DE3237914A1 - HEAT-ACTIVATED ADHESIVE OR SEALANT RESIN COMPOSITION, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

The invention relates to thermoplastic, organic adhesive and sealing resin compositions which, when applied, g

from heat, preferably in an accelerated manner, to a thermoset joint or seal network. In addition, the invention relates to a method for forming a networked connection or

Poetry.
10

Thermosetting or crosslinking resin adhesives are known. Many resin adhesives which undergo irreversible chemical and physical change and become essentially insoluble are known. Thermosetting adhesives containing both condensation polymers and addition polymers are also known. Examples are urea-formaldehyde, phenol-formaldehyde and melamine-formaldehyde adhesives, as well as epoxy, unsaturated polyester and polyurethane adhesives. In addition, US Pat. No. 3,723,568 discloses the use of polyepoxides and optionally epoxy polymerization catalysts. US Pat. No. 4,122,073 describes a thermosetting resin obtained from polyisocyanate, polyanhydrides and polyepoxides. According to these patents, the crosslinking takes place by reaction with available reaction sites in the base polymers. US Pat. No. 4,137,364 teaches the crosslinking of an ethylene / vinyl acetate / vinyl alcohol terpolymer using isophthaloyl biscaprolactam or vinyltriethoxysilane, the crosslinking being achieved before the heat activation and additional crosslinking by heat after the application of the adhesive. US Pat. No. 4,116,937 describes another process for thermal crosslinking by using the polyaminobis-maleimide class of flexible polyimides.

3 ^> ben that can be hot melt extruded ^{up to 150 0 C.}

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and crosslinking at higher temperatures subject. In these last two patents, the thermal crosslinking is also through Reactions of the specific crosslinking agent with

Fused reaction points of the base polymers reached.

Virtually all of these thermosetting adhesives the formation of the connection depends on the chemical cross-linking reaction, which in most cases is caused by heat is accelerated to get the connection in a reasonable time. Furthermore, in many cases, e.g. B. Epoxy adhesives, two or more components directly be mixed prior to making the connection. this

requires rapid application, since the crosslinking reaction starts immediately when mixing and is irreversible is. Accordingly, there is a need for a one-part thermosetting adhesive that is applied and then, if necessary, can be stimulated to harden.

Methods for achieving delayed adhesion are known from the prior art. For this purpose, please refer to the U.S. Patent 2,653,880, U.S. Patent 2,653,881, and U.S. Patent 4,059 which disclose the use of thermoplastic polymers • ^ describe which slowly crystallizing segments contain.

On the other hand, connect thermoplastic adhesives that are used in the form of solutions, dispersions or solids only in a physical way. Probably the most important method to use of thermoplastic adhesives is the hot melt process where bond formation occurs when the polymer melt solidifies between the substrates to be bonded. The obtained in this way

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Joints reach their final strength faster than those obtained with solution-type adhesives. Apparently the thermal stability of the thermoplastic resin determines its potential utility as 5

Hot melt adhesive. So that the thermoplastic acts as a hot melt adhesive can be used, it must also have a low melt viscosity so that the application of the Adhesive to the substrates to be bonded is possible at an acceptable rate. Ordinary means this is that the polymer must have a low molecular weight. However, many thermoplastic materials can cannot be used as a hot melt adhesive as they do not have:, sufficient cohesive strength at the low molecular weights, required for application to a substrate

are, own. For example, polyolefins are made with

low molecular weight, especially low molecular weight Low-density polyethylene widely used in hot melt adhesives for sealing corrugated cardboard boxes, for flanging used by multi-wall bags and similar applications,

but they do not have sufficient strength to be used in the building sector such as in plywood production to become. In addition, they do not have sufficient heat resistance to allow components to be connected to be able to be used, the meanwhile increased

Temperatures such as in the engine compartment or exhaust area of

Automobiles are exposed. This means that thermoplastic adhesives cannot be used there where the adhesive in situ is again exposed to elevated temperatures which cause the adhesive to sag

and thereby allows the connection to be broken.

Many two-part component materials are known in the art known that are cured in situ at elevated temperature, e.g. B. epoxy and urethane resins. The hardening

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times are, however, relatively long, which is an on-line production in a continuous process. The hardening time can be reduced considerably by heating

but such practices are rarely used

applies, since external heating also leads to the substrates or components to be connected being heated. In the case of heat-sensitive substrates or components to be connected, ν . B. thermoplastics, heating can lead to damage or deformation =

The invention is now based on the object of a one-component adhesive composition to create that is solvent-free, can be applied as a hot melt adhesive and with

is thermosetting in a minimum of time. Furthermore, a 15

Method can be created in which an adhesive composition applied as a hot melt adhesive and then by a thermally excited initiator at 'a further increased Temperature can be cured to a thermoset adhesive. In addition, the invention is based on the object of a To create single component adhesive composition, which as free film, tape or as a preformed seal can be applied. Further advantages and properties of the invention result from the following description.

To achieve this object, a heat-activatable adhesive composition is proposed which is characterized is through

(1) a member of the group consisting of

(a) a liquid, ethylenically unsaturated monomer, 30th

Oligomer or Prepolymor with the formula

R 35

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in which R is hydrogen or CH ₃ , R. is an organic radical and η is at least 2

(b) an epoxy resin having at least 2 ^ C-C groups

and O

(c) a mixture of (a) and (b),

(2) a thermal initiator and

(3) a thermoplastic adhesive material selected from the group consisting of polyesters, polyvinyl acetate, polyamides, butadiene-acrylonitrile copolymers, styrene-butadiene copolymers, Styrene-isoprene copolymers, styrene-ethylene-butylene copolymers, Ethylene-vinyl acetate copolymers, Ethylene-ethyl acrylate copolymers, ethylene-propylene-5

Diene monomer and mixtures thereof.

After application to the parts to be connected or sealed, the composition according to the invention forms when applying heat, preferably by electromagnetic techniques including dielectric and induction heating, a thermoset compound or seal. Although the composition according to the invention and the method of formation of the present invention

a thermoset joint or seal suitable 25

are, the invention is intended below for the sake of brevity explained essentially on the basis of adhesive bonds will.

