Semi-Solid Primer Composition

(19) United States US 20030164222A1 (12) Patent Application Publication (10) Pub. No.: US 2003/0164222 A1 Kneafsey et al. (43) Pub. Date: Sep. 4, 2003 (54) SEMI-SOLID PRIMER COMPOSITIONS (76) Inventors: Brendan J. Kneafsey, Dublin (IE); John Guthrie, Kildare (IE) Correspondence Address: Henkel Loctite Corporation 1001 Trout Brook Crossing Rocky Hill, CT 06067 (US) (21) Appl. No.: 10/276,421 (22) PCT Filed: May 30, 2001 (86) PCT No.: PCT/IE01/00070 (30) Foreign Application Priority Data May 31, 2000 (IE) ......................................... .. 2000/0439 Publication Classification (51) Int. Cl.7 ...................................................... .. C09J 5/04 (52) U.S. Cl. ........................... .. 156/314; 524/387; 401/55 (57) ABSTRACT A composition comprising at least one carrier solvent, at least one primer component and at least one gelling or solidifying agent is provided. The composition according to the invention may he provided in the form of a soft solid, for example, in the form of a stick. A two-part adhesive system is also provided, comprising at least one anaerobic product and a composition comprising at least one carrier solvent, at least one primer component Where the primer component is a cure promoting agent and at least one gelling or solidifying agent. A two-part adhesive system comprising a cyanoacry- late adhesive and a composition having at least one carrier solvent, at least one primer component and at least one gelling or solidifying agent is also provided. A pack is provided comprising a shaped mass of a composition which includes at least one carrier solvent, at least one primer component and at least one gelling or solidifying agent, and a container (1) for the composition which has a mechanism for expelling the shaped mass. Patent Application Publication Sep. 4, 2003 US 2003/0164222 A1 US 2003/0164222 A1 SEMI-SOLID PRIMER COMPOSITIONS FIELD OF THE INVENTION [0001] The present invention relates to semi-solid primer compositions, particularly well suited to promoting the bonding of substrates, such as those constructed of non- polar or highly crystalline materials or for promoting the cure of otherwise slow curing products. BRIEF DESCRIPTION OF RELATED TECHNOLOGY [0002] Primers have long been used to promote the bond- ing of substrates which otherwise are not readily bonded together to a satisfactory extent by adhesive alone. The primer promotes adhesion to the surface. Materials which do not bond satisfactorily with adhesive alone are often referred to as “difficult-to-bond”. Where both surfaces to be bonded are difficult-to-bond, both may be primed prior to attempted adhesion. Primer is applied to the surfaces to be bonded, to “activate” or “prime” the surface for reception of later applied adhesive. Certain primer components are thus often referred to as adhesion-promoting agents” or “adhesion- promoting primers” as they can promote subsequent adhe- sion of substrates with a conventional adhesive. [0003] The types of surface (substrate) which are difficult- to-bond with adhesives, especially with cyanoacrylate adhe- sives, are widely recognised and include non-polar or highly crystalline substrates. [0004] Non-polar substrates typically have low surface energy which is due to an absence of polar groups on the surface to be bonded. Polar groups are generally thought to raise the surface energy to the level needed to give satis- factory adhesion with conventional adhesives. [0005] Non-polar substrates are often constructed of poly- olefins in particular linear polymers of simple olefins, such as polyethylene, polypropylene, polybutene, polytetrafluo- roethylene and the like, including their copolymers; poly- acetals, plasticised PVC (polyvinyl chloride), polyurethane, EPDM (ethylene-propylene diamine monomer) rubber, ther- moplastic rubbers based on vulcanised polyolefins and the like. [0006] Difficult-to-bond materials which are widely rec- ognised include those with a waxy or paraffin-like surface character; a low critical surface tension of wetting; and which may have at their surface a weak boundary layer. [0007] It will be appreciated therefore, that the main function of an adhesion-promoting primer is to promote adhesion in cases where curing (polymerization) occurs readily but where adhesion may not take place at all or to a desired extent. As stated above this a scenario typical of cyanoacrylate adhesives. [0008] A second function of a primer composition may be to promote cure of the curable composition. Primer compo- nents which have this function are referred to herein as “cure-promoting”. In some instances curable compositions may provide a desired degree of adhesion but achieve adhesion at an undesired rate. For example the curable composition may cure to give sufficient adhesion but may do so only very slowly so that [text missing or illegible when filed] bonded must be kept in contact over a period of hours or even longer. While relatively long cure times are Sep. 4, 2003 desirable in some instances, a shorter cure time without deleteriously affecting bond strength is desirable for many other purposes. Slow cure is a property associated with many products including those termed “anaerobic” products. These are polymerizable products which are stable and remain unpolymerized in the presence of air (oxygen in particular) and which tend to cure rapidly in the absence of air. [0009] It is normal for an initiator component of a cure system to be excluded from the primer composition so that the primer composition is absent an initiator component. [0010] It is known to provide cure-promoting primer com- positions for the purpose of decreasing cure times. In such cases the cure-promoting primer is applied (usually by application in solution form as described below) to the desired substrate and the curable composition is then applied to the surface treated with primer. The cure-promoting primer acts to decrease cure times by accelerating the cure of the composition but without for example diminishing bond strength of adhesives, or sealing capability of sealants. [0011] It is possible that any given primer may have dual functionality i.e. promoting adhesion and promoting cure though it is usual for primers to be classified as having one of these main functions. [0012] The present invention is concerned with primers in general including both adhesion-promoting, and cure-pro- moting primers. [0013] Application of a primer composition which com- prises a primer component in a solvent to a substrate to be primed is typically by way of a brush or some such other applicator, to form a layer or coating on the surface. The coating is then typically dried, or allowed to dry for a period, before bonding with adhesive is attempted, and to ensure that the surface is properly primed. In this respect at least for adhesion-promotion primers the solvent is normally a vola- tile one i.e. evaporates readily at room temperature leaving behind the primer