DE2944787A1 - ADHESIVE MATERIAL AND METHOD FOR CONNECTING TWO AIR-TROUBLE-FREE SUBSTRATES USING THE SAME - Google Patents

Description

DIPL. ING. HEINZ BARDEHLt PATENT ADVOCATE

File number:

Munich, November 6] 979

29A4787

My reference: P 2973

Applicant: nostik GmbH

Gattenhöferweq 3G 63 70 Oberursel

Adhesive composition and method of joining two airtight substrates using the same

description

The invention relates to improved adhesives and activators suitable therefor; it relates in particular to new, improved adhesive compositions and a method for adhesive or adhesive bonding of two airtight substrates at ambient temperature.

Various polymerizable preparations or compositions are known which are believed to cure through free radical polymerization of their ethylenically unsaturated components. In the field of polymerizable adhesives, for example, reactive liquid or flowable adhesive masses are known which cure by addition polymerization of the monomeric components at room temperature with the formation of adhesive bonds between the surfaces of various different materials.Adhesive masses that are intended to cure between opaque, impermeable or other materials with formation an adhesive bond, may contain or consist, for example, of one or more polymerizable acrylate or methacrylate ester monomers, a source of free radicals such as a peroxide, hydroperoxide, perester or peracid, and an activator for interaction with the source of free radicals Initiation of the polymerization of the monomers at room temperature. The source of free radicals and the activator are advantageously stored separately from one another before the adhesive is used, some of which may be contained in a mixture with the monomers during storage, so that a two-part adhesive mass is obtained, which hardens to form an adhesive bond, when the two parts are brought together in the absence of oxygen.

- *. 29U787

One particularly convenient method is to use reactive liquid or flowable adhesives become a part the adhesive mass containing the activator before application another part of the adhesive mass from the polymerizable Monomers and the free radical source in the form of a primer coating applied to a surface to be connected. This method allows the use of the adhesive mass without it it is necessary to mix the two parts together before application. The activator is expediently one those which, with respect to the monomers, are in non-stoichiometric Quantities can be used.

While the adhesive bonds formed in this manner are very beneficial, certain amine-aldehyde reaction products that are effective as activators are liquid materials with a certain degree of toxicity and a strong odor. In view of the growing demands for non-toxic materials It is desirable to develop an adhesive composition which contains an activator system with the lowest possible toxicity and low odor. In this connection it should be mentioned that one is considering the use of solid materials as activators, but in the area of adhesives a commercially acceptable level of technical performance must also be achieved, which usually means that the materials are not in their solid state Form can be present in the bond. It has also been found that amine-aldehyde reaction products, previously preferred as activators, lead to cured adhesive bonds which tend to discolor significantly under the influence of light. This tendency is seen as a disadvantage for adhesive bonds, especially those that are visible, e.g.

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between glass and other translucent or transparent materials.

An object of the present invention is to provide an improved Indicate adhesive mass that contains or consists of one or more polymerizable monomers with one or more acrylic or methacrylic acid residues per molecule, a free radical source and an activator to interact with the source for the free radicals to initiate the polymerization of the monomers.

It has been found that adhesive compositions that work at ambient temperature are curable with the formation of adhesive bonds between, for example, opaque, impermeable substrates without external application of Heat, light or other radiation, may contain or consist of polymerizable acrylic or methacrylic acid esters, one Source of free radicals and an activator made of an organic material which can be easily derived from the easily accessible leuco-sulfuric acid ester of an indigo or thioindigo dye.

According to the invention usable activators contain or consist from an organic material that has a 5-membered ring containing a sulfur or nitrogen atom in its molecule, having, which is connected to a substituted or unsubstituted aromatic ring system of the molecule and which is connected to a first Carbon atom of the 5-membered ring is bonded, the first carbon atom to a second carbon atom of the 5-membered Ring and is bound to a third carbon atom, which is not a member of the 5-membered ring, but a member of an aromatic

-JT -10

or heterocyclic ring system, wherein the structure is such that the C = C bond between the first and the third carbon atom is a single bond, wherein a substituent R, on the second carbon atom and a substituent R «on a fourth carbon atom, the one Is a member of the second aromatic or heterocyclic ring system, which is bonded to the third carbon atom, are present, wherein the substituents R. and R "and the organic material are such that the organic material in the presence of the source of free radicals under a Adhesive bond-forming conditions can be converted into a diketo form, in which R ₁ and R ^ each in = 0 and the CC bond between the first and third carbon atoms are converted into a double bond.

