FR2507610A1 - AQUEOUS EMULSIONS OF ALKYD RESINS FOR PAINTS AND VARNISHES DRYING WITH AIR - Google Patents

Abstract

THE BINDER OF THESE PAINTS CONSISTS OF A MIXTURE OF 25 TO 45 BY WEIGHT OF AN ACRYLIC MODIFIED ALKYD RESIN CONTAINING IN PARTICULAR 7 TO 13 BY WEIGHT OF A POLYETHYLENE GLYCOL WITH A MOLECULAR WEIGHT 500 TO 5000, HAVING AN INDEX OF ' ACID OF 25 TO 70 MG OF KOHG AND AN INTRINSIC VISCOSITY INDEX OF 9 TO 12 MLG, AND OF 55 TO 75 BY WEIGHT OF A URETHANE-MODIFIED ALKYD RESIN, AIR-DRYING, WITH A LIMIT OF VISCOSITY OF 8 A 16 MLG, THE CARBOXYL GROUPS OF THE MIXED BINDER BEING NEUTRALIZED BEFORE EMULSIFICATION WITH AN AMINE OR AMMONIA IN QUANTITY CORRESPONDING TO A MAXIMUM ACID INDEX OF 20 MG OF KOHG.

Description

Aqueous emulsions of alkyd resins for paints and varnishes drying at

  The present invention relates to aqueous emulsions based on combinations of alkyd resins with acrylic modification and urethane modification for

  paints and varnishes drying in the air.

  There is already a series of patents in the

  which are described alkyd resins with acry-

  as a binder for paints and varnishes

  water-repellent and air-drying (see, among others, United States Patent No. 4,133,786 and British Patent

  No. 1,117,126). The use of oil has also been described.

  water-dilutable urethane or alkyd resins

  with urethane modification dilutable with water in paints

  tures and varnish secha? to the air (cf among other European patents Nos. 0 017 199 and 0 018 665, patents of the French Patent No. 17 45 343 and 23 23 546, US Pat.

4.017 514 and 4 116 902).

  However, both groups of binders have

  specific disadvantages Resins

  acrylic cation, due to the acid reactivity

  unsaturated fat decreased by copolymerization, do not give

  instead of moderate cross-linking, so that paint and varnish films have poor

  In addition, these resins require a high degree of

  portion of toxic amines that are toxic to neutralize

  acid groups urethane oils and residues

  urethane-modified alkyds are

  In addition, here again, large amounts of amines are required to stabilize the emulsions. The combination of urethane oils or urethane-modified alkyd resins, in the emulsified state, with polyvinyl latices or

  polyacrylics (U.S. Patent No. 3,919,145).

  However, because of the presence in these binder emulsions of the inert, non-crosslinkable latex fraction, only moderate quality of the film is achieved, so that these products can not be

  used only for paintings called "House-Paints".

  It has now been found that air-drying emulsions having excellent film-forming properties are obtained which are emulsified in water.

  combinations of acryl-modified alkyd resins

  based on siccative fatty acids, presenting a

  acid content of 25 to 70 mg KOH / g and about a% content of polyethylene glycol with air-drying urethane-modified alkyd resins. These emulsions contain only a very small proportion of amines. -Volatile, and they are very stable They wet the pigments perfectly and therefore can easily be transformed into high gloss finishing paints or highly pigmented primer undercoats They dry quickly, -

  and they give films with good stability.

  It is known that modified alkyd resins

  acrylic and urethane modified

  very poor compatibility with other binders. It was therefore impossible to foresee that in such combinations,

  the addition of positive properties could be achieved

components.

  The invention therefore relates to emulters

  aqueous alkyd resin compositions which can be used as binders for air drying paints and varnishes, the emulsified resin fraction consisting of a mixture,

  prepared in the presence of not more than 20% by weight (as

  binder solid substances) of solvents

  organic compounds at a temperature of 50 to 1000 C,

  (A) 25 to 45% by weight of an alkyd resin to be modified

  air drying acrylic composition, the resin containing, with other acrylic and / or vinyl monomers, from 4 to% by weight of acrylic and / or methacrylic acid and from 7 to 13% by weight, preferably from 9 to at 11% by weight, of a polyethylene glycol of average molecular weight 500 to 5000, and having an acid number of 25 to 70 mg KOH / g and a limiting viscosity number (measured in 200-chloroform). C) 9 to 12 ml / g, and (B) 55 to 75% by weight of a modified alkyd resin

  air-drying urethane having a viscosity index of

  intrinsic cosity of 8 to 16 ml / g (measured in chloroform at 200 C), and

  the carboxyl groups of the binder mixture being neutral

  before emulsification in water by a quantity

  of amine and / or ammonia corresponding to an

20 mg KOH / g maximum.

