Curable adhesive compositions containing reactive multi-functional acrylate

ES 2 301 769 T3

DESCRIPTION

Curable adhesive compositions containing reactive multifunctional acrylate.

Related requests

EP 1 424 379 is pending with the European Patent Office and refers to similar content.

Technical field

The present invention relates to adhesive compositions especially well adapted for use in anchoring materials in or to concrete or masonry products, and to anchoring methods. More particularly, this invention relates to curable adhesive compositions comprising polymerizable vinyl-containing compound (s) and reactive multifunctional acrylate compound (s), to methods for bonding using such compositions, and to bonding structures produced using such compositions or methods.

Background of the invention

Many applications require a material to be anchored in either concrete or masonry products. For example, anchor bolts are used in various fields of engineering and construction as strength or reinforcement elements in rock formations, or in masonry or concrete structural bodies. The bolts, which are usually metallic, are inserted into holes in rock formations, or in masonry or concrete structural bodies, and are fixed or anchored therein by means of an anchoring composition. Objects that have been attached to concrete or masonry products using anchor bolts include electrical conduits, panels, pipes, and wall sections. Adhesive anchors are preferred over mechanical anchors for anchoring in concrete or soft masonry products because, among other reasons, adhesive anchors place less stress on concrete or masonry products. As used herein, the term "masonry products" will include stone, brick, ceramic tile, cement tile, hollow concrete block, and solid concrete block.

Curable synthetic resins are known to be used as a primary adhesive for the secure holding of bolts, anchor rods and similar devices in solid rock, masonry products and concrete. Typically, but not exclusively, some of the starting components of the adhesive composition are kept separate from each other and are then combined at or near the point of attachment. In such so-called two-part systems, the components that are kept separate until the time of use are combined on site and then inserted into the anchor bolt, the hole or hole prepared to house the bolt, or both. Thus, the formation of the cured adhesive body that attaches the fastener to the base structure begins approximately at the time the fastener is placed in its final position.

Many of the curable adhesive compositions currently used in industry, and in particular in the field of anchoring in or to concrete, rock and similar materials, are based on compounds that polymerize or cure by addition polymerization of monomers, oligomers, prepolymers and Similar compounds that have at least one ethylenic unsaturation in the molecule and therefore undergo vinyl addition polymerization cure. For example, many adhesive compositions based on epoxy resin and acrylic material cure by this mechanism in this manner.

Although curable adhesive compositions that have heretofore been used as anchoring compositions have performed with a certain degree of success, applicants have come to appreciate that an unexpected and dramatic improvement in performance is not only desirable but possible.

Summary

The present invention relates to a curable adhesive composition for anchoring materials in or to concrete or masonry products, comprising:

to. a polymerizable vinyl ester compound;

b. an ethylenically unsaturated monomer reactive with said polymerizable vinyl ester,

c. from about 5% by weight to about 10% by weight of reactive multifunctional acrylate;

d. curing catalyst; Y

and. activator.

ES 2 301 769 T3

As used herein the term "reactive multifunctional acrylate" refers to "compounds that have at least two acrylate functionalities that are reactive", under the conditions used to cure the adhesive, with at least one of the compounds involved in the curing reaction or formed by the curing reaction. As used herein, the term "acrylate functionality" refers to a functional group having the general structure illustrated below:

<img file="ES2301769T3_D0001.tif" />

wherein R can be any group that does not substantially interfere with or prevent reaction of the multifunctional acrylate compound with the polymerizable resin. In preferred embodiments, R is independently H or a substituted or unsubstituted alkyl, aryl, oxyalkyl, arylalkyl, or oxyalkylaryl. In highly preferred embodiments, each R is H.

The composition of the present case is distinguished with respect to the teachings of document US 2002/010 282 which corresponds to document US-A-2003181571, by the fact that it includes, as a polymer, vinyl ester, while document US '282 does use of acrylate.

More generally, the resin of US'282 is copolymer + monomer of alkyl acrylate ester or monomers of methacrylic acid and alkyl acrylate ester, while the resin of the present case is compound of polymerizable vinyl ester + ethylenically unsaturated monomer + multifunctional acrylate.

Thanks to that, the composition of the present invention shows high extraction at high temperature.

It should also be noted that a composition very similar to that of the present case has been the subject of the parallel application EP 03 292 799.0 (EP-A-1 424 379) which claims the priorities of the same days.

In particular, the present invention realizes claims 2-7.