The organic materials thus defined include, for example Compounds with the following formulas:

and

Ct

-yr- 29U787

in which R. and R.sup.1, which are identical to or different from one another may represent radicals of the -OX type, the group OX preferably denoting an OH group or a group which can be converted into an OH group by a simple chemical treatment, for example of an ester group.

Preferred activator compounds of the general ones mentioned above Class includes materials that differ from the dyes Anthrasol 04B, Anthrasol orange HR, Anthrasol gray IBL, Anthrasol pink IR extra, Derive anthrasol blue AGG and anthrasol pressure black. Each of these dyes is characterized by a conjugate Double bond system that has two ring systems * in common, one or both of which form a 5-membered heterocyclic ring with a Represents (represent) nitrogen or sulfur atom. The preferred materials are further characterized in that the above said heterocyclic or aromatic rings for their part each over two carbon atoms of the ring to aromatic Rings are bonded, with at least one of the rings being a substituted aromatic ring or an element of a substituted one It can be assumed that the commercially available Dyes are in the form of the sodium salts of the sulfuric acid ester of their leuco form, and for the purposes of the present invention they are converted into a form (hereinafter referred to as the active form) in which they are immersed in an acidic medium (generated by the ^ Monomers) represent valuable activators for the invention. The conversion to the active form can be achieved in that the ester in an organic solvent, for example a · « lower aliphatic alcohol, especially methanol, which contains a small amount of water, dissolves.

050026/0868

It is believed that in the active form the ester groups have been converted to hydroxyl groups which are oxidizable in an acidic medium in the presence of a free radical generator such as a peroxide to form free radicals, as in the table below II shown schematically in relation to Anthrasol 04B.

The leuco-sulfuric acid esters formerly referred to as "indigosols" are also referred to as "solubilized indigoid cup dyes" and ^M leuco cup dyes "and are marketed in the form of their sodium salts under various trade names including " indigosol " and" anthrasol ".

The preferred activators are solids, the organic in aue reaching, in a volatile solvent for application to a substrate are soluble. They are to be considered odorless, non-toxic materials, and when combined with acrylic and methacrylic ester monomers and a source of free radicals, they give adhesive bonds at room temperature with good strength and applicability between opaque, impermeable substrates of various materials. It has been found that adhesive bonds formed with these activator bonds between translucent or transparent materials also have good strength and good applicability. Although a pale color through

the dye may occur, the adhesive bonds are under the influence of light does not become increasingly discolored to the same extent as bonds that are based on the use of activators have been produced by amine-aldehyde reaction products

The free radical source and activator are kept in separate containers before use. The source for free Radicals are preferably together with the polymerizable monomers in a first part or adhesive part of the adhesive mass Contained along with inhibitors and they are kept in polyethylene bottles that contain a considerable amount of atmospheric oxygen included to ensure the storage stability of the first part. The activator is preferably stored in the form of a solution in an organic solvent and forms the second part, the activator preparation of the adhesive mass. The activator preparation is preferably in dark colored bottles or in stored in a light-impermeable aerosol container.

It is clear that the activator preparation is not in stoichiometric Quantities must be mixed with the adhesive part of the adhesive mass. When using the activator preparation part and the Adhesive part of the adhesive mass (composition) can be mixed with one another immediately before use, or the activator preparation can be applied to one or both substrates and the polymerizable composition can then, for example, be applied to the activator on the substrate. the Activator preparation preferably contains a sufficient amount of an organic solvent so that the activator preparation can be easily applied to the substrate, for example by brushing, in order to have a very good after evaporation of the solvent

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29A4787

Form a thin solid coating. Alternatively, the activator preparation can be contained together with a propellant in an aerosol container from which the required quantities can easily be taken. If necessary, the activator preparation can contain additional materials, such as a film-forming polymeric material or a liquid polymerizable monomer, such as a methacrylate ester monomer such as 2-hydroxypropyl methacrylate or trimethylolpropane trimethacrylate, or a mixture thereof, in order to produce the required coating on the substrate.

