CA1102031A - Copolymer solution consisting of acrylic resin and its use in coating composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A copolymer solution consisting of A) 10 to 30 % by weight of inert organic solvents and B) 70 to 90% by weight of copolymers prepared by simultaneous and joint polymerisation and condensation reaction in the presence of mixtures of diacyl peroxides or peresters and alkyl hydroperoxides or dialkyl peroxides as polymerisation initiators by heating to 165 to 180°C, a mixture of said inert solvents A) having a boiling range from 150 to 200°C and components a) 5 - 24 % by weight of glycidyl esters of ?-alkylalkanemonocarboxylic acids and/or ?,?-dialkylalkanemonocarboxylic acids of the following empirical formula C12-14H22-26O3, followed by slow uniform addition of a mixture of b) 12 - 30 % by weight of hydroxyethyl acrylate and/or hydroxethyl methacrylate, c) 1 - 10 % by weight of acrylic acid, d1) 20 - 50 % by weight of styrene and d2) 5 - 35 % by weight of methyl methacrylate, components a, b, c, d1, and d2 and components A and B
respectively having been employed in quantities to a total up to 100 % by weight each and with the proviso that the components a, b, and c have been employed in such quantities to obtain copolymers having a hydroxyl group content of 3.5 to 6.5 % by weight.

The present invention relates further to a process for the preparation of said copolymer solutions. The copolymer solution can be employed either in reactive lacquers in an amount of 60 - 80 % by weight together with 20 - 40 % by weight of an organic polyisocyanate or in a coating composition which dries by physical means in an amount of 20 - 80 % by weight together with 20 - 80 % by weight of a thermoplastic copolymer.

Substrates of the most diverse types, for example porous or non-porous substrates, such as textile non-wovens, leather of plastics can be coated with these mixtures. In every case high-gloss, pore-free, elastic and solvent-resistant coatings having a very hard surface are obtained.

Compared with the known copolymers, the advantages of the instant copolymers in combination with polyisocyanates are better solvent-resistance, higher abrasion resistance and better resistance to weathering in the Florida climate.
Moreover, clear lacquers or pigmented lacquers do not exhibit crater formation or blistering.

Description

Z~31 Thls is a division of copending Canadian Pa~ent Application Serial No. 276,756, filed 22 April 1977. .

The prese~at invention relates to a special copol~ner solution consisting of acrylic resin con-taining 70 to 90~' ~y weight of copolymer solids and 10 to 30So by weight of. solvent.
The invention also relates toa.process for the manufact~re of the copolymers which are present in the copolymer solution;
additionally, the invention relates to the use of the copol~m~r solution for the ma~ufacture of coating compositions for lac-quer systems of 10~J solvent content which contain polyisocya-nates and ~hich contain the copolymer manufact-ured according to the invention as a resin componen~ ~Jhich carries hydroxyl groups.
It is also an object of the-present invent~on to provide a process for t.he manufacture of the copolymer solutions and their use as a binder componen~, the sheet-like s~ructures which can be produced therefrom having, however, considerably improved properties in various respects~ Th s inciudes the ~.
property that a lacquer .~hich contains ths new copolymer solu-tions in combination with organic polyisocy~lates, when applied to a metallic substrate, after drying in the air or three to four da~s at temperatures of about 20C9 should cure in such a way tha.t the film no longer swells under the action of water and a}so cannot be -e~oved mechanically by scratching, even if the film is e.~posed for a brief period to water at temperatures . 2 ~,. . .

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2~31 .

o~ 50 - 70~C.
It ls al;o a ~ur-ther objecl; of the presen-t invent:iorl that -thc copolylller so:lutions oI the invcn-tion, in combination ~Ji-th o-ther copol~rmer solutions ~Jhich are bui]-t up, as thermo-plastic copol~ners, rrom a basis oI lo~er alkyl me-thacrylates and acrylic aci(l or methacrylic acid, should mal~e i-t possible to manufacture coa-ting agen-ts ~hicll dry at room temperature, by physical means5 by solven-t evaporatlon, -to give f`ilms ~hich have outstanding properties.
It is a :rurther aim Oî the present invention to provide an acrylic resin ~lhich contains hydroxyl gl~OUpS an,d.~`lhiCh, in combination with polyisocyanates, prov:ides the binder basis for air-drying lacquers and stoving lacquers ~Jhich are suitable for top lacquering in the automobile industry, the lacquer bein~
present a~ter stoving in layer thicknesses of about 40 to 80 ~m and the top lacquer being loca-ted directly on top of the stoved primer of electrocoating lacquer.
In the modern methods of the present time for lacquering motor vehicles in an automobile fac-tory, the coachwork parts are usually provided, after phosp~la-ting, with a primer of electro-coating lacquer and this is stoved to give a plastic coatin~.A spraying lacquer or a coating composition, which lS generally designated a filler, is then applied to this plastic coating, usually by a spraying process, and stoving is carried OUt again.
~ he automobile lacquer ~ormulation ~hich contains pig-ment i;s then applied, in the desired pigmentation, to this two-layer coat of lacqùer or primer by spraying and the auto-mobile body is stoved again.

, l~ '$31 The ~!ho:lc co~ i.ng, ~hich, as e~.p:t.aj.ncd abov~, consis-ts of thlee l.lycrs, llas a ].tyer thicknccs after stov.ing of 70 -100 llm~ -the fraction rel~t:ing to thc outer layer of top lacqucr being 30 -l;o ~10 ~lm In the course o.~ rationalisa-tion me-thods in the autorno~ile i.ndustry ef~orts are bein~ made to change ovcr from the three-layer system -to a -t~To-layer build-up.
In -thisS the electrocoat lacquering or ano-th.~r equivalen-t primer is inten(led to for,n the first coating layer and -there--aI-ter -the final coa-t of lacquer is intended -to be bui.lt up by -means of t~he pig~nen-ted lacquer, but -the total thickness of the layers applied is intended to have, in -total, the same layer thic'~ness. Using the conventional automobile top lacqucrs, howeverS it is not possible, ln the custornary spraying and stoving treatment, to produce, from lacquer for;nulations con-taining pi~nent, coatings ~hich, after drying in the air or af-ter stoving, give lacqu~r films ~Jhich are completely uniform (that is to say Iree from so-called curtaining and free from .
craters and blisters). ~ ~
. It is the aim of the present invention to provide an ~ :
acrylic resin ~ich contains hydrox~l groups and ~Ihich, in com-bination with polyisocyanates, provides the binder basis for air-drying lacquers and stoving lacauers ~hich are suitable for top lacquering in the automobile industry, the lacquer being present, after stoving, in layer thicknesses of about 40 to 80 ~m and the top lacquer being located directly on top of the stoved primer of electrocoating lacquer. In addi-tion, the copol~ners according to the invention, and also the coat-ing/binder combinations consisting of the copolymers according ' !

ll~lZ~
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to thc invcnl;ion and ~hc polyisocyanltes, shoul~ bc misciblc and compati~le with thcrmoplastic copolymc~s ~hich are solu~Jc in or~lic solvcnts; The use of thc thermoplastic copoly-mers m~ces possible rapid dryin~, especially when uscd as a repair lacqucring in order to toucll up dcfcctive coats of lacquer. In such cases tacl~-frce dryin~ at room tempera-ture ~rithin 5 -to 10 minu-tes is required and the desired resis-tancc to prcmium-~rade motor fuels is rnct by me~ls of -the new binder combinations af-ter a ~rying time o~ only one hour.
A further particular advantage resides in the ~act that, for example, it is also possible partially to touch up after final asse~bly a lac~uered automobile body on which painting defects still need to be touched up) if the reactive lacquer applied consists of a binder combination of the copolymers manufactured according to the invention and polyisocyanates.
The touching up can be carried out on the par~ially or com-pletely cross-linked binder combinations. - With the binder combinations ~hich are envisaged as a touching-up lacqùer and which consist of 20 to 8~,'~ by weight, preferably 40 to 6~b by weight of copoly~ers manufactured according to the invention and 80 to 2~ by weight, preferably 60 to 4~,' by weight of thermoplastic copolymers, no differences in colour shade are found between the partially or completely cross-linked reac-ti~e lacquer and the touchin~-up lacquer~ provided that the same pigments are employed9 in terms of quantity and type.
In addition, the copolymer solutions according to ~ ~n-~ention, which have a lower ~iscosity,exhibit a better absorption ofpi~nt bo~h when using inorganic pi~ments~ such as, for -o 5~ -. .;;

f~ 31 .

exc~7nplc, t:itani~lQ dio}:idc, or when using orgarlic p:igMents, .such as, for e,;.unl)le J carbon black. ~Ihell -titanium ~ioxide is used as the pigment, -tl1e copo;ylners m.-mufclc-tured accord ing to the invcntion, and also -the reactivc lacquer manli-fac-tured therefrom, still give high-gloss fi:lms at a pignent/
binder ratio of 1.5 -to ~ hile -the kno~n copo].~rners and the ~no~m reac-tive lacquers manufactured therefrolll show a dis tinc-t falling-o:r~ in glo;s a-t -tn~ same level of pigmenta-tion.
In addi-tion, it has been found -tllat the copo~7ymers manufac-tured according -to the invention c~nd the reactive lacquers mcmufac--tured therefro7n produce high-glo.ss lacquers with carbon blaek, .~hile the kno~n copol~ers and the reac-tive lacquers mc~ufac-tured therelrom exhibit matt films at the same level of pig-mentation.
It is a further objeet of the inven-tion to provide a process for the .~anufaeture of soluble orga-nic eopol~ners which ; are produeed as a solution having a solids eontent of 70 to 90~ by.weight, the eopolymer solutions which have been formu-lated ready for spraying having at 25C a viscosity of 25 seeonds, measured in a DIN eup with a four mm flow orifice, -and a solids co~-tent of 40 to 650~ by weight, preferably 45 to 65~' by weight. The copolymer solutions manufactured accord-ing to the imrention thus take aeeount of the demands made by environmental proteetion for binders of high solids content and low solvent content.
The outstanding advantage of the copolymer solutions manufactured according to the invention resides in the fact that it is possi~lo for the hydroxyl groups of the copolymers _6 _ -2~31 to crosslin}; wit~l polyisocyanates at room temperature anci also at elevated temperatures and to produce lacquers of high solids content, in a condition formulated ready for spraying, at a viscosity of 40 seconds, measured at 25 C in a DIN cup having a four mm flow orifice, and at a solids content of 61 to 80%
by weight, preferably 65 to 80% by weight in the clear lacquer.
Numerous proposals have been disclosed to manufacture solvent-resistant and alkali-resistant lacquers by reacting polyisocyanates and copolymers containing hydroxyl groups and to convert them into coatings. DT-AS 1,247,006 (Farbenfabriken Bayer AG, published 10/8/67) describes a process for the manufacture by the polyisocyanate polyaddition process of alkali-resistant sheet-like structures which are obtained from polyisocyanates and copolymers containing hydroxyl groups, but which are not adequately water-resistant after a reaction time of three to four days at 20C. These coatings obtained by this known process are, therefore, not suitable as top lacquers for external lacquerings which are resistant to weathering, since blistering takes place after a very short time and the adhesion of the lacquer to the various metallic substrates falls off and, as a result, the lacquer comes away from the substrate.
It is also known that polyhydroxyl compounds of polyols can be cured with polyisocyanates in order to obtain cross-linked lacquer coatings with good resistance properties.
These combinations also exhibit too low a resistance to water and a lower resistance to weathering of the cured lacquer films.

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Frcnc}~ tcnt ',pecification 1,556,309 ~1ippon Paint. Co., Ltd., published 7/2/G~) describes a coating agent which contains solvent and, as the film-forming constituents, A.
a copolymer consisting of tlj 2-50 parts hy weight of an addition product with a 1.:1 ratio of a carboxyl group of an ~
ethylenically unsaturated acid and an epoxide group of a glycidyl ester of an aliphati.c carboxylic acid having tertiary C atoms, in which the aliphatic tertiary group contaïns 4-26 C atoms, and (2) 98-50 parts by weight of unsaturated, copolymerisable monomers, the total quantity of (1) and (2) adding up to 100 parts by weight, and B. at least one polyisocyanate which contains at least 2 isocyanate groups in its molecule, the polyisocyanate being present, relative to the copolymer, in a quantity of 0.2-5 equivalents relative to the hydroxyl groups of the copolymer.
As the Examples in this French Patent Specifica-tion show, copolymer solutions are obtained which have a solids content of only 48 to 52%. The content of hydroxyl groups in Examples 1 to 10 is 0.8 to 3.18~ by weight in the known co- .
polymers.

