GB1566820A - Anaerobic pressure sensitive adhesive stocks - Google Patents
Anaerobic pressure sensitive adhesive stocks Download PDFInfo
- Publication number
- GB1566820A GB1566820A GB38110/77A GB3811077A GB1566820A GB 1566820 A GB1566820 A GB 1566820A GB 38110/77 A GB38110/77 A GB 38110/77A GB 3811077 A GB3811077 A GB 3811077A GB 1566820 A GB1566820 A GB 1566820A
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- United Kingdom
- Prior art keywords
- pressure sensitive
- anaerobic
- sensitive adhesive
- layer
- adhesive layer
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/22—Presence of unspecified polymer
Description
(54) ANAEROBIC PRESSURE SENSITIVE ADHESIVE
STOCKS
(71) We, LOCTITE CORPORATION, a corporation organised under the laws of the State of Connecticut, United States of America, of 705 North Mountain
Road, Newington, Connecticut, United States of America, and AVERY
INTERNATIONAL CORPORATION, a corporation organised under the laws of
Delaware, United States of America, of 415 Huntington Drive, San Marino,
California 91108, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to anaerobic pressure sensitive adhesive stocks.
Anaerobic adhesive systems are those which are stable in the presence of oxygen, but will polymerise in the absence of oxygen. Polymerisation is initiated by
the presence of a peroxy compound. The cured cross-linked resins serve as sealants and as adhesives.
Typical resin monomers are terminated with polymerisable acrylate esters such as methacrylate, ethacrylate and chloroacrylate esters. The other ingredients typically present are an initiator, preferably an organic hydroperoxide such as cumene hydroperoxide, tertiary butyl hydroperoxide and the like. There is also normally provided a stabilizer against free radical initiation such as a quinone or hydroquinone, in an amount sufficient to prevent premature polymerisation of the adhesive due to decomposition of the peroxy compound. There are also preferably present one or more accelerators which are typically organonitrogen compounds such as tertiary amines, imides, sulphonamides 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 jointed.
When 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
U.S. Patents 2,895,950; 3,041,322; 3,043,820; 3,046,262; 3,203,941; 3,218,305; 3,300,547; 3,435,012; 3,547,851 and 3,625,875.
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 cure.
A problem exists, however, in fixturing other surfaces together with initiatlon and completion of cure and in providing a controlled quantity of anaerobst monomer to the surfaces to be bonded
The present invention provides an anaerobic pressure sensitive adhesive stock comprising::
(a) a first release coating on a self-supporting release liner;
(b) a transferable and curable pressure sensitive adhesive layer having one surface in contact with said first release coating, the pressure sensitive adhesive layer comprising
(i) from 9 to 95 percent by weight of the layer of a thermoplastic resin system
containing at least one thermoplastic polymer which is a vinyl
homopolymer, a vinyl copolymer, a polyurethane, a polyester, a
polyamide, an acrylic polymer, a natural elastomer, or a synthetic
elastomer;;
(ii) from 4 to 40 percent by weight of the layer of a first anaerobic resin
system, containing at least one curable anaerobid resin having a viscosity
from 5 to 1000 cps at 25CC and a vinyl equivalent number from 80 to 2000
and from 0 to 80 percent by weight of the layer of a second anaerobic
resin system containing at least one curable anaerobic resin having a
viscosity greater than 1000 cps at 250C, at least one anaerobic resin in the
first and second anaerobic resin system containing at least two
polymerisable acrylic ester groups, each individually having the formula::
wherein R2 is a hydrogen or a halogen atom or a lower alkyl group
containing from 1 to 4 carbon atoms, the anaerobic resins being present in
an amount of from 4 to 90 percent by weight of the layer;
(iii) from 0.1 to 10 percent by weight of the layer of a peroxy initiator to
initiate cure of the contained anaerobic resins upon the substantial
exclusion of oxygen; and
(iv) from 0 to 10 percent by weight of the layer of an organonitrogen compound
as a latent accelerator in the cure of the contained anaerobic resins and the pressure sensitive adhesive layer providing a static shear strength of at least 10 minutes at a 250 gram load per 0.25 square inch, a 180 peel value of at least 2 pounds; a Polyken tack of at least 700 gram and a loop tack of at least 1.5 Ibs per in2
Drior to cure of the anaerobic resin system; these characteristics being measured at 25 C, 1 atmosphere pressure and at a relative humidity of S0j2%; and
(c) a second release coating on a self-supporting release liner in contact with the opposed surface of the transferable pressure sensitive adhesive layer, the bond of the first release coating to the transferable pressure sensitive adhesive layer being less than the cohesive strength of the pressure sensitive adhesive layer and exceeding the bond of the second release coating for the pressure sensitive adhesive layer to permit the pressure sensitive adhesive layer to be preferentially separated from the second release coating for application and bonding to a substrate prior to separation of the pressure sensitive adhesive layer from the first release coating without cohesive failure of the pressure sensitive adhesive layer.
According to the present invention, there are provided anaerobic pressure sensitive adhesive stocks such as sheets and tapes from which a pressure sensitive adhesive layer including at least one anaerobic resin system which can be completely transferred to one substrate to be bonded to another, and cured upon activation by a peroxy initiator and the exclusion of oxygen.
ihe anaerobic pressure sensitive adhesive stocks conslst of a release liner or liners which provide differential release surfaces to permit separation of a pressure sensitive adhesive layer containing at least one anaerobic resin system from one release surface prior to separation of the layer from the other release surface.
In the situation where a tape construction is employed the web provided by the tape can provide the differential release surfaces. In a typical situation, the surface of lowest release value is on the upper surface of a web, and the pressure sensitive adhesive retained by the undersurface of the tape such that, after applying the pressure sensitive adhesive to the substrate, the pressure sensitive adhesive will then fully release from the undersurface of the tape without cohesive failure of the adhesive layer.