The liquid ethylenically unsaturated monomer, oligomer 30

or prepolymer, d. H. the polyene with a terminal one

Acrylate group, with the formula

O 35 (CH ₂ = CC

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χ ·· η a

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in which R is hydrogen or CH_, R. is an organic one Remainder and η is at least 2, can with the help of various Reactants and can be prepared by various processes. One of these materials with a final 5

digen acrylate group is a Polyethorpolyolurethanpoly-

acrylate formed by reacting a polyether polyol with a polyisocyanate and a hydroxyalkyl acrylate will. Another material can be a polyester polyurethane polyurethane

be acrylate, which by implementation / .ung a polyester polyol

formed with a polyisocyanate and a hydroxyalkylarylate will. Another material in this class is an epoxy acrylate, which is produced by reacting a diepoxide with Acrylic acid is formed. Another suitable material with

a terminal acrylate group is a polyether or a

Polyester acrylate obtained by converting the terminal groups

a polyether polyol or polyester polyol (end-capping) is formed with acrylic acid or with acryoyl chloride. A Another suitable material with a terminal acrylate group is a urethane polyacrylate, which by reaction

of the terminal groups a ·; Diisocyants (end-capping) is formed with a hydroxyalkyl acrylate. The designation "Acrylate" refers to both acrylates and methacrylates. Examples of the above materials

with terminal acrylate groups are inter alia. 1,3-butylene glycol

acrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, Neopentyl glycol diacrylate, polyethylene glycol 200 diacrylate, Tetraethylene glycol diicrylate, triethylene glycol diacrylate, Pentaerythritol tetraacrylate, tripropylene glycol diacrylate,

ethoxylated bisphenol-A-diacrylate, trimethylolpropane triacry-

lat, di-trimethylolpropane tetraacrylate, triacrylate of Tris (hydroxyethyl) isocyanate, dipentaerythritol hydroxypentaacrylate, Pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, Triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, poly-

ethylene glycol 200 dimethacrylate, 1,6-hexanediol dimethacrylate

Hi.

lat, neopentyl glycol dimethacrylate, polyethylene glycol 600 dimethacrylate, 1, S-butylene glycol dimethacrylate, ethoxylated Bisphenol-A-dimethacrylate, trimethylolpropane trimeth-

acrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 5

Diethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, Glycerine dimethacrylate, trimethylolpropane dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol dimethacrylate and pentaerythritol diacrylate.

The epoxy resin to be used in the present invention consists of a material having at least two epoxy groups, d. H.

at least two

Z ^ CC ^ Z- groups. 15th

These compounds can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and with substituents such as chlorine, hydroxyl groups,

Ether residues and the like may be substituted. 20th

The term "epoxy resin" includes all conventional ones monomeric, dimeric, oligomeric or polymeric epoxy materials with a large number (at least 2) functional ones

Epoxy groups. Preferably the materials belong to

the classes that are chemically classified as (a) an epoxidic ester with two epoxycycloalkyl groups, (b) an epoxy resin prepolymer, mainly consisting of the monomeric diglycidyl ether of bisphenol-A, (c) a polyepoxidized phenol

novalak or cresol novolak, (d) a polyglycidyl ether

a polyhydric alcohol, (e) diepoxide of a cycloalkyl or alkylcycloalkyl hydrocarbon or ether or (f) a mixture of the aforementioned compounds can be described. In order to avoid unnecessary detailed description eino, _f Bozug is made to the Encyclopedia

of Polymer Science and Technology, Volume 6, 1967,

Interscience Publishers, New York, pp. 209-271.

Suitable commercially available epoxy esters are preferably S ^ -epoxycyclohexylmethyl-S ^ -epoxycyclohexan-

carboxylate (Union Carbide ERL 4221, Ciba Geigy CY-179), 5

bis- (3,4-epoxy-6-methylcyclohexylmethyl) adipate (Union Carbide ERL 4289) and bis (3,4-epoxycyclohexylmethyl) adipate (Union Carbide ERL 4299).

Suitable commercially available diglycidyl ethers of bisphenol-A are Ciba Geigy Araldite 601O ₅ Dow Chemical DER 331 and Shell Chemical Epon 828 and 826 ..

A suitable polyepoxidized phenol-formaldehyde novolak prepolymer is from Dow Chemical under the designation

DEN 431 and 438 available while a suitable polyepoxidized Cresol-formaldehyde-novolak prepolymer available from Ciba Geigy under the name Araldite 538 is.

A polyglydidyl ether of a polyhydric alcohol based on butane-1,4-diol can be obtained from Ciba Geigy under the Name Araldite RD-2 and from Shell Chemical Corp, based on glycerine, under the name Epon 812 can be obtained.

A suitable diepoxide of an alkylcycloalkyl hydrocarbon is vinylcyclohexene dioxide (Union Carbide ERL 4206) and a suitable diepoxide of a cycloalkyl ether is bis (2,3-epoxycyclopentyl) ether (Union Carbide ERL

0400).

Other examples include the epoxidized esters of polyethylenically unsaturated monocarboxylic acids, such as epoxidized linseed oil, soybean oil, perilla _s oiticica _t tung oil, walnut oil

and dehydrated castor oil, methyl linoleate, butyl lino-

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leat, ethyl 9,12-octadecadienoate, butyl-9,12,15-octadecatrienoate, Butyl eleostearate, monoglycerides of wood oil fatty acids, monoglycerides of soybean oil, sunflower oil, rapeseed oil, Hemp oil, sardine oil, cottonseed oil, etc.

The thermal initiators for the curing of the ethylenically unsaturated group-containing component of Compositions according to the invention are free radicals Initiators selected from substituted or unsubstituted pinacols, azo compounds, thiurams, organic Peroxides and mixtures thereof.

The suitable organic peroxides have the general formula

R-O-O-

in which η = 0 or 1, R is independently selected from hydrogen, aryl, alkyl, aryl carbonyl, alkaryl carbonyl, aralkyl carbonyl and alkyl carbonyl and R _{1 is} alkyl or aryl, the alkyl groups containing 1 to 20 carbon atoms.

Examples of suitable organic peroxides include:

2,5-dimethyl-2,5-di (t-butylperoxy) -heχan, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,3-bis- (cumylperoxyisopropyl) benzene, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, t-butyl peroxyisobutyrate, benzoyl peroxide, p-chlorobenzoyl peroxide, Hydroxyheptyl peroxide, di-t-butyl-diperphthalate, t-butyl peracetate, t-butyl perbenzoate, dicumyl peroxide,

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1,1-di (t-butylperoxy) -3,3,5-trimethyleye lonexane, di-t-butyl peroxide and t-butyl hydroperoxide.

The organic peroxide is added to the composition in a Amount from 0.01 to 10% and preferably 0.1 to 5% based on the weight of the component with the ethylenic unsaturated group added.

Examples of suitable azo compounds include commercially available compounds such as 2-t-butylazo-2-cyanopropane, 2,2'-azobis- (2,4-dimethyl ~ 4-methoxy-valeronitrile), 2,2'-azobis- ( isobutyronitrile), 2,2 'azobis (2,4-dimethylvaleronitrile) and 1.1 x azobis- (cyclohexanecarbonitrile),

The azo compound is the composition in one Amount from 0.001 to 5% by weight, preferably 0.01 to 2 Weight% based on the weight of the component with the ethylenically unsaturated group added.

