DE2057799A1 - Method and means for producing a coating on an object by means of electrical current - Google Patents

Description

DESCRIPTION for the patent application of

Company M # T CHEMICALS INC., New York, N.Y-, / V ^ St.A.,

concerning

"Process and means for producing a covering an object by means of an electric current "

Priority »November 24, 1969 - 7th St-A,

The invention relates to new compositions of matter for the production of coatings deposited cathodically by the electric current, for the production of such compositions of matter as well as methods of making new items, at least some of which are a has cathodic electrodeposition on the surface,

It is known that various organic pavement materials disperse in an aqueous medium and through the electric current of one immersed in the aqueous medium conductive objects can be deposited. In industrial practice the electrodeposition is on o an anode a shark with or without a "cross-linking

109830/1698 _BÄD ORIGINAL

funds deposited. The object provided with the coating is then removed from the bath and a betrayal reaction is carried out by high temperature treatment. The crosslinking can either be through oxidative polymer! of unsaturated groups in the case of a single harsay star or by reacting the added crosslinking agent with the free carboxylic acid groups on electric Ways of deposited resin take place. Anodic deposition is preferred because it involves the crosslinking reaction is catalyzed by the acid developed at the anode.

The anodic * deposition of γοη organic coatings, however, has the disadvantage that metal ions are released, which are formed by the oxidation of the substrate and thereby the coating; becomes contaminated by entrapping them in the precipitated resin. It has now been found that this contamination can be avoided by cathodic deposition. The previously known technology does not allow any heat treatment of these catholic polymers, since no acid is present in order to catalytically influence the crosslinking reaction,

The purpose of the invention is now a new Harzzuaarnmenaetzt to propose which for the production of ηit objects provided with cathodic electrodeposition suitable is. Another feature of he fix ·, du ng consists in proposing a new cathodic resin, dae when it is suspended in an aqueous medium · :, uno is subjected to an electrical potential, Me aui " a suitable cathode, which is immersed in an aqueous medium, to thereby ο in ti rs. related PiIa to form. Another feature of the invention beateht in the fact that a new ancestor for the production of vm

10 9 8 3 0/1698 BAD ORIGINAL

• · a

cathodically deposited films by electrodeposition is suggested.

The invention thus relates to new compositions of matter and to a method of making an electrodeposited article, and is to propose a liquid bath composition in which are dispersed: (a) particles olnea an amine-containing organic covering material with your positive charge, in combination with (b) one blocked multifunctional isocyanate, of which a first Electrode in intimate electrical contact with this bath as a & ode is held, and in the bathroom as second Electrode a conductive object is immersed, at least part of which has a negative charge contains ua'l ala cathode is connected, whereupon an electrical Stroiü is passed through these two electrodes and the bath and in this way an electrodeposition on &? * i object is generated «After the object has been removed from the bath, it is electrodeposited arwerzaij around a water-resistant cross-linked polyraerieiert Surface au result.

I) Ie sxB-un _t ORl-containing organic resin covering composition according to the invention can be produced by vinyl polymerization of unsaturated monomers which contain 5 to 50 parts of an amine compound. "These compositions of substances can also be produced by the condensation of di- or tribasic or even holes, acids with diamines or hydroxyamines.

Another method for dividing the amine-containing Fabric au SGiEraensotungen, which for an electrodeposition

* C 3 S 3 O / 1 6 9

are suitable consists in the use of ammonium salts of fatty acids or quaternary fatty acid amines as emulsifiers for resins or polymers which have no ionic charge «» When using these amine soaps, the emulsified particle then receives a positive one Charge which is applied to the electrically-conductive object migrate, which is immersed as a cathode in the deposition bath.

If the amine in these resins is primary or secondary, so it performs at least two important punctures, namely: (I) 'it gives the polymer a cationic charge when ta is neutralized by an acid and (2) as a result the active hydrogen contained in it becomes points for the networks delivered when the blocked ones Multi-functional isocyanate-containing coating according to the invention is subjected to a heat treatment ο If the amine is tertiary or quaternary, it only imparts its cationic charge, but does not provide points for betrayal. As a result, in conjunction with tertiary and quaternary amines hydrogen-active monomers applied.

Typical amine compounds used for vinyl copolymerization are the following:

(a) amine-containing esters of monofunctional unsaturated Acids of the formula

-R, -Ο- CX> - C w GH,

109830/1698

BAD ORtGiNAi.

wherein R _{1 is} an alkyl, alicyclic or aryl group (preferably with up to about 8 to 12 carbon atoms); R ₈ is hydrogen or an alkyl, alicyclic or aryl group (preferably with up to about θ to 12 carbon atoms}; R ₁ "is (CHg) _n , where η corresponds to the number 1 to 6 and R _{4 is} an alkyl group (preferably with up to about 1 to 8 carbon atoms) or a hydrogenous substance. Examples of such substances are acrylic or methaoryleic acid ethers of t-butylaminoethanol and dimethylaminoethanol j

(b) Mono-containing diesters of difunctional unsaturations Acids such as maleic acid, umaric acid or itaconic acid, those with alcohols of the general formula

K-R, -OH

are esterified, in which R ₁ , R ₈ and R _{9 have} the meanings given above; (

(c) quaternized aain-containing unsaturated esters of the types (a) and (b) given above, wherein R _{8 is} an alkyl, aryl or all cyclic reed (preferably having up to about 8 to 12 carbon atoms); and

(d) Vinyl-containing heterocyclic compounds, such as N-vinylplperidin or N-vinylpynjolidon, uniquely theirs quaternized analogues or an N-vinylpyrldinum halide (such as chloride, bromide, ? luoride or iodide).

