JPS6366872B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention contains, as polymerizable vinyl monomers, vinyl polymers, free radical-generating compounds and adhesive promoters, acid amides or imides substituted on the nitrogen atom by chlorosulfonated alkyl, aryl or alkyl groups. Regarding adhesives. The invention further relates to a method of using an adhesive to bond two surfaces. From DE 23 37 049 A, two-component adhesive compositions based on polymerizable vinyl monomers, such as methyl methacrylate, and polymerization catalysts are known. The purpose of the above adhesive composition is to address the drawbacks of known adhesive compositions based on polymerizable vinyl monomers, namely the lack of storage stability, by adding chlorosulfonated polyethylene or a mixture of sulfonyl chloride and chlorinated polyethylene. , to overcome the often long curing times, insufficient bond strength, and the need for the absence of air. After gluing the two surfaces together, with a very short curing time as a result of the addition of curing accelerators, the resulting bond has a high tensile shear strength, however on the other hand higher temperatures (above 50 °C) are required. properties or properties required for adhesion to oily surfaces or properties in water. Furthermore, improved storage stability is not reliably guaranteed in all cases. A similar adhesive composition was published in German Patent Publication No.
It is described in Publication No. 2525099. Instead of chlorosulfonated polyethylene, other chlorosulfonated polymers or polymers combined with low molecular weight organic sulfonyl chlorides have been used. Examples include alkyl- and aryl-sulfonyl chlorides, such as methane, butane,
tridecane-, 2-naphthalene- or p-toluenesulfonyl chloride or diphenyl ether-4,4''-disulfonyl chloride. However, as tested, these compositions do not have the required tensile shear strength. The use of similar adhesives as unbacked sheets or as films on support materials is likewise already known, for example from German Patent Publication No. 25 24 197. Vinyl monomers and especially reactive It was not previously expected that the above-mentioned drawbacks would be overcome by the use of chlorosulfonated alkyl- or arylmaleimides in adhesives based on vinyl polymers. As a result, it was possible to obtain an adhesive that is resistant to heat, oil and water and has high tensile shear strength.Therefore, the present invention provides 30 to 80% by weight of at least one polymerizable vinyl monomer and at least one 10 to 50% by weight of a vinyl polymer and 0.05 to 10% by weight of a free radical-forming compound as an adhesive component, and as an adhesion promoter, the following formula: (In the formula, R represents an alkylene group having 1 to 25 carbon atoms, or a substituted or unsubstituted phenylene, naphthylene, or phenylene alkylene group having 1 to 4 carbon atoms in the alkylene moiety, and R ₁ and R ₂ each represent represents a hydrogen atom or a C1-C4 alkyl group, or R ₁ and R ₂ are a group in the formula:

Together with [Formula], a saturated or unsaturated heterocyclic ring which may be substituted with one or two methyl groups and does not contain any heteroatoms in the ring other than the nitrogen atom given by the above formula () form. ) The present invention relates to an adhesive containing 0.1 to 15% by weight of an acid amide or imide whose nitrogen atom is substituted with a chlorosulfonated alkyl, aryl, or alkyl group, expressed as a percentage of the adhesive component. Preferably R ₁ and R ₂ are groups:

Together with [Formula], they form a maleimide group which may be further substituted with one or two methyl groups, and R is preferably a phenylene group, but also preferably an O- or p-tolylene group. Preferably used vinyl monomers include:
Methyl or ethyl acrylate, methyl, ethyl, butyl or hydroxyethyl methacrylate, glycidyl methacrylate, styrene,
Examples include chlorostyrene, 2-chloro-1-3-butadiene and/or 2,3-dichloro-1,3-butadiene. Suitable vinyl polymers include, inter alia, acrylonitrile-butadiene-styrene terpolymers (powdered or granular ABS polymers), butadiene-styrene copolymers, isoprene-styrene copolymers, polystyrene and/or chlorinated polyethylene as well as polybutadiene, polyisoprene,
Unsaturated polyesters (alkyd resins), e.g.
Polymers that are not particularly reactive, such as those formed from maleic anhydride and polyethylene glycol or from fumaric acid and the diglycidyl ether of bis-phenol A (with acrylic groups at the ends). Compounds that generate free radicals include, for example: organic peroxides, hydropyloxides, peresters or peracids, especially cumene hydroperoxide or benzoyl peroxide. The amount is preferably 0.05 to 3
Weight%. The adhesives of the invention preferably contain additional components which can further improve the properties of the adhesive and improve the ease of handling during bonding or the speed of bonding. Among these additional components, mention may be made in particular of: (a) 5 to 20% by weight of adhesion promoter, especially methacrylic acid, based on the adhesive component; (b) 0.1 to 10%, especially 5% by weight. The following crosslinking agents, i.e. compounds with several functional groups such as dimethacrylate, for example 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate or divinylbenzene; (c) from 0.1 to 10% by weight, especially 1 to 10% by weight
evaporation inhibitors, such as chlorinated paraffins having 30-70% by weight, especially 50-60% by weight of chlorine;
(d) stabilizers (antioxidants) to extend the storage stability of the adhesive, such as hydroquinone, quinone or 2,6-di-tert-butyl-p; - Cresol (Jonol) 0.1 to 10% by weight, sometimes only 0.1 to 2% by weight; in the case of one-component adhesives, i.e. thermosetting systems, between peroxide and stabilizer; Stabilizers should not be added as they will clearly react with the adhesive and prevent heat curing; (e) Additionally, some may be used as separate additives and some may be used in place of acrylates to improve the adhesive properties of the adhesive. 0.1 to 10% by weight of a modifying mono- or dicarboxylic acid; said components are preferably p-toluenesulfonic acid, tartaric acid, maleic acid, fumaric acid, glutaric acid and succinic acid; (f) adhesion promoter 0.1 from 10% to 10% by weight, especially up to 2% by weight; silanes such as γ-methacryloxypropyltrimethoxysilane are preferred; (g) 0.1% epoxy resin to improve adhesive properties;
0.1 to 10% by weight: known liquid epoxy resins based on bisphenol-A are suitable; (h) 0.1 to 10% by weight of pigments to make the adhesive-applied surface more visible; known inorganic or organic pigments; and (i) the addition of a polyalkylene powder, such as polyethylene powder, which is effective in improving adhesion onto the polyalkylene sheet. When gluing two surfaces together, the adhesives of the invention, which may contain one or more of the additives mentioned above, can be used without or with accelerators (so-called two-component systems). Ru. In the former case, the adhesive is applied to one or both of the surfaces to be bonded and then the two surfaces are left unsuperposed for 15 minutes to 1 hour (or bonded immediately in the case of steel parts); after the open time. , the two surfaces are pressed together and heated at a temperature of 80 to 250°C for several minutes to several hours. It is convenient to leave the joint at room temperature for a few minutes to several hours before heating. When the heating is carried out by high-frequency heating (e.g. with a 500 W industrial high-frequency dielectric device from Hasler AG, Bern), on the one hand the bonding time can be considerably shortened, and on the other hand the so-called open time can be extended (as explained below). ). If the adhesive is used as a one-component system, i.e. without the addition of an accelerator, the method of adhesion is preferably to apply the adhesive to the surface to be bonded and leave the applied area for 15 minutes to several hours. The parts are then bonded, followed by a curing operation at about 100° C. for 1 hour or in a high-frequency oven for several minutes.
