DE2659663A1 - NON-STICK COATING AND ADHESIVE COMPOSITIONS - Google Patents

Description

Patent attorney *: "*
Dr. Ing. WsIiDr AbKz
Dr. D'Gtr.r F-. M ο rf
Dr. Hans-Α. Browns

β lüiflchsn S3, PiMZMUMntr. 28

DECEMBER 30 t976_

ICC-29

LOCTITE (IRELAND) LIMITED Dublin 10, Ireland

Non-tacky coating and adhesive compositions

The invention relates to curable compositions based on monomers of the acrylate type together with free radical initiators. The curing of the composition on contact with oxygen is inhibited, and by using a compatible organic solvent in which an organic polymeric substance with an average molecular weight of at least about 10,000 and a glass transition temperature of at least about O ⁰ C is dissolved, the compositions are in transferred to a non-sticky state. Upon evaporation of the solvent, the polymeric substance forms a film on the uncured surface of the composition causing the surface to be dry to the touch and thereby substantially restricting oxygen passage to the uncured composition. This improves hardening.

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Free radical curing compositions based on acrylate-type monomers such as methyl methacrylate, have long been known. Such compositions are normally represented by organic peroxy compounds, e.g., benzoyl peroxide and methyl ethyl ketone peroxide, or by generators that form free radicals and are activated by radiation, like benzophenone, initiated together with UV light. It has been found that curing such acrylate compositions is inhibited to some extent by contact with oxygen, such as oxygen in the atmospheric air. Although this undesirable inhibition can be avoided to some extent, such as by the application of heat, the The requirement for surface hardening at room temperature is often not met. It is often for ease of use It is desirable to prepare a surface on the adhesive or coating that is dry to the touch prior to this substantial hardening was still achieved.

Recently, the effect of oxygen inhibition has been found and exploited commercially in certain "anaerobic" curing adhesives and sealants. These compositions depend on the exclusion of oxygen from the composition for curing to take place, usually between non-porous surfaces, such as screw connections. These compositions remain liquid when in contact with an appropriate concentration of oxygen such as that found in the atmosphere. In practice this means that the compositions in thin-walled polyethylene containers or in aerosol-like distributors or distribution cans, the preparation of which is described in US Pat. No. 3,736,260, can be preserved. Examples of these anaerobic compositions are detailed in, inter alia, U.S. Patents 2,895,950, 3,218,305, 3,425,988 and 3,435,012 as well as in GB-PS 1 412 940. The compositions depend on the

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Generation of free radicals, usually through a redox reaction, caused by the metal surfaces on which the Compositions are applied as they are used, or catalyzed by previously applied primers will. It has been found that some of these compositions, when exposed to non-ionizing radiation, such as UV light, can be hardened. This is described in FR-PS 73.17729.

An anaerobic composition contains as required ingredients a free radical polymerizable monomer (usually a mono-, di-, or triacrylate or methacrylate) and a peroxy initiator or a photoinitiator or both compounds. You can still accelerate, such as amines and organic sulfimides. If such a composition is to be used for irradiation, such as with UV light, cure, it must also have at least one photoinitiator or sensitizer, such as benzoin methyl ether, or one of the in of the AUS-PS 469 564 described initiators contain. The composition can also contain polymeric thickeners, Contain dyes, including those pigments used in reflective coatings, and plasticizers. To compensate for the shelf life of the compositions with the cure rate can also free radical stabilizers may be required. These stabilizers are usually of the quinone type and are preferred Quinones are ß-naphthoquinone, 2-methoxy-1,4-naphthoquinone and p-benzoquinone. Other stabilizers are described in U.S. Patent 3,043,820. If necessary, compatible Plasticizers are used. The preferred plasticizers are selected from the group of polymeric polyester plasticizers selected as described in U.S. Patent 3,794,610.

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The disclosure content of all of the above-mentioned patents should also apply to the present application.

The anaerobic character of these compositions means that they are suitable for applications such as screw caps or threaded closures, the fastening of bearings or shaft bearings on axles or shafts or spindles or shafts and in other adhesive and / or sealing applications, where oxygen is from. the connection is excluded. However, the anaerobic nature of the compositions causes various difficulties. The fluid that remains outside the bolted connection or the connection line, maintains its liquid or sticky state and never hardens completely. This can be big trouble cause when small parts are put together for transportation purposes as the parts may stick together and no longer be usable. Become well-known Anaerobic compositions used for gluing decorative items, pulls the sticky surface outside the connection easily attracts dust from the atmosphere, and an unsightly and very often dirty line is formed, adjacent to the bonds. If the compositions are used for very fine machine parts or very fine machines, such as clocks, so can any excess composition outside the compound that does not harden, flow into the working mechanism and cause the moving parts to seize up. Another The disadvantage is that the adhesives, although they have very good resistance to solvents and moisture and exhibit good adhesion to a number of surfaces, never because of their sticky outer surface can be used as coatings or finishes, or as embedding materials for electronic parts.