Have suitable thiurams as thermal initiators the formula

in which R, R-, R and R are each hydrogen, a linear or branched alkyl radical having 1 to about 12 carbon atoms, a linear or branched one Alkenyl radical with 2 to about 12 carbon atoms, one Cycloalkyl radical with 3 to about 10 ring carbon atoms, a cycloalkenyl radical with 3 to about 10 ring carbon atoms, an aryl radical with 6 to about 12 ring carbon atoms

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atoms, an alkaryl radical with 6 to about 12 ring carbon atoms, an aralkyl radical with 6 to about 12 ring carbon atoms and, when combined, R. and R _? and R and R. are each a divalent alkylene group

(rC H „-) with 2 to about 12 carbon atoms, a divalen-η 2n

te alkenylene group (-C H "_h ~) with 3 to about 10 carbon atoms, a divalent alkadienylene group (-CH "-) having 5 to about 10 carbon atoms, a divalent group Alkatrienylene group (-C H "_-) with 5 to about 10 carbon atoms, a divalent alkyleneoxalkylene group (-C H OC H_ -) having a total of 4 to about 12 carbon atoms or a divalent alkyleneaminoalkylene group

with a total of 4 to 12 carbon atoms.

Suitable thiurams include tetramethylthiuram disulfide, Tetramethylthiuram disulfide, Di-N-Peηtamethylene thiuram disulfide, Tetrabutylthiuram disulfide, diphenyldimethylthiuram disulf id, D: i pheny] diethylthiuram disulfide and diethylenoxythiuram sulfide and the like.

The thiuram is added to the composition in an amount from 0.005 to 5.0% by weight based on the component with the ethylenically unsaturated group is added.

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The suitable substituted or unsubstituted pinacols have the general formula

Rl R ₃

R ₂ -C - CJ

ι ι

X Y

in which R. and R are the same or different substituted or unsubstituted aromatic radicals, R ₂ ^and R _{4 are} substituted or unsubstituted aliphatic or aromatic radicals and X and Y, which can be identical or different, are hydroxyl, alkoxy or Are aryloxy groups.

Preferred pinacols are those wherein R., R ", R ₃ and R ₄ are aromatic radicals, ine X and Y are hydroxyl groups.

and R ₄ aromatic radicals, in particular phenyl radicals and

Examples of this class of compounds include

Benzopinacol, 4,4'-dichlorobenzopinacol, 4,4'-dibromobenzopinacol, 4,4'-diiodobenzopinacol, 4,4 ', 4 ", 4"' - tetrachlorobenzopinacol, 2,4-2 ', 4'-tetrachlorobenzopinacol , 4,4'-dimethylbenzopinacol, 3,3'-dimethylbenzopinacol, 2,2'-dimethylbenzopinacol, 3,4-3 ', 4'-tetramethylbenzopinacol, 4,4'-dimethoxypinacol, 4,4', 4 ", 4 "'-Tetramethoxybenzopinakol,4,4'-Diphenylbenzopinakol, ^{4,4-dichloro-s} 4", 4 "' - Dimethylbenzopinakol, 4,4'-dimethyl-4""4"'- Diphenylbenzopinakol, Xanthonpinakol, Fluorenonpinakol, Acetophenonpinakol, 4,4'-dimethylacetophenone-pinacol, 4,4'-dichloroacetophenone-pinacol, 1,1,2-triphenylpropane-1,2-diol,

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1,2,3,4-tetraphenylbutane-2,3-diol, 1,2-diphenylcyclobutane-1,2-diol, Propiophenone pinacol, 4,4'-dimethylpropiophenone pinacol, 2,2'-ethyl-3,3'-dimethoxypropiophenone-pinacol,

1,1,1,4,4,4-hexafluoro-2,3-diphenyl-butane-2,3-diol.

Further compounds suitable according to the invention may be mentioned: Benzopinakol-moriomethylether, Benzopinakol-monophenylether, Benzopinako] monoisopropyl ether, benzopinakol monoisobutyl ether, Benzopinacol monoid diethoxymethyl ether and similar.

The pinacol is the composition in amounts of 0.01 to 10 wt.%, Preferably 0.1 to 5 wt.% Based on the weight of the component with the ethylenically unsaturated

th group admitted.

The thermal initiators that are used when the group member is a epoxy resin with at least two

²⁰ ^ \ / ^C ^ -

is, thermal initiators are selected from. Dicyandiamide and BF adducts and diaryliodonium salts. Either these are used as such or in combination with

one of the above-mentioned free radical initiators

used.

The BF "adducts suitable as thermal initiators

^C 6 ^H 5 ^NH 2 ' ^BF 3' ² ' ⁶ " ^Et 2 ^C 6 ^H 3 ^NH 2 * ^BF 3 ^{f EtNH} ₂ - ^BF ₃ ' SeK-Bu ₃ NH-BF ₃ , Et ₃ N ^ BF ₃ , (CgH ₅ ) P-BF,

C ₅ H ₅ NMe ₂ -BF ₃ , pyridine .BF ₃ , and. Et ₃ N-BF, Et O «BF, (HOCH ₂ CH ₂ ) ₃ N. BF ₃ .

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The diaryiodonium salts suitable as thermal initiators in combination with a pinacol are the in U.S. Patent 4,238,587, which expressly states

to the disclosure of this patent with respect to 5

Diaryliodonium salts is referred to. So can the diaryliodonium salts suitable according to the invention are reproduced as follows:

^l '"' a ¹ "'b ^{J IXJ} ' (1)

where R is a C, _ -._. aromatic hydrocarbon residue j \ ο — ί ο;

is, R is a divalent aromatic organic radical, Y is an anion, a = 0 or 2, b = 0 or 1 and the sum of a + b = 1 or 2. Preferably Y is an MQ. Anion in which M is a metal or metalloid Q is halogen and d is an integer from 4 to 6.

The radicals falling under the definition of R in formula (1) can be the same or different aromatic carbocyclic radicals having 6 to 20 carbon atoms, those having 1 to 4 monovalent radicals selected from C ₁ . ". Alkoxy, C,. _. Alkyl, nitro, chlorine, etc. may be substituted. R is especially phenyl, chlorophenyl, nitrophenyl, pyridyl, etc. Radicals included in R in formula (1) are divalent radicals such as

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where Z is selected from -0-, -S-,

OO

2
where RC ₍₁ _ _g , alkyl or ^C (c_i3) A · ^ ^{1 and n is} a

10 is an integer from 1 to 8.

