DE1594032A1 - Adhesives based on polyepoxides - Google Patents

Description

D 3104
"Adhesives based on polyepoxides"

The present invention is an adhesive for a wide variety of materials, which without the supply of heat At room temperature and even at temperatures below this, they form solid connections within a short time leads.

It is known that polyepoxide compounds can be converted into hardened molding compounds by means of so-called Lewis acids. Since the Epoxides react violently with these compounds, such as borofluoride, tin tetrachloride, aluminum chloride, their complex compounds have also been used. For example, the amine complexes of boron fluoride are considered latent Ileißhärter for casting resins usable and have in practice Entrance found. One uses more reactive boron fluoride complexes for the preparation of rapidly at low temperatures curing epoxy resin adhesives, such bonds do not have satisfactory strength.

Q09822 / 15S2

BAD ORiGiNAL

Henkel & Cie GmbH 159403?

Patent department
D 3104 - 2 -

Even with the use of normal, commercially available plasticizers, no firm bonds could be achieved.

It is also known, curable mixtures based on monomeric polyepoxy compounds, PVC plastisols and To prepare complexes of boron trifluoride with amines (French patent 1 305 982). Such masses Admittedly, they adhere well to metal and are suitable for producing coatings, but they have to be used at high can be burned in at higher temperatures. It could not be expected that similarly structured mixtures, which contain other complexes of boron trifluoride, would be able to make cold-curable adhesives. This was not to be expected because the plastisols require relatively high temperatures to gel. aside from that could not be expected that such mixtures would have such a high internal strength that the transfer high shear loads is possible.

It has now an improved adhesive based on polyepoxide compounds found which does not have the disadvantages mentioned and without heat very firm adhesions

009822/1562

BATH

Patent department

D 3104 '- 3 -

supplies between a wide variety of materials. The new adhesive contains the following components:

a) 100 parts by weight of glycidyl ethers of polyhydric phenols with an epoxy value of 0.4 to 0.6, of which a maximum of up to 50 % can be replaced by other curable epoxy compounds

b) 10 to 100 parts by weight of a plastisol based on polyvinyl chloride or copolymers of vinyl chloride with a content of about 30 to 50 %

- of plasticizers

c) 1 to 10 parts by weight of a boron trifluoride complex with organic oxygen compounds or water

d) optionally up to about 200 parts by weight of fillers and pigments.

The glycidyl ethers of polyhydric phenols with an epoxide value of 0.4 to 0.6 are those which are, for example from diphenylolpropane, diphenylolmethane, diphenylolcycloalkanes, dioxybenzophenone, resorcinol, hydroquinone and Epihalohydrins, in particular epichlorohydrin, are obtained in a known manner. The glycidyl ethers of polyhydric phenols but can also partially up to about half through other curable cycloaliphatic or aliphatic epoxy compounds be replaced. For example, the epoxidation products obtained from 2 cyclohexene rings in the Molecule-containing compounds or from polybutadiene

009822 / 15S2

Henkel & CIe GmbH 159403?

Patent department

D 3104 - 4 -

can be obtained, or the reaction products of polyhydric alcohols, such as propanediol, butanediol, glycerol with epihalohydrins ^

The plastisol is a plasticizer-containing paste made from commercially available polyvinyl chloride powder or from copolymers of vinyl chloride with copolymerizable compounds such as vinylidene chloride, vinyl acetate, acrylonitrile. The plastisol should have a plasticizer content of ^ O to 50 %. Suitable plasticizers are, for example, dioctyl phthalate, dinonoyl phthalate, tricresyl phosphate, phenolsulfonic acid esters of dodecyl alcohol, cresol sulfonic acid esters of dodecyl alcohol, onyl adipate, ethylhexyl sebacate and mixtures of these compounds. In general, the plastisol also contains other auxiliaries such as stabilizers and, if appropriate, pigments, dyes or fillers.

The hardeners are another essential component of the adhesive according to the invention. These are boron trifluoride complexes with organic oxygen compounds or with water, i.e. with boron trifluoride hydrates. Suitable Organic complexing agents containing oxygen are, for example, lower aliphatic ethers, such as diethyl ether, Diisopropyl ether, dibutyl ether. Also suitable as complexing agents are alcohols, such as methanol, ethanol,

009822/1552 - b -

Henkel & Cie GmbH.