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There are many methods of reducing or eliminating the inhibitory effects of atmospheric oxygen on the Surface curing properties of acrylate compositions used. It has been found that tack-free surfaces can be obtained if the radiation-curable, anaerobic, curing compositions ultraviolet light in the presence of inert gases such as nitrogen, to the exclusion exposed to oxygen. It has also been found that certain types of monomers are resistant to inhibition are less sensitive to oxygen than others and these have been used to make improved compositions. In another method, the compositions are mixed with waxes that surface as they progress sweat out of the polymerization and thereby form a boundary layer against the inhibition by oxygen. However, this method is unsatisfactory because a waxy surface is left, often by sanding or sanding must be removed before polishing. The wax contained in the material also diminishes to a certain extent Extent the adhesive properties of the cured composition. In other processes, compatible compounds are also used, which themselves react with oxygen in the presence of free radicals. In other cases it has been found that by the addition of chain transfer agents the "inhibiting Effect of oxygen on the polymerization can be delayed or eliminated. However, neither of these procedures is completely satisfactory.

The invention relates to anaerobic curing compositions, which, although stable in suitable oxygen-permeable containers, are nonetheless in an unsealed state harden even in the presence of oxygen. The invention also relates to a new method for the exclusion of Oxygen from non-entrapped anaerobically curing compositions that allow the compositions to cure

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is borrowed. The invention also relates to a method with which one can use anaerobic systems as well as systems based on acrylate, whose Surface hardening is inhibited by oxygen, transferred to a non-sticky state.

Surprisingly, it has been found that the addition of a selected dry polymeric substance and a volatile Solvent to a curable monomeric system cure these compositions tack-free. That separates when it evaporates Solvent creates a thin film of the polymeric substance on the exposed surface of the liquid composition away. This essentially rules out the possibility of atmospheric oxygen in contact with the anaerobically curable Material comes, and this hardens accordingly to a hard, tack-free solid. Is one of these according to the invention Compositions are applied to the thread of a standard screw and then the matching nut is put on the When the screw is in place, the anaerobic composition in the thread hardens and results in a blockage. The excess anaerobic composition outside the thread also hardens into a tack-free coating. These Property is both new and useful.

The invention thus relates in particular to a curable adhesive or coating composition. which contains a mixture of: a curable part which contains:

(a) at least one acrylate or methacrylate monomer,

(b) a free radical polymerization initiator;

and an additive part that contains:

. (c) an organic solvent compatible with the curable part,

(d) about 2 to about 200% by weight of an organic polymer with an average molecular weight above about 10,000 and a glass transition temperature of at least about ⁰ ° C., based on the curable part, dissolved in an organic solvent,

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wherein upon evaporation of at least a portion of the solvent the curable composition becomes non-tacky.

The invention further relates to a method for converting a curable adhesive or coating composition upon contact with oxygen in a non-tacky and curable state, according to which an organic solvent compatible with the curable part is added to such a composition, in which about 2 to about 200 Ge , w. % _t, based on the curable part, are dissolved in an organic polymer with an average molecular weight of more than about 10,000 and a glass transition temperature of at least about ⁰ ° C., and at least part of the solvent has evaporated.

The invention also relates to a method for eliminating oxygen from anaerobically curing compositions.

As used in the present application, the term "non-tacky" means the exposed surface of the adhesive or sealant or coating composition is dry, non-sticky and non-sticky to the handle not on adjacent, exposed surfaces of similarly coated objects during normal storage and handling sticks or sticks.

The term "compatible" as used in the present application means that the solvent is with the curable part must be miscible in the concentration used, can be easily removed from the system by evaporation can and that any residual solvent after evaporation no significant adverse effect on the hardening of the shows hardenable part.

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The invention relates to a hardening composition based on acrylate or methacrylate which, in addition to the normal or customary components, contains: a film-forming amount in the sense described above of at least one organic polymeric substance. The polymeric substance is required to have an average molecular weight of at least about 10,000. The molecular weight can be as high as 3,000,000 or even higher provided that the polymeric substance remains soluble in the compatible solvent and has a sufficiently high glass transition temperature, as will be explained in more detail below. Preferably the molecular weight will be in the range of about 10,000 to 1,000,000, most preferably about 10,000 to 50,000. The polymeric substance should furthermore have a glass transition temperature of at least about ⁰ ° C., preferably about 20 to 120 ^° C. * It has been found that this combination of molecular weight and glass transition temperature is characteristic of organic polymers, which are typically soluble in normal organic solvents and which deposit on the surface of the curable composition when the solvent evaporates or exude to the surface of the curable composition. This creates a non-sticky, dry surface that is resistant to the passage of oxygen. Suitable polymeric substances typically have an intrinsic viscosity of at least about 0.2. The polymeric substance is preferably selected from the class which contains: polyalkyl methacrylates, polyacrylates, polyvinyl acetates, polyvinylidene chlorides, cellulose acetate butyrates and polyurethanes. The most preferred class of polymeric substances are the polyalkyl methacrylates such as polymethyl methacrylate and poly (isobutyl) methacrylate. Other polymeric substances can also be used provided that they meet the molecular weight and glass transition temperature requirements noted above, are dissolved in any compatible solvent.