Applicants have found that exceptional results can be achieved in accordance with the present invention by using the present reactive multifunctional acrylate with polymerizable resins comprising, and preferably consisting essentially of, selected polymerizable vinyl ester compounds in combination with a selected reactive diluent for the compounds. polymerizable vinyl ester. Furthermore, applicants have discovered that unexpectedly superior performance is possible when polymerizable vinyl ester compounds are present in adhesive compositions in amounts of from 10% by weight to 30% by weight, and even more preferably from 10% by weight. wt% up to 25 wt%, particularly when such amounts are used in combination with a substantially styrene-free reactive diluent, preferably vinyl toluene, in a vinyl ester: reactive diluent weight ratio of from 0.8 to 3, and even more preferably from 0.8 to 1.5. Furthermore, Applicants have found that unexpectedly superior results are generally achieved when polymerizable vinyl ester compounds are present in adhesive compositions in amounts of from 70 pbwa to 95 pbwa, and even more preferably from 85 pbwa to 95 pbwa, where the term "pbwa" means parts by weight based on the active components, as more particularly defined hereinafter.

One aspect of the present invention provides an adhesive composition comprising polymerizable vinyl ester comprising one or more repeating units and at least one terminal vinyl carboxylate, preferably a C vinyl carboxylate.₃-C₆, where the ratio of the number of repeating units to the number of terminal vinyl carboxylate units is, on average in the composition, from 0.4 to 2.0.

Another aspect of the present invention provides adhesive compositions that are especially well adapted for anchoring materials in or to concrete or masonry products, comprising, in combination with reactive multifunctional acrylate, a polymerizable vinyl ester corresponding to formula (I) below,

<img file="ES2301769T3_D0002.tif" />

in which

Ar is a substituted or unsubstituted aryl radical with a valence of at least two,

ES 2 301 769 T3

R is independently a substituted or unsubstituted divalent radical derived from alkyl, oxyalkyl, arylalkyl or oxyalkylaryl,

R² is independently H, substituted or unsubstituted vinyl carboxylate radical, substituted or unsubstituted epoxy ester radical, or R, for each R_x, x is independently 0 or 1, for each O_Y, and is independently 0 or 1, for each (OR²)_z, z is independently from 0 to 4, provided that at least one and must not be zero if z is zero, and n is from 1 to 5.

An important aspect of certain embodiments of this aspect of the present invention resides in formulating the adhesive to include the polymerizable vinyl ester compounds of formula 1 such that the ratio of 0 to the number of R groups² of vinyl carboxylate is, on average for the composition, from 0.4 to 2.0, more preferably from 0.4 to 0.7 and even more preferably from 0.4 to 0.5.

Generally, the compositions of the present invention also include an ethylenically unsaturated monomer reactive with the polymerizable vinyl ester and compatible with the reactive multifunctional acrylate. It is sometimes common practice to refer to a combination of this type of polymerizable polymer and reactive diluent as a "resin", and such terminology will sometimes be used herein to refer to such combinations. In certain highly preferred aspects of the present invention, the reactive diluent comprises vinyl toluene, and even more preferably does not contain any substantial portion of styrene.

In another aspect of the present invention, the present composition comprises polymerizable vinyl ester having a glass transition temperature (Tg) of from 80 ° C to 130 ° C, and more preferably from 90 ° C to 110 ° C. Preferred compositions also have a thermal diffraction temperature (HDT) of from 90 ° C to 130 ° C and more preferably from 100 ° C to 120 ° C. In certain preferred embodiments, the vinyl ester has a glass transition temperature of 130 ° C and a thermal diffraction temperature (HDT) of about 130 ° C.

Optionally but preferably the present compositions also include a curing catalyst, activator and filler.

An important aspect of the present invention is the provision of adhesive compositions that produce excellent bond strength, particularly at relatively high temperatures. In preferred embodiments, the present adhesive compositions achieve an extraction performance in one hour at a temperature of 23 ° C of at least 70 KN, and in 24 hours at a temperature of 23 ° C of at least about 80 KN, and after 24 hours at 80 ° C has an extraction force measured at a temperature of 80 ° C of at least 50, the extraction force being measured as in the examples herein.

Detailed description of the preferred embodiments

The present invention provides adhesive compositions, and more particularly compositions and methods for anchoring materials to or to concrete or masonry products. Materials to be anchored in or to concrete or masonry products include metallic objects, such as steel bolts, ceramic, other concrete objects or masonry products, plastics, glass, and woods.

The present compositions comprise active components and optionally but preferably certain inactive components. As used herein, the term "active components" refers to those components that participate in curing the composition, either directly as a reagent or indirectly as a catalyst or inhibitor.

As mentioned above, one of the important active components of the present invention is reactive multifunctional acrylate. It is contemplated that numerous compounds can be adapted for use as the reactive multifunctional acrylate of the present invention, and all such compounds are useful within the broad scope of the present invention. In highly preferred embodiments, the reactive multifunctional acrylate is at least trifunctional, and in certain embodiments at least tetrafunctional, and in certain other embodiments at least pentafunctional. Of course, the reactive multifunctional acrylate of the present invention may comprise a combination of two or more multifunctional acrylate compounds, each independently having the same or different levels of functionality. A preferred trifunctional acrylate is trimethylolpropane, which is sold under the trade name SR-351 by the Sartomer Company of Exton, PA, USA A preferred pentafunctional acrylate is dipentaerythritol tetraacrylate, which is sold under the trade name SR-399 by Sartomer Company of Exton, PA, USA.