109830/1698

Preferably, one or more of these are neck-necked unsaturated compounds mixed with monomers, which have no electrical charge and contain no active oxygen, so these are non-functional can be designated after the polymerization. Typical non-functional monomers of this type are unsaturated Hydrocarbons, such as isoprene, butadiene, ethylene, styrene and vinyl acetate and / or vinyl acetate and / or vinyl alkyl esters of dibasic acids and / or unsaturated Common compounds such as vinyl chloride and vinylidene chloride. If desired, increase the number of cross-linking points, which are in addition to the cross-linking points of the amine compounds are to be introduced, so For example, unsaturated active hydrogen containing compounds can be added. Examples are unsaturated Amides such as acrylamide, methacrylamide or their N-alkyl derivatives and / or unsaturated alcohols such as monoesters of diols with unsaturated acids (hydroxypropyl · - or Hydroxyethyl acrylate or methacrylate) »If available a catalyst, a solvent and optionally chain transfer agents, an additional one takes place Polymerization of the mixture of unsaturated compounds " This reaction results in an amine-containing polymer, which is one of the components of the compositions of matter for the Electrodeposition agent according to the invention.

The polycondensation is a different type of reaction, whereby an eel-containing polymer is produced, which as one of the components of the electrical separation compound according to of the invention can be used. A polyester (or polyamide or polyurate or polyurethane) which is attached to has amine groups at its chain ends, can be produced by a polycondanaation reaction.

109830/1698

drive to the production of such condensation products η mol of a difunctional carboxylic acid (such as phthalic, oxalic, Adipic or sebaoic acids and the like) with at least η + 1 Hol of a difunctional, active hydrogen-containing compound are condensed in such a way that the the latter compound contains at least one mole of amine. Typical active hydrogen containing compounds are Diamines, alkanolanines and mixtures of dihydroxy compounds with diamines or alkanolamines ^ The general formula of such condensates can be expressed as follows:

χ γ -K ^ oo ^ -oo-a-oö7 _n χ υ

wherein X and Y denote a hydrogen atom or a C ₁ to C ₆ alkyl, Q denotes a (CH,) _a group and m denotes an integer from 1 to 9. The designation Z means:

- (NR ₈ ) - R ₆ - NR ₅

or - O - R ₆ - O -

or

... ο - Rg - NR ₈ ~

in R _{8 was} hydrogen or a C ₁ to C ₆ alkyl and R _{6 is} (CH ₈ ), in which β is 2 to 9 or a phenyl group.

Such condensation products can also be obtained in such a way that with tricarboxylic acids and multifunctional nellen active hydrogen-containing compounds is worked, with all or part of the active Hydrogen is an amine group. All or part of the chain ends can be amine functional. The condens

109830/1698

sation of these components can be achieved that the raultifunctional acids or their methyl or Ethyl ester with the multifunctional active hydrogen containing compounds are heated or by the fact that the multifunctional acid chlorides or CJhloro formats of diols in organic solvents with aqueous solutions of the multifunctional active hydrogen-containing compounds are implemented. Other Polycondensation products containing amine ends can be used in similar catfish are produced.

The blocked raultifunctional isocyanate is thereby manufactured that a multifunctional isocyanate and at least an atoichiometric amount of a monofunctional nellen active hydrogen-containing compound can be combined. The resulting blocked multifunctional Isocyanate has such properties that when heated in the presence of polymeric materials containing active hydrogen points, the multifunctional isocyanate reacts with the polymer, wherein the monofunctional active hydrogen containing Compound used to block the isocyanate is regenerated as an agent used to block the isocyanate Isocyanates are suitable are compounds which have a single amine, amide, lactam, thiol or hydroxyl group contain. Hydroxyl compounds are preferred Blocking agents and they become accordingly following Reaction equation applied:

R ₈ ^ N «(M) / _k + k RgCH -?

R O

109830/1698

where k is an integer of at least 2 (for example 2 to 8 and preferably 2 to 4), R _{D is} an organic radical that does not react with the isocyanate and Rq is a monovalent organic radical, either a Qj to Cg-alkyl , a heterocyclic, alicyclic or aromatic moiety in the form of a substituted or unsubstituted monovalent group which contains a benzene nucleus. Under dea used herein, the term "multifunction nell * is understood that the compounds in question contain more than one Isocyanatgrupoe on the same molecule ₀

The most preferred blocking agent for the preparation of the blocked multifunctional isocyanate is Phenol. Excellent results can also be achieved when using caprolactam, methanol and naphthol is being worked on.

Typical multifunctional isocyanates that are used are aliphatic isocyanates, such as Hexylenendiieooyanate, the trimer of hexylene diisocyanate, octylene, Diisocyanates, decylene hexalsocyanates, cyclonexyl triisocyanates, Oinylpolyraerisate, which contain isocyanates, and Xthylacrylat or Methacrylat. Preferred aliphatic Diisocyanates are compounds of the formula

N «O0

where r is an integer from 4 to 10, in particular 6 to 8. Typical aromatic isocyanates that can be used are toluene diisocyanate, toluene triisocyanate, di phenyl tetraisocyanate, and naphthyl tetraisocyanate, others

109830/1698

- ίο -

Iaocyanate compounds which can be used are reaction products of one mole of a diol with two Moles of a diisocyanate or reaction products of one mole of a triol with three moles of a diisocyanate.

