DE1646050B2 - PROCESS FOR THE PRODUCTION OF COATS ON ANODIZED ALUMINUM OBJECTS - Google Patents

Description

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The resins mixed from alkyd resins and water-soluble melamine below 100 ° C and composed by neutralis are thermosetting resins, sation, ζ. B. with ammonia water, made soluble, but you can also first make water-soluble by the specified - when mixing a water-soluble melamine VinyJmonomer modified unsaturated alkyd resin at a temperature in the range of ⁵ , z. B. with ammonia water, normal temperature up to 100 ° C with an alkyd ^{and es} ^ ^{011 only n} ^ ^t mix a water-soluble melamine resin of the aliphatic acid process with a ^{resin at} normal temperature.
Acid value of 10 to 80 and an oil content of exactly 0 to 80% must be obtained in ^{the indicated processes, the alkyd resin to an} optimal content of unsaturated organic when heating a mixture of a saturated ^{10's acids in} the constituents of the vinyl resins or unsaturated aliphatic Look for acid as his ^{or her} optimal acid value of the alkyd resins. Oil component, ethylene glycol, glycerine, poly- ^{For the} preparation of solutions of the heat-curable ethylene glycol, an epoxy component or other ^resins, all emulsion-forming or hydrous polyhydric alcohols can be used as alcohol-compo- soluble materials; the appropriate component, adipic acid, sebacic acid, maleic ^{acid- 15} resin concentration, can be selected depending on the anhydride or other polybasic acid method used. The usual Harzais acid component and a minor amount concentration is in the range of 3 to 40%. This cyclohexanone, toluene, or other organic concentration enables the electrical adsorbent solvent to be obtained or ^{tlon the resin particles} . The best

2o results are obtained at concentrations from 5 to

_ when mixing with an alkyd resin of around 20% as well as a voltage and an initial current

Esterification process that involves the esterification of a density within a safe and economical

Mixture of dehydrated castor oil, sa range obtained.

franöl, the above-mentioned multi-value The core of the process according to the invention

term alcohol and a small amount of an um- 25 consists in using the porous aluminum oxide film

esterification catalyst such as caustic potash, cold or hot water immediately after the

is obtained, after which also the above-electrolytic oxidation wash him into a

\ Creamed polybasic acids are esterified. to immerse the resin solutions described above, the resin particles an electrical

Resins, which consist of a vinyl resin and a water- 30 electricity charge and then adsorption

Soluble melamine are thermosetting resins, the resin on the porous film are on electrical

bring about a mixture of organic ways to produce them.

Solvents such as methanol, ethylene glycol mono- When the porous alumina film are colored butvläther or cyclohexanone, unsaturated acids, is supposed to be used immediately after the electrolytic oxyw ie acrylic acid or methacrylic acid, vinyl mono- 35 dation the adsorption of the dye in the porous kidneys, such as styrene or acrylic acid esters, self-alumina film and only afterwards according to the network Vinyl monomers, if necessary, such as the electrical adsorption of the resins - mechylolacrylamide, Polymerization catalysts and led. But you can also use water color in enough Add large quantities of polymerization regulators by heating while resting, so that the resin solution is colored Ren is polymerized to a vinyl polymer, 40 is, and only then the mixing and the further that with a water-soluble melamine resin under the above-described treatments for heating and Heating mixed below 100 ° C, carry out by neutralizing the heat hardening. So not everyone Acid components with ammonia water or restricted colored products with a soft handle - triethylamine or treating the polymer with. Become heat-resistant color ammonia water Made water-soluble and then used 45 substances or pigments as colors, one can using water-soluble melamine at normal temperature to produce products that are completely free of thermal effects is mixed. Changes are.