In Example 1 = 0.8~ of hydroxyl groups in Example 2 = 1% of hydroxyl groups in Example 3 = 1.26% of hydroxyl groups in Example 4 = 1.52% of hydroxyl groups in Example 5 = 1.41% of hydroxyl groups in Example 6 = 1.41% of hydroxyl groups in Example 7 = 1.66% of hydroxyl groups in Example 8 = 1.85~ of hydroxyl groups in Example 9 = 1.85~ of hydroxyl groups

3~ .

in ~Y~amplc! L0 - ~.]~3 56 oC kly~roxyl grollr)s;
If -l;he procedure indicatecl in French Patent Specifica--tion 1755G,309 is-~lc~n i~Llo~l~l,and the hydroxyl group conterl-t in the copolymers is :increascd, the vi-cos:i~y is also increased.
If the viscosity is reduced by dillltion with ~ylene to 25 seconds at 25C, measured in a DIN cup having a ~ mm :Elow orifice, the solids con-ten-t of the copolyrner solu-tions also decreases I-t ca~mot, ho~rever, be inferred from French Pa-tcnt Specifica-tion 1,5555309 -that it is possible5 by selecting certain solvents and a certain range of quantities of a com-bination of various pol~nerisable monorners and using a combination of initiators, to manufac-ture copolymer solutions t~hich have a substc~ntially higher solids con-tent and ~rhich open up the use of the ne;J copolymers as binders for lacquer systems which are based on acrylates and have a low solvent content.
The particular advantage of the copol~er so3utions manufactured according to the inven-tion resides in the ~act that the viscosity decreases when the hydroxyl group content in the copolymers is increased. ~hen diluted with xylene to a viscosity of 25 seconds at 25C, measured in a DIN cup having a ~ mm flo~ orifice, the solids content o~ the copolymer solutions manufactured according to the invention is then increased.
It has been found, surprisingly, that the copolymers which have been manufactured according to the invention ~nd which have a hydroxyl group content of 3;5 to 6.5, preferably .~ .. . .
~ , - .
, ~ 2~31

4.5 to 5.5, ,0, lead to :Lower viscositie~s than do the known.
copolymers of t]le s~ne hy~ro~yl group content Thus, whe~
dissolved -to form a 70~' s-trcngt~l by wei.gh-t soltlt:i.on i.n ethyl--glycol ace-tate, the copolyrner solutions manufactured accord.ing to the inven-tion have viscosi.t.ies of U to Z/~, pre:~erably X -to Z3~ measured on the Gardner-Holdt scale a-t 20C. Proof of thi.s s-tatemen-~ i.s alforded by a comparison bettleell -the copoly~
mer solution manufac-tured accord:i.l1g -to the invention in ~x~mple 1 and the Inown compar:ison copoly1ners 3 and 4. ~s 7G5' strength by wei.gh-t so].utions in eth.ylglycol ace-tate 9 -the com-parison copol~Tmers 3 &~ld 4 leacl to higher viscosities whi.ch are higher than Z6~ measured on the Gardner-Holdt scale a-t 20C.
Comparcd with the kno~ copolymers, the copolymers manufactured according -to the invention display the following advan-tages in the comhillation with polyisocyanates: better solvent-resist~ce, higher abrasion resistance and better resistance to ~eathering in the Florida climate. In add.i-tionS in the combination with polyisocyanates, the copolymers manufactured according to the invention produce lacquers of a higher solids content, having a solids content of 61 to by weight, preferably of 65 to 80o by ~Jeight, in the clear lacquer, when diluted with acetone, xylene or butyl aceta-te to a viscosity of 40 seconds at 25C, measured in a DIN cup ha~ing a 4 mm flow orifice. ~hen such clear lacquers or pigmented lacquers are applied by spraying to steel sheets and are exposed to the air for a short time and subseauently sto~ed, high dry film layer thicknesses o~ 70 to 80 ~m are obtained, which do not exhibit crater formation or blistcring.
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_10 _ ' ~ 2~31 The kno~n~ 1 acqucr combi.nations w~-lich are dcscribed in Frerlch Pa-tcnt Sp~ci.fication 1,556,309, only produce a solids contcnt of 10 -to 60~' by weight in -the clear lacquer ~lhen diluted with ace-tone, bu-tyl aceta~c or xylene -to a viscosity o~ 40 seconds at 25C. ~1hen such clear lacquers or pigmented lacquers are applicd by spraying to steel sheets and are exposed to the air ~or a shor-t time and subsequen-tly stoved, lower dry ~ilm thicknesses o~ 40 to 50 llm are obtained, which in addi-tion also - exhibit crater fo~nation and blistering.
The subject of the i~venti.on is a copolymer solution consisting of A) 10 to ~0% by weigh-t of inert organic solvents which are custo~ary in the lacquer indus-try, and B) 70 to 90~'0 by weigh-t o~ copolymers which have been manufactured by heat-ing to 150 to 180C, in the presence of mixtures of diacyl peroxides or peresters and alkyl hydroperoxides or dialkyl peroxides as the polymerisation initiators, a mixture of inert solvents having a boiling range of 150 to 200`C and the compo-nent to be esterified, that i5 to say a) 5 - 24% by ~reight of glycidyl esters of a-alkylalkanemonocarboxylic acids and/or 20- a,a-dialkylalkanemonocarboxylic acids of the following empir.i-ula C12_14H22_263, with the slow, uniform addition of b) 12 - 30% by weight of hydroxyethyl acrylate and/or hydroxy-ethyl methacrylate, c) 1 - 10% by weight of acrylic acid, dl) 20 - 50% by weight of styrene and d2) 5 - 35/0 by weight of ~ethyl methacrylate, the components a, b, c, dl and d2 having been employed in such quantities that their sum adds up to 100% by weight ~nd the polymerisation and condensation reac-tions proceeding simul-taneGusly and jointly and the additional .

11~2~

condi-tic)n ~ ing t]1at the components a, b and c havc been ernp:loyccl:in ;uch qua~l;ities -tha-t lho copo]yrnçrs h~ve a hydroYy:l grou]~ con-tent of 3.5 -to 6.5,' by wcig11-t, it bei-n~
necessary -tha-t -t~le cornponents ~ and B a~d up -co 100,' by weic~ht.
The corJoJymers first ~entioned are charac-terised in -tha-t a 70,S streng-th by weight solution of copol~ner in e-thyl-glycol acetate has a vis~osity, rneasured at 25C, of U -co Z4 on the Gardner--~Ioldt scale and a solution formu:La-ted ~ith xylene -co a viscosity of 25 seconds a-t 25C, wich a DIN cup having a 4 mm flow orifice, has a solids content of l10 -to 655' by weight. The preferred ernbo~iment of the copolymer solution is charac-terised in that a 70~ s-trc-ngth by weight solution of copolymer in ethylglycol acc-ta-te hds a viscosity, measured at 25C, of X to Z3 on the Gardner-Hold~
scale cmd a solvtion fo~nulated with xylene to a viscosity of 25 seconds at 25C, ~ith a DIN cup having a 4 mm flo~ orifice, has a solids content of 45 to 65% by weight.
A special embodiment of the copolymer solution is characterised in that a 70% strength by weight solution of the copolymer in ethyl~lycol aceta-te has a viscosi-ty, measured at 25C, of Z2 to Z3 on the Gardner-Holdt scale, and a solution formulated with xylene to a viscosi-ty of 25 seconds at 25C, measured by means of a DIN cup having a 4 mm flow ori~ice, has a solids content of 47% by weight.
A preferred embodiment of the copolymer solutioh is characterised in that it consists of A) 20 to 25% by weight of inert organic solvents which are customary in the lacquer industryj and B) 75 to 805' by weight of copolymers which have _ lla-, l~iV2~31 ' been malluL.I.c1ur((1 by llec-l-tin~ to 150 -to 1~0C~ .i.n t}le pres~nce o~ Ini~turc, o~' tert.-l~utyl perl~c~n~o.lte an(l cumenc hyciroI)cr-oxide as tllc polymerisat.ion in:it~ tors, a Inixture o~ inert.
solvents havi.rlg a boili.ng ran~e O:r 150 to 200C and -the corn-poncnts to be es-ter.ified, that i.s to say a) 11 - 12S by ~eight o.f glycidyl es-t~rs of a-alky:l.alkancrnonocarl~o~,yli.c acids and/
or ~,a-di~lkylalkanemonocarboxyl:i.c aci.ds o~ the following a C12~ TI22 2603, ~Jith the S10WJ unifo~rn addi-tion. of b) 25 - 26~ by w~i~nt of hydro~yethyl acrylate c~d/
or hydroxyethyl methacrylate, c) 3 - 4// by we~i.ght of acr-ylic acid9 dl) 44 ~ 48% by wei.ght of ~.ty~ene cmd ~2) 10 - l~,S by weight of me-thyl me-thacrylate J thc compollents aS bs c, dl and d2 havi.ng been employed in SUC}l ~uantit:l es tha-t, their s~ adds up -to lO~S by ~eight c~d the polymerisation c~. condensation reac-tions proceeding simull.aneous~y and Joilltly and the addi-tional condition applying thcît the componellts a, b.and c have been e~ploye~ in such quantities that the copo].ymers h.a.ve a hydroxyl group content of 4.5 0.~% by weightJ it being neces-sary that the components A ~ld B add up to 100,6 by weight.
A further subject o~ the inven-tion is a process for the manufacture, in organic solventsS of copolymers which are soluble in organic solvents by copolymerisation of alkyl acrylates, hydrox~ralkyl acrylates, styrene and an a,~-unsatu-rated carbo~ylic acid with simultaneous esterification by glycidyl esters of a-alkylalkanemonocarbox~lic acids and/or ~,a-dialkylalkanemonocarbo,Yylic acids, by heatillg in the pre-sence of polymerisation initiators, characterised in that a mixture consisting of A) 10 to 3~1~ by weight of inert organic ~2~31 501VC'll l,S ~ ).J.`(` CUXtOlnary iJI tllC laccluer indu,c~,-try ~nd B), 90 to 70~ by ~!c,i,~ht of a rcactioll m:iY.I;ure cons:isting of the coml~onents a, b, c, dl a.nd. d2 is rc~ctcd9 thc inert orgc1nic solverlt and tlle cornponents to be csl:el:i,fied, tha-t; i5 to say a) 5 - 2~1% by ~e,igh-t of g].ycidyl est;ers O:r a--alkylalkc~l~emono-carboxyli.c acids an~/or a,a-dialkyla'lk~lcmonocarbo~ylic acids of the fo:llo~ing elllpiri,c~11 formu.l,a C12_14H22 ,~6 3 heatcd -tc 165 -to 1~0C and a mi,Y,ture consistin~ of b)'12 -30Q/0 by ~ei~ht OI hydrox~ethyl acryla-te ~ld/or hydroxye thyl methacrylate, c) 1 - 10'~ by ~.~eight of acr~Jlic ac:i.d, d1) 20 50~0 by weig~ht of styrene and d2) 5 - 35~' by ~eight of me-thyl methacrylate, the components a, b, c, dl and d2 being ernplGyed in sucn quantities that their sum adds up to lOO~;o by weigh-t J
being adde~ slo~;~ly ~ld uniformly, in ,tche presencc of mixtures o~ diacyl peroxides or peresters and alkyl hydroperoxi.cles or dialkyl peroxides as -the ~olymeris~tion initiators, &nd, in the course thereof, the temperature being kept bet~ieen,.165C
at the s-tart ancl 1~0C a-'c the end, un'il the solids content of the solution has reached the theoretical value of bet.Yeen 70 and 80~o by weight, tt~le pol~nerisation and condensation reactions proceeding si.multaneously and .jointly and the additional condition applying that the components a, b arLd c are employed in such quantities that the copolymers have a hydroxyl group Gontent of 3.5 to 6.5~ by weight.
A preferred embodiment of the process is characterised .
in ~hat a mixture consisting of A) 10 to 25,~ by wei~ht of ethylglycol ace-tate and B) 90 to 75~ by weight of a reactio mixture consisting of the components a to d2 is reacted, the - 13 - .
~)Preferably a mixture .of glycidyl esters of a,a-dialkyl-alk~nemonocarboxylic acids h.~vi.ll~ a In:i.nor ~ontellt (up t;o ~,J. a~ou~ r~ r,]l~ of ~ i}~ ) o~ r~i.(3yl cst~r~ o~
,, a-~lkyJ..llk~ncmonocarbolr~rli.c acids o, the s~id emp:iri.cal ~O~ It21~ the mi.xture havin~ an cpox:i~le e~l~iira'lent oJ.','~0 Z~31 col~ponenl: to bc e-;tcri:Cie(l, that is to say a) 10 - 2/lS' by .
~eight oI g]ycl~yl estcrs of.~-a]kyl.llk~nemonocarbo;ylic acids and/ol a,~-dialky~L~11kanemonocarboxylic ac.ids of the following empirical formula C12~ 22_2~,03 , g ith the ethy~gl~rcol acetatc to 165 to 1~0~ an~ a mix-ture consis-ting of b) 18 - 26~' by ~Jeigll-t of hydro~yethyl acrylate and/or hyd.roxyethyl ~nethacrylate, c) 2 9~ by wei.ght of acrylic ac:id, dl) 20 - 50~/0 by ~ei.gh-t of styrene, d~) 10 - 35~' by weigh-t of met}~yl methacrylate~ e) 1 - ~ 5~ by weigh.-t of dibenzoy:L pero~ide or -ter-t. butyl peroctoa-te or tert.~butyl perbenzoate c~nd el) 1 ~ 3~ by wei~h-t of cumene hydroperoxide . or di-tert.-butyl peroxide, the componen-ts a, b, c 5 dl a~d d2 being employed in such quantities that their sum adds up to 100C~6 by weight, bein~ added slo~/ly and uniform~ly and, in the course thereof, the tempera-ture being kept between 165C at the start and 175C at the end, ulltil the so7ids content of the solution has reached the theoretical value of bet~ieen 75 and 90~ by ~eight, the polymerisation and condensation reac-tions proceeding .jointly and simul-t~leously and the add~-tional condition applying that the cornponen-ts a, b and c are employed in such quantities that the copolymers have a hydroxyl ~roup content of 4 to 5.5% by weight~
The most preferred embod.iment of the invention relates to a process in which a mixture consisting of A3 15 - 25~o by weight of ethylglycol acctate and ~) 85 - 75';~ by weight of a reaction mixture consisting of the components a to d2 is reacted, the component to be esterified, that is to say a) 10 - 24% by weight of glycidyl esters of a,a-dialkylalkane-. - 14 -~)Already explained in the preccding text ~ ~ , . . .