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can and form a non-sticky surface when at least some of the solvent evaporates.

The concentration of polymeric substance must be related to its solubility in the chosen volatile solvent stand so that the substance quickly solidifies as a surface film of a solid polymer after a relatively small Amount of solvent has evaporated. The concentration can range from about 2 to about 200% by weight, based on the curable portion (i.e. the monomer plus initiator and optionally accelerator) of the composition. Preferred the concentration of polymeric substance is in the range from about 3 to 160% by weight, based on the curable part of the composition, lie. Specified as a percentage based on the total composition (i.e. curable part plus Additive part), the concentration of polymeric substance usually in the range from about 1.5 to 60%, preferred about 2 to 30%. Below about 1.5% will generally be Insufficient polymeric substance to form the tack-free surface with low oxygen permeability is present be. Above about 60%, the viscosities and other properties of the liquid composition can become undesirable change and the properties of the cured composition may deteriorate.

The solvent used must be compatible with the components of the curable composition (as defined above) be. Chlorinated hydrocarbons are preferred. A second preferred class of solvents includes "reactive" Solvent. This term means that any solvent that is present in the composition after evaporation remains, can copolymerize with the acrylate or methacrylate components of the composition. Preferred reactive Solvents are methacrylate esters with a low molecular weight

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cell weight, e.g., methyl methacrylate, butyl methacrylate and Isopropyl methacrylate. Compositions containing compounds from this class of solvents have the additional advantage that there are no voids or bubbles in the coating after aging. With non-reactive solvents (which continue to evaporate during and even after curing) Unsightly voids and holes can occur, and the result is a coating that is resistant to chemicals and the environment has inferior durability than when the above-mentioned preferred copolymerizing ones Solvents can be used. The amount of solvent used will be determined by preliminary tests. She hangs on the solubility of the selected polymeric substance, the volatility of the solvent, the desired viscosity the composition and other factors familiar to those skilled in the art. Generally the solvent concentration is not critical and can range from about 2 to 98-6, based on the entire composition. The curable monomer can itself, at least to some extent, for the polymeric substance can be a solvent as long as it has the ability of the polymeric substance to achieve the intended purpose to meet, does not bother.

As indicated, the compositions according to the invention are in. . ·. non-tacky state while they are still uncured (or only slightly cured) by at least part of the Solvent is evaporated. Ideally, the solvent will be completely evaporated. However, this is not in all Cases required. The key requirement is that sufficient solvent be removed so that it is on the surface Sufficient polymeric substance is deposited in the curable composition and causes the curable composition is transferred in a non-sticky state. The exact amount of solvent used in a given composition

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tion must be removed can be determined by simple preliminary tests and of course depends on the particular components used. The evaporation required can be due to the natural behavior of the volatile solvent can be achieved. The rate of evaporation can be further increased by applying heat or vacuum. It will not removing all of the solvent, obviously sufficient solvent must be removed to remove the residue does not significantly interfere with the hardness or properties of the composition. When using "pure, active" solvents it may be possible and often preferred to have a substantial amount of solvent for the co-reaction with the monomer or monomers remains.

Any of a wide variety of known monomers that are free radical cure and can be used as the monomer belong to the acrylate and alkyl acrylate (e.g. methacrylate) types. Typical examples of such materials are methyl methacrylates. Curable compositions based on such monomers become more known through exposure Initiators that form free radicals, such as benzoyl peroxide, methyl ethyl ketone peroxide, azo-bis-isobutyronitrile, etc. polymerized. Such initiators are activated by the application of some heat, as is well known to those skilled in the art.

Numerous generators which form free radicals and are sensitive to ultraviolet are known for such monomer systems.

The preferred monomers used in the compositions of the invention are used are those which usually have anaerobic curing properties as previously described. A particularly suitable class of monomers are those described in the aforementioned US Pat. No. 3,425,988.

