CA1247283A - Aqueous acrylic interpolymer coating dispersion - Google Patents
Aqueous acrylic interpolymer coating dispersionInfo
- Publication number
- CA1247283A CA1247283A CA000407386A CA407386A CA1247283A CA 1247283 A CA1247283 A CA 1247283A CA 000407386 A CA000407386 A CA 000407386A CA 407386 A CA407386 A CA 407386A CA 1247283 A CA1247283 A CA 1247283A
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- CA
- Canada
- Prior art keywords
- monomers
- acrylate
- water
- weight
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Abstract
Abstract of the disclosure:
Aqueous copolymer dispersions can be prepared from styrene, methyl methacrylate, esters of acrylic acid, hydroxyalkyl (meth)acrylates, unsaturated monocarboxylic or dicarboxylic acids, acrylamide and/or methacrylamide, N-methylolacrylamide and/or N-methylolmethacrylamide or etherified N-methylol(meth)acrylamides, when the monomers and the ratios of their amounts are specifically selected, by copolymerization in the presence of an emulsifier and a radical-forming initiator, which dispersions, in combi-nation with aminoplast resins, provide thermosetting coat-ing agents with outstanding properties. These coating agents provide surface coatings which have high elasticity, resistance to weathering, good adhesion and freedom from flaws.
Aqueous copolymer dispersions can be prepared from styrene, methyl methacrylate, esters of acrylic acid, hydroxyalkyl (meth)acrylates, unsaturated monocarboxylic or dicarboxylic acids, acrylamide and/or methacrylamide, N-methylolacrylamide and/or N-methylolmethacrylamide or etherified N-methylol(meth)acrylamides, when the monomers and the ratios of their amounts are specifically selected, by copolymerization in the presence of an emulsifier and a radical-forming initiator, which dispersions, in combi-nation with aminoplast resins, provide thermosetting coat-ing agents with outstanding properties. These coating agents provide surface coatings which have high elasticity, resistance to weathering, good adhesion and freedom from flaws.
Description
~Z~72~
IIOE ~1/170 ~hc~ invelltiorl rc~lates to a ~rocer;~ for the pr~.
~ para~ion o~ an aqueous copoLyrner dispers;orl and the use of this dispersion ~or the preparatiorl of coatings ~Ih;ch can be crosslinked by heat tthermosetting co~tings)O
S Aqueous copolymer dispers;ons are of partlcular ;nterest for the preparat;on of thermosetting coatin~s, because they are not flammable and are less physioloyically objectionable than coating a~ents contain;ny solvents.
Furthermore, there is no neccssity to recover a cost!y solvent. In addition to the properties wl);ch are requircd of all plastics dispers;ons, such as ~ood flow behavior and thus processability~ freedom from coagulat;on~ stora~e and heat stability, it is also particular;y important for copoiyrner dispersions whicil are to be used as binders for the preparat;on of thermosett;ng coatin~s that coating agents are obtained which are readily pigrnented ~nd adhere well~ which dry even at room temperatu~e and which show no cracks or other ;rregularit;es ;n the f;~m~ The coa'cin~s o~ta~ned from these should then bc curable by heat;~ ~reat ment. For tllis purpose, the copolymers on which the dis-persions are based have reactive groups in the molec~lle shich react ~Ji h react;ve groups of certa;n resir-s, ;n par-- ticular aminop-a~t resins~ so that the b;nder crossl,nks~
Irl addition to the advanta~es such as~ for exar~ple~
lo~ v;scosity a. a hi.gh content of solids~ h;gh moleclllar weight and the absence of volatile solventsr ~q~leous co-polyr~er d;spersiolls also have disadval1tages for therrno-settin~ coatings such as, for example, a lac~ of pigment Jett;n~, aî defici~1t ~ nt b~ldin~ cc-x-;lci-l:y ancla ]ac~ '0 1~47~ 3 v~ adllc~ion lo the sub3trate by th~J coa~ing aqents pte parecl by m~c\ns oP th;s cl;spers;on antl an ina~equate elas-t;city of the baked ~;lms Mixtures of aqueous polyacrylate dispersions w;th polyepox1des as the reactive partl\er are knowr) ~cf. German Auslegeschrift 1~199,~20 = ~ritish Patent 84~350).Lacquer films o~ these m;xtures becorae br;ttle on weathering and turn yellow under the action of UV light~
Copolymers in aqueous d;spersion wh;ch are ~a~lly produced from ~,~-unsaturated carbonitriles and hich can be crosslinked with ar,lino- or phenol-formalde-hyde condetl.at;on products are also known ~cf~ German AuslegeschriTt 1,24B~194). However, these products are unsuitable as b;nders for h;gh-qual;ty lacquers for rnetals, s;nce the lacquer filma prepared frOlh the(n do not fUlri l practical requirements in respect of the tendency to turn yellow, flexibility and adhes-ion.
