DE1120045B - Method for bonding metals - Google Patents

Description

INTERNAT. Tbsp. C 09 j

GERMAN

PATENT OFFICE

D33504IVc / 22i

REGISTRATION DATE: JUNE 9, 1960

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL: DECEMBER 21, 1961

For bonding objects, in particular metals, adhesives have become known which harden under vinyl polymerisation in the presence of catalysts, especially redox systems. Such adhesives usually consist of monomer-polymer mixtures. Have special meaning obtained those adhesives based on unsaturated polyester resins and polymerizable, monomeric vinyl compounds are built up. Among the redox systems used to cure them those that have proven to be particularly effective are those made of peroxide compounds on the one hand and Amines, especially tertiary amines, are built up on the other hand.

It is also known to bond metals with the aid of adhesives, for example essentially of at least one monomeric, unsaturated, polymerizable compound, at least one polymeric compound and a polymer with the grouping

/ —CH ₂ -C = CH-CH _a - \

\ CI Y _n

and / or acrylic acid and with the aid of a known catalyst, preferably one Redox system, can be polymerized.

Mixtures are also known as metal adhesives, which essentially consist of at least one unsaturated Polyester, at least one polymerizable acrylic or methacrylic ester, at least one with the polyester compatible polyvinyl ether and curing catalysts exist.

It is also known to reinforce plastics with fibers. These include, for example, with Glass fiber reinforced unsaturated polyester resins and textile fiber reinforced phenolic resins.

When using the above metal adhesives, the general procedure is that the first to be glued Parts coated with the adhesive, then placed on top of each other and, if necessary, under lighter Apply pressure to be held in the appropriate position for a short time until there is sufficient initial adhesive force is reached. The polymerization then proceeds with further hardening.

In general, there is a tendency to use metal adhesives only for bonding thin sheets and small areas To use parts because otherwise the application of the adhesive required special care. When bonding thick metal objects, particular difficulties often arise. If you have an adhesive with a good brushing method for bonding metals

Applicant:

German gold and Süber refinery formerly Roessler, Frankfurt / M.,

Weißfrauenstr. 9

Dr. Erich Bäder, Hanau / M., Has been named as the inventor

capable consistency, there is a risk that this adhesive between the parts to be glued flows out. This risk is particularly great with vertical glue joints, which occur in many assembly work, ζ. B. in bridge construction, inevitably result. One tries to stop this leakage by applying To prevent an adhesive with a tough consistency, difficulties arise in uniform Applying the adhesive layer. Furthermore, there were previously concerns about the bonding of large areas Parts, with large tolerances, no flawless bonds can be obtained.

In order to avoid such disadvantages, metal bonds have already been made with the aid of polymerization adhesives, with the aid of peroxidic adhesives Catalysts the polymerisation takes place at the splice and to solidify fibrous materials, Tissues and the like are present (German Auslegeschrift 1 057 709). In this known method the procedure is such that one or more accelerators are added to the adhesive mixture and the peroxide compound is only added to this mixture shortly before the gluing is carried out. However, this resulted in processing times that were sometimes felt to be too short, so that in general only smaller batches could be processed.

Redox systems have become known as catalyst combinations for these known adhesive processes, which in addition to a peroxide a tertiary, aromatic amine or an N-dialkylolamine or contain a compound having a labile chlorine atom.

It has now been found that, with particular advantages, metals can be obtained using

109 750/542

3 4

Since peroxide polymerisation catalysts are used, small amounts of polyvinyl acetate, polyvinyl and accelerators hardening by polymerisation chloride, ketone aldehyde resin etc. can be added. Metal adhesives and fibers, especially for some purposes, it is further advantageous to glue fillers, fabrics, mats and the like, using a metal adhesive such as slate powder, barium sulfate and finely divided material for this purpose, which contains a peroxidic 5 SiO ₂ and the like. to mix in. The addition of a small amount of catalyst contains, used if one according to the invention quantities of Päraffin is also possible,
Used in accordance with fibers, fabrics or mats and the like.
Contains chlorine atom, or with an N-dialkylolamine, the best results with the invention which contains at least one aromatic radical, i ° process are achieved, however, if one uses adhesives or with a tertiary aromatic amine, its substances, which essentially consist of at least boiling point higher than + 230 ° C, have been pretreated with a monomeric, unsaturated, polymerisation. capable compound, at least one polymeric

For carrying out the compound according to the invention and a polymer with the grouping

