CA1070877A - Anaerobic pressure sensitive adhesive composition - Google Patents
Anaerobic pressure sensitive adhesive compositionInfo
- Publication number
- CA1070877A CA1070877A CA219,201A CA219201A CA1070877A CA 1070877 A CA1070877 A CA 1070877A CA 219201 A CA219201 A CA 219201A CA 1070877 A CA1070877 A CA 1070877A
- Authority
- CA
- Canada
- Prior art keywords
- anaerobic
- composition
- pressure sensitive
- resin system
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/91—Polymer from ethylenic monomers only, having terminal unsaturation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/912—Polymer from nonethylenic monomers only, having pendant unsaturated group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/92—Polyurethane having terminal ethylenic unsaturation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/936—Encapsulated chemical agent
Abstract
ANAEROBIC PRESSURE SENSITIVE ADHESIVE COMPOSITION
Abstract of the Invention There is provided a curable anaerobic pressure sensitive adhesive composition, a mixture of a curable anaerobic system and a high molecular weight polymer system. The mixture which may include a tackifier and other functional additives constitutes a pressure sensitive adhesive and exhibits elastomeric properties.
There is also provided in the composition an initiator system necessary to permit curing of the anaerobic pressure sensitive composition upon activation by the exclusion of oxygen. One or more accelerators for cure may also be provided.
In one embodiment a component of the catalyst system may be either absent and provided later or latently present in microspheres which upon rupture will enhance the curing operation.
Abstract of the Invention There is provided a curable anaerobic pressure sensitive adhesive composition, a mixture of a curable anaerobic system and a high molecular weight polymer system. The mixture which may include a tackifier and other functional additives constitutes a pressure sensitive adhesive and exhibits elastomeric properties.
There is also provided in the composition an initiator system necessary to permit curing of the anaerobic pressure sensitive composition upon activation by the exclusion of oxygen. One or more accelerators for cure may also be provided.
In one embodiment a component of the catalyst system may be either absent and provided later or latently present in microspheres which upon rupture will enhance the curing operation.
Description
, Backgrour.d of the Invention :
. . i . " :, , .;
~naerobic adhesive systems are those which are stable ~n the presence of oxygen, but will polymerize in the absence of 20 ioxygen. Polymerization is initiated by the presence of a pero~y ;compound. The cured, cross-linked resins serve as sealants and -as aahesives. :
qypical resin monomers are terminated with polymerizable acrylate esters such as methacrylate, ethacrylate and chloracry-X5 late esters. The other in~redients typically present are an . initiator, preferably an organic hydroperoxide such as cumene ~ydroperoxide, tertiary butyl hydroperoxide and the like. There ~s also normally provided a stabilizer:~gainst free radical initia-tion, such as a quinone or hydrsquinone, in an amount sufficient 30 to prevent premature polymerization of the adhesive due to decom-position of the peroxy compound. -There are also preferably pres~nt .
j: :
1070~77 one or more accelerators which are preferably nitrogen-contain-ing compounds such as tertiary amines, imids, sulfamids and the like which promote the rate of cure.
Cure will be accelerated by the presence of a suitable metal, such as a transition metal, or its ion.
An anaerobic adhesive is applied to one or both of the surfaces to be joined. ~hen the two surfaces are joined and oxygen excluded, cure will be initiated. As is well known, surfaces such as glass may require application of a suitable accelerator such as a transition metal compound, which will increase the rate of cure upon the substantial exclusion of oxygen or air;
Anaerobic adhesives have been well published in the art as for instance, in applicants U.S. Patents 2,895,950 issued July 21, 1959; 3,041,322 issued June 26, 1962;
3,043,820 issued July 10, 1962; 3,046,262 issued July 24, 1962; 3,203,941 issued August 31, 1965; 3,218,305 issued November 16, 1965; 3,300,547 issued January 24, 1967; 3,435,012 issued March 25, 1969; 3,547,851 issued December 15, 1970 and 3,625,875 issued December 7, 1971. ~.
Anaerobic adhesive systems are typically supplied from a water-like liquid to a light-weight grease in consistency.
One end-use application is to apply the adhesive to the threads of a bolt or mating nut which are then assembled.
The adhesive fills the spaces between the threads which excludes oxygen and enables cure. In the normal situation, the metals present in the bolt or the nut accelerate c;ure.
A problem exists, however, in fixturing other surfaces together with initiation and completion of cure, and in '0 providing a controlled quantity of anaerobic monomer to ~ - 2 -.: . . . - . . , . : . . .
1~)70877 the surfaces to be bonded. No prior art composition provides the desirability and convenience of instant fixturing merely by finger pressure combined with sufficient cured strength to provide bonds of structural integrity.
:~:
- 2a -. : ,, ., ; , ~ ... .;. :,:, . ..
1~70877 Summary of the Invention According to the present invention, there are pro-vided anaerobic pressure sensitive adhesive compositions which can be applied from or as sheets, tapes and the like to . substrates to be bonded by cure upon the exclusion of oxygen.
The anaerobic pressure sensitive adhesives composi-tions of this invention include a curable anaerobic resin system containing one or more anaerobic resins combined with a thermoplastic polymer system containing one or more high molecular weight thermoplastic polymers, the combination of which alone or upon inclusion of a tackifier, constituting a pressure sensitive adhesive system upon evaporation of es-sentially all of the solvent present. Further, there is pro-vided in the anaerobic pressure sensitive adhesive composi-tion an initiator system which is latent until made active by substantial exclusion of oxygen, preferably in combination with a suitable accelerator.
According to one aspect of the invention there is provided a cur~ble anaerobi~c pressure sensitive adhesive composition comprising a mixture of : (a) about 35 to 99 percent by weight of an anaerobic resin system which is stable in the presence of oxygen and which contains at least one anaerobically curable resin having at least one poly-merizable acrylate ester moiety; (b) about one to about 65 percent by weight of a thermoplastic polymer system containing at least one high molecular weight urethane polymer capable of combining a substantial quantity of said anaerobic resin system; (c) about 0.5 to about 20 percent, based on the total weight of (a) and (b), of a catalyst system for said anaerobic resin system, said catalyst system comprising a peroxy compound, an organic compound for accelerating cure of said ~,~ r . . . . ~
~7~877 , , anaerobic resin system and a stabilizer for said anaerobic resin system, said anaerobic pressure sensitive adhesive, when in an essentially solvent-free state, being permanently tacky at room temperature and having a static shear strength of at least about two minutes at a 250 gram load per 0.25 square inch and a 180 peel value of at least about 0.5 lb per inch, and curable upon substantial exclusion of oxygen.
In one embodiment, if the anaerobic pressure sensi-tive adhesive system contains free transition metal ions, then at least the peroxy initiator may be encapsulated in microspheres which, upon rupture, and upon the exclusion of oxygen, will initiate cure. In an~ther embodiment, a suitable metal accelerator may be encapsulated.
If metals which act as accelerators are present and an encapsulation technique is not employed, then the metals should be inactivated. This may be accomplished by scavenging each component of the system with a chelating agent, which may then be removed, if desired.
me thermoplastic polymers used in the preparation of the pressure sensitive anaerobic compositions of this invention are preferably of sufficient molecular weight so as to be - 3a -D
. . ., ~. .
.,- ~ . .
Il 107087r7 1 elastGmcric at room te~pcrature. ~urthcr~ thcy must be cap~ble of being com~in~d with the anaerobic resins and not ~reatl~
intcrfere with the creation of a cross-linked latticework of the anaerobic resins and prevent bending of the cure~ anaerobic 5 polymer to the selected substrates to be joined.
In general, the amount of anaerobic resins combined with the thermoplastic polymer will range from about 35 to about ~9% by weight based on the total weight of the anaerobic resins provided and the thermoplastic polymer(s) with ~hich it is 10 combined, and, if present, a tackifier but exclusive of the amount o~ initiator system adde~. The preferred amount of anaerobic resin(s) cor.~ined in the thermoplastic polymer(s) is from about 55 to about 95% by weight.
In addition, the thermoplastic polymer must be selected lS such that the composition alone or with tackifiers and upon ¦the inclusion of an initiator system will form, after solvent evaporation, a curable pressure sensitive adhesive layer or film of sufficient cohesive strength to be applied to a substrate from differential release surfaces without disruption of the ; 20 layer or film. The fully formulated, essentially solvent-free anaerobic pressure sensitive adhesive should be elastomeric at room temperature.
In addition, anaerobic pressure sensitive adhesive ompositions should when applied to a surface, wet the surface 25 and conform to the intricacies of the surface so that a uniform ond will be created upon cure and that cure will extend through-ut the layer of applied anaerobic pressure sensitive composition o maximize cohe~ive bond strength To constitute a suitable pressure sensitive adhesive o ~his nature, the net composition when free of solvent should .' . ' ', . .
