DE1720717A1 - Paint and cover binders - Google Patents

Description

A.nntrichä- @, ot: r fixa ,, i # sb ## t. # The Ejcfindumg concerns an elel_triech abscheidbaxa Anst! riche-oder ffibcrzuE @ sbind @ rwani @ e @ die eis iinucci Polycarboneltureh = 3rz and hereby dtwch ioriisiertcl # i Strnhlikig hiermI t copoayme2is -. Grbaro VLnyl Monomers at thlilt.

Although similar bandages can also be mined with an Ublicban solvent and boldly applied in accordance with the usual methods, they are especially useful for internal diners and aqueous solutions of ADi; .tioverhiudungen are suitable and are particularly suitable for use when circulating electrically soldering objects through electrically induced deposition. @like ßun that their Ahacheltie2ti =; practically directly proportional. to that by the bass z ", kytichen dem nt. tlt @ nx ...; i ehena @: n Giigenntand and one ge; cnllberr @ i, ah, @. @_dr i Ei.csirtroda going direct current. This bit line is next sic: A; = lii film ah, which unfolds an electrical Wiiteratand enhesprechead of the lows and whose training rate is therefore terminated at eiis # .r mazimalon strength for a given voltage. This Ptlme are virtually einhei of a practical strength, provided that there is a practically equal electrical induction when the work piece is coated on real surfaces, practically what is unsteady, I and I ground quickly into a non-sticky state by means of ostrich energy.

A variety of methods are known for making clay silozanes. These include controlled hydrolysis of Silozsven, Pbljuerisation a Biloxane -from lower Kolekulargewicht in the presence of a ltkoxjeilane, ümeetzuag of Silieiumtetraehlorid with an alcohol and the like .. Silozene, their preparation and their incorporation into organic resins are described in the American patents 3 154 5971, 3074 904 , 3 044 980, 3 044 979, 3015 637, 2 996 479 $ 2 973 2's7, 2 937 230. 2 909 549 vad 2 877 202 described.

The Anetrichebinderharze according to the Eh "findulf have cyclisohen in-your Molekularetruktur calibration tone and / or incorporated aoyoliechen siloranes dissipating Silikonbeatandteile, the excellent result of witterungebeetändigkeitseigenschaften erhalte- NEN Ubersuge, and have a sufficient number of olefinic a, B-Nichteättigungeeinheiten to a rapid oooolnaerieation with yinvl monomers, the tinyl monomersan more than about 1 and less than about 15, preferably more than about and less than about 1495 and preferably about 9 %: about 14 % by weight of the organic Bin4ers wear The erfindungsgemUe 811iko. 22U-Itixge Polycarbonsnvy eherz has a molecular weight above e-wa 1000, an acid number above about 30, an elektrisr -ie $ Äquivalentgevicht 3.m range of about 1000 to about 2C 000 and about 0.5. up to about 390 olefinic a, U unsaturation per 1000 molecular weight units and consists of at least 10 % by weight of a divalent siloacane et. Preferably, there are about 20 am about 40 wt .-% of the resin from divalent Silozanresten which may up to 50 weight amount .-% This Polgcarbonsäureharze have a molecular weight above above about 1000, advantageously in the range of about 2,000 to about 20,000 or more, about 0.5 to 3.0, preferably about 0.8 to about 2.0 olefinic a, B unsaturations per 1000 units of the Holexular weight, an acid number above about 30, atapielbweiee'30 am 300 u4d usual 40 am 12g, as well - an electrical Iquivgl.entaewicht ranging from et »1000'm about 20 000 voraugn- * weep 1000 am 3000th - The term "siloxane" used here refers to compounds the bonds - Si - 0 - Si - or - C - 0 - S1 - or se @ n -Si @ -O-Si-O-) Si- show, with the remaining yalenes ta nu are saturated by carbon atoms, carbon atoms, hydroxyl groups or an oxygen atom, which connects a silicon atom with a fixed valence of this type with a further silicon atom . The suitable Si.Icrn-io have at least two reactive groups in their molecular structure before they are incorporated, for example hydrocyclic or carbon dioxide groups.

The A.netri ehe- odei according to the invention! The coating binder consists essentially of about 85 to about 99 % by weight of silicone-containing polycarboxylic acid and about 1 to about 15 % by weight of yinyl monomers. the resin is a Kolekulargewicht above about 1000, a Säuresahl above about 30, an electrical Iquivalentgewicht in the range of about 1000 to about 20,000 has and about 0.5 to about 3.0 oletinische a, 8-Richtoättigungen per 1000 units having the Molekulargevichtea and at least about 10 wt .-% consists of a ready-to-use Silozanreut. Preferably, there are about 15,% = bie about 50 wt. Of the resins from Breiwertigen Siloranresten.

To prepare the resins read wen der..Zrfindnng to #erwendinag en ao elieotien 811osam01okälg contain rrorteilhaiter: travel at least 3 911iciunatone yes Koleiul with corresponding oxygen bonds. The preferred ncyolic 8iloxanes can be represented by the following general formula: Wherein n is at least 1 beträgti% a) a monovalent hydrocarbon radical having from 1 t.is 8 go: llenstoffatomen, preferably a C1 - C4 - Alkylres-t, or b) a monovalent Tolclenwsfleer "-stoffozyrest having 1 to 8 carbon atoms, preferably a C1 C4-Alkozyrest or a) a Hydrozylrest or d) a hydrogen atom wrobei at least two of by a% -Si-O-Si-g-binding getprenntenx groups consist of either b) or e).