ES 2 301 769 T3

Although the applicants do not intend to be bound by or by any particular theory of operation, it is believed that the reactive multifunctional acrylates of the present invention act to provide numerous and effective crosslinking sites for the adhesive composition as it cures, thereby improving density and other properties. physics of the cured adhesive, such as pull-out force and fire resistance.

The relative amount of reactive multifunctional acrylate included in the present compositions can vary widely depending on numerous factors, such as for example the functionality of the compound, and the other components of the composition. However, preferred embodiments of the present adhesive compositions comprise from 1 percent by weight (% by weight) to 40% by weight of reactive multifunctional acrylate, more preferably from 3% by weight to 30% by weight, and even more preferably from 5% by weight to 10% by weight. It is also preferred that the present adhesive compositions comprise from 5 pbwa to 30 pbwa of reactive multifunctional acrylate, more preferably from 10 pbwa to 30 pbwa, and even more preferably from about 10 pbwa to 25 pbwa. As used herein, the designation "pbwa" means parts by weight based on the total active components in the adhesive composition. In addition, unless specifically stated otherwise, the percentages by weight and pbwa of the components in the present adhesive compositions as specified herein refer to the composition after it has been formulated for use in conjunction. . Thus, for two-part compositions of the type described hereinafter, the pbwa values ​​and percentages refer to the adhesive composition based on the combination of parts A and B of such compositions.

In addition to active components, the present compositions comprise at least one polymerizable compound, preferably in the form of a resin. Although the remainder of this specification will refer to compositions based on vinyl ester resins, it will be appreciated by those skilled in the art that the descriptions contained herein regarding vinyl ester resins may be adapted for use in connection with other types of resins.

The present compositions comprise at least one polymerizable vinyl ester compound and optionally but preferably a reactive diluent for the polymerizable vinyl ester compound. Other active components that are included in certain preferred embodiments include catalyst (preferably a free radical catalyst), chain transfer agent, inhibitor (preferably a free radical inhibitor), activator, promoter, impact modifier, crosslinking agent, and crosslinking agent. coupling. As for inactive components, in certain embodiments it is desirable to include filler, non-reactive diluent, thixotropic agent, fragrance, antifoam agents, wetting agents, and fungicides in the composition.

It is contemplated that the relative proportions of the components included in the present compositions may vary widely depending on numerous factors, such as for example the environment of contemplated use, the desired strength of the bond to be formed, the particular materials to be bonded. and other factors. However, preferred aspects of the present adhesive compositions comprise from 5 percent by weight (% by weight) to 50% by weight of polymerizable vinyl ester compound, more preferably from about 10% by weight to 40%. by weight and even more preferably from 10% by weight to 30% by weight. It is also preferred that the present adhesive compositions comprise from 20 pbwa to 65 pbwa of polymerizable vinyl ester compound, more preferably from 25 pbwa to 60 pbwa and even more preferably from 30 pbwa to 60 pbwa.

As described above, the present compositions preferably contain polymerizable vinyl ester compound as a vinyl ester resin including reactive diluent. Although the relative amounts of reactive vinyl ester diluent can vary widely within the scope of this document, it is generally preferred that the vinyl ester resin comprises from 35% by weight to 65% by weight, based on the total weight of the resin, of the reactive diluent, the remainder preferably consisting essentially of polymerizable vinyl ester compound. In such embodiments, it is preferred that the present adhesive compositions comprise from 20 percent by weight (% by weight) to 70% by weight of vinyl ester resin, more preferably from about 30% by weight to 50% by weight. weight and even more preferably from 35% by weight to 45% by weight of said resin. It is also preferred that the present adhesive compositions comprise from 70 pbwa to 98 pbwa of such resins, more preferably from 75 pbwa to 95 pbwa and even more preferably from 85 pbwa to 95 pbwa of such resins.

The composition can be dispensed using various methods known to those of skill in the art. For example, the composition can be dispensed using a dual cartridge device similar to a sealer gun, or the composition can be dispensed using a glass or coated capsule. The composition can also be dispensed in bulk from bulk containers using meter-mix equipment, which is known to those of skill in the art. US Patent Nos. 4,651,875, 4,706,806, and 4,729,696, refer to the use of glass capsules to dispense the composition in the form of a two-part system. It is recognized that the amounts of the various components of the anchor composition may vary depending on many factors, including the type of delivery system used.