  Acrylic modified alkyd resins

  used as component (A) in the aqueous emulsions

  have the characteristic properties indi-

  below, the intervals indicated for the

  PEG and the proportion of acrylic and / or methacrylic acid, as well as the ranges indicated for acid numbers and intrinsic viscosities are of critical importance. For the other parameters, the preferred ranges of values have been indicated.

  and can be varied within widely

  due. Fatty acid content of unsaturated oils 25 to 50%

  Content of aromatic monocarboxylic acids

  ticks or cycloaliphatic: 0 to 20%

  Content of aromatic dicarboxylic acids

  Ticks or cycloaliphatics: PEG content: (preferably polyalcohols content other than PEG: acrylic / methacrylic acid content: content of acrylic and / or vinyl monomers not carrying a reactive functional group outside the 15x

7 to 13%

9 to 11 X)

8 to 20 X

4 to 10 X

  double bond: 10 to 26 x Acid number: 25 to 70 mg KOH / g Hydroxyl number: 30 to 100 mg KOH / g Intrinsic viscosity number 9 to 12 ml / g (chloroform, 200 C)

  In the emulsions according to the invention, the

  acrylic-modified alkyd sines act primarily as emulsifying resins for the resin

  alkyd-urethane and dispersing agents for the pigments

  For good stability in the storage of emulsions of paints and varnishes, it is therefore necessary that in this component, the hydrophilic stabilizing groups are fixed so as to be as resistant as possible to hydrolysis. For this reason, polyethylene glycol ( PEG) is preferably incorporated by a method described

  in the Austrian Patent Application No. 365,215.

  We operate as follows: in a stadium

  reaction, the PEG is reacted with a

  double molar titer of a monoepoxidized fatty acid ester;

  the ester of fatty acid modified with PEG is then

  embedded in the alkyd resin by transesterification.

  Epoxidized fatty acid esters are

  goods corresponding to the formula:

X CH CH Y C O Z

  in which X represents a C 2 -C 8 alkyl radical, in which X represents a C 2 -C 8 alkyl radical, Y represents a C 7 -C 12 alkylene radical and Z represents

  a saturated hydrocarbon radical, aliphatic, cycloaliphatic

that or aromatic in Cl-Cl O.

  These compounds are obtained by epoxidation of

  ter monoalcohol with monounsaturated fatty acids.

  Among these acids, there will be mentioned, for example, lauroleic acid

  that myristoleic acid, palmitoleic acid,

  oleic acid or erucic acid.

  the epoxidation products of the esters of the acid

  The alcohols components are saturated, aliphatic, cycloaliphatic and aromatic monoalcohols of Cl-Cl O. The epoxidation is carried out by known methods, for example using hydrogen peroxide and formic acid. answering the formula

  above contains an epoxide group per molecule

  and must be contained in a proportion of at least 75%

  in the industrial mix There are also

  goods of this type in commerce: manufacturers' leaflets

  cants define them as n-alkyl esters or

  isoalkyls of epoxidized fatty acids.

  Suitable polyethylene glycols are those having an average molecular weight of from 500 to 5,000. They are reacted in the presence of a catalyst in a molar ratio of 1: 1.7 to 1: 2.1 with the compound

  epoxidized, by etherification In the ideal case, the molecule

  The PEG molecule is bound on both sides by ether linkages on a fatty acid ester. Industrially, the catalyst is added to the PEG, after dehydration by distillation under vacuum with a catalyst.

  heated to a temperature of 100 to 150 ° C.

  the epoxy compound in several hours and

  holds the temperature until the epoxide index

  has fallen below 0.01 The catalysts that con-

  These include sulfuric acid, perchloric acid, aluminum chloride and trifluoride.

of boron.