The cyoliechen @ siloian molecules $ u of this use contain at least 3; preferably $ to 12 and usually not more than 18 silicon atoms per colectile with corresponding oxygen bonds. _ The oyelieehen Silozans can be in the form of a compound of the following formulas: I) 7rn, 8i n Ono marin n an odd ponAtive integer of at least 3, n ' = 2n and n " m n, as well as 1 a) a solid carbonate residue, preferably a C1-C4 alkyl rent or b) a monovalent carbon dioxide with 1 to 8 carbon atoms, preferably a Ct-C4 alcohol or o) a Hydrozplreet or d) a hydrogen atom, where at least two of the Z-Si-O- Si - = - bond separate groups Z either from b) or c). An example is given by the following formally : II) In, 3in 0n "where n is an odd poe" oltf rre integer of at least 5, n # = u + 3 and n " 6, 6 + 3 or 6 + rain a multiple of 3 and % are the meanings given under I. owns.

An example of this is the following structural formula: III @ 7 @, 81. Onp where n denotes 6 or a multiple of @ 6, n ' 8, 8 + 6 or 8 + a multiple E: of 6, n "= 8, 8 + 9 or 8 + a multiple tone 9 and I has the meanings given for I. An example is given by the following structural formula: or by a gondansati onadimereo, -trimerea and the like formed therefrom with the loss of water or alcohol.

III) ln, Sin 0n "where n is an even positive integer of at least., N 's n + 4 and. N" a 4 v 4 + 3 or -4 + a multiple fron 3 , novie X those in I has given meanings.

An example of this is the following structural formula where m the UM 0 vein a pon. -tt, in resin number. means. Y) x, Sin 0n " where n is an even positive integer of at least 8, n ' = n f 2 and n" = 11, 11 + 3 or 11 @. einhrfacher @. ann 3 and Z has the meanings given for I.

_ An example is given by the following structural formula: where m is a positive integer .

The eilikonmodifizierten resins in the invention keep corresponds at least about 10, advantageously weep about 15 to about 50, and preferably about 20 am about 40 wt .-% silicone, that is structures which are derived from siloxanes which have at least 2 reactive moieties derived .

The above-mentioned and further advantages of the invention result from the following description in conjunction with the accompanying figures, in which FIG. 1 shows a schematic view of the arrangement of a device embodiment which can be used for carrying out the covering within the scope of the invention, FIG. 2 shows a Schematic meilaxaicht of an embodiment of one of the two electron discharge devices shown in FIG. 1. 2 is a porspektivlache view of an embodiment goze ig teu device is used, Fig. 4 a gombinativu Ven ter-support grid and heat dissipation, which is a part of the device shown in Fig. 2, Fig. 5 is a porspektivische view comparable one with openings provided Fenaterhalterutgsbautelle, which serves as a frame for the sheet metal window of FIGS. 2 and 3 and holds this window in contact with the window support grid and the heat dissipation according to FIG. 4 and Feg. S shows a view taken along line 6-6 of FIG.

1 holds a drum support stand 11 the drum 13. The drum 13 made of a suitable non-conductive material, for example wood, plastic and the like. Unwinding from the drum 13, the sheet metal web 15 runs over Laerlaufhulzen 17 the same or different design as the idle whale of the Pig. 6 , which is described below. The idler roller 17 is rotatably mounted on a shaft 19, which in turn is supported by a vertical aging component 21. The shaft 19 is a non-conductor , and the idler roller 17 is electrically isolated from earth. The sheet metal material 15 läui't over the clusters or roller contact 23. The contact 23 is carried by a metal shaft 25 and is in electrical contact with it. In a first embodiment, the contact 23 is rotatably mounted on the shaft 25 , while in a second embodiment the contact 23 is fixedly mounted on the shaft 25. The shaft 25 is supported by a horizontal support member 2? held. The supporting component 2? represents a non-conductor and is supported by the vertical support member 21st In a first embodiment , the shaft 27 is formed from a hollow shaft . where part of the full 25 is in the wool 2? extends and is rotatably held therein. in a second embodiment , the wool 25 is fixedly attached to the end of the shaft 27. After the electrical connection with the contact 23 has been made, the adhesive material 15 is immersed in an aqueous bath 29 , which represents a diaper of the paint binders described above and below, water and an amino compound. The bath 29 is contained in an oversize tank 31 which serves as a grounded cathode of an electrodeposition cell . Dsr Tenk 31 is in electrical contact with a conductor 3 @ * which in turn is electrically connected to an electrical DC power source 3>. Also in electrical contact with the power source 35 is a conductor 379 which is again in electrical contact with the. Metal shaft 25 is above holder 39 and conductor 41. An electrical circuit is formed on these wines = that of the sheet metal. 15, contact 239 bath 29, grounded tank 31, conductor 33, power source 35, conductor 37, switch 39, Teeiter 41 and shaft 25 contains.

A difference of the electric: potential is aufreehterlialten between the sheet material 15 and the tank 31 that is greater than the Abseheidungsgrenzgpannung of the resin applied. The applied herein, the term "Absoheidungsgrenzepa = ung" or "threshold voltage" refers to the minimum voltage at which a Absoheidung an electrically wAerstühenden film of the overall resin added is started. This tension will vary somewhat with the resin employed and / or the composition of the resin-amino compound dispersion-forming mass. This minimum voltage is usually above about 5 volts and below about 20 volts. However, in order to achieve suitable dwell times for the fraxfe in the intended industrial coating operations, a voltage above approximately 50 volts is required. Usually this voltage is in the range from about 100 to about 250 volts. The upper limit of this potential difference is determined by the potential at which the deposited film breaks if it is held within the Hades during the dwell time . Again, of course, this will vary with the given resin, but the value is usually below about 500 volts. In the preferred embodiment, at least the majority of the films are electrically irreversible under the coating conditions, ie, with current reversal.

