DE1232299B - Coating, impregnating and adhesive agents that harden due to the action of heat and are based on aqueous solutions - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09d

German: 22 g -10/01

Number: 1232 299

File number: B 61197IV c / 22 g

Filing date: February 9, 1961

Opened on: January 12, 1967

The invention relates to aqueous or water-containing solutions of mixtures of substances for the production of thermosetting Coatings, impregnations and bonds that are insoluble, resistant to water, are very hard, elastic, transparent, smooth and bright.

It is known to consist of soluble polymeric substances or mixtures of substances under certain conditions are capable of forming insoluble products on their own or through interaction with one another, based on solutions of the substances or mixtures of substances in organic solvents, insoluble polymers to manufacture on materials of the most varied kinds. To do this, the solutions are left on the materials generally dry completely or partially and produced by warming or heating, if appropriate in the presence of hardeners, d. H. Substances that affect the chemical interaction of solid components influence one another in the desired sense, the insoluble polymers. To this Way you can z. B. lacquer-like coatings, coatings, laminates, impregnations, finishes and make bonds. The starting materials for the process mentioned are above all relative See high molecular weight, mostly water-insoluble condensation products of formaldehyde with phenol Substances such as phenol or cresol, as well as urea, melamine, guanidine or the derivatives these nitrogen compounds are used.

You have these so-called "phenoplasts" or "aminoplasts" to yourself, mixed with one another and used in a mixture with alkyd resins, as well as certain N-methylol groups or etherified ones N-methylol groups containing and also mostly water-insoluble, not from urea, melamine or Guanidine derived polymers.

Since working with organic solvents is relatively expensive and occasionally also has other disadvantages, such as odor nuisance or the risk of fires, explosions and damage to health, attempts have also been made to make insoluble, water-resistant polymers from soluble, especially water-soluble substances or mixtures of substances in a manner similar to that already set out above, but starting from aqueous solutions. For this purpose, on the one hand, the corresponding water-soluble monomers or oligomers have been used instead of the already mentioned relatively high molecular weight substances or mixtures of substances which are usually only soluble in organic solvents. On the other hand, one has already modified, relatively high molecular weight, water-soluble polymers through the incorporation of compounds containing carboxyl groups.
Impregnating and adhesive based on
aqueous solutions

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Hans Wilhelm,

Dr. Herbert Willersinn,

Dr. Karl Kohl, Ludwigshafen / Rhine;

Dr. Eberhard Wegner, Frankenthal (Palatinate)

or polycondensates processed together with such water-soluble compounds, which at increased Ability to react temperature with carboxyl groups to cross-linked in the course of the application, insoluble Products. It has also been proposed to use polymers of acrylic or methacrylic acid amide and copolymers of acrylic and methacrylic acid amides and copolymers to use these amides with acrylic or methacrylic acid and optionally together with formaldehyde or precondensates of formaldehyde with phenoplasts or aminoplastic substances use. This measure makes it possible to use a wide variety of materials from aqueous solutions Kind of producing products that are no longer soluble in water and organic solvents. However, these are not always able to meet all requirements, as they are still sometimes in contact with water swelling, are sometimes relatively brittle and mostly opaque, as well as in the production of coatings with thicker layers, they tend to form cracks and wrinkles and often darken at higher temperatures. Because of these properties, the processes mentioned have proven themselves particularly in paint technology cannot generally enforce.

According to an older, not previously published proposal, insoluble, water-resistant, very hard, transparent, smooth and light stove-enamelling on materials of various kinds from water-soluble mixtures of substances and starting from aqueous or water-containing solutions of these Generate mixtures of substances when you use mixtures of substances made from certain copolymers

609 757/384

3 4

of acrylic or. Methacrylic acid amides with various medium soluble polycondensates with a

Esters of acrylic or methacrylic acid on the one hand, special copolymer and in particular the

a phenoplast, on the other hand, as well as an optional addition in water or aqueous ammonia, more soluble

and advantageously an aminoplast available polyester to the already proposed combinations

are. For a number of areas of application, 5 functions of certain reactive polycondensates are too special.

the copolymers obtained in this way, however, still len copolymers.