The Aktivatorzubereitung may conveniently be up to 5 wt -.% Of the selected organic activator in an organic solvent such as acetone or methanol. In the presence of a source of free radicals, these activator preparations cause curing of the polymerizable adhesive compositions with one or more ethylenically unsaturated compounds in air-free adhesive bonds. The time required for setting or curing the adhesive mass is comparatively short and it can be further reduced by incorporating certain sulfur-containing compounds or transition metal compounds into the activator preparation. The term "transition metal" used here is to be understood as meaning a metal which has more than one stable valence state and which is able to form complexes, suitable examples of which are in particular vanadium, chromium, manganese, iron, cobalt, nickel and Copper. Can for achieving a quick setting time (a fast curing) to mixtures of these materials, eg a mixture of 0.1 to 1 wt -.% Of the solution of the sulfur-containing compound and 0.05 to 0.5 wt .- / o of Solution of the transition metal compound. The prefer-

Ö30020 / 08Sft

th materials are in the commonly used organic Solvents soluble.

Sulfur compounds which can be used in the activator preparations according to the invention include, for example, organic thiols, organic disulfides and organic sulfur compounds which also contain nitrogen in their molecule. Suitable organic thiols (RSH) include dodecyl mercaptan, octyl mercaptan, phenyl dimercaptan, and thioglycolic acid. Suitable organic disulfides (RSSR ¹ ) include pheryl disulfide. Suitable organic compounds that also contain nitrogen in their molecule include thioacetamide, tetramethylethiouram disulfide, thiocarbanilide, thiourea, l-allyl-2-thiourea, 2-mercaptothiazoline, 2-mercaptobenzothiazole and 2,5-dimercapto-1,3,4- thiadiazole

Transition metal compounds which can be used in activator preparations according to the invention include compounds which containing the metal, in the form of a solder joint, e.g. with a ß-diketone or ethylene or propylenediamine, or in the form of a compound of an organic acid or an alcohol, such as naphthenates (e.g. from cobalt, nickel, manganese), octoates (e.g. from copper), hexoates and propionates (e.g. from iron). Preferred materials are acetylacetonates of vanadium, copper, cobalt and iron.

Polymerizable materials that can be used in adhesive compositions according to the invention contain monomers which, according to the Radical mechanism are polymerizable and they contain preferably one or more acrylate or methacrylate groups per molecule. These materials include the diacrylates and di-

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29U787

methacrylates of mono-, di-, tri- and tetraethylene glycol, the Trimethacrylates of trihydroxy alcohols such as trimethylolpropane trimethocrylate, compounds of acrylic acid and methacrylic acid with terminal hydroxy and glycidyl such as 2-hydroxypropyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, and the like Reaction products of the latter, which preferably have two or more terminal acrylate or methacrylate groups, e.g. those derived from 2-hydroxypropyl methacrylate and pyromellitic dianhydride, and acrylates and methacrylates, the derived from epoxy resins; and mixtures thereof. Polymers such as butadiene / acrylonitrile and polymethyl methacrylate can be used can also be contained in the adhesive part together with adhesion promoters, acrylic acid or methacrylic acid and, if necessary, normal additives for adhesive compounds.

In the adhesive part there are also inhibitors (e.g. hydroquinone or 2,6-di-t-butyl-4-methylphenol), which prevent undesired polymerization of the monomers.

Acrylates and methacrylates preferably used in the adhesive compositions are tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 2-hydroxypropyl methacrylate and glycidyl methacrylate and an oiacrylate derived from an epoxy resin and mixtures of two or more thereof.

Suitable sources of free radicals include organic peroxides (including the hydroperoxides), peresters, and peracids. Preferred materials are cumene hydroperoxide and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane.