The sheet metal material 15 coming from the bath 29 has a continuous resinous coating of practically uniform thickness. The electrodeposited film is preferably subjected to radiation energy causing polymerization immediately after its formation, ie, before significant post-deposition dehydration occurs . The polymerization is gewöhalioh within a period zrisohen few seconds'm $ u, einigen.Minuten after the workpiece has left the bathroom, berirkt, .voraugs eat within a space of less than a minute later.

After the tiperzogene sheet material has left the Ubersugebad 15 29 na runs through the idle roller 43 from which a Ausflihrungeform @ 'enlarged in FIG. 6 is shown. The roller 43 is attached via bearings 45 and 47 inside and on the roller holder 49 . The roller 43 has a drum-like structure, i of a central shaft! .3-1, which extends through the bearings 45 and 47 and rotated therein, a tubular support member 43-2, which is fixedly mounted en the shaft 43-1 and whereby 43-1 goes, annular support members 43-3 and 43-4., which are fixed on the base member 43-2 at opposite ends thereof almost, are constructed to slide in advance of the th of the blowing material 15 ; the roll separating werdenlwodurch never pulled over the roller 43 comes to regroup. The contact between the sheet metal material 15 and the carrier components 43-3 and 43-4 should be kept at a minimum, since the coating on the sheet metal material 15 in this case has not yet hardened and is easily smeared. Therefore , these support components should be as narrow as advisable and have the shape of abrasive surfaces , whereby the contact with the sheet material is practically reduced to a line at the edges of the same . The idle roller 43 st non-conducting and tend dat isolated; B1 ecshmaterial 15 opposite the earth.

laughing passing through the Leerlauf`xalze 43, the coated sheet material 15 is between a pair of El.eirtronenausaendunge # -einheiton performed "which are mounted within the housing 51, whereby the Polymerieation of on the Bleahmatarial 15 electrically deposited coating will be bidding. A au this purpose, suitable Elektrononaussendeeinrichtung illustrating an example of Elelrtronenauseendungseinheiten within the housing 51 is shown and in FIGS. 2 to 5 discussed in detail in connection with the description of these figures. laughing the Durchgwag between the above aufgeftihrten 8lektronenauenendungseinheiten, the sheet material 15 whose it exerts beflndlicher, .c - ug zua KLE @ Arig free state polymerized # 3ier-t is wound on a AufaUmerulle 61 the roller 61 is made of a non-conductive material, whereby the sheet Substantive 15 is isolated gGgenüber the fade... Roller 61 is rotatable on a roller holder stand 63 befeotig- @. The roller 61 has a central shaft component 61-1 which is connected to an electric motor 65 . The motor 65 is in electrical connection with a power source 35 via conductor 67, Snhalter 69 and conductor T1: The motor 65 is also electrically grounded.

When the genünachte Me ng e 3n coated Mach material is received on the roll 6,1, the power source is turned off for all cycles, the sheet material 15 between ßehluoe 61 and roller 61 removed, the roller 61 from the roller holding Runge stator 63, a new take-up roll on of the ball receiving stand 63 is inserted, the sheet material 15 is attached to the new roll and the process is started again.

Even if in tens. 1 only L ^ white electron emission units; shown Bind, ic; z seP understandably that the speed with which the B- # echaacsrlal is moved through the polymerization zone can be increased by increasing the number of electron emission units used to polymerize the coating. In the same wines, the slope of the cover bath can also be increased: in order to allow an increased linear speed when passing through - ° u. The Mektronenaussenduni teinheit within the Gehäuenc 51 are in electrical connection with the earth via serene 55 and with the graftquGlI.e 7.5 via ': eitar 53, switch 55 and serene 57, as described below aueftii) rj.f.ea1. In Fig. 2 is a sectional view - the lower window of an Elok- tronenbeeeheleration.gimgsrohre® 10 °) shows that an IiauptgehMuse 101 with a cathode arrangement "0 r contains. The cathode arrangement order 103 consists of a% af, hcden housing 105 with a längli ehen opening 107, which extends over a main part of the upper side extends. the housing 105 is located a pair of spaced Samnlsehienen 109 and 111, between which Im electrical connection with it a Plural of wolfremdraht.Mden 1`3 is kept, which as Irstlio-- to serve. The opening 107 is i-on of such size and shape, that a hand of electrons emitted by the threads 113: be govicht in the celebration area. At Ausnhrein # gen using a% atr: r-otreblo can change a- the magnetic field ; ewanclt -r:; defi, u dgn Blektroraenat: ralcl so to calibrate the gc @ wi @: a @ -cht @@ Verte.f7.zuag of the markets at the FenetercLerfiänez #rreIcht wi: r3. Zn elekfiriec bei ° Vvrblsi- dung with the Sammai nehlenen 109 l Zv. 111 oteher cheerful 11J and 117, each of which is in operation with an electric connection the negative ikdotella e @ Mer e1 ektriechen G1 calibrate t: romkraft: - quQI.3.A stands, ie the Krattquelin 35 Uber cheerful 53, switch 55 and conductor 571 as kn compound mi j Fig. 1 beochrleben. The conductors 115 and 117 are insulated from the housing 101 and the housing 105. The energy released to the negative conductors 115 and 117 is regulated by conventional electrical regulating devices, not shown, so that a slight difference in the electrical potential, for example 5 volts, between the negative conductors 115 and 117 for the purpose of setting an electrical current through the threads 113 is maintained.