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the. These monomeric polyacrylate esters can be made by a variety of methods, but these include Method most suitable for testing, the reaction of a monofunctionally substituted alkyl or aryl acrylate ester, the one active hydrogen atom on the functional Contains substituents. This monofunctional material with a terminal acrylate group is combined with an organic polyisocyanate reacted in a suitable ratio so that all isocyanate groups are converted into urethane or ureide groups. The monofunctional alkyl and aryl acrylate esters are preferably the acrylates and methacrylates, the functional ones Hydroxy and amino groups on their 'non-acrylate part. Acrylate esters that can be used in the present invention have the formula

R ¹ O
HC = CC-0-R ² -XH (;)

where R

X means -O- or -N-,. wherein R represents a hydrogen atom or a lower alkyl group having 1 to 7 carbon atoms stands,

R denotes a hydrogen atom, a chlorine atom, a methyl or ethyl group and
ρ

R means a divalent organic group, such as

a lower alkylene group having 1 to 8 carbon atoms, a phenylene or naphthylene group.

These groups, when suitably reacted with a polyisocyanate, result in a sealing monomer of the following formula

R ¹ O

I Il

> 2

H ₂ C = CCORXC-NH B (2)

1 2
wherein R, R and X have the definitions given above, η denotes an integer from 2 to 6 inclusive and B

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70983 5

a polyvalent organic group such as an alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl or heterocyclic group Group means. These groups can be substituted or unsubstituted be.

The terms "acrylate" and "polyacrylate" as used in US Pat present application include their methyl, ethyl and halogen homologues.

Examples of hydroxy and amine containing materials that are suitable for the preparation of the above-mentioned monomeric products, such compounds as hydroxyethyl acrylate, Hydroxyethyl methacrylate, aminoethyl methacrylate, 3-hydroxypropyl methacrylate, aminopropyl methacrylate, hydroxyhexyl acrylate, tert-butylaminoethyl methacrylate, hydroxyoctyl methacrylate etc. «

Examples of polyisocyanates that can be used include toluene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylene methane diisocyanate, dianlsidine diisocyanate, 1,5-naphthalene ^{diisocyanate, 4,4 t} -diphenyl ether diisocyanate, p-phenylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, cyclohexylene diisocyanate, nonamethylene diisocyanate, octadecamethylene diisocyanate, 2-chloropropane diisocyanate, 2,2'-diethyl ether diisocyanate, 3- (dimethylamine) pentane diisocyanate , Tetrachlorophenylene diisocyanate, 1,4-3-heptene diisocyanate and transvinylene diisocyanate. Still other polyisocyanates that can be used are the higher molecular weight polyisocyanates obtained by reacting polyamines containing terminal, primary and secondary amine groups or polyhydric alcohols such as the alkane and alkene polyols such as glycerol, 1,2, 6-hexanethanol, 1,5-pentanediol, ethylene glycol, polyethylene glycol, bisphenol-A, 4,4'-dihydroxyphenyl

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dimethylmethane-substituted bisphenol-A et al., with an excess on any of the isocyanates described above. These urethane or ureide polyisocyanates with higher Molecular weight can be expressed by the following formula

H 0
O = CNR ^ -NCX-

B (3)

where B, X and η have the meaning given above

■ x

and R means an organic group, such as an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group with 2 to 20 carbon atoms.

Preferred organic polyisocyanates are the higher alkenyl diisocyanates, the cycloalkenyl diisocyanates and the aromatic diisocyanates, which have more than 8 carbon atoms and are preferred Contain 15 to 30 carbon atoms, such as octamethylene diisocyanate, Durol diisocyanate, 4,4'-diphenyl diisocyanate, and the above-mentioned higher molecular weight polyisocyanate reaction products.

See U.S. Patent 3,425,988 for further details.

Other useful monomers are the polyacrylate esters made by the formula

H ₂ C = CCO

O R

It I

- [M-O] -C-C = CH-

(4)

in which R is a hydrogen atom, a halogen atom or an alkyl group having 1 to about 4 carbon atoms, ρ is an integer equal to at least 1 and is preferred

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1 to about 4 and M is at least 2 carbon atoms containing organic group with a total binding capacity or valence of ρ plus 1 means »With regard to the upper limit of the number of carbon atoms in M, monomers of virtually any value can be used. As a practical matter, there is a general upper one Limit of about 50 carbon atoms, preferably 30, and most preferably about 20. For example, M can be an organic Group of formula

0 0

-Y-OCZC-OY ^

1 2

mean wherein each of the substituents Y and Y is an organic one Group, preferably a hydrocarbon group, the at least Contains 2 carbon atoms and preferably 2 to about 10 carbon atoms, and Z is an organic group, preferably a hydrocarbon group containing at least one carbon atom and preferably contains 2 to about 10 carbon atoms, means.

Another class of suitable polyacrylate ester monomers are the reaction products of di- or tri-alkylol amines (e.g. ethanolamines or propanolamines) with acrylic acids, as described in FR-PS 1 581 361.