Fahrens are all natural and synthetic fibers, 15 / CH C = CH CH \

for example polyamide, polyester fibers and the like, /]

suitable. The fibers can either be used as such or \ Cl /
in the form of mats and in particular in the form of

Tissues are used. However, and / or acrylic acid are preferred. The polymers used with fiberglass fabric. Asbestos and sisal fibers from the above-mentioned grouping are also used with advantage. Purpose - known under the name »NEOPREN«. As a monomeric way, they are impregnated with the mere, unsaturated, polymerizable connection adhesive before use. According to the preferred embodiment, liquid vinyl compounds, styrene or its homologues, acrylic acid esters, preferably first of all the parts to be bonded with a layer of methacrylic acid ester, alone or in a mixture of the adhesive known per se, can be used in the process according to the invention. Then used together. Polystyrene is advantageously used as the polymeric fibers impregnated with the same adhesive.
Fabric, mats and the like between the parts to be glued. In the case of glued surfaces that fit well, this cannot exceed _{10 ° / 0.} For many purposes, however, the priming with adhesive is omitted; 30 brought an acrylic acid addition of less than 3%, it is sufficient to choose the one soaked with adhesive. The neoprene content will preferably bring tissue between the adherends. less than 15 percent by weight, based on the total

As an adhesive, all known per se are kept mixed. In most cases it is sufficient Vinyl polymerization in the presence of peroxidic already an addition of 5% · As particularly suitable Catalysts and accelerators, especially 35 types of neoprene have been shown that do not work with Redox systems, hardening substances and mixtures of substances, sulfur or sulfur-containing compounds, suitable for modification. Adhesive embellishments of this kind have proven particularly good. These adhesives can also contain esters Mixtures proven, which essentially consist of a fumaric acid or maleic acid, in particular Monomer-polymer mixture exist and contain the fumaric acid dimethyl ester. The content of this preferably in the cold, d. H. without heat, 40 substances should preferably be less than 5% of the total cured can be. Such mixtures, the mixture amount. In addition, it is also beneficial For example, on the basis of unsaturated adhesive, so-called casting resins can also be used. Under Polyesters and polymerizable vinyl compounds casting resins are those with a monomer, z. B. build up, are in the French patents monostyrene, mixed condensation products 1 162 866, 1 109 816, 1 121 769 and in Belgium 45 polyhydric, optionally unsaturated alcohols Patent No. 579,366 has been described. Especially with polybasic, optionally unsaturated ones however, adhesives that essentially understand carboxylic acids are suitable. The addition of these castables made of at least one unsaturated polyester, resins should preferably be below 10%, at least one polymerizable acrylic or optionally small amounts of Methacrylic ester, at least one with the polyester 50 stabilizers, such as hydroquinone, are added, Compatible polyvinyl ether and, hardening catalyst The addition of dyes and fillers is also sators exist. Such unseeded are preferably possible.

In the case of the

tables, polyhydric alcohols, such as glycol, and, in short, the peroxidic processes according to the invention

-chain polybasic, unsaturated, organic catalysts 55 in amounts of up to 4 ° / ₀ and expedient

Acids, such as fumaric acid and maleic acid, build up moderately in as evenly a distribution as possible

are. The preferred polyvinyl ether is added to polyvinyl. Examples of those in question

methyl ether. The methacrylic acid methyl ester is catalysts are benzoyl peroxide, lauroyl peroxide,

preferably used. In addition, certain benzoyl peroxide chlorinated in the nucleus, such as 4,4'-para

Shares of higher dicarboxylic acids, ζ., Β. Adipic acid 60 chlorobenzoyl peroxide or 2,4-dichlorobenzoyl peroxide,

or phthalic acid, as well as higher glycols, e.g. B. tert. Butyl perbenzoate and the like. Among the compounds that

Hexanediol, can also be used. Also contain a labile chlorine atom in the molecule, include

still further monomeric and polymeric compounds, for example hydrochloric acid and its salts in particular

be included in the adhesives, e.g. B. other meth-organic bases, preferably the tertiary amines,

acrylic acid or acrylic acid esters, such as butyl methacrylate, 65 Furthermore, quart chlorides,

also small amounts of vinyl acetate, styrene, vinyl betaine or hydroxylamine derivatives according to the Belgian

toluene, etc. Of the latter, however, should see patent 545 139 and the French

only a few percent are added. On polymers. Patent specification 1 141 742 can be used. you will be

Applied in amounts of 0.05 to 2.0% to the fibers, fabrics and the like.