A conductor 119 represents the positive conductor and is in electrical connection with the 3, housing 101 and with the earth, ie via the conductor 55 of the pig. 1.

At the bottom end of the housing 101 by suitable Pentetelleinrichtungen such Schräuben, älareem, bolts and the like. Fastened is calibrated and a wäxmeabführunga-- äenstew-gslterungsgitter 121. D "grating 121 is shown in Big in detail. 4. When * is the AuefUhrunrgeform 4 .a® grating .'hiervon 121 of swab or vein or aluminum alloys and has a centrally mounted läugeeretrecke / calibration, .- la öffuaag 123. Bfne plurality of cross-members 125 is seated in:. ', Fitzen 127, and extends across the calibration Opening 123. Grid 121 also has a plurality of screw holes 129 to connect the housing 101 : with the penster holder® block shown below. 151 : The grid 121 has a circumferential notch 131 which is shaped so that there is never a line 133 for the supply o @ nor W.1rmƒaut3tauechflfieeigkeit.beiepieilsureiee Wagear, in ii.neauetaulac=ri'@eei'ohitng to the grille 121. Below the grille 121 there is the window forming window ibe shown in Fig. 3141. The disk 141 is made of a thin sheet of metal, which can be made of aluminum, an alloy of aluminum containing minor amounts of lithium, titanium, beryllium, magnesium and / or Thor, stainless steel and the like. The pane 141 forming the window is shown enlarged in FIGS. 2 and 3 in order to facilitate its specification and identification in the drawings . It is attached so that it completely covers the opening 123 of the grid 121 and extends a sufficient length further on each side of the opening 123 in order to be attached to the grid 121 by the pen holder lens 151. The disk 141 forming the penster is in electrical connection with the housing 101 and serves as an anode.

The window bracket block 151, which is described in greater detail in Pig. 5 is shown has a centrally disposed opening 153 of substantially gleichet Dimension and shape as the opening 123 and has a plurality of S3hraublöche: m 155. The opening 153 frames the window in a suitable wines. The screw holes 155 provide a means for attaching the bracket block 151 to the grille 121 so that the window pane 141 is clamped to the grille 121. The lenaterhalterungeblock 151, the window forming disc 141, grating 121 and housing 101 are joined bƒiƒstigt in the above-described manner, if necessary, appropriate seals, gaskets and the like., Not shown, are used, a vacuum tight seal Dess ren the unte- Bathing the housing 101 is formed . Also shown in Figure 2, part of the HN.echmaterials 15 of thirty. 1, which passes through an electron beam of the above-besohriebenen accelerator and a beam-like sound an equal accelerator which is mounted below the Verkettlckes.

The electrons causing the polymerization are supplied by the accelerated electrons in an evacuated tube, ie the tube 100 and) when the electrons from the tube reach the coating through a suitable shutter window, for example the window- forming pane 141 described above, the coating is polymerized.

In order to obtain a surface coverage, the electrons come out of the tube in the form of a ribbon and the object to be irradiated can be moved through the electron ribbon . The electron transmission unit described above is only one example of a number of such devices which are suitable for this purpose , for which reference is made to American patent steps 2,602,751 and 2,680,814 . The main housing 10'I, the window-forming disc 141, Feneterhalterungsgitter 121 and Fonsterhal.terungsblock 151 with suitable seals, locking devices and the like include, and defining a substantially gas-tight emission chamber! Is practically mized by unshown Meitungs- and gnmpeinrichtungen gaseva, for example, an air pressure down to about 1r5 mm Ng. The forming the electron window disk 141 by the pour even energy electrons from the Beechleunigungerohr should be as thin as possible, for example 0.0025, am, so that the electrons pass only with minimum energy loss. On the other hand, the pane 141 forming the window must have sufficient mechanical strength to withstand a pressure difference of about one atmosphere, since the inside of the evacuated mission ships is exposed and the outside is usually exposed to atmospheric pressure.

Although in the illustrated embodiment was to be coated 1% rkstücr from a strip material which is, of course, that the workpiece tann also consist of a series of Einselgegenetänden walking $ ugsbad by transferring while continuous to a dertiber .-- conveyor hän -. gen Hei such Aunftihrungefora are modified the positions of the flektronenbeaehleunigungeeinheiten according to the shape and size of the werkstleke, for example by mounting neitliehe from the path of conveyor belt pm hang- friechUbersogenen the workpiece. Can be mmeleinrichtungen of the strip material in a variety of ways modified by the functions of the respective devices shown is satisfied - is of course also, DA8, trap the workpiece from a palm material con- sists, the feed means, conveyors, loading devices and S #. .

With regard to the coating materials, "anatrich" by electrically induced separation is understood here to mean that the separation of finely ground pigment and / or filler in the binder, that is to say, the size of synthetic resin and oi.nyl monomers, also means that the binder is separated without pigment and / or Ftilletoff.oder only with a very low content rings thereon, said binder, however gewünachtenfelle colored leg can, and the other of Abacheidung waeserabaeinenden Oberfläehenftbersugemaneen that contain the binder, and which are generally analogous to e-mail, Anstriche- or paint brooms can be designated, with the overlay material. for such Abseheidung here as * An. This means that the binder, which is converted into an inherited film by the electrical separation and finally converted into a film that is permanent under normal operating conditions by means of electrons introduced by means of electrons, can jinagepamt or, in practice, all but no, what ss about the formation of the film wiz: i oder er can be used as Tttgerotuff for pigments and mineral fillers and; or other resins are used, whereupon he tricked: i # Wirkuni for the isolation of filming.

