' least two acrylic or substituted acrylic moneties) monomers and polymers. Monoacrylate esters can also be used, especially if the nonacrylate portion of the ester c`ontains a hydroxyl or amino group, or other reactive substitute which serves as a site for potential crosslinking.
Representative of suitable anaerobically polymerizable materials which can be employed in the practice of the in~ention are the following non-limiting materials: -(I) Polyacrylates comprising the reaction products of at least two mols of acrylic and substituted acrylic acids with appropriate alcohols having at least two hydroxyl groups, such as di-, tri-, and tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di(pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di(chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, tetramethylene glycol diacrylate, neopentyl glycol diacrylate and trimethylopropane triacrylate.
~II) Polyacrylates comprising the reaction product of at least two mols of acrylic and substituted acrylic acids with di- and tri-alky101amines.
99~
(III) The reaction products of acrylic and substituted acrylic acids with hydroxyl-containing saturated polyesters obtained by condensation o~
alipatic and aromatic acids, such as adipic acid, sebacic acid, dimeric fatty acid, phthalic acid, isophthalic acid, and terephthalic acid with an excess of one or more polyols having at least two hydroxy groups, such as glycerol, trimethylol propane, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and polyethylene glycol.
(IV) Monoesters of acrylic and substituted acrylic acids, that is, esters containing a single acrylate or substituted acrylate group, especially such esters wherein the nonacrylate moiety possesses a single polar group selected from the group consisting of labile hydrogen, heterocyclic ring, hydroxy, amino, cyano and halogen polar groups.
Representative monoesters include cyc10hexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxyethyl lS methacrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethyl acryla-te and chloroethyl methacrylate.
(V) The reaction products of an excess of acrylic and substituted acrylic esters contain;ng an active hydrogen in the nonacrylate moiety of such esters with organic polyisocyanates, including isocyanate-functional /}
prepolymers. Preferably, the active hydrogen is the hydrogen of a hydroxy, primary amine or secondary amine. Typical acrylic and substituted acrylic esters include, without limitation, hydroxyethyl methacrylate, cyanoethyl acrylate, t-butylaminoethyl methacrylate and glycidyl methacrylate. Typical polyisocyanates include, without limitation, toluene diisocyanate, 4,4'-diphenyl diisocyanate, ; di-anisidine diisocyanate, cyclohexylene diisocyanate9 2-chloropropane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diethyl ether diisocyanate, 3-(dimethylamino) - pentane diisocyanate, isophorone diisocyanate, tetrachlorophenylene diisocyanate -1,4 and trans-vinylene diisocyanate. Other useful polyisocyanates are the isocyanate-functional-prepolymers obtained by reacting an excess of at least one polyisocyanate, such as those described above, with polyamines containing terminal primary and secondary amine groups or polyhydric alcohol such as glycerol, 1,2,6-hexane triol, 1,5-pentane diol, ethylene glycol, polyethylene glycol, trimethylol propane, polyethers and hydroxy-functional polyesters.
.
_ 4 _ ~ J ~, ~07~4 (VI) Reaction products of acrylic and substituted acrylic acids with epoxy compounds and hydroxy-functional polycarbonates. For d complete discussion of anaerobically polymerizable materials, including monomeric and polymeric materials, reference is made to U.S.A. Patents Nos. 2,895,950; 3,041,322; 3,043,820; 3,046,262; 3,203,941; 3,218,305;
3,300,547; 3,425,98~; 3,457,212; 3,625,930; 4,007,323; 4,018,851;
4,107,38G; and French Patent No. 1~581,361.
Naturally, anaerobically polymerizable materials can be used in combination. Many of such anaerobically polymerizable materials, especially of the polyrneric type, are quite viscous and are - advantageously mixed with lower viscosity anaerobically polymerizable materials.
Substantially all of the known polymerization initiators which have been employed with anaerobic adhesive and sealant compositions can be utilized in the practice of this invention. Among the more widely used are organic peroxides, especially hydroperoxides derived from hydrocarbons having up to 18 carbon atoms and peroxides having a half-life period of 10 hours at a temperature in the range of 80C to 140C, with organic hydroperoxides being currently preferred.