To the group of N-dialkylolamines, which at least contain an aromatic residue in the molecule, include, for example, diethylol-p-toluidine, diisopropylene - ρ - toluidine, diisopropylene - m - toluidine, din-butylene-p-toluidine.

Examples of tertiary aromatic amines whose boiling point is higher than + 23O ⁰ C are the following compounds: tetramethyldiaminodiphenylmethane, diacetic acid ester of diethylol-p-toluidine and N-tert-butylene-N-methylaniline. Of course, both types of amines in question can also be used simultaneously. They are preferably used in combination with acrylic peroxides. It goes without saying that the amines used are insensitive to oxidation.

In addition to the amines and the compounds that contain a labile chlorine atom in their molecule, can on the fibers also other components of known accelerator systems, in particular copper compounds, be applied. This also includes organic sulfur compounds, such as a-aminosulfones, «-Oxysulfones and mercaptans. Of these, the «-aminosulfones, which are at least one aromatic radical contained in the molecule, and the mercaptans are preferably used. It is also possible to add the mentioned accelerators to the adhesive mixture as additional components.

The above-mentioned substances can be applied to the fibers by methods known per se, such as Soaking, spraying, etc. and expediently subsequent drying take place. The fabrics will preferably used in the form of a solution. Any liquid that is volatile can be used as a solvent and are able to dissolve the substances mentioned. Examples are methyl methacrylate, Methyl acetate, acetone, methanol and water.

Of course, when applying them, care must be taken that the equipment of the mat, etc. with Sizing, finishing and finishing agents as well as binders are not removed if possible. This can be done in done primarily through a professional selection of the solvent used. Feel like that for example mats which have been impregnated using methanol or water are soft and loosely, while on the other hand when using, for example, methyl methacrylate or Methyl acetate as a solvent can detect a slight hardening. After this treatment the Substances in a very fine distribution on the surface of the fibers, fabrics, mats and the like. Those treated like that Fibers are very durable and can be stored for almost any length of time.

When the method according to the invention is carried out, the peroxide is as uniform as possible Distribution-containing adhesive mixture with the fibers, fabrics, mats and the like the amines or the compounds which have a labile chlorine atom in fine distribution on their Surface contained in contact, so that a quick and even hardening of the adhesive can be done. This can be carried out either at room temperature or at an elevated temperature will. As the adhesive mixture, as long as it does not come into contact with the fibers, fabrics and the like is brought, contains only the peroxide compound, the requirements for long processing times are given, so that in practical use larger batches for a period of several weeks can be available without the mixtures suffer a loss in the strengths to be achieved. · As a further advantage of the invention Process is recorded that after this the bonds with a simple two-component system can be executed. According to the method according to the invention, large-area Bondings that are subject to high requirements, even with large tolerances, are flawless Bonding can be achieved. The achievable strengths are available to those involved in bonding smaller parts can be reached, not after.

Another advantage of the method according to the invention is that the achievable shear stress at large overlaps is almost the same size as small overlaps. This means another Simplification of the gluing process because less attention needs to be paid to this point.

Furthermore, the shock and impact resistance of the bonded parts is improved by the method according to the invention.

In general, the stability of metal adhesive connections lies below the tensile strength in the seer pull test. This difference is in application of the method according to the invention is less large.

It is advisable to use thinner fabric when gluing small parts and to use and for large areas thick parts with corresponding tolerances to use coarser and / or thicker fabrics. The number of stitches and the mesh size should be coordinated so that the Meshes are penetrated so well by the adhesive that a quick and perfect wetting he follows. It is also advantageous, prior to gluing, the metal surfaces according to known methods pre-treat. This includes degreasing and, in particular, cleaning with a sandblasting fan.

example 1

100 g of a glass fiber fabric are mixed with a solution of 2.5 g of diisopropylene-p-toluidine in 120 ml Soaked in methanol and dried. After storage for 30 days, the fabric is covered with a Adhesive of the following composition coated on both sides and well saturated:

56 parts of monomeric methyl methacrylate,
39.9 parts of polystyrene,

3 parts NEOPRENE WRT,

0.5 parts acrylic acid.