Unsaturated alkyd modified by vinyl resins. Sometimes it is desirable to have the resin solution up to

Resins are thermosetting resins, for the production of which temperatures from 30 to 50 ⁰ C have to be heated, since the

that of the unconditionally unsaturated components 50 heating the resin solutions, the resin particles are mobile

Alkyd resin formed in methanol, makes ethylene glycol and turns them into an electrically adsorbable

added monobutyl ether or other organic solution state. If they are not heated, it can

agents are dissolved and graft polymerisation of an electrical adsorption is sometimes impossible,

Mixture of unsaturated organic acids as because of the pH of the solution while the resin bath

Acrylic acid or methacrylic acid, vinyl monomers, 55 is used continuously, due to the enrichment

such as acrylic acid esters or styrene, self-crosslinking ammonia, amines or the other, in

Monomers such as methylolacrylamide, if necessary, small amount of additives present, increases

Peroxide polymerization catalysts and polymer are necessary to make the resin water soluble

sationregulatoren is carried out, after which the so and an emulsion to stabilize. You can

The resulting vinyl monomers of the modified un- 60 heat the solution to such an extent that its stability is not achieved

saturated alkyd resin with ammonia water z. B. impaired and their pH by evaporation

neutralized to make them water-soluble. excess ammonia and amines

Furthermore, for the production of which is obtained from the vinyl law.

resins of modified unsaturated resins and water-die with resin in the manner indicated above Soluble melamine resins composite heat-treated 65 electrolytic oxidation films curable resins the foregoing, through vinyl are cured at a temperature at which a monomeric modified unsaturated alkyds with crosslinking hardening of the thermosetting used water-soluble melamine resin takes place at a temperature resins. Usually optimal prevail

The transesterification reaction became ^{5 wH nitrogen}

Conditions if one is at temperatures of 120 "? *»! "* ^ _A temperature between 230 and

hard up to 160 ^° C. for 10 to 60 minutes *. Im- "Hurche led; after cooling were

B e i s ρ i e 1 1 S TeUe phtic anhydride and 50 parts of cyclo-

^P _L u «! R ₇ n _ff eeeben and the stiffening at one

After degreasing of fat and after giving way to 5 * ^εχ * ™ ° * ^U f | f _scne n 180 and 210 ⁰ C under cover, an aluminum plate was 1 hour at 20 C in. ^p? r _"dharzes having an acid value of 50 by a 15 ° / ₀ sulfuric acid electrolyte containing ^em ^ Vr _{{100 Tei} i _s of the alkyd resin were then added at a Gleichstronidurchgang of 1.5 A, -m- getunru ykolmonobutyläther, neutralized

electrolytically oxidized. _ ™ ¹ ^ _0,. · _Laundri ßrigem ammonia and diluted

Thereafter, the adhering sulfuric acid was denoted with j *! ^ . _{washed to a} concentration of solid electrolytes! The resulting with ^w * ^s * ^c _ ", _In ^ ₆₅₆₁ manner one obtained a product with the resin which was _{completely soluble in the electrolytic oxidation substance.} BUdeten FUm were used in the procedures of the following i: ^osun £ Γ ~ _solution mixed with water soluble examples. Mdamin resin in a ratio of 1: 1, to which (dissolved)

Example 2 ^{15 based on} substance. The mixture became just water

Γ. ^e ιVo / diluted based on the total content

In a reactor of suitable size, the resin solution _{with up to 15 / o bs} ' _{tanA from it}

Produce a stirrer, a thermometer and a reflux to (f ^Ios f ^ divorce, was cooler, there were added 42.5 parts of ethylene for the ^ ⁰ £ _eispie ^^ l 1 obtained elektroelvkolmonobutyläther and 44.5 parts of methanol em- ao Danacn \ vuiu ^^ _{with 80} γ direct current

iesfeeds and heated to 70'C. While maintaining lytisch oxyüie e _{current density of 400 m} A / dm * a reflux temperature of 70 ⁰ C were ι minute in the resin solution in the example

5.5 parts of methacrylic acid, treated manner described. Then close. * Man

25 parts of ethyl acrylate, _{as it was} out of the bath, washed it lightly to the end

a 44.5 parts of methyl methacrylate, from adhering excess resin and heated

■ 1 5 parts of styrene, _{it to} harden ¹ Z ₂ hours at 130 C when hardening

1.5 parts of benzoyl peroxide _{continued the} crosslinking of the

x 1 part of dodecyl mercaptan surface adsorbed resin. It made up vcti

η ji u, _r7 fiim being excellent anodized

L ₁ were mixed together until the solution was achieved and together were 30 endlessly "" ^^^ ttn .