~92~31 monocarbox~lic acids of the follo~ing ernp:!r:ical lormula C13H2LI03 ~) whicllllave been obtained by reacti.ng propylene trimer, carbon rrlonoxide ancl ~/ater ancl consist a:Lmost exclu sively O:r rnollocarboxylic acids havlng hi~hl.y hranchccl C~0 chains, ~)eing h~atcd with lhe ethy]glycol acetate to 165 to 175C and a mix-ture consisting of b) 1~ - 26% by weight of hydroxye-t~lyl acrylate alld/or hydroxyethyl me-thacryla-te 9 C ) 2 - 9~ by weigh-t of acrylic acid, cll) 20 - 505~ by ~leight of s-tyrene, d2) 10 - 35/0 by wei.~ht of methyl methacryla-te$ e) 1 -~~0 by ~Yeight of -tert.-bu-tyl perben~oate and e') 1 - 2 5% by ~reight of cumene hyclroperox:ide, dissolved to orm an 80%
strength solution in a mixture of a~.cohols, ke-tones and cumene, it being necessary -that the surn of the monomers a to d2 adds up to lOO~o by weight, being added slowly and unifo~nly in the course of 6 to 10 hours and, in the course thereof, tlle termperc~-ture being kept at 170 + 5C, until the solids conten-t of the solution has reached the theoretical value of bet~Yeen 75 and 85S' by ~eight, the polymerisation and condensation reactions proceeding .jointly and simultaneously and the copolyrners having a hydroxyl group contcnt of l~ to 5.5% by weigh-t.
A preferred embodiment of the process of the invention is characterised in that a mixture consisting of A) 20 to 25~o by weight of inert organic solvents which are custornary in the lacquer industry and B) 75 to 805'o by weight of a reac-tion mixture consisting of the components a, b, c, dl and d2 is reacted, the inert organic solvent and the colnponents to be esterified, that is to say a) ~1 - 12~o by weight of glycidyl esters of ~-allcylall~nernonocarboxylic acids and/or ~,a-dialkyl-- 15 - ~ .
lrcady explained in thc precedir.g text;.
... , . .

11~2~3~ .
alkanclllollocarboY~lic aci.~s of the followl~g er~ ir:;cal lor.mula .C12 ~ 22 2f,3 I-), be:ing heated -to lC5 to 1~0C and a mixtuIe COI1SiSt.~ cf b) 25 - 26~ br wei gllt OL hy~roxye-thyl acrylate and/or hydroxyet;hyl me-thacryl.l~e, c) 3 45~ by wcight of acryl:ic acid, dl) 44 - ~ h by weight o~ styrcne and cl2) 10 -16% by weigh-t o.~ me-thyl rnet~lacrylat;e, tlle colrlponents a, b, c, dl and d2 bei.ng employed. l-n sucll quan-titi.es -that -their sum adds up to lOOqb by weight, bei.llg added s]owly and uni:-ormly, in the presence of mixtures ol -tert.-bul;yl pcrben~oate and cunene hydroperoYide as the pol~nerisation ini-tiators, and, in the course -thereof, -the tem~era-ture being kept between 165C a-t the s-tart and 1~0C a-t -the end, until -the so.Lids content of the solu-tion has reached the value of 80 -~ 1~ by weighl, the pol~neri~.ation and condensation reacti.ons proceeding simul-taneously and jointly, so tha-t the copolymers have a hydro~yl group content o~ 4.5 ~ 0.~ by weight.
A fur-ther preferred embodiment of the process of the - invention is characterised in -that a mixture consisting of A) 20 - 25~ by weight of ethylglycol ace-ta-te and B) 75 - ~056 by weight of a reaction mixture of the components a to d2 is reacted, the componen-t to be esterified, that is to say a) 11 -12% by ~Jeight of glycidyl esters of a,a-dialkylalkanemono-carboxylic acids of.. the following empirical fo~ula C13H2~03 ~) which have been obtained by reacting propylene trimer, carbon monoxide and water and consist almost exclusively of monocar-boxylic aci~s ~aving highly branched C10 chains, beingr heated with the ethylglycol acetate to 165 to 170C and a mixture consisting of b) 25 - 26~' by weight of hydroxycthyl acrylate lrcady cxplaillcd in thc prcccdi~O text.

.

~ 2~31 ' and/or hycllo}~ye-~h~Jl mothacry:l.ate, c) 3 - I~,b by we:ig~lt of acryllc aci~S dl) 4~ % by weigh-t o:L' styrene, d2) lO
16% by weigllt oI me-thyl Ine-thaclylate, e) 2 - 2,5% by we:i~h~
of -tert.-butyl perbcnzoatc and e') l- 1.5% by we;.ght of curnene hydropeJ.~oxide, dissoJ.ved -to form an ~S~ strength so'lu-tion in a mi.~ture of a].cohols, ketones and cumene, i.-t bei.ng neccssary that -thc surll of the monomers a to d2 a.dds up to lOOQ,~ by ~Jei.ght, bei.ng ~ldded slo~ly an~l uniform'ly in the course of 6 -to lO hours and, in the course thereof:, -the -tempe-rature being hep-t at 170 ~ 5C, until -the solids con-tent of the solu-tion has reached a va].ue of 80 + lS' by wei.gh-t, -the polymerisa-tion ~d condensation reactions proceecling joi.ntly and simultaneously and the copolymers h,aving a hydroxyl group conten-t of 4.5 ~ 0,3~ by wei.ght.
The inven-tion also rela-tes to -the use of the new copoly~ers for the manufacture of reac-tive lacquers.
~ nlen the new copolymers are used in reactive lacquers, the componcnts A' and B' are preferably used in thè following quanti-ties: (A') 60 - 80~ by weight of copolymers ~hich con-tain hydroxyl groups and have been manufactured according tothe invention and (B') 20 - 40% by wei~ht of an organic poly-isocyanate, it being necessary that (A') and (B') together add up to numerical values of lOO,S by weight.
A particularly preferred embodimcnt of the use com-prises: (A') 63 - 6~% by weight of copolymers which contain hydroxyl groups and have been manufactured according to the invention and (B') 32 - 37% by.weight of an organic triiso-cyanate which has been obtai.ned by reacting 3 mols of .

l l;~Zg~3~ .

hexaulctll~J:l.crlc ~:ii.socyar~ale ~nd 1 Inol of rater, it hei.ng neces-sary thcit I\' al~ ]3' add up to numeri.cal value-; of l00S' by weigh-t .
In a fv.rther use of the ne~ copolymerc; in coating a~ents whi.c}l dry hy physi.cal means i.n ~he .air, these copolymers are employed in quanti-ti.es of (~ 0 - ~0,~ by weigh-t of copo]y~lers ~lhich contain hy(3roxyl groups and have been manufactured accord:ing -to the invention and (B'!) 80 -20~ by ~leight of a therrnop].as-ti.c copolymer manu.fac-tured from 98 - 9~.5' by wei.ght of mothyl methacrylate and/or ethyl meth-acryla-te and 0. 5 - 2% by weight of methacryli.c acid or acrylie acid, it being necessary -tha-t the componen-ts add up to lOO,S
by weight.
The therllloplastic copolymers (B") are mamlfactured Dy aissolving the monomers in aromati.c solventsS such as~ for example, benzene, toluene or xylene, and heat;ing the mixture to a temperature of 60 to 120C, preferably ~0 to l00C, and addlng -the polymerisation initiator, for example dibenzoyl peroxide or tert.-butyl peroctoate or tert.-butyl pe-benzoate, preferably dissolved in aromatie solvents, to the mixture of monomers in the course of about l -to 5 hours, preferably 2 to 4 hours, and earrying out polymerisation a-t 80 to 100C.
Polymerisation is carried out here to give a solids content of 40 to 55~' by wei~ht. The proportion of peroxide is 0.4 to 1% by weight, relative to the mixtures of monomers employed.
The thermoplastic copolymers, which are present, dissolved in toluene or mixtures of xylene and n-butanol, as 40,' strcn~th - by weight solutions, have viscosities of W - Z5 at 25C on .

, l~f~Z~3 the Gardncr-llold~ scalc~
Surprisingly, thc copolym~rs manufactured accordiny to the invention also providc the good compatibility with thermoplastic copolymers which is required. On the other hand, the known copolymer solutions exhihit no compatibility with thermoplastic copolymers. The particular advantage of the compatibility of the copoly~er solution (~'), manu~actured according to the invention, with the thermoplastic copolymers (B") resides in the fact that it is possible to touch up blemishes in a finished coat of lacquer after final assembly of, for example, a finished autombile body, it ~einq intended that the coating agent according to the invention, which consists of the copolymers manufactured according to the invention and polyiso-cyanates, should be overlacquered. When binder combinations consisting of 20 to 80% by weight, preferably 40 to 60% by weight, of copolymer manufactured according to the invention and 80 to 20% by weight, preferably 60 to 40% by weight, of a thermoplastic copolymer are used, outstandingly rapid and tack-free drying results within 5 to 10 minutes at approx. 20C.