component. The solvent does not there- fore interfere with the [text missing or illegible when filed] adhesion process—acting only as an inert carrier solvent for placing the adhesion-promoting primer compo- nent on the substrate. For cure-promoting primers the sol- vent may be a polymerizable monomer or oligomer which may take part in the polymerization process during bonding. Accordingly these solvents are not usually considered “inert” in the sense that the participate in the subsequent bonding process. They do however act as carrier solvents for the primer component. Monomeric or oligomeric solvents do not tend to evaporate to any appreciable extent after application so that they are not normally considered volatile. These compositions will most usually be liquid also. [0014] The nature of such primer compositions can result in difficult handling for example unwanted spillage, run-on of the coating applied, and the cumbersome task of having to use an applicator or brush. It is desirable to provide a more easily handled and potentially safer form of primer compo- sition. [0015] Primer compositions typically include at least one priming compound or agent which is the primer component of the composition. Various primer components and primer compositions are described below. [0016] It is desirable therefore to provide a primer com- position in a consumer-friendly manner to allow for ease of US 2003/0164222 A1 handling etc. Presenting primer compositions in consumer- friendly forms and/or packages is a difficult task as the primer component must not have its adhesion- or cure- promoting capabilities deleteriously affected by the form, or package, in which it is presented for use. [0017] Various types of adhesive compositions are avail- able commercially ranging from low viscosity (liquid) com- positions to gels and other medium viscosity compositions to higher viscosity products such as pastes, and soft-solid products. [0018] It is known to thicken or gel adhesive such as cyanoacrylate adhesives with polymethylmethacrylate or thixotropic agents such as those described in U.S. Pat. Nos. 4,447,607 and 4,533,422 (Litke). [0019] It is also known for instance to formulate adhesives as “stick” compositions. The patent literature on stick adhe- sives is extensive and covers a broad range of adhesive types, from emulsion adhesives through solvent based adhe- sives, to contact adhesives, as well as gelling and solidifying additives for the preparation of the sticks ranging from thermosetting through natural polymers to inert fillers. A well known example of one such adhesive stick sold under the trade name PrittStickTM by Henkel KGaA which is an emulsion-based adhesive. [0020] In the patent literature the following patents typify the type of composition in which adhesive components have been formulated as soft-solids, and more particularly sticks. U.S. Pat. No. 5,433,775 discloses an adhesive stick consist- ing of a water based preparation of starch derivatives and a soap gel as the shaping gel-forming component. See also U.S. Pat. No. 5,371,131. [0021] U.S. Pat. No. 3,846,363 relates to an adhesive crayon composition containing a sorbitol-benzaldehyde reaction product as an additive. U.S. Pat. No. 4,639,475 discloses an adhesive stick composed of the reaction product of sorbitol and/or xylitol and benzaldehyde as the gel- forming composition together with an adhesive resin which is the reaction product of methyl vinyl ether/maleic acid anhydride copolymers with partially neutralised acid phos- phate esters of non-ionic wetting agents of the lower alky- lene oxide adduct type. [0022] Japanese unexamined patent application laid open (Kokai) 51-103939 describes a stick-like epoxy adhesive and a stick-like epoxy hardening agent which is used there- with. The sticks are obtained by suitably compounding gelling agent or/and water is and/or organic solvent with liquid or solution type epoxy adhesive and epoxy hardening agent. [0023] DE 199 57 677 A1, published after the priority date of the present application, of Henkel KGaA describes a cyanoacrylate adhesive, coating or sealing material which also contains at least one condensation product of an alde- hyde or ketone with a polyol. [text missing or illegible when filed] may be in stick form. [0024] While a wide variety of sticks have been described, no prior publication has suggested that a primer composition could be made in stick form at all, let alone while main- taining its primer functionality. It would therefore be advan- tageous to provide a primer composition in stick form. SUMMARY OF INVENTION [0025] The present invention provides a primer composi- tion suitable for formulation/presentation in stick form. The Sep. 4, 2003 primer composition may promote subsequent bonding of non-polar or highly crystalline substrates such as polyole- fins, or similar plastics substrates with low surface energy, with adhesive such as cyanoacrylate adhesives. Alterna- tively or additionally to being adhesion-promoting, the composition may act as a cure-promoting agent to promote cure of the curable product depending on the primer com- ponent chosen. The compositions allow for ease of applica- tion and/or handling, and allow for accuracy in application without running on of the primer composition. [0026] [0027] [0028] (a) at least one carrier solvent; In particular the present invention provides: a composition including: [0029] (b) at least one primer component; and [0030] (c) at least one gelling or solidifying agent. [0031] The composition is easily cast in stick form and is very useful in his respect. The present invention thus pro- vides primer compositions typically for use with an adhe- sive. In particular the adhesion-promoting primer composi- tions of the present invention have been demonstrated as being effective adhesion-promoting agents for example as a cyanoacrylate primer composition which is particularly use- ful for promoting adhesion of polyolefins. The cure-promot- ing compositions within the present invention have been shown to be effective as cure-promoting agents particularly with [text missing or illegible when filed] adhesives and sealants. [0032] More particularly, the present invention relates to the preparation and use of primer compositions in stick form, to promote the bonding of non-polar or highly crys- talline substrates with adhesives, especially with cyanoacry- late adhesives or alternatively to promote cure of curable products in particular to promote the cure of anaerobic products. [0033] The curing or polymerization of a film of adhesive such as cyanoacrylate, between two materials, does not necessarily result in a strong bond, particularly if the mate- rials are non-polar, and if the polymerization of the adhesive is excessively rapid, a very weak bond or no bond will result. The adhesion-promoting compositions of the present inven- tion help to alleviate this non-bonding problem. The cure- promoting compositions of the present invention have been