Aqueous copolymer dispersions are aLso known ;n ~hich~the copolymers on wh;ch they are based contain Inono-mer un;ts wh;ch hûYe hydroxyl groups but no nitrogen tcf.~erman Offenlegungsschr;Tt 2,252,065 = U.S. Patcnt 4~152,688). By ~eans of these dispersions~ the gloss and the scratch resistance of the lacquer f;lms prepared from them can adm;ttedly be improved~ but~ e~en in this case, the flexibility of the lacquer films is inadequate for practical requirements.
Moreoverf aqueous copolymer dispersions are knoun, for the prepar~tion of which aroraatic monov;rlyl monomers are copolymer;~e~ with esters of acrylic or methacrylic 7Z~3~
-- ,.,~ ..
ar;d and moliolilels havin~ hydroxyl, alnide, amine, carbo~l or e~poxide ~rollps ~cf. Germln 0-Ffenlegungsschr;~ten
IIOE ~1/170 ~hc~ invelltiorl rc~lates to a ~rocer;~ for the pr~.
~ para~ion o~ an aqueous copoLyrner dispers;orl and the use of this dispersion ~or the preparatiorl of coatings ~Ih;ch can be crosslinked by heat tthermosetting co~tings)O
S Aqueous copolymer dispers;ons are of partlcular ;nterest for the preparat;on of thermosetting coatin~s, because they are not flammable and are less physioloyically objectionable than coating a~ents contain;ny solvents.
Furthermore, there is no neccssity to recover a cost!y solvent. In addition to the properties wl);ch are requircd of all plastics dispers;ons, such as ~ood flow behavior and thus processability~ freedom from coagulat;on~ stora~e and heat stability, it is also particular;y important for copoiyrner dispersions whicil are to be used as binders for the preparat;on of thermosett;ng coatin~s that coating agents are obtained which are readily pigrnented ~nd adhere well~ which dry even at room temperatu~e and which show no cracks or other ;rregularit;es ;n the f;~m~ The coa'cin~s o~ta~ned from these should then bc curable by heat;~ ~reat ment. For tllis purpose, the copolymers on which the dis-persions are based have reactive groups in the molec~lle shich react ~Ji h react;ve groups of certa;n resir-s, ;n par-- ticular aminop-a~t resins~ so that the b;nder crossl,nks~
Irl addition to the advanta~es such as~ for exar~ple~
lo~ v;scosity a. a hi.gh content of solids~ h;gh moleclllar weight and the absence of volatile solventsr ~q~leous co-polyr~er d;spersiolls also have disadval1tages for therrno-settin~ coatings such as, for example, a lac~ of pigment Jett;n~, aî defici~1t ~ nt b~ldin~ cc-x-;lci-l:y ancla ]ac~ '0 1~47~ 3 v~ adllc~ion lo the sub3trate by th~J coa~ing aqents pte parecl by m~c\ns oP th;s cl;spers;on antl an ina~equate elas-t;city of the baked ~;lms Mixtures of aqueous polyacrylate dispersions w;th polyepox1des as the reactive partl\er are knowr) ~cf. German Auslegeschrift 1~199,~20 = ~ritish Patent 84~350).Lacquer films o~ these m;xtures becorae br;ttle on weathering and turn yellow under the action of UV light~
Copolymers in aqueous d;spersion wh;ch are ~a~lly produced from ~,~-unsaturated carbonitriles and hich can be crosslinked with ar,lino- or phenol-formalde-hyde condetl.at;on products are also known ~cf~ German AuslegeschriTt 1,24B~194). However, these products are unsuitable as b;nders for h;gh-qual;ty lacquers for rnetals, s;nce the lacquer filma prepared frOlh the(n do not fUlri l practical requirements in respect of the tendency to turn yellow, flexibility and adhes-ion.