1 have, prior to curQ, a static sheax strength of at least about 2 minutes at a 250 gram load per 0.25 s~uare inch and a 180 peel value o~ at least about 0.5 lb per inch, prefcrably at least about /~ l.0 l'b per inch when using standard test methods.
,~ ; ~are~f/~ b~
Description of the I1L~I L ~
According to the present invention there are provided curable anaerobic pressure sensitive adhesive ccmpositions which will cure in the presence of a peroxy or perester compoun~ and in the absence of oxygen.
B~ the term "anaerobic resin system" as used herein, there is meant one or more anaerobicresins having at least one, preferably two, polymerizable acrylate ester moieties, normally on the ends of the backbone, which will polymerize or cure in the l ~resence of a peroxv initiator and upon the substantial exclusion ¦ of oxygen or air, and preferably also in the presence of a ¦ suitable accelerator system.
¦ lllustrative, but in no wise limiting, of the anaerobic ¦ resins which can be used in the preparation of pressure sensitive 20 ¦ adhesive compositions of the invention are polymerizable acrylate ¦ esters. ~s usea herein, "acrylate esters" include the alpha-¦ substituted acrylate esters, such as the methacrylate, ethacrylate, ¦ and chloracrylate este~s.
¦ Of particular utility as adhesive monor.lers are polyr,~eriz-~5 ¦ able di-and other polyacrylate esters since, because of their ¦ ability to form cross-linked polymers, they have more highly . ¦ desirable adhesive properties. However, monoacrylate esters can ¦ be used, particularly if the non-acrylate portion of the ester contains a hydroxyl or amino group, or other reactive substituent 3 which serves as a site for potcntial cross-linkirg. Examples of .' . ,' , ,, - 5 ~
:. :
ll 1070877 ¦¦m nomors of this type are hydroxyethyl meth~crylatc, -y~noethyl ~j ¦acrylate, t-butylaminoethyl methacrylate and glycidyl methacrylatc. .
¦Anaerobic pro?erties are imparted to the acrylate ester monomers .
¦by combi.ning with them a peroxy polymeriæation initiator as dis- .
5 ¦cussed more fully below. . .
¦ One of the most preferable groups of polyacrylate esters ¦which can be used in the adhesives disclosed herein are polyacry-¦late esters which have the following.general formula. ¦~
1Oll U o : r ~ Rl\ R; 1 !~
¦ R l IC~ C ) -c-C ¦ -C-C-CN2 ~11 ¦wherein Rl represents a radical selected from the group.consisting 15 ¦o hydrogen, lower alkyl o from 1 to about 4 carbon atoms, . ¦hydroxy al~yl of from 1 to about 4 carbon atoms,.and the radical . 1 O , ~2) -CH2-O-c-cl-cH2 ¦R2 is a radical selected from the group consisting of hydrogen, : haloJen, and lower alky~ of from 1 to about 4 carbon atoms; R3 is ¦a radical selected from the group consisting o hydrogen, hydroxyl, and ~5 . O .
-o-c-C-CH2 . ( ) , .. R2 , .i ' m is an intcger ec~ual to at l~ast 1, ~.cJ., from 1 to about 15 or hic~her, and preferably from 1 to about 8 inclusive; n, is an in~c-3 ger eclual to at least 1, ~.c3-, 1 to ~bout ?0 or more; and p i.s O!lC
. .. . ,' ..
._ ~70877 - of the following: 0,1.
The polymerizable polyacrylate esters utilized in ~ !
accordance with the invention andcorresponding to the above general formula are exemplified by, but not restricted to the fo;Llowing materials: di-, tri- and tetra-ethylene glycol dirnethacrylate, dipropylene glycol dimethacrylate, poly-ethylene glycol dimethacrylate, di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetra-ethylene glycol di(chloracrylate), diglycerol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate and tri-methylol propane triacrylate.
Yet, another class of acrylate esters are those which are formed by the reaction of:
(a) an acrylate ester containing an active hydrogen atom in the alcoholic moiety of the ester; with (b) an organic polyisocyanate.
Compositions including this general type of ester are disclosed in U.S. Patent No. 3,425,988 issued February 4, 1969. Preferab-ly, the active hydrogen is the hydrogen of a hydroxyl or a primary or secondary amine substituent on the alcoholic moiety of the ester, and the polyisocyanate is a diisocyanate. Naturally, an excess of the acrylate ester should be used to ensure that each isocyanate functional group in the polyisocyanate is substituted.
The most preferred of the acrylate esters used in the manner described in the preceding paragraph are those in which the acrylate ester is a substituted alkyl or aryl acrylate ester, most preferably having the formula:
H2C = C - C-o-R4-x-ll (4) .
. : . .. , ~ .
1 wherein ~ O- or -N-, where R5 is a hydrogen atom or ~ mono-valent h~drocarbon radical containing up to 10 carbon atoms, and is preferably a hydrogen atom or an alkyl or aralkyl rad cal w1th ~¦
from 1 to 10 carbon atoms; R2 is as defined above; and R is an / 5 alkylene radical with from 1 to 10 carbon atoms, or a divalent arornatic radical containing up to 14 carbon atoms, prcferably phenylene, biphenylene or naphthylene.
Naturally R5 and R4 can contain any substituents or linkages which do not adversely affect the molecule for its t 10 intended use herein. ¦
Typical polyisocyanates which can be reacted wit-n the above acrylate esters to form polyacrylate monomers are toluene diisocyanate, 4,4'-diphenyl diisocyanate, di-anisidine diisocya-nate, cyclohexylene diisocyanate, 2-chloropropane diisocyanate, 1 4,~'-diphenylme~hane diisocyanate, 2,2'-die~hyl ethe_ dii~o~yanat~
3-(dimethylamino)- pentane diisocyanate, tetrachlorophenylene diisocyanate-1,4 and trans-vinylene diisocyanate. Still other polyisocyanates that may be used are higher molecular weight polyisocyanates obtained by reacting an excess of any of the above 20 described isocyanates with polyamines containing terminal, primary and secondary ~mine groups, or polyhydric alcohols, for example, the alkane and alkene polyols such as glycerol, 1,2,6-hexanetriol, 1,5-pentanediol, ethylene glycol, polyethylene glycol, 4,4'-dihydroxydiphenyldimethylmethane and condensation products of ~5 alkylene oxides with 4,4'-dihydroxydlphenyldimethylmethane.
Other acceptable monomers which can be used~in the com-positions according to the invention are acrylate terminated epoxy or estcr units, i.e., reaction Froducts of acrylic acid Witll hydroxy tcrminatcd ester or epoY.y coml~ounds, or lo~/ pblymcrs 3 thercof. Also contemplated by this invention are any other anaerobically curing monomers which, with their respcctive . , ` '1 - 8 -` !
. . .
ll 10~0~37~ I !
... , - ' I
1 initiators, accelerators and stabilizers, i.e., inhibitors, are formulatled according to the lnstant invention into a pressure sensitiv~e anaerobic adhesive having the ad~antageous properties of the compositions of the instant invention.
S Naturally, any of the above described acrylate and poly-acrylate ester monomers can be used in combination, if desired.
The presently preferred anaerobic monomers are triethyl-eneglycol dimethacrvlate; the reaction product of hydro~ypropyl methacrylate with methylene-bis-phenyl-4, 4'-diisocyanate; 2 .
0 polymer formed by methacrylate capping of a 1:1 adduct of toluene diisocyana e and hydrogenated 2,2-bis (4-hydroxyphenyl) propane as well as mixtures thereof. ~¦
There may also be present reactive monomers such as ! !
acrylic acid, methacrylic acid and the like which will cross-link 15 with anaerobic monomers.
By the term "thermoplastic polymer system," as used herein, there is meant one or more high molecular weight thermo-'plastic polymers which, alone or in admixture, have a high enough -~
,average molecular weight in order that the resultant curable t 20 anaerobic pressure sensitive ad~esive co~positlon will have suf~i~
cien~ cohesive strength to be transferred from a conventional s~, release surface to one substrate to be bonded to another substrate, alone, or in combination with a tackifier. Suitable average ;
molecular weight will, of course, vary depending upon the type ~5 of thermoplastic polymer or polymer mixtures used, as well as upon the tackirier or tackifiers used, if any. Although it is desired that the p~lymers employed be compatible with the anaero- j bic resin system, they may be incompatible formin~ a heterogencous systcm which rcmains pressure scnsitive and transferablc in naturc 3 and capable of curing.
` .'' _ g ~
7~1i377 ~ I~
, ' ' . ll The ~lord "combincd" is used herein to indicate any workable com-bination, regardless o~ its physical form, of one or more thermo-plastic polymers wi~h one or more anaerobic monomers. Thus, a .
given combination may be a solution or otherwise ana may or may not be hornogeneous, provlded only that it is useful in the pressure sensitive anaerobic composition of the invention. i , Typical of the thermoplastic polymers which can be used , are polyvinyl chloride, polyvinyl ethers, polyvinyl acetates;
acrylic based polymers; polyurethanes, polyesters, polyamias, 0 natural and synthetic elastomers and the like as well as mixtures t thereof. The preferred thermoplastic polymers are polyvinyl ,chloride, polyurethanes,polyesters and zcrylic based polymers.