In preferred dispensing methods, the anchor composition is formed by mixing a first composition (sometimes referred to herein as part "A") that contains the resin, and that may contain an inhibitor to prevent premature polymerization, but not includes no substantial amount of catalyst from

ES 2 301 769 T3 and a second composition (sometimes referred to herein as part "B") that contains the catalyst and remains separate from part A until use. Typically, mixing of part A and part B occurs immediately prior to use of the anchor composition. For example, when the anchor composition is dispensed using a dispensing gun, the first composition and the second composition, which are contained in separate cartridges from the dispensing gun, can be mixed as they are ejected from the cartridges and applied or either to concrete or masonry products, or to the material to be anchored to concrete or masonry products, or to both. Similarly, when the anchoring composition is dispensed using a glass capsule, the capsule is typically comprised of two chambers containing the first composition and the second composition, respectively. When the glass capsule is crushed, the two chambers are crushed and the contents are allowed to mix, forming the anchor composition. For embodiments where the anchor composition is dispersed in bulk, Part A and Part B may be stored in separate bulk containers and combined by pumping with mixing at the appropriate rate to prepare the anchoring composition.

Although the present invention has been described above in the form of a two-part composition, it is contemplated that it is possible to formulate adhesives in accordance with the present invention as a one-part adhesive, and such formulations are within the scope of the present invention. For example, it may be possible to formulate the present adhesives as a single component anaerobic adhesive, and such formulation is within the scope of this document.

It is also generally contemplated that the amount of catalyst used in the present compositions can vary widely depending on numerous factors, the present adhesive compositions preferably comprise from 0.5% by weight to 10% by weight of catalyst, more preferably from 1%. % by weight to 8% by weight and even more preferably from 2% by weight to 6% by weight of catalyst. It is also preferred that the present adhesive compositions comprise from 0.5 pbwa to 25 pbwa of catalyst, more preferably from 5 pbwa to 20 pbwa and even more preferably from 5 pbwa to 15 pbwa of catalyst.

Initiators and activators, if included in adhesive compositions of the present invention, as preferred, are preferably present in amounts up to 0.05% by weight to 1% by weight and even more preferably from 0.1% by weight. weight up to 0.5% by weight. It is also preferred that the present adhesive compositions comprise from 0.1 pbwa to 5 pbwa of initiator and even more preferably from 0.1 pbwa to 1 pbwa.

Promoters are usually used in amounts up to about 0.5% by weight of the composition and preferably from 1 part per million to 0.5% by weight of the entire composition.

The preferred aspects of the above-noted components other than reactive multifunctional acrylate, along with the type and amounts of other additives in the present compositions, are described in detail below.

The polymerizable vinyl ester compound

It is contemplated that known methods for the formation of polymerizable vinyl ester resins and compounds can be adapted in view of the teachings contained herein to form compounds and resins in accordance with the present invention, and all such materials are considered to be within the scope of this document. In preferred embodiments, the polymerizable vinyl ester of the present invention is formed by reacting an epoxy compound with an ethylenically unsaturated carboxylic acid, anhydride, or alcohol, usually with the use of a polymerization inhibitor to prevent the vinyl ester resin from gel. In view of the teachings contained herein, it is believed that the vinyl ester resin according to the present invention can be prepared by any of the methods disclosed in any of the following patents: U.S. Patent Nos. 3,256,226 issued to Fekete and Cols. and No. 3,317,465 issued to Doyle and Cols., both assigned to HH RobertsonCo .; No. 3,345,401 issued to May; No. 3,373,221 issued to May; No. 3,377,406 issued to Newey; and No. 3,432,478 issued to May, all assigned to Shell Oil Co .; No. 3,548,030 issued to Jernigan; and No. 3,564,074 issued to Swisher et al., both assigned to Dow Chemical Co .; No. 3,634,542 issued to Dowd et al .; and number 3,637,618 issued to May, both assigned to Shell Oil Co.

Preferably, the epoxyvinyl ester is prepared by reacting the polyepoxide and the acid or derivative thereof in appropriate amounts, generally with heating and in the presence of a catalyst, such as a trivalent chromium salt, such as for example CrCl₃; or a phosphine; alkali salt, onium; or a tertiary amine, for example tris (N, N-dimethylaminomethylphenol). Optionally, the epoxyvinyl ester resin may be formed in the presence of a non-resinous, vinyl monomer, preferably not including styrene and preferably including vinyl toluene. The resulting product which is a combination of the polymerizable vinyl ester and reactive diluent will then constitute what is referred to herein as a "vinyl ester resin" and more specifically an "epoxy vinyl ester resin".

Examples of epoxy compounds that can be used in such forming reactions include, but are not limited to, those found in bisphenolic-type epoxy resins, epoxy-novolac type resins, amine-type epoxy resins, copolymerized epoxy resins, epoxy resins multifunctional and the like. Prefe

ES 2 301 769 T3 arguably, the epoxy resin used to form the present polymerizable vinyl ester has about 2 to about 3 of an average number of epoxy groups in the molecule.