Representative organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauroyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl perbenzoate, di-t-butyl-diperoxyphthalate, 2,5-dimethyl
-2,5-bis-(t-butylperoxy)-hexane, bis-(1-hydroxycyclohexyl) peroxide, t-butyl-peroxyacetate, 2,5-dimethyl-hexyl- 2,5-di-(peroxybenzoate), t-butyl peroxy-isopropyl carbonate, n-butyl-4,4-bis-(t-butylperoxy) ; valerate, 2,2-bis(t-butylperoxy)-butane and di-t-butyl peroxide. Other known initiators for anaerobic compositions can also be used, for example, a mixture of n-dodecyl mercaptan and o-sulfobenzoic imide. The polymerization initiators, of whatever type, are typically employed in an amount in the range From 0.01 to 20 percent by weight, preferably 0.1 to 10 percent by weight, based on the total weight of anaerobically polymerizable materials.
The organophosphorus compounds which are employed in the practice of the present invention have the characteristic formula O O .
Il 11 CH2 = C - C - O - A - P - OH;
- Rl OH
, lZ~75~4 wherein Rl is selected from the group consisting of hydro-gen, halogen, an al]cyl group having from 1 to 8, preferably 1 to 4, carbon atorns, and CH2=CH-; and A is selected from the group consisting of -R 0- and ~R tn, wherein R is an aliphati.c or cycloaliphatic group containing from 1 to 9, preferably 2 to 6, carbon atoms; R3 is an alkylene group having from 1 to 7, preferably 2 to 4, carbon atoms; and n is an integer from 2 to 10. Representative organophos-phorus compoundSinclude, withou-t limitation, 2-methacry-loyloxyethyl phosphate, 2-acryloyloxyetheyl phosphate, methyl-(2-methacryloyloxyethyl) phospha-te, ethyl meth-acryloyloxyethyl phosphate; ethyl acryloyloxyethyl phos-phate, methyl acryloyloxyethyl phosphate and ethyl acry-loyloxye-thyl phosphate. The organophosphorus compounds are present in a concentration from 0.05 to 20, preferably 0.1 -to 10, percent by weigh~, based on total weight of anaero-bically polymerizable material.
While substan-tially any individual or mi.xture of individual anaerobically polymerizable material,. accelera-tor or organophosphorus compound discussed herein can be utilized in forming anaerobic sealants and adhesives in accordance with this invention, it is a critical feature of this invention that such anaerobic adhesive and sealant 25 compositions contain at least one dimethyl arylamine having the general formula Y ~ Z) - N /
wherein Z is methylene, X is CH or a nitrogen atom; Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8, preferably 1 to 4 carbon atoms and alkoxy having from 1 -to 8, preferably 1 to 4 carbon atoms; a is zero or l; and b is 1 or 2. Exemplary of such tertiary diemthylaryl amines are N,N-dimethylaniline, N,N-dimethyl aminomethyl phenol, N,N-dimethyl-p--toluidine and N,N-dimethylaminopyridine. The dimethylaryl amine compounds are employed in a concentration in the range from 0.01 to 10, preferably 0.5 to 5 percent by weight, based on total weight of anaerobically polymerizable material and organophosphorus compound.
In addition to the necessary anaerobically pol-merizable ma-terials, initiators, or organophosphorus com-pounds and dimethylaryl amines, the ~ 6a -~ ~207~
anaerobic adhesive and sealant compositions can contain optional additives conventionally employed in such compositions, such as accelerators, pol~nerization inhibitors, thickeners, plasticizers, dyes, and the like, which may be-used in concentrations as normally employed in the prior art. Representative accelerators include aromatic hydrazines;
ter-tiary amines other than, the herein-described dimethylaryl amines;
ferrocene compounds; carboxylic hydrahydrazides; N, N-dialkyl hydrazines:
carboxylic sulfimides; mercaptans; transition metal salts; sulfonyl hydrazones; organic disulfonamides; and organic sulfonic acid hydrazides. The present discovery is particularly surprising bècause, although the herein-described dimethylaryl amines have been disclosed as equivalents to tertiary amines such as triethylamine as accelerators in curing anaerobic compositions which do not contain the herein-described organophosphorus compounds, the tertiary amines other than the dimethylaryl amines are generally ineffective as accelerators for anaerobic compositions which do contain such organophosphorus compounds.