After a drying time of a further hour at 20C, coats of lacquer with a hard surface are obtained which are resistant to premium grade motor fuels.
The organic solvents which are customary in the lacquer industry, such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, ethyl acetate, butyl acetate, glycol monomethyl ether-acetate, glycol monoethyl ether-acetate (referred to herein also as ethylglycolacetate) glycol monobutyl ether-acetate, acetoacetic acid methyl ester, acetoacec~c acid ethyl ester, acetoaceti~

. ~. , .

i~ 2~3~
aci.d. buty:L e-lcr, bcrl~cne, tol.~lene, Yylene and/or aroma-tic solvent mix-tures ~lav~ g a ~Oi.lirlg r;~rlp,C' of 150 to 200~C, arç
usecl, ind.ivi.clua.lly or a~ mixtures, as the component ~.
Organi.c solvents,i.ndividua]ly or as m:ixtures, wh:Lc}l have a bo:iling rc~ge of 150 to 2GO~C are prcferred. These include, for e~amp]c, e-thylgIycol ace-tate, acetoacctic acid mcthyl ester~ acetoaceti.c acid ethy]. ester a.nd aroma~ic sol-ven-t mixtures having a boiling range of 150 to ].80C.
Ethylglycol acetate is particularly sui.-table in the manufac-tur~
of -the copolymers accordlllg -to the invention. It can be .
removed, partly or who]ly, by distilla-tion and can be replaced by low~boiling solvents which have a better solubili-ty for the copol~ners according to the i.nvention. Ace-tone, methyl ethyl ketone, methyl isobutyl ketone, ethyl ace-tate and butyl acetate àre particularly suitable for this purpose.

5 to 24, preferably 10 to 24, % by wei.ght of glycidyl esters of -alkylalkanemonocarboxylic acids and/or a,a-dialkyl-alkanerlonocarboxylic acids of the following ernpirical formula C12 14H22 263 are used, individually or as mixtures, as the component a. The empirical formula C3H50 applies to the glycidyl radical in the glycidyl esters of -the -alkylalkane-monocarboxylic acids and/or a,a-dialkylalkanemonocarboxyl.i.c acids. The mixtures of a-alkylalkanoic acids and a,~-d.ialkylalkanoic acids represent monocarboxylic acids which ntain a Cg, C10 and Cll cha.in. The manufacturing pro-cesses for the manufacture of the a-alkylalkanemonocarboxylic acids mentioned in the preceding text are based on the pioneer-ing work of Dr; H. Koch of the MaY-Planck-Institut f~r .. . .
- ' ~
/, ~2~3~

Koh'lenf()rsc}lul-lg in ,~ lhoim, I1`c-~cral ~epublic oL Gerlna.n~.
'~he acids are cornp:l.etely sa-l;ura-ted ~ld are~ vcry hi~hly sub-sti-tute(l on the carbon atom :in the ~-position. Acids ~hich have -t~o hydro~;en a-toms Oîl the ~-carbon a-tom are no-t present and only 6 - 7% of the.se acids contain a hydro~en atom~ Cyclic rnaterial is also prcsent (Deu-tsche ~arben Ze:i.-tschri.~t, No. 10S Year 16, page 435). It .is prefer-' able to ernploy ~^all~yla.llcanemonocarbo~ylic acids andlor ~,a-dialkylallianemonoc2rbo~ylic acids ~hich have been obtained. by reacting propylene -trimer, carbon monoxide and ~ater and which consist almost exclusively of monocarboxylic acids havin~
highly branched C10 chains. The empirical fo~ula of -the glycidyl ester compound is C13H2~03.
12 to 30~O by weight of hydroxye-thyl acrylate and/or hydro~yethyl me-thacrylate are employed as the component b.
Hydroxyethyl acrylate impar-ts high elasticity to the copolymers.
This is particularly required in cases where the metal sub-strates are shaped by an impact process. A further out-standing property of hydroxyethyl acryla-te in the copolyrners according to the invention consists in promotin~ the wetting of the pigrnent~ especially in the case of organic pig~ents and carbon black. Hydroxyrnethyl methacrylate imparts to the copolymers according to the invention a par-ticularly h~
film hardness, which is particularly required when formulating polyisocyanate reactive clear lacquers in two coat metal effect lacquering.
. 18 to 260/o b~; wei~ht of hydrox~ethyl acrylate are- used ' particularly preferentially as the component b, sinc~

. . - 21 -,, .

l~LF~21~3~ , particul~r:Ly :Lo~ vi...coslt:ies leci.d to a hi.gh so:l.ids content in the condit:i.on rc.ldy :ror spraying . l to 10~6 by weight o~ acrylic acid, prcferlbly 2 to 9~/0 by weight of acry:lic aci.d, are employecl as the cornponcnt c.
20 to 50~ by wcight of s-tyrelle, ~Ihich gi.ves second order trans:ition temperatures o.f abou-t 100C as a homopolymer ~nd can -thus be regarded as a so--callecl hard monomeI ~Jhich .impar-ts the ~esired film hardness to -the copolymers according -to -the inven-tion5 are employed as the component dl.
5 to 3~0 by ~eight of methyl rnethacryl~-te, preferably lO -to 35~ by weigh-t, are employecl as the componen-t d2 As a copolymerisa-tion cornponent, methyl methacrylate imparts to the copolyrners ~ccording to the invention a particu.larly high resistancc to ~eathering, especially in ~/eatherlng -tests in the Florida climate.
Peroxide mixtures consis-ting of at le~st two peroxides are used as the polymerisation initiators in the manufacture of the copolymers according to the invcntion. The peroxide mixtures have various chemical compositions; Peroxides of the first group e are represented by diacyl pero~ides, such as dibenzoyl peroxide, or peresters, such as tert.-butyl per-benzoate, tert.-butyl peroctoate or -tert.-butyl perisononanate.
Peroxides of the second group e' are represented by alkyl hydroperoxides, such as tert.-butyl hydroperoxide and cumene hydroperoxide, or dialkyl peroxides, such as di-tert.-butyl peroxide or dicumyl peroxide. The peroxide mixtures used are in each case l.to 3.5% by weight of a peroxide from the first group e and 1 to 3% by weieht of a peroxide from the , . . .' '~

~L~VZ~3~

SeCOrlCl gr'Oup9 reLa.tive ~0 Loo/6 by ~/eight o~ the compon~nt-;
a, b, c, dl and d2 - The follo~ing combinations of pero~i~es from ~roups one ~d t~o are employed: dibenzoyl peroxi~e/ter-t.-bu~yl hydroperoxlde; diben~oyl peroxide/curnene hydroperoxide;
dibenzoyl pero~;d~/dic~nyl peroxlde; -tert.-bu~ l perb_nzoat~/
butyl hydrope~roY.ide; ter-t.-butyl perbenzoate/c-lrncne hydro-peroxide; tert.-butyl p~rbenzoate/di-tert.-butyl peroxide;
tert -butyl perben~oa~e/dic~umyl pcroxidc; ter-t.-bu-tyl per-octoate/ter-t.-butyl hydroperoxide; -tert.-bu-tyl peroctoate/
cumene hy~roperoxide; -tert.-butyl peroc-toa-te/di-~lert.-but~l peroxide; -tert.-butyl peroc~toa-te/dicumyl peroxlde; ter-t.
butyl perisononanate/tert.-butyl hydroperoxide; -ter-t.-butyl perisononanate/cumyl hydroperoxide; tert.-butyl perisononanateJ
di-tert.-butyl peroxide; or tert.-butyl perlsononanate/dic-unyl peroxide;
The follo;~ing combinations o~ peroxldes a~e included in the preferred embodiment: dibenzoyl peroxide/cur~ene hydro-peroxide; di~enzoyl peroxide/di-tert.-butyl peroxide; tert.-butyl peroctoate/cumene hyd~operoxide; tert.-bu-tyl peroctoate/
di-tert.-butyl peroxide; tert.-butyl perbenzoate/cumene hydroperoxide; and tert.-butyl perbenzoate/di-tert.-butyl peroxide. Peroxide mixtures which contain, relative to 1006 by weight of the components a, b, c, dl and d2, the component e having 1.5 to 2.5% by ~Yeight of tert.-butyl perbenzoate and e~
having 1 to 2.556 by weight of cumene hydroperoxide, dissolved to form an 8~ strength solution in a mixture of alcohols, ketones and cumene, are the most preferred embodiment.

~ - 23 -l~Z~31 :Ct i, :~urld, sur~ is:irl~ly, that, :in the m~st prefclrcd embodi-ment ol the pelo,:icl( mi~-t~res ~mcl in the most prelerred ernbocliment of the copolymer solut:ion 7 75 to ~5~0 strcngt:h by weigh~ copolym~r solutions in eO~ylg:Lycol aceta-te are obtainecl~hich d:isp:Lay a viscos:ity at 25C oI X - Z3 on the -- Gard~er~ oldt sca]e as a 70~0 strength by wcigh-t solution in e-thyl~rJ~col acetate, ancl display a sollds con-tent of 45 to 65%
by wei~ht wherl an ~osh strength by we:ight; solution in ethyl~
glycol acetate is dilu-l;ed wi-th xylene -to a viscosity of 25 secon(3s, rneasured at 25C in a DII~ cup having a 4 mrn flo~J
ori~ice.
~ he peroxide rnix-tures are generally dissolved in the monorners or are added separa-tely to the polynlerisa-tion medium, the solvent or -the solven-t mixtures. In some cases it is also possible to dissolve small proportions of the peroxide mixtures, up to 20C~ by weight of -the quanti-ty of peroxides employed, in the solvent or the solvent mixtures and to add uniformly the residual quantity OL the peroxide mixtures, separately from the monomers or dissolved in -the ]a-tter, to the polymerisation medium, solvent or solvent mixture. It proves particularly suitable to dissolve the tert.-butyl per-benzoate of the peroxide mixtures in the monomers and to add uniformly the mixtures which have been prepared, within a time of 6 to 10 hours, to the polymerisation and condensation mediu~
consisting of the solven-t or solvent mi~ture and the glycidyl esters of a-alkylalkanemonocarbox~lic acids and/or a,~-diallsyl-alkanemonocarboxylic acids. The optimwn lowcring of visco-sity, ~lhich leads to the copolymers accordin~ to the invention, ~1~2~?31 is achievcd by ~his rncans. Thc reaction of the acrylic acid with -the g].ycidyl cst~rs of a,cc-di.alkylalkan~rnonoc~r-boxylic acids proceeds approximately accordin~ to the following formula: /
1~3 CH2-C~I-COO~{ + C~ -C~-CH2-O-CO-C-C5 7~1 15 O C~3 /jO CH3 C~l2-CH-C o-c~2-c~-c~2-o-co-l-c5_7H11-15 .or lO . OH Cl~3 ~P f CH2=C~-C o-c~-cH2~ 2-o-co-T C5~7 11-15 . OH

The reaction between the carboxyl and the glycidyl groups is carried out under the conditions of 0.95 to 1.1 mols of acrylic acid per mol of glycidyl esters of a,~-dialkylal~ane-monocarbox~lic acids of the follo~.ling empirical formula C12 14H22 263~ having an epoxide equivalent of 240 - 250.
The acid number of the copolymers is 5 to 12 and is made up by excess acrylic acid and by the or~anic acids formed as a scission product in the decomposition of peroxi~es, which acidity is to be regarded as extraneous ~cid. The hydroxyl group content of the copolymers is 3.5 to 6.5, perferably 4 to 5;5, S by wei~lt. The content of hydroxyl groups ill the copolymers is calculated by me~ns of the following formula:
. . . . . . .