Aqueous copolymer dispersions are aLso known ;n ~hich~the copolymers on wh;ch they are based contain Inono-mer un;ts wh;ch hûYe hydroxyl groups but no nitrogen tcf.~erman Offenlegungsschr;Tt 2,252,065 = U.S. Patcnt 4~152,688). By ~eans of these dispersions~ the gloss and the scratch resistance of the lacquer f;lms prepared from them can adm;ttedly be improved~ but~ e~en in this case, the flexibility of the lacquer films is inadequate for practical requirements.
Moreoverf aqueous copolymer dispersions are knoun, for the prepar~tion of which aroraatic monov;rlyl monomers are copolymer;~e~ with esters of acrylic or methacrylic 7Z~3~
-- ,.,~ ..
ar;d and moliolilels havin~ hydroxyl, alnide, amine, carbo~l or e~poxide ~rollps ~cf. Germln 0-Ffenlegungsschr;~ten
2~211,1~9 clnd 2,709,308 - (J~S~ Patencc; -~,9~2~l6~ and 4~020~219 c7nd 8r;tish Paterlt 1~574~7~1~. However, thf:se dispersions cannot be converted b~ customary recipes in.o high-quali~y thermosettirly white lacquers, s;nce, after baking, lacquer films are obtained ~h;ch have blisters~
low gloss and 1nadequate resistance to chemicals.
The object of the invention is to make an a~ueous 1~7 dispersion of a copolymer uhich can ~e crosslinked with an aminoplast resin under the action of heat, and which ~eads to particularly flexible and ~lawless coatings fO1`
metal~ic substrates.
X~ has now been found that an aqueous copolymer 15 dispers;on ean be prepared from styrerle, esters of acrylic andJor methacrylie aeid~ acrylic and/or methacrylic aeid~
acrylam;de and/or ~eth~cr)~lalllide~ N-methylolacrylc7mide and~
o~ N~methylo~methacrylami~e, when the monomers and the ratios of their amounts are seleeted in a cer~a;n manner~
by polyrnerization ;n the presence of an anion;e and, if appropriate, a non-ionic emulsif;er and a radical-forming initiator, ~Ihich dispersion in eomb-inat;on ~ith an amino~
plast resin provides thermosetting coatings w;th excep~
tional properties. These eoatings pro~ide h;ghly elastic ~eather-resistant surfaee coc7tings which have good adhesion and are free of flaws on metalliG substratesO
The invention relates to a process for ~he prepar-ation o-~ a~ aqueous dispers;on of copolymers~ ~hicl7 ean be crosslinked ~ith am noplasts by the ~ction o-f hea~ by .