with 20 parts of methylolacrylamide at intervals of aluminum objects

_n V ₂ hours in five equal portions into the reactor

given d. After the addition was complete, the ^{example was heated}

the reaction mixture at the same temperature with stirrer, thermometer and

c stirring cooled for a further 4 hours under reflux 35 _R J _"fl ^ 'J ^' _were tatteten reactor 50 parts

then to 60 <C from which Jj ^ Säurekompo- tg ^^^ SJter and 37 parts of methanol neutralized 1, component with 28 ° / _o aqueous ammonia and ^ethylene comparable S ¹ y _s ^{1 kO} T _"n ° J? _urde until the

d i W up to a salary of 30 · / «Jgg» * ^ "d

component with 28 ° / _o aqueous ammonia and ve ^y Sy _s t _n J? _urde until the onset of the

c thinned with water to a content of 30 · /. «Jgg» * ^ " _U nte _r Maintain the back

}, Solid substance. ".US.

Λ In this way an aqueous resin flow was obtained

Ij solution, which is fully dispersed with water 5 parts of acrylic acid,

·, Let thin. This resin solution was diluted further 5 _Te ji _e hydroxyethyl acrylate,

with water up to a solids concentration of 20 parts of ethyl acrylate,

> 10 ° / ₀ and control the resin solution for the elec- 45 parts of methyl methacrylate,

troab separation. 45 5 parts of butyl acrylate,

The anodized aluminum obtained in Example 1 and 1.5 parts of benzoyl peroxide

Hlö d to 25 ⁰ C il Ddlptan

The anodized 1.5 parts of Beyp obtained in Example 1

was in the resin solution obtained, which at 25 ⁰ C 0.5 part of dodecyl mercaptan

f Glih i

was held as an anode for DC einge- _Ah _ _{tanden of} i /. hour in five equal servings

dives; after having made a steel plate of non-weeding before '/ * ^ una S ^

Ί had connected rusting steel to a cathode, 50 l the reactor device. Hours with stirring

; the treatment was carried out by "^" ^ JJ * IXu _{5 e} rt _e after cooling

IV for ₂ minutes a direct current of 100 V and and under RuckriulJ ^ne "} ™ ^Is . ¹ .r,, · and diluted

^ an initial current density of 500 mA / dm · through- £ S ^ mpagente m ^^^ ™

\ sent. Then you took the product from the then the mixture with w ** b

Bath out, washed it lightly, _{to remove any adhering over- 55} ^ 30 ^ an Ftoteutatonj Wassgr

s to remove schüssiges resin, and heated it in this way ernieii πιι, "mixed

Cure 30 minutes 15O ⁰ C. In this way, constantly expanding soluble resin solution ^^ e solution νenin FRUITS

Treated anodized aluminum objects were kept ^^^ Α ^ ΓΑΪ excellent durability. ^ ^ "^", ^ together _{at 80} o _{C for} 1 _hour

' react. Then the solution was diluted with water

^ B e 1 s ρ 1 e 1 i up to a total content of solid substances of

] In one with a stirrer, a thermometer 15 % to make the resin solution for the electrical

, and a reactor equipped with a reflux condenser. Ai _liminJlim A _e, n _e; the one with an injection device for nitrogen and 65 the electrolytic "fjf» ^^^, ^

was connected to a separation pipe, were game 1 treat you m_ this resin solution ^ at

332TeUe soybean oil, 120 parts glycerin and 20 ⁰ C with 60 V direct current with an initial current

- 0 2 parts of sodium methylate fed. At a density of 200 mA / dm *; after that one took it off