found to promote (accelerate) curing of otherwise slow curing products. [0034] Suitably the composition is the form of a soft-solid. The composition may be formulated in stick form, for example by casting. [0035] Suitably component (a) the carrier solvent com- prises an organic solvent in which the primer component is stable. Component (a) may be an organic solvent such as ethanol, methanol, acetone, methyl ethyl ketone, 1,1,1- trichloroethane, 1,1,2-trichloro-1,2,2,-trifuoroethane or mix- tures thereof with each other or with other solvents such as an azeotropic mixture of 1,1,2-trichloro-1,2,2,-trifluoroet- hane with acetone. Desirably the solvent is ethanol. The solvent is desirably an inert carrier solvent where the primer composition is an adhesion-promoting one. [0036] The function of the solvent is to provide a suitable concentration of the primer component so that a coating of US 2003/0164222 A1 selected thickness can be applied to a surface. Therefore, any common solvent in which the primer component is stable will suffice. The solvent will usually dissolve the primer component though dissolving is not essential provided the solvent acts to provide a dilute (and thus disperse) form of the primer component for subsequent application. Certain active primer components used in this invention [text missing or illegible when filed] adhesion on non-polar and highly crystalline substrates While certain others pro- mote curing of curable products such as anaerobic adhe- s1ves. [0037] Component (c) is suitably the condensation prod- uct of the reaction of at least one aldehyde and/or ketone with a polyol. [0038] Suitable polyols include those with at least one of a 1,2-diol, 1,3 diol or 1,4 diol structure. The diols may additionally have other groups such as ether, acid, amido, cyano, hemiacetal or halogen. Examples of suitable polyols include 1,2-ethandiol, 1,3-propandiol, 1,2-propandiol, 2,3- butandiol, 1,4-butandiol, 2,2-dimethyl-1,3-propandiol, 2,2- bis(hydroxymethyl)-1,3-propandiol, 2-(bromomethyl)-2- (hydroxymethyl)-1,3-propandiol, 1,3,4-butantriol, 1-phenyl-1,2,3-propantriol, 1,2-hexandiol, neopentylglycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3-propan- diol, hexantriol-(1,2,6), 2-(2-hydroxyethoxy)butan-1,3,4- triol, glycerine, di and polyglycerine, diglycerindiacetate, trimethylolpropane, di-(trimethylolpropane), trimethylole- thane, pentaerythritol, bicyclo [2.2.1] heptane-2,3,5,6-tetrol, 2,2,3,3-tetrahydroxybutandiacid, dipentaerythritol, sorbitol, formitol, xylitol, inositol, glucitol, glucose, saccharose/su- crose, starch, cellulose, ascorbic acid, partially or fully hydrolysed polyvinylacetate, 9,10-dihydroxy stearic acid methyl ester, diacetylsorbitol and methylglyceride. [0039] Most suitable polyols are sorbitol, xylitol and man- nitol especially sorbitol. [0040] Suitable aldehyde or ketones include those which have at least one substituted or unsubstituted aromatic, heteroaromatic or alicylic ring. These polyols may have additional groups such as ether ester, amide, cyano and halogen. [0041] Examples of ketones include cyclopentanone, cyclohexanone, cycloheptanone, 1-(3,3-dimethylcyclo- hexyl)-ethanone, 1-cyclopropylethanone, 3-methyl-5-pro- pylcyclohex-2-en-1-one, dicyclopropylmethanone, 4-tert- butylcyclohexanone, dicyclohexylmethanone, 4-methylcyclohexanone, 1-(1-methylcyclopropyl)-etha- none, (4-chlorophenyl)-cyclopropyl-methanone, 1-(1H-pyr- rol-2-yl)-ethanone, 1-(2,4,6-trimethylphenyl)-ethanone, 1-(2-furanyl)-2-propanone, 1-(2-naphthalenyl)-ethanone, 1-(2-thienyl)-1-propanone, 1-(4-bromophenyl)-ethanone, 1-(4-methoxyphenyl)-ethanone, [text missing or illeg- ible when filed] alenyl)-ethanone, 1,1-diphenyl-2-pro- panone, 1,2-diphenylethanone, 1,3-diphenyl-2-propanone, 1-phenyl-1-butanone, 1-phenyl-1-decanone, 1-phenyl-1- dodecanone, 1-phenyl-1-hexanone, 1-phenyl-1-octanone, 1-phenyl-1-pentanone, 1-phenyl-1-penten-3-one, 1-phenyl- 1-tetradecanone, 1-phenyl-2-butanone, 1-phenyl-2-pro- panone, 1-pyrazinyl-ethanone, 2,2,2-trifluoro-1-phenyl- ethanone, 1-(2-furanyl)-ethanone, 1-(2-pyridinyl)-ethanone, 1-(2-thienyl)-ethanone, 4-chloro-1-(4-fluorophenyl)-1-bu- tanone, 4-phenyl-2-butanone, 1-phenyl-ethanone, bis-(2-hy- droxyphenyl)-methanone, bis-(4-chlorophenyl)-methanone, cyclopentylphenylmethanone, cyclopropyl(4-methoxyphe- Sep. 4, 2003 nyl)-methanone, cyclopropyl-(4-methylphenyl)-methanone, cyclopropyl-2-thienyl-methanone, cyclopropylphenyl- methanone, 1,5 -diphenyl-1,4-pentadien-3-one, phenyl-2-py- ridinyl-methanone, 2-bromo-1-(4-nitrophenyl)-ethanone, 2-naphthalenylphenyl-methanone, 3-chloro-1-phenyl-1-pro- panone, 4-(4-hydroxyphenyl)-2-butanone, 4-(4-methox- yphenyl)-3-buten-2-one, 1-(4-pyridinyl)-ethanone, 1-(4-hy- droxyphenyl)-ethanone, 1-phenyl-1-propanone, 4-phenyl-3- buten-2-one, diphenylmethanone, 1-phenyl-2-butanone, 1-phenyl-2-buten-1-one, bis-(4-methylphenyl)-methanone, 2-methyl-1-phenyl-1-propanone, 2-chloro-1-phenyl-etha- none, cyclopropyl-(4-fluorophenyl)-methanone, 1-(p-meth- oxyphenyl)-2-propanone, cyclohexylphenylmethanone and phenyl-(2-thienyl)-methanone. [0042] The following aldehydes are exemplary for use in the present invention: benzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,6-dichlorobenzaldehyde, 2,4-dini- trobenzaldehyde, 3,4-dichlorobenzaldehyde, 3-fluoroben- zaldehyde, 4-bromobenzaldehyde, 2-methyltetrahydroben- zaldehyde, tetrahydrobenzaldehyde, 2-methyl-5- isopropylcyclopenten-1-aldehyde, 2,2,4- trimethylcyclohexa-4,6-dien-1-aldehyde, 3(4)-methyl-1- propylcyclohexen-3-aldehyde, 1,3(4)-dimethylcyclohexen- 3-aldehyde, 2-methyl-1-propylcyclohexen-3-aldehyde, 3-cyclohexen-1-aldehyde, 2,3,4,5,6-pentafluorobenzalde- hyde, 2,4,6-trihydroxybenzaldehyde, 4-tolylacetaldehyde, 2-methylbenzaldehyde, 4-hydroxybenzaldehyde, 3-methyl- benzaldehyde, 2-hydroxy-1-naphthalaldehyde, 4-methyl- benzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, cin- nam-aldehyde, 3-nitrobenzaldehyde, 2-pentylcinnamaldehyde, 4-diethylaminobenzaldehyde, 4-methoxybenzaldehyde, 2-phenylpropionaldehyde, 2-methoxycinnamaldehyde, 4-methylbenzaldehyde, phe- noxyacetaldehyde, methylpyrrol-2-aldehyde, 2,5-dimethox- ytetrahydrofuran-3-aldehyde, 2,5-dipropyl-3,4-dihydropy- ran-2- , [text missing or illegible when filed] 2,5- diethyl-3,4-dihydropyran-2-aldehyde, 2,5-diisopropyl-3,4 dihydropyran-2-aldehyde, 2,5-dimethyl-3,4-dihydropyran- 2-aldehyde, 2,5-dibutyl-3,4-dihydropyran-2-aldehyde, thiophen-3-aldehyde, indol-3-aldehyde, pyridine-3-alde- hyde, pyridine-4-aldehyde and n-methylpyrrole-2-aldehyde. [0043] Desirable aldehydes include benzaldehyde, 3-chlo- robenzaldehyde and 3-fluorobenzaldehyde. [0044] Particular acetals and ketals include: di-O-ben- zylidenmannitol, di-O-(2-chlorobenzylidene)mannitol, di-O-(4-nitrobenzylidene)mannitol, di-O-(3-fluoroben- zylidene)mannitol, O-benzylidenesorbitol, di-O-benzylide- nesorbitoldiacetate, di-O-(2-chlorobenzylidene)sorbitoldi- acetate, tri-O-(4-chlorobenzylidene)sorbitol, O-benzylidenethreitol, O-benzylidene tartaric acid