  The etherification product thus obtained (di-

  polyethylene glycol ether) is then reacted

  by transesterification, with the splitting of monohydric alcohols

  valents of the monoepoxidized compound originally used, with the polyols, fatty acids and / or oils customary in the preparation of alkyd resins and optionally aromatic monocarboxylic acids and / or a part of the dicarboxylic acids provided in the presence of Suitable catalysts such as litharge or calcium hydroxide at a temperature of about 2500 ° C. The monoalcohol liberated from the starting material is removed quantitatively by distillation. The carboxyl groups of the acrylic-modified alkyd resin must consist, in the interest of resistance to hydrolysis, of at least 80%, and preferably at least 90%, of acrylic acid or copolymerized methacrylic acid groups. ,

  for the preparation of this component, the

  described in patent application No. 365,215.

  In this process, a mixture of acrylic esters is copolymerized

  vinyl compounds and methacrylic acid

  with some of the fatty acid to be used in the

  and then the copolymer formed by the remaining components of the alkyd resin is esterified. The formulation of the resin and the reaction conduct are selected.

  so that at the end of the reaction,

  in the free state that sterically hindered tertiary carboxyl groups,

  which are derived from methacrylic acid and are

  This process has the advantage of giving products which dry well because only a part of the fatty acids is affected in its drying properties by the copolymerization. Because of the structure described for acrylic-modified alkyd resins, it exists between the hydrophilic groups determining the stability of the emulsion (PEG chains and carboxyl groups) and the ester bonds closest to the large molecular segments

  which decisively retard the attack

  only by water and therefore the hydrolytic split

of the load-bearing link.

  For the choice of raw materials, besides

  the average molecular weight of PEG, the nature of mono-

  acrylic and / or vinyl mothers who do not wear

  other functional group is also important.

  The best emulsion stability is achieved by using

  reading esters of acrylic and / or methacrylic acid

  and long-chain alcohols such as acrylate 2-

  However, these monomers have a strong plasticizing effect and thus affect the drying and the hardness of the

  Therefore, it is necessary to adjust according to the

  In each case, the properties of the product are obtained by appropriate choice of the monomers. Good general properties are obtained, for example with mixtures of isobutyl methacrylate and vinyltoluene. The choice of the other raw materials is less critical. unsaturated all products with an iodine number greater than 125 Aromatic and cycloaliphatic monocarboxylic acids, dicarboxylic acids and polyalcohols may be selected by

  the specialist according to the usual criteria.

  Where appropriate, alkyd resins with

  can also be prepared by a method described in the technical literature by making

  however, be careful that the criteria set out above

  for example, the presence of carboxyl groups of

  Thus, for example, a PEG-modified alkyd resin can initially be prepared at an acid number of less than 5, which is then copolymerized with a mixture of acrylic esters,

  vinyl and the amount of acrylic acid and / or

  thacrylic acid necessary for the final acid number.

  The urethane-modified alkyd resins used in the emulsions according to the invention as component (B) are water-insoluble resins which are known in principle from the specialist as binders for paints and varnishes in solution in of the

  organic solvents By weight, they form the con-

  main constituent of the solid resin contained in the emulsions according to the invention and therefore have a decisive influence on the formation of the film and the

  properties of the film As a result, for their

  tion, particular attention will be paid to a

  rapid drying and good cross-linking of the film

by oxidation.

  Urethane modified alkyd resins

  preferably used for emulsions according to the invention.

  are characterized by the following properties: Fatty acid content of unsaturated oils: 45 to 65 t

  Monocarboxylic acid content, aromatic

  or cycloaliphatic content: 0 to 20 content of polyalcohols: 15 to 25 content of polycarboxylic acids: 8 to 20 X content of diisocyanates: 8 to 25% acid number: less than 5 mg of o EH / g hydroxyl number: 20 at 80 mg KOH / g Limit viscosity number: 8 to 16 ml / g (chloroform, 20 c C)

  The indicated ranges of values are

  for the emulsions of the invention for which

  relates to the intrinsic viscosity index

  For the other parameters, it was indicated

  preferences, but they may vary in

extended limits.

  Suitable unsaturated fatty acids are

  those which contain isolated double bonds and

  judged and have an acid number greater than 125.