Metals or metalloids included in M in formula (1) are transition metals such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs, rare earths like the lanthanides, e.g. Cd, Pr, Nd, etc., actinides like Th, Pa, U, Np, etc. and metalloids such as B, P, As, Sb, etc. Complex anions made by MQ. are for example

AsF ₆ ", SbF ₆ ", FeCl ₄ ", SnCl ₅ ", SbCl ₅ ",

etc.
20th

Some of the diaryliodonium salts useful in the present invention are the following:

no α

- 19 -

These thermal initiators are added to the system in an amount of 1 to 10% by weight, based on the epoxy resin.

When a component with an ethylenically unsaturated Group and an epoxy resin can be used in combination to produce a thermosetting adhesive it is necessary as a thermal initiator both the aforementioned free radical types and the types to be used for curing epoxy resins in the specified amounts to obtain a co-cured adhesive.

The diaryliodonium salts and BF "adducts are per se - ύ

suitable to initiate the crosslinking reaction but preferably because of the higher curing speed in combination with a Pi.na.kol described herein used.

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The thermal initiator can be applied to the system in different ways Way to be admitted. So the thermal initiator per se with the component with the ethylenically unsaturated Group or the epoxy resin. Furthermore 5

The thermal initiator can be in the reactive diluent or in well-known, commercially available ones Solvents such as dibutylphthalate, ketones, e.g. acetone and methyl ethyl ketone or chlorinated hydrocarbons such as methylene chloride can be dissolved or suspended and then added to the system.

The thermoplastic adhesive material component of the heat-activatable organic adhesive resin

Settlement can be made up of various saturated and unsaturated-5

th thermoplastic polymers and copolymers where the term "copolymers" includes terpolymers, tetrapolymers, and the like.

These thermoplastic adhesive materials together 20th

with the rest of the organic resin composition can be in the form of a hot melt adhesive as a one-component adhesive can be applied. These thermoplastic adhesive materials consist of 100% non-volatile materials,

i.e. they do not contain water, solvents or other 25

volatile carriers. They are solid or liquid at room temperature, but become more flowable at elevated temperatures and thus allow easy application. Suitable thermoplastic adhesive materials include polyamides, Polyvinyl acetate and polyester resins, ethylene vinyl acetate (EVA) copolymers, ethylene-ethyl acrylate (EEA) copolymers, Butadiene-acrylonitrile copolymers and styrene-ethylene-butylene copolymers. Some of the newer materials of the more conventional "Gurnmi" -V.irianten are the block copoly-

meren, styrene-butadiene oiler styrene-isoprene, which under 35

under the brand name "Krai.on". These

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thermoplastic adhesive materials are sometimes used in conjunction with secondary components such as waxes, plasticizers, reactive diluents, fillers and antioxidants. Wax acts as a non-volatile solvent for the thermoplastic adhesive material and reduces the melt viscosity. Plasticizers, reactive diluents or liquid modifiers are used to a limited extent in order to impart flexibility, specific usage and viscosity properties to the hot melt compounds. Are fillers used to reduce costs _? Color regulation and used to improve corrosion properties. Antioxidants are used to suppress oxidation during compounding and use.

One suitable thermoplastic adhesive material is the thermoplastic segmented copolyesters described in U.S. Patent 4,059,715, which is incorporated herein by reference. These are solid, non-sticky, very cohesive, solvent-free thermoplastic polymers that are not subject to cold flow and are non-blocking below their melting temperatures, but become very sticky and bondable when they melt. They consist essentially of about 5 to 75 wt.% Amorphous Estereinheitcn and 95 to 25 wt.% Crystallizable Estereinheilen connected by the Esterbindungen. The term "crystallizable" encompasses both crystalline ester units and units which are capable of becoming crystalline. The crystallizable ester units in the copolyesters have the formula

O O

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and the amorphous ester units have the formula;

OO
-CR ^ C-OR.0-,

in which R. of residues (remaining after removal of Caboxylgruppen remain) of one or more. Diacids selected from saturated aliphatic dicarboxylic acids with 4 to 10 carbon atoms (the residues of these acids contain 2 to 8 carbon atoms) and aromatic dicarboxylic acids selected from terephthalic acid, isophthalic acid, phthalic acid, 4,4 * -benzophenonedicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4 '-Diphenyletherdicarboxylic acid, 4,4'-diphenylthioetherdicarboxylic acid and 4,4'-diphenylamine dicarboxylic acid, R _? consists of radicals (which remain after removal of the hydroxyl groups) of one or more saturated aliphatic diols having 2 to 12 carbon atoms, R is R ^ or R-, R is R ₀ or R ^ , R_ is the divalent radicals with 22 to 50 carbon atoms, which remain after removal of the carboxyl groups from saturated aliphatic dimer acids (i.e. the polymerized and hydrogenated product of two molecules of an ethylenically unsaturated fatty acid with about 12 to 26 carbon atoms, so that the dimer acid is saturated and contains 24 to 52 carbon atoms) , and R _ß consists of the divalent radicals that remain after removal of the hydroxyl groups from a long-chain aliphatic dial with an average molecular weight of 200 to 4000 (preferably 400 to 2000), provided that at least one of R "and R. in

* 5 τ *

each amorphous ester unit is R _K or R_ and that when R is aromatic, R_ _{3 is} 6 to 12 carbon atoms

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and the content of amorphous units is 50 to 75% by weight. The copolyesters have differential thermal analytical melting temperatures of about 25 to

150 ° C according to that described in U.S. Patent 4,059,715 5

Determination and inherent viscosity of at least 0.5 dl / g and usually not more than 1.5 dl / g (measured in 0.3 g / dl solutions of the polymer in chloroform at 25 ° C). The "open" time (the time between deposition and definition of permanent connection) the copolyester be at least about 1/4 minute at 20 ⁰ C and usually not more than about 1 h at 20 ⁰ C. The copolyesters are also substantially completely soluble in toluene at 25 ° C. at a ratio of about 10% by weight of copolyester and 90% by weight of solvent. Preferably

the copolyesters have melting points of at least 40 C so that they are solids at ordinary temperatures are.

Suitable short chain acids, short chain diols and

long-chain diols for the production of thtrmoplastiscnen segmented copolyesters are those in U.S. Patent 4,099,715 materials described. A particularly suitable thermoplastic copolyester contains residues of adipic acid, a C "_- dimer acid formed from linoleic acid (han

name "EMPOL 1010" from Emery Industries), 1,4-cyclohexanedimethanol and a poly (oxytetramethylene) glycol having a molecular weight of 2000 and one hydroxyl equivalent of approximately 56 (available under the trade designation "Polymeg 2000" from E, I. DuPont Co.).