, ~y a "catalyst system'' there is meant an acid or base ,catalyzed system typically containing at least one peroxy initïator, pre erably, althou~h ~ot necessarili, a~ eas~ c..e accele-a ~r , which preferably is a nitrogen containing compound and preferably, jalthough not necessarily, at least one stabilizer against free ,radical polymerization for the anaerobic resin system. t~
! Typical of the peroxy compounds which may be employed 20 as initiators are the hydroperoxides, preferably organic hydro-peroxides of the formula R6OOH, wherein R is generaIly a hydro-carbon radical containing up to about 18 carbon atoms, preferably an alkyl, aryl or aralky~ radical containing from 1 to about 12
. . i . " :, , .;
~naerobic adhesive systems are those which are stable ~n the presence of oxygen, but will polymerize in the absence of 20 ioxygen. Polymerization is initiated by the presence of a pero~y ;compound. The cured, cross-linked resins serve as sealants and -as aahesives. :
qypical resin monomers are terminated with polymerizable acrylate esters such as methacrylate, ethacrylate and chloracry-X5 late esters. The other in~redients typically present are an . initiator, preferably an organic hydroperoxide such as cumene ~ydroperoxide, tertiary butyl hydroperoxide and the like. There ~s also normally provided a stabilizer:~gainst free radical initia-tion, such as a quinone or hydrsquinone, in an amount sufficient 30 to prevent premature polymerization of the adhesive due to decom-position of the peroxy compound. -There are also preferably pres~nt .
j: :
1070~77 one or more accelerators which are preferably nitrogen-contain-ing compounds such as tertiary amines, imids, sulfamids and the like which promote the rate of cure.
Cure will be accelerated by the presence of a suitable metal, such as a transition metal, or its ion.
An anaerobic adhesive is applied to one or both of the surfaces to be joined. ~hen the two surfaces are joined and oxygen excluded, cure will be initiated. As is well known, surfaces such as glass may require application of a suitable accelerator such as a transition metal compound, which will increase the rate of cure upon the substantial exclusion of oxygen or air;
Anaerobic adhesives have been well published in the art as for instance, in applicants U.S. Patents 2,895,950 issued July 21, 1959; 3,041,322 issued June 26, 1962;
3,043,820 issued July 10, 1962; 3,046,262 issued July 24, 1962; 3,203,941 issued August 31, 1965; 3,218,305 issued November 16, 1965; 3,300,547 issued January 24, 1967; 3,435,012 issued March 25, 1969; 3,547,851 issued December 15, 1970 and 3,625,875 issued December 7, 1971. ~.
Anaerobic adhesive systems are typically supplied from a water-like liquid to a light-weight grease in consistency.
One end-use application is to apply the adhesive to the threads of a bolt or mating nut which are then assembled.
The adhesive fills the spaces between the threads which excludes oxygen and enables cure. In the normal situation, the metals present in the bolt or the nut accelerate c;ure.
A problem exists, however, in fixturing other surfaces together with initiation and completion of cure, and in '0 providing a controlled quantity of anaerobic monomer to ~ - 2 -.: . . . - . . , . : . . .
1~)70877 the surfaces to be bonded. No prior art composition provides the desirability and convenience of instant fixturing merely by finger pressure combined with sufficient cured strength to provide bonds of structural integrity.
:~:
- 2a -. : ,, ., ; , ~ ... .;. :,:, . ..
1~70877 Summary of the Invention According to the present invention, there are pro-vided anaerobic pressure sensitive adhesive compositions which can be applied from or as sheets, tapes and the like to . substrates to be bonded by cure upon the exclusion of oxygen.
The anaerobic pressure sensitive adhesives composi-tions of this invention include a curable anaerobic resin system containing one or more anaerobic resins combined with a thermoplastic polymer system containing one or more high molecular weight thermoplastic polymers, the combination of which alone or upon inclusion of a tackifier, constituting a pressure sensitive adhesive system upon evaporation of es-sentially all of the solvent present. Further, there is pro-vided in the anaerobic pressure sensitive adhesive composi-tion an initiator system which is latent until made active by substantial exclusion of oxygen, preferably in combination with a suitable accelerator.
According to one aspect of the invention there is provided a cur~ble anaerobi~c pressure sensitive adhesive composition comprising a mixture of : (a) about 35 to 99 percent by weight of an anaerobic resin system which is stable in the presence of oxygen and which contains at least one anaerobically curable resin having at least one poly-merizable acrylate ester moiety; (b) about one to about 65 percent by weight of a thermoplastic polymer system containing at least one high molecular weight urethane polymer capable of combining a substantial quantity of said anaerobic resin system; (c) about 0.5 to about 20 percent, based on the total weight of (a) and (b), of a catalyst system for said anaerobic resin system, said catalyst system comprising a peroxy compound, an organic compound for accelerating cure of said ~,~ r . . . . ~
~7~877 , , anaerobic resin system and a stabilizer for said anaerobic resin system, said anaerobic pressure sensitive adhesive, when in an essentially solvent-free state, being permanently tacky at room temperature and having a static shear strength of at least about two minutes at a 250 gram load per 0.25 square inch and a 180 peel value of at least about 0.5 lb per inch, and curable upon substantial exclusion of oxygen.
In one embodiment, if the anaerobic pressure sensi-tive adhesive system contains free transition metal ions, then at least the peroxy initiator may be encapsulated in microspheres which, upon rupture, and upon the exclusion of oxygen, will initiate cure. In an~ther embodiment, a suitable metal accelerator may be encapsulated.
If metals which act as accelerators are present and an encapsulation technique is not employed, then the metals should be inactivated. This may be accomplished by scavenging each component of the system with a chelating agent, which may then be removed, if desired.
me thermoplastic polymers used in the preparation of the pressure sensitive anaerobic compositions of this invention are preferably of sufficient molecular weight so as to be - 3a -D
. . ., ~. .
.,- ~ . .
Il 107087r7 1 elastGmcric at room te~pcrature. ~urthcr~ thcy must be cap~ble of being com~in~d with the anaerobic resins and not ~reatl~
intcrfere with the creation of a cross-linked latticework of the anaerobic resins and prevent bending of the cure~ anaerobic 5 polymer to the selected substrates to be joined.
In general, the amount of anaerobic resins combined with the thermoplastic polymer will range from about 35 to about ~9% by weight based on the total weight of the anaerobic resins provided and the thermoplastic polymer(s) with ~hich it is 10 combined, and, if present, a tackifier but exclusive of the amount o~ initiator system adde~. The preferred amount of anaerobic resin(s) cor.~ined in the thermoplastic polymer(s) is from about 55 to about 95% by weight.
In addition, the thermoplastic polymer must be selected lS such that the composition alone or with tackifiers and upon ¦the inclusion of an initiator system will form, after solvent evaporation, a curable pressure sensitive adhesive layer or film of sufficient cohesive strength to be applied to a substrate from differential release surfaces without disruption of the ; 20 layer or film. The fully formulated, essentially solvent-free anaerobic pressure sensitive adhesive should be elastomeric at room temperature.
In addition, anaerobic pressure sensitive adhesive ompositions should when applied to a surface, wet the surface 25 and conform to the intricacies of the surface so that a uniform ond will be created upon cure and that cure will extend through-ut the layer of applied anaerobic pressure sensitive composition o maximize cohe~ive bond strength To constitute a suitable pressure sensitive adhesive o ~his nature, the net composition when free of solvent should .' . ' ', . .
1 have, prior to curQ, a static sheax strength of at least about 2 minutes at a 250 gram load per 0.25 s~uare inch and a 180 peel value o~ at least about 0.5 lb per inch, prefcrably at least about /~ l.0 l'b per inch when using standard test methods.
,~ ; ~are~f/~ b~
Description of the I1L~I L ~
According to the present invention there are provided curable anaerobic pressure sensitive adhesive ccmpositions which will cure in the presence of a peroxy or perester compoun~ and in the absence of oxygen.
B~ the term "anaerobic resin system" as used herein, there is meant one or more anaerobicresins having at least one, preferably two, polymerizable acrylate ester moieties, normally on the ends of the backbone, which will polymerize or cure in the l ~resence of a peroxv initiator and upon the substantial exclusion ¦ of oxygen or air, and preferably also in the presence of a ¦ suitable accelerator system.
¦ lllustrative, but in no wise limiting, of the anaerobic ¦ resins which can be used in the preparation of pressure sensitive 20 ¦ adhesive compositions of the invention are polymerizable acrylate ¦ esters. ~s usea herein, "acrylate esters" include the alpha-¦ substituted acrylate esters, such as the methacrylate, ethacrylate, ¦ and chloracrylate este~s.