~ s ~ Z~33 copnlyln~ri2at;0rl of styrene ancl/or metllyl Ine~hacrylate as the "harden;rlg" ccnilporlent~ 2~-cl:hylllex)~l acryliltc arl~l/or butyl acrylate and~or ethyl acrylate ~IS the"plast;ci~.er"conpo~
nent, hydroxyelhyl ~Ineth~acrylate and/or hy~roxypropyL
S Ctneth~ctcrylctte~ acryl;c ac;d and/or methacrylic acid and ar amide and/or an N-lnethylolarnide al1d/or an etheri~1e~
N-nlethylolalnicle of an~ unsaturated carboxylic ac;cl ;n ~he aqueous phase in thc preser1ce of an em~llsif;er and a radical-forlning initiator~ which colnl~rises copolymeri~.ing a mixture of .~ 3O
~ -60% by ue;ght of methyl Inethacrylate or styrene or a rn;x~ure of these monomers, lI,. 3~50X by wei~ht of ethyl acrylate, bu~yl acry~ate - or 2^ethylhexyl acryla~e or a mixture of these monoMers~
Ilï. ~t5% by lei~ht of hydroxyethyl acrylate, hyclroxy etl1yl methacrylate~ hydroxypropyl acrylate or hydroxypro~
pyl meth3crylate or a mixture of these monomers~
IV. 7~5X by weight oF acryliG acid or meti1acrylic ac;d or a mi~ture of these monomers and V. U~5~5X by weight of an am,de or N-methylolam;de or an etherified N-methylolamide of an~C,~ ~unsaturated carboxyl;c ac;d or a mixture of monomers of th;s typer The ;nvention also relates to the use vF the copoly mer d;spersion~ obtained by this processg for the prepara-t;on o-F coa~;ngs \~hich car, be crosslinked under the action oF
heat~
Methyl me1hacrylate is preferably used as the harden~
;n~ contponent Io Styrene can also be used alone~ With regard to the res;stance to weatl1erin~, in particulr~r the UV stabi-47~3~ 6 -li ~y, the alnount of s~cyrenc shoulcl advclllta~eously not ~e mor~
than 3U% by ~lei~jht relat',ve ~o the ~otal alllOUIlt: oF GIOllOmer l'he process of polymer;~n'c;on accord;ng to the - invention ;s carried out as arl emu(s;on polymer;zat;on i!l S an a~ueous rnedi'um ;n the kno~n equ;pment~ for example in a Gtnd~
vess~l provided with a st~r~hclvlng arr~n~ts ~or heatin~and ccx~l ing~ The addition of the mo~omers can ~)e ~arried out ir such a raanr,er that a solut;on of the total ~ater, the em-lls;f;er and a part of the initiator is in;tially intro~
duced and the mixture of monomers and~ separate from but in parallel to th;s, the remainder of the in7tiator are slowly added at the polymeri2ation temperature. However, it is a.so possible initially to ;ntroduce a part of the water and thc emuls;fier and to prepare a pre-emulsion i5 f om the rcmainder of the water ar,d tl,e cmuls;f;er and from the monomers, ~Jh;ch pre-emulsion is introduced into the polymerization mediumr the initiator a~a;n he1n-J added separately~ The poLymerization is preferably carried out in such a manner that 30-50% by ~eight of the w3ter and 'l0-50% by weight f the emulsif;~r or, if appropr;ate, mixture of emulsifiers, are init;ally ;ntroduced and a pre~
emuls;orl ;s prepared from the monomers, the rema;ning part of the water and the residual emulsifiers, wh;ch pre~
emuls;on is metered ;nto the heated mater;al which has been ;nitially introduce~ over 1-3 hours. The polymer;~ation temperature is in the ranye ~rom 20 to 100C, preferably ~0 to 90 C D
The ratio of the amounts of the monorners and the water is selected so that the result;ng copolyrner dlspers;on .
~Z~7~1~3 li3Si a SCJ~ COnterl~ O~ 30 to 6U% by ~leicJnl:, pleFera~;ly
low gloss and 1nadequate resistance to chemicals.
The object of the invention is to make an a~ueous 1~7 dispersion of a copolymer uhich can ~e crosslinked with an aminoplast resin under the action of heat, and which ~eads to particularly flexible and ~lawless coatings fO1`
metal~ic substrates.
X~ has now been found that an aqueous copolymer 15 dispers;on ean be prepared from styrerle, esters of acrylic andJor methacrylie aeid~ acrylic and/or methacrylic aeid~
acrylam;de and/or ~eth~cr)~lalllide~ N-methylolacrylc7mide and~
o~ N~methylo~methacrylami~e, when the monomers and the ratios of their amounts are seleeted in a cer~a;n manner~
by polyrnerization ;n the presence of an anion;e and, if appropriate, a non-ionic emulsif;er and a radical-forming initiator, ~Ihich dispersion in eomb-inat;on ~ith an amino~
plast resin provides thermosetting coatings w;th excep~
tional properties. These eoatings pro~ide h;ghly elastic ~eather-resistant surfaee coc7tings which have good adhesion and are free of flaws on metalliG substratesO
The invention relates to a process for ~he prepar-ation o-~ a~ aqueous dispers;on of copolymers~ ~hicl7 ean be crosslinked ~ith am noplasts by the ~ction o-f hea~ by .