The anaerobic and sealing compositions of this invention can be produced as a single-package system by simply mixing the components at room temperature. Alternatively, and preferably, the compositions can be produced as two-package systems in which either the dimethylaryl amine or the organophosphorus compound is provided as one package and all other ingredients are mixed into a second package. It is generally preferred to isolate the organophosphorus compound from the remainder of the composition.
When employed as a single-package system, small quantities of the compositions are introduced between the surfaces to be bonded, after which the surfaces are contacted so as to exclude air or oxygen. When ; used as a two-package system, the two packages can be intermixed at time of use to form a single composition. Alternatively, the package containing the dimethylaryl amine or organophosphorus compound can be applied as a primer to at least one of the mating surfaces with the package containing the main adhesive or sealant mass being applied as a covercoat over the primed or unprimed mating surface, as desired.
The compositions of the present invention are especially adapted to treating non-vitreous non-porous materials, such as metals.
The invention is further described in the following example, which are preferred embodiments of the invention and are not to be construed in limitation thereof.
, .
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Example Polymerizable anaerobic forrnulations are prepared having the compositions shown in Table I, with all concentrations in parts by weight9 unless otherwise noted. The formulations are used to adhere steel (solvent wiped, 1010 cold rolled steel) or aluminum (solvent wiped 2024~T3 aluminum) lap strips toge-ther, that is, steel-to-steel and aluminum-to-aluminum. The bond area is 65 square cm with an uncontrolled glue line of approximately 0.02 to 0.05 rnm. The strips are pulled apart with an Instrom tester in a tensile shear test (ASTM D-1000-72) commonly used in the adhesive industry. In the data, "handling time" is the time required for polymerization to advance to the degree that the bonded assembly can be moved as a unit by manipulating, that is, touching, one of the lap strips.
As can be seen from the data, anaerobic polymerizable formulations which contain no mono-organic esters of phosphoric acid (compositions 1, 5 and 9 of Table I) require a minimum of two hours to cure at room temperature and may fail to cure in as lony as three days. The addition of the phosphate ester retards the room temperature cure even more so that three days is the minimum cure time if a bond develops at all (compositions 3, 7 and 11 of Table I). As can be seen from the data of compositions 2, 6 and 10 of Table I, the addition of dimethylaryl amine compounds unexpectedly significantly speeds the cure of the adhesive and, in the case of compositions 1 and 2, makes the difference between curing and not curing at room temperature. Comparison of compositions 4, 8 and 12 with 3, 7 and 11 clearly shows that the addition of dimethylaryl amine compounds overcomes the retarding effect of the phosphate ester~ In each case, the anaerobic pol~nerizable compositions containing dimethylaryl amine compounds cure at room temperature at significantly more rapid rates than do the same compositions without the tertiary dimethylaryl amine compounds.
.
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The organophosphorus compounds which are employed in the practice of the present invention have the characteristic formula O O .
Il 11 CH2 = C - C - O - A - P - OH;
- Rl OH
, lZ~75~4 wherein Rl is selected from the group consisting of hydro-gen, halogen, an al]cyl group having from 1 to 8, preferably 1 to 4, carbon atorns, and CH2=CH-; and A is selected from the group consisting of -R 0- and ~R tn, wherein R is an aliphati.c or cycloaliphatic group containing from 1 to 9, preferably 2 to 6, carbon atoms; R3 is an alkylene group having from 1 to 7, preferably 2 to 4, carbon atoms; and n is an integer from 2 to 10. Representative organophos-phorus compoundSinclude, withou-t limitation, 2-methacry-loyloxyethyl phosphate, 2-acryloyloxyetheyl phosphate, methyl-(2-methacryloyloxyethyl) phospha-te, ethyl meth-acryloyloxyethyl phosphate; ethyl acryloyloxyethyl phos-phate, methyl acryloyloxyethyl phosphate and ethyl acry-loyloxye-thyl phosphate. The organophosphorus compounds are present in a concentration from 0.05 to 20, preferably 0.1 -to 10, percent by weigh~, based on total weight of anaero-bically polymerizable material.