0300 ^ 0/085

To explain the invention in more detail, exemplary adhesive compositions according to the invention are described in more detail below, However, it should be pointed out that these examples only serve to illustrate the invention and this in no way refers to it is limited.

Any of the exemplary adhesive compositions described below came in two parts. A first part or adhesive part consisted of one or more polymerizable materials with a or more acrylate or methacrylate groups per molecule and a source of free radicals. A second part or activator preparation part consisted of an activator that came with the source for free radicals (at the time of intimate contact between the two parts) can cooperate when placed between two impermeable substrates in the absence of oxygen is to effect the setting (curing) of the adhesive to the substrates without external application of heat or actinic Linking radiation together.

Using those given in Table I below Components in the specified there

Exemplary first parts of the adhesive masses, which were liquid or flowable at 20 ° C., were produced by weight.

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-AT -

Table I. component

exemplary first adhesive part

Tetraethylene glycol dimethacrylate Trimethylol propane - trimethacrylate 2-HydroJcypropyl-methacrylate Diacrylate (A), glycidyl methacrylate derived from an epoxy resin

Acrylic acid Pyromellitic dianhydride Butadiene / acrylonitrile rubber (B) Butadiene / acrylonitrile rubber Cumene hydroperoxide Hydroquinone

2.6-0i-t-butyl-ij.-methyl phenol

1 2 .3 3 .3 32 - - 20th 15th 30th 30th 35 .5 35 .5 ■ - 30th 15th - 3 3 10 7th 7th - 1 1 5 - .2 - .2 - 5 .0 5 .0 3 3 3 0.1 - - - 0 0 100.1 100 100

The diacrylate (Α) used was a reaction product of acrylic acid and an epoxy resin (made from epichlorohydrin and bisphenol A with an epoxy equivalent weight of 182 to 194 and a viscosity at 25 ° C of 100 to 150 poise) in a molar ratio of 2: 1. It is believed that the reaction product contains a significant amount of difunctional material with two functional acrylate groups per molecule.

It was the case of the butadiene / acrylonitrile rubber (B) used Perbunan N3807NS from Bayer AG. The butadiene / acrylonitrile rubber (C) used was Hycar 1401H80 from Goodrich Company.

030020/086

The first parts of the adhesive compositions were prepared by dissolving the rubber in a mixture of the di- and trimethacrylate monomers, the 2-hydroxypropyl methacrylate and the Inhibitors. The rubber (C) can be dissolved directly in this mixture at 75 ° C. However, the rubber (B) must first be dissolved in methylene chloride and this solution must then be mixed with the mixture of the di- and trimethacrylate monomers, 2-hydroxypropyl methacrylate and the inhibitor and then the methylene chloride must be removed under vacuum. The pyromellitic dianhydride became that containing the rubber Mixture added and this mixture was heated for 2 hours at 80 C, whereby a reaction product of the dianhydride and 2-hydroxypropyl methacrylate molecules. In the end after the mixture was cooled to room temperature, the glycidyl methacrylate, acrylic acid and cumene hydroperoxide were added.

Various exemplary activator preparations were produced by dissolving various leukocupine dyes, which are available under the trade name Anthrasol, in methanol as a solvent. The precipitate formed (which was presumably sodium sulfate) was filtered off and the remaining solution, which contained the active form, was in used the following tests. The structural formulas show the active form of these dye materials in solution, as well as one oxidized form of the active form, which is formed when reacting with a hydroperoxide with the formation of free radicals and water, as indicated in Tables II and III. It follows that each of these active forms is made from an organic material consists, which has a 5-membered ring in its molecule,

which contains a sulfur or nitrogen atom attached to a substituted or unsubstituted aromatic ring system of the Molecule is bound and that to a first carbon atom of the 5-membered ring is bonded, the first carbon atom to a second carbon atom of the 5-membered ring and to a third carbon atom, which is not a member of the 5-membered ring, but a member of an aromatic or heterocyclic one Ring system, is bonded, the structure being such that the C-C bond between the first and the third carbon atom is a single bond, with a substituent R 1 on the second carbon atom and a substituent R ^ on a fourth Located carbon atom, which is a member of the second-mentioned aromatic or heterocyclic ring system, the is bonded to the third carbon atom, the substituents R. and R "and the organic material being such that the organic Material converted to diketo form in the presence of the free radical source under the adhesive bond formation conditions in which R, and R «are each converted into = 0 and the C-C bond between the first and third carbon atoms is converted into a double bond. In the following Tables II through VIII, the active forms I through VI are derived from anthrasol materials as indicated below:

Active form no. derived from I. Anthrasol 0I4B II Anthrasol orange HR III Anthrasol gray IBL IV Anthras olros a IE Extra V .Anthrasol Blue AGG VI Anthras oil pressure black IGR

630020 / 085Ö

In Examples 1 to 4, the solutions were prepared using 1 wt -.% In the solution of the selected Anthrasol materials. In the solutions of Example 2 were 0.5 in addition to the materials Anthrasol -.% Used of the selected organic sulfur compounds. In the solutions of Example 3 were 0.1 in addition to the Anthrasol material -.% Ubergangsrnetaliverbindungen * used in the solutions of Example 4, in addition to the material Anthrasol 0.5 part by weight jC an organic sulfur compound and 0.1 wt -.% of a bond Ubergangsmetaliver used. The components of the activator preparations are given in Tables IV, V, VI and VII below *

Examples 1 - 4

The setting time (curing time) of various adhesive-activator combinations at standard room temperature (23 + 2 C) and a humidity of about 50 % was determined on glass plate substrates. The glass was wiped with a solvent and a thin layer of the activator formulation was applied to one of the surfaces to be bonded and the solvent was allowed to evaporate. Example 1 of the first exemplary adhesive parts was applied in the form of a thin layer and the glass plates were pressed together so that they partially overlapped with the adhesive in between and with the exclusion of air from the adhesive by pressing the substrates together firmly. The bonds were tested by pulling the glass plates apart by hand. When this was no longer possible, the adhesive was considered to have set (hardened). The shortest time after which the bindings are no longer opened manually

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2944707

could be recorded as setting time (curing time). The results thereby obtained are as follows Tables IV, V, VI and VII are given. It was found that the time within which the activators after application on the surface retained their activity was on the order of 2 hours.

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Tobelle II structural formulas

2944707

Anthrosol 04B

active form I from anthrasol 04B

oxidized form from Anthrasol 04B

fcr

£ R00H

63002 & / 08S *

active connection no.

Tobelle III structural formulas active form

oxidized form

HjCjgO OC ₂ H ₅ -

Il

^C > c- ^C

H ₅ CjO

OH

CH ₃ OH

03002Ö / OSB CH ₁

Table III - continued Structural formulas

active connection active form no.

CH ₂ , OH OH oxidized form

OU 0

+ 2R-O- + EB ₂ O

Y \

29U787

Table IV Results of Example 1 - Setting Time (Cure Time)

Activator containing the active form
No. Setting time
(Curing time) I. 1 - 1 ^ hours II 1 _ 1J- " III 1 - 1ε » IV 1 - 1J- η V 1 - 1J ·,. VI 50 minutes

Table V

Results of Example 2 - Setting Time (Cure Time)

Containing sulfur 50 6th I. Active form No. V 30th 6th VI link 3 15th min. 90 min. 7th 15th min. Dodecylmer captan min. 10 min. 5 min. Thioglycolic acid Tetramethyl 16 Hours. 6 hours 21st Hours. thiur amdisulf i d min. 15 minutes. min. Thiocarbanilide 2k ρ min 2.5 min. H min. Allyl thiourea 2,5-dimercapto- min. 23 min. min. 1,2, l; -thiadiazole 2-mercapto Hours. 2 hours. Hours ' benzthiazole III 25 min. Ij- min. 6 hours 15 minutes. 3.5 min. 11 min. 1 H.

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Table VI Results of Example 3 - Setting Time (Cure Time)

Transition metal compound __ Cu (II) Active form: V. (Ill) Acetylacetonatw I. Acetylacetonate v 0.1Ji in methanol III 0.1ji in methanol V VI 75 min. 11 min. 30 min. II4. min. 70 min. 9 min. 28 min. 7 min.