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the bath, washed off any excess adhering to it with water. The anodized aluminum was then treated

from the entire resin and hardened it by heating Example 1 for one hour in the manner described in Example 2

to 120 " ^J C. in the resin solution obtained at 30 ⁰ CI ¹ Z ₂ minutes

Example 5 ^ ^an ^ ^m ' ¹ ^ ^' direct current with an initial current

5 density of 600 mA / dm ² . The product was made from the

1. In the manner described in Example 3, the bath was removed, a transesterification was carried out by washing with water, the 330 parts of saffron oil were freed from excess resin and 100 parts of glycerol and 0.2 part of sodium methylate were hardened by heating at 150 ° C for half an hour,
concerned; then was made by adding 220 parts. -I ₇
Phthalic anhydride an alkyd resin with an acid io example /

worth 30 manufactured. By polymerizing 20 parts of alkyd resin with

2. In a reactor of Examples 2 and 4, an acid value of 10.35 parts of cyclohexanone, 20 parts of the alkyd resin formed in Example 4, 13 parts of isopropyl alcohol.lOTeilenMethanol.l.STei-55 Parts of ethylene glycol monoethyl ether and 32 parts of methacrylic acid, 42 parts of methyl methacrylate, Methanol divided a mixture of 5 parts 15 42 parts of ethyl acrylate and 1.5 parts of benzoyl peroxide Methacrylic acid, 5 parts. Hydroxyethyl methacrylate. was obtained in the manner indicated above 40 parts of ethyl acrylic, 5 parts of methacrylic acid, 5 parts dilution with triethylamine and water one millile Styrene and 1.5 parts of benzoyl peroxide and a chige white emulsion.

20 parts of methylolacrylamide in five portions and this emulsion was mixed with a water it was added at intervals of ^{1 and} ₂ hours at boiling temperature »ο soluble melamine resin in a ratio of 1: 1, based on door. After the addition was complete, the mixture was heated to the solid substance content and diluted with reflux for a further 4 hours with stirring. Water was then cooled to a total solid substance content and the methacrylic acid was neutralized at 20 ° ₀ . This emulsion also showed ethylamine excellent over a long period of time on storage and the alkyd resin, according to the acid value with di-. When diluted with water up to a 15 stability and settled as a resin solution for the electro-concentration of solid substance of 30 °. _o received deposition use.

a resin solution which is unlimitedly soluble in water. The anodized aluminum obtained according to Example 1

This solution was further diluted with water until it was in the manner indicated in Example 2 in

a solid substance content of 15 ⁰ Z ₀ , this resin solution being used for 1 minute with 50 V direct current

treated a resin solution suitable for electrodeposition at 30 and 200 mA / dm ^2. The products were taken

received. out of the bathroom, she washed to remove

Thereafter, the electrolytically oxidized adhering excess resin was treated with water and

They hardened aluminum from example 1 in that in example 2. by setting them at the 5th hour to 130 ^c C

Written way ^{heated at 25 0} C in the resin solution.

IV for ₂ minutes with 100 V direct current and 35 Durability, appearance and feel of the further 300 mA, dm * initial current density. It was taken from the anodized aluminum bath obtained in the above-described manner and thereafter with water from adhering- minium objects were excellent,
washed free of the resin; by half an hour.
heating to 130 ° C was cured. Example p

40 Regarding the solutions of the resin baths of Examples 2 to 7

Example 6 was added 5% of a red water-soluble dye

to. In this way, colored products were obtained with

1. In a reactor of Example 3 were 192 parts soft to the touch.
Trimethylolpropane, 132 parts of sebacic acid, 67 parts of Example 9
aliphatic safflower acid and 8 parts cyclohexanone 45 (comparison example)
fed in and heated to 200 "C for esterification,

where an alkyd resin with an acid value of 50 is placed in a reaction vessel equipped with a stirrer,

received. a thermometer and a reflux condenser.