- 25 .
, , .
~; . . . . . . . .

samp],e wei.~ of compoun(l b o:t OI~ = 1 mo:l oI 011 :i rl ~r y~ con ~:cl~ r~_~()}ry~ ue-r> X 100 ____ _ _ _______ ~ _ ._ _ noloc~ r t~ ht of th~ x total s~nple wc:i.g11t compou~ col1laining hy~lro,;yl of thé cornponents a groups -to d2 Thus~-the rea,ti.orl product form(d from 1 mol of acrylic ac:id, which correspon~s to 72 g of acryl.ic aci.d, and from 1 mol of glyci.dyl esters of a5~-~ial]~y~al.lra~elllonocarboxylic acids of.
-the followin~ empirical fol~nula C12~ 22 ~6 3 - g average epo}~id.e equivcl].ent o.. 245 and correspondi.ng to 245 Æ
of glycidyl es-ters, gives a molecular ~leight of 317. Under the conditions of an equivalen-t conversion~for ~0 g of the gly-cidyl es--er mentioned in the preceding text~he resu]t is 2.94 g of acrylic acid, whicll corresponds to a sample weight of 12.94 g of -the compo~lld containing hydroxyl groups. The IollotJing nu~erical expression tnen applies to the formula set out in the preceding text:
1 _ x 12.94 ~ x 100 = 0.69~o of OH
317 g x 100 g total sample weight of the components a -to d2 The other compounds which contain hydroxyl groups have the followlng molecular weights: hydroxyethyl acry]ate molecular ~ --.
~eight 116 and hy~roxyethyl methacrylate molecular weight 130.
The following percentages of OH result for 255~ by weight of hydroxyethyl acrylate in accordance wi-th the following numeri-cal expression: .
7 ~!; x ~6 ~: x 100 = 3 . 81~o Of OH
116 g x 100 g total sample weight of the componen-ts a to d2 _ 26 ~

.

i~ 2~31 rl'he suln of' bot]l cornpovnds containing hydroxyl ~roups, the reaction pl''O~UC't; from g]ycidyl estcr and acrylic ac:id as we~l as h~droxyetl-lyl ~cry:Latc, givcs a hydrox~l group contc;nt of 4.5Sb of OI-I.
If the conditions are maintained so tha-t the components a, b and c are eInr~Loyecl in such quan-ti-ties lhat -the copolymcrs have a hydro~yl group contcn-t of 3.5 -to 6.5C' by weigh-t, prefcr-ably 4 -to 5.5,~ ~y ~7eight, the compo~ents a c~d b should be adjus-ted to -the co-n~onent c in such a ~ay the,t the dcsired hydro~yl group content is achievecl.
This means tha-t ~hen smaller percentages by weight of the componen-ts a and b are employedS higher percentages by weight o~ -the component c must be selected in order to manu-facture the copol~J~ers according to the invention. If higher percentages by ~eight of the components a and b are employed, smaller percentages by ~-eight of the component c must be selected in order to manu acture the copolymers according to the invention.
The starting point in this approach m;ls-t always be that the copolymers according to the invention are intended to produce as high a solids c.ontent as possible, ihe relevant test viscosity being the dilution of the copol~ner solutions with xylene to a flo~ viscosity of 25 seconds at 25C, measured in a DIN cup having a 4 mm flow orifice.
The copolymers according to the inven-tion are manufac-tured by heating a mixture of the solve1lts or solvenl mix-tures, which preferably have a boiling range~of 150 to 180C, and the glycIdyl esters of /-alIcylallcanemonocarboxylic acids and/or .

Z13~1 .

~ dialkylall~ ncnlo~loc~ o}rylic acids, di.ssolved.in the 501~
ven-t, -to lG5 to 1~0C in a rcaction ~lask The m:ixturcs.
of monomcrs aS b, c, dl and d2 and the pero}ride mlx-tures e a-nd e' are a~ded to thi.s heated m:iYturc in the xeaction ~lask separatcly or, preI`erably, to~ether, slo~lly, uni~ormly ~d ovcr a per~xl o~ -time of 6 to lO hours, the po:l.ymerisa-tion temperature not being allo~le~l to fall below 155C. Af-tcr the addition of monomer ancl peroxide, polymerisation is con-tinued for a further 2 to 3 hours at re:r~v.x ternpera-ture un-til the sol:ids conten-t of -the solu-ti.on has reclchcd the theoreti.cal value of be-t~leen 70 and 9~% by ~eight. The copolyrners manufacture(l accordin~ to the invention MUSt have -the pre-de-termined -test viscosi-ty of Y to Z4, measured on the Gardner-Holcl-t scale 5 ~or 70,' strength by ~e~ght CGpOl ymer solutions in ethylglycol acetate. The copolymers are manufactured subject to the condition that the polymerisation and conden-sa-tion reactions proceed simultaneously and jointly at 165 to 180C.
These new copolymers can be used as the component h in reactive lacquers together with a polyisocyanate component B; The followin~ polyisocyanates can, for ex~mple, be employed as the component B. Ethylene diisocyanate, ~ro-pylene diisocyanate, tetrame-thylene diisocyanate, hexamethy-lene diisocyanate, 1,3-dime-thylbenzene diisocyanate, 1,l~
dimethylcyclohexane diisocyanate, l-methylcyc1ohexane-2,4-diisocyana-te, 4,4'-methylene-bis(cyclohexyl-diisocyanate), phenylene diisocyanate, 2,4-toluylene diisocyanate, naphthyléne diisocyanate, 3-isocyanatomethyl-3,5,5-trimetllylcyclohexyl .

-- 28 -- .

, 32~3~ .

isocy.lna~;c~ ly,..i.ns~ (1.i,.i,socy;.~ te, tr:iphcnylMethanc trl:isocya--natc, trim--t'~y~.ber1;~c~le-2,4,G-tri:isocylnate, ].-rncthy'lb~.:n~cne-2,/~,6--tr:i,isocyan(lte and dip~-1cny:l.~2~ll,4'-triisocyana1;e; di-isocyanatcs or trii,-,ocyana-tes inanufactured by reactlnb~ a poly:isocyana-l;c ~1ith a low-molccula:r di.ol or trio:L (for cxc~ple e-thylene glycol, propylene glycol, l,3-blltylene glycol, neo-pentyl glycol, 2,2,l~-trimcthyl-l,3-pen.tanedi.ol, he}anediol,' -tri.rnethy].olpropane or -tri1n~t}ly.1.0~e-tl~ane); c~nd GyanUrateS
which have been obta.ined by reac-ti.n~ thc said cli:isocya.nates Jith -the I'orm~-tion of a rin~ particul.arly valuable po'ly-iSOGyanate is the triisoG~Jc~nate con-taini.ng biure-t groups ~'nich is obtainecl by reac-ting 3 mols of hexcamethyl'ene diisocycmate and o-ne mol of water.
Ins-tead of -the polyisocyanates, it is also possible to use compou1lds which split off polyisocyanate.s, and also the reaction products, contai.ning isocyanate groups, of polyhydric alcohols with polyisocyanates 5 for exc~mp].e the reaction pro-d,uc-t from l mol Or -trimethylolpropane and 3 mols o~ toluylene diisocyanate, and also trimerised or polymerised isocyanates such as are describedS say,'in German Patent Specificati.on 951,168 (Farbenfabriken Bayer AG, ~ublished 4/10/56).
In addition, it is also possi.ble to use a reaction pro~
duct, havirAg a NC0 content ol 16 ^^ 17% by weigh.-t, formed from l mol o~ water and 3 mols of hexarnethylene dlisocy~la-te.
The last-mentioned reaction product from water and hex~nethy-lene diisocyanate is particularly preferred. The NC~
content of the reaction product applies to a 75~ strength æolution in xylene!ethylglycol acetate;

. ~ .

~1~2q~3~

Thc rc~.c~ion o:L tllc~ copolylllcrs ~ cont~linil-lg h~dro~1 groups witl-l-t})~ orgc3nic polyi.socyanates }3 when used in reac-~ve lacquers c~n be carricd out at 0.5 to 1.3 NC0 grGups per - hydro~yl group, depelld:ing on thc cnd use of -the react~on pro-ducts It is preferclble -to carry ou-t tlle reaction in such a way that -thc quantit:ies of -the or~anic po:lyisocyanate, rela-tive -to -the to-~al hydro~l cont~1l-t of the componcn~ts pres~nt in the r~action mixtureS are present in a ~lua~-tity oI 0.7 to 1.0 isocyana-tc group p~r hydroYyl group.
In order -to use the new Gopolymers, the mixtures of copolyrners A containing solven-t and con tair3ing hydroxyl groups and of polyisocyanate B are applied -to the appropriate sub-stra-tes in the sirnplest manner ima~inable, possibly after add-ing kno~m auxiliaries, such as levelling a~ents, pigments or dyestuffs,.by spraying, dipping, pcuring, brushing or other suitable measuresS and the sheet-like structures are dried at room temperature; in special cases, perhaps ~hen usin~ co~-pounds which spli-t off isocyanates, it is possible to s-tove the coatings; this depends essentially on the substrates used and on the requirernents set by practica]. use on the coatings.
The copol~ners ~ ich can be obtained by the process can be employed, together with polyisocyanates, for the pro-duction of coatings or coverings in the reactive lacquers-already illustrated, on substrates of the most diverse types, -for example porous or non-porous substrates, such as textile non-wovens, leather or plastics; The production of coat-ings on wood or metals should be singled Ollt particularly.

. - - 3~ -2~31 In every c).se h:igll--glo;s, pore-:rree, clas:l;ic .arld solverl~-resi.stcl]lt coatin~s ~IJhich have a vcry hard sur:~ace and ~1hlch can be -treated bot~-l with s-l;rong inorganic acids and ~Jith strong allca1:i rnctal hydroxide solutions ~lithou-t the coa.t.Lngs being attacked e~erl to -the sligh-test extent, are obta.~ned~
Coa-tings o.~ -this -t~pe display, i.n addi-tion9 an ou-tstanding resistance to ~leat}lering and resistance -to yello~ing.
In pigrnentrd coating compositiol~s based on thc poly isocyanate reac-tive lacquer/~inder solutiolls according -to the inven-tion the -to-tal conten-t of solids in the coating composi-tion is bet~een 62 and 90% by ~Jeigh-t, preferab].y between 67 and 90% by weight. The ratio o~ pigment to binder can be bet~reen 1:20 and 2:1. The following can be added a.s pig-men-ts: inorganic pi~nents, such as chrome yellow, Prussian - blue, Bruns;rick green and ti-tanium pigments 5 for exc~lple titanium dioxide, ex-tended titaniun pig~ents (whicll are extended either with precipi.tated or wi-th natural ex;tenders, such as alkaline carth metal sulphates, for example calcium sulphate and barium sulphate), tinted titanium pi.gmen-ts and ~:.
: 20 tit~lates, such as barium, tin, lead and ma~esium ti-tanates.
Other iypes of inorganic pigments can also be used, for example zinc sulphide pigmen-ts, such as zinc sulphide 9 lithopone, extended zinc sulphide pigments, such as lithopone on a calcium base, and zinc sulphide extended with natural extenders, zinc oxide or antimony oxide or organic pigments, that is to say . .
organic dyestuffs wllicll are free from sulphonic acid groups, carboxylic acid groups or other groups which ~mpart solubility in water Pigments also include, conceptually, other - 31 - ~

.

~2~3~

water-insoluble orgallic ~yestu~fs, for example calcium or barium lakes of azo dyestuffs.
The constituents of the sloving lacquers to be used can be processed to give lacquers by customary ~rocesses, preferably as follows. The pigment and a suitable quantity of solvent are mixed with part of the copolvmers accordinq to the invention to give a pasty or solid pigment paste. After the mixture has been thoroughly dispersed in a stirred ball mill, the remainder of the copolymer and other additives are added to the resulting paste or dispersion and the mixture is then for-mulated, using the solvents, preferably xylene, butyl acetate and/or ethylglycol acetate or acetone, to a sprayable viscosity at a solids content of 62 to 90~ by weight, preferablv 67 to 90%
by weight, of non-volatile substances.
Example 1 (component A 21.9% by weight, component B=7~.1% by weight 28 g of ethylglycolacetate (component A) and a) 11.7 g of glycidyl esters of ~,a-dialkYlalkanemonocarboxylic acids of the following empirical formula C13H2403, having an epoxide equivalent of 240-250, (designated in the following text only as glydicyl esters of ~ dialkylmonocarboxylic acids) are heated to 167C in a flask equipped with a stirrer, a reflux condenser and a water separator as well as a thermometer, and a mixture consisting of b) 25.5 g of hydroxyethyl acrylate, c) 3.3 g of acrylic acid, dl) 46.2 g of styrene, d2) 13.3 g of methyl methacrylate, it being necessary that the ~ by weight of the components a, b, c, dl and d2 (component B) add up to 100% by weight.

.