Bisphenol type epoxy resin compounds that can be used include those found in bisphenol type epoxy resins A, F and S, each such compound preferably having 2 glycidyl groups in its molecule. Commercially available examples of bisphenol A type epoxy resin having 2 glycidyl groups in the molecule include those available from Reichhold under the trade designation EPOTUF® 37-140. Commercially available examples of bisphenol F type epoxy resin having 2 glycidyl groups in the molecule include those available from Reichhold under the trade designation EPOTUF® 37-138. In certain embodiments, bisphenol S type epoxy resin having 2 glycidyl groups in the molecule, and brominated bisphenol A type epoxy resins, which preferably also have 2 glycidyl groups in the molecule, can also be used.

Epoxy-novolac type resin compounds can also be used, and such resins are exemplified by phenolic novolac, cresolic novolac, aliphatic, alicylic and monocyclic epoxy resins.

Aliphatic type epoxy resin compounds can also be used, and such resins include, among others, hydrogenated bisphenol A type epoxy resin, having 2 glycidyl groups in its molecule. Such resins are commercially available from Reichhold under the trade designation EPOTUF® 37-051.

Alicyclic type epoxy resin compounds can also be used, and such resin compounds include, but are not limited to, alicyclic diepoxyacetal, dicyclopentadiene dioxide and vinylcyclohexene dioxide and the like, which have 2 epoxy groups in the molecule. Such epoxy resin compounds having an epoxy group in the molecule include vinylhexene monoxide and glycidyl methacrylate.

Monocyclic type epoxy resin compounds can also be used, and such resin compounds include, but are not limited to, resorcinol diglycidyl ether and diglycidyl terephthalate.

Amine-type epoxy resin compounds can also be used, and such resin compounds include, but are not limited to, compounds having 4 glycidyl groups in the molecule.

These epoxy resin type compounds can be used alone or in combination. The average number of glycidyl groups in the epoxy resin molecule is preferably from 1 to 6, more preferably from 2 to 4, and even more preferably from 2 to 3.

In preferred embodiments, the epoxy compound used to form the polymerizable vinyl ester of the present invention corresponds to formula (II) below:

<img file="ES2301769T3_D0003.tif" />

in which

Ar is substituted or unsubstituted aryl,

R is a substituted or unsubstituted divalent radical derived from alkyl, oxyalkyl, arylalkyl, or oxyalkylaryl, alkyl or arylalkyl,

R¹ is independently H or R, for each R_x, x is independently 0 or 1, for each O_Y, and is independently 0 or 1, for each (OR²)_z, z is independently 0 to 4, x, y, and z are each independently 0 to 5 as long as x and y cannot both be zero, and n is 1 to 5.

Examples of vinyl carboxylic acids and related compounds that can be used in the formation of the present polymerizable vinyl esters include ethylenically unsaturated mono and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, fumaric acid, maleic acid and anhydride. maleic, unsaturated (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate

ES 2 301 769 T3 of propyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, dodecyl (meth) acrylate and the like, nitriles such as (meth) acrylonitrile, amides such such as (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide and diethylaminoethyl (meth) acrylamide. For certain embodiments, methacrylic acid is preferred. Examples of alcohols having an unsaturated group include, but are not limited to, half esters derived from unsaturated dicarboxylic acids and / or unsaturated alcohols such as hydroxyalkyl acrylates, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) hydroxybutyl acrylate, pentaerythritol tri (meth) acrylate and glycerin di (meth) acrylate. Preferably, the related unsaturated acid or compound is one in which the reactive vinyl group is a terminal group.

With regard to the reactivity, flow performance and miscibility of the polymerizable vinyl ester resin, it is generally preferred that the vinyl ester resins of the present invention have an ester number of from 0 to 25 mg KOH / g resin and which, when available in the form of a 50 to 70% solution of reactive diluent monomer, have a viscosity of from 50 to 2000 mPa s at 23 ° C.

Generally, the polymerizable vinyl ester is present in the anchor composition in the range of from 20% to 90% by weight of the entire adhesive composition and even more preferably in an amount in the range of 20% to 70%.

In preferred embodiments, the vinyl ester corresponds to formula III below:

<img file="ES2301769T3_D0004.tif" />

in which

Ar is a substituted or unsubstituted aromatic radical with a valence of at least two,

R is independently a substituted or unsubstituted divalent radical derived from alkyl or arylalkyl,

R³ is a hydroxyl-substituted divalent radical derived from an alkyl radical,

R⁴ is independently a vinylcarboxyl radical or an epoxy radical, provided that the ratio of n to the number of R groups⁴ vinylcarboxyl is, on average for the composition, from 0.4 to 2.0, and n is from 1 to 5.

In highly preferred embodiments, the polymerizable vinyl ester corresponds to formula (IV) below:

<img file="ES2301769T3_D0005.tif" />

where n is from 1 to about 5 and where the ratio of n to terminal vinyl units is, on average for the composition, from 0.4 to 2.0. A vinyl ester composition corresponding to formula (IV) is available from Reichhold under the trade name Norpol Dion Ver 9165 in a 65% by weight solution with vinyl toluene.