~ s ~ Z~33 copnlyln~ri2at;0rl of styrene ancl/or metllyl Ine~hacrylate as the "harden;rlg" ccnilporlent~ 2~-cl:hylllex)~l acryliltc arl~l/or butyl acrylate and~or ethyl acrylate ~IS the"plast;ci~.er"conpo~
nent, hydroxyelhyl ~Ineth~acrylate and/or hy~roxypropyL
S Ctneth~ctcrylctte~ acryl;c ac;d and/or methacrylic acid and ar amide and/or an N-lnethylolarnide al1d/or an etheri~1e~
N-nlethylolalnicle of an~ unsaturated carboxylic ac;cl ;n ~he aqueous phase in thc preser1ce of an em~llsif;er and a radical-forlning initiator~ which colnl~rises copolymeri~.ing a mixture of .~ 3O
~ -60% by ue;ght of methyl Inethacrylate or styrene or a rn;x~ure of these monomers, lI,. 3~50X by wei~ht of ethyl acrylate, bu~yl acry~ate - or 2^ethylhexyl acryla~e or a mixture of these monoMers~
Ilï. ~t5% by lei~ht of hydroxyethyl acrylate, hyclroxy etl1yl methacrylate~ hydroxypropyl acrylate or hydroxypro~
pyl meth3crylate or a mixture of these monomers~
IV. 7~5X by weight oF acryliG acid or meti1acrylic ac;d or a mi~ture of these monomers and V. U~5~5X by weight of an am,de or N-methylolam;de or an etherified N-methylolamide of an~C,~ ~unsaturated carboxyl;c ac;d or a mixture of monomers of th;s typer The ;nvention also relates to the use vF the copoly mer d;spersion~ obtained by this processg for the prepara-t;on o-F coa~;ngs \~hich car, be crosslinked under the action oF
heat~
Methyl me1hacrylate is preferably used as the harden~
;n~ contponent Io Styrene can also be used alone~ With regard to the res;stance to weatl1erin~, in particulr~r the UV stabi-47~3~ 6 -li ~y, the alnount of s~cyrenc shoulcl advclllta~eously not ~e mor~
than 3U% by ~lei~jht relat',ve ~o the ~otal alllOUIlt: oF GIOllOmer l'he process of polymer;~n'c;on accord;ng to the - invention ;s carried out as arl emu(s;on polymer;zat;on i!l S an a~ueous rnedi'um ;n the kno~n equ;pment~ for example in a Gtnd~
vess~l provided with a st~r~hclvlng arr~n~ts ~or heatin~and ccx~l ing~ The addition of the mo~omers can ~)e ~arried out ir such a raanr,er that a solut;on of the total ~ater, the em-lls;f;er and a part of the initiator is in;tially intro~
duced and the mixture of monomers and~ separate from but in parallel to th;s, the remainder of the in7tiator are slowly added at the polymeri2ation temperature. However, it is a.so possible initially to ;ntroduce a part of the water and thc emuls;fier and to prepare a pre-emulsion i5 f om the rcmainder of the water ar,d tl,e cmuls;f;er and from the monomers, ~Jh;ch pre-emulsion is introduced into the polymerization mediumr the initiator a~a;n he1n-J added separately~ The poLymerization is preferably carried out in such a manner that 30-50% by ~eight of the w3ter and 'l0-50% by weight f the emulsif;~r or, if appropr;ate, mixture of emulsifiers, are init;ally ;ntroduced and a pre~
emuls;orl ;s prepared from the monomers, the rema;ning part of the water and the residual emulsifiers, wh;ch pre~
emuls;on is metered ;nto the heated mater;al which has been ;nitially introduce~ over 1-3 hours. The polymer;~ation temperature is in the ranye ~rom 20 to 100C, preferably ~0 to 90 C D
The ratio of the amounts of the monorners and the water is selected so that the result;ng copolyrner dlspers;on .