The disadvantages of curing at temperatures higher than those of two-component systems (the second component being an accelerator) are offset by the advantages of longer open times. Open time means the amount of time an adhesive applied to a substrate can be left without losing its adhesive properties. The longer open time is obtained because the layers can be applied somewhat thicker than could be applied with a two-component system, and the outer layer prevents air influence deeper into the coating. This is because, as a result, the deeper layers can retain their activity for a longer period of time. Furthermore, one-component systems have the advantage of being easier to apply. One-component adhesives can be conveniently processed into adhesive films or sheets, with or without a substrate or support. For the production of films with a support, the liquid adhesive of the invention can be applied to the support, for example a backing made of glass fibers or a backing made of acrylate, and then dried. The film is virtually or completely odorless and no longer tacky. Coating can be done on both sides of the support and the film can be dried for 1 hour at room temperature or for several minutes (5-10) in a stream of air. To produce films or sheets without a support, the adhesive of the invention is cast into a film onto a support, for example a polyethylene sheet, and then dried at room temperature. Films or sheets of this type can also be produced by extrusion rolling the adhesive. The film or sheet is colorless, but can be given the desired hue by adding dyes or pigments to the adhesive. Compared to the films or sheets described in DE 24 29 378 A1, those produced from the resin mixtures of the invention generally cure at lower curing temperatures (temperatures of 80-90° C.) and in a shorter time. ) and peel strength. Curing accelerators that can be used in two-component systems are secondary or tertiary amines as well as condensation products of primary or secondary amines with aldehydes, preferably N,N
-dimethylaniline or N,N-dimethyl-
Examples include p-toluidine, or a condensation product of 1 mole of aniline or butylamine and 3 moles of butyraldehyde. Some suitable accelerators are described in US Pat. No. 3,591,438. Bonding can be accomplished by first applying an accelerator to one or both of the surfaces to be bonded, then applying an adhesive to one or both surfaces, and subsequently laminating the two surfaces. The accelerator can also contain colored pigments for better discrimination from the adhesive. It is also possible to spray the accelerator onto both sides to be bonded which have already been coated with adhesive. After 5 minutes to 1 hour, a bond with a tensile shear strength value of 10 to 20 N/mm ² was obtained, and after 24 hours,
Values of 30N/mm2 or ^more can be measured. Another method is to add the promoter to the adhesive immediately before the gluing operation and then apply the adhesive mixture to one or both of the surfaces to be bonded. However, in this case, care must be taken to ensure that the adhesive mixture maintains its adhesive properties from mixing to adhesion. The amount of curing accelerator can be up to 50% by weight, preferably from 0.1 to 5% by weight of the adhesive. Suitable surfaces for adhesion are metal surfaces, such as steel, aluminum and aluminum alloys, including e.g. magnesium and silicon, copper and its alloys, so-called "zincrometalls" (zinc-chlor alloys), or polyamides, Surfaces of polar polymeric materials such as polyurethane, polyester, glass-fiber reinforced plastics, wood, glass, ceramic or paper, and coated surfaces. By using two-component systems, it is also possible to perform underwater gluing operations, for example, steel-to-steel or concrete-to-steel. In such cases, the use of higher viscosity accelerators such as amine-aldehyde products is particularly effective. The adhesives of the invention are also suitable for gluing pretreated polyethylene sheets in admixture with polyalkylene powders. Adhesives can also be used for bonding two different materials, for example metal and coated sheets. In this case, it is advantageous if the one-component system according to the invention is used first to form a film on the coated sheet, for example made of polyester, to be adhered. After drying, it can be stored in a roll at room temperature and transported by wheel, and the rate of decrease in adhesive strength is very slow; when stored in a refrigerator, the initial adhesive strength can be preserved for several months. There is. This is then placed on a metal surface and cured and bonded at elevated temperatures. The adhesive sheet is particularly suitable for gluing metal surfaces with or without a support. Place this sheet between the surfaces to be glued. This is pressed together, for example with a clamp, and held at a temperature of 80 to 100° C. for at least 15 minutes. In the formula, R ₁ and R ₂ are groups:

Maleimide, which forms a maleimide group together with [Formula] and serves as a base for a compound in which the maleimide group may be substituted with one or two methyl groups, is disclosed in, for example, US Pat. No. 3,618,290 or US Pat. 2444536 or German Patent Publication No. 1934791. The imides produced by these methods are then chlorosulfonated, for example by reaction with chlorosulfonic acid. In this way, N-
When the arylmaleimide is reacted with the above acid excess, the chlorsulfoaryl-maleimide is obtained in high yield and in a short time. Examples of the preparation of several adhesion promoters are described below: (a) Chlorsulfonated 1-naphthyl-N-maleimide 39.6 g (0.404 mol) of maleic anhydride and 110.0 g of methylene chloride in a 750 ml sulfonation flask. and dissolve by gentle heating (first solution). 57.2 g (0.4 mol) of 1-naphthylamine are dissolved in 50 g of methylene chloride and this solution is slowly added dropwise to the first solution. This reaction is exothermic. After addition of the naphthylamine solution, the suspension formed is cooled to 20° C. and 61.4 g of acetic anhydride are slowly added dropwise, during which time the solution becomes viscous.
0.42 g of cobalt naphthenate are then added dropwise, followed by 20.2 g of triethylamine (the reaction is exothermic). Cool the temperature with an ice water bath.
Adjust to 35°C and stir the reaction mixture at 35°C for 3 1/2 hours. The solvent is then removed in a rotary evaporator without heating and 20 ml of ice water are added to the residue with stirring. Store this mixture in the refrigerator overnight to crystallize the product. 100ml of ice water for each of these crystals
ml twice by suction filtration, then filtered off and dried. Finally, this product is recrystallized from 100 ml of acetone to give a crystalline product with a melting point of 115°C.
64 g (yield 71%) is obtained. According to elemental analysis, the product has the following formula: matches the structure of 87.38 g (0.75 mol) of chlorosulfonic acid is placed in a reaction vessel and cooled to 10°C. 22.5 g (0.1 mole) of 1-naphthylmaleimide are dissolved in 58 g of methylene chloride and the solution is added dropwise to the chlorosulfonic acid with vigorous stirring over a period of about 1 1/2 hours. The cooling bath is then removed and the solution is stirred at room temperature for 4 hours. 100 ml of water and 150 g of acid are placed together in a beaker and, with vigorous stirring, the chlorosulfonic acid solution is added over 25 minutes at 0° C., forming a light colored suspension. After stirring for 1.5 hours, 130 ml of CH ₂ Cl ₂ was added,
Stir the mixture for 10 minutes. The mixture is then separated in a separatory funnel and the aqueous phase is extracted twice with 50 ml each of CH ₂ Cl ₂ . Combine the _two CH ₂ Cl phases and add water to each layer again.
Extracted twice with 50 ml each, followed by separation and Na ₂ SO ₄
Dry with. The solvent in the clear solution is removed in a rotary evaporator without heating. Crystallization of this residue gives about 19 g of product; melting point: 184-186°C. The elemental analysis value and mass spectrum of the product are expressed by the following formula: matches the structure of (b) Chlorsulfonyl succinimide Succinic anhydride 40.0g (0.4mol), methylene chloride 110.0g, aniline 37.2g (0.4mol), acetic anhydride 61.4g (0.6mol), cobalt naphthenate 0.42
g and 20.2 g (0.2 mol) of triethylamine,
In a 750 ml sulfonation flask equipped with a stirrer, thermometer, addition funnel and heating and cooling baths,
Proceed as follows: aniline is added dropwise to succinic anhydride and methylene chloride with stirring so that the addition is complete after 3/4 hour (exothermic reaction);