too little elastic. It has z. B. shown that paints The invention was based on the object from from the components mentioned in addition to their good, very large number of the known, for coatings, Properties, such as their hardness, have the disadvantage of impregnations and adhesives can be relatively sensitive to impact, shock and io materials that lead to a myriad of multi-component bending loads to be. This manifests itself then tengemischen can be combined to select a mixture which is soluble in aqueous media, for example on a painted metal sheet, and which is in Formation of cracks in the paint or detachment of the paint - the heat to coatings with particularly advantageous layer when the sheet can be hardened repeatedly with hard counter properties. The solution to such Stands beaten or on round bars with a relative 15 task can neither by usual series tests small diameter can be bent and stretched again, still can be achieved due to the will. It is therefore desirable, starting from the properties of the components, the properties of the water-soluble substances to be able to produce polymers, processed, d. H. of the stoved mixtures which are not only hard, but also elastic. predict as they are processing with each other It has now been found that coatings, im-20 with the formation of new products and intermediates impregnations or bonds on materials that react. It was therefore surprising that the most varied Type with particularly advantageous mixtures according to the invention when processing in Shafts can be produced if one produces products which are insoluble, against the heat, by means of heat action-hardening substance mixtures based on water-resistant, very hard and yet elastic, aqueous or water-based solutions used by 25 are transparent, light and smooth on the surface, Mixtures of unexpectedly many advantageous properties to-

A. 40 to 88.5 percent by weight of at least one in Sjf *. In addition, there is the advantage that the Mixtures according to the invention soluble in water or aqueous ammonia are in the form of their Polymer from aqueous solutions, d. H. without the often undesirable

\ * «, ·« P. _u . _A , .. -j 3o use of organic solvents,

^a) J ^a Ϊλ 5? _{Can be processed} by weight Acrylsaureamid. _{Compared to the} known aqueous or methacrylic acid amide or a mixture of coating agents _based on the combination of these two amides and of acrylamide copolymers with aminoplast condensate

b) about 65 _saten to 35 weight percent of an ester, such as acrylic acid or methacrylic acid have been described with a ₃₅ in the USA. Patent 2,862,901, the erfindungseinwertigen, non-polymerizable alcohol mixtures according distinguished primarily by the fact that, or from a mixture of such esters; and partially produced hardened coatings are not brittle, but are representative of these esters, elastic and against water at room temperature

c) if necessary and advantageously are persistent for up to days. Metals made with it In addition, 30 percent by weight of a monoester of the 40 finishes does not tend to rust Acrylic acid or methacrylic acid with a layer between the metal and the lacquer layer.

Dihydric or higher alcohol or a mixture of substances according to the invention are present

Mixture of such esters and everything for the production of lacquer-like coatings and

d) if appropriate, other monomeric copoly coatings are suitable, with the good properties merisable compounds in subordinate 45 of the process products are particularly advantageous for Quantities, where the sum of the percentages are valid, but can also be z. B. for Her-Quantities of substances a) to d) is 100, and the creation of laminates, impregnations, dressings

T _{,, Λ} ,., "-".,.,. . Doors and bonds are used.

B. 10 to 58.5 percent by weight of at least one m.,. , ", ..". " .., ..,.,
As WasseroderwäßrigemAmmoniaklöslichenPheno-, η water or aqueous ammonia losiehe plastic or a corresponding oligomers ⁵ ° mixed ^ S? "** ite (A) are particularly suitable as before, ^, * ^b whose K value (according to H. Fikentscher, Cellulose

chemie, 13, p. 58, 1932) is between about 15 and 60

C. optionally and advantageously up to about and which are produced by precipitation polymerization, 48.5 percent by weight of at least one in water, especially the aminoplasts which are soluble by the method according to the German or aqueous ammonia ₅₅ see Auslegeschrift 1195 050 and in particular the or a corresponding oligomer or . Mono- according to the method of the German Auslegeschrift meren and 1150 526 produced water-soluble mixed poly-

the merisate as a further and essential component of the invention. For lacquers and especially for stoving lacquers

_ ",,. . ,. Such copolymers are particularly good

D. 15 to 50 percent by weight of at least one in _6o suitable, the ester component (b) of which consists of acrylic acid-water or aqueous ammonia-soluble Kon- _äth ylester or of ester mixtures, the reduction product from a polyvalent _{car- ates about 35} weight percent acrylic acid ethyl ester and a polyvalent Alcohol contains no _{other acrylic} . _or methacrylic acid esters. As such are preferably to be considered

where the sum of the percentages of the 65 draw the methacrylic and especially the acrylic acid substances A to D is 100. esters of methanol, n-propanol, i-propanol and The feature of the invention is thus a special tert-butanol and the monoester (c) of the ethylene combination different specific, in water glycol, propylene glycol (1,2), propylene glycol (1,3)

5 6

and of butanediol (1,4) and its isomers. Often- received that one pigments or the solutions