¦ Of particular utility as adhesive monor.lers are polyr,~eriz-~5 ¦ able di-and other polyacrylate esters since, because of their ¦ ability to form cross-linked polymers, they have more highly . ¦ desirable adhesive properties. However, monoacrylate esters can ¦ be used, particularly if the non-acrylate portion of the ester contains a hydroxyl or amino group, or other reactive substituent 3 which serves as a site for potcntial cross-linkirg. Examples of .' . ,' , ,, - 5 ~
:. :
ll 1070877 ¦¦m nomors of this type are hydroxyethyl meth~crylatc, -y~noethyl ~j ¦acrylate, t-butylaminoethyl methacrylate and glycidyl methacrylatc. .
¦Anaerobic pro?erties are imparted to the acrylate ester monomers .
¦by combi.ning with them a peroxy polymeriæation initiator as dis- .
5 ¦cussed more fully below. . .
¦ One of the most preferable groups of polyacrylate esters ¦which can be used in the adhesives disclosed herein are polyacry-¦late esters which have the following.general formula. ¦~
1Oll U o : r ~ Rl\ R; 1 !~
¦ R l IC~ C ) -c-C ¦ -C-C-CN2 ~11 ¦wherein Rl represents a radical selected from the group.consisting 15 ¦o hydrogen, lower alkyl o from 1 to about 4 carbon atoms, . ¦hydroxy al~yl of from 1 to about 4 carbon atoms,.and the radical . 1 O , ~2) -CH2-O-c-cl-cH2 ¦R2 is a radical selected from the group consisting of hydrogen, : haloJen, and lower alky~ of from 1 to about 4 carbon atoms; R3 is ¦a radical selected from the group consisting o hydrogen, hydroxyl, and ~5 . O .
-o-c-C-CH2 . ( ) , .. R2 , .i ' m is an intcger ec~ual to at l~ast 1, ~.cJ., from 1 to about 15 or hic~her, and preferably from 1 to about 8 inclusive; n, is an in~c-3 ger eclual to at least 1, ~.c3-, 1 to ~bout ?0 or more; and p i.s O!lC
. .. . ,' ..
._ ~70877 - of the following: 0,1.
The polymerizable polyacrylate esters utilized in ~ !
accordance with the invention andcorresponding to the above general formula are exemplified by, but not restricted to the fo;Llowing materials: di-, tri- and tetra-ethylene glycol dirnethacrylate, dipropylene glycol dimethacrylate, poly-ethylene glycol dimethacrylate, di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetra-ethylene glycol di(chloracrylate), diglycerol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate and tri-methylol propane triacrylate.
Yet, another class of acrylate esters are those which are formed by the reaction of:
(a) an acrylate ester containing an active hydrogen atom in the alcoholic moiety of the ester; with (b) an organic polyisocyanate.
Compositions including this general type of ester are disclosed in U.S. Patent No. 3,425,988 issued February 4, 1969. Preferab-ly, the active hydrogen is the hydrogen of a hydroxyl or a primary or secondary amine substituent on the alcoholic moiety of the ester, and the polyisocyanate is a diisocyanate. Naturally, an excess of the acrylate ester should be used to ensure that each isocyanate functional group in the polyisocyanate is substituted.
The most preferred of the acrylate esters used in the manner described in the preceding paragraph are those in which the acrylate ester is a substituted alkyl or aryl acrylate ester, most preferably having the formula:
H2C = C - C-o-R4-x-ll (4) .
. : . .. , ~ .
1 wherein ~ O- or -N-, where R5 is a hydrogen atom or ~ mono-valent h~drocarbon radical containing up to 10 carbon atoms, and is preferably a hydrogen atom or an alkyl or aralkyl rad cal w1th ~¦
from 1 to 10 carbon atoms; R2 is as defined above; and R is an / 5 alkylene radical with from 1 to 10 carbon atoms, or a divalent arornatic radical containing up to 14 carbon atoms, prcferably phenylene, biphenylene or naphthylene.
Naturally R5 and R4 can contain any substituents or linkages which do not adversely affect the molecule for its t 10 intended use herein. ¦
Typical polyisocyanates which can be reacted wit-n the above acrylate esters to form polyacrylate monomers are toluene diisocyanate, 4,4'-diphenyl diisocyanate, di-anisidine diisocya-nate, cyclohexylene diisocyanate, 2-chloropropane diisocyanate, 1 4,~'-diphenylme~hane diisocyanate, 2,2'-die~hyl ethe_ dii~o~yanat~
3-(dimethylamino)- pentane diisocyanate, tetrachlorophenylene diisocyanate-1,4 and trans-vinylene diisocyanate. Still other polyisocyanates that may be used are higher molecular weight polyisocyanates obtained by reacting an excess of any of the above 20 described isocyanates with polyamines containing terminal, primary and secondary ~mine groups, or polyhydric alcohols, for example, the alkane and alkene polyols such as glycerol, 1,2,6-hexanetriol, 1,5-pentanediol, ethylene glycol, polyethylene glycol, 4,4'-dihydroxydiphenyldimethylmethane and condensation products of ~5 alkylene oxides with 4,4'-dihydroxydlphenyldimethylmethane.
Other acceptable monomers which can be used~in the com-positions according to the invention are acrylate terminated epoxy or estcr units, i.e., reaction Froducts of acrylic acid Witll hydroxy tcrminatcd ester or epoY.y coml~ounds, or lo~/ pblymcrs 3 thercof. Also contemplated by this invention are any other anaerobically curing monomers which, with their respcctive . , ` '1 - 8 -` !
. . .
ll 10~0~37~ I !
... , - ' I
1 initiators, accelerators and stabilizers, i.e., inhibitors, are formulatled according to the lnstant invention into a pressure sensitiv~e anaerobic adhesive having the ad~antageous properties of the compositions of the instant invention.
S Naturally, any of the above described acrylate and poly-acrylate ester monomers can be used in combination, if desired.
The presently preferred anaerobic monomers are triethyl-eneglycol dimethacrvlate; the reaction product of hydro~ypropyl methacrylate with methylene-bis-phenyl-4, 4'-diisocyanate; 2 .
0 polymer formed by methacrylate capping of a 1:1 adduct of toluene diisocyana e and hydrogenated 2,2-bis (4-hydroxyphenyl) propane as well as mixtures thereof. ~¦
There may also be present reactive monomers such as ! !
acrylic acid, methacrylic acid and the like which will cross-link 15 with anaerobic monomers.
By the term "thermoplastic polymer system," as used herein, there is meant one or more high molecular weight thermo-'plastic polymers which, alone or in admixture, have a high enough -~
,average molecular weight in order that the resultant curable t 20 anaerobic pressure sensitive ad~esive co~positlon will have suf~i~
cien~ cohesive strength to be transferred from a conventional s~, release surface to one substrate to be bonded to another substrate, alone, or in combination with a tackifier. Suitable average ;
molecular weight will, of course, vary depending upon the type ~5 of thermoplastic polymer or polymer mixtures used, as well as upon the tackirier or tackifiers used, if any. Although it is desired that the p~lymers employed be compatible with the anaero- j bic resin system, they may be incompatible formin~ a heterogencous systcm which rcmains pressure scnsitive and transferablc in naturc 3 and capable of curing.
` .'' _ g ~
7~1i377 ~ I~
, ' ' . ll The ~lord "combincd" is used herein to indicate any workable com-bination, regardless o~ its physical form, of one or more thermo-plastic polymers wi~h one or more anaerobic monomers. Thus, a .
given combination may be a solution or otherwise ana may or may not be hornogeneous, provlded only that it is useful in the pressure sensitive anaerobic composition of the invention. i , Typical of the thermoplastic polymers which can be used , are polyvinyl chloride, polyvinyl ethers, polyvinyl acetates;
acrylic based polymers; polyurethanes, polyesters, polyamias, 0 natural and synthetic elastomers and the like as well as mixtures t thereof. The preferred thermoplastic polymers are polyvinyl ,chloride, polyurethanes,polyesters and zcrylic based polymers.
, ~y a "catalyst system'' there is meant an acid or base ,catalyzed system typically containing at least one peroxy initïator, pre erably, althou~h ~ot necessarili, a~ eas~ c..e accele-a ~r , which preferably is a nitrogen containing compound and preferably, jalthough not necessarily, at least one stabilizer against free ,radical polymerization for the anaerobic resin system. t~
! Typical of the peroxy compounds which may be employed 20 as initiators are the hydroperoxides, preferably organic hydro-peroxides of the formula R6OOH, wherein R is generaIly a hydro-carbon radical containing up to about 18 carbon atoms, preferably an alkyl, aryl or aralky~ radical containing from 1 to about 12
2 carbon atoms. Typical examples are cumene hydroperoxide, methyl S ethyl ketone hydroperoxide and the like.