~Z~7~1~3 li3Si a SCJ~ COnterl~ O~ 30 to 6U% by ~leicJnl:, pleFera~;ly
3 ~ ~ O .~ ' t~ 3 ~
rhe er,luls;f;el employed is pret'eral~ly a s;n~le an;orlic enluls;fiel or a mixture of several anionic cmulsi fiersO Examples of an;onic elnulsifiers are the alkal; metal salts OT the hem-isulfates of alkylphenols or alcohols~
and also the hem;sulfates of oxethyLate~l alkylphenols or oxethylated alcohols, pre~erably the alkal; metal salts of the heM;sulfate of a nonylpherlol ~hich has been re-acted ~iith 4-5 moles of ethylene oxide per mole, and also alkyl sulfonate or aryl sulfonate~ sodium lauryl sulfate~
sodium laur~lethoxylate sulfate and secondary sodium alkane~
sutfonates, the carbon chains of which contain 8~20 carbon atoms. The amount of the anionic emulsifier ;s 0~1-5.0%
by weight, preferably 0.5-3.0X by wei~htr relative to the monomers~ In addition~ in order to increase the stab;lity of the aqueous copolyn\er ~isp~rsion, it is possible also tv employ a non^-ionic emulsi-fier oF the type of an ethoxyl-ated alkylphenol or fatty alcohol, for example the addit;on product of 1 mole of nonylphenol and 4 30 moles of ethylene oxide mixed with an anion;c emulsifier~ also in an amount of 0~l-5.0, preferably 0~5-3~0% by ~eicght, relati~e to the monomersu ~ he process accord;ng to the invention is carried out in ~he presence of a radical--Forming ini~ia~orr in part;cular a perox;de compound~ The init;ator is soluble in water or in monomers. A ~ater soluble ir,itia~or is prefera~ly used~
Suieable initiators are the customary inorc~lnic .
Z~3 per--compounds, e;pec;aLLy a~non;um peroxydislllrcl~c~ or al~al; r~tal ~eroxydic;lJlfatcs, for ex;inlple s;odium peroxy-disulfate and potassium peroxycl;slJlfatc, also ammon;uln or alkali metal peroxycliphosphate and organ;c peroxides~ for example~ benzoyl peroxide, and 2lso organic peresters, such as perisopivalate~ to some extent in combination with reducing agents, such as sodium disulfite~ hydrazine, hydroxylamine and llith catalytic amounts of accel~rators, su~h as iron, cobalt~ cerium and vanadyl salts.
In order to re~ulate the rnolecular weight, com-pounds arr~ employed ~hiCil can be used as cha;n terminators in the polymerizat;on of acrylate monoraers. Apart from perhalo~enated hydrocarbons~ any compound having the general formllla R-SH (R = alky~ aryl or aralkyl~ can be used. R is pre~erabiy an aliphati~ hydrocarbon rad;cal hav;ng 2-18 carbon atoms; examples of suitable regulators are ethyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, laury' mercap~an and t-dodecyl mercaptan. The reglllator is empLoyed in an amount of 0~01~5nO% by weight, preferably Zo nf 0~5-3nO% by ~leight~ relcltive to the total of the IDOI10-mers. If a particularly high molecular ~eight is deManded for certain areas of use, the emulsion polymerizat;on is carried out without a regulator.