  For example, the fatty acids of soya,

  flax or tall oil and the fatty acids of

  dehydrated castor oil and wood oil Fatty acids can be used in the free state or in the form of glyceride oils or polyol esters

  prepared Dar synthesis The choice of monocarboxylic acids

  aromatic or cycloaliphatic liquids, polyalcohols and dicarboxylic acids is not critical and can be easily done by the specialist depending on the

  properties and characteristics sought.

  The appropriate diisocyanates, for a good drying speed and a good film hardness,

  aromatic products such as 4,4'-di-

  phenylmethane diisocyanate and toluylene diisocyanate.

  80% industrial mixture of 2.4% and 20% is preferred

2,6-toluylene diisocyanate.

  The urethane-modified alkyd resins are prepared in two stages of operation. A low molecular weight, high hydroxyl content alkyd resin is first prepared by the usual procedures. An inert solvent is then added and then at -60.degree. The diisocyanate is then brought to -110 ° C and maintained at this level until the NCO content has fallen to less than 0.1% and until intrinsic viscosity index

  In some cases, the molecular weight can be

  and the urethane group content by adding small amounts of lower monoalcohols such as

  methanol or ethanol These alcohols are added to the mixture

  reaction before the diisocyanates.

  To prepare the emulsions, the mixture is mixed

  acrylic modified alkyd sine and alkyd resin

  with urethane modification in the desired proportions.

  If the products still contain a water-insoluble solvent from the preparation, it is carefully distilled in vacuo. The auxiliary solvent is then added under stirring in the maximum amount of the product.

  % relative to the solid resin The solvents

  the most appropriate compounds are the alcohols and

  alcohols; monobutyl ether and ethylene glycol are preferred. Finally, to partially neutralize the

  carboxyl groups, amines and / or ammo-

  The nature of the appropriate amines is known from the

  It is preferred to use triethylamine and

  dimethylethanolamine or mixtures of these amines

with other amines.

  An advantage of the emulsions according to the invention is that they require only a small amount of amines corresponding to the neutralization of 20 units.

of maximum acid number.

  Finally, the water is introduced with stirring

  vigorous in 1 to 3 hours at a temperature of 40 to 60 ° C.

  Milky emulsions, transparent in color, are obtained

  thin, with good storage stability.

  with no particular problem, give layers of

  prat and cover layers that dry quickly.

  The products can be used in the pigmented state oul

  no, if appropriate after the addition of auxiliary products

  res usual, by brushing, immersion, spraying, sprinkling among others Drying

  takes place at room temperature; however, in

  In industrial series, forced drying is preferred. If reactive crosslinking agents are used in the

  heat, emulsions can also be cooked according to the

  temperature, for example between 100 and

1300 C.

  The following examples illustrate the invention without however limiting its scope. In these examples, the parts and percentages are by weight unless otherwise stated. The values given for the intrinsic viscosity indices have been determined in chloroform ( CHF) or dimethylformamide (Dr MF)

  at 20 C and are expressed in ml / g.

  I) Preparation of Polyethylene Glycol Diethers: Polyethylene glycol diethers (PEI and 2) are prepared in the composition indicated in Table I below by operating as follows: for drying the polyethylene glycol, it is heated to 10 ° C. to 1200 ° C. and kept under vacuum at this temperature until no more distillate is passed. The temperature is then reduced to 110 ° C. and the complex is added.

250-7610

  of BF 3 is then added in 5 hours, regularly,

  the epoxidized fatty acid ester and the temperature is maintained.

  at a temperature of 1100 C until the epoxide number has fallen to less than 0. The bulk of the BF 3 catalyst is then removed under vacuum using

  a little toluene as a training agent.

Table 1.

PE 1 2

PEG 1500 750 -

PEG 3000 750

PEG 600 150

Diethyl ether complex

BF 3 5 5.7

EPF 1,380 -

EPF 2,380

  PEG: polyethylene glycol (the number indicated is the weight

  average molecular weight of the glycol used).

  EPF 1: according to the manufacturer's instructions, it is a nalkyl epoxystearate, molecular weight 377,

  4.5% epoxide oxygen content.

  EPF 2: according to the manufacturer's instructions, it is an isoalkyl epoxystearate, molecular weight 380,

  4.5% epoxide oxygen content.

  II) Preparation of qras-acrylic acid copolymers:

  The composition and characteristics of the

  polymers are reported in Table 2 below.

Table 2: Copolymers.