methyl- ester, O-cyclohexylidenglycerine, O-cyclohexylidene ascor- bic acid and O-benzylidene-9, 10-dihydroxy stearic acid methylester. [0045] Suitably the aldehyde is benzaldehyde, 3-chlo- robenzaldehyde or 3-fluorobenzaldehyde especially benzal- dehyde. Suitably the polyol is sorbitol, xylitol or mannitol especially sorbitol. The condensation product may be di-O- benzylidene mannitol; di-O-(3-fluorobenzylidene) mannitol or di-O-benzylidene sorbitol especially di-O-benzylidene sorbitol. [0046] Component (c) the gelling or solidifying agent is useful for the preparation of a stick from the solutions containing the adhesion-promoting agent. [0047] Suitable gelling agents for inclusion as component (c) include acetals of sugars, particularly acetals of sorbitol, US 2003/0164222 A1 which are particularly effective as gelling agents. One such gelling agent includes di-O-dibenzylidene sorbitol (also referred to simply as dibenzylidene sorbitol) sold by Roquette Freres, France under the trademark DisorbeneTM. Other acetals such as those described above have also been found to be useful. [0048] Acetals of sugars, particularly natural sugars, for example acetals of sorbitol, [text missing or illegible when filed] previously used as gelling agents for the preparation in stick form and these materials are useful in the present invention. [0049] Suitably component (c) the gelling or solidifying agent has a concentration in the solvent from about 0.01% to about 20%, such as about 0.01% to about 15%, typically from about 0.05% to about 10% for example about 0.1% to about 5% by weight by weight based on the total weight of the composition. [0050] It is desirable that a solution of the active primer component in the solvent should have a concentration of about 0.001 to about 30% by weight based on the total weight of the composition for example from about 0.01 to 20% by weight based on the total weight of the composition. Suitable concentrations are about 0.005 to about 15% such as about 0.005 to about 10% by weight based on the total weight of the composition for example about 0.001 to about 5% by weight based on the total weight of the composition such as 0.01 to about 2% by weight based on the total weight of the composition. [0051] Desirably the primer component is an adhesion- promoting agent. [0052] Suitably (where adhesion-promotion is desired) the primer component is selected from: [0053] 1,5-diazabicyclo[4.3.0]non-5-ene having the formula: / N [0054] 1,8-diazabicyclo[5.4.0]undec-7-ene having the for- mula: N / [0055] or 1,5,7-triazabicyclo[4.4.0]dec-5-ene having the formula: NH N U/J Sep. 4, 2003 [0056] (ii) triphenyl phosphine, or [0057] (iii) ethylenediamine or derivatives of ethylenedi- amine according to the formula: R R \ / N— CH2— CH2—N / R R [0058] wherein each R, which may be the same or differ- ent, represents hydrogen, an alkyl, alkenyl or alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, a nitrogen-, sulphur-, or silicon-substituted group having up to 8 carbon atoms or a heterocyclic group having up to 8 carbon atoms which may be unsubstituted or substituted with hydroxy, ether oxygen or sulphur; or [0059] (iv) an imidazole having the formula: R1 [0060] wherein R1 may be hydrogen; an alkyl group that is unsubstituted or substituted with an OH group or with an (alkyl-O)3Si group, wherein the alkyl radical has 1 to 4 carbon atoms; an aryl-alkyl group with 7 to 10 carbon atoms; or an imidazole-CO group, and R2 may be hydrogen or an alkyl, aryl, or aryl-alkyl group with up to 17 carbon atoms, with the condition that one of the substituents R1 or R2 has an aromatic character and X is one of the groups CH—CH or CR3R4 CRSR5 wherein R3, R4, R5 and R6 independently of one another represent hydrogen, an alkyl group with 1 to 4 carbon atoms, or an aryl-alkyl group with up to 17 carbon atoms. [0061] Suitably (again particularly where adhesion pro- motion is sought) the primer component (component contains at least two nitrogen atoms. Desirably the primer component is a compound of the group above, in par- ticular 1,8-diazabicyclo[5.4.0]undec-7-ene. [0062] From among the ethylenediamines labelled as primer component (iii) above, suitable ethylenediamines are those according to the formula give above wherein each R, which may be the same or different, represents hydrogen, an alkyl, alkenyl or alkoxy group, having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, a nitrogen- or sulphur-substituted group having 1 to 8 carbon atoms or a heterocyclic group having up to 8 carbon atoms which may be unsubstituted or substituted with hydroxy, ether oxygen or sulphur. [0063] Desirably ethylenediamine primer components are those wherein at least one R is aryl, or each R is other than hydrogen and at least one R is other than methyl. [0064] Desirably the composition comprises as primer components one or more of: N,N,N‘,N'-tetraethylethylene- diamine and at least one of N‘-benzyl-N, US 2003/0164222 A1 N‘dimethylethylenediamine, N‘phenylethylenediamine, dimethylethylenediamine or aminopropyl-bis(2-ethylhexoxy)-silane. N,N-diethyl- N,N'-dibenzyl-N,N‘- N-2-aminoethyl-3- [0065] Examples of the primer component labelled as (iv) above include the imidazole compounds include: those derivatives where X is —CR3R4—CR3R6- especially 4,5 dihydroimidazole; these compounds may also be referred to as imidazolines. [0066] Desirable primer components include those imida- zole compounds referred to above where X is —CR3R4— CR3R6—, R1) R2) R3), R4, R3 and R6 desirably have the following significance: R1 is hydrogen or a hydroxyalkyl group, R2 is an aryl or an aryl-alkyl group with to 17 carbon atoms and R3, R4, R3, and R6 independently are each hydrogen or an alkyl group with 1 to 4 carbon atoms. More desirably R1 is hydrogen or a hydroxyethyl group, R2 is a benzyl or phenyl group, and R3, R4, R3 and R6 are hydrogen. A particularly advantageous imidazoline derivative for use in the invention is 2-phenyl-[text missing or illegible when filed] [0067] Typical examples of aryl or aralkyl groups that can be the substituent R2 are phenyl, naphthyl, tolyl, xylyl, benzyl, and naphthylmethyl groups. Typical examples of alkyl groups with 1 to 17 carbon atoms that can likewise form the R2 group are methyl, ethyl, propyl, butyl, pentyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, and heptadecyl groups; straight chain alkyl groups are most useful. In addition, mixtures of these 2-alkylimidazole derivatives can also be used, containing alkyl groups of different chain lengths from the above list. Typical examples of alkyl groups with 1 to 4 carbon atoms and aryl groups that can form the substituents R3, R4, R3 and R6 can be obtained from the above list. [0068] When X is —CH=CH—, R1 and R2 desirably have the following significance; R1 is an aryl group with 7 to 10 carbon atoms or an imidazole-CO group and R2 is hydrogen or an alkyl group with 1 to 4 carbon atoms. Most desirably R1 is a methyl or benzyl group and R2 is hydrogen or a methyl group. [0069] Other