In the instance of sheet construction, the lower release surface is provided by at least one of the sheets or webs.
The pressure sensitive adhesive layer comprises, based on the total weight of the components of the layer, from 4 to 40 percent by weight of the layer of a first anaerobic resin system containing at least one curable anaerobic resin having a viscosity from 5 to 1000 cps at 250C and a vinyl equivalent number of from 80 to 2000; from 0 to 80 percent by weight of the layer of a second anaerobic resin system containing at least one curable anaerobic resin having a viscosity greater than 1000 cps at 250C and including normally solid resins, at least one anaerobic resin contained in each of the anaerobic resins systems containing at least two polymerisable acrylic ester groups, each individually having the formula:
wherein R2 is a hydrogen or a halogen atom or a lower alkyl group containing from 1 to 4 carbon atoms; from 9 to 95 percent by weight of the layer of a thermoplastic resin system containing at least one thermoplastic polymer which is a vinyl homopolymer, vinyl copolymer, polyurethane, polyester, polyamide, acrylic polymer, natural elastomer, a synthetic elastomer which may and preferably does include a tackifier; from 0 to 10 percent by weight of the layer of an organonitrogen compound and from 0.1 to 10 percent by weight of the layer of a peroxy initiator preferably a hydroperoxide. The total amount of anaerobic resins present in the layer is from 4 to 90 percent by weight, preferably from 35 to 60 percent by weight based on the total weight of the layer.The layer when in a substantially solvent free state, has a static shear strength, at a 250 gram load per 0.25 in2 of at least 10 minutes; a Polyken tack of at least 700 grams; a loop tack of at least 1.5 Ibs per in2 and a 1800 peel value of at least 2 Ibs, the composition being curable upon the substantial exclusion of oxygen. When cured the composition will provide a lap shear of at least 100 psi. When used in combination with a surface primer, fixturing, i.e. immobilisation of the pressure sensitive adhesive layer will be realised within 24 hours.
The pressure sensitive adhesive layer may be homogeneous or heterogeneous in nature.
When heterogeneous, the anaerobic resin system may be separate from the pressure sensitive adhesive or combined in part with the pressure sensitive adhesive. As between the two, however, cohesive integrity is not disrupted during transfer.
As part of the construction, there may be included an interlayer, which may or may not have anaerobic properties but which will add flexural strength, particularly when lap constructions are required.
In the construction, the webs to which the adhesive layer is applied may be impervious to the organonitrogen compounds which often serve as latent accelerators for the anaerobic resin system, as some have been found to migrate through a conventional paper base used in conventional pressure sensitive tape and sheet constructions. Loss of the accelerator may hinder the cure. To avoid this, organonitrogen compounds which have a low vapour pressure at ambient temperatures are preferably employed as accelerators.
To enhance rate of cure, the surfaces are normally primed with an active accelerator such as tetramethyl thiourea or the like.
In one embodiment, if the anaerobic pressure sensitive 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 another 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.
The thermoplastic polymers used in the preparation of the pressure sensitive e anaerobic compositions of this invention are preferably of sufficient molecule weight so as to be elastomeric at room temperature. Further, thea must be compatible with the anaerobic resins and should not interfere with the creation of a crosslinked latticework of the anaerobic resins. In addition, the thermoplastic polymer must be selected such that the composition alone or with tackifiers and upon the inclusion of an initiator system will form, after evaporation of essentially all the solvent, 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 layer or film.The fully formulated, solvent free anaerobic pressure sensitive adhesive should be elastomeric at room temperature.
Further, anaerobic pressure sensitive adhesive compositions should, when applied to a surface, wet the surface and conform to the intricacies of the surface so that a uniform bond will be created upon cure and that cure will extend throughout the layer of applied anaerobic pressure sensitive composition to maximise cohesive bond strength.
In the accompanying drawings:
Fig. 1 illustrates one construction for a pressure sensitive anaerobic adhesive stock in sheet form.
Fig. 2 illustrates another construction for a pressure sensitive anaerobic adhesive stock in sheet form which includes an interlayer.
Fig. 3 illustrates a tape construction.
Fig. 4 illustrates a construction in which a provided adhesive system is heterogeneous.
According to the present invention, there are provided anaerobic pressure sensitive adhesive stocks, such as sheets and self-wound tapes, from which an adhesive layer including an anaerobic resin system can be completely transferred to one substrate to be bonded to another and cured upon the exclusion of oxygen.
With reference to Fig. 1, the basic construction for sheets consists of a first web 10 providing a release coating 18, and a second web 12 providing a second release coating between which there is contained an anaerobic pressure sensitive adhesive layer 14. The webs provide differential release surfaces to permit preferential removal of one of the webs from the adhesive layer before removal of the other.
Fig. 3 illustrates a typical construction for a tape where the differential release liners 18 and 18a are contained on opposite sides of the web. Surface 18 has the highest release properties.
The pressure sensitive adhesive layer of the stock construction comprises, based on the total weight of the components of the layer from 4 to 40 percent by weight of a first anaerobic resin system containing at least one curable anaerobic resin having a viscosity from 5 to 1000 cps at 250C and a vinyl equivalent number of from 80 to 2000 at 250C and from 0 to 80 percent by weight of the layer of a second anaerobic resin system containing at least one curable anaerobic resin having a viscosity greater than 1000 cps at 250C and including normally solid resins and wherein at least one anaerobic resin of each of the anaerobic resin systems contains at least two polymerisable acrylic ester groups, each individually having the formula:
wherein R2 is a hydrogen or a halogen atom or a lower alkyl group containing from 1 to 4 carbon atoms; from 9 to 95 percent by weight of the layer of a thermoplastic resin system containing at least one thermoplastic polymer which is a vinyl homopolymer, a vinyl copolymer, a polyurethane, a polyester, a polyamide, an acrylic polymer, a natural elastomer, or a synthetic elastomer, preferably including a tackitler; from 0 to 10 percent by weight of the layer of an organonitrogen compound which serves as a latent accelerator and from 0.1 to 10 percent by weight a peroxy initiator, preferably a hydroperoxide. The total amount of anaerobic resins present in the layer is from 4 to 90 percent by weight, preferably from 35 to 60 percent by weight based on the total weight of the layer.
