DE1519052C - Heat-hardening coating and adhesive - Google Patents

Description

1 2

It is known to cover objects by using adhesives in which they are in spite of the presence of

then a resin which is not undesirable in a suitable halogen-containing vinyl polymer

Plasticizer for this is dispersed, applied and caused blistering.

Coating then to a suitable setting temperature. The invention now relates to a thermosetting one

heated. Numerous coating agents and adhesives based on a substance are suitable for this method.

Polyvinyl resins, especially polyvinyl chloride and copolymers from '-

mers of vinyl chloride with other unsaturated a) a dispersion of a halogen-containing vinyl poly-

Monomers. In this way, tough merisats are easily obtained in one at room temperature

and abrasion-resistant coatings, which, however, _{contain the} softening softeners,

partial property that they can be used on most io,. .. ".... "....

Surfaces adhere very poorly. ^b > ^an _R ^r epoxy bond with an epoxy equivalent

^Γ ^ ° ^ ^{Γ as} PY ^emer ™™ & ^{vo "b 5} f ^{50 Ge"}

It was further suggested that the adhesion strength ^ ^{Γ. Γ} ° ^ ^than previous year ^emer ™™ & ^{vo "5 b} f

to improve significantly from such coatings, weight percent of the vinyl polymer.sats and

^{by adding epoxy resins c} ) a hardening agent to the coating compounds,

and hardeners, which are characterized both with the epoxy resins as 15 that is as hardening

also react with the vinyl polymers, incorporated. medium one free of primary amino groups, through

Curing agent which only works with the epoxydverbin- condensation of a volatile ketone with a

fertilize, but do not react with the vinyl resin, containing at least two primary amino groups

do not give good adhesion. The amount of amine produced condensation product and moisture

Epoxy resin is 5 to 50 percent by weight of the vinyl it contains.

resin. Although this process improves greatly, it has been found that compositions of this type The degree of adhesive strength of vinyl resin coatings, however, suffers excellent adhesive strength on the various with the disadvantage that they have the most cured surfaces and also one Film easily bubble. This »bubble formation- very strongly reduced tendency to the formation of bubbles effect «is particularly pronounced when the curable 25 show when heated, when they are used for the production of Mixture stored at room temperature with relatively thick surface coatings before use would; the well-known compositions are turned.

thus have the further disadvantage of a short Da in the compositions according to the invention

Shelf life. hardeners used no primary amino

For the crosslinking of the mixtures of epoxy groups containing 3 °, they react with polyvinyl

Resins and polyvinyl halides and / or copoly halides not quickly at room temperature, and

merging of vinyl halides with other vinyl - they therefore also do not cause premature formation of

monomers are mainly aliphatic ^ polyamines hydrogen chloride. Condensation products from this

has been used, as in the British patent type, which does not contain amine hydrogen at all

777 052 is described. The blistering will contain 35 such. B. those made of ethylenediamine and

apparently produced by the reaction between which a ketone hardly react in

Crosslinking or hardening agent and the halogen- absence of moisture. Under the influence

containing vinyl polymer causes; it becomes freer of moisture and heat, however, it becomes free

Hydrogen chloride is split off, which amine is released when gelling, and it takes place quickly and

the composition remains enclosed in the cover. 4 ° effective hardening without simultaneous formation of

In the case of very thin coatings, this effect does not occur with bubbles. If desired, you can call the

particularly disturbing in weight because the .Main amount of positions is a compound with chemically bound

Hydrogen chloride can escape before gelation; Water that is at or below the hardening temperature

on the other hand, in the case of films of more than 0.05 mm thickness, z. B. hydrous calcium sulfate,

the formation of bubbles noticeably. This is especially important to add 45. This will result in faster hydrolysis

disadvantageous because essentially "solvent-free": the amine-ketone condensation product to the free one

Amine causes coatings usually applied as thick films.

be to the cost of applying several under the curing conditions that evaporated

To spare coatings. There is thus a need for free, volatile ketone rapidly. The addition of a water

after compositions which have a lower tendency to give a connection, however, as a rule

to show the formation of bubbles and at the same time a liquid, since the vinyl polymer usually still has traces

Maintain good adhesive strength. Contains water, from the manufacturing process

Furthermore, it was already known (cf. for example come from; these traces of moisture are sufficient for German Auslegeschrift 1 010 677, German patent - the hydrolysis during heating.. ·.
writing 889 501), as a hardener for epoxy resins condensate 55 If the new compositions according to the invention remain protected from moisture by volatile ketones with amines, they have to be used. However, these were used exclusively for the general storage curing of epoxy resin compositions at room temperature, with a stability of several weeks, which means a further disadvantageous blistering effect due to those of these halogen-containing vinyl resin compositions over the known compositions.