The reactive diluent

In general, it is contemplated that the teachings of the present invention may be used to great advantage in connection with any one of the large number of known reactive diluents, particularly reactive monomers. Examples of reactive diluents that can be used in connection with the broad teachings herein include, but are not limited to, aliphatic vinyl compounds such as vinyl, propene, and butene chloride, aromatic vinyl compounds such as styrene, vinyl toluene, divinylbenzene, and pt. -butylstyrene, diene compounds such as butadiene, isoprene, chloroprene and pentadiene. Such reactive diluents can be used alone or in combination. However, the preferred aspects of the present invention contemplate avoiding styrene in the composition, and for this reason the preferred compositions do not contain a substantial amount of styrene. In highly preferred embodiments, the reactive diluent comprises vinyl toluene, and preferably comprises at least 50% by weight of vinyl toluene and even more preferably at least 70% by weight of vinyl toluene, the remainder of the components constituting the reactive diluent being, if There are, free of any substantial amount of styrene.

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Although it is contemplated that the amount of reactive diluent relative to the amount of polymerizable vinyl ester in the composition can vary widely depending on numerous factors particular to each application and contemplated use, it is generally preferred that the weight ratio of vinyl ester: reactive diluent is from 0.8 to 3, more preferably from 0.8 to 1.5 and even more preferably from 0.8 to 1.3. Optionally but preferably the polymerizable vinyl ester is soluble in the reactive diluent.

Inhibitor

Inhibitors, and particularly free radical inhibitors, are known to those skilled in the art. A preferred free radical inhibitor is hydroquinone. Other suitable free radical inhibitors include, but are not limited to, trimethylhydroquinone, hydroquinone monomethyl ether, t-butylcatechol, and naphthoquinone. It is also contemplated that more than one free radical inhibitor may be employed in the anchor composition. The polymerization inhibitor preferably comprises, more preferably comprises in a major proportion, and even more preferably consists essentially of hydroquinone. Of course, another inhibitor can be used alone or in combination with hydroquinone, such as, for example, parabenzoquinone, methylhydroquinone, catechol and the like which are conventionally used as polymerization inhibitors.

Although it is contemplated that the amount of inhibitor in the composition can vary widely depending on numerous factors particular to each application and contemplated use, it is generally preferred that the inhibitor is present in amounts of from 0.005% by weight to 5% by weight and even more preferably from 0.01% by weight to 0.1% by weight. Optionally but preferably the polymerizable vinyl ester is soluble in the reactive diluent.

Initiator

The vinyl ester resin composition of this invention can be easily cured by adding a curing catalyst, initiator, or both. Representative initiators include the aldehyde-amine condensation product, organic sulfonyl chlorides, tertiary amines, or mixtures thereof. For example, such a condensation product can be prepared from butyraldehyde and a primary amine, such as an amine which is, for example, aniline or butylamine. Also suitable as activators are tertiary amines, such as N, N-dimethylaniline, N, N-dimethyl-toluidine, N, N-diethylaniline, N, N-diethyl-toluidine, N, N-di- (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (hydroxypropyl) -p-toluidine, and the like. A preferred activator is N, N-di- (2-hydroxyethyl) -p-toluidine. Curing catalysts include organic peroxides such as methyl ethyl ketone peroxides, t-butyl peroxybenzoates, benzoyl peroxides, and dicumyl peroxides.

Although it is contemplated that the amount of inhibitor in the composition can vary widely depending on numerous factors particular to each application and contemplated use, it is generally preferred that the inhibitor is present in amounts of from 0.005% by weight to 5% by weight and even more preferably from 0.01% by weight to 0.1% by weight. Optionally but preferably the polymerizable vinyl ester is soluble in the reactive diluent.

Thixotropic Agents

The present anchoring composition can also comprise a thixotropic agent. The preferred thixotropic agent of the present invention renders the composition more fluid, ie, less viscous, when stirred, stirred or mixed or otherwise subjected to such shear forces. It is useful to include a thixotropic agent in the anchoring composition to ensure that the composition has the desired viscosity during application and after applying the composition. In addition, a thixotropic agent can be added to an anchor composition to prevent sedimentation of other solid components of the composition and to increase the viscosity of the composition. The thixotropic agent also makes it easier to dispense the composition since when a shear force is applied, for example ejection of the composition from a dispensing gun, the thixotropic agent makes the resulting composition less viscous, and therefore easier to expel. dispensing gun cartridges. The thixotropic agent can be found in the anchoring composition in an amount in the range of from 0.5% by weight to 10% by weight, and more preferably from 1% by weight to 5% by weight. The use of a thixotropic agent is not normally needed when dispensing the anchoring composition using a glass capsule. An example of a suitable preferred thixotropic agent is fumed silica. Also contemplated are the various silicas prepared by the various methods known in the art, including silicon tetrachloride pyrolysis and precipitation. Other suitable thixotropic agents include the various organoclays and various fibers. In some anchoring compositions, the thixotropic agent can also be considered a filler. A suitable silica thixotropic agent is Aerosil. RTM. R202, available from Degussa Corporation of Ridgefield Park, NJ It is also contemplated that more than one thixotropic agent may be used in the anchor composition.