Other suitable thermoplastic adhesive materials are other thermoplastic polyesters (e.g. "5096" from Cooper Polymers, Inc.), thermoplastic polyurethanes (e.g. "Q-thane PH 56" from K.J. Quinn

Co., Inc.), thermoplastic polyamides (e.g. * "Coramid

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2430 "from Cooper Polymers, Inc.)," Elvamide "from DuPont and "Macromelt" from Henkel, thermoplastic rubbers (e.g. "Kraton 1101" and "Kraton 1107") Shell Chemical Co.) and ethylene vinyl acetate (e.g. "ELVAX 40" from Firn ^ a E.I. DuPont de Nemours Co., Inc. and "Ultrathene" from USI). Other suitable components in the composition according to the invention thermoplastic adhesive materials include butadiene-acrylonitrile copolymers, sold under the trade name "Hycar" from B.F. Goodrich are available Urethane acrylates, urethane epoxies and urethane polyenes. In addition, other suitable thermoplastic materials are polyvinyl acetate such as polyvinyl formal and Polyvinyl butyral. The thermoplastic adhesive material

is in the composition in amounts from 1 to 95 % By weight of the composition, with the remainder from the component having the ethylenically unsaturated group and / or made of epoxy resin.

In those cases where the thermoplastic adhesive material contains ethylenic unsaturation, e.g., styrene-butadiene copolymers and ethylene propylene diene monomer, it is possible that upon heating co-cure with the ethylenically unsaturated component takes place. if

the thermoplastic adhesive material does not

Contains groups, it only acts as a matrix for the wettable components with ethylenically unsaturated Groups or epoxy groups and thereby provides additional

Adhesive properties. 30th

The compositions according to the invention can, if desired such additives as antioxidants, inhibitors, fillers, antistatic agents, flame retardants, Thickeners, thixotropic agents, surfactants, viscosity modi

fication agents, plasticizers, tackifiers and the like

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contain. Such additives are usually premixed with the component having the ethylenically unsaturated group or epoxy compound before or during the compounding _K dierungsstufe. Suitable fillers that can be added to the system to reduce costs include natural and synthetic resins, glass fibers, wood flour, clay, silicon oxide, aluminum oxide, carbonates, oxides, hydroxides, silicates, glass flakes, borates, phosphates, diatomaceous earth, talc, kaolin , Barium sulfate, calcium sulfate, calcium carbonate, wollastonites, carbon fibers and the like. The aforementioned additives can be used in amounts up to 500 parts by weight or more, preferably about 0.005 to about 300 parts by weight per 100 parts by weight of the organic resin composition 5

to be available.

In addition, you can use oxygen scavengers and antioxidants such as hydroquinone, pyrogallol, phosphoric acid, triphenylphosphine, t-butyl hydroquinone, t-butyl catechol, p-benzoquinone, 2,5-diphenylbenzoquinone, 2,6-di-t-butyl-p-cresol etc. the system in conventional amounts of 0.001 to 2.0 wt.% Based on the ethylenically unsaturated or the epoxy component can be added.

The heating step is usually conducted over a period of 1 sec. To 30 minutes at a temperature of 70 to 200 ° C and preferably 90 to 170 ⁰ C, which is sufficient to provide the composition completely to a solid thermoset adhesive or sealant product harden.

The heating stage using a thermal Initiator for curing the organic adhesive resin

composition can be done in several ways 35

will. In simple systems, the adhesive can be

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setting applied manually to a substrate

be contacted with another substrate

and heating the assembled system in an air oven

g until a thermoset joint results.

In addition, and preferably, electromagnetic heating can be used as a faster and more effective curing agent, especially if the substrates to be connected are plastic materials, can be used. In addition to the Electromagnetic interconnection techniques are helpful in terms of forming high strength connections faster Cure times of joints and automated handling of parts and assembly.

Electromagnetic heating can be used when joining (1) plastic to plastic, (2) plastic to metal and (3) Metal can be used with metal. For example, dielectric heating can be used to connect M) and (2)

o _{0 to be} used when dio adhesive composition

contains sufficient polar groups to rapidly heat the composition and allow it to adhere to the substrates associate. Inductive heating (induction heating) can also can be used to connect (1), (2) and (3). That is, if at least one of the substrates is an electrical conductive or ferromagnetic metal, the heat generated therein by conduction to the adhesive composition Transferred, which in turn reduces the hardening process Formation of a thermoset adhesive is initiated. In the case where both substrates are plastics it is necessary to use an energy-absorbing material, i.e. an electrically conductive or ferromagnetic Material, preferably in fiber or particulate form (0.037 to 2.0 mm) to the adhesive composition " give. The energy absorbing material becomes ordinary

32379U

in amounts of 0.1 to 2 parts by weight per 1 part by weight added to the organic adhesive resin composition. It is also possible to place the plastic substrate at the bond point impregnate with particles of the energy absorbing material to use induction heating. However, care must be taken to ensure that the plastic does not warp.

^ q The particulate electromagnetic ^ energy-absorbing Material, that when using induction heating is used in the adhesive composition, can one of the magnetizable metals such as iron, cobalt and nickel or the magnetizable alloys or

._ be oxides of nickel and iron and nickel and chromium and iron oxide. These metals and alloys have high Curie points (388-1116 ⁰ C).

When using induction heating, electrical-suitable _"0 conductive materials include the noble metals, copper, aluminum, nickel, zinc as well as carbon black, graphite and inorganic oxides.

There are two suitable Forrm-n of the high-frequency heating, _ _c whose selection is determined by the material to be joined. The main consideration is whether the material is a conductor and a non-conductor for electrical current. If the material is a conductor such as iron or steel then the inductive method is used. If the material is an insulator such as wood, paper, textiles, synthetic resins, rubber, etc., dielectric heating can also be used.

Most natural or synthetic polymers

__ are non-conductors and accordingly for the dielectric 35

Suitable for heating. These polymers can be a variety

BATH ORIGINAL

comprised of dipoles and ions that align themselves in an electric field and rotate to get their alignment to maintain in the field when the field oscillates. the

polar groups can be in the polymer backbone or 5

they can consist of side groups, additives, extenders, pigments, etc. For example, loose fillers such as carbon black can be used as additives in an amount of 1 % in order to increase the dielectric response of the adhesive. When the polarity of the electric field is reversed millions of times per second, the resulting high frequency of the polar units creates heat in the material.

The uniqueness of dielectric heating lies

in its uniformity, speed, specificity and effectiveness. Most plastic heating processes such as conductive, convective or infrared heating are surface heating processes where it is required is to set a temperature in the plastic and then heat by conduction to the main part of the Transferring plastic. Accordingly, the heating of plastics by these methods is proportionate slow process with a non-uniform temperature, which leads to overheating of the surfaces.

In contrast, the dielectric generates heating

the heat in the material and is therefore uniform and rapid and eliminates the need for heat transfer by line. In the dielectric heating system suitable according to the invention, the electrical

Frequency of the electromagnetic field 1 to 3000 megahertz, the field being generated by an energy source of 0.5 to 1000 kilowatts.