Basically unnterttci.e .. ie.aa the olliko = odified hair according to the Erfiuj.uiig from merely confessed Binderhareen I $ ääurah that 9iƒ SoWrahl ZueamuceA Can be electrodeposited with vinyl menomers from an aqueous dispersion as well as with vinyl monomers of this kind by means of actrons of relatively low energy, For example, 50,000 to 500,000 K electron volumes are deposited in such a film In,>., Polterielaräar Bind.

The invented bath for coating an anode by means of electrical indu2ie.v be deposition consists 3. essentially of an aqueous slide of a paint, the predominant part of which is the film-forming anode that binds an allikontigea polycarboxylic acid with a) a lolekulargetti (: rt above about s000, b) about 0.5 to about 3.0 alefinishe a98 unsaturations yes 1000 bring in the molecular weight, a) an acid choice in the range Drin about 30 to about 300 and d) an electrical equivalent weight swirchen about 1000 and about 20,000J with at least 10 oep.-96 of the same consist of a divalent 3ilozanreat, and about 1 to 15 wt .-% Pixjlwnomerer, based on the total weight of the binder, contains polyoarbonsgurehars in the aqueous dispersion with a sufficient amount of a water-soluble amino compound is neutralized, so that the Polycarbonsäurehars as anioni.- shear \ polyelectrolyte is maintained, whereby the zone Entration of the binder in the aqueous dispersion between about 0.5 and about 35 weight percent. Preference is given to the centering of the obstacle in the aqueous dispersion about 3 to about 12 wt. With regard to the bath 29, the aqueous dispersion contains about 0.5 to about 40% by volume of the dispersed binder material, advantageously from about 3 to about 12%. As a dispersion auxiliary applied water-soluble amine over- bond lies something in excess of the amount that is necessary Is to effect an intimate dispersion of the resin and to this the behavior of an anionic polyelectrolyte borrow . The optimal amount of arm turning aainoverbi, n- Jung ignores the number of skyscrapers in the Harz Mountains. Pslls of the received tene pf-Vert is sufficiently high, the bath 002 absorbs from the atmosphere, sow not - a regulation of the atmosphere is applied. The concentration of the imino compound or Anino compounds also affect the electrical resistance of the bath and was allowed to be excessive if the bath resists substantially below a value of about 500 oh »-m Mlt. The proportion of amine used is in excess the minimal to the issuance of a behavior of an anionisahen Polyelectrolytes for = iirti3 special binder resin or resin mixture required in the bath. Concentrations from about 15 to 5 "K times this minimuan turned out to be ßeeii @ Aet. D3: ~ spexifiochee resistance of the bath lies ahead. In the meantime, between about 700 and about -1000 ohm-cm. A higher Badwilerstend results a dfinneren coating at a given Potentlalunterechied and vice versa. It kMenen baths with a pH as low as about 5 am, and up about 10 sow been verwendrt. Vorteilhaftorxei se but is de.- pH between about 6.5 and about 8t5 and preferably between about i ', 0 and about 7.5.

The viasity of Hades is advantageously kept under a waiting rate of about @ 0 times the viasity of the water. Badtempera wuren in the range of 15 am about 5M facilitate retention of Badetabllität and verhindf, Tii a Poolymerisatian within the bathing.

The term "water-soluble ether compounds" used here is used in conjunction with ammonia and water-soluble ayaines. Ammonia jet is a more useful process for the partially neutral neutral tone of the acidic short or harsgemine less advantageous, since the working conditions are very useful and small increases are inconsistent The amines used oind .4m1.oA, the in essence of 20 cC to the extent of at least 1 tiev .-% of T, rUMUIV, Pie1 i rü n! _Nr7, cijid hi erz ug ch ö @@ A: x 11A3 -V9mi.ne and monoamines, such as Monoäthanolaaa3.n, diethanolamia, Triäthanolßmin, N-Methjläthanolausi.n, H-Aminoäthyläthanolemia, N-Methyldiäthsnolamin, "lonoi®opropsnolemin, Diieopropanolmin, Triinopropanolam.in®," polyglycoline C2 "], like for example ff40 # '2c3H6NH2, hyd:, - oacylamine, butanolemine, heaanolemine, methyldiethanolamine, octanolemine and allqrlenoaydreaktioneprQdukte ton Kono- # and polyamines; for example a rejection product of iti @ ylendiemin and d, heuryldoxy with itbylene oxide Ithylene or propylene Ithjrlendiemin, diethylenetriamine, triethylenetetraein, hexmethylenetetremin, tetraethylene pentamine, propylenedimine, 1,3-diaminopropane, imino-bis-propylamine and similar compounds as well as mono-, D1- and trismines with lower alkyl groups from C1 to 089, for example mono-, Dl- and trieth'lamin.