  Cl C 2 C 3 C 4 C 5 C 6 Linseed fatty acids 44.5 37.5 37.5 37.5 20 15 Safflower fatty acids 17.5 Dehydrated castor fats 7.5 Isobutyl methacrylate 30 , 12.5 44 34.5 30 n-Butyl methacrylate n-Butyl acrylate 8 Methyl methacrylate 5.5 Vinyltoluene 5.5 31 6 10 Styrene 6 Methacrylic acid 19.5 19 18.5 22 22 18, Acid value, nmg KCH / g 207192 186 209 207 190 Intrinsic viscosity index

(EMF) 5.3 5.8 5.5 6.0 5.9 6.2

  The polymerization is carried out in solution in xylene at a theoretical concentration of 90% for the reaction mixture, at a temperature of 135 to C. The 2/3 of the previously dehydrated fatty acids are heated in vacuo with half of the xylene. then the mixture of the monomers and the mixture of the remaining fatty acids and the remainder of xylene with the peroxidic catalyst is regularly added in 6-8 hours. This is a mixture of 3 parts of tert-butyl perbenzoate with 1 part of 50% dibenzoyl peroxide. , for 100

parts of the final product.

  When the mixture was added, maintained at -1400 C until a residue analysis indicated a polymerization rate of at least 95%.

  is too slow, we correct with the help of a part of

tert-butyl benzoate.

  III) Preparation of alkyd resins with acry-

lique (comfoant A).

  The composition and characteristics of these "emulsifying resins", abbreviated hereinafter "RE" are

  reported in Table 3 below.

Table 3.

RE 1 RE 2 RE 3 RE 4

1st part

PE 1 120 120 120

PE 2 115

  Pentaerythritol 110 110 110 110 p-tert-butylbenzoic acid 120 120 60 120

* Flax acids 20 20 -

  Tall oil fatty acids 115 Calcium octanoate (4% Ca) 0.5 0.5 0.5 0.5 Zinc octanoate (8% Zn) 0.25 0.25 0.25 0.25 Part 2 Fatty Acids of Dehydrated Ridin 40 40 Linseed Fatty Acids 30 20 Tall Oil Fatty Acids 30

Linen fatty acids

fords (50% conjugation) 50 70 -

  Phthalic anhydride 50 55 65 50 Tetrahydrophthalic anhydride 13 8 13 Part 3 Copolymer Cl +) 380

C 2 + Copolymer) 270 -

  Copolymer C 3) 250 Copolymer C 4 +) 310

Linseed fatty acids 60 65 -

  PEG content (%) 10.2 10.2 9.5 9.4 Methacrylic acid content (%) 5.9 8.8 6.1 8.8 Acid value (mg KOH / g) 33 44 41 45 Index of intrinsic viscosity 11.2 11.7 9.8 10.6 +) The values given refer to the resin at 100 X. To prepare the emulsifying resins,

  using the following procedure: the first step is

  first portion at 2500 C until substantially all of the monoalcohol from the PEG-modified fatty acid esters ("PE") is released by transesterification and

  distilled For this purpose, it takes about 1.5 to 3 hours.

  Then cooled to 200 C and the second part is added.

  It is then esterified by azeotropic distillation with xylene to an acid number of less than 5%.

  then adds the 3rd part and we continue the esterification

  until the final values are reached In the final phase, the reaction is carried out under vacuum, and the xylene used as azeotropic entraining agent is eliminated

almost totally.

  The procedure used for the preparation

  resins RE 1 to RE 4 is preferred because it gives

  which dry well and have excellent properties.

  However, the resins may also be

  be prepared by the usual practical procedures, by copolymerizing an intermediate alkyd resin

  at low molecular weight with the monomer mixture.

  This procedure is described below with reference to the resin RE 5:

  141 parts of pentaerythritol are transesterified

  tol, 154 parts of PE 1, 154 parts of p-tert acid -

  butylbenzoic acid, 26 parts flaxseed fatty acid at 250 ° C. in the presence of 0.65 parts of calcium octanoate (at 4%) and 0.32 part of zinc octanoate (at 8%); with the reaction water, about 15 parts of a distillate are obtained

  insoluble in water Then 2200 C 290

  flaxseed, 64 parts of phthalic anhydride

  and 17 parts of tetrahydrophthalic anhydride and the esterification is continued with the azeotropic (xylene) recycle to an acid number of less than 5 mg KOH / g. The product is diluted with xylene to a

  final 85% solids.