Typical Petteäurearainverbindungen, which are all emulsifiers can be used by the following formula printed t

R ⁺ .

wherein each of R ⁺ , R ⁺ "*" and R ^{+++ are} independently selected from the group containing a hydrogen atom, a methyl group, OH ₈ CH _3p , (ΟΗ, Ο) Η and

, where ρ and t are integers from 1 to 18 and q. are an integer from 2 to 30. Examples of suitable fatty acid amine compounds which, according to the invention can be used are: Diethanolamine, Xthyldiethan Öl am in, Triieopropanolamin, "/ Ethylenediamine, Stearylamine, N-ethylcyclohexylamine, 2-ethylhexylamine, soybean amine adduct with 10 to 15 moles of ethylene oxide, stearyl araine adduct with 40 moles of ethylene oxide

A blocked multifunctional isocyanate compound is added to each of the amine-containing organic polymers, so that the weight ratio of reactive groups of the amine-containing polymer to the blocked Leocyanate groups is about 2/1 to 1/5. The received Mixture is then dispersed in water, usually with cooling, around the cathodic electrodeposition material

109830/1698

Composition according to the invention.

Typical preferred cathodic resin compositions made and used in accordance with the invention are as follows (all parts are based on weight, unless otherwise specified):

TABLE I.

Ingredient Quantity ( parts by weight)

minimum maximum before

1. Cation! See 8 polymer; 20 95 60

Reaction product of 75 to 95 crew «« parts of the monomer that contains no ionic charge and has no active hydrogen, such as ethyl, methyl, butyl or octyl acrylates or methacrylates with 25 to 5 parts of one unsaturated amine, such as t-butylaminoethyl ethacrylate "

2ο Blocked Iaocyanatt 5 70 20-40

Reaction product of one mole of dioyanate with a molecular weight of 150-3OO and one mole Phenol (or triisocyanate (MoI-Gewe 300-45O) with three mol Phenol);.

3rd organ lahe β Löatm gsmlttel: 30 200 20-50

A ketone or ester ether or aromatic hydrocarbons

Oemäes of the invention will be the. amine-containing positively charged polymeric organic flooring compounds by mixing the blocked multifunctional isocyanate compounds with the amine-containing polymer in weight ratios from about 5x1 to 1 s 3 obtained.

109830/1698

for example E · 3 a 3. g acid neutral:!, si art vicrden. «change di ^ ae Xn is deposited in an amount which is sufficient to with about 10 to 100 f> the theoretical amine value ö.ee amine-containing polymer ! sats au respond-. i) ^'s .e mixture is stirred and the M'uorrang one small amount of water v / ith the amine-stop * gen polymer and blocked., rnultilfunktionellen ϊaonysnatYerbindung "added" to these κν. • improve or modify CSU' and can ea other substances may also be added, such as pigments, Diep fillers, ssusätzXiche v ^ asserlöaliohe or in ^water: rglerbare harae (such as epoxy resins, _ζ ώ Β ο, the polymeric reaction products of Epj tiiilorhydrin and bis-phanol A), powdered "metals iiüWa fienn dex ^s Gleoharsphase is added (in i'olgetide.u al "oil phase beiaeiühnet) water, firstly beeir AHT-the-mixture of a Wassar-in - Ö3. emulsion cont in the · the 'Ul Xn represents inuierl. iohen phase is present on the so-called _t Umltehrpunkt kekren the phases., wherein the Yiasaer the continuous phase and the ö.l the diapergierte phase "the resulting Stoffauaaxamenoet can ung ^ are then further diluted with water to βληβ composition resulting au n, which contains about 5 to 23 ^ _5, preferably about β to 15 GeWc- $ solids »a; In the. dispersed in an aqueous medium to provide a cathodic electrodeposition composite solution,

Another method of producing the 'oil- water emulsion is that the oil phase is slowly mixed with vigorous stirring (for example, using a stirrer with high gas resistance) to the water conjugate5, which neutralizes the required amount Acid contains »The rope size of the emulsion obtained in this way can possibly be further reduced and it was by homogenizing the emulsion using

109830/1698 BAD ORlGiNAt

- TH.

suitable colloidal bowl ,

.aoexamples of "synthetic organic polymer!" eaten, dta by heating, by free Radikalkatalyae or by 'ionic catalysis of the specified ingredients swecks Herötellung the polymers geiaäas the invention • use can be X, are in the following table XX auaainmerigeottiJtl-t ;, wherein it should be noted that one Amlngruppe the Groups -KH ₂ and -F-II are included and all unsaturated peaks of fvalonzen over Kohl% m-8t off atom »aa the polymer! satmole'kü] .. bound yes