The composition when in a substantially solvent free state, has a static shear strength for a 250 gram load per 0.25 in2 of at least 10 minutes. a Polyken tack of at least 700 grams, a loop tack of at least 1.5 Ibs per in2 and a 1800 peel value of at least 2 Ibs such being measured at 250C, 1 atmosphere pressure and at a relative humidity of 50+20/ The composition is curable upon the substantial exclusion of oxygen. When cured the composition will provide a lap shear of at least 100 psi. When used in combination with a surface primer, fixturing, i.e. immobilisation of the pressure sensitive adhesive layer will be realised within 24 hours.
The anaerobic resins useful in the practice of this invention are polymerisable di- and other polyacrylate esters since, because of their ability to form cross-linked polymers, they have more highlv desirable adhesive properties. However, monoacrylate esters and/or amides can be included as diluent anaerobic resins.
Examples of monomers of this type are hydroxyethyl methacrylate, cyanoethyl acrylate, t-butylaminoethyl methacrylate, glycidyf methacrylate, acrylamide, methacrylamide and the like. Anaerobic properties are imparted to the acrylate ester monomers by combining with them a peroxy polymerisation initiator as discussed more fully below.
One of the polyacrylate esters which can be used in the adhesives disclosed herein are polyacrylate esters which have the following general formula:
wherein R represents a hydrogen atom, a lower alkyl radical of from 1 to 4 carbon atoms, a hydroxy-alkyl radical of from 1 to 4 carbon atoms, or a radical of the formula
R2 is a hydrogen or a halogen atom or a lower alkyl radical of from 1 to 4 carbon atoms;
R3 is a hydrogen atom or a hydroxyl group or a radical of the formula
and m is an integer equal to at least 1, e.g., from 1 to 15 or higher, and preferably
from 1 to 8 inclusive;
n is an integer equal to at least 1, e.g., 1 to 20 or more; and p is 0 or 1.
The polymerisable polyacrylate esters used in accordance with the invention
and corresponding to the above general formula are exemplified by but not
restricted to the following materials; di-, tri- and tetraethylene glycol dimeth
acrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ditpentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetra
ethylene glycol di (chloroacrylate), diglycerol diacrylate, diglycerol tetrameth
acrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl
glycol diacrylate and trimethylol 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 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. Preferably, 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: wherein X is -0- or
where R5 is a hydrogen atom or a monovalent hydrocarbon radical containing up to 10 carbon atoms, and is preferably a hydrogen atom or an alkyl or aralkyl radical with from 1 to 10 carbon atoms; R2 is as defined above; and R4 is an alkylene radical with from 1 to 10 carbon atoms, or an aromatic diradical containing up to 14 carbon atoms, preferably phenylene, biphenylene or naphthylene.
Naturally R5 and R4 can contain any substituents or linkages which do not adversely affect the molecule for its intended use herein.
Typical polyisocyanates which can be reacted with the above acrylate esters to form polyacrylate monomers are toluene diisocyanate, 4,4'-diphenyl diisocyanate, dianisidine diisocyanate, cyclohexylene diisocyanate, 2-chloropropane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diethyl ether diisocyanate, 34dimethylamino)-pentane diisocyanate;, tetrachlorophenylene diisocyanate, 1,4 and trans-vinylene diisocyanate.Stili other polyisocyanates that may be used are higher molecular weight polyisocyanates obtained by reacting an excess of any of the above described isocyanates with polyamines containing terminal, primary and secondary amine 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 alkylene oxides with 4,4'dihydroxydiphenyldimethylmethane.
Other acceptable monomers which can be used in the compositions according to the invention are acrylate terminated epoxy or ester units, i.e., reaction products of acrylic acid with hydroxy terminated ester or epoxy compounds, or low polymers thereof. Also contemplated by this invention are any other anaerobically curing monomers which, with their respective initiators, accelerators and stabilisers, i.e., inhibitors, are formulated according to the instant invention into a pressure sensitive anaerobic adhesive producing the advantageous properties of the stocks of the instant invention.
One of the anaerobic resins must have a viscosity less than 5 to 1000 cps as measured at 250C and have a vinyl equivalent number of from 80 to 2000. The resins are normally liquids at one atmosphere and 25"C. Illustrative of such anaerobic resins there may be mentioned diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaethylene glycol dimethacrylate, pentaethylene glycol diacrylate, hexaethylene glycol dimethacrylate, hexaethylene glycol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, ethoxylated bisphenol A dimethacrylate (epoxylated 2,2 bis-(hydroxyphenyl) propane dimethacrylate) ethoxylated bisphenol A diacrylate and the like as well as mixtures thereof.
The presently preferred anaerobic monomers having a viscosity greater than 1000 cps as measured at 250C, include the reaction product of hydroxypropyl methacrylate with methylene-bis-phenyl-4,4'-diisocyanate; a polymer formed by methacrylate capping of a 1:1 adduct of toluene diisocyanate 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 with anaerobic monomers.
By the term "thermoplastic resin system", as used herein, there is meant one or more thermoplastic polymers preferably of relatively high molecular weight which, alone or in admixture, have an average molecular weight such that the resultant curable anaerobic pressure sensitive adhesive composition will have sufficient cohesive strength to be transferred from a conventional 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 of thermoplastic polymer or polymer mixtures used, as well as upon the tackifier or tackifiers used, if any.Although it is desired that the thermoplastic polymers employed be compatible with the anaerobic resin system, they may be incompatible forming a heterogeneous system which remains pressure sensitive and transferrable in nature and capable of curing.