  82.5 parts of the reaction solution are heated.

  85% at 1320 ° C. In 6 hours, a mixture of 11.8 parts of the 85% intermediate alkyd resin, 11 parts of isobutyl methacrylate and 6 parts of acid is added.

  acrylic and 3 parts of vinyltoluene, as well as

  0.8 parts of di-tert-butyl peroxide in 18.2 parts of xylene at 132 ° C. After reaching a solids content of greater than 74.5%, the xylene and the residual monomers are removed. under vacuum at 140-160 ° C and maintain this temperature until

  achieves an intrinsic viscosity number (CHF) of about 10.

  The product, having a PEG content of 10.3% and an acrylic acid content of 6%, has an acid value of 36-mg KOH / g and a limiting viscosity number (CHF) of 9.9 .

  Preparation of the RE 6 resin: 154 parts are transesterified

  1 part of PE1, 141 parts of pentaerythritol, 154 parts of p-tert butylbenzoic acid, 26 parts of safflower fatty acid as for the resins RE 1 to RE 4 in the presence of 0.65 part of calcium octanoate and 0.32 parts of zinc octanoate 320 parts of copolymer C 5, 120 parts of safflower fatty acid, parts of conjugated fatty acids (conjugation ratio 50%, 125 135, commercial product CONJUVANDOL 50), 64 parts of phthalic anhydride and 17 parts of tetrahydrophthalic anhydride, and is first esterified with azeotropic (xylene) recycle towards the end.

  of the vacuum reaction, until we reach the

  dice of acid and the value / n / wanted.

  The intermediate product has a PEG content of 10.4%, a methacrylic acid content of 7.1 X and an acid value of 39 mg KOH / g with a

  intrinsic viscosity (CH C 13) of 10.6.

  Preparation of the resin RE 7: is maintained in a protective gas atmosphere for 2 hours at 250 C 141 parts

  of pentaerythritol, 100 parts of p-tert-butylbenzoic acid, 20 parts of benzoic acid and 160 parts of

  of sunflower fat, then 90

  of the conjugated fatty acids which were used for the RE resin 6, 50 parts of sunflower fatty acid and parts of a polyethylene glycol of average molecular weight of about 1500, then 75 parts of phthalic anhydride and parts of tetrahydrophthalic anhydride, then another 320 parts of the C 6 copolymer, and esterified as described for the RE 6 resin. The intermediate product has a PEG content of 9.8, a methacrylic acid content of 5.9, an index of acid of 34 mg KOH / g

  and an intrinsic viscosity number (CHC 13) of 10.3.

  IV) Preparation of urea modified alkyd resins

thanne (UK):

  The composition and characteristics of the

  Urethane-modified alkyds are reported in Table IV below:

Table 4.

-RU 1 RU 2 RU 3 RU 4 RU 5 RU 6

  Part I Fatty acids of tall oil 380 280 380 300 +/- 50 +) 100 Oil; from Carth Ixne 300)

Fatty acids of safflower 650 -

  Linseed fatty acids 150 Dehydrated castor oil 120 Pentaerythritol 86 47 104 47 204 47 Trinmethylolpropane 9 Glycerine 106 67 106 Sorbitol (at 70) 300 Benzoic acid 8 P-tert-butylbenzoic acid 60 Calciun octaniate (at 4% Ca) I Octanoate, from plomib (at 0% Pb) 04.5 Part 2 Phthalic anhydride 90 100 100 85 100 100 3rd part Trimellitic anhydride 20 Part 4 Methanol 2.5 -4.6 5.0 4.5 10.5 6.9 th part Toluylene diisocyanate ('IDI) 1) 82 140 135 131 188 137 TDI content (% Acid value (mgq KOH / g)

11.9 18.6 16.4

1.5 0, 8 1, 2

17.8, 2

7.1 15.5

0.6 1.3

Table 4 (continued)

RU 1 RU 2 RU 3 RU 4 RU 5 RU 6

  Indioe of intrinsic viscosity 13.6 10.8 10.4 9.9 10.3 12.5 Solids (solvent: (CHF)

methylmonobutyl ether of ethyl

  ethylene glycol = EB) 91% 91% 91% 91% 91% 91 +) Industrial flax fatty acid isomerized to approximately 50%

of conjugated linoleic acid.