The reaction mixture is then stirred for 1 hour at about 42°C. After cooling to room temperature, acetic anhydride is added dropwise to this mixture over 15 minutes, followed by first the cobalt compound and then the triethylamine. The color turns purple and the mixture reacts slightly exothermically to form a solution. The temperature is maintained at 35° C. for 3 hours, then the mixture is left overnight. Then concentrate on a rotary evaporator without heating: the product crystallizes. 20g ice
is added to the reaction product and the flask is stored in the refrigerator for one day. The product is then filtered, washed with ice water and dried. Recrystallization of this product from acetone gives 60 g (86% yield) of crystals;
Melting point: 153℃. Elemental analysis Calculated value:
C 68.56%, H 5.18%, N 7.99% Actual values:
C 68.50%, H 5.10%, N 8.0% This product (N-phenyl succinimide)
8.75g (0.05mol), 44g of chlorsulfonic acid
(0.38 mol) slowly. This mixture undergoes an exothermic reaction and becomes a solution. This solution was heated at 60℃.
After stirring for 5 hours, the color changes to dark. Add the contents of the flask dropwise to 100 ml of water containing 150 g of ice. After about half an hour, 100 ml of methylene chloride is added to this mixture; the mixture is stirred for 10 minutes,
Separate the methylene chloride phase. This basic mixture is extracted twice with 20 ml each of CH ₂ Cl ₂ and then separated. The combined methylene chloride phases are washed twice with 20 ml each of water and then separated. The methylene chloride phase is dried over Na ₂ SO ₄ , filtered and concentrated in a rotary evaporator. The product melts at 190-193°C (recrystallized from acetone). Analysis: Calculated values: C 43.89%, H 2.95%,
N 5.12%, S 11.71%, Cl 12.95% Actual values: C 42.5%, H 3.0%,
N 4.9%, S 11.8%, Cl 12.3% (c) Chlorsulfobenzylmaleimide Chlorsulfonic acid was prepared using the equipment used in (b).
87.4 g (0.75 mol) and 18.7 g (0.1 mol) of benzylmaleimide are mixed at 60° C. for 5 hours.
After this time the solution is added dropwise to ice water and the mixture is stirred for 30 minutes. The mixture is then extracted with methylene chloride as described under (b). The product, which is initially liquid, slowly crystallizes. Example 1 35 g of ABS powder are dissolved in a mixture of 54 g of methyl methacrylate and 10 g of methacrylic acid at room temperature (RT). Add 2 g of p-chlorosulfophenyl-maleimide to the homogeneous emulsion and continue stirring for 2 hours. 1 g of ethylene glycol dimethacrylate is subsequently added and the mixture is stirred for 3 hours at room temperature. Finally 0.5 g of cumene hydroperoxide is added and the mixture is stirred for a further 3 hours and then removed from the reaction vessel. The resulting adhesive mixture (hereinafter referred to as mixture A) had a viscosity of 122 PaS (spindle No. 6: 10 rpm) using a Brookfield viscometer. A portion of this mixture is used to join two metal strips. This sample is 12.5mm x 25.0
It has an overlapping surface of mm. One sample consists of two steel strips, Al-Mg-Si 1 alloy (Mg-0.6
-1%, Si: 0.7-1.3%, Mn: 0-0.5%)
Other specimens consisting of two strips are available, for example Schweiz, Aluminum AG.
An adhesive compound is formed by applying a thin layer of said mixture to a metal strip, obtained under the trademark Anticorodal 100B from the company Aluminum AG (hereinafter referred to as "Al.alloy"). A known curing accelerator (accelerator 1) consisting of 3 mol of butyraldehyde and 1 mol of aniline in another metal strip.
(For example, "Accelerator 808"
Apply “Accelerator808” (DuPont). Immediately after application, the two strips are pressed together, clamped together and then cured. The tensile shear strengths obtained after curing Mix A with various supports for 24 hours at room temperature are listed in Table 1.

