DE1915576A1 - New coating agents - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG * 'r \ A rcn r

1 91 5b £ 7

Our reference: O.Z. 26 097 Wbg / Pä

67OO Ludwigshafen, March 26, 1969 New coating agents

The invention relates to coating compositions which can be hardened by heat and which _{contain a substance containing 1 J} 2-diazacyclohexanedione-3> 6 ring systems and a substance containing aldehyde groups.

The invention is based on the object of providing a coating agent develop that has a high storage stability that is convenient can be processed, which provides coatings that can be hardened by heat, which are resistant to organic solvents and dilute mineral acids, which have high hardness and low brittleness and that adhere permanently to a wide variety of materials.

It has been found that these requirements are met by coating agents, which are characterized in that they contain

a) one per molecule at least two 1,2-diazaoyclohexanedione 3 ^ 6 ring systems containing substance,

b) one per molecule at least two aldehyde groups or methyl ketone groups containing substance and, if applicable

c) Solvents, thinners, fillers, thickeners and / or hardener.

The coating agents are something new for the plastics sector Linking system. When the coating is heated (hardened), components a and b combine with one another in such a way that each by converting a 1,2-diazacyclohexanedione-5j6 ring system with an aldehyde group with release of water a 1-alkylideneamino-1-aza-cyclopentadione-2,5-ring system arises:

+ OCH> ^N N - N »CH

As component a of the new coating agents are all pro MoIe-59V619 / 654/667/68 · .-,., -. - 2 -

009 8 42/054 3 originally inspected

- 2 * - OZ 2β 097

% 191557-e

kül having at least two 1 ^ -diazacyolohexandione-jSiö ring systems Substances suitable. The carbon atoms 4 and 5 of this 1,2-diazacyclohexanedione-3,6 can be linked to one another by a single or a double bond. One of those carbon atoms 4 and 5 or both have the remainder as substituents Part (or parts of the molecule which, by definition, contain at least one another 1,2 ^ diazacyclohexändione ->, 6-ring. has.

Suitable representatives of this class a are, for example

1. the cyclic dihydrazides of tetracarboxylic acids, their COOH groups are bound in pairs to geminal carbon atoms, how

HN

HN

CH

■ 0 Ii C

- NS

CH

NH

NH

2. Copolymers which contain maleic hydrazide in polymerized form, d. H. the grouping as a chain element

- 3

009842 / 0S43

ORIGINAL INSPECTED

O.Z. 26 097

191557C

CH- CH—-

O = C C = O. Such products are

N-N ^, for example, easily accessible through

^H implementation of the corresponding copoly

merging maleic anhydride with hydrazine.

The preferred copolymers have a proportion of maleic hydrazide of less than 50 % of the monomer units, in particular 5 to 30 %. Suitable comonomers are, for example, all olefinically unsaturated compounds that can be copolymerized with maleic anhydride, such as olefins, vinyl aromatics, vinyl chloride, vinyl esters, vinyl ethers, acrylic acid and methacrylic acid and derivatives of these acids, such as nitriles, esters, amides and N-alkoxyalkylamides.

The molecular weight of the copolymers can vary within wide limits and is generally between 550 and 1,000,000, preferably between 2,500 and 500,000, in particular between 5,000 and 40,000.

3 · by the addition of maleic anhydride to olefinically unsaturated oils, diene polymers or rubbers and subsequent reaction with hydrazine obtainable products which

Groups or

= 0

N N ""

H H

OH = CH CH C Groups included.

0 »O ^ ^ C = 0 ^ -NH-NHK

Exceptional products are easily accessible through the reaction of hydrazine with maleinized oils , diene polymers or rubbers, as described by D. Hummel in Kunststoff-, Lack- und Gummanalysis, KarIHEianser-Verlag, Munich, 1958, page 11? ff., describes. The basis for the implementation are e.g. B. linseed oils, wood oils, butadiene oils, polybutadienes, polyisoprenes, butadiene-styrene and isoprene

009842/05 * 3

ORia INSPECTED

- ) fr - OZ 26 097

Styrene copolymers and analogous copolymers based on. or-methyl styrene and natural rubbers. All conversion products are suitable, which contain at least two maleic anhydride groups per molecule, the content of maleic anhydride groups in the product, depending on the molecular weight, can vary within wide limits, for example between 1 and 60, preferably 5 up to 25 percent by weight.