To replenish the carboxylic acid in the bath as the operation progresses, additional binder concentrate is set continuously or proportionally. This concentrate can, if desired, contain such substance. For easier diepreading , the concentrate is "rorteilh &ftet" in the pore of a concentrated aqueous dispersion, which, called a pigment and pigment base, contains about 50 to 95 % by weight of a polycerbonic acid resin (pure or extended) and about 1 to 10 (km .-% based on the weight of soluble Aminverbindungeng the Polyc & rT) oneäureharaes containing Stimulates water. The Axsdr'.c: e "Stralm.iangi '," ieniF3ierL-nde radiation "and" Strahlungsjnergie "mean radiation with a minimum energy of 50,000 Eledteo: 3envclt or an equivalent value to it. The'>> preferred The method for hardening films from the present Ausichn'Underu on the original layers, on which they are applied, consists in that such films are subjected to a beam of electrons which cause the polymerization, which at their point of emission, ie

.ektronenvolt upon exit from the Xlektronenfenater, within the range of from about 100 000 to about 450,000, preferably about 200 000 to about 350 000. Z) or an equivalent value do this.

By changing the distances between the electron source and the film with respect to the potential of the beam, the difference in the rate of polymerization with respect to depth can be minimized. Within the potential ranges listed above, it is preferred to maintain a minimum voltage of about 25,000 volts at a distance of 2.5 cm between the emitting device and the film to be cured. According to this method, the distance between the emitting device and the film on the workpiece can be varied by about one to two centimeters, the minimum margin that is compatible with the contour of the workpiece. Common is; ahn distance of 'about 5 to about 45 cm. The most effective. Correlation of the space distance with the Ealasionspotential Wizd increas-en: vIchtig old an increase either the distance or space Filmtie.fe. Hei the narrower intervals are the voltages at the bottom of Bereichpe used with success. Higher inne- # half of this range have been required at larger distances permissible ge voltages to give the depth in the desired GlcichmäBigkeit the Polymeriaationsgescliwindigkeiten regard. When operating in the range of about 200,000 to 300,000 electron volts, advertising the distances in the range of about 5 to about 30 cm preferred. Although the tolerance varies somewhat with the Pilmzusammensetzung upon exposure, the time the films required to achieve a virtually complete polymerization at its maximum depth should usually not be greater than twice the value of the time for the polymerization of the leichtesten poljmerieierbarea part of the films is required . Since this is preferably less than 195 times the ßeitrauures that for the first polymerization & sielung required ist.'Die.femperatur of the fungi may not eo high leg that significant evaporation of the most volatile components before or the same takes place during the Polgmerisßtion. Within these limits ER- located dosages reported from about 0.01 to about 15, preferably from 0.1 to 10 megarads / sec. as suitable.

The term "wheel" means a dosage of radiation that results in the absorption of 100 ergs of energy per gram of anti-inflammatory agent, ie film coating. Particularly suitable poly aarboasäurf, ngrze or- harzgemieche are composed of Aorylmononeren. The term "! Vrflmoncmere" means a mono a.8-unsaturated monocarboanic acid or fete? The same and includes, without being limited thereto, acrylic alxre, alkacrylic acids, for example methacrylic acid, esters of acrylic acids and rylic acids with monohydric alcohols, for example glyeidyl methacrylate, 2-hydroxyethyl acetate acrylate and the like.

The Sguretebl of the resin without noticeable anhydric groups can be determined with ION according to the ASTM standard method 555-54 . - all a noticeable number of anhydride groups is present, - the acid number can be determined by adding. A sample of 1.5 to 2 grams of the heart parts are heated under reflux for one hour with 50 ml. of an aqueous 5.0 n-EOH and 5 ml of pyridine, then with 0.5 n-HQI, Z = phenolphthalein endpoint is titrated.