Other useful monomers are polyacrylate esters of the following formula

O
H ₂ C = CC-Cj

(κ * C. / \ r R5 -O I. _R. ⁵ I. C. I. C. - I * ⁵ / C. [I. f)

- f

-CC = CH, R ⁴

(5) j

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wherein R is a hydrogen atom, a lower alkyl group with 1 to about 4 carbon atoms, a hydroxyalkyl group having 1 to about 4 carbon atoms, or a group of the formula

Ii L

-CH _o -0-CC = CH _Q is where R is as defined above

has, R is a hydrogen atom, a hydroxyl group or a

Group of formula

-0-CC = CH ₅

means q is an integer of at least 1, e.g. 1 to about 15 or more and preferably 1 to about 8, s is an integer of at least 1, e.g. 1 to about 40 or more and is preferred is about 2 to about 10, and r is 0 or 1.

Typical examples of polyacrylate esters represented by the above formula are di-, tri- and tetraethylene glycol dimethacrylate, Di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, Tetraethylene glycol di-chloroacrylate), Diglycerine diacrylate, diglycerine tetramethacrylate, butylene glycol dimethacrylate, Neopentyl glycol diacrylate and trimethylol propane triacrylate.

Although it has been found that the di- and other polyacrylate esters, and in particular the polyacrylate esters described in the preceding section are particularly suitable Monoacrylate esters can also be used. When using monoacrylate esters, it is particularly preferred to use one To use ester, which has a relatively polar alcoholic part of the molecule. Such materials are less volatile as the low molecular weight alkyl esters, and, more importantly, the polar group makes it intermolecular Attraction during and after hardening, and thereby

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one holds better hardening properties as well as more permanent sealing compounds or adhesives. Most preferred the polar group is selected from the following group: labile hydrogen, heterocyclic ring, polar hydroxy, Amino, cyano groups and polar halogen atoms. Typical examples of compounds that fall into this category are Cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, Hydroxyethyl acrylate, hydroxypropyl methacrylate, tert-butylaminoethyl methacrylate, Cyanoethyl acrylate and chloroethyl methacrylate. Anaerobic compositions based on Mer such monoacrylates are described in more detail in US Pat. No. 3,435,012 mentioned above.

Another useful class of monomers is that described in U.S. Patent 3,944,521. These monomers possess the formula

(6)

where the aromatic groups are substituted or unsubstituted

ated benzene rings or other aromatic groups. Around

R denotes hydrogen atoms, alkyl, aryl, hydroxyalkyl

7 ß

groups or halogen atoms, and R 'and R represent

R ¹¹ OR ¹² R ¹³

wherein χ denotes an integer from 1 to 20 and preferably from 1 to 5, and R ¹¹ , R and R * denote hydrogen atoms, alkyl, alkoxy groups or halogen atoms.

Examples of aromatic groups other than benzene are naphthalene, anthracene and other polynuclear groups. The alkyl groups

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can be methyl, ethyl and other primary, secondary or
be tertiary alkyl groups and the hydroxyalkyl groups can be, for example, hydroxyethyl groups. The preferred halogen atom is a chlorine atom.

The preferred monomer of this class is the dimethacrylate of propoxylated bisphenol-A, the number of propoxyl radicals in the chain preferably being 1 to 5 ; other
Groups are propoxylated bisphenol-C-dimethacrylate, ethoxylated bisphenol-A-dimethacrylate and ethoxylated bisphenol-A-diacrylate.

As stated above, the anaerobic compositions described are created by mixing a peroxy initiator with one or more of the acrylate esters described above.
manufactured. While certain peroxides (generally dialkyl peroxides) have been described as suitable initiators, for example in US Patents 3,419,512 and 3,479,246, the hydroperoxides are much better and are thus preferred.

The real advantage of the non-hydroperoxide initiators is that they act as co-initiators with the hydroperoxides, which makes the curing properties of the anaerobic composition more universal
will.

Hydrogen peroxide can be used, but the preferred ones Polymerization initiators are the organic hydroperoxides. Such materials are also included in this definition such as organic peroxides or organic peresters, which decompose with the in situ formation of organic hydroperoxides or hydrolyze to do this. Examples of such peroxides and peresters are cyclohexyl and hydroxycyclohexyl peroxide and tert-butyl perbenzoate, respectively.