As accelerators there may be mentioned liquid and solid organo- nitro~en compounds including but not limited to organic amides such as formamidc, succinimide and t~e like; tertiary ~mincs such as tribu~ylamino, tricthylaminc, hexamethyl para-
As accelerators there may be mentioned liquid and solid organo- nitro~en compounds including but not limited to organic amides such as formamidc, succinimide and t~e like; tertiary ~mincs such as tribu~ylamino, tricthylaminc, hexamethyl para-
3 rosaniline and the like; aromatic tertiary amines such as dimel~hyl ,.~ , ,, . ', ',.j - 10- ~
. ` '', t '': ~ :
~ 0877 11 ¦paratoluidcne and the lik~; organic sulimidcs such as benzoic . ¦sulfimidc and the like; as well as mi~:tures thcrco~, Noxmally . ¦solid organo-nitrogen co~pounds are paxticular3.y preferrcd as ¦the~ have the le.ast.effect on the viscosity of the resulting S ¦compos.ition as well as the least tendency to migrate ~rom the ¦composition.
¦ Typical stabilizers are quinones, hydroauinones, and ¦sterically hindered phenolic compounds.
.. ¦ Depending upon the amount of anaerobic resin systcm 10 ¦contain~d i.n the polymer syste~, the amount of înitiator plus t - ¦accelerator added will generally range from ahout 0.5 to about ¦20 percent or more by weight based on the total weight of the ¦polymer system plus anaerobic resin system, and if present, a . ¦tackifier.
15 ¦ By the term "anaero~ic pressure s~nsitive adhesiv~,"
¦there is meant a mixture of the thermoplastic polymer system, .
¦anaerobic resin system and the catalyst system and, if desired, . la tackifier, which in a solvent-free state is permanently tacky ¦at room temperature, and which firmly adheres to a ~ariety of 20 ¦ordinary surfaces upon contact without the need of more than ¦finger pressure. Further., it must conform to the surface ¦irregularities of normal surfaces and have a sufficient shear . ¦modulus to resist remo~al subsequent to application to a surface.
¦ ~o ~,eet these.criteria, the net, essentially solvent-~5 ¦free composition must have static shear strength of at least 12 minutes using a 250 gram test weight and a 0.25 square inch ¦test sur~ace and a 180 pcel strength of at lcast 0.5 lb per inch, . prcforably 1.0 lb par inch, when measurcd by the standard tests spccificd hcrcin and will scparatc from a con~cntio~al rclc~sc 30 surfaco such as a silicone coating and the lik~, wlthout cohcsive f~ilura.
.' - 11- .. -, : ` - ` ' '``-1 70877 ~
As indicatcd, a tackificr may be employed to induce or enhance pressure sensitive prope~ies. Typical tackiriers are li~
rosins, rosin derivatives, terpenes, synthetic tacky resins, ~ow molecular weiqht polyacrylates and the like as well as mixtures thereof. The tackifi~rs employed in general have a molecu1ar weight less than about 5,000, pre~erably below about 1,00 The anaerobic pressure sensitive adhesive compositions ;~
o this invention normally contain substant;al quantities of ,j anaerooic resins in order that the thermoplastic polymer system 10 employed will not interfere to any great extent with thorough and complete cross-linXing or curing of the anaerobic resin system and to maximize ultimate bond upon cure. The anaerobic pressure sensitive adhesive compositions may contain, based on a total weight of anaerobic resin system and the thermoplastic polymer lg ~ystem, and i~ present, tackifi.ers, from 35 to 99~ ~y weight anaerobic resin systemj preferably from about 55 to about 95% by weight and more pxeferably from about 70 to about 90% by weight~
For certain applications, care should be taken in pre-paring the anaerobic pressure sensitive adhesives of this invention ~0 to cope with trace transition metal ions which may be present in each constituent of the composition, including the anaerobic resin ,system and the thermoplastic polymer system, typically picked up from the vessels and systems used in their production.
If allowed to remain in the composition, the transition ~5 metal ions, while present in concentrations too low to complete cure, may, even at room temperature, consume a certain quantity of the peroxy initiator. As a result, sufficicnt tacXiness may be retained so that pressure sensitive adhesive properties will not be dcstroyed, but th~ ability of the composition to cure may . ~, 3 diminish to a degree that ultimate bond strength will not be .
,1, .~
70~77 . . . .
1 structural. That is, a cross-linked latticework will not dcvelop throughout the applied pressure sensitivc composition and cohesive failure may result. If necessary, the effect of transition metal ions in the compositions of this invention may be controlled by means, such as chelation, known to the art. When accelerated cure ~is desired, however, transition metal compounds (e.g., copper salts) may advantageously be used as primers or activators exter- I
nal to the pressure sensitive anaerobic composition of the inven-tion.
One way to cope with the metal ions is to scavenge the~
prior to or follo~7ing their ad~ixture in a mutually compatible solvent prior to casting of the pressure sensitive adhesive layer onto a release liner, which may also require scavenging.
Typical of the solvenis which are employed for dissolving the constituents of the pressure sensitive compositions are non-polar aliphatics, aromatics, alcohols and the like which will not affect the peroxy compound, Ketones, for instance, should be 'avoided. Among the suitable solvents there may be mentioned Itoluene, isopropyl alcohol and mixtures thereof.
20 , If the constituents of the pressure sensitive adhesive composition are properly scavenged, the active metals can be rein-troduced, but in another form. Rather than being active in the composition, their effe~t may be rendered latent by encapsulatin~
them in microspheres such that they will not be in contact with ~5 the peroxy initiator until the microspheres are ruptured upon the application of pressure to react with the peroxy compound to accelerate cure. `
An alternative route to prevent premature cure durin~J
shelf life or storaqe is to encapsulate tl~e peroxy compound alone 30 or with its accelerators. Then the active metals or metal ions . . '' ',, 7(~877 lll 1 ¦c n be left in the pressure sensitive adhesive composition without fear that premature curc or deactivation will occur.
¦ With care being taken to isolate the pero~ compouDd ¦of the catalyst system by encapsulation or the elimination or 5 ¦isolation of active metal or metal ions, the pressure sensitive .
¦adhesive ingredi.ents can be cast into a film on release coated ¦~urfaces or surfaces to be bonded without fear that premature ¦cure or deactivation will occur~ .
¦ Weight of pr~ssure sensitive a~hesive composition applie_ lO ¦to a surface to be bonded may be varied over a wide range with the ¦general object of achieving surface wetting for a strong and ¦tenacious bGnd. Typical coating weights are, after solvent evapor-¦ation, from about 12 to about 40 grams of net solids per square 1meter.
l~ ¦ When the anaerobic pressure sensitive adhesive is appl.iec ¦'to differential release surfaces, it is required that the applied ¦anaerobic pressure sensitive adhesive layer be removable from the ¦release liner of maximum interfacial bond,.typically a silicone . ¦coated liner, for transfer to a substrate without cohesive disrup-~0 ¦ tion of the anaerobic pressure sensitive adhesive layer. It is :~ ¦desirable for any given a~plication to have the coating as thin as . conveniently possible when the surface(s) to which the anaerobic ¦pressure sensitive adhesive is applied provides the active metal . ¦ accelerator. Cross-linking will then rapidly occur throughout ~5 ¦ the anaerobic resin and the surfaces will be bonded together. If the coating is too thicX, longer cure times will be.required or .~ . there ~ould be ~ormed an internal weakness which could result in coh~sive failure of the partially cured resin.
~5 an altcrnativc, b~ emulo~inq micro-enc~psulated .
3 ~ccelerators within the pressure sensitive adh~sive composition, . . '. '/
. - 14 ~
7087~
1 greater cure ratcs and compl~te cure c~n be realized. Sur~ace ¦~
¦ priming with accelerators m~y also be employed. t In substance, the total anaerobic pressure sen~itive adhesive system acts as a binding ac~ent for the anaerobic mono~crs 5 until cure is co~plete and then the residual constitucnts only t serve as fillers for the system. However, higher thermopl~stic , polymer syst~m concentrations can also aid in improving flexural :strength of the cured composition at some poten'cial sacrifice in shear strength.
0 The typ~s of produc'.s typically formed are the self~ ' wound tapes, the surface of the supporting tape having differen--tial release properties, sandwich constructions in which the L~
anaerobic pressure sensitive adhesive composition is contained Ibetween two carrier liners having differential release surfaces, 1 an2 simil ar products. All that is necessary i9 that the anaerobic pressure sensitive adhesive layer be transferable to a substrate and completely separated from its carriers to leave ~nly an anaerobic pressure sensitive adhesive in contact with the substrat2 to be bonded to another substrate. i~
~0 Of course, it is also understood that the lic~uid anaero-bic pressure sensitive adhesive can also be applied directly to a surface to be subsequently joined to another surface, provided the solvent is removed before such joining.