imidazole primer compounds useful in the present invention include those of the Formula: [0070] wherein R1 is a C1-C4 alkyl group optionally sub- stituted with a phenyl group, and R2 is hydrogen or a C1-C4 alkyl group. [0071] Desirably the composition when solidified has the consistency of a soft-solid or waxy mass. The Theological properties of the mass of product should be such that the mass has a stable geometric shape. It is desirable that the shaped mass e.g. a stick, is applicable by manual rubbing against the substrate to which it is to be applied. The soft or semi-solid mass should be shearable under relatively modest Sep. 4, 2003 manual pressure to [text missing or illegible when filed]ease of application. Under shear forces the solid may liquify to form a film (or smear) of the composition on the surface. It is desirable that the shaped mass retains its shape, for example when stored at 20° C. for a number of days for example at least about 10 days, more desirably for a number of weeks or months. The composition exemplified herein have proven to be stable over a number of months in such conditions. The cast composition has the ease of handling advantages of a completely solid material yet remains easily dispensable. PrittStickTM is one commercially available semi-solid mass sold as an adhesive stick which is well known as a dispensable adhesive. [0072] The primer composition composed of one of the above primer components as a solution in a (solidified) solvent is normally of such concentration that the thickness of the coating can be controlled to achieve the full effects of this invention. [0073] The present invention also provides a composition described above wherein the primer component is a cure- promoting agent. Suitably the cure-promoting primer com- ponent is selected from substituted thioureas, a compound having a sulphur-containing free radical source, a compound containing an oxidisable transition metal or a compound containing one of the groups [0074] Most desirable are compositions wherein the primer component is a compound containing an oxidisable transition metal. The transition metal is desirably selected from those elements in the groups (columns) of the Periodic Tables containing Cr, Mn, Fe, Co or Cu. The transition metal may be selected from Cu, Cr, Co, Fe, and Mn, more particularly Cu(I), Cu(II), Co(II), Mn(II), Mn(III) or Cr(II). Particularly useful are those where the transition metal is selected from Cu(I) or Cu(II), especially those compounds which are salts of these particular forms of Cu, for example salts of carboxylic acids, beta diketones or beta keto esters. Particular salts are Cu(II) 2-ethylhexanoate or Cu(II) acety- lacetone. [0075] Where the primer component is a cure-promoting primer for anaerobic products [text missing or illegible when filed] may be a polymerizable monomer or polymer- izable oligomer for example alkyl methacrylate esters such as methyl or ethyl methacrylate. In the embodiment the polymerisable monomer or oligomer may interact with the polymerization process and thus form part of the cured product. The monomer or oligomer should provide the desired concentration of primer component. The solvent may thus for example be methyl or ethyl methacrylate. [0076] The invention also provides a two-part adhesive system comprising at least one cyanoacrylate adhesive and (ii) an adhesion-promoting primer composition accord- ing to the present invention as defined above. Suitably the cyanoacrylate is an alpha cyanoacrylate. [0077] Suitable cyanoacrylate adhesives for use with the adhesion-promoting primer of this invention are represented by the general formula US 2003/0164222 A1 H2C= C— COOR1 CN [0078] wherein R1 is alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl, haloalkyl or another suitable group. The lower alkyl alpha-cyanoacrylates are preferred, and in particular methyl, ethyl, n-propyl, n-butyl, isobutyl, isopro- pyl, allyl, cyclohexyl, methoxyethyl or ethoxyethyl cyanoacrylates are preferred. Many alpha cyanoacrylates can be obtained commercially as one component instant adhesives, in which form they may be used in a method of assembly of this invention. [0079] The present invention also provides a two-part adhesive system comprising at least one anaerobic prod- uct and (ii) a cure-promoting composition as described above. Suitable anaerobic products are described below. [0080] The invention also relates to the solidified product of a composition as described above. Suitably the compo- sition is solidified in a desired geometric form, for example in a cylindrical shape. Any suitable shape which allows for ease or handling is desired and such shapes are typically referred to as sticks. One method of preparing a soft-solid or semi solid mass of the composition includes the steps of: [0081] heating a composition comprising (a) at least one carrier solvent; (b) at least one primer component; and (c) at least one gelling or solidifying agent, to a desired temperature; and [0082] (ii) allowing the composition to cool or cooling the composition sufficiently to set the composition. [0083] Typically the composition will set (solidify to a soft-solid) at a temperature of below about 30° C. for example at about 15-22° C. [0084] The invention also relates to a shaped mass pre- pared by the method just described and particularly a mass shaped in a stick form. [0085] While these commercially available cyanoacry- lates are composed principally of alpha cyanoacrylate mono- mer, the formulation may contain stabilisers, thickeners, adhesion-promoters, plasticizers, dyes, heat resistant addi- tives, impact resistance modifiers, perfumes, diluents and such like. These adjustments may also be used with anaero- bic products. [0086] It will be appreciated that if the composition is cast before cooling to its set temperature then it will take the shape of the container or mould in which it is cast. It is desirable that the composition be cast in a desired geometric shape for example as a stick for example a stick of a generally cylindrical shape. The person skilled in the art will appreciate that the pre-and post-casting composition will have essentially the same compositional make-up, with mainly physical changes from liquid to solid occurring during casting. Little or no solvent will be lost during the casting process. The amounts of the various components thus remains essentially unchanged as between the liquid and solidified compositions. No appreciable volume change occurs during casting. Sep. 4, 2003 [0087] In a further aspect the invention provides a method of bonding a first (non-polar) [text missing or illegible when filed] to a second substrate (which may be polar or non-polar), which comprises treating (by priming) the first (non-polar) substrate(s) by applications of a composition according to the present invention, applying a cyanoacrylate (suitably an alpha cyanoacrylate) adhesive to the treated surface(s) and contacting the substrates for sufficient time (and with sufficient pressure) to allow them to bond to each other. In this way a bonded assembly is created. In the case where the substrates to be bonded are both non-polar or otherwise difficult-to-bond materials of that type, both sub- strates may be primed with a composition of the invention. The composition may suitably be applied by (manually) rubbing the primer stick on the substrate. If the non-polar substrate is to be bonded to a polar or more active substrate, only the non-polar substrate needs to have applied the primer. Following application of the primer to the non-polar substrate(s), the bond may be completed using cyanoacry- late adhesive in the normal manner. This method is espe- cially useful for priming polyolefin substrates. This method may also be used with anaerobic products where the sub- strate to which the product is applied is not necessarily a non-polar one. Anaerobic products may seal between rather than bond together two substrates. [0088] The invention relates also to a bonded assembly created by this method. The invention thus discloses the use of a primer composition in the manufacture of a castable primer stick composition for example a primer stick for priming substrates (for subsequent bonding with adhesive). The adhesion-promoting compositions of the invention may be used to prime non-polar or highly crystalline substrates. [0089] The invention also provides an easy to use and consumer-friendly pack comprising: [0090] a shaped mass of a composition according to the invention (a cast composition); and [0091] (ii) a container for the composition, the container having a mechanism for expelling the shaped mass. Desir- ably the shaped mass is moveable between a position where the shaped mass projects from the container, and a position where the shaped mass is substantially located (retracted) within the container. [0092] The composition may be cast directly in the con- tainer. Normally the container [text missing or illegible when filed]bular and most often of cylindrical shape. The container may be of the type having a displaceable mecha- nism for example a carrier for displacing the mass of the composition relative to the container. The carrier may move the mass so that it projects from the container, or retract the mass so that it is housed within the container. In this way the mass may be extended for application to a substrate or retracted for storage. The container may comprise a cap for protection of the mass when the composition is not in use. Desirably the container has means for manual adjustment of the position of the mass or carrier, for example where the carrier is reciprocally threaded on a winding mechanism and can thus be extended or retracted by rotation of the winding mechanism in one of two directions. [0093] It will be appreciated by those skilled in the art that a multitude of suitable containers may be used with the shapes masses or sticks of the present invention. Typically used containers are those with propulsion mechanisms to propel the stick out of the container. Many such containers are known for example for deodorants/anti-perspirants, and make-up such as lipstick etc. US 2003/0164222 A1 BRIEF DESCRIPTION OF THE FIGURES [0094] FIG. 1 is a side (part-sectional) elevational view of a container suitable for holding the composition of the present invention; and [0095] FIG. 2 is a top View of a carrier which forms part of the container of FIG. 1. DETAILED DESCRIPTION OF THE INVENTION [0096] Many primer components and primary composi- tions have been developed for use in bonding of substrates, in particular difficult-to-bond substrates as described above. Some primers components and primer compositions are now discussed. In accordance with the present invention the primer components disclosed below in the documents dis- cussed may be taken and formulated in a composition of the present invention for casting in stick form. [0097] For example, Japanese patent application Nos. 52-98062, 56-141328 and 57-119929 suggest the use of primers prepared by dissolving a chlorinated polyethylene or chlorinated polypropylene or a fatty acid modified acrylated alkyd resin in an organic acid. [0098] Primer based or organometallic compound are also known. For instance, European patent application no. 0 129 069 A2 discloses the use of a primer comprising at least one organometallic compound, for use with alpha cyanoacrylate adhesives, which is useful in bonding non-polar substrates. Japanese patent application No. 61023630 proposes orga- nometallic primers for joining plastic models. U.S. Pat. Nos. 5,292,364, 5,110,392 and 4,818,325 also disclose the use of primer compositions containing organometallic compounds for use with cyanoacrylate adhesives. [0099] Primers for polyolefins comprising modified or grafted polyolefins such as chlorinated polyolefins, ethylene/ vinyl acetate copolymer or ethylene/propylene terpolymer, (ii) a crosslinking binder and (iii) crosslinking agents, are disclosed in European application No. 0 187 171A. German application No. DE 3601518-A suggests the use of primers for polyolefins comprising an organometallic compound and an organic polymer; the organometallic compound being a metal alcoholate and the term “metal” including metalloids, phosphorous, boron or silicon atoms Japanese application No. 61136567 describes a titanate primer for bonding polypropylene. [0100] The English language abstract [from JAPIO data- base, accession no.1987-018486] for Japanese application No. 60157940 discloses a primer composition based on a solution of 4-vinyl pyridine as an essential ingredient, and 3,4-lutidine as an optional ingredient, for bonding polyole- fins, polyacetal, polyamide, polyester, boron-polymer, sili- cone or PVC. [0101] The Derwent Abstract [Accession no. 19942559135] for Japanese patent application JP 610 0839 discloses dialkylamino diazabicycloundecene primer com- positions for use with cyanoacrylate adhesives for plastics bonding. For example polyolefins and EPDM. The com- pounds, are those of formula I below Sep. 4, 2003 [0102] (R, R1=C1_14 alkyl, benzyl). [0103] U.S. Pat. No. 5,314,562 describes a method for bonding substrates, one of which is a plastic, comprising (a) applying to the plastic substrate a primer solution of an adhesion-promoting ethylenediamine compound dissolved in a solvent, (b) allowing the primer solution to dry, (c) applying an alpha cyanoacrylate adhesive to one of the substrates and (d) joining the substrates. The active adhe- sion-promoting agent is dissolved in a solvent and applied as a primer solution. [0104] German patent publication no. DE 40 35 680 describes imidazole derivatives which are useful as adhe- sion-promoting agents. [0105] German patent publication DE 40 17 802 A1 also relates to imidazole derivatives which are useful primers for inclusion in the compositions of the present invention. In particular the document discloses primer compounds of the Formula: N E A 2 N R R1 [0106] wherein R1 is a C1-C4 