2~3~

e) 2.7 g of tcxl.--~)ut;y:l. pollJen~.oatc -- ZSol~y ~/eieht 1nd c') 2 0 g oI ~0,'. trcllg~h cumene hy~ropcroxiclc - l 25' by ~rei.c~;ht, -the % by ~rci.gllt fig~lres relat.ing to thc total mix-ture oi` the components ~ an~ B, is a~docl uniform].y, at a tcmpera.ture which ri.ses -to 170C, in tlle coursc of 7 hoursS ~hile the mixture ~oils and the reflux is cooled. /~fter the addi.tion is cornp]e-te, po].ymerisation is con-tinued lor a further 2 holirs un-til a solids contcn-t ol 81.0~o by weight :is reachecl Thi~
exarnp].e illustra-tes the most preferre~ elnbodilnen-t of the inven-tion.
The aci.d nurnber of tlle solid constituen-t is 7.5.
The viscosity of a 70~ s-trength by ~eight solution in ethyl- -glycol acetate is Z2 to Z3 on -the Gardller-Holci-t scale.
en -the solution is formula-ted with ~lene to a viscosity of 25 seconds at 25C, measured in a DIN cup having a 4 ~m flow orifice 9 it has a solids content of 47C~ by weight.
The copolyrner has a hydroxyl group content o* 4 5~ by weight.
Comparison test accordill~ to the state o he art Compari.son tes-t 1 (~.~ith reference -to the Example in French Patent Specification 1,556,309, which is the nearest appro~ch to the invention).
The hydroxyl group content, relative to the copolyrners 9 in Examples 1 to 10 in Frenc.h Patent 1,556~309 is as follows:
in Example 1 = 0.8 5~0 of hydroxyl groups in Example 2 - 1 % of hydroxyl groups in Example 3 = 1.26 % of hy~roxyl groups .
in Example 4 = 1.52 ~ of hydroxyl groups in Ex~mple 5 = 1.41 % of hydroxyl groups .
. - 33 -.

i~V Z~ 3~

in E~amplc ~ l % o~ hy~roYyl gro~ s in }~ample 7 -= 1.6~ ~' of hydro,yl groups in ~alnple ~ 5 ,' ol hydro}.y~ groups in Exarnple 9 = 1.~5 ~' of hydroxyl groups in Example 10 = ~ % ol hydroxyl group~.
Exalnple 10 in French Pate~t Specirica-tion 1,556,309, ~rhich has a hyclroxyl grou~ content of 3.1~%, is thc lleare5t clpprOaCh to the invention. The proced~re described in Exalllple 10 of French Patent Specir:ication 1,556,309 is ~ollowed.
parts by ~eight of 2-hydroxyetllyl methacrylate, parts by weight of methyl methacrylate, parts by ~eight of styre-ne, parts by weight of ethyl acrylateS
parts by ~ei~ht of the reaction produ~t obtained in accordance with reac-tion (a), 1.~ par-ts by weight of lauryl mercap-tan, 1.5 parts by weight of azoblsisobutyronitrile parts by ~Jeight of butyl acetate, parts by weight of ethyl acetate, parts by ~leight of toluene, parts by ~reight of ethylglycol acetate and parts by weight of xylene were converted into a copolymer solution. The viscosity of the 5~6 strength by weight solution is R on the Gardner Holdt scale.
The copolymer solution exhibits a considerable sediDlent and is also turbid; The solid constituents which had pre-cipitated could be filtered off by filtration. The ; - 34 -,~. .
. f~;`, ' ' ~

~ 2~31 turbi~ity o:C ~ resill solutioll could no-t l~c removed.
hell the solut,ion ,is Lorrnulate(l ~lith xylel~c to a viscosity of 25 seconcls at 25 C, mcasured in a DIN cup having a 4 rnm ~lo,7 orifice, i-t has a solids con-tell-t of 37% ~y weight; The copol~nc-,~r has a hydroxyl group content of 3;18% by wei~ht.
Comparison tes-t ~ reference -to the state o~:' t,he ar-. and the inventive concceT)-l-,ion of t~le pres~nt invent:'l,on Coml~arison test 2 The procedure clescribcd in Comparison tesl, 1 is followed;
but only -the monomers wcrt?alignt?ci with Exarnple 1 according -to the inve-n-tion. The follo~lin~ were used: 25.5% by weig'n-t of hydrox~yethyl acryla-te, 13.3~o by weigh-t of methyl methacry-late, 46.2//o by ~/eigh-t of s-tyrenc and 15~' by ~/eigh-t of reaction product obtained in accordanc,e ~rith reac-tion (a) of French Pa-tent Specification 1,556,309'. The copolymer solution exhibited a particularly s-trong, millcy -turbidi-ty which COUl d not be removed by filtration. The copolymer has a hy~rox~l group content of 4.5~ by wei~ht; The viscosity of the 5 streng-th by weight solution ~las Z at 20C, measured on the Gardner-Holdt scale. ~len -the solution was formulated with xylene to a viscosity of 25 seconds at 25C, measured in a DIN cup having a l~ mm flow orifice, a solids content of 28~6 by weight resulted.
~omparison test 3 The procedure described in Example 1 of the present invention was carried out, but, in divergence, polymerisa-~ion ~as carried out at a temperature of 160C and tert.-bu-tyl perbenzoate alone was used. The viscosity of the 70~' , - 35 - , ' ' , ~2~'31 strenyth by weight so]ut:ion in ethylglycol acetate, measured on the Gar~ncr-ilo]dt scale, is higher tha~ Z6 The resin solution exhibits a turhidity which could not be removed by filtration. When the solution was formulated with xylene to a viscosity of 25 seconds at 25C, measured in a DIN cup having a 4 mm flow orifice, a solids con-tent of 38% by weight resulted.
Comparison tes_ 4 The procedure described in Example l of the present invention was carried out, but, in divergence, poly-merisation was carried out at a temperature of 160C and cumene hydroperoxide alone was used, as an 80% strength solution in a mixture of alcohols, ketones and cumene. The viscosity of the 70% strength by weight solution in ethylglycol acetate, measured on the Gardner-~oldt scale, is higher than Z6 The resin solution exhibits a strong turbidity which cannot be removed by filtration. When the solution was formulated with xylene to a viscosity of 25 seconds at 25 C, measured in a DIN cup having a 4 mm flow orifice, a solids content of 34% by weight resulted.
Example 2 A. 28 g of ethylglycol acetate and a) 24 g of glycidyl esters, as described in Example l, are heated to 172C
in a flask equipped with a stirrer, a reflux condenser and a water separator and a thermometer, and a mixture consisting of b) 19.1 g of hydroxyethyl methacrylate, c) 7.2 g of acrylic acid, dl) 28.1 g of styrene and d2) 21.6 g of methyl - ''~-i'' ~ 31 methacr~l.alc~ :it l~ i.ng ne(,esiary th.lt thc ~0 by we:i.gh-t o:C the components a, b, c, dl and ~2 a~d up tc) lOO~o b-y we:i&rht~
e) 2.7 & of ter-t.-l)u-tyl perbcn%oatc -- 2% by weight and e') 2.0 g of ~0,0 strength cumenc hyclroperoxi.de . 1,2% by weight, - -the ~/~ by ~re:i~h-t figures rela-ting to -the total mixture of componen-ts A and B, is added ~mi.formly .in thc course of 7 hours while -the mixturè boils and -the reflux i.s simultaneously cooled. A~ter the acldi.tion lS compl cte, polyMeriSation iS
con-tinued ~or a fur-thcr 2 hours until a solids con-tent of 80C~S
by wei~ht has been reached, The aci.d numbcr of the solid component is ll. The v:iscosity of -the 70S' streng~th by weight solution in ethylglycol acetate is Y - Z, measured on the Gardner-~loldt scale. l!lhen the solution is forrnulated ~Jith xylene -to give a viscosity of 25 seconds a-t 25Cs measured in a DIN CUp having a 4 mrn flow orifice, it has a .
solids con-tent of 52,S by weight. The copol~ner has a hydroxyl group content of 4.17~ by weigh-t. The copol~^~er solution contains no insoluble solid cons-titucrlts and is free from turbidity.
Preparation of the~mopl~s~ y~
600 g of toluene, 200 g of ethyl methacrylate, 4 g of' acrylic acid and 296 g of rnethyl methacrylate are hea-ted to reflux temperature in a flask equipped with a stirrer and a reflux condenser and a water separator, and the following mixture, consistin~ of: 150 g of toluene and 3.5 g of di-benzoyl peroxide, as a 75% streng-th suspension in water, is added uniformly in the course of 2 hours. After a poly-merisation time of 2 hours, a further 2 g of dibenzoyl . - 37 -~ 2~!39, , pcroxide, as a ~,', strcng-th suspension in ~atcr, are aclclcd ancl polymerisati.on is con-tinued under re~l.ux. The solids con- -tcnt o~ the solution is ~lO,' by ~e.~ght. 'l`lle viscos:i.ty.of the solu-tion exhibits a valuc of X - Y~ measureid at 25C on the Gardner-Holclt scale. The aci(l nurnber i5 5.
Prepara-tion of thermo~la~tic cor~ ner 2 .
300 g of xy:Lene, 1.5 ~ of methacrylic acid a~d 300 g of methy] me-thacryla-te are heatcd -to 85C in a Ilas1s equipped wi-th a stirrer and a reIlux condenser ~ld a wa-ter separator9 and the following mixturcS consis-ting of: 50 g of x~rle-ne and 2.5 g of dibenzoyl peroxide5 as a 75,'0 s-treng-th suspension in wa-ter, are added uniformly in the course of ~ hours. Aft~r polymerisa-tion for 2 hours a-t-the same terr.pc-rature, one fu~er gram Of diben~oyl peroxide, as a 75,~ s-treng-th suspen-sion in wa-ter, are added and pol~er~sation i.s continued for a further 2 hours until the -theoretical solids content of 46%
by weight has been reached. ~hen the solu-tion is dilu-~ed ~rith n-butanol to 40yO by weight, it has a viscosity of Z3 - Z4,-measured at 25C on the Gardner-Holdt scale; The acid number of the poly~er is 4.
Example ~
~ ~ei~ht of co~o.lYmel and 3~0 by wei~ht of an or~nic triisocvanate, both rela-tive -to the __ weight of solid.
61.6 g of copoly~er 1 solution in e.hylglycol aceta~e (obtained according to Ex~mple 1, dissolved solids 81% by weight) are dissolved in a 1 : 1 mixture of xylene and ethyl-glycol acetatc together with 28;6 g of a 75,0 s-trength by 2~l3~

cight solutic)rl o:C a tri.i..socyllnltc ~hich has a ~C0 conten-t of 16.5 to 17.0,S by weight .arl(l has been ob-ta.:ined by reacti.ng 3 mols of hexame-thylene diisocyana-te and 1 mol of ~ater.
0 5 g ol di.etllyle-tilanolalnine is acldcd and thoroughly mixed and the rnixture is forrnulated by add:in~r xylene to a spraying viscosity, namel.y 25 seconds a-t 25C, mea.sured in a DIM C~lp having a l~ mm flo~l ori:Cice. The lacquer was applied to glass shee-ts at a we-t f:ilrn l~yer thickness of 90 ~rn and was dried in -the air a-t 18 to 20C. The pendulum hardness, io measured by K~nig's mcthod (DIN 53,15r~), is ~0 seconds after one day, 140 seconds after three clays and 180 seconds after seven days. Films which had been sto-ved at ~0C for 30 minu-tes gave pendulum hardness figures of 102 seconds, rising to 1~0 seconds af-ter being stored for one day at room tempèra-ture and to 202 seconds after 3 daysr Films ~rhich had been stoved at 120C for 30 minutes ga~re pendulum hardness figures -~
of 203 seconds which did not change further on storage.
The cured ilms were particularly insensitive towards the fingernail test and had very good resis-tance against xylene and acetone.
After weathering for 18 months in the Florida clima-te, a top lacquering (pigmented with 0.6 part by weight of rutile:
1 part by weight of binder combination) ~hich had been applied to primed zinc-phosphated steel sheets exhibited a loss of gloss of only 10,~ compared with gloss measured before the weathering.
Black lacquers with a particularly high gloss are obtained if 20 parts by weight of carbon black .~ogether ' ~Z~3~L

~ith 2'~0 ~arts by ~JC~i~]~t oi' co~)olymc~ 1 so:Lution, ca]cium naphthc~nate and silicorlc oil, as a l~o strcngth sol~;t:ion in xylcne, ancl using a corrcs~onding quan-ti-ty o~ xylenc and butyl acctate, are subjec-te~l -to a grinding process :Eor c~out 30 to t~o rninutes, using a sand rnill~ ~tcr add:ing a fur-ther 270 parts by weigh-t o~ copoly~ r 1 solution and f'ormu-latin~ the mixturc ~ith ~rylene/ethylglyco:L acetatc in -the proportions of 1:1 to a v:;scosity of 25 seconds in a DIN
cup having a 4 mm flot~ orifice, lacquers ~J~ich are stable to floccula-tion for several tnonths are ob-tained; A reactive lacquer based on 70,~ by ~eigh-t of copol~7~ler c~ld 30S, by ~eigh-t of an organic triisocyanate ~/rhich has been ob-tained by reac--ting 3 mols of he~c-~ethylerle diisocyanate and 1 mGl of water~
is prepared. Coatings which have been ~ ~uccd there~r:ith~
and ~hich are stoved at 80C for ~0 minutes give f'ilms with an insensitive surface, so that in the repair lacquering , of vehicles the adhesive masking tapes cc~n be removed whi]e the films are in an incompletely cooled condition and assembly can be carried out. After storing for 8 hours at 23C, the pot life of a clear lacquer co~bination prepared from copolyDIer 1 ethylglycol acetate solution and -the triisocyanate and formulated with xylene to a viscosity of 25 seconds, is such that the viscosity is 40 seconds, measured a-t 25C in a DIN cup having a 4 mm flow orifice. The resul-~ of this is that the binder combination can be used throughout a working day of at least 8 hours, since a doubling of ~iscosity to 50 seconds is tolerated by the lacquer user.