In maize it is also advantageous if the monomer-soluble colorants are added. When processing too

Mixture as monomers (d) or as a partial replacement of lacquer-like coatings, it will often be useful

for the amide component (a) up to about 10 weight the solutions according to the invention substances for Percent of special amides, such as maleic acid, 5 improvement of flow and film formation,

Fumaric acid, itaconic acid diamide, crotonic acid amide, such as glycol ethers, acetals, glycols, dimethylformamide,

to add ring-shaped amides, such as vinyl pyrrolidone, vinyl sulfones, sulfoxides, diacetone alcohol,

caprolactam. For the production of lacquer-like coatings from the

Suitable phenoplasts (B) are the usual, from mixtures according to the invention, the aqueous formaldehyde and phenolic substances, such as phenol solutions, for example on wood, metal, plastic and cresol, resins or their oligomers, using the usual methods, provided they are applied be soluble in water or aqueous ammonia, for example by spraying, brushing on, pouring on and at elevated temperature with carboxylic acid pouring, rolling on, flooding, dipping or soaking, amide groups and optionally other reactive groups capable of by heating the objects treated in this way, e.g. B. hydroxyl groups to react 15 to temperatures between 100 and 230 ⁰ C, preferential. The production of such phenolic resins is wise about 160 to 180 ⁰ C, over a period of z. B. in the book by DS Gould, "Phenolic about 10 to 120 minutes, preferably 15 to 60 Minu-Resins", 1959, New York, Reinhold Publishing Co., th, are insoluble, water-resistant, very or by H. Hultzsch in "Chemistry of Phenol - hard, elastic, transparent, smooth and bright_ Proharze", Springer-Verlag, Berlin (1950), dealt with. 20 products available. The varnish-like over-

As aminoplasts (C) the usual ones are suitable, features are also characterized by a preferred formaldehyde and certain nitrogenous substances, it has a good adhesion to the substrate. built-up resins or their oligomers as well as in Cases also the corresponding monomers, mixtures according to materials of another kind, eg. B. provided that they soak fabrics, fleeces or paper in water or aqueous ammonia and after are soluble. Treat drying at higher temperatures according to the present invention, useful resins can be z. B. using In this way, z. B. Impregnations Manufacture of urea, thiourea, melamine, ameline, or laminates by one or Guanidine, dicyandiamide, glyoxalureides, such as glyoxal - several layers of the resin solution treated di- and monoureide, ethylene urea, as well as of 30 materials on a substrate or over-substitution products and derivatives of the compounds mentioned above and given compounds at elevated temperature to win. The production of such, if under pressure and deformation, hardens. Here too Aminoplast is e.g. B. in the book by J. F. B 1 ai s, is the adhesion between the treated "Amino Resins", 1959, New York, Reinhold Pub Material and the synthetic resin according to the invention lishing Co., dealt with. 35 excellent.

As condensation products (D) from polyvalent ones, it is often expedient to cure the carboxylic acids of the invention and polyhydric alcohols are suitable resins in the presence of the oxymethyl groups the usual from polyvalent polymerizable pen-containing resins customary auxiliaries that the or non-polymerizable cyclic and acyclic chemical hardening influence favorably, look through Carboxylic acids and polyvalent cyclic and 40 lead. Suitable auxiliaries of this type are mostly Polyesters obtainable from acyclic alcohols or their acidic compounds, such as carboxylic acids Oligomers, provided they are in water or aqueous or esters and salts of inorganic acids, which are below Are soluble in ammonia. According to the present reaction conditions react acidic or acidic Condensation products useful in the invention can be split off, such as ammonium nitrate and ammonium z. B. using maleic acid, fumaric chloride.

acid, itaconic acid, trimellitic acid, pyromellitic acid, The parts mentioned in the examples are by weight

Heptadecanedicarboxylic acid and ethylene glycol, propylene parts. . · 1 1

lenglycol, the butanediols, pentanediols, hexane Example 1

diols, glycerol, trimethylolpropane, hexamethylene one produces 20% strength aqueous solutions in each case

glycol, 2,2-dimethylpropanediol, the cyclohexane 50 from

win diols and alkoxylated glycols. The A. 40 parts of a water-soluble copolymer,

Structure of such condensation products is z. B. that by precipitation polymerization of 55 parts

the book by J. R. L a w r e η c e, "Polyester Resins", methacrylic acid amide, 30 parts of acrylic acid ethyl