Components of the amLn .-- quantity

Beaeichiaung containing polymer! Eal.stoff- ■ (G-ev / c .--- ^ beaogen

on polymer ■■

A ι, K thy! Acryl at -35

2 c methyl methacrylate 40

3 > t '-' Butyl am inoäthylmetJk · acsry-

la'ti 25

100

: '... Ko shylmetbacx'ylai; ^ 5

'4, styrene J: C

4- t-Bvitylaminoathyi -

meth acryl at. eat

Ö - 1, A ^; ;: iiy '-. ac: rylat ■ - ^V O

> o Ma ijhylmetiiatiry'J at -Uj

"5 .. Siyrol J.C

4 · / HydroxypropyJmcthacry.la'ii 10

5- DlaiethyJ.atninathy: 'r (ioi; hacryi at; tO

ges & .Vi \ 1OG

, ft *. 109830 / 16SB

J [I

Components of the amxn-
containing polymer!
add srnni e η set ζ ung D;: iuisthyltereplitha "'a I go »aiii: Vinyl acetate Π ο ng «
[(rev ;, - fi lie · '
on / 'olynierlsu,: i
tr ij et: e ußßw}, oh fc j Ί_ 1] r iae thyl ο 1 pr op a η Dibutylmaieat 4 i _f 8 2, ti, Iv -Dimethylathenolamln t-Butylaiainoäthyltßethae% "yl IB, 7 ■ 5- St anno oc: oat Butyl peruclate 4, 3Ji ί sobutyl ketone riodecsyliaeroaptan O ₅ T 5,:. toluene .,. ^ Q Batanol ICO ₅ O # Io - ::: i _; 8th 2, ••• 6.7 at IC, 9 4, r> = 0.3 6, 7-

00.0

According to the invention, the particles d .-) a · -m ^! , r'lial "uigoi .. orgaaiechen B» lag; nater: 5al3 hergti £> v .->; ·. · '■ - würlea ... iir lii · Komol nieren von 40 ööw -> - $ eir ^ r -viny) po'.ymeri abarenciv iwi'n hal * 'iigen unaffected Veruindi-'rgj C to> 0 n -; -; w .. / ^f - ii: -nftr vlnylpolymeri3i.6rbaTöi'i unsättiglea a; 7dvojc, yyo .v.-b ': nc-aiig od. «r imgeaä ^ t.ig ^ en Aci'.kVviivoiiidru.j anc' ^!. ra ud (-iet-iri.-.- '.3Ui *.? η: . 'clr'i:: uiiiisch (; n imgöBätt, Igten Varbinc UHf _3. Λ ^ r;; · γ λ & ^ οϊγ. Ιΐ above j? .vei of places Ίη!;, d? e ωί "^;> J. so ^ ai ^ att-r 're ag "^ eu kannnon _o Die Te * lohen deu am content i. gen ^ r ^ s. nx ^ A ^ r? B« ag mat β rl ale konn ^ u au π atner combi na'j \ αι V'ni ^ ■. ■■ ■: <40 G-öw. an area contenti.gea unsaturated verbs ro'ung- ■ · ..:. ^ ^ a wii.- ,. Vi.nylpolyme.rina -oJ.on goer 'g / iet is, C b; i; .i - ;. ^r ; Ci -v /; / ■ y''ni ·· saturated v.n Hydroxyvör'bxndung o-'t.ir - "a ^ -yHä-fct-i ..:;. «« Amid.

10 9 8 3 0/1698

BAD ORtGIf ^ AL

• ■ •• .iro'vidMi'gj djt- au 3: 5 na? VinylpoijTaivri sation suitable i «i and mruideaböiia öiner .icmiaoh unsaturated: - gten connection, the! Ν essential .free 1st vca S- ^ e ?! s that recifei against isocyanates :! onefähig öind, wolK-d the amine-containing unsaturated Vö ^ bijocluiigi Ü.L &% \ X? Vin ^ ge lpolyTuerisation ^v e-'gn '·' ¹ '. Is-j aäßgewstiXt' w.vü. from dfjr group "Beate starting from Amir enöan comprising polyamides _£ PoIyestern, Poljrester-ami to, I ^J oXyhaTustoffen and

ernäs * ^ Another feature of the invention is that

g des multifimktiGne3.1en laonyana-je used t selected'from the group consisting of Cris-, H- ■ 6-cyanatühe.K; yl) - 'OiUX ¹ ^ t. an aliphate see or alicy; * " ^J. see DüBocyanat with 6 to 20 carbon atoms or

len {preferably rn.it to au. Ll5 carbon and an aromatic di- * cdar triifocyanate, the X I ^ ö ": Benzoi.ringe containsl" ^1. , The lv.lock.verv · -? multifunktto-De ₁ I ¹ H Isoejanat can be selected v / erdon from the group beai'β be Ud auss

■ (a) eanern KoMeiisatipnsprodukt τοη one mole of a diol with eiiii ^ a Molefeulace weight of 62 Ma 5 pounds i3O. and two hol

■ [>> · a condensate principle of a tripfilB with a Molecular weight from 102 "to 5000 and three moles of Diieoeysnat?