The word "combined" is used herein to indicate any workable combination, regardless of its physical form, of one or more thermoplastic polymers with one or more anaerobic monomers. Thus, a given combination may be a solution or otherwise and may be homogeneous or heterogeneous, provided only that the resultant combination produces an anaerobic pressure sensitive adhesive stock of the type according to the present invention.
Typical of the thermoplastic polymers which can be used are vinyl homopolymers and copolymers such as polyvinyl chloride, polyvinyl ethers, polyvinyl acetates, copolymers of vinyl pyrrolidone and the like; acrylic based polymers; polyurethanes; polyesters; polyamides; natural and synthetic elastomers and the like as well as mixtures thereof. The preferred thermoplastic polymers are copolymers of vinyl pyrrolidone, acrylic polymers and mixtures thereof.
As indicated, a tackifier may be employed to induce or enhance pressure sensitive properties. Typical tackifiers are rosins, rosin derivatives, terpenes, synthetic tackifying resins, low molecular weight polyacrylates and the like as well as mixtures thereof. The tackifiers employed in general have a molecular weight less than 5000, preferably below 1000.
By "catalyst system" there is meant an acid or basic catalysed system typically containing at least one peroxy initiator, preferably, although not necessarily, at least one accelerator which is preferably an organonitrogen compound and preferably, although not necessarily, at least one stabilises against premature free radical polymerisation for the anaerobic resin system.
Typical of the peroxy compounds which may be employed as initiators are the hydroperoxides, preferably organic hydroperoxides of the formula R6OOH, wherein R6 is generally a hydrocarbon radical containing up to 18 carbon atoms, preferably an alkyl, aryl or aralkyl radical containing from 1 to 12 carbon atoms.
Typical examples are cumene hydroperoxide, methyl ethyl ketone hydroperoxide and the like.
As accelerators there may be mentioned liquid and solid organonitrogen compounds including but not limited to organic amides such as formamide, succinimide and the like; tertiary amines such as tributylamine, triethylamine, hexamethyl pararosaniline and the like; aromatic tertiary amines such as N,N'dimethyl paratoluidene and the like; organic sulphimides such as benzoyl sulphimide (saccharin) and the like; as well as mixtures thereof. Organonitrogen compounds which have a low vapour pressure at ambient temperatures are particularly preferred as they have the least effect on the viscosity of the resulting composition as well as the least tendency to migrate from the composition.
Typical stabilisers are quinones, hydroquinones, and sterically hindered phenolic compounds.
By the term "anaerobic pressure sensitive adhesive" there is meant a mixture of the thermoplastic resin system, anaerobic resin systems, catalyst and, if desired, an accelerator and/or a tackifier, which is an essentially solvent free state is permanently tacky at room temperature and which firmly adheres to a variety of 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 removal subsequent to application to a surface.
Anaerobic resins containing a cure system are, as provided, normally liquid to grease-like in consistency and packaged in containers of a type where
provided to preclude premature gellation or cure. Molecular mobility this aids stability.
When rendered less mobile as part of a pressure sensitive adhesive composition, factors change.
One has been found to be loss of normally liquid accelerators due to diffusion of the accelerators to the surface of the adhesive layer, followed by evaporation.
Another is deactivation due to peroxy initiator reaction with active metals or metal ions which may be contained in the paper normally used in release liner construction.
Accelerator loss by diffusion and evaporation can conveniently be controlled by employing accelerators having reduced vapour pressure, preferably an organonitrogen compound which is normally solid at room temperature. The preferred organonitrogen compound is saccharin.
Where the accelerator is normally a liquid, accelerator loss can also be controlled by providing an impervious or barrier layer to control diffusion of the accelerator.
This, as shown in Fig. 1, can be provided by thin barrier coats 16 coated with release surfaces 18, typically a silicone release agent bonded to backing papers 20.
If the barrier coat 16 is sufficiently thick so as to become a self-supporting film, then the backing papers 20 can be eliminated.
A convenient barrier coat or self-supporting film is polyethylene, particularly low density polyethylene, as low density polyethylene is normally prepared in the absence of a metal catalyst and does not contain a catalyst residue.
Other impervious polymers which are also free of available active metals or metal ions may also be employed.
Conventional or specially treated papers may be employed as the support web 18 for the release liners 20. In this instance, migration of the accelerator can be diminished or overcome by other routes.
One is to package the end product with impervious sheet construction enclosures such as polyethylene bags or wrappings.
Another is to provide additional accelerator to the adhesive composition employed such that while migration will occur, sufficient accelerator will remain in the adhesive composition to ensure cure of the anaerobic resin within normal time periods. The increased accelerator level should be accompanied by a corresponding increase in inhibitor level.
With reference now to Fig. 2, there may be included as part of the composite construction an interlayer 22 to improve flexural bond strength in structural adhesive applications.
One property which must exist in many structural adhesive applications is a high degree of torsional shear which is to a great extent unrelated to lap shear.
Torsional or flexural resistance to failure may be important to many end use applications.
To provide increased torsional shear there may be provided an interlayer 22 which will combine with or be bonded to the provided pressure sensitive anaerobic resin system upon cure.
There can, for instance, be provided a self-supporting film such as a polyester, like Mylar ("Mylar" is a Registered Trade Mark), which will, under curing conditions employed, establish a bond to the over and undercoated layers of pressure sensitive adhesive providing an anaerobic resin system which will bond to the interlayer 22 and to the substrates to be joined to provide flexural strength to the joint.
As an alternative, there may be provided in the interlayer 22 an anaerobic resin which enhances the bond strengths upon cure while also improving torsional strength.