While substan-tially any individual or mi.xture of individual anaerobically polymerizable material,. accelera-tor or organophosphorus compound discussed herein can be utilized in forming anaerobic sealants and adhesives in accordance with this invention, it is a critical feature of this invention that such anaerobic adhesive and sealant 25 compositions contain at least one dimethyl arylamine having the general formula Y ~ Z) - N /
wherein Z is methylene, X is CH or a nitrogen atom; Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8, preferably 1 to 4 carbon atoms and alkoxy having from 1 -to 8, preferably 1 to 4 carbon atoms; a is zero or l; and b is 1 or 2. Exemplary of such tertiary diemthylaryl amines are N,N-dimethylaniline, N,N-dimethyl aminomethyl phenol, N,N-dimethyl-p--toluidine and N,N-dimethylaminopyridine. The dimethylaryl amine compounds are employed in a concentration in the range from 0.01 to 10, preferably 0.5 to 5 percent by weight, based on total weight of anaerobically polymerizable material and organophosphorus compound.
In addition to the necessary anaerobically pol-merizable ma-terials, initiators, or organophosphorus com-pounds and dimethylaryl amines, the ~ 6a -~ ~207~
anaerobic adhesive and sealant compositions can contain optional additives conventionally employed in such compositions, such as accelerators, pol~nerization inhibitors, thickeners, plasticizers, dyes, and the like, which may be-used in concentrations as normally employed in the prior art. Representative accelerators include aromatic hydrazines;
ter-tiary amines other than, the herein-described dimethylaryl amines;
ferrocene compounds; carboxylic hydrahydrazides; N, N-dialkyl hydrazines:
carboxylic sulfimides; mercaptans; transition metal salts; sulfonyl hydrazones; organic disulfonamides; and organic sulfonic acid hydrazides. The present discovery is particularly surprising bècause, although the herein-described dimethylaryl amines have been disclosed as equivalents to tertiary amines such as triethylamine as accelerators in curing anaerobic compositions which do not contain the herein-described organophosphorus compounds, the tertiary amines other than the dimethylaryl amines are generally ineffective as accelerators for anaerobic compositions which do contain such organophosphorus compounds.
The anaerobic and sealing compositions of this invention can be produced as a single-package system by simply mixing the components at room temperature. Alternatively, and preferably, the compositions can be produced as two-package systems in which either the dimethylaryl amine or the organophosphorus compound is provided as one package and all other ingredients are mixed into a second package. It is generally preferred to isolate the organophosphorus compound from the remainder of the composition.
When employed as a single-package system, small quantities of the compositions are introduced between the surfaces to be bonded, after which the surfaces are contacted so as to exclude air or oxygen. When ; used as a two-package system, the two packages can be intermixed at time of use to form a single composition. Alternatively, the package containing the dimethylaryl amine or organophosphorus compound can be applied as a primer to at least one of the mating surfaces with the package containing the main adhesive or sealant mass being applied as a covercoat over the primed or unprimed mating surface, as desired.
The compositions of the present invention are especially adapted to treating non-vitreous non-porous materials, such as metals.
The invention is further described in the following example, which are preferred embodiments of the invention and are not to be construed in limitation thereof.
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Example Polymerizable anaerobic forrnulations are prepared having the compositions shown in Table I, with all concentrations in parts by weight9 unless otherwise noted. The formulations are used to adhere steel (solvent wiped, 1010 cold rolled steel) or aluminum (solvent wiped 2024~T3 aluminum) lap strips toge-ther, that is, steel-to-steel and aluminum-to-aluminum. The bond area is 65 square cm with an uncontrolled glue line of approximately 0.02 to 0.05 rnm. The strips are pulled apart with an Instrom tester in a tensile shear test (ASTM D-1000-72) commonly used in the adhesive industry. In the data, "handling time" is the time required for polymerization to advance to the degree that the bonded assembly can be moved as a unit by manipulating, that is, touching, one of the lap strips.