ίΐ ^Λ once a copolymer, produced by Viny! polymeri aaticm -from ^ - to? 0 G-ew * ^ C5 - anatoäthylac3? yla1i or metliacrylat iind a Bleekisrungsmitiel _s selected from the group consisting

SADORIGINAL 109830/1 698

(A) an O ₂ big Cq aliphatic or all

cyclic alcohol?
(, B) phenol?
(C?) Oaprolactainj

(D) an O ^ to C _ß aliphatic amine and

(E) an aliphatic amide

A special bath of liquid can be poured onto a heat-curable, hard-like material with a molecular weight of 50 to 20,000 in amounts of up to 50 % by weight

the weight of the mixture of amine-containing organic Covering material and the blocked multifunctional sonell Contain isocyanates, the heat-curable bar κ airfei ge Material is selected from the group baatehene au ^ s

(A) polyepoacydone;

(B) Tel? / Sulfides $ and

(0) Formaldehyde condensates of phenols, urea en ynd MelaaiSnen-

The ioneil s for the preparation of the blocked isocyanates iixiltifunkt Isoeyanat used may be selected v / ground from the group consisting of W iris - "(N'-6 - _{cyanatohexyl)!} -Biur <rc ₁

an aliphatic or alicyclic diisocyanates having 6 to 20 carbon atoms or Esterradikalen vorsugsweiae {zn with up 25 carbon atoms); and an aromatic di- or triocyanate containing 1 to 2 bensol rings

Typical in the heat-curable resinous materials which can be used geraäss of the invention, be sitting a molecular weight of JOO to 2O _n OOO and they can be used in amounts of up to 50 wt _o j £ be so-called s on dia mixture d "ö on containing organic covering material and

109830/1 698

BATH ORIGINAL

- it -

of the blocked multifunctional isocyanate can be used, the liquid bath composition according to the invention can contain organic or inorganic pigments in amounts up to 40 % based on the total weight of the organic film-forming material.

Cathodic electrodeposition can be performed by inserting the object in question into the cathode aqueous bath medium is immersed, which the positir charged cathodic electrodeposition substances - * '

Settlement according to the invention, an electrode being immersed in the bath as an anode. The object to be provided with the electrodeposition is then immersed in the bath in which an amine-containing organic coating material with a positive charge combined with a blocked Isooyanafcverbindungen is diapered, whereby sunäoh-st a first electrode is kept in intimate electrical contact with the bath as an anode and a conductive object is immersed in the bath as a second electrode, at least part of _{which carries a negative charge as a cathode P} whereupon an electric current flows through the Electrodes is led and on this *

Whiteness on the immersed electrically conductive part of the The object is electrodeposited, whereupon the counterpart provided with the electrodeposition Stand is heated to a water-resistant cross-linked polymerized to give the surface of the pavement «

The invention is explained in more detail in the following examples, without being restricted thereto.

^BATH

109830/1698

S ^ akjfcio ^ satoiVfö wt. - ^! lh

Met.hy lma thaor y lat '00

3 ο t-Butylaminoathylmtrt / hacrylat *. * · 0.

4., Äso- bis --- (ieobatyronltril) "ü

5 * ButyXiaercap-iropropionate -Si:

6 "MefchyläthyJJ ^ ti'Gon-LööungsiQlttel 44 ^! >

Implementation. jier_. Jlol ^ mer isajji oru_

The component 6 wii'd In a 2. ' fasriabnriee avc ·; G- ae Oo e! '. Ehende8 reaction vessel introduced _} daa with c.:iL\cjr stirrer, thermometer, condensate'i'. οΟ.'οβΛζ''ύ ·} oh'car and i) provided in a nitrogen inlet tube -,. a'c, DaB Vo -iun ^ KmIt If: 1 is under a piece of st ο ff atmosphere under V "er ',' , ο ι dung a Heisiaante'.la to 80 ° O erwäz'iiit and including '.. U oho genami: ·;:.; ί Response / ionastoffβ sti ^ DTS n in the course of 5 ^ 4 Jb ^3tund; iη a "j .: L gradually auge set at .. After the addition is finished, <l; ^{ .a Har ^ .- ogi.-n held at 80 ⁰ O for a further 3 to 6 hours, then abgr-ilrühi. i and bottled.

Amine content A ge Polymer iaat Substance 2uaainmen set

I. Methyl methate trylate 600

2 c butyl aorylate 2 ^: j0

3 ^ t Butylarainoäthylinathacrylac 150

4. Meroaptoethanol, Ό

5 > » Asse-bis · (isobutyronitrile) JO

6, At hylenglyicolraonome thy lather 69 *>

BATH ORIGINAL 109830/1698

.Dr_vchfuhrung dwr _Pol ^ grijsa & 1_οη ^

SämT, 3.iolae six Reactionssteife werdU.i in a £ 1 sive SS3, u ,, ^ öaktionsgefäijs of Example 1 introduced the tenses' c-iir w: .rd at 15 ° O increases, and the "iVärraaquelle is then removed throughput e ^ otliarniischß WärraeeabYackluag increases the

temperature to "βθ * 0 and is' held here diu * cii external cooling hour" after which dsim df "äiieeere Wärmeciuelie e; xmd attached lac iemperatur the 2 Ms EO 5 hours ⁰ G gehaH-en wird-

Hegtet j oaaet offe gew, _:: T_eile

3 :. SthyJ acrjlat 1500

S ₆ Methyl hate acrylate 400

3 '' styrene 100

4 · - Hydroxypropyl methaeyy XaI- 100

υ ». Diethylinomethylmethaex'yla'i; 100

6 .. Butyjffiivroaptüpropionat 30

7 .. Az; o b-s (iacisOiiyronitrii.! / IO

B ο. £ butane. "". .- 425

Ba is carried out in the same manner as described in Example 2 ^ ^";