As component b of the new coating agents, all are at least Aldehyde groups or substances containing methyl ketone groups are suitable. Suitable representatives of this class of substances are, for example

1. aliphatic, cycloaliphatic and aromatic dialdehydes and Bis-methyl ketones, such as glyoxal, succinic dialdehyde, terephthalic acid dialdehyde and p-phenyl-bis-methyl ketone. Are very suitable aromatic dialdehydes in which both aldehyde groups are bonded to carbon atoms of an aromatic ring system, for example the ring system of benzene, thiophenes, diphenyls, diphenylmethane, triphenylmethane, N-methyldiphenylamine, N-methylcarbazole, Naphthalene, anthracenes, diphenyl oxide and 2,2-diphenylpropane. Instead of dialdehydes it is of course also possible to use their corresponding acetals, the behave like dialdehydes in the subsequent reaction with the hydrazide.

2. Homo- and copolymers of acrolein and vinyl methyl ketone, especially those that contain more than 2 percent by weight of carbonyl groups. In the preparation of the copolymers can all customary, copolymerizable with acrolein or vinyl methyl ketone Monomers are used, such as olefins, diolefins, vinyl ethers, vinyl esters and derivatives of (meth) acrylic acid. Suitable Comonomers are, for example, styrene, butadiene, 2-cyanobutadiene, Isoprene, acrylic acid, methyl methacrylate, butyl. acrylate, acrylonitrile, vinyl methyl ether and vinyl thioethanol. the The homopolymers or copolymers are produced by customary methods of solution, suspension or emulsion polymerization, how they z. B. in Houben-Weyl-MUller, methods of organic Chemistry, Volume 14 I, Georg-Thieme-Verlag, Stuttgart ', page 180 ff. (1962).

009842/0 54 3 -original inspected

O.Z. 26 097

191557C

The quantitative ratio in which components a and b are used ■ can fluctuate within wide limits and generally lies between 1: 0.1 to 1: 2. The components are expediently used in such a ratio that, in a mixture, per 1,2-diazacyclohexanedione, 3,6 ~ ring 0.5 to 1.5, in particular 0.8 to 1.2, preferably 0.95 to 1.05, aldehyde or methyl ketone groups are present.

The new coating agents can be used as additional components Contains solvents or thinners. Hydrocarbons, alcohols and ethers are particularly suitable. Polar ones are preferred Solvents which expediently boil below 180 ° C. at normal pressure. Benzene, toluene, xylene, ethanol, butanol, for example, are suitable, Tetrahydrofuran, monomethylglycol, dimethylglycol, and more Dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric acid triamide, Glacial acetic acid and acetic anhydride. Water is also a suitable diluent; the coating agent is then in the form of a dispersion.

The amount of solvent or diluent can vary within wide limits and, for example, 0.1 to 20 times the amount of Components a and b. Solvent mixtures can of course also be used be used. Leave the most suitable agent and its optimal amount for a certain selection of substances can easily be determined by experiment.

The new coating agents can also contain customary fillers and thickeners contain, such as titanium dioxide, iron oxide, lead oxide, also polyvinyl alcohol or polyacrylic acid.

The coating agents can also contain small amounts of hardeners or catalysts which accelerate the reaction between the hydrazide groups and the carbonyl groups in the formation of coatings. Suitable catalysts are, for example, acids or acidic ones Substances such as glacial acetic acid, acetic anhydride, phthalic acid and p-toluenesulfonic acid. Already amounts of 0.01 percent by weight, based on the mixture, affect the reaction rate. The optimum amount of catalyst can be determined through experiments.

The new coating agents are used for the production of

009842/0543 ORIGINAL INSPECTED

-β - OZ 26 097

Coatings and varnishes on a wide variety of materials. For this purpose, the object to be coated is coated with a thin layer of the agent. When heated to temperatures between 50 and 250 ^° C., in particular 100 to 200 ° C., preferably -100 to 150 ^° C., an elastic to hard, well-adhering, temperature-resistant coating that is resistant to most chemicals is formed by condensation and crosslinking reactions.

The optimal curing time and curing temperature can be determined for a the given system can easily be determined by experiments.

The parts mentioned in the examples are parts by weight. the k values are according to H. Pikentscher, Cellulosechemie 13 (1932), p 58j determined.

example 1

100 parts of a maleinized linseed oil with a fraction "of 12 percent by weight of maleic anhydride are transferred durch.Zugabe of 10 parts of hydrazine hydrate and 3-stUndiges heating to 60 ⁰ C in the entsprechendenHydrazidgruppen containing linseed oils; to this reaction solution 13.4 parts terephthalaldehyde are supplied to the The resulting solution was then poured on as a film of about 50 / u and stoved for 30 minutes at 150 ^° C. The film showed ^{no decomposition within 30 minutes at temperatures of 200 °} C. The resulting film is insoluble in toluene, butanol, dimethylformamide and has a pendulum hardness according to DIN 53 157 in see. of 106.