Patent department

D 3104 - 3 -

panol, propanediol-1 , J>, butanediol-1,4 and others more. In addition, phenols such as phenol itself, cresol, resorcinol, hydroquinone, diphenylolmethane or their methyl or ethyl ethers and others can also be used as complexing agents. The complexing agents mentioned can also be present in a mixture. Thus, according to a preferred embodiment, the boron trifluoride etherate is dissolved in additional aliphatic alcohol such as propanediol, butanediol or butylene glycol when it is used. The complexing agents mentioned reduce the reactivity of boron trifluoride only relatively little. This distinguishes them from other complexing agents, for example from the organic amines, which reduce the reactivity of the boron fluoride to such an extent that they can only be used as heat hardeners.

In addition to the compounds mentioned, the adhesives according to the invention can also contain fillers and pigments, for example aluminum oxide, silica, alumina, rock flour, titanium dioxide, magnesium oxide, soot, iron oxide and others more. In addition, smaller amounts of other auxiliaries can be added. Come as such Resin-like products such as coumarone resin, indene resin or light and heat stabilizers in question.

To use the adhesives according to the invention, mixing is carried out

009822/1562 - 6 -

Henkel & Cie GmbH

Patent department

D 3104 - 6 -

expediently first glycidyl ether of polyhydric phenol with the plastisol and later adds the boron trifluoride complex immediately before the gluing is carried out. It is advantageous to use the same in additional plasticizer or in for better dosing and handling to solve additional complexing agents.

With the adhesives according to the invention, the most varied Materials can be glued to one another or to one another as required, such as metal, glass, Stones, concrete, ceramics, wood, chipboard, cardboard, plastics. Among the metals are, for example the following named: aluminum, iron, copper, nickel, chromium, zinc, brass, tin, titanium. Among the plastics to be glued are for example mentioned hard polyvinyl chloride or hardened bodies made of melamine resin, urea resin or Phenolic resin.

The bonds can be made after cleaning the documents and applying the adhesive in a thin layer be carried out in the usual way by joining the adhesive parts. In some cases it may be advisable to compress the materials to be glued together. Included

However, only a slight pressure of from 0.05 up to a few kg / cm * required. After a period of 15 to 60 minutes , high strengths are achieved. Even at temperatures

009822 / 1SS2 - 7 -

Henkel & Cie GmbH Patent department

D 3104 - 7 -

Flawless bonds can be carried out a little below the freezing point. Under these conditions other curing agents fail or take an extremely long time.

If the adhesive points are heated to higher temperatures for a long time, no embrittlement occurs, i.e. the The shear strength of the bond is retained.

009822/1552

Henkel & CIe GmbH Patent department

D 3104

Example 1;

Changing amounts of a PVOPlastisol were added to a mixture of 10 g each of a commercially available liquid epoxy resin (epoxy value 0.52), produced by reacting diphenylolpropane with epichlorohydrin. The plastisol consisted of 70% of a commercially available polyvinyl chloride powder (K value 70) and ^ O # a mixture of dioctyl phthalate and Phthalsäuredidecylester (ratio 60: 40) to the mixtures of epoxy resin and plastisol were respectively 0.8 g of a solution of ^ O ^ » Added solution of boron trifluoride dietherate in 1,4-butylene glycol. With the adhesive mixture obtained in this way, aluminum sheets measuring 100 × 20 × 2 mm were coated thinly and fixed with a wooden clamp so as to overlap by 20 mm.

The table below shows the ratio of plastisol to epoxy resin and the tensile shear strength measured after 15 minutes refer to.

Tabel

g plastisol
10 g epoxy resin Tensile shear strength at 20 ⁰ C
in kg / cm ² 1
2 120
280
272

009822/1552

Henkel & Cie GmbH 159403? Patent department

D 5104 - 9 "

For comparison, adhesions were also carried out, in which, however, no plastisol was added. In this Fall was the tensile shear strength measured after 15 minutes

75 kg / cm. If 2 g of the plasticizer were used instead of the plastisol, consisting of a mixture of dioctyl phthalate and decyl phthalate on 10g epoxy resin added, a tensile shear strength of 100 kg / cm was measured after 15 minutes.