10983 0/1698

Quantities and

1. Phenol 468 g

Tetrahydrofuran ( ¹ JiEF) 126 ml

2ο stannous octoate O ₅ 28 g

THF 6.3 ml

3-> Tri ~ (i so oyauathexyl} - = - biuret 921.2 g

THF IYO, 6 ml

4, THP 94 ml

The reactants (1>, and (2) are introduced into a J idter summary Rwndkolbenflaeche which equipped with einor stirrer, condenser, thermometer, addition funnel and a GaBeinlassrohr ISS · :; Lind to below 35 ⁰ C cooled, the reaction substance (3) is then reacted rapidly and the temperature was ^{kept below 35 0} O by cooling. The dropping funnel is rinsed out with the reaction substance {4}, which is then added to the reaction vessel. The reaction is exothermic and the temperature rises to 50 within about 40 minutes ⁰ CL The temperature is kept at 50 to 55 ⁰ O for 1/2 to 1 hour, if held by further heating, then increased to 70 ⁰ C and held until a 0 ß> isocyanate value has set « which is the case after about 2 hours.

109830/1698 ^aAD

BIoσki arte multifunction ella Iaοcyanatver bi invention reac tion nsstoffe Meng s ^

1. Trimethylolpropane 53.6 g (0.4 mol)

dry 2-butanone 93.7 g (116.3 ml)

2 _a tolylene isocyanate 208.8 g (1.2 mol)

3 «. Phenol 113.9 g (1.2 mol) 2-butanone (dry) 72.25 g (90 ml)

40 stannous octoate 0.4 g

2 butanone 16.0 g (20 ml)

Working method:

fa) The reactant (1) is filled into a 1 frlterkolben equipped with siner stirrer, condenser, thermometer, Zusatatriehter and a nitrogen inlet tube and the reaction vessel is heated to 45 to 5O ⁰ C j

(b) the reactant (2) is added over 1 to 1.5 hours, the temperature is set at 5O ⁰ C.,

(c) The reaction is continued until the Pro ζ entgehalt of isocyanate (WOO) # 15.4 by weight, which is the case after about 2 hours, and then cooled to 3NC ° C; Cd) the reaction substance (3) is added and the reaction is ^{carried out at 7O 0} O and held at this temperature for 4 hours? and on what

(e) the reaction substance (4) is added and the reaction is continued until an adjustment of O # NGO, which is the case after about 25 hours »

BATH ORIGINAL

108-830 / 1608

Ji! LiiMi '^ £ ^ i; 2Si3a§, .l2 £. ^ I.? A- ·' ^ Y / lVJ ^ JliLVi !; ^

Manjreu

.1 Oaprolaetam 1700 '.f.V' J «

2, methyl ethyl ketone 1515 ΐ ^. · '1β (14:56 mJ>

3 'l'ris- (iaocyanatohsxyl)' - biuret 2920 Toils

4. Stannous octoate 1.46 TeJIe

5. Methanol '48 parts!

Working method:

The caprolactam and 500 ml of the ketone »are in eir.e: ·.» 5 liter round-bottomed flask which is equipped with a stirrer, Stickstoffeinlaasrohr condenser and dropping funnel "The Roaktionsgefäas is heated to a temperature of 6O ^fl 0, by a Wärtu * coat during which time the stannous octoate as a solution in 40 NIJ Kr. is added inn solvent "Dan biuret is dissolved in the remainder of the solvent and heated to 80 ⁰ G wU'd this solution is added to the reaction vessel over a period of 1/2 hour augesei.z" t · Bi β temperature and this maintained until the percent isocyanate content is below 0.1 fo, during which time the methyl alcohol, eye is wlrdo After course of half an hour will obtain the blocked multifunctional isocyanate product.

EXAMPLE 7

Elektroabscheid ung ^ composition

Components Quantities (Clew ₀ parts)

Ι «Amine-containing polymer solution of Example 2 (60/6 non-volatile material, NVM) 600

2. (80 t> HVM) phenol ^ blocked a? Ris ~

isocyanate according to Example 6 ._ 338

3 ο epoxy resin 2/0

4 :. red iron oxide in dispersion K) O

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BADORiGlNAL

Artoitgweipc ^

DVE components (1) and (2) are at intermediate Geschwln "digksiten homogeneously mixed, after which the component άεχιη \ 4) of the j'iisclrung is added under high speed clock: Sine sufficient amount of acetic acid is added to the _t AraingehaXU up to ICO φ to neutralize the theory *. 100 parts of deionized water are added at high stirring speed, whereupon the epoxy resin component 13} Su is dispersed in the mixture. Deionized water is sucked to give a 30 NVM bath which is used to produce an electrodeposition according to the method of Example 9, which is still to be followed.

EXAMPLE ^ a

Elektroabacheldunga composition of matter

Components Quantities (fieWc parts)

1, alumina-containing polymer

f? e ■ #. lm / t) of example 3 1,073

2c phenol blocked multifunctional isocyanate compound des
Example 5 (80 f> JSVH) 313

egg

The constituents fl) and (2) are mixed with moderate stirring "

ml Ve iti Kinder ^ fina-ischt, - whereupon acetic acid (50 f> des ^;

thoo ^ et'Ji ropes. Amlnwertee) and water added? / Ground to Bi.nr 15 # i.ge. Eraulsion au devoted Electrodeposition nrfsj IGT according to Example 9 = The obtained ge in the heat · - ^1-Haeri rfce Äiia 'is smooth, hard, glossy water-resistant and ·

Original

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EXAMPLE 9 Electrodeposition composition of matter Ingredient Quantity (parts by weight)