Yet another alternative is to provide a perforated web which may or may not be bonded to the anaerobic resin upon cure. In this instance, the perforations and the like become an integral part of the total cured polymer system to add desired flexural strength.
With reference now to Fig. 3, there is shown a configuration for a self-wound tape construction. All of the parameters set for the constructions described above apply.
Where a paper web 20 is used, it may, depending on packaging and service conditions, preferentially be dual coated with polymeric materials 16 upon which there is provided the differential release surfaces 18. In the alternative, there may be simply provided a single polymeric film 16 having applied differential release surfaces 18 and 18a.
In either event, it is preferred that the bond of the pressure sensitive layer including an anaerobic resin system have the lowest bond to release layer 18 as compared to release layer 1 8a to provide the most convenient transfer characteristics.
As indicated, with reference to Figs. 1, 2, 3 and 4 the differential release surfaces 18 or 18 and 18a necessary for adhesive transfer can be provided by varying the nature of the release surface, typically a silicone release coating, or through their method of fabrication.
While nowise limiting, where common silicone release materials are employed, the adhesive compositions, independent of their ultimate configuration, are typically applied from solvent systems or by other suitable film casting techniques. By applying the adhesive to one release surface, a greater bond will be created between the adhesive layer and the release surface due to some interaction while the second release surface has a relatively weak physical bond to the provided pressure sensitive adhesive layer.
Pressure sensitive adhesive layers provided in accordance with the present invention may be applied by a variety of known means. In either event, the total layer is applied through a solvent system, whereas the second release coated layer is typically applied subsequent to solvent evaporation.
Another method of providing the differential release surfaces is to have the surface which is to be of lowest release value paper coated with a matte-finished polymeric layer, such as polyethylene, to which the release coating is applied followed by application of the adhesive layer. Because of interaction during solvent evaporation, the applied film becomes more strongly adherent to the release surface associated with the matte-finished polymer. The opposed release coating is applied to a smooth finished polyethylene or other polymeric coating. The bond only being physical, provides the required differential release surfaces.
With reference now to Fig. 4, there is provided yet another construction useful
in accordance with the present invention. In that construction, there is employed a
heterogeneous combination of a pressure sensitive adhesive 24 associated with an
anaerobic adhesive 14 which may also be pressure sensitive in nature.
This is to meet the situation where there is required a bond between the
surfaces to be bonded which is initially higher than that which can be provided by
an anaerobic pressure sensitive adhesive prior to cure of the contained anaerobic
resins.
Anaerobic resins do have a diluent effect on whatever polymer in which they
are dissolved or otherwise combined. As a result, many conventional pressure
sensitive adhesives have higher bond strength than can be achieved when
combined with anaerobic resin.
To meet this need, there is contemplated the use of the heterogeneous
combination in which a high bond strength pressure sensitive adhesive is employed
to fixture two substrates together under high load or shear condition. There is also
provided a viscoelastic anaerobic resin layer 14 which will not dilute the pressure
sensitive adhesive and, upon cure, will provide the ultimate bond strength between
the two surfaces. The viscoelastic anaerobic resin layer is of a nature that it has
sufficient cohesive strength to preclude film splitting during transfer so that
portions of the anaerobic resin will not remain with the release liner(s) during the
adhesive transfer operation.
In this combination, the two systems provided may exist as alternate bars 24
and 14, as shown in Fig. 4, or as alternate dots or a heterogeneous system capable
of laying down immiscible polymers by conventional manufacturing techniques.
What is also important in the heterogeneous combination is that the anaerobic
adhesive layer, whether it be anaerobic alone or also pressure sensitive in nature,
have sufficient integrity and viscosity per se or through the addition of fillers so as
not to dilute the pressure sensitive adhesive.
In this combination there may be achieved high initial bond strength due to
the presence of the undiluted pressure sensitive adhesive and high ultimate bond
strength as a consequence of the subsequent cure of the anaerobic resin system.
The configuration shown in Fig. 4 can be employed for the constructions shown in
Figs. 1 and 2 or for Fig. 3, upon the addition of another release layer (not shown) to
the exposed side of paper layer 20.
Independent of the construction employed, care must be taken in preparing
the tape and sheet construction to prevent premature cure or loss of activity during
shelf life.
The anaerobic pressure sensitive adhesive compositions employed in the
fabrication of sheets and tapes in accordance with this invention normally contain
sufficient quantities of anerobic resins in order that the thermoplastic resin system
employed will not interfere to any great degree with thorough and complete cross
linking or curing of the anaerobic resin system and to provide desired bond upon
cure. The anaerobic pressure sensitive adhesive compositions must contain. based
on a total weight of anaerobic resin system and the thermoplastic resin system and
if present, tackifiers, from 4 to 90 percent by weight total anaerobic resins,
preferably from 35 to 60 percent by weight.In small quantities, the anaerobic resin
upon cure immobilises the balance of the composition to prevent "creep' or sag although lap shear may be relatively low, e.g. 100 psi. At higher concentrations, high lap shear bonds in excess of 1000 psi may be easily realised.
For most applications, care should be taken in preparing the anaerobic pressure sensitive adhesives of this invention 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 resin system, typically picked up from the vessels and systems used in their production.
If allowed to remain in the composition, the transition 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, sufficient tackiness may be retained so that pressure sensitive adhesive properties will not be destroyed, but the ability of the composition to cure may diminish to a degree that ultimate bond strength will not be structural. That is, a cross-linked latticework will not develop throughout the applied pressure sensitive composition and cohesive failure may result. If necessary, this effect 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 external to the pressure sensitive anaerobic composition of the invention.
One way to cope with the metal ions is to scavenge them prior to or following their admixture 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 solvents which are employed for dissolving the constituents of the pressure sensitive compositions are nonpolar 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 toluene, isopropyl alcohol and mixtures thereof.