Table 2-4 below shows the tensile shear strength (N/mm ² ) of several adhesives according to this example as a function of curing time (Table 2), as a function of test temperature (Table 3) and as a function of test temperature (Table 3). It is shown as a function of the post-curing temperature (Table 4); it also shows the tensile shear strength in water and after storage with adhesive on oiled metal surfaces, and finally the so-called critical temperature. As a comparative example (V1), a mixture according to DE 2337049 with the following composition was tested in parallel. Chlorosulfonated branched polyethylene 32.6g Ethyl methacrylate 46.6g Methacrylic acid 9.3g 2,6-di-tert-butyl-p-cresol
0.5g Cumene hydroperoxide 0.9g 1,3-butylene glycol dimethacrylate
0.9g Pigment 3.6g Liquid epoxy resin with epoxy value 5Val/Kg
1.6g γ-methacryloxypropyldimethoxysilane
0.5g

【table】

【table】

[Table] Cured at room temperature for 24 hours and then at 100℃ for 1 hour,
The tensile shear strength at 75°C after storing the etched Al alloy sample in water at 40°C for 7 days was 19.6 N/mm ² using mixture A, and 19.6 N/mm 2 for mixture V1.
When using , it is 12.0N/mm ² . The tensile shear strength of the oiled steel samples cured for 24 hours at room temperature is 19.1 N/mm ² using mixture A and 10.8 N/mm ² using mixture V1. Finally, when tested to determine short-term dimensional stability under heating, etched Al alloy samples exhibited critical temperatures (Tk ₂ value)
give. This critical temperature is the temperature at which a bonded sample separates under a certain tensile load. This is an indicator of short-term dimensional stability under heating and is 12mm
Tensile shear strength (DIN 53 283
Measurement is carried out as follows using the test sample of
Apply a constant load of mm ² . Then increase the temperature per hour until the bond separates.
Uniformly raise the temperature at a rate of 12°C. The temperature at which separation occurs is indicated as the critical temperature. In a further comparative test, one metal sprit of a polished steel sample was
Mixture V2 according to Example 27 of publication no. 2525099, i.e. polychloroprene ("Neoprene W")
(commercially available as “NeoprenW”) 25% by weight,
Methyl methacrylate 61% by weight, methacrylic acid
10% by weight, liquid bisphenol A epoxy resin 3
% by weight and 1% by weight of ethylene dimethacrylate, 56 mmol of methanesulfonyl chloride for every 100 parts of polychloroprene, 100 parts of the mixture.
A mixture containing 0.5 parts of cumene hydroperoxide per part] and the other metal strips are coated with "Accelerator 808" and the tensile shear stress is measured after 24 hours at room temperature. No measurable adhesion is obtained. Examples 2 to 10 (see also Table 5) The process is carried out as described in Example 1 with the following modifications: 2 3 g of p-chlorosulfonylphenyl-maleimide instead of 2 g adhesive component (Mixture B): The addition of 1% di-tert-butyl-p-cresol as a stabilizer considerably increases the storage stability of Mixture B (Mixture B'). 3 Instead of 2 g of p-chlorosulfophenyl-maleimide, p-chlorsulfophenyl-
1 g of maleimide and γ-methacryloxypropyltrimethoxysilane (“Silane A174”)
1 g of "Silan A 174") is used (mixture C). 4 Instead of 1 g of ethylene glycol dimethacrylate, 1 g of butylene glycol dimethacrylate is used (mixture D). This mixture D can also be prepared as follows: 54 g methyl methacrylate, methacrylic acid
10 g and 2 g of p-chloro-sulfophenyl-maleimide are thoroughly stirred at room temperature for 15 minutes.
Butylene glycol-(1,3)-
1 g of dimethacrylate and 0.5 g of cumene hydroperoxide are added and the mixture is stirred for 45 minutes at room temperature. 35 g of ABS powder are then added to the mixture and stirring is continued for 30 minutes at room temperature. Store this mixture in a cool place. 5 In addition to mixture A, a cross-linked methacrylic acid compound having a COOH group which is a weakly acidic cation exchanger (“Amberlite IRC-50”)
Add 2 g of finely ground IRC-50” (mixture E). 6. 17.5 g of ABS powder instead of 35 g of ABS powder.
and 17.5 g of polystyrene (mixture F). 7 Instead of 54 g of methyl methacrylate, use 54 g of ethyl methacrylate, use 1 g of butylene glycol dimethacrylate instead of 1 g of ethylene glycol dimethacrylate,
p-Chlorsulfophenylmaleimide 2g
(mixture G). 8 Instead of 2 g of p-chlorosulfophenyl-maleimide and the accelerator formed from butyraldehyde and aniline, 3 g of p-chlorosulfophenyl-maleimide, i.e. mixture B (see Example 2) and the curing accelerator Dimethyl-p-toluidine is used as the dimethyl-p-toluidine. 9 Mixture B (see Example 2) was used, in addition to which a liquid cation exchanger of the secondary amine type consisting of N-lauryl-N-trialkylmethylamine ("Amberlite LA2") was added.
(Mixture H). 10 Add 56% chlorine to Mixture D (see Example 4).
Contains chlorinated paraffin (Hoechst AG's "VP Holder Flex")
Add 10g of ``VP Hordarlex SP'' (mixture J). Using the above mixture, the tensile shear strength of the surface-polished test sample "Anticorodal" made from magnesium and silicon-containing aluminum alloy (Al alloy) after curing at room temperature for 24 hours is shown in Table 5.
It had a N/mm ² value shown in .