alkyl group optionally sub- stituted with a phenyl group, and R2 is hydrogen or a C1-C4 alkyl group. [0107] The Derwent Abstract [Accession no. 1994- 107035] for Japanese patent application JP-A-6057218 dis- closes a primer composition containing a tert-amine, where the three groups are each a hydrocarbon group, but at least one among them is a long chain hydrocarbon group con- taining 8 to 24 carbon atoms. The active adhesion-promoting agent is applied by dissolution in isopropanol. WO 91/ 18956 discloses imidazole derivatives such as 1-benzyl-2-meth- ylimidazole, 1-benzylimidazole, 1-(2-thyl)-2-phenyl-4,5-di- hydroimidazole, 2-phenyl-4,5-dihydroimidazole, and N,N‘- carbonyldiimidazole, for use as primers in the bonding of plastics, including polyolefins, with cyanoacrylate adhe- s1ves. [0108] U.S. Pat. No. 4,869,772 discloses di- and tri- azabicyclo primer compositions for use in bonding non- polar substrates. The active adhesion-promoting agents are dissolved in a solvent, applied as a solution, and allowed to dry leaving the adhesion-promoting agent on the substrate before subsequent bonding with cyanoacrylate. [0109] EP 0 333 448 (equivalent to U.S. Pat. No. 5,079, 098) discloses primer solutions (in low surface tension US 2003/0164222 A1 organic solvents) of quaternary ammonium compounds of the formula: R4N+ A‘ where R is alkyl, hydroxyalkyl, aryl, alkaryl, aralkyl, and alkenyl, optionally substituted by het- eroatoms; A‘ is an anion with pKa>0 in deprotonation equilibrium reactions. [0110] Anaerobic products with which certain primer compositions (in particular cure-promoting primer compo- nents) of the present invention are useful include polymer- izable compositions which are often in the liquid state. The (polymerizable) anaerobic product remains unpolymerized in the presence of air but polymerizes upon exclusion of air. This property of anaerobic products finds application as for example a sealant between closely fitting metal surfaces. Anaerobic product placed between closely fitting metal surfaces such as flanges cures due to a lack of air. [0111] Anaerobic products such as adhesives and sealant compositions are known in the art. Examples of documents which describe these products include U.S. Pat. Nos. 2,895, 950, 3,043,820, 3,218,305 (all to Krieble) and 4,287,330 (Rich) the entire contents of each of which is expressly incorporated herein by reference. [0112] In particular U.S. Pat. Nos. 2,895,950 and 3,043, 820 disclose anaerobic sealant compositions comprising polymerisable compounds of the formula: ‘Ii i i ‘Ii H2C:(|Z—C—O (CH2)m (I: (|:—o C—(|I:CH2 R’ R” H R’ P II [0113] where R is selected from hydrogen, —CH3, —C2H5, —CH2OH, and 0 || —cH2—o—c—c=cH2 Ry [0114] radicals, R‘ is selected from hydrogen, chlorine, methyl and ethyl radicals; R“ is selected from hydrogen, —OH radical, and O —o—c—c=cH2 Ry [0115] radicals; m is an integer equal to at least one, e.g. from 1 to 8 or higher, for instance from 1 to 4, inclusive, n is an integer equal to at least 2, for example from 2 to 20 or more, inclusive, and p is 0 or 1. Anaerobic compositions including these polymerizable compounds are useful in conjunction with the primer compositions of the present invention in particular those primer compositions of the present invention identified as being cure-promoting. Sep. 4, 2003 [0116] U.S. Pat. No. 3,218,305 discloses anaerobic prod- ucts containing polmerizable compounds of the formula: ‘Ii i i ‘Ii H2c=c|:—c—o (CH2)m (I: (|:—o c—(|:=CH2 R’ R” P H R’ n [0117] where R is a radical selected from hydrogen, C1-C 4 alkyl, or C1-C4 hydroxyalkyl or O —cH2—o—c—c=cH2 Ry [0118] radicals, R‘ is selected from hydrogen, halogen, and C1-C4 alkyl; and [text missing or illegible when filed], m, n and p, are as defined above. Anaerobic compositions including these polymerizable compounds are useful in conjunction with the primer compositions of the present invention in particular those primer compositions of the present invention identified as being cure-promoting. [0119] In particular polymerizable compounds useful in the present invention may be: ‘Ii i i ‘Ii H2c=c|:—c—o (CH2)m (I: (|:—o c—(|:=CH2 R’ R” H R’ P II [0120] where R is a radical selected from hydrogen, C1-C4 alkyl, or C1-C4 hydroxyalkyl or O —cH2—o—c—c=cH2 Ry [0121] radicals, R‘ is selected from hydrogen, halogen, and C1-C4 alkyl, OH; and R“ is selected from hydrogen, —OH radical, and O —o—c—(:=cH2 Ry [0122] radicals; m is an integer equal to at least one, e.g. from 1 to 8 or higher, for instance from 1 to 4, inclusive, n is an integer equal to at least 2, for example from 2 to 20 or more, inclusive, and p is 0 or 1. US 2003/0164222 A1 [0123] These polymerisable compounds are typically for- mulated in a composition which contains at least sufficient components to make the composition curable. The person skilled in the art will, depending on the polymerizable monomer selected, consider any further appropriate compo- nents. Typical further components for inclusion include an initiator which may independently initiate or assist initiation of polymerization in the absence of air. These initiators are often oxidising agents. These initiators include peroxides for example hydroperoxides such as cumene hydroperoxide. [0124] A further component which may be added is a reducing agent. Typical reducing agents include tertiary amines and for instance U.S. Pat. No. 4,287,330 (Rich) discloses rhodanine and organic hydrazines which are effec- tive accelerators for the cure of anaerobic compositions. Other suitable reducing agents are well known to those skilled in the art. Another potential component is a co- catalyst (for example saccharine) which may catalyse poly- merization of the polymerizable compounds. [0125] Suitable compositions for use with primer compo- sitions of the present invention are described in detail in our co-pending Irish application entitle “SEMI-SOLID ONE- AND TWO-PART COMPOSITIONS” filed on even date herewith in the name of Loctite (R&D) Limited. [0126] The use of primer solutions to facilitate more rapid cure, greater through depth cure, or improve adhesion to substrates has been considered also for anaerobic products. These primer solutions have been proposed in particular for use on substrates which do not have readily leachable metal ions or polar groups to facilitate effective adhesion. U.S. Pat. Nos. 4,990,281 (Clark), 3,970,505 (Hauser), 3,591,438 (Toback), 3,625,930 (Toback), among others disclose the use of various types of primers. The teaching of each of these documents is expressly incorporated herein by refer- ence. A common feature of all these primer composition is that the active ingredient is contained in a solvent and the primer solution has to be applied from the liquid state with a variety of techniques. [0127] The ’505 patent teaches the use of in particular a substituted thiourea (in conjunction with an acid) as a cure accelerator for anaerobic products. The substituted thiourea (optionally together with the acid) can be