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ICC-29 "free"

Although in the general concept of the present invention The nature of the organic hydroperoxides is not critical, the general class of hydroperoxides can be identified by the Formula R 0OH are represented, wherein R is generally a hydrocarbon group up to about Contains 18 carbon atoms, and preferably an alkyl, aryl or aralkyl hydrocarbon group containing about 3 to about

14th
Contains 12 carbon atoms. R may be any substituent or a different bond, namely, a hydrocarbon, or other substituents contain ^J, ^ is not adversely affected thereby, the intended effect of the hydroperoxide. Typical examples of such organic hydroperoxides are cumene hydroperoxide, tert-butyl hydroperoxide, methyl ethyl ketone hydroperoxide and hydroperoxides obtained by oxygenating various hydrocarbons such as methylbutene, cetane and cyclohexene, and various ketones and ethers including certain compounds represented by Formula 5 above, get v / earth.

The organic hydroperoxide initiators can be used within wide ranges, for example up to about 20% by weight, based on the composition. Most often, however, they are used in amounts not greater than about 10 percent by weight of the composition, since amounts above can adversely affect the strength and durability of the cured composition. Although lower amounts can be used in some cases, about 0.1% by weight of the composition is the usual lower limit. Preferably, the hydroperoxide initiator will be present in an amount of from about 0.1 to about 5 percent by weight , based on the composition.

Common additives for anaerobic compositions are latent ones Polymerization accelerators, compounds that are themselves the

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Hardening tang does not initiate, but the hardening after the Accelerate curing once the polymerization initiator has started. A large number of polymerization accelerators is known. Generally, any polymerization accelerator can be used in the present invention can be used, which can be incorporated into the anaerobic compositions without losing the essential properties these compositions are eliminated.

Among the polymerization accelerators, the earliest Used in anaerobic compositions are the amines. The most commonly used are tertiary amines, such as tributylamine and triethylamine. Essentially the entire class of tertiary amines can be used in such compositions can be used, and the class can be generalized by the formula

NR ¹⁵ R ¹⁶ R ¹⁷

are represented in which each of the substituents R, R and

17th
R 'represents a hydrocarbon group containing up to about 10 carbon atoms. Of course, the hydrocarbon groups can contain other substituents or bonds which do not adversely affect the ability of the amines to perform the desired function. Preferably each of the substituents R, R and R 'is an alkyl, aryl or aralkyl group containing up to about 8 carbon atoms.

The N, N-dialkylarylamines are particularly effective tertiary amines. Typical amines within this class can be obtained by the the following general formula

R ¹⁸

\ _N -B (R ²⁰ ) _t

R ¹ * *

where E is a carbocyclic aromatic

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Ring means one of the group consisting of phenyl and naphthyl groups

18 19
is selected; R and R are hydrocarbon groups that contain up to about 10 carbon atoms and are preferred lower alkyl groups with 1 to 4 carbon atoms:

20th

t is 0 or an integer from 1 to 5; R is a hydrocarbon group containing up to about 5 carbon atoms, and preferably a lower alkyl or lower alkoxy group with 1 to 4 carbon atoms, provided that,

20th
when R denotes a substituent in the ortho position, t is greater than 1.

In the anaerobic compositions according to the invention, primary and secondary amines can also be used as accelerators. Particularly preferred primary and secondary amines are the primary and secondary alkyl amines, most preferably those wherein each alkyl group contains up to about 10 carbon atoms. A separate and very preferred class of secondary amines is the class of heterocyclic secondary amines, particularly heterocyclic secondary amines containing up to about 20 carbon atoms. It is further preferred to use those amines in which the heterocyclic ring is hydrogenated. Typical examples of such compounds are pyrrolidine, piperazine and 1 , Z ^ tb-tetrsfoyaero quinoline.

Another very valuable class of accelerators are the organic sulfimides, i.e. organic compounds that OHO

Il t Il

contain the group -SNC-. Because of the great effectiveness of It

the SuIfimide as an accelerator for anaerobic compositions, Compositions containing sulfimides are a particularly preferred embodiment of the invention. Although the broad

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ICC-29 oJS

te class of organic sulfimides that can be used with success are the sulfimides that are most commonly used by the following formula

OHO

Il

21-22 wherein each of the substituents R and R is a hydrocarbon group containing up to about 10 carbon atoms and preferably contains up to about 6 carbon atoms.

21 22

R and R can have any other bonds and substituents, which does not adversely affect the effect of the sulfimide for the intended use of the anaerobic composition

21 22

influence, included. R and R together, including the sulfimide group, can form a heterocyclic ring or form a polymeric heterocyclic ring system. Of the organic sulfimides, benzoic acid sulfimide is the most common preferred.

An even more preferred composition is one which contains a sulfimia, particularly benzoic acid sulfimide with either a heterocyclic secondary amine or a tertiary Ν, Ν-dialkylarylamine, both of which were described above, contains. These types of systems are discussed in great detail in U.S. Patent 3,218,305.

Other, less active accelerators can also be used in the compositions of the invention. Typical examples such accelerators are succinimide, phthalemide and formamide.