Another preferred group of Polycarboneäureharzen are heart of the polyester type. The Dicarboneäuten used for this purpose, or. Anhydrides can be both aromatic and aliphatic . The extent gewUnechte en o3 efiniecher Nichtngtti.gung is egg npol ymerleation unge nIlftigter Carbonoäan, Beinspielaweien mal.einsäure,: @ einriiurennhyäridt ntmnr..päure fetraäydroplthal ßliure and the like. Achieved. This can also be done with unsaturated aliphatic alcohols, like vinyl or all.ylal.kahol, etherified higher polyolet both will. The electrical louivaZ.entgewizh 'a given resin or Harzgemiechee is referred to as the amount of resin or Na "mixture, each of the energy used elektrin.ohen hargd under the following conditions operations abeaheidet calibration. For this purpose, the value of a farad in Coulomb herein to 1V7,88 (atomic weight of silver) @ 0 001 118 is (grams of silver, which are deposited by a Coulomb from a silver nitrate solution) taken or 96, 493rd Thus there has been cH, trap 0.015 grams of coating deseen * Änteil to Binderpolycarboneäurehsra 90 wt .-% in years, and the remainder thereof from the used for Diepereion in the bath amine compound is, Ubertregen and Au of the anode for each used "Ooulorb in the method deposited , the electric Iquiraleatgetioht the. Resins about 1303 or 0.01s z 0.9: 107.88 a, ooll @ e. Star Neck the. banish further disturbances - the electrical Iqui- » Leatgrwgt a seaside Pbiyoarbonnlitrebsrses or @ drers.nahen easy and convenient with typiselmn V «tbe- conditions are found if they are set up as follows become: a lblycurbonharskonaentrat will dureb at 65, S6 #C pendiiohee mix 50 ßramm P blyosxbonebuureäera,. e Graus den.tillierten Vaeeer and Diin.opropamla u in in such Amount, so that a pB value of the Harsdiaperrioa of 7.8 or slightly lower after the concentrate to a 5% -iae ßars »naentration with specially distilled water # dwmdit results. The concentrate is then 'to one liter Dilution with additional itilliertem of-water so that a calibrated 5 96 - strength resin concentration of Disp obtained Iraion are ER-. If an insufficient amount of amine has been used, the pH value of the apero ion is below 7 "8 , the pH value is brought to 7" 8 with a small amount of diisopropanolamine . The diapersion is poured into a metal tank, expanding wider visual walls practically parallel and at a distance of 2.54. cm from the surfaces of a thin sheet metal anode . The tank is connected as a flleicha tromkathode and the direct current anode is a 10.17 c * wide squared of 20 cauge, which is immersed ire the bath 7, & 2 cm deep. At a bath temperature of 26967 IC is EIA tlleiuha trom therein rend of aer de anodes to the cathode 100 by a minute VnIt ion an external power source. wigelegt, whereby the 8trorantd.rke Jtroh using a voulometere is measured, and the current is then switched off. The Amden plate is removed immediately, topped up with distilled water, baked for 20 minutes at s -1761.67 IC and then weighed. Ba will tell that aibotliahea volatile Naterisl, for example vasear and amine , are removed for prsürtiache purposes from the hilm by the baking. The difference between the weighed weight of the fresh Ineohes and the end stock of the baked Bleohee, divided by the coua, ombe of the current used times. 101.88 and divided by 0.001118 gives the electrical equivalent of the resin for the purposes of the present invention. As "vinyl monomers", all of the conventionally reactive vinyl compounds which are usually reactive to the a: ts conomers can be considered. Your Pltichtigk-ince nIaht use in the invention ausNOhließt. Blow Urylchlorid md similar compounds are iasbesordere the above auigefßhrten "acrylic monomers" as well as Styral and its derivatives such as lliqrletyrole, he rv traktorra neighborhood, as a mixture of two or very such Terbindungen suitable Hls Binderbeetandteil. These vinyl monomers are preferably from about T to about 14.5 wt .-% of the binder. Mixtures of styrene are particularly good and MethyL, -nmthacrylet, which, preferably in amounts of about 9 to 14% by weight of the binder used in primeval earth. Is preferred even if the conomers represent the acidic, silicate, unsaturated loosen te Polyoarboiylhara. In the following there have been examples for r ülersug @ wsterialiea, which at the prairtlechen lae Führuag of the 1l @ tit @ dmo @ etageeetst Verden given. .8eirt @ iel 1 Am silumodified Pdlyaarbonsäurshars P blyeottrtyp / was made from the following components a Get Gram ml Maleic anhydride 0.63 Tetrahydrophoric anhyaride 1s61 Neopentyl glycol 2.48 Polysilozane (25% by weight) 17590 % ylol 70 Bydroquinone 092827 As a Pblyoilosan.wuräe available in trade (Dow Corning 8-6018) cycliechee Polyailozan with hydrorylfhnktionellen groups of following Zigen chat verwendets Hydrozylgehelt, because Stark percent kondensierber 5015 "f" i. 005 Durcheohnittsmolekulargewicht 1600 Yereinigungegevicht 400 Refraitioneindez. 1j31 ble 1v539 8rrsichuagepunkt after Dnrran .-Qüeokeilbernethode ec (10F) 93 (200) Mir60% l , ejetofi idol Specific dish at 251V 1.075 fiekoaitäg at 25 ° C, Centipoiaen 33 Gerdner-Holdt 1-1 glycol, Polysilox.a and% ylol were in a four-neck flask of one liter brought to a temperature of about 160 bie about 16511C for about 2 hours under Rtltren Stiokstoitatmo®phäre and heated. the Reaktionegemise was abgekOhlt to about 125 to about 130 aC, Maleineäureanhgdrid, Tetrahydrophthaleäureenhydrid and $ ydrochinon added and the temperature slowly to about 190 increased to about 200 4C , where they then for about 3.5 hours to an acid number of about 47, 'T g was kept. The heating was then stopped, the xylene was stripped off, and the mixture was cooled to about 80 ° C. About 45 gram of styrene and et "45 grams Nsthylmethacrylat. were added as vinyl compounds. The acid solution of this binder solution became darb. determined and was et » 43r4. Serve Binderidsung is ansoUieOend as binder A beseiob "t. Inside WAmsee mräe a »the following» estmäteiltm presented x fitemdioryd 90 .... :. . lin @ dlr 1 nut styrene Z, 0x l @ et @ etbnos @ ltt?, 0 e This Gerisah varde in an elth7.e 4 * äraoht aad r U rrnd Fast forward about 38 hours. This grind becomes »O oUleSead beseiabnet as Mshlrsese 1 . The resin and monomare diapers ion was made from: the following components: Mahlmange '! 13, 8 Binder A 66.2 "Diiaopropanolßaiin?, 3" Distilled Water 31297 "Amine and water were mixed in a still-rindiness smelter. The meal and the binder were pre-mixed and poured into the vortex of a runny mixture of amine and water. The orhal tone mixture was mixed further for 10 minutes.

spell was interrupted Klsohen for 5 minutes and mndchließend still five minutes to * eestzt. Mixing was interrupted for 20 minutes. and then continued for 5 minutes with honor. After 5 minutes the dispersion was distilled at 400 grams. Water ferments. The Mmleion obtained had about 10% by weight Feotetotfe.

D.ieae ltulaion was placed in a tank that contained. It was used as the cathode of an E. The metal foil material was coated by applying a difference between the electrical potential of the cathode and the (anode) of about 100 volts for one minute. The sheet material was removed from the bath in a nitrogen atmosphere and the practically uniform and continuous coating thereon pelymerieiort to the tacky state by applying an electron beam to the coated sheet. was conducted. The following radiation conditions were applied - Voltage 275 Eleitronenlrilovolt Current - 15 - MilliaigOre ßesantdosierung 10 Msgsxed passages through the beam 2-line resistance 3 meters (10 ft) / minute atmosphere nitrogen Distance from Elelrtronsnteneter to XerkstUoi 1798-09 (79) 8ciERIM, 2 - - -The procedure of example 1 was repeated, but .- $ increases the concentration of pigment in the bath at separate batches, at 15, 20 and 25 ßew the Baäfeststoffe.