If the constituents of the pressure sensitive adhesive composition are properly scavenged, the active metals can be reintroduced, but in another form. Rather than being active in the composition, their effect may be rendered latent by encapsulating them in microspheres such that they will not be in contact with the peroxy initiator until the microspheres are ruptured upon the application of pressure to react with the peroxy compounds to accelerate cure.
An alternative route to prevent premature cure during shelf life or storage is to encapsulate the peroxy compound alone or with its accelerators. Then the active metals or metal ions can be left in the pressure sensitive adhesive composition without fear that premature cure or deactivation will occur.
With care being taken to isolate the peroxy compound of the catalyst system by encapsulation or the elimination or isolation of active metal or metal ions, the pressure sensitive adhesive ingredients can be cast into a film on release coated surfaces without fear that premature cure or deactivation will occur.
Coating weight of the cast pressure sensitive layers may be varied over a wide range with the general object of achieving surface wetting for a strong and tenacious bond. Typical coating weights are, after solvent evaporation, from 20 to 80 grams of net solids per square meter.
What is required is 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 disruption of the anaerobic pressure sensitive adhesive layer. It is desirable for any given application 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 the anaerobic resin and the surfaces will be bonded together. If the coating is too thick, longer cure times will be required or there would be formed an internal weakness which could result in cohesive failure of the partially cured resin.
As an alternative, by employing microencapsulated accelerators within the pressure sensitive adhesive composition, greater cure rates and complete cure can be realised. Surface priming with an active accelerator may also be employed alone or in combination with the latent organonitrogen compounds.
The surface primers are in general, compounds containing either an or a
S -N=C group. Many are disclosed, for instance, in U.S. Patent No. 3,625,930. The preferred compounds are substituted thioureas having the general formula:
wherein each R6, R7, Ra and Ra is individually a hydrocarbon group containing up to 10 carbon atoms, preferably, alkyl, aryl, or alkenyl and most preferably containing up to 6 carbon atoms. Alternatively Ra can be a hydrogen atom.
Illustrative compounds include tetramethyl thiourea, tetraethyl thiourea, tetrabutyl thiourea, dimethyl diethyl thiourea, trimethyl thiourea and the like. Tetramethyl thiourea is the preferred primer.
In substance, the total anaerobic pressure sensitive adhesive system acts as a binding agent for the anaerobic monomers until cure is complete and then the residual constituents only serve as fillers for the system. However, higher thermoplastic polymer system concentrations can also aid in improving flexural strength of the cured composition at some potential sacrifice in shear strength.
The types of products typically formed are the self-wound tapes, the surface of the supporting tape having differential release properties, sandwich constructions in which the anaerobic pressure sensitive adhesive composition is contained between two carrier liners having differential release surfaces, and similar products. All that is necessary is that the anaerobic pressure sensitive adhesive layer be transferable to a substrate and completely separated from its carriers to leave only an anaerobic pressure sensitive adhesive in contact with the substrate to be bonded to another substrate.
In the following Examples, one or more of the following anaerobic resin systems were employed for the formulation of anaerobic pressure sensitive adhesive compositions.
Resin I
Approximately 75% of a reaction product of two moles of hydroxypropyl methacrylate with one mole of methylene-bis-phenyl-4,4'-diisocyanate and 25% triethylene glycol dimethacrylate.
Resin II
A polymer formed by hydroxypropyl methacrylate capping of a 1:1 adduct of toluene diisocyanate and hydrogenated 2,2-bis(4-hydroxyphenyl) propane.
The following test methods were employed in evaluating the pressure sensitive properties and properties of the cured end products. In determining pressure sensitive adhesive load bearing properties, the adhesive composition was cast on a suitable support such as paper or Mylar ("Mylar" is a Registered Trade Mark).
Static Shear Strength-Federal Test Method Std. No. 147B, Method 20.1 (Load
250 grams 0.25 in2) in minutes.
180C Peel (dynamic-12"/min)-ASTM D-100/68 in Ibs.
Polyken Tack Test-ASTM D-2979-71, in grams.
Loop Tack-Tape and Label Manufacturers Institute-in lb/in2-Modified by
using 8"xl" sample.
Vinyl equivalent number is the ratio of molecular weight to the number of ethylenically unsaturated bonds in the molecule.
Unless otherwise indicated all measurements set forth in the specification and the Examples were determined at one atmosphere pressure and 25"C. In determining physical properties of an adhesive layer relative humidity was 50+2 /,,.
Except as otherwise stated the tackifier used in the Examples was Cellolyn 21 80H, an abiatic acid resin derivative manufactured and sold by Hercules
Incorporated.
Example 1
There was prepared a pressure sensitive adhesive composition of the formula shown in Table I.
TABLE I
Component V0 by weight
Resin I 40.50
Resin II 13.50
Thermoplastic polyvinylpyrrolidone copolymer 17.55
Thermoplastic acrylic resin known as RA-1753, manufactured by Monsanto Chemical Company 17.55
Tackifier 8.10
Hydroquinone 0.027
Saccharin 1.62
Luperox (hydroperoxide) 1.20
The ingredients were dissolved in a toluene-ethyl acetate blend as the solvent to a 55% by weight solids content and coated to a thickness of 3 mil on a first release liner having a first release surface. After solvent evaporation, there was applied a second release liner having a release surface of lower adhesion to the formed pressure sensitive adhesive layer.The curable anaerobic pressure sensitive adhesive layer of approximately 2 mils thickness had an initial static shear of 18 minutes at a 250 gram load per 0.25 square inch and a 1800 peel value of 4.8 Ibs/in width. Polyken tack value was 850 grams and loop tack 3 lbs/in2.
Clean, rolled steel plates measuring l"x3" were surface coated with tetramethyl thiourea as the primer accelerator. The pressure sensitive adhesive was transferred to one plate and the other applied in overlapping relationship. Overlap was about 2 inches. Fixturing time was 18 minutes, and after 3.5 hours, the lap shear tensile strength was 1200 psi.