As can be seen from the data, anaerobic polymerizable formulations which contain no mono-organic esters of phosphoric acid (compositions 1, 5 and 9 of Table I) require a minimum of two hours to cure at room temperature and may fail to cure in as lony as three days. The addition of the phosphate ester retards the room temperature cure even more so that three days is the minimum cure time if a bond develops at all (compositions 3, 7 and 11 of Table I). As can be seen from the data of compositions 2, 6 and 10 of Table I, the addition of dimethylaryl amine compounds unexpectedly significantly speeds the cure of the adhesive and, in the case of compositions 1 and 2, makes the difference between curing and not curing at room temperature. Comparison of compositions 4, 8 and 12 with 3, 7 and 11 clearly shows that the addition of dimethylaryl amine compounds overcomes the retarding effect of the phosphate ester~ In each case, the anaerobic pol~nerizable compositions containing dimethylaryl amine compounds cure at room temperature at significantly more rapid rates than do the same compositions without the tertiary dimethylaryl amine compounds.
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Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An anaerobic adhesive and sealant composition comprising a) at least one anaerobically polymerizable material having at least one terminal ethylenically unsaturated group;
b) at least one organic peroxide;
c) from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material, of at least one mono-organic ester of phosphoric acid having the formula (IMAGE) wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2=CH-; A is selected from the group consisting of -R2O-and ? R3O ? n wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10; and d) from 0.01 to 10 percent by weight, based on total weight of said anaerobically polymerizable adhesive and sealant composition, of at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom; Y
is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2.
b) at least one organic peroxide;
c) from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material, of at least one mono-organic ester of phosphoric acid having the formula (IMAGE) wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2=CH-; A is selected from the group consisting of -R2O-and ? R3O ? n wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10; and d) from 0.01 to 10 percent by weight, based on total weight of said anaerobically polymerizable adhesive and sealant composition, of at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom; Y
is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2.
2. An anaerobic adhesive and sealant composition according to claim 1 wherein said organic ester of phosphoric acid comprises 2-methacryloyloxyethyl phosphate.
3. An anaerobic adhesive sealant composition according to claim 1 wherein said tertiary amine comprises N,N-dimethyl-aniline.
4. An anaerobic adhesive and sealant composition according to claim 3 wherein said organic ester of phosphoric acid comprises 2-methacryloyloxyethyl phosphate.
5. A two-part anaerobic adhesive and sealant composition comprising A) a first part comprising a) at least one anaerobically polymerizable material having at least one terminal ethylenically unsaturated group;
b) at least one organic peroxide; and c) from 0.01 to 10 percent by weight, based on total weight of said anaerobically polymerizable adhesive and sealant composition, of at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom;
Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2; and B) A second part comprising at least one mono-organic ester of phosphoric acid having the formula wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2=CH-; A is selected from the group consisting of -R2O- and ? R3O ? n, wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10, said organic ester of phosphoric acid being present in an amount from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material present in said first part.
b) at least one organic peroxide; and c) from 0.01 to 10 percent by weight, based on total weight of said anaerobically polymerizable adhesive and sealant composition, of at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom;
Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2; and B) A second part comprising at least one mono-organic ester of phosphoric acid having the formula wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2=CH-; A is selected from the group consisting of -R2O- and ? R3O ? n, wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10, said organic ester of phosphoric acid being present in an amount from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material present in said first part.
6. An anaerobic adhesive and sealant composition according to claim 5 wherein said organic ester of phosphoric acid comprises 2-methyacryloyloxyethyl phosphate.
7. An anaerobic adhesive and sealant composition according to claim 5 wherein said tertiary amine comprises N,N-dimethyl-aniline.
8. An anaerobic adhesive and sealant composition according to claim 7 wherein said organic ester of phosphoric acid comprises 2-methylacryloyloxyethyl phosphate.