Loads

The anchoring composition of the present invention also preferably comprises one or more fillers. Fillers are typically added to compositions for a variety of reasons, including to reduce the shrinkage of the composition that can occur during polymerization and to reduce the cost of the composition, as fillers replace a portion of more expensive components of the anchor composition. The charge can also provide a force

ES 2 301 769 T3 improved bonding of the anchor composition when polymerized and help prevent sedimentation of other particulate materials in the composition. Generally, the filler is a solid inert, inorganic particulate compound. By inert is meant that the filler does not interact deleteriously with any other component of the composition. Examples of suitable fillers include, but are not limited to, crushed glass, glass beads, quartz, silica, limestone, alumina, various clays, diatomaceous earth, and other materials such as mica, powdered flint, cryolite, trihydrated alumina, talc. , sand, pyrophyllite, fixed target, granular polymers such as polyethylene, hollow glass and polymer beads, zinc oxide, novaculite, calcium sulfate, and mixtures thereof. Preferred fillers are quartz, glass, and silica. Fillers can be treated with coupling agents to improve bonding to the polymer matrix. Examples of coupling agents that can be used to treat fillers are silanes, titanates, and zirconates.

Preferably, the present compositions contain fillers in an amount of from 10% to 80% by weight of the composition, more preferably from 20% by weight to 70% by weight and even more preferably from 30% by weight. weight up to 50% by weight.

The exact particle size of the filler will depend on the desired consistency of the composition and the method of dispensing the anchor composition. For example, fillers having a large average particle size (300 µm (microns) and above) can plug static mixers that are used in dispensing systems such as dispensing guns. On the other hand, fillers having a large particle size can be used in glass capsules. Preferred particle sizes are 50 µm (microns) or more. However, in cases where filler is used to prevent settling of other particulate matter in a composition, a particle size less than 50 µm (microns) may be desired. It is also recognized that a filler having a particle size less than 50 µm (microns) can be used in combination with other fillers, some having particle sizes greater than 50 µm (microns).

Other additives

The anchor composition can also contain a fragrance. A fragrance is used in an anchor composition to mask any odor from the composition that is thought to be undesirable or unpleasant. A preferred fragrance is Atlanta Fragrance 16332. Similarly, a pigment can be used to color the anchor composition. Suitable pigments are known to those skilled in the art.

Preferred Two Component Adhesives

In one embodiment of the present invention, the anchor composition is formed by mixing a first composition and a second composition. The first composition contains the polymerizable vinyl ester compound and preferably also at least a substantial amount, and preferably substantially all of the reactive diluent if present. The first composition preferably also contains an inhibitor to inhibit curing of the adhesive until desired, and the second composition contains a free radical catalyst. When the first composition and the second composition are combined, polymerization occurs.

In a preferred embodiment, the first composition comprises vinyl ester and a filler. The first composition may also comprise a thixotropic agent, a chain transfer agent, a free radical inhibitor, a fragrance, an activator, a promoter and / or a pigment. The second composition preferably contains a free radical catalyst. The second composition can also include a filler, a thixotropic agent, a fragrance, and / or a pigment. It is also contemplated that both the first composition and the second composition may contain some of the same components.

The weight ratio of the first composition to the second composition may be in the range of 1 to 1 to 40 to 1. Preferably, the weight ratio of the first composition (part A) to the second composition (part B) is 10 with respect to 1.

Examples

The following examples are provided to illustrate particular embodiments of the invention.

Experimental protocols

Preparation of two-part anchoring compositions

The appropriate amounts of polymerizable vinyl ester resin are prepared. The appropriate amount of inhibitor, activator, fragrance, and other components is added to the resin. The composition is mixed, preferably using a dispenser. The thixotropic agent is then added with shear mixing followed by addition of the filler. If more than one filler is to be included in the anchoring composition, it is preferable to add the first filler, then mix, then add the second filler, and so on until the desired number of fillers has been added to the composition until part A of the composition is complete. The same general procedure as described above is used to prepare part B consisting of thixotropic catalyst, filler, pigment, and other components.

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The above preparation procedure is used for the examples, except for the comparative example, in which case the adhesive was prepared according to the instructions provided.