The optimal amount of accelerator, that can be incorporated into a given anaerobic composition. The following general However, rules can be used. Bsi tertiary ami-

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ICC-29. ⁰ ^

Larger amounts of up to about 8% by weight, based on the composition, or even higher amounts, can optionally be used. At amounts above about 5% , however, little, if any, additional benefits are obtained. Most preferably, these tertiary amine accelerators are used in amounts of from about 1 to about 4 weight percent based on the anaerobic composition. The succinimide, phthalamide and formamide accelerators can also be used in substantial amounts, up to about 8% by weight of the composition, or in greater amounts. They are preferably used in amounts of about 1 to about 5 % by weight . The SuIfimid- and heterocyclic secondary amine accelerators are generally used in amounts of less than about 4 wt.%, Based on the anaerobic composition. In the special case when a sulfimide is used together with a heterocyclic secondary amine or an N, N-dialkylarylamine, the total amount of both accelerators preferably does not exceed about 4% by weight, based on the anaerobic composition, and each component is in one Amount not used above about 3% by weight.

In the anaerobic compositions according to the invention can other ingredients are used. In preferred embodiments, polymerization inhibitors are used to protect against a sham polymerization before the time of intended use. It was found that the Quinones are a particularly effective class of polymerization inhibitors and these can be used. Examples such quinones are ß-naphthoquinone, 2-methoxy-1,4-naphthoquinone and p-benzoquinone. Compositions containing such inhibitors are detailed in the above mentioned U.S. Patent 3,043,820.

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ICC-29 ⁰ ^.

Other typical functional ingredients that may optionally be used to make the compositions technical To impart desirable properties are thickeners, dyes, adhesives, thixotropic agents and plasticizers, particularly those polyester plasticizers described in U.S. Patent 3,794,610.

Such functional materials can be used in any combination and proportions may be used provided they reflect the nature and essential properties of the composition not adversely affect. With exceptions that may be present in some cases, these materials are used not used in amounts above about 50% by weight, based on the total composition, and preferably in amounts not more than about 20% by weight, based on the composition. The anaerobic compositions described above can be used in the generally using any known blending technique getting produced. Certain other ingredients that may be added may not be readily soluble and if such additives are used (e.g. silicon dioxide) it may be necessary to mix them in Use high shear forces.

The following examples illustrate the invention. example 1

In this example, normal anaerobic compositions are compared with the compositions of the invention. That Monomer I used in this example has the formula

= (CH ₃ ) COOCH ₂ CH ₂ OCONh-

- (PR)

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9 8 3 5/0604

ICC-29 <M

wherein (PR) is the propylenetriol oligomer without its three hydroxyl groups means. A general process for the preparation of the monomer I is described in GB-PS 1,430,422, among others.

Compositions A, B and C are made by simply adding the following ingredients in the proportions given mixed.

Parts by weight

(1) Monomer I 95

(2) ethoxylated bisphenol-A-

diacrylate - - 95

(3) Benzoin isobutyl ether 4 4 4

(4) Cumene Hydroperoxide III

(5) poly (methyl methacrylate) 19

(6) methyl methacrylate 77

Total weight at established

Material 140 g 10 g 50 g

Component 5 is the polymeric compound used in the present invention. It has an intrinsic viscosity in chloroform at 25 ⁰ C 2.5 to 3 »0 and is obtained from the Imperial Chemical Industries, Limited, under the trade designation CA-603rd Component 6 is the volatile solvent; it is a reactive solvent in the sense described above. Component 3 is a photoinitiator that reacts when exposed to UV radiation by releasing free radicals. Ingredient 4 is a peroxy catalyst that forms free radicals. Ingredients 1 and 2 are polymerizable monomers in the usual sense that can polymerize to form the cured adhesive or coating composition.

The compositions B and C are known compositions, in each of which for conversion into a fiction, contemporary addition

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ICC-29 oi9

composition the addition of part of the composition A.

is required.

Compositions A (90 g) and B (10 g) are under manufacture the composition D according to the invention mixed well. The composition A (50 g) and the composition C (50 g) are mixed well to produce composition E according to the invention.

The respective compositions B and C (state of the art) and D and E (according to the invention) are tested as follows. A thin film of the composition is smeared onto a microscope slide and exposed to a Philips MB / ü 400 watt ultraviolet lamp irradiated at a distance of 10 cm.

All compositions are converted to hard solids, B and D in 2 min and C and E in 1 min.

The known compositions B and C keep a fatty one or sticky surface that is still there after several hours. Compositions D and E according to the invention are dry to the touch within 30 seconds of exposure time with the lamp and stay dry indefinitely afterwards.