, ---40 ~

~l~ZQ!3~ .
F~ In~
Reactivc l~o(lu~?r hJ~ (l on 70,', h~ rht of co~olymer .~n~1 7JO
,h-~ o r an orl~.nic trii ocy ~ ho-lh r~la-tive -to -the ~e~ o~
62.5 g of copolyMcr 2 ethylgl~col accta-te solution (obtaine(l according to EYample 2, dissolve(l ;olids Z0~ by weight) are disso]ved in a 1:1 mi}-ture of ,y:lene and cthyl-~lycol aceta-te -toge-ther with 2~.6 g of a 75'~ ;tren~t:h by weight solution O:r a -triisocyanate whiCh has a N~0 content of 16.5 - 17.0% by weight and ~hich has been obtained by reac-ting 3 mols of hcY.ame-thylene diisocyana-te and 1 mol o~ ~ater, and 0.5 g of diethylethanolaMine iS miY~ed in c~nd the mixture is formulated with xylene to a spraying viscosi-ty of 25 seconds at 25C, measured in a DIN cup havin-r a 4 Mm flow o-rifice5 ~ld is applied -to glass sheets at a wet film laycr thicl~ness of-90 ~m and dried in the air at 18 to 20C. The pendulum hardness, measured by K~nig's method (DIN 535157), is 45 seconds after one day, 110 seconds af-ter three days and 160 seconds after seven days. Films which had been s-toved at 80C for 30 minutes gave pendulum hardness fi~lres o~ 75 seconds, rising after s-torage at 23C for one day to`l~0 seconds and to 162 seconds after four days. Films ~Jhich had been stoved at 120C for 30 minutes gave pendulum hardness figures of 165 seconds which did not change further on stora~e~
The cured films were particularly insensitive towards premi~-grade motor fuels and ~ylene.
After 16 months weathering in the Florida climate, a top lacquering (piO~ented with 0.65 part by wei.ght oI rutile:

.

. -- 41 --.

11~2~3~

1 T)art by ~rcig}ll. o:f l~inder combi~ ion) ~/hich had bcell appl:Le~
to prilne(~ ,ialC-pllOspll.l ted S l;cel S}~ICe l;S g.lVe a los.; of gloss of only 12~o CO]llparC~d ~it3~ glo;. meas~lred bcfore thc ~eathcr:i.ng~
Further comr)araliv~ cests -l~ rlemon-.-l;r(~l;e -lhe technica~ r ss achicved ~sses~ment oC ~ c a~l~e~r.3nce of the cooolvmer olu~iorlc Thc resi.li solu-tions are ass~s;ed for the llocculation of solid 9 insolubl~ consti-tuents ancl for turbidi-ty in t~e resin solu-tions. ~s tes-~shave s}~o~rn5 the sol.id, insoluble constitucn-ts can be i`illered off. Turbidi-ty in the resin solu-tions is not removed by liltra-tion (see Table 1).
1 = clear solution (highest value) 5 = very strong, milky turbidi-t~7 (lo~res-t value) 0 = no floccula-tion ~ = flocculation of solid cons-tituen-ts As the results in Table 1 sho~, the copolymer solu~ion manufac-tured according to the invention is markedly superior to the known copolymer solutions.
Preparation of black to~ lac~uers and assessme1lt of th ~ ss of the fi.lms . . .
With the aid of a sand mill, grinding for a period of about 60 minutes, a lacquer is prepared from the follo~Jing components: .
270 g of copolymer solution manufactured according to the invention, from Example 1, 20 g of carbon black, - _--~

.
4 g of diethylethanolc~mine, ~ ~2 -~1~D2'~

o g o:r si,:l.icooa~ oiJ,, ~IS ~ str~nclt~l solu-Lion in xyl~ne, 0 e o~ ca'.],ciulll napllt~ena-le7 l:iquid ~/ith a 1-1,/ calciuln content;, 65-g of butyl ace-ta-te and 70 g O:r xylene.
~fter adding a fv;r-thcr 270 g O:r copolymer so:Lution manufac-ture~l according -to the inven-tion, in accordance with Ei~nple 1, and dilu-ting wi-th a solvent rn:i~ture cornposed of equal pc-lrtS by weigh-t of ~ylene~ and bu-t~rl aceta-t~ to a flow viscosity of 23 seconds a-t 20C, rneasured in a DIN cup having a 4 mrn flo~J
orifice, the lacquer is poured on,-to vertical glass sheets c~nd.
the degree of gloss is tes-ted a~ter the solvent has evaporated.
High-gloss films are obtained which e~libit no deposition OI
pigmen-t in the range between 1 and 10 ~lm~ The proportion by weight of binder to pi~nent is 95.60~' by weighl o~ binder to 4;4% by ~Jeigh-t of pi~ment. The pi~llentat.ion and -the ... . .
draining off are carried out in an identical manner for -the copolymers in Cornparison tests 1, 2, 3 and /~ ~nd the gloss and the deposition of pigment of the lacauers are asscssed.
As the results in Table 1 sho~J, the copol.~ller solution manu-factured according to the invention is supe-rior to the kno~;.
copo~ymer solutions.' 1 = high-gloss films with no deposition of pigment (highest value) 5 = matt films and very considerable deposition of pigmen~
; (lowest value) .

'.

3~

.
Teslin,!r t~lC: co~ ity oî i;]-le col-~ol.ymcr ~olllt:ion.s .~coordin~
to t]~e .i~ ent:ion~ o:l- h~almnl.~ ~. alld ~.~ arl(3. th(~ Cornnarison tests.
1 and ~ t;he l~ er;no~a~l;.c co~oLvr.rleIs 1 anfl 2 _~
62 par-ts ~)y weigh-t of -the copo].yme.r so~.uti.on obt~in.ed according to ~xclmple 1, consistirlg of 50 parts by weight of copolymer and 12 par-ts by ~/eight oi` ethy:l.glycol ace-tate, are mixed ~i-th 1?5 parts ~y ~cight of t]le -ther3noplcls-tic copolymer solu-tion 1, consis-ting of 50 par-ts by ~!cight Or -thermoplastic copolymer and 75 par-ts by ~leight o:E -'coluene, and -the mixture is diluted ~ith a so:l.vent mixture consisti.ng of xylene and butyl acetate in a 1:1 ra-ti.o by ~-eight -to a soli.ds conten-t of 40s' by ~reight and is applied to glass sheetsS a dry film layer thickness of 250 to 300 ~.m being achi.eved. After drying at room tempelature, -the appearance and the cor.~patibili.ty of -the films were inves-tiga-ted, This mixture consis-ts o:C 50,~ by weight o~ copolymer 1 according to the inve-ntion and 505' by weigh-t of the ther~oplasti.c copolymer 1, The copol~ner solutiohs manufac-tured according to the invelltion, of Example 1 and 2, and the copol~ners from Comparison tests 1 and 2 were mixed with the thermoplastic copolymers 1 and 2 in the manner described above and -l;he Mixtures were applied to glass sheets and the resul-ting films were assessed. As the results in Table 2 show, the copol~ner solutions manufactured according to the invention are markedly superior to the kno~
copolymer solutions.
Test for appearance of film: 1 = high-gloss (highest valuc) . 5 = very cloudy film (lowest value) -- 4~ --.
~. . . . .

~ 2~3~

Testinr l;}~f l-)o-l lilt o~ rc.lctive lac~ 0l;
8G.6 ~ oL the copo:Lym~J- so:lut;:ioll m.~nufacturecl accor(l:ir to thc invention, of` ~Yample ~ md l~o g of a 75~0 strength by weight solution o~ a triisocyanate ~^/hic]:l contains biurct groups and has a NC0 content; oi` 16 5 -to 17.0SS by ~eight and has been obta:ined by reactin~ -tl-ree mols of he~ ethylene diisocylnate and one mol of ~ater, are mi~ed ancl are di:Lute~ t~ith Y~ylene to a flo~r viscosi-ty o~ 25 seconds a-t 25C, measured in a DIN cup having a 1~ mm flo~ ori~:ice, and -thc- rise in viscosity is determined af-ter 6 hourci storage at 23C. The miYinr ratio is 70,~ by ~eight of -the copolymer manufactured according -lo -th~
inven-tion, irom Example 1, ancl 30,' by ~e~gh-t oï the triisocya-nate ~7nich contains biuret groups.
A comparlson combinatio-n is composed OI 70,~0 by ~ei~ht of copol~ner from Comparison -test 2 and 30~o by ~eignt of -the triisocyanate-which cor.-tains biuret groups.
A further comparison combination is cornposed of 77S' by weight of copolymer from Comparison -test 1 and 23~' by weight of the triisocyanate ~Ihich cointains b-iuret groups, as described in French Patent SpeciLication 1,556,309.
The viscosity is adjus-ted in the same way, using the solvent mixture described above. As the r~sults in '~abie 3 show, the reactive lacquers according to the invention are markedly superior to the known reactive lacquers, since they have a longer application life.
Preparation of_~i~nented t~o-comnonen-t reactive lacquers and __ .
testing the tcndency of the ~toved films to l~m off The ratio in the combination is 65rS by ~eight of .. .

.

2~33L

copc~].y.mer ma~ acturecl accordil-)g to the inven-tion and 35% by wei(Jht of ~ri.isocyanate con~aillincJ biuret groups. .The pro-portion by weight of pigmcnt: binder is 42% by weight: 58%
by weight.
A lacquer paste i5 prepared hy grindiny in a bal].
mill for 24 hours from the following components: 80 g of co-polymer solution manufactured according to the invention of Example l, 73 g of titani.um di.oxide (ru~i.le), 0.5 g of diethyl-ethanolamine, 2.5 g of silicone oi] as a 1.% strength solution in xylene, 2 g of calcium naphthenate, liquid with a 4% calcium content, 4.5 g of bentonite as a 10% strength by weight solution in xylene/methyl isobutyl ketone in the proportions by weight of 86:4, and a solvent mixture consisting of xylene and ethyl-glycol acetate in the proportion of l:l by weight. To this mixture are added 46.6 g of a 75% strength by weight solution of a triisocyanate which contains biuret groups and has a NCO content of 16.5 to 17.0% by weight and has been obtained by reacting 3 mols of hexamethylene diisocyanate and one mol of water, and which is dissolved in a mixture of xylene and ethylglycol acetate.
This mixture is then diluted with a mixture of xylene, butyl acetate and ethylglycol acetate in the proportions of l:l:l by weight, to a flow viscosity of 22 seconds at 23C, measured in a DIN cup having a 4 mm. flow orifice. This reactive lacquer is applied by the spray application process to vertical steel sheets in such a way that dry film layer thicknesses of 80 ~m are achieved.