9. A two-part anaerobic adhesive and sealant composition comprising A) a first part comprising a) at least one anaerobically polymerizable material having at least one terminal ethylenically unsaturated group;
b) at least one organic peroxide; and c) from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material, of at least one mono-organic ester of phosphoric acid having the formula (IMAGE) wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2-CH-; A is selected from the group consisting of -R2O- and ? R30 ? n , wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10; and B) a second part comprising at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom;
Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2, said tertiary amine being present in an amount in the range from 0.01 to 10 percent by weight, based on total weight of said first part.
b) at least one organic peroxide; and c) from 0.05 to 20 percent by weight, based on weight of anaerobically polymerizable material, of at least one mono-organic ester of phosphoric acid having the formula (IMAGE) wherein R1 is selected from the group consisting of hydrogen, halogen, an alkyl group having from 1 to 8 carbon atoms and CH2-CH-; A is selected from the group consisting of -R2O- and ? R30 ? n , wherein R2 is an aliphatic or cycloaliphatic group having from 1 to 9 carbon atoms, R3 is an alkylene group having from 1 to 7 carbon atoms, and n is an integer from 2 to 10; and B) a second part comprising at least one tertiary amine having the formula (IMAGE) wherein Z is methylene; X is CH or a nitrogen atom;
Y is selected from the group consisting of hydrogen, hydroxy, amino, alkyl of 1 to 8 carbon atoms and alkoxy having from 1 to 8 carbon atoms; a is zero or 1; and b is 1 or 2, said tertiary amine being present in an amount in the range from 0.01 to 10 percent by weight, based on total weight of said first part.
10. An anaerobic adhesive and sealant composition according to claim 9 wherein said tertiary amine comprises N,N-dimethyl-aniline.
11. An anaerobic adhesive and sealant composition according to claim 9 wherein said organic ester of phosphoric acid comprises 2-methyacryloyloxyethyl phosphate.
12. An anaerobic adhesive and sealant composition according to claim 11 wherein said amine comprises N,N-dimethylaniline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18702680A | 1980-09-15 | 1980-09-15 | |
| US187,026 | 1980-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207944A true CA1207944A (en) | 1986-07-15 |
Family
ID=22687315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000385830A Expired CA1207944A (en) | 1980-09-15 | 1981-09-14 | Fast curing phosphate modified anaerobic composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5783572A (en) |
| CA (1) | CA1207944A (en) |
| DE (1) | DE3136512A1 (en) |
| GB (1) | GB2084161B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380613A (en) * | 1981-07-02 | 1983-04-19 | Loctite Corporation | Gasketing and sealing composition |
| JPS59129278A (en) * | 1983-01-14 | 1984-07-25 | Kuraray Co Ltd | Adhesive for dental and orthopedic surgery |
| US4452944A (en) * | 1982-02-11 | 1984-06-05 | Lord Corporation | Structural adhesive formulations |
| US4467071A (en) * | 1982-09-13 | 1984-08-21 | Lord Corporation | Epoxy modified structural adhesives having improved heat resistance |
| JPS61101579A (en) * | 1984-10-23 | 1986-05-20 | Toagosei Chem Ind Co Ltd | Photocurable anaerobic adhesive composition |
| GB8810411D0 (en) * | 1988-05-03 | 1988-06-08 | Ici Plc | Adhesive compositions |
| JP3512464B2 (en) * | 1994-04-08 | 2004-03-29 | 株式会社ジーシー | Metal surface treatment agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51132234A (en) * | 1975-04-21 | 1976-11-17 | Suriibondo:Kk | An anaerobic adhesive composition |
| US4223115A (en) * | 1978-04-24 | 1980-09-16 | Lord Corporation | Structural adhesive formulations |
-
1981
- 1981-09-14 GB GB8127734A patent/GB2084161B/en not_active Expired
- 1981-09-14 JP JP14538981A patent/JPS5783572A/en active Pending
- 1981-09-14 CA CA000385830A patent/CA1207944A/en not_active Expired
- 1981-09-15 DE DE19813136512 patent/DE3136512A1/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2084161A (en) | 1982-04-07 |
| DE3136512A1 (en) | 1982-05-13 |
| JPS5783572A (en) | 1982-05-25 |
| GB2084161B (en) | 1984-06-13 |
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