Tobelle VII Results of example 4 - setting time (curing time)

Organi see -sulfur compound + 0.1Ji 0.5Ji thio K) .1Ji 0.5Ji thio ♦ o.iji and transition metal compound Cu-AcAc glycolic acid «: 3U-AcAc carbanilide Cu-AcAc li min, + 0.1Ji 13jm ± n, + o.tji I ^ mixes. Ii min .. V -AcAc 15 minutes. V -AcAc 1 min. Active form o.5ji Aiiyi- i £ min, 30 see. 13 min. US see. 2 min. I. thiourestef 1J- min, 30 see. 11 min, \\ S see. 1Y min. III + 0.1Ji 30 see. t ^ 5 see. V V-AcAc 30 see. I4.5 see. VI 20 see. 20 see. 20 see. 20 see.

(V-AcAc stands for vanadium (lll) acetylacetonot) (Cu-AcAc stands for copper (II) acetylacetonot)

2 9 U 7 fi 7

From the results of Examples 1 to 4 it can be seen that a setting time (hardening time) of less than 2 hours at room temperature the combination of the first exemplary part 1 of the adhesive and the activator can be achieved with selected dye derivatives. It can also be seen from this that the setting times (curing times) at room temperature can be reduced by incorporating selected Sulfur compounds or transition metal compounds alone or in combination. In this way you can through appropriate selection of the materials setting times (curing times) at room temperature of a few seconds or several minutes or even hours be achieved.

It should be noted that the setting times (hardening times) on glass substrates were determined for comparison between different combinations of adhesive part and activator part is not excessively influenced by possible catalytic effects of the substrate surface on the curing reaction will. In practice, these adhesive compositions must be capable of forming bonds by curing at room temperature using any of a variety of substrate materials, some of which (e.g., steel, copper, brass and stainless steel) has a significant effect in terms of reducing setting time (hardening time) and some (e.g. Chrome, zinc and tin) have a lesser effect or even no significant effect (e.g. PVC) on the setting time (curing time) to produce satisfactory adhesive bonds.

Another factor that needs to be considered is that the adhesive masses must be usable and efficient in

COPY

29Λ4787

Connection with various impermeable, opaque or transparent materials without additional heat or light from the outside supplied or any curing treatment among a variety from normal ambient temperature conditions within the range of at least about 5 to about 30C.

Example 5

To determine the strength of the adhesive bonds that are using were produced by adhesive compositions according to the invention, the second and third exemplary formulations of an adhesive (first

Part) used in combination mLt two selected activator preparations for joining "different substrates under standard room conditions (23 + 2 ° C and about 50 % RH). The component amounts used in the selected activator preparations are given in parts by weight in Table VIII below.

Table VIII component

exemplary activator preparations

Anthrasol Blue AGG 2-Hyclroxypropyl-Methacrylat Trimethylol propane

trimethacrylate Allyl thiourea vanadium (IV) oxide

acetyl_acetonat Acetyl-acet on Methanol

(a) '(b) 1.5 1.5 1.5 3.0 1.5 - 1.5 1.5 0.3 _ 0.3 - 93 A 9k- 0 100.0 100.0

/ rt Q K rt

Copy

These activator preparations were prepared by dissolving the anthrasol blue AGG in the methanol with stirring and then allowing the mixture to stand for 2 hours at room temperature. The precipitate was removed and then the remaining components added to the solution with stirring. The solutions were placed in dark colored glass bottles with a The screwed-on cap is filled with a brush fixed to the inside of the cap.

The setting time (curing time) on glass at room temperature was determined for many samples in the same way as above using the second and third exemplary first adhesive parts together with the exemplary activator preparations (a) and (b). The results obtained are in the Table XI given.

Trial bindings were made and tests were subjected to the Determine the tensile shear strength, peel strength and impact strength of the bonds. The test bindings were as follows indicated prepared using substrate materials that have been pretreated in the manner indicated in Table IX was.