Example II
There was prepared a base composition as shown in Table II.
TABLE II Component % by weight
Resin I 41.67
Resin II 13.89
Thermoplastic polyvinylpyrrolidone copolymer 18.05
Thermoplastic acrylic resin known as RA-1753 manufactured by Monsanto Chemical Company 18.05
Tackifier 8.33
The above composition was catalysed with varying amounts of Luperox, a hydroperoxide, as the contained initiator and saccharin, when used, as the contained accelerator. In each test the formulated pressure sensitive adhesive with the initiator and accelerator, to the extent present, was transferred to cold rolled steel plates (1010--1020), previously cleaned in perchloroethylene and then surface primed with tetramethyl thiourea as an additional accelerator and after adhesive lamination the plates secured to each other in overlapping relation. Initial securement was achieved by virtue of the pressure sensitive adhesive nature of the transferred film. The plates measured 0.5 to 3.5 inches. The overlap of plates was 0.5xl inch. For the test, fixture time is the time required for one plate of the laminate to become immobile with respect to the other. The results are shown in
Table III.
TABLE III
Lap shear
Fixture After 24 hrs.
Catalyst system, % by weightibi time (psi)
Test Initiator Accelerator Total min psi
0.1 0 0.1 120 320
2 0.2 0 0.2 65 555
3 0.3 0 0.3 39 740
4 0.4 0 0.4 19 565
5 0.5 0 0.5 30 495
6 0.1 0.1 0.2 55 550
7 0.3 0.1 0.4 37 825
8 0.4 0.1 0.5 22 735
Control 0 0 0 - 50 'b'Based on total dry weight of anaerobic resins, thermoplastic resins and tackifier.
Example III
Using a procedure comparable to that described in Example I there was prepared an anaerobic pressure sensitive adhesive composition as shown in Table
IV.
TABLE IV
Component V by weight
Resin I 49.7
Resin II 17.9
Thermoplastic acrylic resin known as RA-1753
manufactured by Monsanto Chemical Company 26.5
Tackifier 2.6
Saccharin 2.0
Luperox 1.3
The composition cast into a film of approximately 2 mils in thickness and in a
solvent free state displayed the physical properties shown in Table V.
TABLE V
Static shear 10 minutes 180 peel 5 Ibs
Polyken Tack 1100 grams
Loop tack 3.5 lbs/in2
Example IV
There was prepared an anaerobic pressure sensitive adhesive composition as
shown in Table VI.
TABLE VI
Component % by weight
Epoxylated bisphenol A dimethacrylate 35.0
Thermoplastic polyvinylpyrrolidone copolymer 30.5
Thermoplastic acrylic resin known as RA-1753 manufactured by Monsanto Chemical Company 30.5
Saccharin 2.8
Luperox 1.25
Hydroquinone 0.001
When cast to a film, of approximately 2 mil thickness, the essentially volent
free film had the physical properties shown in Table VII.
TABLE VII
Static shear 180 minutes 180 peel 2 Ibs
Polyken tack 725 grams
Loop tack 1.6 ibs/in2 Example V
There was prepared an anaerobic pressure sensitive adhesive of the
composition shown in Table VIII.
TABLE VIII
Component % by weight
Resin I 40.5
Resin II 13.5
Thermoplastic polyvinylpyrrolidone 35.2
Tackifier 8.1
Saccharin 1.6
Luperox 1.1
When cast into a film of approximately 2 mils thickness the essentially solvent free film had the physical properties shown in Table IX.
TABLE IX
Static shear 10 minutes 1800 peel 5 lbs
Polyken tack 1000 grams
Loop tack 3 Ibs/in2
Example VI
There was prepared an anaerobic pressure sensitive adhesive of the
composition shown in Table X.
TABLE X
Component % by weight
Triethylene glycol dimethacrylate 9
Thermoplastic polyvinylpyrrolidine copolymer 34.4
Thermoplastic acrylic resin known as RA-1753
manufactured by Monsanto Chemical Company 34.4
Tackifier 15.8
Saccharin 3.2
Luperox 3.2
When cast into a film of approximately 2 mil thickness, the essentially solvent
free film had the physical properties shown in Table XI.
TABLE IX
Static Shear 54 minutes 1800 peel 2 Ibs
Polyken tack 700 grams
Loop tack 2 Ibs/in2
Following the procedure of Example II, lap shear strength were determined prior to cure and following cure. Lap shear after 24 hours cure with use of the primer was 500 /n greater than the lap shear determined without cure of the contained anaerobic resin.