If the film is made under otherwise identical conditions, but without any addition. of daldehyde, burnt in, it is in all three stated Solvent-soluble, the film also shows a pendulum hardness <80.

If the film is used under all other conditions, however, » of a maleinized linseed oil that does not react with hydrazine hydrate was baked and thus does not contain any hydrazide groups; so it is soluble in all three specified solvents and has a pendulum hardness of <80.

009842/0543 originally inspected

-? - . OZ 26 097

V 1 91 5 5 7 e

If 100 parts of a copolymer of butadiene and acrylic acid amide, which contains 10 percent by weight of acrylic acid polymerized and has a k value of 39 (l- ^ ig in dimethylformamide), dissolved in 100 parts of toluene and mixed with 13 * 4 parts of terephthalaldehyde, takes place under staining the deposition of gel bodies and after 60 min. at room temperature and 3-10 min. at 60 ⁰ C, the solution is fully crosslinked. In contrast, the polymers containing hydrazide groups do not crosslink at room temperature after the aldehydes have been added, but "only when heated from 100 ° C., ie mixtures of polymers containing hydrazide groups with compounds containing carbonyl groups have a virtually unlimited storage time at room temperature.

Examples 2-14

The procedure is as described in Example 1, but the following If polymers containing maleic acid hydrazide groups are used, the following results are obtained:.

No. Type and amount of the polymer content of soluble pendelin Parts hydrazid- ity of hardness

group films

100 natural rubber, k-value 10 108, 0.1- ^ ig toluene in 500 Share toluene

100 natural rubber, k-value 10 42, l- # ig in toluene in 250 Share toluene '

100 polybutadiene, k-value 16, 10 3- # ig in toluene, 1,2-vinyl content 85 %

100 polybutadiene, k-value 21, 10 3- # ig in toluene, 1,4-cis-portion approx. 90 %

100 butadiene / styrene copolymer, 10 k value 18, 3- # ig in toluene, styrene content 20 %

100 butadiene / * - methyl styrene 10 copolymer, k value 18, 3- # ig in toluene, ac -Methyl styrene content 30 %

009842/0543

72 106 110 130 i4o

No. Type and amount of polymers Percentage of hydrazide in parts

groups

0..Z «26 097

Solubility-Pendularity of the hard film

100 natural rubber, k-value 108, 0.1 gig toluene in 500 Share toluene

100 natural rubber, k value 42, 1- ^ ig in toluene in 250 Share toluene

100 polybutadiene, k value 16, 16.5 3S-30 in toluene, 1,2-vinyl

share 85

100 polybutadiene, k value 21, 3- # ig in toluene, 1,4-cis-

Share approx. 90 %

100 butadiene / styrene copolymer, k-value l8, 3- # ig in toluene, styrene content 20 %

.13 Rubber as in Examples 2 - 7, without the addition of terephthalaldehyde

Starting rubber for Examples 2 - T, but not soluble in modified form with hydrazine hydrate

soluble

78 80

109 116

135

< 60

< 60

Examples 15-19

The procedure is as described in Example 1, but instead of terephthalaldehyde If other aldehydes are used, the following results are obtained:

No. Type and amount of the aldehyde Solubility Pendulum hardness'

ohc-vv- ⁿ ^ """^ v-cho ^W ch} '- = ^

18th

24

009842/084 117

124

9 -

- % - OZ 26 097

No. Type and amount of the aldehyde Soluble- Pendulum

hardness

17 OHC - </ V - ^ / vy - CHO 15 - 119

"19 like 15» but using + ζ 6θ

not with hydrazine hydrate
modified maleinized
Linseed oil

Example 20

To 100 parts of a styrene / maleic hydrazide copolymer A with a k value of 70 ( 1% in toluene), which contains 10.8% maleic hydrazide and 10% dissolved in toluene, 50 parts of a copolymer B are obtained Methyl methacrylate / yinyl methyl ketone with a k value of 58 ( 1% strength in toluene), which contains 19% vinyl methyl ketone and 30% strength in toluene, is added and mixed homogeneously. The resulting solution is spread out as a 50 / U film and ^{baked at 150 °} C. for 30 minutes. The film shows no decomposition within> 0 minutes even at temperatures of 200 ^° C., it is insoluble in organic solvents such as toluene, dimethylformamide, butanol, ethyl acetate or mixtures thereof. The pendulum hardness according to DIN 53 157 in sec. Is 146. Films from A (without B) or B (not A) are soluble under the same baking conditions and {have pendulum hardness <60.