Induction heating is similar to dielectric heating, but it is not there
the differences:

but is not identical with it. There are the following

SAD ORIGINAL.

a) Magnetic properties take the place of dielectric properties,

b) instead of electrodes or plates, a coil is used used to couple the load and

c) Induktionsheizungselemenιe couple a maximum Power to the load. The generation of heat by induction occurs through the rise and fall a magnetic field ;; around a leader at each Reversing an AC power source. The practical development of such a field; is generally through proper positioning of a conductive coil is achieved. If another electrically conductive material exposed to the field, an induced current can be generated. Difse induced currents can

are in the form of random or eddy currents, the to. lead to the generation of heat. Materials that are both magnetizable and conductive, generate heat more easily .ils materials that are only conductive. Due to the magnetic components

te generated heat is there :; Result of the hysteresis or the arboit performed when rotating magnetizable Molecules. Furthermore, the generation of heat is a result of the flow of eddy currents.

Polyolefins and other plastics are neither

magnetically still conductive in their natural state.

Therefore, they do not generate heat by themselves due to induction.

The use of the electromagnetic induction heating method for adhesive bonding of plastic structures has been shown to be possible by using selected electromagnetic energy absorbing materials in an independent adhesive layer or seal that adheres to the surfaces to be connected are adapted, between-

switched so that the electromagnetic energy,

3ÄD ORIGINAL

due to the adjacent plastic structures (free of such energy-absorbing materials) passes through such energy-absorbing materials slightly concentrated in the adhesive composition

and is absorbed and therefore hardening quickly 5

the adhesive composition to a thermoset

Adhesive initiated.

In electromagnetic induction heating technology, electromagnetic energy-absorbing goodbye has long been used Different types of materials are used. For example, inorganic oxides and powdered metals are incorporated into connecting layers and electromagnetic radiation been exposed. In any case, the type of

Energy source the selection of the energy-absorbing material. 15th

When the energy absorbing material is made of fine particles with

ferromagnetic properties and these particles effectively insulated from one another by other particles which do not contain a conductive matrix material is the heating effect essentially limited to those from the 20th

Hysteresis effect results. As a result, heating is limited to the "curio" temperature of the ferromagnetic Material, or the temperature at which the magnetic properties of the material cease to exist.

The electromagnetic adhesive composition according to

of the invention can be in the form of an extruded tape, molded gasket, or cast film. In liquid form, it can be applied by brushing, spraying or dipping onto surfaces to be connected

surfaces are applied.

The adhesive composition described results when properly Use (· ΐη solvent-free connection system that enables the connection of metal or plastic ■ -.- ■ - · ■.

objects without expensive surface pretreatment

BM) ORIGINAL

32379U

permitted. The electromagnetically induced compound reaction is rapid and can be linked to automated manufacturing processes and systems are adapted.

It has been found that induction heating can be used to achieve a concentrated and localized heating zone the electromagnetic adhesive compositions described above can be activated and a bond can be created by an induction heating system, which with an electrical frequency of the electromagnetic field of about 5 to about 30 megacycles and preferably about 15 to 30 megacycles, wherein the field from an energy source from about 1 to about 30 kW and preferably about 2 to 5 kW is generated. The electromagnetic field is applied to the objects to be connected used for less than about 2 minutes.

As mentioned earlier, the electromagnetic induction connection system and the improved electromagnetic adhesive compositions according to the invention applicable to joining metals, thermoplastics and thermoset materials including fiber reinforced thermoset materials. 25th

The invention is to be explained in more detail with the aid of the following examples. Unless otherwise stated, refer to all parts and percentages are based on weight. The shear strength properties of the adhesives under stress

by tensile loading were obtained according to ASTMD 1002-64

2 ■ ·
to 6.45 cm overlap area, determined.

Y _

SAD ÖPJGSNAL

32379U

example 1

Production of diphenyliodonium tetrafluoroborate 20 g of silver retrafluoroborate were dissolved in 20 g of water in a beaker at 60 ^° C. while stirring. 33.52 g of 97% diphenyliodonium chloride were dissolved in 720 g of water in another beaker at 60 ° C. while stirring. The silver tetrafluoroborate solution was slowly poured into the diphenyliodonium chloride solution and the precipitated AgCl was removed by filtration. The filtrate was cooled for 2 days, which resulted in the formation of white crystals. The filtrate was thawed and filtered again. The resulting white crystals were washed with water, air dried and then dried in vacuo overnight. There were

11.1 g of white crystals were obtained. The filtrate was on 2/3 of its volume in a Bucchi rotary evaporator concentrated and then chilled. After thawing at room temperature, the filtrate was filtered again and the white Crystals were collected as indicated above. The resulting long white needle-shaped crystals weighed 28.6 g and had a melting point in the range from 132 to 137 ° C.

Analysis:

For ^c ₁₂ ^H ₁₀ ^BF ₄ ^[ · " ^c = 39.16; H = 2.72; B = 2.94;

F = 20.67; I = 35, -51.

Found: C = 39.15; H == 2.64; B = 3.04; F = 20.55; I = 34.98,

Example 2 30

Curing of the wärmea ktiviι Tbaren adhesive composition 8 g of a polyamide with a softening point in the range from 87 to 100 C, which is sold under the trade name "Macromelt-6071" by Henkel Adhesives Co., were in a 50/50 methyl alcohol methylene dichloride -Lö-

BATH ORIGINAL

solvent dissolved at 40 C. 2 g of a bisphenol A diepoxide, under the trade name "DER-331" from the company Dow Chemical Co., along with 0.06 g benzopinacol and 0.06 g diphenyliodonium trefrafluoroborate added to the solvent. After all Adhesive composition materials in the solvent were dissolved, the solvent was removed in vacuo at 30.degree removed. Five samples for lap load tests were prepared by using the adhesive composition thus obtained was applied to a rolled steel substrate, which with a similar substrate to form a Overlap of 3.2 cm was clamped together «The clamped substrates were 20 minutes in a Forced air circulation oven with a temperature of 160 C.

After removing from the oven and cooling to room temperature

+ 2 door, the lap shear strength was 169.4 * - 26 kg / cm.

A comparison test without bisphenol A diepoxide gave
20th

an overlap shear strength of 29.5-4.9 kg / cm.

The following examples in Table 1 show the shear strength properties different heat-activatable adhesive compositions. In all examples the thermo-

_ ₅ plastic adhesive material in a solvent, ie

50/50 MeOH / CH ₂ Cl ₂ or CH ₂ Cl _{3 dissolved} at 40 ° C. The component with the ethylenically unsaturated group and / or the component with the epoxy groups was then dissolved. Then the thermal initiator was in the solvent

₃₀ solved. The solvent was removed in vacuo and the

remaining solid heat activated adhesive composition

was applied between two 3.2 cm overlapping substrates. Five sets of test samples were made for each adhesive composition manufactured. The substrates were clamped together and placed in a single temperature forced air oven for 20 minutes

BATH ORIGINAL

■ 32379 U

of 160 ⁰ C given. The test samples were removed from the oven, unclamped, and allowed to cool to room temperature before the lap shear strength measurements

2
(kg / cm). The mean of the five

The results are shown in Table 1.