Example 2:

A mixture of 10 g of epoxy resin as in Example 1 and 5S of the plastisol used there was produced. In addition to 0.8 g of the 30% solution of boron trifluoride dietherate in butylene glycol, a paste of 55 % kaolin and 45 % of the mixture of dioctyl phthalate and decyl phthalate was added. With this mixture, aluminum sheets measuring 100 20 χ 2 mm 10 mm were coated with an overlap and fixed with a wooden clamp.

After 15 minutes, the tensile shear strength became 200 kg / cm

measured at 20 C. If the measurement was carried out at 60 ° C,

2 ο 2

the value was 95 kg / cm, while at 80 C it was 65 kg / cm had sunk.

- 10 -

009822/1552

Patent department

D ^ 104 - 10 -

If the adhesive joint was aged for 3 hours at 100 ° C, was the shear strength 230 kg / cm at 20 C. Accordingly, it was none Embrittlement occurred.

With the same adhesive, steel sheets were made with the trade name ST 37 bonded and shear strengths around 150 kg / cm measured. Bonding of rigid PVC panels measuring 100 × 20 × 4 mm resulted in tensile shear strengths of 60 kg / cm.

Example 3:

A mixture was produced from the following components: 7 g epoxy resin (example 1), 5 g plastisol (example 1), 2 g coumarone resin, 1 g aluminum oxide. The mixture was stirred with 0.8 g of a 30 # strength solution of the complex compound of 1 mol of boron trifluoride and 2 mol of phenol in 1,4-butylene glycol, which was thickened with 0.1 g of aluminum oxide and 0.1 g of Aerosil. With the adhesive produced in this way, aluminum sheets measuring 100 × 20 × 2 mm were coated thinly and glued with an overlap of 10 mm under the pressure of a wooden clamp. After one hour of storage at 20 ° C, a tensile

2 ο 2

Shear strength of 190 kg / cm at 20 C and 90 kg / cm 60 C measured.

If concrete parts were bonded with the adhesive mixture, material breakage was observed when tearing.

- 11 -009822 / 15S2

Henkel & Cie GmbH 159 k 032 Patent department

D 3104 - 11 -

Furthermore , pieces of glass measuring 100 × 20 × 4 mm were bonded with the same adhesive. After storage for one hour at 20 ° C., material breakage was observed in the tensile test.

Example for:

A mixture was prepared from the following components: 10 g of epoxy resin (made from diphenylolpropane and epichlorohydrin, epoxy value 0.53), 5 g of the plastisol according to Example 1, 5 g of a paste of 55 % kaolin and 45 % dioctyl phthalate and decyl phthalate (weight ratio 60 : 40), 0.8 g 30% solution of the dihydrate of boron trifluoride in butylene glycol. With this mixture, aluminum sheets measuring 10 × 20 × 2 mm were coated with 10 mm overlapping, placed one on top of the other and fixed with a wooden clamp. After 1 hour, a tensile shear strength of the bonded sheets of 175 kg / cm was measured.

009822/155?

Claims (3)

Henkel & Cie GmbH 1594Ö35 "patent department D 3104-12 - claims 1) Adhesive based on polyepoxy compounds, without Heat supply hardens, characterized by a combination of the following components: a) 100 parts by weight of polyvalent glycidyl ethers Phenols with an epoxy value of 0.4 to 0.6, of which a maximum of up to 50 % can be replaced by other curable epoxy compounds b) 10 to 100 parts by weight of a plastisol based of polyvinyl chloride or copolymers of vinyl chloride with a plasticizer content of about 50% to 50% c) 1 to 10 parts by weight of a boron trifluoride complex with organic oxygen compounds or water d) optionally up to about 200 parts by weight of filler fen and pigments. 2) adhesive according to claim 1, characterized in that the complex of boron fluoride of boron trifluoride and a lower aliphatic ether, an alcohol or a phenol is formed. 3) Method according to claim 1 and 2, characterized in that that the complex of boron fluoride is formed from boron trifluoride and diethyl ether. (Dr. Raec ******, * f + , patent attorney 009822/155 Jfcen.Vollm. 152 / 195Q