Pairs of platelets of 100 mm 25.4 in large pretreated Substrates were brushed with the activator solution and allowed to dry, the solution being in the form of a thin layer of the

Activator compound on each platelet weighing

2 about 5 to about 10 mg per cm remained. The exemplary first part was applied to only one of the platelets and the pair of platelets were aligned and compressed to allow air

030020/0858

-vr-

exclude and achieve an overlap of 12.7 mn «it the adhesive between the overlapping parts in a layer about 0.1 mi thick.

The tensile shear strength of the test bindings was measured at 23 ° C. (in N / sm ² ) 24 hours after the test bindings had been formed; the bonds were aged at 23 ° C. An Instron test machine was used to pull the bonds apart at a rate of 1 mm per minute. The force required is given in Table X.

The school strength of test compounds, which had been aged at 23 ⁰ C for 24 hours, was determined at 23 ° 6 using a scarf angle (Abziehwinkels) of 90 and a separation speed of 30 mm per minute. The force required to initiate the separation of the bonds is given in Table XI in the "Initial Force" column and the force required to continue the separation of the bonds is given in Table XI in the "Peeling Force" column.

The impact strength of the sample compounds was determined at 23 ⁰ C using a Schlagpendeii according to ASTM D 950-72. The area of overlap was 6.45 cm. The samples were aged for 24 hours at 23 ° C prior to testing. The results are given in Table XI in N χ cm / cm »

For many uses in the field of adhesives Tensile shear strength results of about 4 N / m "or more are considered satisfactory and Table IX shows that that values in this order of magnitude can be achieved with use

030020/0856

the adhesive compositions according to the invention with various different materials that are suitable for bonding have been pretreated. The results of the peel or peel and impact tests show that the adhesive compositions according to the invention are satisfactory for many purposes.

Table IX Example 5 Surface and preparatory treatments

Substrate No. Material and Treatment

1 mild steel; degreased and sandblasted

2 mild steel; oily surface untreated

3 mild steel; rinsed off with acetone and dried

4 aluminum; sandblasted

5 aluminum; pickled and dried

6 aluminum; rinsed with acetone and dried

7 brass; sandblasted

8 brass; rinsed with acetone and dried

9 chrome plated steel; sandblasted

chrome plated steel; rinsed with acetone and

dried cadmium plated steel; rinsed with acetone and

dried stainless steel; rinsed with acetone and dried tin plated steel; rinsed with acetone and

dried zinc plated steel; sandblasted zinc plated steel; rinsed with acetone and

dried

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Table IX - continued

16 copper; sandblasted

17 copper; rinsed with acetone and dried

18 PVC; wiped with a solvent

19 glass; wiped with a solvent

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Table X Example 5 - Certainty (N / um)

example
more liable
first
adhesive
part example
stick acti
va tor accessories
. riding 1 2 3 k 5 6th 7th Substrate. Nx. 9 10 11 12th 13th 9.5 15th 16 17th 18th 19th 2 a B.1 £ 10.C 21.1 5.07 16 .: 6.C 6.86 11.7 lij-.S 9.7I4 5.8 9.1 Ο.76 0.6f I4..93 3 a 7.6: 11.2 2.11 8th 2.6 6.82 6.C 5.I4.3 5.6 0.91 0.9: 3.13 7.5 u-eii

Table XI Example 5 - Setting or curing time

Peel and peel strength

Impact resistance

exemplary
the first,
adhesive
part exemplary
Ak t i va port-to loading
riding Setting time
Substrate. No. 19 .SffcffWeetiakeit Sleep fixity
Substrate no. 1 2 a (Seconds ' Substrate # 3 (N. cm / cm) 2 b 10-20 Anfin ^T g ^> tU * ^nm ) peel
strength strength 77 3 a 90 - I8O 15.3 2.9 ' 3 b 10-20 29 90-180 I4..9 2.5

OC ₂ H ₅ -

CH, OH

CH,

α α

+ 2R-0 * +

030020/0856

-3fc-

CH ₃ OH

+ 2R-O. + 2H ₀ O

030020/0856

- ¹ V?