In the following Examples, one or more of the following ~5 anaerobic resin systems were employed for the formulation of anaerobic pressure sensitive adhesive compositions:
RESIN I
Approxim~'cely 75~ of a r~tction procl-tct of two ~oles of hydro~:ypropyl methacrylate with onc mol~ of methylcn~-bis-phcny~-3 4,4'-diisocyanatc and 25~ triethylcncc~lycol dimcthacryl~tc.
' , 1.
_ 15 - ' ~ : ' " '' ; ~ , 1~70877 RESIN II
Approximately 66~ of a polymer formed by hydroxypropyl methacrylate capping of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,7-bis t4-hydroxyphenyl) propane, 26~
hydroxypropyl methacrylate, 7% acrylic acid and 1% meth-acryloxyproplytrimethoxysilane.
The following test methods were employed in evaluating the pressure sensitive properties and properties of the cured end-products. In determining pressure sensitive adhesive properties, the adhesive composition was cast on a suitable - support such as paper or Mylar ~
Static ShearjStrength - Federal Test Method Std.
No. 147B, Method 20.1 ( Load 250 grams).
180 Peel (dynamic - 12"/min ) ASTM D-1000/68 Lap Shear - ASTM D-1002/64 EXAMPLE I
To a heated flask equipped with a stirrer and a reflux condenser there was added 1800 grams of toluene, 1200 grams of Resin I and 300 grams of Resin II. The mixture was heated with stirring at 70C. until a homogeneous solution was formed.
To the stirred solution there was added 300 grams of a thermo-plastic vinyl chloride copolymer known as VAGH-270 anufactured and sold by Union Carbide Corporation, and the mixture stirred until it again became homogeneous. To the resultant mixture there was added with stirring 180 grams of an aqueous alcoholic solution containing a chelating~agent for trace transition metal ions. The solution was held at a temperature between 40-50C. and stirred for three hours and the chelated transition metal ions removed.
To this sol~tion there was added 70 grams of cumene hydroperoxide containing quinone, 37 grams of benzoic sulfimide and 37 grams of methylene-bis-dimethylaniline to form a catalyst 1070877 1~
1 system solution.
The anaero'~ic pressure sensitive adhesive solution was coated onto~ the release surface of a bacXin~ sheet fa'~ricated ~xom a p'lastic f~lm and a paper having a silicone release coating. j, S Coating ~eight after solvent removal was 28 grams per square meter. Another release sheet was applied to protect the anaerobic pressure sensitive adhesi~e.
A portion of the anaero~ic pressure sensitive aahesive 1 ~, was tested for pressure sensitive ~roperties. When ap~lied to a L
0 paper support, the 250 gram static shear value was 5.5 minutes. ¦
The 180 peel test value on a Mylar support was 1.75 ]bs/in and ailure was cohesive. Surface tack was about 2 inches. ¦, Two aluminum alloy plates measuring l"x4"xl/16" were ,~
each etched on one end with a mixture of chromic and sul~uric 1 acids to form z roughened surface. ~o one roug'nened DU~ '2-2 ~h2-e was applied a 1/2"xl" layer of the anaerobic pressure sensitive adhesive. The roughened end of the other plate was placed on the - -anaerobic pressure sensitive adhesive in overlapping relation ', thereby excluding oxygen and initiating cure. The copper in the aluminum alloy accelerated cur~: and the anaerobic pressure sensi-tive adhesive bonded plates were allowed to cure for 24 hours atroom t~mperature. The bonded ~lates were tested in an Instron tester and the bond was found to give a lap shear tensile value , of 900 psi.
Z5 , - EXNMPLE II
. ' To a react:or equipped with a stirrer there ~as added a~
room temperature and with agitation 5Q0 grams of toluene and 350 grams o~ tackifier kno~n as Aro~ene 8318 (manufactured ~
, 3 ~shland Chemical Co.). Agitation was continued until a solution r~sulted.
. '' . ' '.
; , ' ' _ ll 1070877 j~~
1 To anothcr reactor there was added with stirrin~ 2700 1~
¦ grams of a poly~reth3ne resin known as Witcobondtm-308, (manu~ac- ,¦
¦ tured by ~itco Chemical Co ) 500 grams of toluene and 1000 grams i ¦ o~ isopropanol until a solution was formed.
5 ¦ The contents of ~oth reactors were com~ined and thorou~h- i ¦ ly mixed. To the resultant solution there was added 500 ~rams o~ `
¦ an alcohol solution containing a chelating agent ~or transition jl ¦ metals and the mixture stirred for three hours at room tempera~ure.
To the solution there was added ~000 grams of Resin I an~
0 the mixture stirred until a solution xesulted. ¦~
To the resultant solution there was added a catalyst s~stem comprising 240 grams of cumene hydrope~ox.ide containing _0 quinone, 2~0 grams of -benzoi~c ulfimide and 240 grams of methylene-bis-dimethylaniline. ;
As in Example I, the anaerobic pressure sensi.ive adhe- ;
sive was coated on the release surface of a support and residual solvent removed to form an anaerobic pressure s~nsïtive layer of a~
weight of 28 grams per square meter. The formed adhesive layer was protected with a second release coated sheet.
The resultant anaerobic pressure sensitive adnesive layer, prior .o cure, was determined to have a 250 gram static shear value of from 2.2 to 3.4 hrs, a 180 peel value of 1 lb/in.
. and a surface tack about 1 inch.
The procedure of Example I to determine lap shear was ~5 repeated. The lap shear tensile value was determined to be about 1200 psi.
., . . ' ., ,'. I ,,',..
. . ,. ~ ,. . ...
3 . . .
.. , , `'.','',' ' ',,,,'.
~ l8 -~, - t : ., ,' ~ :
. ` '', t '': ~ :
~ 0877 11 ¦paratoluidcne and the lik~; organic sulimidcs such as benzoic . ¦sulfimidc and the like; as well as mi~:tures thcrco~, Noxmally . ¦solid organo-nitrogen co~pounds are paxticular3.y preferrcd as ¦the~ have the le.ast.effect on the viscosity of the resulting S ¦compos.ition as well as the least tendency to migrate ~rom the ¦composition.
¦ Typical stabilizers are quinones, hydroauinones, and ¦sterically hindered phenolic compounds.
.. ¦ Depending upon the amount of anaerobic resin systcm 10 ¦contain~d i.n the polymer syste~, the amount of înitiator plus t - ¦accelerator added will generally range from ahout 0.5 to about ¦20 percent or more by weight based on the total weight of the ¦polymer system plus anaerobic resin system, and if present, a . ¦tackifier.
15 ¦ By the term "anaero~ic pressure s~nsitive adhesiv~,"
¦there is meant a mixture of the thermoplastic polymer system, .
¦anaerobic resin system and the catalyst system and, if desired, . la tackifier, which in a solvent-free state is permanently tacky ¦at room temperature, and which firmly adheres to a ~ariety of 20 ¦ordinary surfaces upon contact without the need of more than ¦finger pressure. Further., it must conform to the surface ¦irregularities of normal surfaces and have a sufficient shear . ¦modulus to resist remo~al subsequent to application to a surface.
¦ ~o ~,eet these.criteria, the net, essentially solvent-~5 ¦free composition must have static shear strength of at least 12 minutes using a 250 gram test weight and a 0.25 square inch ¦test sur~ace and a 180 pcel strength of at lcast 0.5 lb per inch, . prcforably 1.0 lb par inch, when measurcd by the standard tests spccificd hcrcin and will scparatc from a con~cntio~al rclc~sc 30 surfaco such as a silicone coating and the lik~, wlthout cohcsive f~ilura.
.' - 11- .. -, : ` - ` ' '``-1 70877 ~
As indicatcd, a tackificr may be employed to induce or enhance pressure sensitive prope~ies. Typical tackiriers are li~
rosins, rosin derivatives, terpenes, synthetic tacky resins, ~ow molecular weiqht polyacrylates and the like as well as mixtures thereof. The tackifi~rs employed in general have a molecu1ar weight less than about 5,000, pre~erably below about 1,00 The anaerobic pressure sensitive adhesive compositions ;~
o this invention normally contain substant;al quantities of ,j anaerooic resins in order that the thermoplastic polymer system 10 employed will not interfere to any great extent with thorough and complete cross-linXing or curing of the anaerobic resin system and to maximize ultimate bond upon cure. The anaerobic pressure sensitive adhesive compositions may contain, based on a total weight of anaerobic resin system and the thermoplastic polymer lg ~ystem, and i~ present, tackifi.ers, from 35 to 99~ ~y weight anaerobic resin systemj preferably from about 55 to about 95% by weight and more pxeferably from about 70 to about 90% by weight~
For certain applications, care should be taken in pre-paring the anaerobic pressure sensitive adhesives of this invention ~0 to cope with trace transition metal ions which may be present in each constituent of the composition, including the anaerobic resin ,system and the thermoplastic polymer system, typically picked up from the vessels and systems used in their production.