2. In a reactor of Examples 2 and 4 were allowed, 35 parts of cyclohexanone, 13 parts of 20 parts of the alkyd resin obtained according to 1. 35 parts of 50 isopropyl alcohol, 10 parts of methanol and 20 parts of cyclohexanone, 13 parts of isopropyl alcohol and IOTefle alkyd resin obtained in Example 6 is incorporated-methanol and sets at boiling temperature a mixture; it was then heated until the onset of the return of 3 parts of methacrylic acid and 40 parts of Methykneth bus; 3 parts of methacrylic acid, acrylate, 42 parts of ethyl acrylate and 1.5 parts of benzoyl 45 parts of methacrylate, 42 parts of ethyl acrylate and peroxide in five portions at intervals of V / s hour 55 1.5 parts of benzoyl peroxide at intervals of V / s hour were added. After the addition was complete, the five portions were added to the reaction vessel. Polymerization for a further 6 hours under reflux After the addition was complete, the polymerization was continued, then cooled, the alkyd resin reaction was neutralized for a further 6 hours under reflux according to the acid value and the methacrylic acid was also carried out; Then it was cooled. Finally, triethylammine, and diluted with water up to 60, triethylamine was added in the amount corresponding to a solid content of 30%, giving a resin solution which was unlimitedly soluble in neutralization of the alkyd resin according to the acid number of water. and the methacrylic acid was required. Furthermore, this resin solution was mixed with a water-based solution that was diluted with water to a content of 30% of soluble melamine resin in a ratio of 1: 1, on the solid substance. This solid matter content was then referred to; then diluted 65 resin solution with a water-soluble melamine resin with water up to a content of 15% in a ratio of 1: 1 (based on solids) ver-solids. This solution was then used as a resin mixture and with water up to a content of 15% solution for electrodeposition. diluted in solid matter. The one with the so obtained

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water-soluble melamine resin mixed water-soluble resin solution was kept at 20 ° C; in it became that in example 1 obtained alumina immersed for 2 minutes to cover its surface with the water-soluble Coat resin. Thereafter, the thus treated alumina was washed and then washed heated in the oven at 150 ° C for 30 minutes.

The physical properties were between that according to the method according to the invention and compared aluminum product obtained by the known dipping process.

The results are given below:

10

procedure Immersion process test according to the invention slight on Acid resistant normal eating speed intense Alkali Resistant normal corrosion speed intense Mortar Resistant normal corrosion speed normal intense CASS test normal corrosion strong up SO ₂ -GaS- weak on swelling resistance swelling peeled off resistance normal against cooking of the water normal Solvent- normal resistance strong yellowish Tobacco smoke pale yellow discolored resistance lich discolored 3H Endurance test 4H

35

The above tests were performed as follows:

Acid resistance:

Judged by the appearance after placing the sample in a for a period of 5 hours 5% hydrochloric acid solution was immersed.

Alkali Resistance:

Evaluated according to the layer on the surface of the sample after it has been immersed for 5 hours at room temperature in a 5 ° / _o strength caustic soda solution.

Mortar resistance:

Judged by the appearance after the sample was immersed in a mixture of cement for 144 hours: Sand: water = 1: 3: 1 was immersed.

CASS test:

Judged by the appearance after the sample for 163 hours with an aqueous solution of NACl (5 percent by weight) was sprayed, the pH of which was adjusted to 3.1 to 3.3 using acetic acid (JIS D0201 method).

Resistance to SO ₂ -GaS:

The sample was exposed to the steam of an _{aqueous solution saturated with SO 2} -GaS for 115 hours, after which the layer on the surface was evaluated.

Resistance to boiling water:
The sample was immersed in boiling water with 0.1 "' ₀ detergent.

Solvent Resistance:

Assessment after immersion in xylene for 144 hours at room temperature.

Tobacco smoke resistance:

Assessment after 24 hours of contact with tobacco smoke.

Endurance test:

Scratches caused by a pencil on the coated surface, whereby the lead hardens is divided into 9 degrees.

This comparative example clearly shows the Superiority of the method according to the invention! emerged.

