DE2239094B1 - Isocyanate-modified alkyd resins - contg phenol resin modified unsatd fatty acid component - Google Patents

Abstract

Water-dilutable isocyanate-modified alkyld resins, useful as binders for aq. air-drying lacquer systems for quick-drying primers, and having 30-70 (30-50) acid index and 20-120 (30-100) OH-index, contain intercondensed salts of basic cpds. and gps. of drying fatty acids modified with phenolic resins. Phenolic resin - modification lowers drying times, e.g. to 75 min. as against 180 min. for compsn. contg. no phenolic resin. The isocyanate- modified alkyd. resins are urethane- and opt. amide gp. -contg. alkyd resin polysemiesters, prepd. from polyols, isocyanates, polycarboxylic acids, pref. tetrahydrophthalic acid, and reaction prods. of unsatd. fatty acids or esters with 1-30 wt.% phenolic resins (calcd. on unsatd. fatty acid).

Description

2. An aqueous air-drying lacquers according arrival magazine 15 1745 336 S. 6. Lines 11 et seq.).

Claim 1. characterized in that the iso-subject matter of the present invention are 1 u

cyaiiat-modified alkyd resins alkyd resin poly- ν.äUrfee. air-drying varnishes based on \. :

Halbesier of the tetrahydrofluoric acid are also salts basic compounds and radicals r> ■

Acid numbers from 30 to> 50 and hydroxyl numbers from lizierter. Drying acid condensation:

3D to have IDO. '' 20 stops. l * oeyana iodified alkyd resins !! 1.

Acid numbers from 3d to about 70 and Hydroxylza! ι from 20 to about! 2U. which is characterized by -η.

that uie alkyd resins are modified to dry.

I eltic acid residues of modified with phenolic resins. Contains 25 drying fatty acids.

The isocyanai-modified alkyd resins are i

The invention relates to water-thinnable alkyd ethane and optionally amide groups!

Resins as binders for aqueous air-drying lacquer alkyd resin poly half esters available from polyalcohols.

systems that are particularly useful in the area of fast isocyanates. Polycarboxylic Acids and L m ^ eizung ^ pi -

Use linden drying primers. 3 ° dukteii unsaturated fatty acids or c.ren ester r ..;

They are water-dilutable. with residues drying 1 to 30 percent by weight, based on the up.l ·. ·

Fatty acids modified alkyd resins with an acid number of saturated fatty acids, on phenolic resins: gel -.- nenL ·. ■

Of about 30 to about 70 and a hydroxyl number of can additionally monocarboxylic acids for the Ik

about 20 b ^; s about 120 known, the urethane and possibly position of the Alkydharzpolyhalbesier Nutzi .:.

Amidgruppeii included (German Offenlegungssehrift 35 linden.

1 917 162). Although these binders have their own Fs, in view of the teaching of the German, «.Chaft that she. considered as aqueous systems, disclosure regulation 1 745 336 surprisingly and nn :; Drying quickly (with a drying * - foreseen that the invention, with mushrooms from about 2 to 5 hours), but they are the resin-modified 'drying fatty acids'. Requirements for fast-drying primers that comply with isocyanai-modified alkyd resin polyningsy stones are placed, by no means can the half-size grow without subsequent modification. Copolymerization with vinyl or vinylidene vein nn.-Es has also already been used to fertilize other than binding agents in aqueous lacquer systems Way too quick drying and waterproof in the German Offenlegungsschrift 1 917 162 hean paintwork delivering, aqueous binders to 45 different binders with regard to drying time. w ic succeeded. in that unsaturated fatty acids are clearly superior to phenol -.lie examples show. With Resins have been implemented and thus water-thinned, aqueous lacquer systems based on cerium are acceptable Bindemittclsysieme were developed (see. MäCen binders one gets coatings that only German Offenlegungssehrift 1 745 336), This Vcr- need surprisingly short drying time and Usually, however, the serious post-drying adheres to a very good water resistance after drying part of the fact that all unsaturated fatty acids have only about the and very good hardness.

Way of addition with loss of valuable unsuitable polycarboxylic acids for the production of

Saturated double bonds with the phenolic resin around binders are aromatic, hydroaromaticc and

can be set. aliphatic di-. Tri- and tetracarboxylic acid or their

In this way, numerous derivatives which form esters in the air, such as phthalic anhydride,

drying animal painting \\ icliliuc double bonds isophthalic acid. Terephthalic acid. Tetra and llexa

of the binder is lost. Also important double hydrophthalic acids and their anhydrides. Triniellite

bindings of the binder lost. It also has acid anhydride. Pyromellitic anhydride, maleic

Procedure has the disadvantage that most natural acid anhydride. Adipic acid, succinic anhydride,

borrowed fatty acid mixtures not used- 60 chlorinated phthalic anhydrides, hexachloroendome-

bar, tli they still. Portions of saturated fatty acids thyleiitelraliydrophthalsäiirc.