Number: 2944717 Int. Cl. *:> COOJ 3/00 Registration day ;. β. November 1979 Opening day: May 14, 1980

ß <-

ORIGINAL INSPECTED

Claims (1)

Claims 1. Two-part adhesive mass that contains or consists of one or more polymerizable materials with one or more acrylate or methacrylate groups per molecule, a source of free radicals from an organic peroxide, hydroperoxide, perester or peracid and an activator for cooperation with the source for free ο radicals such _for initiating the addition polymerization of the polymerisierbnren materials, characterized in that the activator contains or consists of an organic material that contains in its molecule a 5-membered ring containing one sulfur or nitrogen atom bonded to a substituted or unsubstituted aromatic ring system of the molecule is bound. and which is bonded to a first carbon atom of the 5-membered ring, the first carbon atom being bonded to a second carbon atom of the 5-membered ring and to a third carbon atom that is not a member of the 5-membered ring but a member of an aromatic or heterocyclic ring system, where the structure is such that the CC bond between the first and the third carbon atom is a linear bond, with a substituent R. on the second carbon atom and a substituent R- on a fourth carbon atom, which is a member of the second aromatic or heterocyclic ring system mentioned, which is bonded to the third carbon atom, wherein the substituents R. and R "and the organic material are such that the organic material in the presence of the CueJIc for free radicals under conditions in which the Formation of the adhesive bond occurs, can convert into a diketo form in which R ₁ and R ₃ respectively ls in = 0 and the CC bond between ORIGINAL INSPECTED The first and third carbon atoms are converted into a double bond, whereby the adhesive mcisse in the intimate
Contact between the components of the adhesive mass, which are arranged between two impermeable substrates in the absence of air from the adhesive mass, is cured, whereby the substrates are adhesively connected to one another. °. Adhesive mass according to claim 1, characterized in that the activator contains or consists of a material of the formula C OH 3. Adhesive composition according to claim 1 or 2, characterized in that that the activator contains or consists of a material of the following Formulas H ₅ C ₂ O Γι 1 0 0 '?, 0/0 W h H 2944737 OH Bt- pH CH: ce 29A4707 -A- 4. Adhesive mass according to one of claims 1 to 3, characterized in that that the activator also contains a sulfur-containing compound or a transition metal compound or a mixture thereof. 5. Adhesive composition according to claim A _1, characterized in that the sulfur-containing compound is an organic one Thiol, disulfide or a compound that is in their Molecule also contains nitrogen. 6. Adhesive composition according to claim 4, characterized in that the metal compound is vanadium (III) acetylacetonate, Copper (II) acetonylacetonate or vanadium (IV) oxide acetylacetonate acts. 7. Adhesive mass according to one of claims 1 to 6, characterized in that that a first part of the adhesive mass contains or consists of a polymerizable material made of tetraethylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, 2-hydroxypropyl methacrylate, Glycidyl methacrylate, a diacrylate derived from an epoxy resin, or a mixture of two or more thereof and the source of free radicals, and that a second part of the adhesive mass contains or consists of an activator, as stated in one of the preceding claims. 2944737 8. Adhesive composition according to claim 7, characterized in that the second part also contains 2-hydroxypropyl methacrylate or trimethylolpropane trimethacrylate or a mixture thereof. 9. Adhesive mass according to one of claims 7 to 8, characterized in that the first part of the adhesive mass of polymer-f ^ baren monomers, in particular 2-hydroxypropyl methacrylate, in a mixture with an amount of pyromellitic dianhydride. 10. A method for the adhesive (adhesive) joining of two air-impermeable substrates at ambient temperature, characterized in that using two substrates with in appropriately pretreated surfaces on the surface one or both substrates applies an activator preparation, which is a solution of an activator in one volatile alcoholic solvents, as in any of the Claims 1 to 6 and 8 indicated, is drying the preparation lets, on one of the surfaces, a part of an adhesive composition that contains or consists of one or more polymerizable Materials with one or more acrylate or methacrylate groups per molecule, a source of free radicals from one organic peroxide, hydroperoxide, perester or peracid, applies, the substrates in intimate contact with the preparation (adhesive mass) with the exclusion of air and with complete polymerization of the polymerizable materials presses together to form an adhesive bond between the surfaces. fi30020 / 08HÄ