29 waiting to get excellent ir results. Betspiel 3 The process according to Example 1 was repeated:, however, the polysiloxane used in Example 1 an equivalent amount of a commercially available (Dow Corning - Sylkyl 50 ;: methoxylated partial hydrolysis of monophenyl and phenyl methyleilene in essentially of Dimethyltriphenyl-trimethoxytrisiloxan the following typical properties was: 470 Durchschnittemolekulsrgewicht association weight 155 specific gravity at 25 ° C 19105 viscosity at 25 "C, 13 centistoke En was a uniformly Uberaogen (s, obtained with an excellent cured coating sheet is provided.

The polymers used according to the invention can be passed through. Implementation of a base polymer with at least two functional groups per KolektU., Ie hydroxyl, amine, carboxyl, anhydride, a meroapto or epoxy groups, with an organic compound with olefinic a., 8-unsaturation, preferably di- or polyaarbonic acid or -aahydrides . Since the polymer is electrodeposited, the polymer product obtained must contain a sufficient number of ionizable functional groups within its molecular structure to permit its dispersion in an aqueous bath and subsequent electrical deposition, for example disoccupable carboxyl groups in the case of anodic deposition. This lonisierbaren groups may be contained from the beginning in the above-mentioned base polymer or the organic compound, with which this is set equal. The products are preferably linear copolymers with terminal olefinic α, 0-unsaturations. The vorste- immediate term "base polymer" includes Fri. Scope of the present description Diners, trimers and tetramethyl as well as poly- mers of higher Kolekulargevioht. As another example of eriindungege®äß usable olefinically unsaturated polymers are condensation products of SB Epouyharzen with ungeeättigten polyvalent carboxylic acids such as aB Ztakoneäure or Ztakonsäureanhydrid listed.

The invention has been besohriebsn in the above with reference to preferred exemplary "Uhrungsiormen, without being limited thereto.

Claims (1)

S 1. Silicon-containing acidic resin with numerous carboryl groups with a molecular weight above 10009, an 8 acid number above about 30, an electrical equivalent weight in the range of about 1000 bib about 20,000 and with about 095 to about 310 olefinic saturations per 1000 units the Holekulergorichta, WO at least about 10 t .-% of the resin is now composed a "zweiwerügen Siloent. 2.) Haas after Änepruch 1, dsdo @ L_ae »nezelghp t; that about 20 am about. 40 % by weight of the resin consist of divalent silage rods. 3.) Lnetriche- or ÜberzugebiWer, et dnroh give a content fron about 85 to about 99 9 «.-% of a eililmnbaltig" Polloarboneänreha "ee and about enispreohend f until et» 15 wt .-% of Vinylmm11renr wherein naive discloses a läleku " large Vicht above 1000, an acid number of above about 30, a * lektriaohee iqaivalentgewieht tu range from about 1000 to about 20 00C) and about t3,5 am about 3.0 olefinisohe o, S-1000 Niohteattigungern Binheiten of Hhlekgargewtohtee and has at least about 10 aew4,% of the mmiwnrtigen S, tlosanreeten exists. 4.) Anetrichebinder to claim 3, thereby, & e, r-iahnet, that about 15 am about 50 % of the Hsrsee to the sweixertigen Silozanreeten exist. 5.) Beard binder after claim 3 or 4, characterized aekeaaseiohnet that the resin of a polyester Harm with olelinisoher a, 8-Uiohtsrttigung and a Silosan is i. 6.) Amtriohabinder according to claim 3 to 5, äonirroh $ ekennseiohtstt that the Ylnylmonomeren about 7 to about 14, 5 wt .-- x amount of the binder. Z.) Anstri Chsbinäer according to claim 3 to 6, dduroh ikennseioh-Wt that the Vi "imoaaer» a » consist of styrene and / or Nethylnsthacrylat and, for example. 9 represents about 14 Ger .-% of the binder. 8.) NA mm over an anode the'ah alektrisoh caused separation'kennsaiohnet by a% "* Ciae Disp.raion of a" triohsmsa ", which as a" iefdea share of the film-forming? Arbbindere eia sUikonbaltiges Pblyoarbonssiohnres with a) a Nolekgiohtio fron about 1000 b) etm 095 to about 390 oletinische a, d-Biohtsittigaag per 1000 units of Kolekalanwiahtee, o) a 8äurstahl in the range fron about 30 am about 300 UUD d) an electrical lquivalentgewieht: wipe about 1000 and about 20 000 with at least 10 Qer .-% of the same from sweiirertigen siloxane exist, and about 1 to about 15'Gew .-% vinyl monomers, based well the weight of the Binderä containing, said-Polyearbonmäurehnra in the wteorigen dispersion having a except be calibrated amount of water-soluble amine compounds to to maintain the Pol'earbonsäurehars as -anioninahen polyelectrolyte, is neutralized and the concentration of the binder in the aqueous dispersion is about 09.5 to about 35 ßsw.4. 9. ) Bath after 1 "pruch 8, daduroä, e -,. Make sure that the concentration of the binder in the aqueous dispersion is about 3 to about 12 G". -% amounts to.