BATH ORIGINAL

Conventional curing of adhesive compositions

Example Thermoplastic acrylate or epoxy group member (wt.%) Initiator (wt.%)

κ ft

No. Adhesive material Weight% DER 331 1.4 butane TMOP-TA - Type diol-diglyci- • dyl ether 3 Butadiene 14% acrylic nitrile 100 Copolymer 79.84 - <· 4th ti - - 19 _S 96 5 Styrene Isoprene 100 Copolymer 79.84 - - - 6th ti _ _ 19.96 7th Polyvinyl 100 formal ¹ 73.89 - -, - ' 8th '·' 89 _S 11 24 _S 63 - - ■ 9 Il 73.89 _ -, 9 _s 90 10 ti 24.63 - 11th Polyvinyl 100 butyral - -

Overlap Shear Strength, kg / cm ^a

Steel ^e fiberglass reinforced polyester

4 ₉ 57 ⁹

Benzopinacol, 0 _s 2

7.03 ⁹ Benzopinacol _s 0 _s 2 13 _s 0

14.1

Arnim: BF "-Äddukt ^J 1, 48 189 _s benzopinacol _s 0.99 31.6 1.48 132.3 dicyanodiamide _s

- ■. . 50.6

S.

42 ₅ 2

Continued Tab. 1

Polyvinyl 89.11 - , 63 butyral 73.89 24 , 80 13th 11th 74.40 24 , 63 14th Il 73.89 24 15th Il 16 Polyvinyl 89.82 _ butyral 89.91 - , 58 17th Il 47.16 23; 18th 11th 19th Ethylene 28% vinyl acetate- 100 _ Copolymer ^m 20 · Ethylene 28% vinyl acetate- 74.81 _ Copolymer ^m 49.75 - 76 21 79.05 19 22nd Il 100 _ 23 Polyamide " 89.91 24

9.90

9.98 9.99

23.58

24.94

Benzopinakol, 0.99 147.6 amine: BFg adduct ^j , 1.48 182.8 onium salt ¹ , 0.79 119.5 onium salt, 0.74 +
Benzopinacol, 0.74 167.3 azobisiso

butyronitrile, 0.2 tetramethylthiu ran

disulfide, 0.1
Onium salt 2.8 +
Benzopinacol 2.8

Benzopinacol, 0.25
49.75 "0.50

Onium salt, 0.59 +
Benzpinacol, 0.59

9.99 benzopinacol, 0.1

75.9

49.2

56.2 40.5

15.5 40, -1

70.3 78.7 84.4

78.7

84.4

119.5

25th Polyamide ⁰ 100 26th Il 79.05 27 Polyester ^ 100 28 It 89.82

19.76

9.98

Onium Salt ^ O.SO +
Benzopinacol, 0.59

Peroxide ⁹ , 0.20

49.9

108.3 16.2 74.5

CO K5 CO

Ir ■ - ta- -

3237-9U

- 38 -

Footnotes:

(a) cured at 160 ⁰ C for 20 minutes, then overlap shear strength measured at room temperature, wherein alie overlaps 3.2 cm, respectively, unless otherwise

₅ indicated;

(b) DER 331 = bisphenol A diepoxide, commercially available from Dow Chemical;

(c) TMOP-TA = trimethylolpropane triacrylate;

(d) SR 209 = Sartomer tetraethylene glycol dimethacrylate, commercially available from Sartomer;

(e) Unless otherwise specified, steel as received;

(f) Hycar 1041, commercially available from B. F. Goodrich; (g) 6.45 cm overlap on degreased steel; (h) Kraton 1107, commercially available from Shell

Chemical;
(i) Formvar 5195E, j average molecular weight

10,000 to 15,000, Monsanto;
(j) Leepoxy B-550, commercially available from the company

Leepoxy plastics;
(k) Butvar B-76, number average molecular weight 45,000

up to 55,000, Monpinto;

(1) Diphenyliodonium betrafluoroborate; (m) Ultrathene 636-04, softening point 106 ⁰ C, commercially

available from USI Chemicals; (n) Macromelt 6900, softening point 130 to 150 C, Henkel

Adhesives Co .;
20 (ο) Elvamide, melting point 145 to 160 ° C, DuPont;

(p) Dynapol S-142, softening point 99 ° C, Dynamit Nobel; (q) 1,1-Di (t-butyiperoxy) -3,3, δ-trimethylcyclohexane, im

Commercially available from Pennwalt.

BAD ORIOINAL

32379H

The examples in Table 2 show the shear strength properties various heat-activated adhesive compositions, when the thermosetting is done by dielectric heating. The adhesive compositions were made as prepared in the examples of Tatelle 1, with a Overlap of 3.2 cm applied between two substrates and 2 minutes by redio frequency radiation at Hardened 200 volts and 0.8 amps direct current.

BAD ORiQSWAL

Table 2 RF dielectric curing of adhesive compositions

Example thermoplastic acrylate or epoxy no. Adhesive material component (wt.%) Type of initiator (wt.%)

29 30

31 32

33

% By weight OF 331 ^b TMOP-TA ⁰

polyamide 89.91 89.91 - 63 9 - , 99 Polyvinyl 58 23 butyral 89.91 - 9 , 99 ti 73.89 24, Il 47.16 23, 9 , 58 Ethylene vinyl acetate copo- lymer , 99

Benzopinacol, 0.1

BenzoDinakol, 0.1 amine.BF_ adduct ^f , 1.5

Onium salt 2.8 + benzopinacol 2.8

Benzopinacol, 0.1

Overlap Shear Strength

kg / cm ^{2 a}

fiberglass reinforced

polyester

60.5

30.2 34.5

40.4 42.2

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Footnotes:

(a) cured for 2 minutes; Overlap 3.2 cm;

(b) DER-331 = Dow bisphenol-A-diepoxyd;

(c) TMOP-TA = trimethylol pmpane triacrylate;

(d) Macrometl 6900, Henkel Adhesive Co .;

(e) Butvar B-76, Monsanto;

(f) Leepoxy B-550, Leepoxy Plastics; '

(g) Ultrathene 636-04, USI Chemicals Co .; (h) Diphenyliodonium tetrafluoroborate.