3% of a hardening paste (50% benzoyl peroxide in dibutyl phthalate) is added to this mixture. admitted. The soaked fabric is inserted between the iron parts to be glued, without special Apply pressure. The iron parts are made of structural steel »St 37.12«. The bonding will carried out in two layers, overlapping. The dimensions of the base plates are 120 -34-10 mm and that of the cover flaps 120-34-5 mm. The ones to be glued Surfaces have been pretreated beforehand with a sandblasting blower. The overlap length of the bond is 50 mm. After a storage time of one day at room temperature, the shear breaking load of the bond is determined to be 9500 kg.

Example 2

As described in Example 1, a glass fiber fabric is soaked and dried. After a Storage time of 75 days, it is coated on both sides with an adhesive of the following composition and well saturated:

25.0 parts by weight of polyvinyl methyl ether

("LUTONAL" M 40, commercial product from BASF),

15.0 parts by weight of unsaturated polyester resin ("PALATAL" K 211/6, commercial product of BASF) (both legally protected trademarks),

10.0 parts by weight of monomeric vinyl toluene,
49.2 parts by weight of monomeric methyl meth-

acrylate,

0.3 parts by weight paraffin,
0.01 part by weight of hydroquinone,
2.0 parts by weight of highly disperse silica.

4 parts by weight of benzoyl peroxide paste (50% in dibutyl phthalate) are also added to the adhesive. With this, parts made of structural steel »St 37.12« are glued in a single overlap. the Adhesive surface has a dimension of 51 x 34 mm, the overlap length is 51 mm and the width 34 mm. After a storage time of 24 hours at room temperature, a Shear breaking load of 3600 kg measured.

Example 3

A glass silk mat (600g / sqm) is per 100 g of its weight with 120 ml of a solution of 0.3 g of phenylethyldibutylamine hydrochloride, 0.3 g of bis (tolylsulfonmethyl) amine and 0.3 ml of Cu solution (1000 γ Cu ⁺ VmI ) treated in methyl methacrylate. After this treatment, the glass mat is stored at room temperature for 100 days. The adhesive listed in Example 2 is used to produce the metal bond. However, the peroxide is tert. Butyl perbenzoate (50% in phthalate plasticizer), used in an amount of 1.6 ml. 0.2 g of bis (tolylsulfonmethyl) amine (50% in phthalate plasticizer) are also added to the mixture. The gluing is carried out as indicated in Example 1. After a storage time of 24 hours at room temperature, the shear breaking load is 5300 kg.

Example 4

The glass silk mat used in Example 3 is per 100 g of its weight with 120 ml Treated solution of 0.3 g of triethylamine oxide hydrochloride in methanol. After the treatment, the Mat stored at room temperature for 100 days. The adhesive mentioned in Example 1 is used for bonding used. The peroxide catalyst used is that mentioned in Example 3. It also contains 0.2 g bis (tolylsulfonmethyI) -amm paste and 0.1 ml the copper solution. All additives are calculated on 100 g of the adhesive. As in Example 1 indicated, carried out. After a storage time of 3 days at room temperature, a Shear breaking load of 3600 kg measured.

Claims (6)

PATENT CLAIMS: 1. A method for bonding metals using metal adhesives that harden by polymerization in the presence of peroxide polymerization catalysts and accelerators, and fibers, in particular fabrics, mats and the like an accelerator system, in particular copper compounds and / or organic sulfur compounds, characterized in that such fibers or fabrics or mats od Contains at least one aromatic radical, or with a tert. aromatic amine, the boiling point of which is higher than + 230 ° C, and optionally additionally with a further component of an accelerator system, in particular copper compounds and / or organic sulfur compounds, have been permanently impregnated. 2. The method according to claim 1, characterized in that pretreated fibers, fabrics, Mats or the like used that have been impregnated with the metal adhesive. 3. The method according to claim 1 or 2, characterized in that between the to be glued Metal parts that are provided with an adhesive layer that has not yet hardened with Fibers, fabrics, mats and the like soaked in the same adhesive. 4. Process according to claims 1 to 3, characterized in that one is im consisting essentially of a monomer-polymer mixture, preferably in the cold curable adhesive used. 5. Process according to claims 1 to 4, characterized in that one is a glass fiber fabric used. 6. Process according to Claims 1 to 5, characterized in that the compound which contains a labile chlorine atom, the hydrochloride of an organic base, preferably one Amine, in particular a tertiary amine or a quaternary ammonium compound, is used. Considered publications:
Lüttgen, "The Technology of Adhesives", 1959, Part 1, pp. 585, 593, 598, 599. © 109 750/542 12.61