  ++) 80% of the 2,4 and 20% isomer of the 2,6- isomer.

  Urethane modified alkyd resins

  are prepared by the following procedure:

  first of all from the first part and the

  2nd part, by esterification at 2200 C, an aluminum resin

  low molecular weight kyde having an acid number

  less than 2 For resin RU 1, it is necessary to trans-

  proud the oils used in the first part by the polyalcohols before the addition of the second part

  achieves this by heating the first part to 250 WC

  than a diluted sample in the ratio of 1: 6

  by ethanol is soluble in clear at 20 C.

  For resin RU 4, after having reached a

  acid dice less than 2, the temperature is lowered to C and the third part is added. It is then maintained at -1700 C until an acid number of 12 to 13 is reached by assisting the esterification towards

by applying a slight vacuum.

  The reaction of the intermediate alkyd resins thus obtained with the diisocyanate and methanol is carried out in 60% solution in toluene with resins.

  alkyds, toluene and methacrylate are added.

  The mixture is heated to 500 ° C. The TDI is then added and the solution is heated to 100 ° C. The temperature is maintained at this temperature level until the NCO content has fallen below 0.1% and the viscosity index has been reached

  If it is necessary, we add small amounts of

  The toluene is then distilled under vacuum until the resin has a solids content of about 80%. 10 parts of ethylene monobutyl ether are then added.

  glycol per 100 parts of solid resin and further distilling

  under vacuum until complete elimination of toluene (

solid substances: 91%).

  Examples 1 to 7: The strength and characteristics of the emulsions of Examples 1 to 7 are reported in Table 5 below:

Table 5.

: The number 1 2 3 4 5 6 7

1) 40

  -, 1) 1) 1) 1) 1) 1) 1) 2) 2) 2) 2) 2) 2) TEA 2 a) DMEA H 20 Solids content (%) o 'Viscosity Y Pa s) 3) Content in EB (%) Amine content (%) Flash point according to A BEL-PENSKY

-

4 u

-

-_ 71.5

- 66 -

_NOT

9 9 8

1.59 1.73 2.34

0.7 0.76 1.03

105 132

45 40

9.7 9.7 9.9

2.6 2.8 7.4

6.75 6.75 6.0

1.03 1.12 1.35

  1.95 0.86 9.8 6.9 6.75 1.26 8.5 1.87 0.83 9.6 3.3 6.75 1.22 1.93 0.85 9.6 4 8 6.75 1.2 (1.93 0.85 9.9, 6.75

6 1.26

  more than 650 C. -Exemx RE 1 RE 2 RE 3 RE 4 RE 5 RE 6 RE 7 RU 1 RU 2 RU 3 RU 4 RU 5 RU 6 EB - N - 1) 100% 2) 91% 2 a) triethylamine 3) Measurement at BROOKFIELD RVT, 6, 100 rpm, 200 C.

  The emulsions are prepared in the following manner

  In this case, the emulsifying resin, the urethane modified alkyd resin and the EB are carefully mixed for 60 minutes at 80 ° C. The temperature is then lowered.

  600 C and introduced with stirring the mixture of amines.

  After 30 minutes, the temperature is further lowered to 500 ° C. and water is added. The water is added in 60 to 90 minutes with vigorous stirring while maintaining the temperature between 40 and 50 ° C. The mixture is stirred for a further 30 minutes.

  minutes after the end of the bill.

  Tests of emulsions of Examples i to 7.

1 Storage stability test.

  To shorten the test time, the emulsions are diluted to 30 ° C. and maintained at 700 ° C.

  there is no absolute proof that the results of this

  However, experience has shown that emulsions which resist for one week at these conditions are stable in storage for at least six months under normal conditions.

  of this test are reported in Table 6 below.

  2 White paint test 2% of a siccative mixture 4) compatible with water and 1% of an agent are added to the emulsions.

  anti-skin (in both cases compared with the

  lide) and digested with 35% demineralized water is then pigmented with titanium dioxide 5) in a vibrating mill ("Red Devil") at a ratio of pigments binding 0.8: 1 After drawing the paint on the

  ice cream, we study the drying, the gloss and the resistance

  water to the film at a film thickness

  dry weight of 30 μm (the results are reported in

Table 6 below).