WHAT WE CLAIM IS:
1. An anaerobic pressure sensitive adhesive stock comprising:
(a) a first release coating on a self-supporting release liner;
(b) a transferable and curable pressure sensitive adhesive layer having one surface in contact with said first release coating, the pressure sensitive adhesive layer comprising;
(i) from 9 to 95 percent by weight of the layer of a thermoplastic resin system
containing at least one thermoplastic polymer which is a vinyl
homopolymer, a vinyl copolymer, a polyurethane, a polyester, a
polyamide, an acrylic polymer, a natural elastomer, or a synthetic
elastomer;;
(ii) from 4 to 40 percent by weight of the layer of a first anaerobic resin
system, containing at least one curable anaerobic resin having a viscosity
from 5 to 1000 cps at 250C and a vinyl equivalent number from 80 to 2000
and from 0 to 80 percent by weight of the layer of a second anaerobic
resin system containing at least one curable anaerobic resin having a
viscosity greater than 1000 cps at 250C, at least one anaerobic resin in the
first and second anaerobic resin system containing at least two
polymerisable acrylic ester groups, each individually having the formula:
wherein R2 is a hydrogen, or a halogen atom or a lower alkyl group
containing from 1 to 4 carbon atoms, the anaerobic resins being present
in an amount of from 4 to 90 percent by weight of the layer: : (iii) from 0.1 to 10 percent by weight of the layer of a peroxy initiator to
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
1. An anaerobic pressure sensitive adhesive stock comprising:
(a) a first release coating on a self-supporting release liner;
(b) a transferable and curable pressure sensitive adhesive layer having one surface in contact with said first release coating, the pressure sensitive adhesive layer comprising;
(i) from 9 to 95 percent by weight of the layer of a thermoplastic resin system
containing at least one thermoplastic polymer which is a vinyl
homopolymer, a vinyl copolymer, a polyurethane, a polyester, a
polyamide, an acrylic polymer, a natural elastomer, or a synthetic
elastomer;;
(ii) from 4 to 40 percent by weight of the layer of a first anaerobic resin
system, containing at least one curable anaerobic resin having a viscosity
from 5 to 1000 cps at 250C and a vinyl equivalent number from 80 to 2000
and from 0 to 80 percent by weight of the layer of a second anaerobic
resin system containing at least one curable anaerobic resin having a
viscosity greater than 1000 cps at 250C, at least one anaerobic resin in the
first and second anaerobic resin system containing at least two
polymerisable acrylic ester groups, each individually having the formula:
wherein R2 is a hydrogen, or a halogen atom or a lower alkyl group
containing from 1 to 4 carbon atoms, the anaerobic resins being present
in an amount of from 4 to 90 percent by weight of the layer:: (iii) from 0.1 to 10 percent by weight of the layer of a peroxy initiator to
initiate cure of the contained anaerobic resins upon the substantial
exclusion of oxygen; and
(iv) from 0 to 10 percent by weight of the layer of an organonitrogen
compound as a latent accelerator in the cure of the contained anaerobic
resins, and the pressure sensitive adhesive layer providing a static shear strength of at least 10 minutes at a 250 gram load per 0.25 square inch, a 1800 peel value of at least 2 pounds; a Polyken tack of at least 700 grams and a loop tack of at least 1.5 Ibs per in2 prior to cure of the anaerobic resin system; these characteristics being measured at 250C, I atmosphere pressure and at a relative humidity of 50+2 Sn; and
(c) a second release coating on a self-supporting release liner in contact with the opposed surface of the transferable pressure sensitive adhesive layer, the bond of the first release coating to the transferable pressure sensitive adhesive layer being less than the cohesive strength of the pressure sensitive adhesive layer and exceeding the bond of the second release coating for the pressure sensitive adhesive layer to permit the pressure sensitive adhesive layer to be preferentially separated from the second release coating for application and bonding to a substrate prior to separation of the pressure sensitive adhesive layer from the first release coating without cohesive failure of the pressure sensitive adhesive layer.
2. An anaerobic pressure sensive adhesive stock as claimed in Claim 1 wherein component b(i) also includes a tackifier.
3. An anaerobic pressure sensitive adhesive stock as claimed in Claim 1 or 2 wherein pressure sensitive adhesive layer (b) is a homogeneous mixture comprising (i), (ii), (iii) and, if present (iv).
4. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 3 wherein the anaerobic resin having a viscosity from 5 to 1000 cps at 250C is triethylene glycol dimethacrylate, epoxylated 2,2-bis-(4-hydroxyphenyi) propane dimethacrylate, or a mixture thereof.
5. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 4, wherein the anaerobic resin having a viscosity greater than 1000 cps at 250C is a reaction product of two moles of hydroxypropyl methacrylate and one mole of methylene-is-phenyl-4,4'-diisocyanate, a polymer formed by hydroxypropyl methacrylate capping of a 1:1 adduct of toluene diisocyanate and hydroxylated 2,2bis (4-hydroxyphenyl) propane.
6. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 5 wherein the vinyl copolymer is a copolymer containing vinylpyrrolidone.
7. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 6 wherein the organonitrogen compound is saccharin.
8. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 7, wherein the first release coating and the second release coatings are contained on opposed sides of a common release liner and the stock is formed into a roll, the second release coating being on the undersurface of the release liner.
9. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 7 wherein the first and second release coatings are contained on separate release liners.
10. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 9 wherein the pressure sensitive adhesive layer including the curable anaerobic resin system comprises a first pressure sensitive adhesive layer separated at least in part from a second pressure sensitive adhesive layer by an interlayer to which the two pressure sensitive adhesive layers are secured, the interlayer providing support for the first and second pressure sensitive adhesive layers.
11. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims
I to 9 wherein the pressure sensitive adhesive layer is heterogeneous and which includes pressure sensitive adhesive segments containing at least one of the thermoplastic polymers contiguous to viscoelastic anaerobic resin segments, the viscoelastic anarobic resin segments having sufficient cohesive strength to prevent film splitting during transfer.
12. An anaerobic pressure sensitive adhesive stock as claimed in any of Claims 1 to 11 wherein the anaerobic resins are present in an amount of from 35 to 60 percent by weight based on the total weight of the layer.
13. An anaerobic pressure sensitive adhesive stock substantially as described with particular reference to any of the Examples.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/722,872 US4039705A (en) | 1974-10-07 | 1976-09-13 | Anaerobic pressure sensitive adhesive stocks |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1566820A true GB1566820A (en) | 1980-05-08 |
Family
ID=24903768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB38110/77A Expired GB1566820A (en) | 1976-09-13 | 1977-09-13 | Anaerobic pressure sensitive adhesive stocks |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2873177A (en) |
GB (1) | GB1566820A (en) |
-
1977
- 1977-09-12 AU AU28731/77A patent/AU2873177A/en not_active Abandoned
- 1977-09-13 GB GB38110/77A patent/GB1566820A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
AU2873177A (en) | 1979-03-22 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] |