Claims (2)

and to form an endless film and thereby to produce treated anodized aluminum products that are resistant to adhesive strength, corrosion 1. Process for the production of coatings. Strength and surface quality superior on objects made of anodized aluminum have less than 5 properties. Use of electrophoresis, thereby anodized The film treated according to the invention indicates that the aluminum versus aluminum differs from the one used in the stood in coating an aluminum oxide film with a a bath of an aqueous solution or dispersion solution of a water-soluble resin or a resinous resin thermosetting resin immersed in an io emulsion immediately after the electrolytic oxy anode connected, while a cathode dation in the usual manner, for. B. by spraying, is also immersed in the bath, an equal immersion, has been applied, in principle Subjected to current treatment, washed, and heated by the agitation and adsorption of the resin will. particles on the oxidized film by electrical means 2. The method according to claim 1, thereby generating 15. indicates that a dye-containing With the method according to the invention it is possible Bath is used. so uniform contact resin films as well as products to produce with a special grip, as it is not possible with the previously known coating methods. 20 would have been borrowed. Is further according to the invention If a water-soluble resin with a small grain diameter is used, one can achieve that the resin The invention relates to a method for producing particles electrically into the pores of the oxide film Coatings on objects of anodized penetrate, leaving a very firmly adhering resin film Aluminum using electrophoresis. 25 receives. When thereafter the heated resin is hardened. According to a known method is anodic, the structure of the porous film oxidized aluminum immediately changes a lacquer after-treatment after the electrolytic oxidation of y-Al ₂ O ₃ in subject; dipping varnishes based on y-Al ^ · H ₂ O (boehmite) based on water, ammonia or amines contained in water-cresol resins / phthalic esters or based on soluble resin or the aqueous resin emulsions copolymers of vinyl chloride and vinyl ether 30, ie , applied. The properties of the pores of the film treated in this way can, however, be unsatisfactory for completely closed aluminum. will. Furthermore, it is already known in the usual way, in particular when the water-soluble resin pretreated metals, e.g. B. aluminum, from wäßri- particles with a small diameter electrically in the When alkaline dispersions of drying oils are adsorbed onto 35 pores of this film, the electrolytic way to deposit films, the pores as they are closed with the resin particles, finally washed, dried and heated. In this way, with the method according to the In this method, however, a film must be produced in a disadvantageous invention, which in his Way to the aqueous system reinforcement materials, adhesive strength and corrosion resistance the so far thermosetting films prepared in which according to be admitted. pores that are still unsealed after hardening are present These disadvantages of the previously known methods are being made is superior. avoided in the method according to the invention. Some examples of thermosetting resins used in the method according to the invention will be applied to the aluminum method according to the invention Minium object immediately after manufacture of the anodized 45 can be: The heat reaction products or meschicht in a bath of an aqueous solution or dispersible mixtures between vinyl resin and vinyl ion of a thermosetting resin, immersed in a resin or between an alkyd resin and a water-soluble one Anode connected, while a cathode is made of melamine resin, modified by vinyl resin if necessary is immersed in the bath, a DC-saturated alkyd resin and the heat reaction products subjected to action, washed and heated. 50 or mechanical blends between a vinyl The method according to the invention has - in the modified unsaturated alkyd resin and a comparison with the known method - a larger water-soluble melamine resin.
Effectiveness and thus enables anodized These vinyl resins include thermosetting vinyl resins, Aluminum objects with excellent corrosive properties a mixture of organic for their manufacture sion strength and electrical insulation capacity 55 solvents, such as methanol, ethylene glycol mono, without the good looks, the smooth butyl ether (butyl cellosolve) or cyclohexanone, un-grip and other valuable properties of the saturated organic acids, such as acrylic acid, methides anodized acrylic acid or maleic anhydride, self-crosslinking aluminum articles made by known methods get lost. the vinyl monomers, such as methylolacrylamide or The method according to the invention comprises the 60 methylol methacrylamide, polymerizable vinyl mo-use thermosetting resins in the form of aqueous nomeren, such as styrene or acrylic acid esters, poly solutions or emulsions, immediately after merization catalysts, such as benzoyl peroxides or the electrolytic oxidation by means of direct current lauroyl peroxides, and polymerization regulators, such as tension a Kataphoic - the resin particles on the dodecyl mercaptan or carbon tetrachloride, to the film surface of the aluminum and thus a 65 carrying out the polymerization with stirring
Adsorption of the thermosetting resin is heated electrically, after which the acidic components are brought about with ways. It also includes the ammonia water or triethylamine neutralized who-heating the adsorbed resin to harden it to make the resin water-soluble.