Contain the monocarboxylic acids suitable for reaction with the phenolic resin except for the uncommon are capable and then as free fatty acids the oversaturated fatty acids are z. B. benzoic acid, toluic acid. weaken Zugseigeiischafieii. Biitylbenzoic acid. Hexahydrobenzoic acid, abietic

This restriction is used in the German Offenlegungsschrift.

legimgsscliri! ¹ I 74> 336 taken into account when referring to suitable unsaturated fatty acids or their esters

Ropes d. / hurry 20 it is written that only such are z. B. linseed oil. Soybean oil, wood oil. Safflower oil, ricin oil,

natural I e'.isiuretiemische de "Viuviiu earn. Cottonseed oil. Peanut oil, tall oil fatty acid as well as the

fatty acids or hydride, toluylene diisocyanate and alkyd resin, obtainable from the oils mentioned

Rctic acid fractions, as well as those from natural, non-half-ester formation of tetrahydrophthalic anhydride. A

saturated oils or fatty acids diircb conjugation of such binders should have acid numbers between 30 and

or isomerization obtained prodi, '.te. "" Have 50 and hydroxyl numbers between 30 and 100.

Suitable polyalcohols are 2. B. Glycols, such as 5 For the production of paints and especially the

Ethylene glycol propylene glycol, butanediols. Hexane primer paints the paint raw materials in zvveck-

diols. Ether alcohols, such as di- and triglycols, oxäthy- mäßiger manner in water-miscible solvents

lated bisphenols, perhydrogenated bisphenols, trimethylol pre-dissolved, such as ethylene glycol methyl ether

ethane, trimethylolpropane, glycerine, pentaerythritol, or ethylene glycol monomethyl. -ethyl- and -butyl-

Dipentaerythritol, mannitol and sorbitol. _l0 ether, alcohols. Ester. Ketones. Ketone alcohols or

Aliphatic isocyanates are suitable. eycloali- lower ethers.

phatic. aromatic mono-. Di- and even poly- The usual amines can be used as neutralizers

isocyanates, such as phenyl isocyanate, stearyl isocyanate, such as ammonia. Ethylamine, diethyl and trietliyl

Cyclohexyl isocyanate. Ethylene diisocyanate. Toluylenediamine and trimethylamine, mono-. Di- or tri-

isocyanate-2.4 and -2.6. Diphenylmethane-4,4'-diiso- 15 ethanolamine or dimethylethanolamine are used

cyanate. Naphthylene-1,5-diisocyanate. 3.3'-DJcIiIOr- be. In some cases, alkali hydroxide can also be used

d.4 bisphenylene diisocyanal. Hexamethylene diisocyanate used alone or in mixtures with amines

: .it. 1 ripher.y ¹ metl; an-4.4'.4 "-triisocyanate and 1-No-linden. The amount of amine addition depends on

tyanato-3- (isocyanalometh> l) -3.5.5-trimethyl-c \ clo- the acid number. If the acid number is low, the

licxan. The isocyanates are generally used in a degree of neutralization, expediently at 100 ",.

gen of at least 2 percent by weight, based on lying.

.Binder, used. For the production of the paints, the usual

Suitable phenolic resins see those in the literature as auxiliaries. Drying agents. Pigments. Fillers, however

Reactive phenolic resins are known to be responsible for the conversion process, as are other resins such as melamine resins. Phenolic resins,

products made from phenols and formaldehyde, mixed with natural resins or other paint raw materials

ethereal products with alcohols. L'm ^ elzungspro- be.

The following examples illustrate the invention. the

I ormaldchydh.'r / en. as they are called Tiocknung- and parts are Gewiehi-parts.
Haue air-drying and regenerative additives

heat-drying alkyd resins are added ₃₀ Example
(Wagner Sa rx: Lackkunstharze p. 49, p. 54

Alcohols and S. 79 Tungophen B. H ο u b c n-W e y L 3900 parts of soybean oil fatty acid are combined with 640 parts

Methods of Organic Chemistry 14 2. p. 308, an oil-reactive. modified with natural resin acids