【table】

[Table] Example 11 5 g of chlorinated paraffin are added as an evaporation inhibitor to mixture D (see example 4) (mixture K). Bonding was done after a certain open time, i.e. the length of time during which the mixture was applied to the surface of the test strip and still retained adhesive force when pressed onto a second strip for bonding. The other operations were the same as in Example 1. The test specimens used are again strips of Al. alloy; curing takes place at room temperature for 24 hours. Table 6 shows curing accelerator 1 (Acc.1) (=condensation product from 3 mol of butyraldehyde and 1 mol of aniline) and curing accelerator 2 (Acc.2) (=N,N
-dimethyl-p-toluidine) and the correspondence when using mixture A (Example 1) and comparative mixture V1 (see Example 1) for comparison. Indicates the value to be used.

Table Examples 12-17 These examples show that certain additives do not weaken the adhesive properties and may even enhance them. In all of these examples the basic mixture is
It consists of 35% by weight of ABS powder, 54.0% by weight of methyl methacrylate, 10% by weight of methacrylic acid, 1% by weight of butylene glycol dimethacrylate, 0.5% by weight of cumene hydroperoxide and 3.0% by weight of p-chlorosulfophenyl-maleimide. Various acids and anhydrides are added in amounts of 2 g. The accelerator used is usually Acc.1 but in some cases Acc.2. The test specimen consists of an Al. alloy strip; curing is done for 24 hours at room temperature. The tensile shear strength is shown in Table 7.

[Table] Example 8 Adhesion in water Mixture A (see Example 1) is applied to one of the specimens in water, and the curing accelerator (Acc. 1) is applied to the other specimen, also in water. The two strips are joined together and cured in water at room temperature. The tensile shear strengths (N/mm ² ) are shown in Table 8, along with the corresponding values obtained with comparative mixtures.

[Table] Example 19 This example represents the adhesive action of two different adhesives without accelerator, and the results are shown as a one-component system and as a comparative mixture with the addition of Accelerator 808 as an accelerator. (V1 in Example 1
compared with the results obtained by using The following mixtures are used according to the invention: Mixture D: 35 g of ABS powder are dissolved at room temperature in a mixture of 54 g of methyl methacrylate and 100 g of methacrylic acid. 2 g of p-chlorosulfophenyl-maleimide are added to this homogeneous emulsion and the whole is stirred for 2 hours. 1 g of butylene glycol dimethacrylate is then added and the mixture is stirred for a further 3 hours at room temperature. Finally, 0.5g of cumene hydropyloxide is added to this mixture;
Stir this again for 3 hours. Mixture K: 5 g of chlorinated paraffin are added to mixture D as an evaporation inhibitor. Method: Mixtures D, K and V1 and V1 with accelerator are applied to the test specimens in the manner described in Example 1. The surface of the metal strip is polished, oiled or degreased. Unlike Example 1, adhesive is applied to both metal strips (no accelerator is used except in one of the comparative tests). Immediately after application, the strips are pressed together and secured with clamps, then incubated for 1 hour at room temperature and another 1 hour at 100°C.
Allow time to cure. The tensile shear strength (N/mm ² ) is then measured. The results are summarized in Table 9.

【table】

Example 20 Mixture L 35 g of ABS powder are dissolved in 54 g of methyl methacrylate and 10 g of methacrylic acid at room temperature. In this homogeneous emulsion, chlorsulfonaphthyl-(1)-
Add 2 g of maleimide. Add this mixture to 2
After stirring for an hour, 1 g of butylene glycol dimethacrylate was added and the mixture was stirred at room temperature for a further 3
Stir for an hour. Then cumene hydroperoxide
0.5 g is added and the mixture is stirred again for 3 hours. (a) Mixture L is applied to a polished aluminum alloy metal strip in the manner described in Example 1: Accelerator (Acc. 1) (formed from 3 mol of butyraldehyde and 1 mol of aniline) is applied to the second strip. Apply to the strip. Press the two strips together and cure at room temperature for 24 hours. A tensile strength of 19.7 N/mm ² is measured. (b) When mixture L is used as a one-component system, 2
A sheet of aluminum alloy metal strip was coated with mixture L alone for 1 hour at room temperature and then at 100°C.
Cure for 1 hour and finally at 240°C for 30 minutes.
The subsequent tensile strength is 22.4 N/mm ² . Example 21 Mixture D according to the invention (see Example 19) is applied twice on both sides of a glass fiber backing using a laminating hook and allowed to dry for 1 hour at room temperature. The thickness of the dry non-tacky film is approximately 0.56 mm. (This film can be stored between polyethylene sheets in the refrigerator for several months without loss of adhesion). The film is placed between two test strips, then pressed and kept at 100°C for 1 hour. The two test strips form a test specimen with an overlapping surface of 12.5 mm x 25.0 mm. The tensile shear strengths of several samples are shown in Table 10 below.