1. Amine-containing polymer solution des

Example 1 (£ 70 NVM) 713

2ο phenol-blocked triisocyanate

(80 / L NVM) of Example 5,375

3 ο phenolic resin solution (60 i » NVM) 333

4 ο titanium dioxide pigment 200 Note! The component (3) is a polymer! Mixture of the allyl ethers of mono-, di and Trimethylol phenols "

Working methodι

The titanium dioxide and part of the phenolic resin solution are mixed and ground on a three-roll mill. The paste is removed from the mill and diluted with the reed of the phenolic resin and the mixture of components (1) and (2). Sufficient acidic acid is added to neutralize the composition to an amine value of the acrylic resin8 of 50% of theory. Delonized water is then slowly added with moderate agitation to give an oil-in-water emulsion having a total of 10 # nonvolatile material. The bath is filled into a stainless steel vessel, which forms the anode for the electrodeposition. The object to be provided with the covering is immersed and a direct current with a voltage of 100 to 200 volts is applied. After one minute, an object provided with the coating is removed from the bath, rinsed and ^{subjected to a heat treatment at 110 to 20O 0} C for 15 minutes, whereby an excellent adhesive electrical coating is obtained.

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äAD ORIGINAL

EXAMPLE 10 Clear metal precipitating substance composition Component Quantity (Gewo-parts)

1. Amine-containing polymer solution dee

Examples 3 Io214

2ο phenol-blocked triisocyanate compounds

binding of example 5 185

3. Acetic acid 22

Ko Deionized Water 12,500 Working method:

Ingredients (1) and (2) are mixed with moderate stirring mixed together, whereupon the component (3) is added and mixed in homogeneously. Finally will the deionized to Waooer slowly while stirring vigorously added until conversion to an oil-in-water emulsion has taken place. The rest of the deionized Water is added to adjust the emulsion to a solids content of about 10 wt .- ^. The bathroom will Filled in a plastic tank, which contains stainless steel plates as anodes clamped to the rare. The object to be provided with the clear coating is immersed in the bath, under a tension of 150 *

Volt electro-treated, removed from the bath, rinsed well and heat treated ^{at a temperature of 125 to 20O 0 O for 30 to 15 minutes.} A hard, clear, glossy film is obtained which is resistant to the effects of moisture and salt.

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EXAMPLE 11 Elektro Absehe idungs-fabric composition

component Amount (gen 1. Amine-containing polymer solution of the
Type B 600 2. Phenol-blocked diisocyanate compounds
binding of example 5 225 3. Phenolic resin solution 330 4th Titanium dioxide pigment 150 Working method:

Work is carried out in the same way as in Example 9 and a pigmented sheet metal covering with excellent adhesion is achieved.

BBI3PIBL 12

BIe ktro separation »- substance« composition Ingredient Quantity (parts by weight)

1. Amine-containing polymer 10sung des Example 2 (60 * RVH) 600

2. Phenol-blocked multifunctional Isocyanate compound of Example 6

(70 t ÄVM) 257

3 60 jfege Melamin-Poraald ehyd ^ Hari-

solution 300

4 * red beech oxide pigment 280

Working style

(A) The component (4) and part of the component (3) is ground on a three-wheel mill, whereupon the The rest of the constituent (3) and the constituents (1) and (2) are put together and milling is continued for 1/2 hour.

(b) 6 parts of acetic acid are added and mixed well.

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(o> Deionized water is slowly added to to give a paste with vigorous stirring and around the Making oil-in-water emulsion.

(d) The electrodeposition takes place according to Example IO

and a coating is formed which is resistant to saline spray and wetting and which is an excellent coating for steel objects.

15th

BlektroabBcheldunga - substance composition I Ingredient Quantity (parts by weight)

1. Amine-containing polymer solution des Example 1 600

2. Oaprolactaa-blocked isocyanate compound according to Example 6 170

5. glacial acetic acid 63 al

Work »shows

Beatand parts (1) and (2) are mixed together with gentle stirring and component (3) is then added to the mixture. A sufficient amount of distilled water is slowly added to produce a water-in-oil emulsion su, whereupon more water is quickly added in a sufficient amount to produce a 10 *

Gew.-ji non-volatile material containing EIe kt ro abecheldungebad ssu result. In this «bath, steel objects are provided with an electrical coating according to Belaplel 1, which have a smooth, well-adhering slektro surface with excellent adhesion and smooth coverage in preserved under cut parts.

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- ze -

EXAMPLE 14 Blektroabacheleida "composition of matter Component Quantity (Grew. -Parts)

1. Fatty acid amine ⁺ 50

2. Hydroxyl-containing acrylic acid ζ

( £ 70 NVM) 70

3. Phenol-blocked isocyanate compound of Example 6 (80 f> NVM) 375

4. Phenolic resin (60 * NVM) 3OvO 5 'Russ 10

⁺ Distilled primary fjaurylamine, which contains 1 ^ C ₁₀ and 99 f> 0 ^ 2 or distilled primary tall oil fatty acid amine, which contains 1 S * C ₁₆ , 9 f> C ₁₈ (saturated) and 90 # C ₁₈ (unsaturated) «

Work «shows

The rues and part of the phenolic resin solution are mixed and ground on a three-roll mill. The paste is removed from the mill and mixed with the remainder of the phenolic resin and the mixture of components (1) and (2). Sufficient acetic acid is added to neutralize the amine value of the acrylic hair to 50% of theory. Then deionized water under medium agitation is slowly sugesetst to form an oil-in-Waaeer Emulaion-st 10 fi Pest off share yield. The bath is immersed in a stainless steel kettle which forms the anode for the electrodeposition. The object to be provided with the covering is immersed and a voltage of 100 to 200 volts direct current is applied. After one minute, the object provided with the coating is removed from the bath, rinsed and ^{subjected to a heat treatment for 15 minutes at 15 "> to 20O 0} C, in order to produce an electrical coating with excellent adhesion.