1960, New York, Reinhold Publishing Co., to corresponds _este r and 15 parts of butanediol in

to take. 55 n-butanol according to the method according to

The invention obtained from Polymerisatkom- German Auslegeschrift 1150 526;

component (A), the Phenoplastkomponente (B), the _{part u} ^ p _{he water soluble} nolharzes,

_{Condensate component} (D) and optionally and produced by alkaline condensation of

preferably the aminoplast component (C) her- ^ _{1 and formaldehyde d} ^ ratio 1: 2

Provided homogeneous, aqueous or water-containing 60 -. ₇ q _O £.

ammoniacal solutions. These should ',

preferably contain about 10 to 40% solids, ^c x 20 parts of the tetramethylolglyoxaldiurem;

but, if desired, higher or D. 1.5 parts of an ammonia-soluble polyester can also be used

low-percentage solutions can be used. with the acid number 54.5, produced by condensation

Sometimes it is advantageous to use the aqueous solutions of pyromellitic acid and neopentyl glycol

Water-miscible organic solvents in a molar ratio of 1: 4 (is dissolved in aqueous

add, e.g. B. alcohols, ethers, ketones. Colored ammonia to a solution with the pH 7

Products can be easily made up 8).

The four solutions, their solids content in ^total

55.2% copolymer (A), 15.2% phenolic resin (B),
2.1% polyester (D) and
27.5% tetramethylolglyoxaldiurein (C)

are put together, mixed well and painted on glass plates. After flashing off for 20 minutes at 170 ⁰ C is baked. The coating obtained in this way adheres firmly to the glass, is very hard, elastic, light, smooth and completely transparent. If you store in water for days, the coating remains practically unchanged.

Example 2

To set each 20% aqueous solutions _of her

A. 40 parts of white water solution copolymer, this through family polymerization of 55 parts Acrylic acid amide 35 parts of acrylic acid ethyl ester and 10 parts of acrylic acid tert-butyl ester according to

T- * f ^ ^T ™ ^na ?, ^{The de} f ^{S Se} "

scripture 1105 050 was received;

B. 10.5 parts of a water-soluble phenolic resin, produced by alkaline condensation of phenol and formaldehyde in a ratio of 1: 2 at 70 ^° C .;

C. 30 parts of the tetramethylolglyoxaldiurein;

D. 1.5 parts of an ammonia-soluble polyester with an acid number of 94.6, produced by condensation of pyromellitic acid and neopentyl glycol in a molar ratio of 1: 3 (it is dissolved in aqueous ammonia to form a solution with a pH of 7 _b j _s g \

The solutions are given, their total solids content

48.8% copolymer (A), 12.8% phenolic resin (B),

36fi % TeSethylolgjyoxaldiurein (C) consists, mixes well and carries the

is baked at 160 C for 40 minutes. The covers adhere firmly to the glass and are clear, smooth, colorless, hard, elastic and waterproof. Its hardness value, measured with the König Albert pendulum, is after after baking 185 seconds, after 10 days of storage in water 185 seconds.

B e i s ρ i e 1 3

25% aqueous solutions are produced in each case from:

A. 50 parts of a water-soluble copolymer obtained by precipitation polymerization of 55 parts of acrylic acid amide, 10 parts of acrylic acid tert-butyl ester and 35 parts of acrylic acid ethyl ester according to? ^ Λ ^ TΓ ^{chderdeutschen Auslegeschnft} 1195 050;

B. 20 parts of a water-soluble phenolic resin prepared by alkaline condensation of Phenol and formaldehyde in a ratio of 1: 2 at 70 ° C;

C. 10 parts of the tetramethylolglyoxaldiurein;

D. 37.7 parts of an ammonia soluble polyester made by condensation of trimellitic acid anhydride, Adipic acid and hexanediol- (1.6)

in a molar ratio of about 2: 1: 8 (is dissolved in aqueous ammonia to form a solution with the pH value 6.5 to 7.0).

. ^Man & ^{bt the} solutions, whose solids content is from ^{tal lns} S

42.4% copolymer (A), 17.0% phenolic resin (B),
32.1% polyester (D) and
8.5% tetramethylolglyoxaldiurein (C)

consists, mixes well, adjusts to pH 8 with ammonia and applies the mixture to glass and sheet iron plates. After flashing off, it is baked at 160 ° C. for 20 minutes. The coatings _{adhere excellently to glass and} sheet iron, are _{M hard, water-resistant, almost colorless, and} extremely _dastic . _Its hardness value, measured with the Albert _{Pendei according to Konj, is after baking}

about 160 seconds on the glass plate. The test ^ _{def elasticity of iron sheets} \ _oh Erich sen resulting depressions of 8.6 mm. The coatings were practically unchanged after 8 days of immersion in water.