If allowed to remain in the composition, the transition ~5 metal ions, while present in concentrations too low to complete cure, may, even at room temperature, consume a certain quantity of the peroxy initiator. As a result, sufficicnt tacXiness may be retained so that pressure sensitive adhesive properties will not be dcstroyed, but th~ ability of the composition to cure may . ~, 3 diminish to a degree that ultimate bond strength will not be .
,1, .~
70~77 . . . .
1 structural. That is, a cross-linked latticework will not dcvelop throughout the applied pressure sensitivc composition and cohesive failure may result. If necessary, the effect of transition metal ions in the compositions of this invention may be controlled by means, such as chelation, known to the art. When accelerated cure ~is desired, however, transition metal compounds (e.g., copper salts) may advantageously be used as primers or activators exter- I
nal to the pressure sensitive anaerobic composition of the inven-tion.
One way to cope with the metal ions is to scavenge the~
prior to or follo~7ing their ad~ixture in a mutually compatible solvent prior to casting of the pressure sensitive adhesive layer onto a release liner, which may also require scavenging.
Typical of the solvenis which are employed for dissolving the constituents of the pressure sensitive compositions are non-polar aliphatics, aromatics, alcohols and the like which will not affect the peroxy compound, Ketones, for instance, should be 'avoided. Among the suitable solvents there may be mentioned Itoluene, isopropyl alcohol and mixtures thereof.
20 , If the constituents of the pressure sensitive adhesive composition are properly scavenged, the active metals can be rein-troduced, but in another form. Rather than being active in the composition, their effe~t may be rendered latent by encapsulatin~
them in microspheres such that they will not be in contact with ~5 the peroxy initiator until the microspheres are ruptured upon the application of pressure to react with the peroxy compound to accelerate cure. `
An alternative route to prevent premature cure durin~J
shelf life or storaqe is to encapsulate tl~e peroxy compound alone 30 or with its accelerators. Then the active metals or metal ions . . '' ',, 7(~877 lll 1 ¦c n be left in the pressure sensitive adhesive composition without fear that premature curc or deactivation will occur.
¦ With care being taken to isolate the pero~ compouDd ¦of the catalyst system by encapsulation or the elimination or 5 ¦isolation of active metal or metal ions, the pressure sensitive .
¦adhesive ingredi.ents can be cast into a film on release coated ¦~urfaces or surfaces to be bonded without fear that premature ¦cure or deactivation will occur~ .
¦ Weight of pr~ssure sensitive a~hesive composition applie_ lO ¦to a surface to be bonded may be varied over a wide range with the ¦general object of achieving surface wetting for a strong and ¦tenacious bGnd. Typical coating weights are, after solvent evapor-¦ation, from about 12 to about 40 grams of net solids per square 1meter.
l~ ¦ When the anaerobic pressure sensitive adhesive is appl.iec ¦'to differential release surfaces, it is required that the applied ¦anaerobic pressure sensitive adhesive layer be removable from the ¦release liner of maximum interfacial bond,.typically a silicone . ¦coated liner, for transfer to a substrate without cohesive disrup-~0 ¦ tion of the anaerobic pressure sensitive adhesive layer. It is :~ ¦desirable for any given a~plication to have the coating as thin as . conveniently possible when the surface(s) to which the anaerobic ¦pressure sensitive adhesive is applied provides the active metal . ¦ accelerator. Cross-linking will then rapidly occur throughout ~5 ¦ the anaerobic resin and the surfaces will be bonded together. If the coating is too thicX, longer cure times will be.required or .~ . there ~ould be ~ormed an internal weakness which could result in coh~sive failure of the partially cured resin.
~5 an altcrnativc, b~ emulo~inq micro-enc~psulated .
3 ~ccelerators within the pressure sensitive adh~sive composition, . . '. '/
. - 14 ~
7087~
1 greater cure ratcs and compl~te cure c~n be realized. Sur~ace ¦~
¦ priming with accelerators m~y also be employed. t In substance, the total anaerobic pressure sen~itive adhesive system acts as a binding ac~ent for the anaerobic mono~crs 5 until cure is co~plete and then the residual constitucnts only t serve as fillers for the system. However, higher thermopl~stic , polymer syst~m concentrations can also aid in improving flexural :strength of the cured composition at some poten'cial sacrifice in shear strength.
0 The typ~s of produc'.s typically formed are the self~ ' wound tapes, the surface of the supporting tape having differen--tial release properties, sandwich constructions in which the L~
anaerobic pressure sensitive adhesive composition is contained Ibetween two carrier liners having differential release surfaces, 1 an2 simil ar products. All that is necessary i9 that the anaerobic pressure sensitive adhesive layer be transferable to a substrate and completely separated from its carriers to leave ~nly an anaerobic pressure sensitive adhesive in contact with the substrat2 to be bonded to another substrate. i~
~0 Of course, it is also understood that the lic~uid anaero-bic pressure sensitive adhesive can also be applied directly to a surface to be subsequently joined to another surface, provided the solvent is removed before such joining.
In the following Examples, one or more of the following ~5 anaerobic resin systems were employed for the formulation of anaerobic pressure sensitive adhesive compositions:
RESIN I
Approxim~'cely 75~ of a r~tction procl-tct of two ~oles of hydro~:ypropyl methacrylate with onc mol~ of methylcn~-bis-phcny~-3 4,4'-diisocyanatc and 25~ triethylcncc~lycol dimcthacryl~tc.
' , 1.
_ 15 - ' ~ : ' " '' ; ~ , 1~70877 RESIN II
Approximately 66~ of a polymer formed by hydroxypropyl methacrylate capping of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,7-bis t4-hydroxyphenyl) propane, 26~
hydroxypropyl methacrylate, 7% acrylic acid and 1% meth-acryloxyproplytrimethoxysilane.
The following test methods were employed in evaluating the pressure sensitive properties and properties of the cured end-products. In determining pressure sensitive adhesive properties, the adhesive composition was cast on a suitable - support such as paper or Mylar ~
Static ShearjStrength - Federal Test Method Std.
No. 147B, Method 20.1 ( Load 250 grams).
180 Peel (dynamic - 12"/min ) ASTM D-1000/68 Lap Shear - ASTM D-1002/64 EXAMPLE I
To a heated flask equipped with a stirrer and a reflux condenser there was added 1800 grams of toluene, 1200 grams of Resin I and 300 grams of Resin II. The mixture was heated with stirring at 70C. until a homogeneous solution was formed.
To the stirred solution there was added 300 grams of a thermo-plastic vinyl chloride copolymer known as VAGH-270 anufactured and sold by Union Carbide Corporation, and the mixture stirred until it again became homogeneous. To the resultant mixture there was added with stirring 180 grams of an aqueous alcoholic solution containing a chelating~agent for trace transition metal ions. The solution was held at a temperature between 40-50C. and stirred for three hours and the chelated transition metal ions removed.
To this sol~tion there was added 70 grams of cumene hydroperoxide containing quinone, 37 grams of benzoic sulfimide and 37 grams of methylene-bis-dimethylaniline to form a catalyst 1070877 1~
1 system solution.
The anaero'~ic pressure sensitive adhesive solution was coated onto~ the release surface of a bacXin~ sheet fa'~ricated ~xom a p'lastic f~lm and a paper having a silicone release coating. j, S Coating ~eight after solvent removal was 28 grams per square meter. Another release sheet was applied to protect the anaerobic pressure sensitive adhesi~e.
A portion of the anaero~ic pressure sensitive aahesive 1 ~, was tested for pressure sensitive ~roperties. When ap~lied to a L
0 paper support, the 250 gram static shear value was 5.5 minutes. ¦
The 180 peel test value on a Mylar support was 1.75 ]bs/in and ailure was cohesive. Surface tack was about 2 inches. ¦, Two aluminum alloy plates measuring l"x4"xl/16" were ,~
each etched on one end with a mixture of chromic and sul~uric 1 acids to form z roughened surface. ~o one roug'nened DU~ '2-2 ~h2-e was applied a 1/2"xl" layer of the anaerobic pressure sensitive adhesive. The roughened end of the other plate was placed on the - -anaerobic pressure sensitive adhesive in overlapping relation ', thereby excluding oxygen and initiating cure. The copper in the aluminum alloy accelerated cur~: and the anaerobic pressure sensi-tive adhesive bonded plates were allowed to cure for 24 hours atroom t~mperature. The bonded ~lates were tested in an Instron tester and the bond was found to give a lap shear tensile value , of 900 psi.
Z5 , - EXNMPLE II
. ' To a react:or equipped with a stirrer there ~as added a~
room temperature and with agitation 5Q0 grams of toluene and 350 grams o~ tackifier kno~n as Aro~ene 8318 (manufactured ~
, 3 ~shland Chemical Co.). Agitation was continued until a solution r~sulted.