Examples 21-25

If you work as described in example 20 * but the type and the amount of the copolymer B varies, the following results are achieved;

No. Type and amount of the copolymer liquid B Soluble- Pendulum

toluene hardness

21 like 20 but 20 parts - 121

22 like 20 but 30 parts - I36

- 10 -

009842/0543 original

Λ: O.z. 26 097

No. Type and amount of the copolymer B Soluble - Pendulum

toluene hardness

23 like 20 but 100 parts -, 167

24 50 parts: methyl methacrylate / vinyl ■. - 159 thioethanol / vinyl methyl ketone in a weight ratio of 60:10:30

30- # in toluene, k-value 64 - "(# in toluene)

25 50 parts: styrene / maleic anhydride / - 164 tert-butyl acrylate / vinyl methyl ketone
in a weight ratio of 50: 10: 20: 20
30- # ig in toluene, k-value 53 (l #
in toluene)

Example 26

To 100 parts of a 30 # strength solution of the copolymer A of styrene / maleic acid hydrazide with a k value of 39 (1 / £ ig in toluene) in a mixture of dimethylglycol and monomethylglycol. (in a weight ratio of 1: 1) are 30 parts of a 50- ^ igen aqueous dispersion of a copolymer B of butadiene and vinyl methyl ketone - the proportion of vinyl methyl ketone is 15 percent by weight and the k value of the copolymer 92 (0.1- # ig in toluene) - Added, mixed and poured on as a film and ^{baked at 150 °} C. for 30 minutes. The result is an elastic, closed coating that is insoluble in organic solvents and has a pendulum hardness of 108.

A film from A without B or a film from B without A under the same conditions Applied and baked are soluble or, in the case of B, cracked and brittle. The pendulum hardness for A alone 70, for B alone not measurable.

Examples 27-37

If you work as described in Example 26, but the type and Amount of the copolymer B varies, the following results are achieved;

- 11

00S842 / 0S43 ';. PWqinal inspected "":

No. Type and amount of the copolymer B 0.Z-. 26 097

Soluble pendulum in hard toluene

27 how 26th but 10 Parts Isopropenyl
methy! ketone 28 how 26th but 20th Parts 29 how 26th but 50 Parts 30th how 26th but B contains

like 26 but B contains vinyl phenyl ketone

50 parts: vinylidene octiloride / vinyl methyl ketone in a weight ratio of 60:40 30 # aqueous, k value 71 (0.1 # in Dimethylformamide)

like 30 but 100 parts

50 parts: butadiene / styrene / vinyl methyl ketone in a weight ratio of 55:35:10 52- ^ ig watery, k-value 102 (0.1-% in Toluene)

60 parts: butadiene / styrene / vinyl methyl ketone / acrylamide in a weight ratio of 54: 34: 9: 3, k-value 105 (0.1- # ig in toluene)

50 parts: butadiene / acrylonitrile / vinyl methyl ketone in the weight ratio " nis 60:30:10, k-value 103 (0.1- ^ ig in dimethylformamide)

like 35 but instead of butadiene - 2-cyanobutadiene, k value 110 (0.1- ^ ig in dimethylformamide)

90

97

105

115

121 143

I60 112

139

139

164

Example 38

To 100 parts of a copolymer of styrene / maleic hydrazide, with a k value of 70.1 % in toluene, which contains 10% maleic acid hydrazide and 10% dissolved in toluene, 13.4 parts of terephthalaldehyde are added and the resultant solution subsequently ßend about / u poured 50 and baked for 30 min. at ⁰ C I50 as a film. The film shows no decomposition at temperatures of 200 ⁰ G, 30.Min ".

The resulting film is insoluble in toluene, butanol, dimethyl

- 12 -

009842/0543

O.Z. 26 097

191557C

formamide and has a pendulum hardness according to DIN 53 157 in see. from 192.

Comparative experiment

If the film is stoved under otherwise identical conditions, but without the addition of the aldehyde, it is still soluble in all three solvents mentioned. (Sec.), The pendulum hardness according to DIN 53 157 of 85. The film shows at temperatures of 200 ⁰ C, after 6-7 min. Decomposition and discoloration.