Patent claim ^: icha:

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Claims (7)

Patent claims: Method for producing an electrodeposition on an object, characterized by a liquid Bath composition in which the following substances are dispersed are: (a> Particles of an amine-containing organic covering material with a positive charge in combination with (b) a blocked multifunctional isocyanate, wherein a first electrode is held in intimate electrical contact with a bath anode, in-the bath as second electrode immersed a conductive object is, of which at least part of its surface has a negative charge as a cathode, then an electrical one Current is passed through the electrodes and thus an electrodeposition is generated on the conductive object, whereupon the electrodeposited article, after removal from the bath, is heated to one water-resistant cross-linked polymerized surface to produce the object. 2. The method according to claim 1, characterized in that that the particles of the amine-containing organic covering material are produced by combining 40% by weight of a vinyl-polymerizable amine-containing unsaturated compound, from 0 to 30% by weight of a vinyl-polymerizable unsaturated compound Hydroacy compound or unsaturated amide compound and at least one non-ionic unsaturated compound which is substantially free from the opposite Isocyanates are reactive » 10 9 8 3 0/1698 3. The method according to claim 1, characterized in that that the particles of the amine-containing organic material have an amine end of the condensation polymer contain, which is selected from the group consisting of amine-terminated polyamides, polyesters, polyesteramides, Polyureas and polyurethanes. 4 η method according to claim 1, characterized in that that that used to produce the blocked multifunctional Isocyanate used is selected from the group consisting of Tri8 ~ (N ~ 6-cyanatohexyl) - biuret, a aliphatic or alicyclic diisocyanate, the 6 to Contains 20 carbon atoms or ester groups and one aromatic di- or triisocyanate containing 1 to 2 benzene rings contains. 5. The method according to claim 1, characterized in that daas daa blocked multi-functional isocyanate selected; .t is selected from the group consisting of ι (a) a condensation product of one mole of one Diols with a molecular weight of 62 to 5000 and awei Hol diisocyanate; (b) a condensation product of a triol with a molecular weight of 102 to 50i ^- X) and three moles of diisocyanate and (c) a copolymer obtained by vinyl polymerisation of 5 to 50 flew, -5t cyanatoethyl acrylate or methacrylate and a blocking agent is prepared which is selected from the group consisting of: (A) a C ₃ to Cq aliphatic or alicyclic alcohol; (B) phenol; (C) caprolaotam; ! 09830/1698 »0 (D) a G to C _{8 8} aliphatlachen amine; and (E) an aliphatic amide. 6. The method according to claim 1, characterized in that the liquid bath composition is a heat-curable resinous material having a molecular weight of 500 to 20,000 in amounts up to 50% by weight based on the weight of the mixture of the amine-containing organic coating material and the blocked multifunctional IeooyanatB contains. 7. The method according to claim 1, characterized in that the liquid bath composition is a resin-like material curable by the action of heat, having a molecular weight of 300 to 20,000 in amounts of up to 30 o * w ₀ - ^ based on the weight of the mixture contains amine-containing organic coating materials and the blocked multifunctional isocyanates, the resinous material curable by the action of heat being selected from the group consisting of: (A) polyepoxydenj (B) polysulfides j and (G) Formaldehyde condensate »sates of phenols, urine» fabrics and melamines η. 8 * Method according to claim 1, characterized in that that the liquid bath composition organic or inorganic pigments in amounts up to 40 wt, - # based on the total weight of the organic film-forming materials contains " 9 · Composition of material for the production of with a Electrodeposition -decorated objects, marked 109830/1698 - 52 - by a bath in which are dispersed: (a) Particles of an amine-containing organic coating material β with a positive charge and (b) a blocked multifunctional isocyanate. ΙΟ »Material composition according to claim 9 for the production of an object provided with an electrodeposition, characterized in that the particles of the amine-containing organic covering material by combining 3 to 40 wt . f> an unsaturated hydroxyl compound or unsaturated amide compound which is suitable for vinyl polymerization and contains at least one ionically unsaturated compound which is free from sites which are reactive towards isocyanates. 11, substance composition according to claim 3, characterized in that the amine-containing · organic covering material is a condensation polymer having amine ends, that is selected from the group consisting of amine ends comprising polyamides, polyesters, polyesteramides, polyureas and polyurethanes. 12 ο St off composition according to claim 9, characterized in that the production of the blocked Isocyanate used for multifunctional isocyanates is selected from the group consisting of tris (N-6-cyanatohexyl) biuret, an aliphatic or alicyclic diisocyanate containing 6 to 20 carbon or ester residues and an aromatic di- or triisocyanate containing 1 to 2 benzene rings M -IMG H HNCKE 0 "L -INO. H. BOMt 0W.-IMG S SIAEaM 109830/1698