HCI split-off cannot occur, as these are contained in the new compositions

Epoxy resin compounds do not contain halogen. Hardening agents are

Surprisingly, the reaction between the amine and the ketone turned out to be under

formed an extraordinarily large number of known epoxy resin cleavage of water. The amine is z. B.

harder (see, for example, Hο u be η - Weyl, Vol. ⁶ 5 with an excess of the ketone, if necessary in

XIV / 2, pp. 499 to 532) just this ketone-amine heated in an inert atmosphere, such as nitrogen gas,

Condensation products as suitable hardeners for the water of reaction and excess ketone

Heat-resistant coating according to the invention and are distilled off. When the ketone used

higher boiling than water and not completely through Fn in the following examples mean parts

Azeotropic distillation with the water removes parts by weight and percentages percentages by weight.

can be distilled according to the, _t ,

complete removal of the water the remaining B e ι s ρ ι e 1 1.

Ketone in vacuo. 5 A curing agent was prepared wip as follows:

For the preparation of said condensation A mixture of 100 parts of D, iäthylenetriamine and

products are as amines in particular polyamines of 250 parts of methyl isobutyl ketone was refluxed

Formula cooked, with the water of reaction in a trap

H _a N (C ₂ H ₄ ) _n H was separated. After depositing 35 parts

ίο Water started the investigation of the infrared spectrum

where rt ^ denotes the numbers 1, 2, 3 or 4, suitable for the reaction mixture that no primary amine

such as B. 'ethylenediamine, diethylenetriamine, triethylene groups were more available. The excess

tetramine and tetraethylene pentamine. Further suitable methyl isobutyl ketone was then applied in vacuo

Dipropylenetriamine, tripropylenetetramine and 120 ⁰ C distilled off. 252 parts of reaction

Tri-, tetra-, penta- and hexamethylene diamine; cyclo- 15 product (hardener A) with a viscosity of

aliphatic amines such as bis (4-amino-3-methylcyclohexane 12 cP at 25 ⁰ C and a nitrogen content of 15.5 ° / _0th

hexyl) methane and 3- (3'-aminocyclohexyl) -n-propyl- Furthermore, a liquid epoxy resin (epoxy resin

amine; also aromatic diamines, such as bis (4-amino-A) with an epoxy content of 5.10 epoxy equivalent

phenyl) methari, bis (4-aminophenyl) sulfone and mvalents / kg produced in a known manner by

Phenylenediamine. ■ ao conversion of epichlorohydrin and 2,2-bis- (4'-hydroxy-

AIs ketones are suitable for the production of phenyl) propane in the presence of alkali,

mentioned condensation products z. B. Acetone, Me- A coating composition was made by mixing

ethyl ethyl ketone, methyl isopropyl ketone, di-isopropyl- the following components are formulated: ketone, methyl isobutyl ketone, di-isobutyl ketone and

Methylcyclohexanone. as polyvinyl chloride paste 80 parts

As vinyl polymers, which in the invention curing agent A 6 parts

appropriate compositions are used, epoxy resin A ... 20 parts

called: polyvinyl chloride, copolymers of vinyl

chloride with other unsaturated monomers, such as this mass was sandblasted mild steel

Vinyl acetate, maleic anhydride, ethylene, acrylic plates 30, applied and for 5 minutes at 180 ° C

nitrile, vinylidene chloride and acrylic acid esters. One can be hardened. The coating, which is an average

furthermore, using polymers which, after treatment, had a thickness of 0.25 mm, was excellent

such as chlorination or hydrolysis, were subjected to adhesive strength and flexibility and also showed in

z. B. chlorinated polyvinyl chloride and partially hydrolyzed its thicker cross-sections are not included

Sized copolymers of vinyl acetate or vinyl acetals 35 bubbles. If in the above formulation the hardening

with vinyl chloride. Replaced as plasticizer for polyvinyl agent A by 2.5 parts of diethylenetriamine

resin you can use the usual types, z. B. phthalates, and thus a coating of the same thickness

Sebacate, phosphate, epoxidized unsaturated acids were applied analogously, this showed after hardening

and alcohols or the esters derived therefrom, although good adhesive strength and flexibility, however

use. 40 he was like that due to numerous trapped bubbles

As an epoxy compound with an epoxy equiva- lent, that it defaces for most applications

lenz greater than 1, which was useless for the manufacture of the.