Examples 39-41

The procedure is as described in Example 38, but the aldehyde exchanged, the following overview will be given Get values:

Try the type and amount of aldehyde

Soluble- pendulum in hardness toluene DIN 53 157

OHC

184

OHC.

CHO

205

178

Examples 42-55

To 100 parts of a copolymer - with a proportion of 35 % styrene, 25 % maleic hydrazide and 30 % acrylic acid n-butyl ester and 10 % methacrylic acid methyl ester with a k> value of 30. l- # ig in toluene - the 20- ^ ig is dissolved in glycol monomethyl ether / xylene in a ratio of 1: 1, different amounts of terephthalate · hyd and different amounts of p-toluenesulfonic acid are added and the results are summarized in the following table:

- 13 -

9842/0543

INSPECTED

Amount of - ϊ9 - / B Burn-in / CO _n
HN o.z. Ib 097 hydes in Aide addition of time 150 ° c cyclic dihydrazides I 1915576 No. Divide acid into in min. Soluble pendulum 3.35 share 30th hardness 3.35 - 30th HN Toluene in lake. 42 3.35 + 0.1 30th ^ CO ^ 90 43 3.35 + 0.5 30th 110 44 6.7 ■ + i, o 30th .124 45 6.7 - 60 139 46 6.7 - 30th 118 47 6.7 + 0.1 60 I32 48 13.4 + 0.1 30th 134 49 13.4 - 30th 153 50 26.8 + 0.1 30th I65 51 26.8 - 30th 171 52 33.5 + 0.1 30th 193 53 33.5 30th 198 54 + 0.1 208 55 Example 56 210 Parts of the 24.6 X NH ^ CO /

and 13.4 parts of terephthalaldehyde

dissolved in 250 parts of glacial acetic acid. One coated with the solution
Glass plate is ^{heated to 100 °} C. for 12 hours. The polymer coating formed is insoluble in organic solvents and has
a decomposition range> 480 ⁰ C.

Examples 57-64

The procedure described in Example 56 is followed, but the reactants varies, the products summarized in the following overview are obtained:

003842/0543

- 14 ORlGIMAL INSPECTED

No. Type and amount of hydrazide Type and amount

of the aldehyde reaction
Time
Hours.

Medium reaction solution temperature

Decomposition range ⁰ C

* ■ »ro

how

24.6 parts

58

59

CO

• CO ^ ^ CO 27.2 parts

29.6 parts

CHO 13.4 parts

OHi

15.4 part ©

OHC - // M-CHO

13.4 parts

like 56 like 56 like 56> 480

like 56 like 56 like 56> 450

like 56 like 56 like 56> 500

ω ■ α
m

60

35.2 parts OCH - // v-CHO like 56 like 56 like 56 > 600

/ NH CO

13.4 parts

9 rn D.

No. Type and amount of hydrazide Type and amount

of the aldehyde

how

24.6 parts

O
ο 62 like 56 98 24.6 parts K) O cn 63 like 56 24.6 parts

OHC

21.0 parts

OHC

22.6 parts

\\ - CH0

22.6 parts

Reak
ions
Time
Hours. Reaction
temperature
⁰ C Solution
middle Disintegrating
settlement
area
oc 10 ISO Cyclohe-
xyIoarbo-
diimld
250 parts ~ 500 5 80 Acet
anhydride ~ 450 250 parts 5 80 Acet
anhydride ~ 420 250 parts

how

24.6 parts

I I

OHC - </ Μ-C- ('\ V-CHO

26.8 parts 80

Acet- ~ 400
anhydride

250 parts

CD ro

cn ο

Claims (2)

Claims O.Z. 2β 097 Coating agents, characterized in that they contain a) one per molecule at least two 1,2-diazacyclohexanedione-J5 »6-ring systems containing substance, b) one per molecule or at least two aldehyde groups Substance containing methyl ketone groups and optionally c) Solvents, thinners, fillers, thickeners and / or hardener. 2. Coating agent according to claim 1, characterized in that they contain components a and b in a weight ratio of 1: 0.1 to 1: 2. J). Coating agents according to Claims 1 and 2, characterized in that they contain components a and b in an amount such that 0.5 to 1.5 aldehyde or methyl ketone groups per 1,2-diazacyclohexanedione-3,6-ring are present. Badische Anilin- & Soda-Fabrik AG 009842/0543