Example 2

Compositions F and G are made by simply mixing the following ingredients in the proportions indicated manufactured.

ethoxylated bisphenol A diacrylate Cumene hydroperoxide tributylamine poly (methyl methacrylate) Methyl methacrylate Total weight of material produced

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Weight 5 Parts 5 F. VJl G 5 95 - 4, 3, 0, G 0, G - 19th - 77 25th 75

ICC-29 δ Φ

Composition F goes well with Composition G below Formation of Composition H mixed.

Adhesive bonds are made by placing the adhesive on a flat surface of weldable steel that is attached to a Sandblower treated applies. Another steel surface is laid over the first, and the two will be with clamped together with a spring clip. This is done using the composition and also the composition F.

.9

■ j

After 5 hours, the clips are removed and it is found that the metal parts are firmly adhered to one another. The excess Adhesive outside of the adhesive bond made with Composition F is moist to the touch. The excess Adhesive outside of the adhesive bond made with Composition H is dry to the touch.

Example 3

Compositions J and K are made as follows:

(1) Poly (methyl-n-butyl methacrylate) (Elvacite 2013 - DuPont)

(2) ethylene glycol dimethacrylate

(3) Monomer II

(4) Monomer I.

(5) hydroxypropyl methacrylate

(6) acrylic acid

(7) tributylamine

(8) cumene hydroperoxide

Monomer I is that defined above. The monomer II has the formula

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Weight Parts J K 31 ·. 69 - 45.0 20.6 28.6 2.8 0.3 2.6

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ICC-29 ii

CH ₂ = C (CH ₃₎ COOC ₃ H ₆ OCONH - / """" V-CH ₃

^ -NHOCO- / S-C (CH _{3) 2}

A general process for the preparation of monomer II is given in GB-PS 1,430,422 cited above.

10 parts of J are added to 90 parts by weight of preparation K Formation, after mixing, of the preparation L.

Thin films from preparations K and L are spread over glass surfaces (microscope slide) and ^{heated in an oven at 105 °} C. for 20 min. They are then cooled to a temperature of 35 ^0C. At this temperature, the surface of preparation K is sticky, that of preparation L is not sticky.

t /

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709835/0604

Claims (13)

Loctite (Ireland) Limited ICC-29 claims 26S9663 1. curable adhesive or coating composition; characterized in that it contains as a mixture: containing a hardenable part (a) at least one acrylate or methacrylate monomer, (b) a free radical polymerization initiator, and containing an additive part (c) an organic solvent compatible with the curable part, (d) dissolved in the solvent, about 2 to about 200 wt. l of organic polymer with an average molecular weight of over about 10,000 and a glass transition temperature of at least about O ⁰ C, based on the curable part, wherein the curable composition does not become tacky upon evaporation of at least a portion of the solvent. 2. Composition according to claim 1, characterized in that net that it contains a UV initiator as initiator. 3. Composition according to claim 1, characterized net that it contains an organic peroxide as initiator 4. Composition according to claim 1, characterized gekenr net that it uses a chlorinated carbon as a solvent » substance contains,. . . .. 5. Composition according to claim 1, characterized ge} dass.sie a reactive'Losungsmitte as a solvent - 29 709835/0604 6. Composition according to claim 1, characterized in that it is an organic polymer and / or polyacrylates Polyalky! Methacrylate contains. 7. Curable anaerobic adhesive or coating composition, characterized in that it contains as a mixture: (a) at least one acrylate or methacrylate monomer, (b) an organic hydroperoxide or perester initiator for free radical polymerization, (c) an organic solvent compatible with the curable part, (d) dissolved in the solvent, about 2 to about 200% by weight of organic polymer with an average molecular weight above about 10,000 and a glass transition temperature of at least about ⁰ ° C., based on the curable part, wherein the curable composition upon evaporation of at least some of the solvent does not become sticky. 8. The composition according to claim 7 »characterized in that it contains cumene hydroperoxide as initiator. 9. Composition according to claim 7 »characterized in that it additionally contains a UV initiator. 10. Composition according to claim 7, characterized in that that it contains a chlorinated hydrocarbon as a solvent. 11. Composition according to claim 7 »characterized in that it is a reactive solvent as the solvent contains. 12. Composition according to claim 7 »characterized in that that it contains polyacrylates and / or polyalky! methacrylates as the organic polymer. - 30 - 709835 / Ü604 26S9663 ICC-29 · · 13. Method for transferring a curable adhesive - · fabric or coating composition containing at least one curable acrylate or methacrylate monomer, in one non-sticky state, characterized in that one (1) adding an organic solvent compatible with the curable composition to such a composition, the solvent containing from about 2 to about 200% by weight, based on the composition, of an organic polymer having an average molecular weight above about 10,000 and a glass transition temperature , are dissolved by at least about O ⁰ C, and one (2) allowing at least a portion of the solvent to evaporate, leaving the composition non-tacky State is transferred. - 31 - 709835/06 (U