The examples in Table 3 / have their own shear strength ■ various compositions when the curing step is carried out using induction heating will lead. The adhesive compositions were as for Examples prepared according to Table 1, the iron filler used being added at the end with stirring. After this the adhesive between two substrates with an overlap

2
area of 3.2 cm had been given, the 2 minutes took place

20 long curing with a 2 kw EMABond generator, model EA-20 at 95 to 100 % load.

ORiQtNAL

.- Thermoplastic RF inductive Table 3 Component (wt.%) .TMOP-TA ⁰ initiator , 13 Overlap I. Adhesive material THE 331 ^b (Weight%) shear strength 'ι:
< P Type wt.% kg / cm ^{2 a} example Curing of adhesive compositions 6.49 , 13 fiberglass * t <t < No. reinforced , ■ ,, Polyamide ⁰ 58.37 Benzopinacol, O polyester <»Ι <
4 i Ethylene Acrylate or epoxy filler 6.49 ₊ 61.2 t < *
A Ä
t <
ί I *
ti < vinyl acetate (Weight%) - 15th t < *
« * T 34 copolyme r ^e 58.37 - Benzopinacol, O , 13 35 Polyvinyl 18.45 17.94 43.9 32379 butyral ¹ "55.35 17.94 Arnin. BF ₃ ¹ - "35.88 35.02 6.49 adduct ⁹ , 1.11
Onium salt 2.15 26.0 36 - Benzopinacol 2, 58.37 Benzopinacol, O 28.7 37 35.02 55.5 38 25.09 23.92 35.02

Footnotes:

(a) cured for 2 minutes; Overlap 3.2 cm;

(b) DER-331 = Dow bisphenol-A diepoxide;

(c) TMOP-TA = trimethylolpropane triacrylate;

(d) Macromelt 6900, Henkel Adhesives Co .;

(e) Ultrathene 636-04, USI Chemicals;

(f) Butvar B-76, Monsanto;

(g) Anchor 1222, Anchor Chem ";

(h) Diphenyliodonium tetrafluoroborate

The compositions used are mostly at room temperature Solids containing .ils reactive hot melt adhesive can be used. That is, the solid composition can

to a molten or plastic mass on a

Temperature below the decomposition temperature of the thermal initiator, and then placed between two substrates to be joined. On cooling down at a lower temperature the adhesive solidifies

a thermoplastic adhesive with properties that sufficient to hold the substrates together. After that, the composite product can be heated to a higher temperature to trigger the thermal initiator and form a thermoset adhesive between the substrates.

Another refinement is the use of the solid

Composition in the form of a film, tape or Be seals that are placed between two substrates to be joined. This is shown in the following examples demonstrated.

.

Example 39

100 g of polypropylene glycol] (MW = 1025 g / mol) was added dropwise to a flask over a period of 6 hours given, the 34 g of toluene diisocyanate in a nitrogen atmosphere contained. The reaction was continued with stirring at room temperature for 4 days. The resulting chain-extended product with terminal isocyanate groups is referred to below as diisocyanate adduct A.

10 Example 40

To 100 g of methylene chloride solvent, 100 g of an epoxy resin containing 357 g / equivalents of OH and commercially ^{available from Shell Chemical Co. under the designation M} fpon-1001F, 0.1 g of dibutyltin dilaurate and 40.89 g Diisocyanate adduct A was added from Example 39. The reaction solution was stirred at room temperature for 24 hours and monitored by IR until no isocyanate could be detected. A thermoplastic, epoxy and urethane-containing composition resulted. To 7.5 g of the composition in methylene chloride 2.5 g of a liquid bisphenol-A-epoxyacrylate, which is commercially available under the name "Epocryl Rei.in-12" from Shell Chemical Co., 0.3 g of diphenyliodonium tetrafluoroborate and 0.3 Benzopinacol was added and stirred until a homogeneous mixture was obtained. The methylene chloride was then removed in vacuo to give a heat activated, solid hot melt adhesive composition The composition was applied at a thickness of 50 to 100 µm between two cold, rolled steel substrates.

The substrates were clamped together and heated to 70 ° C. for 5 minutes. Then they got to room temperature cooled down. After the staples were removed, the thermoplastic composition held the composites together Parts upright. These were then 20 minutes heated to 160 C, which resulted in a thermoset adhesive between the substrates.

BATH ORIGINAL

Claims (1)

"STOLB-EWS * PATENT LAWYERS BESELERSTRASSE 4 D-SOOO HAMBURG 52 W.R. Grace & Co. 1114 Avenue of the Americas New York, N.Y. 10036 V.St.A. EUROPEAN PATENT ATTORNEYS DR. J.-D. FRHR. by UEXKULL DR. ULRICH SRAF STOLBERG DIPL.ING. JÜRGEN SUCHANTKE DIPL.-ING. ARNULF HUBER DR ALLARD BY KAMEKE
pRj ^^ L-HEipggJHULMEYER US 317 672
(18969 ka / do / lü)) October 1982 Heat-activatable adhesive or sealing resin composition, process for their production and their Use patent claims üche 1. Heat activatable organic adhesive or sealing resin composition characterized by (1) a member of the group (a) a liquid, ethylenically unsaturated one Monomer, oligomer or prepolymer with the formula «I. (CH ₂ -CCOJR, ^Λ j η ι in which R denotes hydrogen or CH-, R. denotes an organic Means a remainder and η is at least 2, (b) an epoxy resin having at least two / C-C ^ groups and O (c) a mixture of (a) and (b); (2) a thermal initiator and 32379U (3) a thermoplastic adhesive material from the group consisting of polyesters, polyvinyl acetals, Polyamides, butadiene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, Styrene-ethylene-butylene copolymers, ethylene-vinyl acetate copolymers, Ethylene-ethyl acrylate copolymers, Ethylene propylene diene monomer and mixtures the same. Process for producing a coating on a substrate, characterized in that a thermosetting composition according to claim 1 is produced by mixing, the substrate is coated with the composition and
heated. tet and the coating to harden to 70 to 200 ° C 3. The method according to claim 2, characterized in that the heating by electromagnetic heating he follows. 4. The method according to claim 3, characterized in that that electromagnetic heating by dielectric Heating takes place. 5. The method according to claim 3, characterized in that that electromagnetic heating by induction heating he follows. 6. Use of the cured composition according to claim 1 as a sealant. 7. Use of the cured composition according to claim 1 as an adhesive. 8. A method for bonding two substrates', characterized in that the substrates are treated with a solid, thermosetting composition according to claim 1, the composition is heated to a temperature at which it is sufficiently plastic to act as a thermoplastic adhesive between the substrates to act, which temperature is below the decomposition temperature of the thermal Initialors, is then heated to e> ne higher temperature which is sufficient to decompose the thermal initiator and a ther mogehärt.eter adhesive is formed between the substrates, 9. Composition according to claim 1, characterized in that that the composition is a solid in the form of a film, tape or gasket. BATH ORIGINAL