Table 6.

Example N 1 2 3 4 5 6 7

Stability of the tul

  storage 6) (one CCCCC week at 70 oc) Drying a) off touch 30 55 20 25 20 25 25 (min) b) dust free (min) 60 125 45 60 55 55 50 c) ccmplet drying (hour) 5 , 5 6.5 3 5 3.5 5.5 4 Gloss 7) 73 74 69 76 66 70 73

  Resistance to water) all products have a slight softening

  slow but regenerate quickly without loss of gloss 4) Commercial product HYDRO-CURE from MOONEY,

United States (contains 5% Co).

  ) Commercial product RCR 3 from Tioxide Ltd, United Kingdom.

6) C = correct.

  7) Measurement with the "GR-Comp" gonioreflectometer of the firm

  Paar, Austria), measurement tab 60,% of the

  lon. 8) 24 hours immersion in water at 20 C after 7 days

  drying at room temperature.

  3 Test of a protective undercoat against corrosion

  based on the emulsions according to the invention.

  222 parts of the emulsion of Example 1 are ground at 45% with 50 parts of red iron oxide, 50 parts of lead silicochromate, 70 parts of barium sulfate and 30 parts of talc in the usual manner. ;

  after addition of 2 parts of the commercial product Hydro-

  Cure identified above, 1 part anti-skin agent,

  1 part anti-sediment agent and 1 part anti-sediment agent

  foam, diluted with water to the Rotothinner apparatus at a

  viscosity of 4 m Pa S (about 63% solid).

  Final adjustment of pH at 9.0-9.5 was made by the TEA.

  After a storage period of 4 weeks at 400 C, the paint has not been modified other than a light one

  sediment easily redispersed by agitation.

  Drying times are 20 minutes / 30 to 40 minutes / 2 to 3 hours respectively for non-touch / dust-free / full drying salt spray tested according to American Standard ASTM B 117/64, dried film 7 days in room temperature shows only a slight rust below the grate after a test duration of 120 hours; the takeoff of the grid is only

2 to 3 mm.

Claims (5)

  1 Aqueous emulsions of alkyd resins used   sands as binders for paints and varnishes   in the air, characterized in that the emulsion resin part   sionnée consists of a mixture prepared in the presence of   % by weight at most (relative to the solids   binder) of an auxiliary organic solvent at a temperature of 50 to 1000 ° C, (A) 25 to 45% by weight of an air-drying acrylic alkyd resin, the resin containing, with other acrylic and / or vinyl monomers, from 4 to   X by weight of acrylic acid and / or methacrylic acid   and from 7 to 13% by weight, preferably from 9 to 11% by weight, of a polyethylene glycol having an average molecular weight of 500 to 5000, and having an acid number of 70 mg KOH / g. and an intrinsic viscosity number (measured in chloroform at 20 ° C) of 9 to 12 ml / g, and (B) 55 to 75% by weight of an air-drying urethane-modified alkyd resin with an intrinsic viscosity index of 8 to 16 mlx / q (measured in chloroform at 20 ° C.),   the carboxyl groups of the binder mixture being neutral   before emulsification in water by a quantity   of amine and / or ammonia corresponding to an 20 mg KOH / g maximum.   Emulsions according to claim 1, characterized   in that the alkyd resins of component (A) contain from 25 to 50% by weight unsaturated fatty acid. Emulsions according to claim 1 or 2, characterized in that the alkyd resins of the component   (A) contain from 10 to 26% by weight of acrylic monomers   vinyl or non-functional groups   reagent other than the double bond.   Emulsions according to any one of the   1 to 3, characterized in that the polyethylene-   glycol is bound in the molecule by ether bonds.   Emulsions according to any one of the   1 to 4, characterized in that the car-   of the component (A) consist of at least 80% (meth) acrylic acid groups.   Emulsions according to any one of the   diacations 2 to 5, characterized in that in the residences   alkyds of component (A), to introduce the groups   carboxyl, the ester copolymers were incorporated by esterification   prepared separately from fatty acids of sicca-   with methacrylic acid and vinyl compounds.   and / or acrylics not carrying a functional group other than the double bond.   Emulsions according to claim 1, characterized   in that the urea-modified alkyd resins   thanne component (B) contain from 45 to 65% by weight of unsaturated fatty acids.