Example 4

25% aqueous solutions are produced in each case _:

^A · f wasserloshchen parts of a copolymer, ^"the _n Acrylsaureathylester was obtained according to the process of German Auslegeschrift 1195 050 ^through Fallungspolymensation 50 parts Acrylsaureamid 50TE and ₁ Ie;

B. 23.45 parts of a waterless phenolic resin, produced by alkaline condensation of phenol and formaldehyde in a ratio of 1: 2 at 70 ^° C .;

^c · ^{25 parts of} tetramethylolglyoxaldiurein;

D. 30 parts of an ammonia-soluble polyester, _{produced by the} condensation of trimellitic acid anhydride, adipic acid and hexanediol- (1,6) _{in a molar ratio of} about 2: 1: 8 (is dissolved _{in aqueous} ammonia to form a solution with an nH value of 6 5 up to 7 0)

The solutions and their solids content are released all in all

38.9% copolymer (A), 18.35% phenolic resin (B),
23.3% polyester (D) and

19.45% tetramethylolglyoxaldiurein (C)

consists, mixes well, adjusts _{to pH} 8.0 to 8.5 _{with ammonia and applies the mixtures to glass} . _and sheet iron plates. _{After de} ^ _{ab] üften 20 minutes b} / _{16 (rc burned in. The} coatings adhere very well to glass and _{sheet iron) are small wasse} ^ 5 _{hard est) easily gdb colored and excellent elas} t _{ish. Its} hardness value, measured on the glass plate with the König Albert pendulum, is around 170 seconds after baking. The test of the elasticity of the coatings on sheet iron according to Erichsen shows deep

10

from 5.8 to 6.0 mm. The coatings were practically unchanged after 10 days of immersion in water.

Example 5

In each case, 20% aqueous solutions are produced:

A. 40 parts of a water-soluble copolymer obtained by precipitation polymerization of 55 parts Acrylic acid amide, 35 parts of ethyl acrylate and 10 parts of tert-butyl acrylate according to the procedure of the German Auslegeschrift 1195 050 was obtained;

B. 58 parts of a water-soluble phenolic resin, produced by alkaline condensation of phenol and formaldehyde in a ratio of 1: 2 at 70 ^° C .;

D. 2 parts of an ammonia-soluble polyester having an acid number 52, prepared by condensation of pyromellitic acid and neopentyl glycol in the molar ratio 1: 4 (is dissolved in aqueous ammonia ^ao to a solution with the pH 7 to 8).

The solutions, whose solids content consists of a total of 40% copolymer (A), 58% phenolic resin, are added (B) and 2% polyester (D), mixed together, and carries the mixture on glass plates and iron sheets. After flashing it will be 40 minutes baked at 160 ° C. The coatings adhere firmly to glass, are clear, light and waterproof. Your hardness value, measured with the Albert pendulum according to König, is 210 seconds after stoving and 202 seconds after two days of storage in water.

Claims (1)

Claim: Mixtures of substances that harden through the action of heat for the production of coatings, impregnations or bonds based on aqueous or water-containing solutions of mixtures A. 40 to 88.5 percent by weight of at least one soluble in water or aqueous ammonia Mixed polymer 35 40 a) about 35 to 65 percent by weight of acrylic acid amide or methacrylic acid amide or one Mixture of these two amides and b) about 65 to 35 percent by weight of an ester of acrylic acid or methacrylic acid a monohydric, non-polymerizable alcohol or a mixture of such esters; and partly representative of this Ester c) optionally and advantageously up to about 30 percent by weight of a monoester of acrylic acid or methacrylic acid with a dihydric or higher alcohol or a mixture of such esters and d) optionally other monomeric copolymerizable compounds in subordinate Quantities, the sum of the percentages of the substances under a) to d) being 100, and B. 10 to 58.5 percent by weight of at least one soluble in water or aqueous ammonia Phenoplasts or a corresponding oligomer and C. optionally and advantageously up to about 48.5 percent by weight of at least one in Aminoplasts soluble in water or aqueous ammonia or a corresponding oligomer or monomers, characterized in that the mixtures are used as a further component D. 1.5 to 50 percent by weight of at least one soluble in water or aqueous ammonia Condensation product of a polyvalent carboxylic acid and a polyvalent one alcohol The sum of the percentages of substances A to D is 100. Considered publications:
U.S. Patent No. 2,862,901. 609 757/384 1.67 © Bundesdruckerei Berlin