used as a primer to activate the surface to which it is desired to apply anaerobic product. The substituted thiourea can be formu- lated (optionally together with the acid) in a primer com- position of the present invention. [0128] The ’438 patent teaches the use of a reducing activator which is either a sulphur-containing free radical accelerator, or a compound containing an oxidizable transi- tion metal. The compounds containing an oxidizable tran- sition metal are especially useful in compositions of the present invention and includes those compounds containing the following transition metals: Cu, Cr, Co, Fe, and Mn. Desirable compounds include salts and complexes of these metals including mono- or poly-nuclear and homo- or het- ero-nuclear compounds. [0129] Other transition metal-based compounds are dis- closed in the ’281 patent are desirable for inclusion. These include Cu(II), Co(II), Mn(II), Mn(III) and Cr(II) based compounds in particular salts of these metals. The ’281 patent is particularly concerned with the salts of these metals Sep. 4, 2003 with acid phosphate acrylic monomer. Particular acid phos- phate acrylic monomer disclosed include those of the for- mula: R10 0 cH2=c—c—R2—o—P—A OH [0130] where R1 is H or methyl, R2 is a divalent organic group having from 2 to 20 carbon atoms and the group A is OH or R10 cH2=c—c—o—R2o— [0131] where R1 and R2 are as defined for the formula immediately above. [0132] Suitable metal compounds include copper (I) and (II) salts in particular those of carboxylic acids or those of beta diketones or beta keto esters. Specific examples include for example Cu(II) 2-ethylhexanoate and Cu(II) acetylac- etonate. [0133] A representative of a Cu(II) based primer is Loctite product “Primer NTM”. [0134] Other anaerobic products commercially available from Loctite Corporation Rocky Hill Connecticut, US include the following products sold under the following trade names Loctite 636, Loctite 326, Loctite 648, Loctite 270, and Loctite 290. [0135] The ’930 patent discloses a primer composition for anaerobic adhesives which contains as accelerator a com- pound having one of the following groups: [0136] These compounds are also suitable for use with the primer compositions of the present invention. [0137] A container for holding a cast (solidified) compo- sition of the invention is now described. [0138] FIG. 1 shows a side view of a container 1 suitable for holding a composition of the present invention. The container is cylindrical in cross-section having cylindrical side walls 2. On the base of the container is a knurled wheel 3 which forms part of a propulsion mechanism for a (soft- solid or semi-solid) mass or stick 4 of the primer composi- tion of the present invention. The mass 4 has been cast in a generally cylindrical shape as described in the Examples below. The container further comprises a cap 5 which is snap-fit engageable over the top end 6 of the container 1 to protect the mass 4 of product. The top end 6 is of lesser diameter than the side walls 2 and has a rim 7 which engages in a corresponding recess on the underside of the cap 5 to secure the cap 5 in place. US 2003/0164222 A1 [0139] The knurled wheel 3 is attached to an elongate drive or winding shaft 8 which is centrally located within the housing formed by the side walls of the container. On the winding shaft 8 is located a moveable carrier 9. The carrier 9 is generally cylindrical (from an end View thereof—see for example FIG. 2) and has a short peripheral upstanding wall 10 formed on its base 11. During the casting process the carrier 9 is positioned to secure itself to the lower end 12 of the mass 4 on solidification of the mass 4. Indeed the mass 4 may be cast also with the shaft 8 (and optionally the wheel 3) in place. As best seen from FIG. 2 the carrier 9 has a central threaded aperture 13 in which the threads 16 of the shaft 8 engage. The knurled wheel 3 and the shaft 8 are both [text missing or illegible when filed] for relative rota- tion to the container body. When the wheel 3 is turned in the direction of the arrow it moves the carrier up or down the shaft 8 thus controlling the relative position of the mass and the container. In the position shown the carrier has travelled part way up the shaft, moving the mass to a position where it protrudes from the container. The mass can then be applied by rubbing against a substrate by manual force. Sufficient shearing of the mass takes place to allow it to rub off onto the substrate. No separate applicator/brush etc. is necessary. The composition can be applied with manual pressure. To prevent rotation of the carrier 9 with the shaft, elongate ribs 14 are provided on opposing sides of the internal wall of the container. The ribs 14 run from the base of the container to a position proximate to the mouth if the container. The ribs 14 each engage one of corresponding grooves 15 in the carrier 9 thus preventing relative rotation of the container and the carrier and ensuring that the carrier moves upwardly or downwardly when the shaft 8 turns. The carrier 9 and the mass 4 can be retracted by rotation of the wheel 3 in an opposing direction. [0140] The words “comprises/comprising” and the words “having/including” when used herein with reference to the present invention are used to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. [0141] The following examples will serve to illustrate the invention. EXAMPLES [0142] General [0143] In the following examples the dibenzylidene sor- bitol used was the product DisorbeneTM described above. [0144] Bonding tests were carried out using various sub- strates, including natural polyethylene and natural polypro- pylene as the non-polar substrates, various solutions of the active adhesion promotion compounds as the primer and various grades of cyanoacrylate adhesive commercially available from Loctite (Ireland) Limited, Dublin, Ireland. The bond strength of the resulting joints was determined using conventional [text missing or illegible when filed] following standard test method ASTM D 1002. [0145] The 3 kg Test as described below is the minimum time following assembly for bonds to support a 3 kg weight. The minimum time is determined in accordance with ASTM D1002. Example 1 [0146] 2.0 g of dibenzylidene sorbitol was dissolved in refluxing ethanol (148 g) with vigorous stirring and the Sep. 4, 2003 solution allowed to cool for a short period. Then 1,8- diazabicyclo[5.4.0]undec-7-ene (0.15 g) was added with stirring and the solution was allowed to cool further. The solution was then cast into empty stick cartridges of the type typically used for adhesives such as PrittStickTM (and as described above) and was allowed to cool to room tempera- ture. During this time the solution solidified. The solidified stick was clear (homogeneous) resembling a frozen mass. The solid stick primer solution could then be extruded using the cartridges inbuilt propulsion mechanism. [0147] Test pieces of natural polyethylene of dimensions 100 mm>