P. 318). Phenol formaldehyde resin with a melting

The production of the binders follows after the _{wall of 118 130 °} C and an acid number below 20 to literally known production methods for raw lacquer- 260 ° C in a nitrogen atmosphere. A special production method for founding binders with a viscosity of about 13 "(70" ig.in xylene. Then 1645 parts of the unsaturated fatty acids or of this reaction product with 1458 parts of Irime esters with the phenol _{propellants at temperatures 40} thylolpropaii. 384 parts of diethylene glycol and 1288 parts between 240 and 260 ° C., with the phthalic anhydride possibly esterifying at 220 ° C. up to a transesterification of the oils or esterification of the fatty acids acid number of 3 and a viscosity of 33 "(70" ig necessary polyalcohols at the same time converted into dimethylformamide). At 50 C it is then possible. Then the polycondensate 3850 parts of this process .üsprodukts with 600 I rush combined ₄₅ tolylene diisocyanate and reacted at SO to acids or its anhydride, and optionally 120 C sation this Lmselzungsgcmisches with polycarboxylic, wherein a Ureihanalkydharz the weiie-cn monocarboxylic acids at temperatures be- acid number 2. the FlydroxyIzahl 100 and the viscosity see 150 and 250 C. For the purpose of air-drying- 71 "(50 °. _o ig) in dimethylformamide) arises.
The preferred hydroxyl numbers for the finishes are 120.degree. C., this L'rethanalkydharz. with tetrad of this level. z. B. between 150 and 250 and the _5O hydiophthalic anhydride converted to a poly half ester of the acid number of this stage below 10. Acid number 40, with a resin with a Vis-

Occasionally the reaction then takes place at a viscosity of 69 "(50% in dimethylformamide)

with the isocyanates to Urcihanalkydharzen and in stands. Dus product is 90 ^n, '"strength in Äthylenglykolmono-

In the last reaction step, the formation of the poly semibutyl ether is completely dissolved and then with isopropanol and

ester by reaction with dicarboxylic acid anhydrides !!. ₅₅ ethylene glycol monohutyl ether in a ratio of 1: 1

From the large number of possible combinations of the diluted to a solids content of f> 3 "". These raw materials and manufacturing methods deserve form can be neutralized with triethylamine and with the following selection special attention if there is water set to a solids content of 55% The aim is to develop binders that are then clear and can be thinned with water, making quick-drying and water-resistant 60 Particularly suitable for making quick-drying Grundic primers the creation of invented mixes:
suitable paint raw materials with fatty acid halls

of 20 ils 35 weight percent and phenolic resin - 33.60 parts of the 63% non-neutralized solution,

hold from 2 to 10 percent by weight. Particularly 65 13.70 parts of titanium dioxide pigment rutile,

suitable fatty acids are soybean oil, linseed oil and 0.80 parts of carbon black.

Ricin fatty acid and, as further raw materials, trimethylol - 22.35 parts fillers based on talc and chalk,

propane. Pentaerythritol, benzoic acid. Phthalic Acids !! - 4.55 parts strontium chromal pigment.

1.56 parts of triethylamine. 0.27 Te, le cobalt actoate (6 »/" Co content), 0.45 parts Pb-octoate (24% Pb-content), about 54 parts Mn-octoate (66% Mn-content) 0.27 parts oxime-based anti-skinning agent, 0.45 parts leveling agent, 8.76 parts of uropropanol, 13.15 parts of water.

This paint composition is heated up with water "Thinned binder content and used for drying purposes Smeared glass plates.

FrncknWszrit- 75 minutes.

Drying time based on the same

^T ™ ^ ^nung ^ ¹ _y ^b _{dung ei} „ _e s corresponding.Je.,. "VäßdeuSher OfTenlegungsschnft 1 917 162 put on - ^el \ _Binding means: 180 minutes to the glue line.

Claims (1)

1 2 which contain less than 10 percent by weight of saturated fat claims: acids. To this lost short drying time! 1. Aqueous, air-drying paints can now be achieved again on the base of salts from basic compounds and 5 wedge, in a further step the binding agents Residues of modified drying fatty acids in a copolymerization with vinyl or vinylidene to subject it to isocyanate-modified hindrances containing condensed isocyanate (cf. German Offenlegur Alkydharze !! with acid numbers from 30 to about 70, font 1 745 336, p. 9 ff.). and hydroxyl numbers from 20 to about 120, there is also the fact that the content of mi- - characterized in that the iso- io at least monounsaturated fatty acids mn 10 K-. eyaiiat-modified alkyd resins as residues modi- 30 carbon atoms below 60 percent by weight. ν. ■ - licensed. drying fatty acids residues of preferably less than 30 percent by weight, based on the above Phenolic resins modified drying fat conversion products from unsaturated fatty acids imJ contain acids. Phenolic resins, must lie (see German OfienleguiiL -