Table: Example 22 A film is prepared from mixture D in the manner described in Example 21 and applied to a sample made of etched aluminum alloy. This test sample was then held at 100°C for 1 hour. Peel strength measured according to DIN53 289 is 11.0N/mm. When using the unsupported film obtained from Mixture D, this sample has a peel strength value of 15.8 N/mm. Examples 23 to 28 In the following examples, in each case the respective adhesion promoters were combined with 35 g of ABS (acrylonitrile-butadiene-styrene terpolymer), 54 g of methyl methacrylate, 10 g of methacrylic acid, 1 g of butylene glycol dimethacrylate and cumene hydropyl. Add with stirring to a mixture consisting of 1 g of oxide. The mixture is then applied to a polished steel strip and bonded to another steel strip coated with an accelerator as described in Example 1. Table 11 shows the tensile shear strength of samples cured at room temperature for 15 minutes, 1 hour, and 24 hours, respectively.

[Table] Example 29 0.9 instead of 0.5 g of cumene hydroperoxide
Mixture M, which is the same as mixture D, except that it contains g.
use. 2 g of polyethylene powder (high-pressure polyethylene, e.g. COATHYLENE-P50, commercially available from Bulle, Plast-Labor SA, melting point range 116-119°C and density 0.935); and stir the mixture for 1 hour at room temperature. Using hardening accelerator Acc.1, the polished aluminum strip is bonded to a polyethylene sheet (P-TexN-100) pretreated by corona discharge.
After 15 minutes at 100°C, the peel strength obtained is 7.1 N/mm.

Claims (1)

[Claims] 1 30 to 80% by weight of at least one polymerizable vinyl monomer, at least one vinyl polymer
10 to 50% by weight, as well as free radical-forming compounds
Contains 0.05 to 10% by weight as an adhesive component, and further contains the following formula as an adhesion promoter: (In the formula, R represents an alkylene group having 1 to 25 carbon atoms, or a substituted or unsubstituted phenylene, naphthylene, or phenylene alkylene group having 1 to 4 carbon atoms in the alkylene moiety, and R ₁ and R ₂ each represent represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms, or R ₁ and R ₂ together with the group [formula] in the formula may be substituted with 1 or 2 methyl groups, Forms a saturated or unsaturated heterocycle containing no heteroatoms in the ring other than the nitrogen atom given by the above formula (), where the nitrogen atom is a chlorosulfonated alkyl, aryl or alkyl group An adhesive comprising an acid amide or imide substituted with 0.1 to 15% by weight based on the adhesive component. 2. The adhesive according to claim 1, wherein R ₁ and R ₂ together with the group [Formula] form an unsubstituted maleimide group or a maleimide group substituted with one or two methyl groups. . 3. The adhesive according to claim 2, wherein in the formula, R represents a phenyl group. 4. The adhesive according to claim 1, which contains methyl or ethyl acrylate, methyl or ethyl methacrylate, styrene and/or chlorostyrene as the vinyl monomer. 5 Acrylonitrile-butadiene-styrene terpolymer, butadiene-
Adhesive according to claim 1, which contains styrene copolymers, isoprene-styrene copolymers, polystyrene and/or chlorinated polyethylene. 6. The adhesive according to claim 1, which contains an organic peroxide or a hydroperoxide as a compound that generates free radicals. 7. The adhesive according to any one of claims 1 to 6, wherein the adhesive is in the form of a dry sheet.