Compositions according to the invention are suitable, are two- The polyvinyl used in the above formulation

for example: polyglycidyl ether of multi-chloride paste has the following composition:

Valuable alcohols such as butane-1,4-diol, glycerine, 45 vinyl chloride polymer (1) 50 parts

or N-phenyldiethanolamine, or of polyvalent ones. . .... _D "i" _mi .r n \ * n Τα, Ίο

Phenols such as resorcinol, 2,2-bis- [4-hydroxyphenyl] -vinyl chloride polymer (2) ...... 50 parts

propane or condensation products of aldehydes adipic acid ester plasticizers ... 25 parts with phenols (novolaks), polyglycidyl esters of PpIy polyethylene oxide viscosity carboxylic acids, such as. B. phthalic acid, aminopoly 5 ° lower 2 parts

epoxyde as produced by dehydrohalogenation of the epoxidized soybean oil ....... 2 parts

Reaction products of epihalohydrin and pri-organotin stabilizer .. 0.75 parts

mary or secondary amines, such as n-butyl

amine, aniline or 4,4'-di- (monomethylamino) -di-B e i s ρ i e 1 2

pheriylmethane, are obtained; also by 55

complete or partial epoxidation of ethyl- In the formulation according to Example 1, the

nically unsaturated cyclic or acyclic poly-epoxy resin Ä replaced by 20 parts of epoxy resin B with

olefin obtained products. an epoxy content of 5.2 epoxy equivalents / kg,

The compositions of the invention can do this by reacting epichlorohydrin with N-phenyl

In addition, mineral or vegetable fillers, ethanolamine 60 has been produced in the usual way.

Contain reinforcing agents, pigments and dyes. This formulation was analogous to that in

For example 1, the new compositions can be coated with a thickness of 0.25 mm, Positioning of coatings on ferrous metals, such as soft- which also show no signs of blistering steel, non-ferrous metals such as aluminum, and also glass. . Wood, ceramics or textiles made of polyamide or 65, example 3 Polyester fibers are used. They can also be used as adhesives for bonding two surfaces together. A hardener was prepared as follows: use the materials listed above. A mixture of 65.3 parts and ethylenediamine

Claims (1)

5 6 300 parts of methyl isobutyl ketone was patent claims under nitrogen boiled under reflux, the water of reaction in a trap was separated. After deposition 1. Thermosetting coating and adhesive of 41.5 parts of water showed the investigation on the basis of a mixture Infrared spectrum of the reaction mixture that no 5 _a ) _a dispersion of a halogen-containing vinyl primary amine groups were more present. The polymer in one at room temperature Excess ketone was then in a vacuum with _{non-dissolving effect} the plasticizer, 120 C distilled off. u \ · c u- a ·. · C ,,,. .. ,, «. r- ·, -n ,. · j W _{1 -TT- t} o) an epoxy compound with an epoxy 224 parts of reaction product (hardening '..., ^{R J} .. " ,? · ·>. mediumB) with a nitrogen content of 12 ° / ₀ . ip 'equivalence greater than 1 m of a set of An adhesive cement was made by mixing the following ⁵ to 50 percent by weight of the vinyl poly " .-., ·. mensats and components formulated: c) a hardening agent, Hardener B 7 parts of α λ 'u ι -t- ^ jo ι πι -11.1-Jn -ότι · characterized in that it is as Polyvinyl chloride paste according to Bei- _1J} curing agent one of primary amino groups ^s P ^{iel L} ··· '■ ^{wl hurry} free, by condensation of a volatile Vinyl chloride-vinyl acetate-maleic ketone with at least two primary amino acid anhydride terpolymer 10 parts of group-containing amine produced condensate Epoxy resin A (according to Example 1) .. 20 parts sationsprodukt and contains traces of moisture. Quartz powder 60 parts ²⁰ 2. Thermosetting coating and adhesive Finely divided silicon dioxide ....... 5 parts ^according to claim 1, characterized in that it contains a condensation product as a hardener. The putty was for 20 minutes at 150 ° C which by condensation of a polyamine between glued glass plates or aluminum formula hardened aluminum sheets. During the 25 H ₂ N (C ₂ H ₄ NH) ₇₁ H Hardening only very little flow; after hardening. ^ it showed good flexibility, excellent adhesive strength where η is an integer from 1 to 4, and no signs of blistering. with a volatile ketone.