.

2~-331 '~}lC -t:i.me o'; e,~posure -~o air bct~/een ind:ivi.~ual Gpray applica-t:ions .sl1ou:Ld ~)c at lno.~ 30 secon(ls to one minute. ~f-ter the spray appl:i.cc~.',iorl has been c~rri.ed ollt, -the rnaterial is exposed -to -the air for approY. 5 m:inutes and -tlle lacqucr li.lm is stoved a-~, 120C for 30 minutes.
1 Coln~ari.c;orl -tec,-t ~:r -th~ -t;ell~e~lc~ r~m o.~f The ratio in the combination i.s 7r~/ by ~eigh-t of copoly-mer i`rom Cornparison tes-t 1 and 235' by ~lci~h-t of triisocyarla-te contai-ning bivre-t groups. The proporti.on by ~Jc-ight of pig-rnen-t : binder is 42~' by ~reigll-t : 58~' by ~leigh-t.
2. Com~ari~ n lest of thc te~ e~cv -to_r.un off The ratio in the combina-tion is 65~' by weigh-t of copol~ner from Comparison.-test 2 and 35~5 by weigh-t of triiso-cyanate con-taining biure-t ~roups. The-propor-tion by wei.ght of pigrnent : binder is L~20' by ~leigh-t : 58~ by ~Jeight.
The pigmentation and -,the spray application to ver-'cical steel sheets are carried out in the same ~lay for -the above Comparison tests 1 and 2 as for the copolymer 1 rnc~lufactured according to the invention and ~escribed above. The films are stoved a-t 120C for 30 minutes. As can be seen from Table 3, the reactive lac~uers manufactured according to -the invention are markedly superior -to the kno~ reactive lacquers by virtue of lo~er tendency to run off.
Further com~arison tests with reacti.ve lacauers based on the co olvmer SO~UtiO]lS accordin~ to the invention and ~olviso-P .. - - ~ . ~
cyanates, in comparison with the known reacti.ve 'lacauers o~
French Patent Specification 1,556,309 A reactive.lacquer composed of 7070 by ~eight o~

, .

2~

COpO Lylner', ~}li (`h COI'l'e ';pOrldS to ~) o 6 g O:r. -l;he copol~ner solu-t:ion manuflcturccl accor(l:ing 1;o thc invclltionS of F~.ample 1, and ~0% l)y ~le:i~h-t of triisocyana-t;e, ~lhich corre(;ponds -to 40 g of a 75,0 stren~ by ~ei~ht solution of a tri.i.socyanatc ~lhich has l)ecn preparc~d frorn 3 mols of hexamct]lylene dlisocyanatc and one mol of ~la-ter and ~lhich has a I~C0 content of 16.5 -to 17.05' by ~lei~llt ancl ~hich is dissolvecl in a mi~ture of ~ylene and e-thyl~rlyco:L acetate, is dilu-ted ~litll acetonc -to a f].ow viscosity of 40 seconds a-t 25C, rneasured in a Dïl~ cup llaving a flo~l orifice of 4- mm. The solids content of -this dilute resin sol~tion is de-termined by evapora-ting it at 120 C for 60 mirlutes.
The resin solution is applied by spraying to a steel sheet using one ~d ? half cross--coats, the ma-terial belng exposed to the air for a.pprox. 1 rninute bet~leen each cross-coat. After the lacquere~ steel sheet has been exposed to the air for a time of 5 m.inutes, i-t is sto~ed at 120C for 30 minu-tes. A smoo-th, blister-frce and crater-free lacquer ~Jith a dry film alyer thickness of 70 to 80 ~m ~las obtained.
A reactive lacquer composed of 70S' by ~le.igh-t of co-polymer, which corresponds to 87;6 g of the copolymer solution - according to the invention, of Example 2s and 30,' by ~ei.ght of triisocyanate, which corresponds to 40 g of the triisocyanate described above, is made up by mixing and is diluted as des-cribed above, its solids content is determined and it is used to lacquer a steel sheet. After stoving, the lacquered steel sheet has a dry film layer thickness of 70 t.o 80 ~m and e~libits no cra-ters or blisters;

, , 1~;D2~31 ~ react,ive l,.ac~lu~r cornporied of ~X,0,' by ~eigllt of copolymer ~ Jhicll c~rresponds to Gl.~ g o:C t}le copo'lymer solu--' tion according -to thc inventi,on, frorn E:x~lmplc 1, and 1~3;0~ by ~eight, correc;pond;ng to 11 ~, of :~-isocyanatorn~thyl 3,5,5--trime-thyJcyc'Lo}-le~yl isocyana-te, is Inade up by mi~;ng and is dilu~ed ~ h<~cctone, as d~scribed abo~e, tJ'the ~.-,alne viscosi-~y, i-ts sol:idscontent is determinecl and i-t is used; as described above, -to lacquer a stee] shee-t, AC-ter stovlng~ -the lac-quered steel sheet e~lllbits no folmatlon of craters or blisters and has a smooth surface a-t a dry film layer -thick-ness of 70 -to 80 llm.
A reac-tive lac~ucr composcd of ~2,0^,b by weight of copolyrner 2, ~hich corresponds to 62.5 g of -the copolymer solu-tion manuIact~lred accordin~ to the invention, of Example 2, ; and 18.0,6 by weight, corresponding to 11 g, of 3-isocya-na-to-me-thyl-3,5,5-trimethylcyclohc-xyl isocyanate is made up by mixing and, as described above, is diluted wit'n acetone -to the viscoslty described above. The solids content of the resin solution was determined and a steel sheet was ]acquered and stoved as indicatcd above. The lacquered sheet had a dry film layer thickness of ~0 ~m and gave a sr~ooth, crater-free and blister-free surface.
The known rëactive lacqtlers having the percelltages by weight indicated in Table 4 are diluted with acetone in the same way to a flow viscosity of 40 seconds at 25C, measured in a DIN cup having a 4 mm flow orifice. The resln solu-tions are also applied by sprayingS at one and a half cross- , coats, the material being e~posed to the air in each case for s~, ' , ~l~Z~P31 apr)rO~, 1 m il-ltl 1; ' a~ter ever-y hal:f cro-;s--c.oa-t. ~i-ter the rcact.i.ve ]-lc(lller:;}l~ve becn appl:iecl, the rnatcrial is exposed -to tl1c air ~or 5 rnirJute.; and. stoved at 120C for 30 rninutes.
A-t first5 only films havln~ a dry fi.]m layer -th:ickrlcss o~
40 to 50 I.lm ~cre obtlined.. Tne surface exhibi.tcd ll)a.ny craters and bli.sters If i-t is decired -to reach layer thicknesses of the clry f.ilm of` 70 -to ~0 ~m ~ith the k.no~n reactive lacquers, the spray application prc)ccss must be increasecl to t~o arld a hal~ to -three cros.s-coats. The filn~s ~JIlich t~ere -then s-toved e~hi~ited an even more s-trongly marked forma-tiorl of blisters and craters than the films ha~in~
lo~er dry filln layer thicknesses. In addi-tion) the solicls conten-t of the dilute resin solutions was deteImined as ctes-cribed above.
Additional adv~n-tages for -the copoly.mer solutions according to the inven-tion emerge clearly from these com~;arico~
tes-ts.

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. -- 53 -- ;

Table 4 . _ Solld~ content A~pe~r~nce, after stovin~, ln ',~ by ~Jei6ht of t~.e fLlms o~alned fro~
of the di:Lute~ the reactive lacquer3 . resln solutions . _ ._ Reaetive lac~ucr compo~ed of at 70-80 llm, no blister-70;0 by weiGht of copolymer . . ln~ or crater-formation manufaetur~d accor~ing to the 67.5 .
invention, from ~ample 1, and 3G;' by weight o triiso-eyanate .
Reaetive lacquer composed of 70S~ by tlei~ht of copolymer manufactured accordine to the 70.2 at 70-80 ~m, no blister-invention, from ~xample 2, . ing or crater-formation and 30,0 by weight of triiso- .
eyanate Reaetive lacquer composed of at 70-80 ~m, no blister-82.0,', by ~leight of copolymer ing or erater-formation manufactured according to the 68 inve:~tion, from Example 1, ..
and 18.0S~ by lei~ht of iso-phorone diisoeyanate ~) Reaetive laequer eomposed of at 70-80 ~m, no blister-82.0;, by weight of eo~olymer ing or erater-formation manufaetured aecording to the 72 lnvention, from E~ample 2, and 18-055 by ~/eight of iso-phorone diisoeyanate +) .
Reaetive lacquer composed of . at 40-50 ~m, ~listering 77~ by ~eight of comparison 52 and erater-formation;
eopoly~er 1 and 23~' by weight at 70-80 ~m, increased of triisocyanate blistering and crater-. formation Reaeti~e lacquer composed of at 40-50 ~m, considerable~
70~,~ by ~leight of comparison 47 blistering and erater-.
eopolymer 2 and 30;0 by weight formation; at 70-80 ~m, I
of triisocyanate the whole film is full of blisters and craters Reaetive lacquer eomposed of at 40-50 ~m, blistering 85.7% by weight of comparison . . and erater-formation;
eopolymer 1 and 14.3S~ by 52.5 at 70-~0 ~m, increased weignt of isophorone.diiso- blistering and erater- ¦
eyanate +) for~,ation Reactive lacquer composed of at 40-50 ~m, considerabl~
82.~;5 by wei~ht of eomparison blistering and crater-eopoiymer 2 and ~8.0~ by 48 for~ation; at 70-80 ~m, ' wei6ht Or isophorone diiso- 75~ of the film is full cyanate ~) of bl~sters and craters . . . .
As can be seen from Table 4, the reaetive laequers manufaetured accord- I :
ln6 to the invention are superior to the kno~n reaetive laequers.

I)3-Isocyanatomethyl-3,5,5-trlmethylcyclohexyl isocyanate o 54 o .

7- . ,

Claims (2)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A coating composition which dries by physical means in the air containing as an essential ingredient A) a copolymer solution of I) 10 to 30 % by weight of inert organic solvents and II) 70 to 90 % by weight - both percentages of I) and II) up to 100 % by weight - of copolymers containing hydroxyl groups which have been manufactured by heating to 150 to 180°C, in the presence of a mixture of diacyl per-oxides as polymerisation initiators, a mixture of inert solvents have a boiling range of 150 to 180°C
and a) 5 - 24 % by weight of glycidyl esters of a ? -alkylalkanemonocarboxylic acids and/or ? ,? -dialkylalkanemonocarboxylic acids of the following empirical formula C12-14H22-26O3, or a mixture of glycidyl esters of ?, ? dialylalkanemonocarboxylic acids having a content up to about 10 % by weight of the mixture of glycidyl esters of ? -alkylalka-nemonocarboxylic acids of the said empirical for-mula and having an epoxide equivalent of 240 to 250, to which a mixture of b) 12 - 20 % by weight of hydroxyethyl acrylate and/or hydroxyl methacry-late, c) 1 - 10 % by weight of acrylic acid, d1) 20 - 50 % by weight of styrene and d2) 5 - 35 %
by weight of methyl methacrylate has been added, the components a, b, c, d1 and d having been em-ployed in such quantities that their total is 100 by weight and the polymerisation and condensation reactions having been proceeded simulataneously and jointly and the components a, b, and c, having been employed in such quantities that the copolymers have a hydroxyl group content of 3.5 to 6.5 % by weight and B) a further component said components A and B being applied in a ratio of 20 to 80 % by weight of com-ponent A) and 80 to 20 % by weight of component B) which is a thermoplastic copolymer prepared from 98 to 99.5 % by weight of methyl methylacrylate or both and 0.5 to 2 % by weight of methacrylic or acrylic acid, the sum of the percentages of B) and the components A) and B) always being 100 % by weight.

2. A method for preparing a coating composition as claim-ed in claim 1, which dries by physical means and which comprises mixing the copolymer solution A) with a thermoplastic copolymer B).