Extraction performance

A concrete block of average weight of approximately 0.1 X 0.2 X 0.4 m (4 "X 8" X 16 ") is used substantially free of surface moisture. Typically, five repeated pull-out tests are performed for each adhesive composition tested. First, three equally spaced holes 110 mm deep and approximately 14 mm wide are drilled on the 0.2 X 0.4 m (8 "X 16") side of the concrete block. Afterwards, the holes are cleaned with a brush, with compressed air and vacuum. An adhesive composition is injected into the drilled holes and a type 304 stainless steel rod with 8 threads of 2.5 mm by cm X 1.2 cm (20 threads of 1/4 ”per inch X 12 mm) is inserted into the hole containing adhesive with a twisting motion. Time to extraction test (also referred to as cure time) is in the range of 0.5 hours to 72 hours, as indicated. The stainless steel rod was then connected to an Instron Universal Testing Machine, Model TTC, Instron Corporation, Canton, Mass., And the rods were withdrawn at 5mm (0.2 ") / minute until failure. The maximum load and type of failure were then recorded. Preferably, in an acceptable anchoring composition, the extraction performance in one hour at a temperature of 30 ° C is at least 55 KN, at 24 hours at a temperature of 30C it is at least 65 KN and after 24 hours at 80C as measured at a temperature of 80 ° C is at least 45 KN. Most preferably, the material that has been anchored to the concrete or masonry products, or the concrete or masonry products itself, fails before the adhesive composition. As can be seen from the following examples, the compositions of the present invention can achieve an extraction yield in one hour at a temperature of 23 ° C of at least 75 KN (i.e. 80 KN), within 24 hours at a temperature of 23 ° C of at least 90 KN (ie 94 KN) and after 24 hours is measured at a temperature of 80 ° C of at least 60 KN (ie 62 KN).

Comparative example

A featured commercially available anchor adhesive sold under the trade name HY-150 by Hilti Aktiengesellschaft of Schaan, Liechtenstein is prepared and used according to the instructions provided to measure various performance parameters as set forth in the above protocols. The following results are observed:

Adhesive - HY-150

Extraction, 1 h (KN) - 53

Extraction, 24 h (KN) - 61.8

Extraction, 80 ° C (KN) - 41.6

Gel time, min. (Trombomat) - 9

Pumpability - good (Table goes to next page)

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Example 1

A two part adhesive composition having a weight ratio of part A: part B of 10: 1 and the following formulations for part A and part B are prepared and used according to the above protocols:

Part A

<td>COMPONENT</td><td colspan="2">% in weigh %</td><td>in</td><td>pbwa</td>

<td></td><td>on the</td><td>part weight</td><td></td><td></td>

<td></td><td>TO</td><td>in A +</td><td>B</td><td></td>

<td>Vinyl ester resin *</td><td> 33,08</td><td> 30,07</td><td></td><td> 69,29</td>

<td>Inhibitor (hydroquinone)</td><td> 0,03</td><td> 0,03</td><td></td><td> 0,06</td>

<td>Initiator (Pergaquick A-</td><td> 0,37</td><td> 0,34</td><td></td><td> 0,78</td>

<td> 150)</td><td></td><td></td><td></td><td></td>

<td>Thixotropic agent</td><td> 2,70</td><td> 2,45</td><td></td><td> 0</td>

<td>(Aerosil R202)</td><td></td><td></td><td></td><td></td>

<td>Charge (sand)</td><td> 54,52</td><td> 49,56</td><td></td><td> 0</td>

<td>Acrylate (SR-351)</td><td> 9,31</td><td> 8,46</td><td></td><td> 19,5</td>

<td>* Resin</td><td>ester</td><td>vinyl</td><td colspan="2">understands</td>

<td>about 35% in</td><td>weight of</td><td>compound (s)</td><td>of</td><td>ester</td>

<td colspan="2">polymerizable vinyl according to</td><td colspan="3">present invention and</td>

<td>about 65% in</td><td>weight of</td><td colspan="3">reactive monomer that</td>

consists of vinyl toluene

Part b

<td>COMPONENT</td><td>% by weight in the part</td><td colspan="2">% in pbwa weight</td>

<td></td><td>B</td><td>in A + B</td><td></td>

<td>Catalyst (Cadox 40 E)</td><td> 49,51</td><td> 4,50</td><td> 10,37</td>

<td>Thixotropic agent</td><td> 1,99</td><td> 0,18</td><td> 0</td>

<td>(Tixogel VZ)</td><td></td><td></td><td></td>

<td>Charge (sand)</td><td> 47,52</td><td> 4,32</td><td> 0</td>

<td>Pigment (TiO₂)</td><td> 0,99</td><td> 0,09</td><td> 0</td>

The various performance parameters are measured as set forth in the previous protocols for the adhesive composition and the following results are observed:

Extraction, 1 h (KN) - 80.5

Extraction, 24 h (KN) - 94.5

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Extraction, 80 ° C (KN) - 61.9

Gel time, min. (Trombomat) - 7

Pumpability - good