. '' . ' '.
; , ' ' _ ll 1070877 j~~
1 To anothcr reactor there was added with stirrin~ 2700 1~
¦ grams of a poly~reth3ne resin known as Witcobondtm-308, (manu~ac- ,¦
¦ tured by ~itco Chemical Co ) 500 grams of toluene and 1000 grams i ¦ o~ isopropanol until a solution was formed.
5 ¦ The contents of ~oth reactors were com~ined and thorou~h- i ¦ ly mixed. To the resultant solution there was added 500 ~rams o~ `
¦ an alcohol solution containing a chelating agent ~or transition jl ¦ metals and the mixture stirred for three hours at room tempera~ure.
To the solution there was added ~000 grams of Resin I an~
0 the mixture stirred until a solution xesulted. ¦~
To the resultant solution there was added a catalyst s~stem comprising 240 grams of cumene hydrope~ox.ide containing _0 quinone, 2~0 grams of -benzoi~c ulfimide and 240 grams of methylene-bis-dimethylaniline. ;
As in Example I, the anaerobic pressure sensi.ive adhe- ;
sive was coated on the release surface of a support and residual solvent removed to form an anaerobic pressure s~nsïtive layer of a~
weight of 28 grams per square meter. The formed adhesive layer was protected with a second release coated sheet.
The resultant anaerobic pressure sensitive adnesive layer, prior .o cure, was determined to have a 250 gram static shear value of from 2.2 to 3.4 hrs, a 180 peel value of 1 lb/in.
. and a surface tack about 1 inch.
The procedure of Example I to determine lap shear was ~5 repeated. The lap shear tensile value was determined to be about 1200 psi.
., . . ' ., ,'. I ,,',..
. . ,. ~ ,. . ...
3 . . .
.. , , `'.','',' ' ',,,,'.
~ l8 -~, - t : ., ,' ~ :
Claims (12)
1. A curable, essentially solvent free anaerobic pres-sure sensitive adhesive composition comprising a mixture of:
a. about 35 to about 99 percent by weight of an anaerobic resin system which is stable in the presence of oxygen and which contains at least one anaerobically curable resin having at least one polymerizable acrylate ester moiety;
b. about one to about 65 percent by weight of a thermoplastic polymer system containing at least one high molecular weight urethane polymer capable of combining a substantial quantity of said anaerobic resin system;
c. about 0.5 to about 20 percent, based on the total weight of (a) and (b), of a catalyst system for said anaerobic resin system, said catalyst system comprising a peroxy compound, an organic compound for accelerating cure of said anaerobic resin system and a stabilizer for said anaerobic resin system, said anaerobic pressure sensitive adhesive, when in an essentially solvent-free state, being permanently tacky at room temperature and having a static shear strength of at least about two minutes at a 250 gram load per 0.25 square inch and a 180° peel value of at least about 0.5 lb.
per inch, and curable upon substantial exclusion of oxygen.
a. about 35 to about 99 percent by weight of an anaerobic resin system which is stable in the presence of oxygen and which contains at least one anaerobically curable resin having at least one polymerizable acrylate ester moiety;
b. about one to about 65 percent by weight of a thermoplastic polymer system containing at least one high molecular weight urethane polymer capable of combining a substantial quantity of said anaerobic resin system;
c. about 0.5 to about 20 percent, based on the total weight of (a) and (b), of a catalyst system for said anaerobic resin system, said catalyst system comprising a peroxy compound, an organic compound for accelerating cure of said anaerobic resin system and a stabilizer for said anaerobic resin system, said anaerobic pressure sensitive adhesive, when in an essentially solvent-free state, being permanently tacky at room temperature and having a static shear strength of at least about two minutes at a 250 gram load per 0.25 square inch and a 180° peel value of at least about 0.5 lb.
per inch, and curable upon substantial exclusion of oxygen.
2. The composition of claim 1 wherein the organic compound for accelerating cure is an organo-nitrogen compound.
3. The composition of claim 1 in which a tackifying resin is present.
4. The composition of claim 1 in which the anaerobic resis system is present in an amount of from about 55 to about 95% by weight based on the total weight of said anaerobic resin system and said polymer system.
5. The composition of claim 3 in which the anaerobic resin system is present in an amount of from about 35 to about 99% by weight based on the total weight of said anaerobic resin system, said polymer system and said tackifying resin.
6. The composition of claim 3 in which the anaerobic resin system is present in an amount of from about 55 to about 95% by weight based on the total weight of said anaerobic resin system, said polymer system and said tackifying resin.
7. The composition of claim 1 which contains a micro-sphere encapsulated active metal which is capable of accel-erating cure of said anaerobic resin system upon rupture of the microspheres.
8. The composition of claim 1 which contains an active metal compound capable of accelerating cure when brought into contact with a peroxy compound and wherein the peroxy compound is microencapsulated in microspheres, the cure of said anaerobic pressure sensitive adhesive composition being initiated upon rupture of said microcapsules.
9. The composition of claim 1 in which the anaerobic resin system contains at least one monomer selected from the group consisting of triethyleneglycol dimethacrylate; the reaction product of 2 mols of hydroxypropyl methacrylate with one mole of methylene-bis-phenyl-4,4'-diisocyanate; the hydroxypropyl methacrylate end-capped reaction product of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,2-bis-(4-hydroxyphenyl)propane; and mixtures thereof.
10. The composition of claim 3 in which the anaerobic resin system contains at least one monomer selected from the group consisting of triethyleneglycol dimethacrylate;
the reaction product of 2 mols of hydroxypropyl methacrylate per mole of methylene-bis-phenyl-4,4' diisocyanate; the hydroxypropyl methacrylate endcapped reaction product of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,2-bis-(4-hydroxyphenyl)propane; and mixtures thereof.
the reaction product of 2 mols of hydroxypropyl methacrylate per mole of methylene-bis-phenyl-4,4' diisocyanate; the hydroxypropyl methacrylate endcapped reaction product of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,2-bis-(4-hydroxyphenyl)propane; and mixtures thereof.
11. The composition of claim 1 in which the catalyst system is present in an amount from about 0.5 to about 20% by weight based on the total weight of the anaerobic resin system and the thermoplastic polymer system.
12. The composition of claim 3 in which the catalyst system is present in an amount from 0.5 to about 20% by weight based on the total weight of the said anaerobic resin system, said thermoplastic polymer system and said tackifier system.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/443,223 US3996308A (en) | 1974-02-19 | 1974-02-19 | Anaerobic pressure sensitive adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070877A true CA1070877A (en) | 1980-01-29 |
Family
ID=23759906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,201A Expired CA1070877A (en) | 1974-02-19 | 1975-02-03 | Anaerobic pressure sensitive adhesive composition |
Country Status (8)
| Country | Link |
|---|---|
| US (4) | US3996308A (en) |
| JP (1) | JPS50140538A (en) |
| BR (1) | BR7500984A (en) |
| CA (1) | CA1070877A (en) |
| DE (1) | DE2507068A1 (en) |
| FR (1) | FR2261328B1 (en) |
| GB (1) | GB1498825A (en) |
| SE (1) | SE7501728L (en) |
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-
1974
- 1974-02-19 US US05/443,223 patent/US3996308A/en not_active Expired - Lifetime
-
1975
- 1975-02-03 CA CA219,201A patent/CA1070877A/en not_active Expired
- 1975-02-17 SE SE7501728A patent/SE7501728L/xx unknown
- 1975-02-18 BR BR984/75A patent/BR7500984A/en unknown
- 1975-02-19 JP JP50020798A patent/JPS50140538A/ja active Pending
- 1975-02-19 GB GB6977/75A patent/GB1498825A/en not_active Expired
- 1975-02-19 DE DE19752507068 patent/DE2507068A1/en not_active Ceased
- 1975-02-19 FR FR7505128A patent/FR2261328B1/fr not_active Expired
-
1976
- 1976-09-17 US US05/724,149 patent/US4092374A/en not_active Expired - Lifetime
- 1976-09-17 US US05/724,147 patent/US4092376A/en not_active Expired - Lifetime
- 1976-09-17 US US05/724,148 patent/US4118442A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2261328A1 (en) | 1975-09-12 |
| AU7824375A (en) | 1976-08-19 |
| FR2261328B1 (en) | 1978-12-22 |
| GB1498825A (en) | 1978-01-25 |
| US3996308A (en) | 1976-12-07 |
| SE7501728L (en) | 1975-08-20 |
| BR7500984A (en) | 1975-12-02 |
| US4118442A (en) | 1978-10-03 |
| US4092376A (en) | 1978-05-30 |
| JPS50140538A (en) | 1975-11-11 |
| US4092374A (en) | 1978-05-30 |
| DE2507068A1 (en) | 1975-10-09 |
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