After conlplet;on of the add;t;on of the m;xture of ~5 monomers, the total batch is stirred for a further 1-3 hours at ~0-90c, preferably at 70-85DC. subsequently, the dispersion is adjusted to a pH of 7.5-~5 w;th a tertiary am7ne, for example triethylamine, die~hal1olMorlo-.nethylalaine, trietllanolam;ne, dirnethyLisopropylhydroY~y-s~ lZ~7~33 metllylamill~,. dimt?tl'lylcln~ 0ethanol~ dimethylaminoprbpclnol or d;etr~ rilirloe~ olO A particularly qood ~ merlt wel y of ~he dlspelsit)rls, and tllus l300d technologil.~l coat~
in~ propert;esr are obtaineAcl particularly by the use o~
dieth2nolmonometllylalll;ne~ dimeth>laminoethanol and dirnetllyl~
a~lino~rop~nolO
The copol)~mers obtained by the process accord;n~
tD the in:t7~tiC(l ~ve g]~s~ ~-c~lsltio~ t~r~lt~ s (TG) in th~ rc~ng~
from 0 to +~0C, preferdbly from ~S to ~35~. The minimllm fiLm-fornat;on temperatures tMFT) of the preserlt aqu*ous copolymer dispersions correlate very ~lell with the measured T~ values which are measured by the method of dif~erential thermal arlalysis (DTA) on dried dispersion ~ilmsO The pro~
cess according to the ;nvent;on leads to copolymers \~hich ?5 have a mean partic;e si~e tparticle diameter3 ot 0u05 to 0~15jurn, preferably of 0.07 to 0.12 ,um.
The aqueous copol)mer dispersion o~ta;ned accord-in~ to the inventiorl when mixed with a water-solu~le and/or water-dispersible aminoplast resin, provides thermcsetting Z0 coa~in~s which provide fillers, textur;ng coat1ngs~ top coats and sin~le-layer coatings which are particularly elastic and have particulally high adhesionr corros;on resistance and ~eathering resistance.
Aminoplast resins are understood to be ~hcrnlo-setting reactioll products of aldehydes, preferably form-aldehyder w;th polyfunctional aminesO for example urea~and tria~;nesr such as melaM;ne or benzoguanam;ne. These resins are frequently etherified~ for exarnp;e with me.hanol, in ordeï to promote the solubility in water~ A melamille resin ~L2~72~33 1 !V - . .
which i~ frequen~l~ used is h~x~unethoxynlethylrilelamineO
which ~ (?s clear sol~ltions in wcl~el and tl~us can be metcred especially ~asily and leads to b;nder ~r,i~t-lr~s hav;ng good stora~e stability.
S In additlcrl~ conventional alkylatedO for example butyla~ed~ melamirle-formaldehyde resins can be used~
prov;ded that they satisfy the requ;remel1ts of water-~olub;lity, of compatib;l;ty or of dispersibil;t~ in the finished formulation of the coating system~
?U The aqueous copolymer dlspersions obta;ned accord~
ing to the ;nvention are mixed with the aminoplast resin in sllch a manner that trelative to tlle total resin solids) 5-~OX b~ ~e;ght of am;noplast resin~ preferably 10 30% by weight~ 2re contained in the~ binder m;xture.
t5 The cvpolyrîer d;~pers;ons can be fvrmui~ed ~ith .am;noplast resins to ~ive transparent lac~uers or p;gmented l~c~uers~ The procedure for the manufacture of the lacquers is frequently such th~t pi~ments andtor f71lers, to~ether with custor~ary lacquer aux;liar;es, opt7Onally curing catalysts and optionally ncutraLizers~ are ground ~o a p;g~-rnent paste ~h;ch is then m;~ed with the b;nder system.
However~ it is frequcntly also poss;ble ~or the aminoplast resin to serve as grinding res;n ~pigMent wettin~ agent~
;n ~he manufacture of the pigment pasteO
All the products customary in the paint and varnish ;ndustry carl be employed as pigments and/or f;llers, pro~
vid;ng that they are sufficiently stable under al~al;ne cond;t;ons~ so that the finished coating agent can be stored for several months. The p;gmcnt can be added to . ., ~Z4'72~3 the ~atch in ttle m.rlrler custom~ry in lllc manufaclure of p;tJmerll:ecJ a~ucous er~ lsion pairl1; In l~c~lu~r for~nulat1Ons w;th aqueous copolymer d;spers;(~ns, ~:ilC ~Jloss ;S ~requc~ntl,yimp~oved if thc p;.Jme~t is rnilled ;nto the am1noplast res;n and tl1en the aqueous p;gm~l1t paste i5 miJ~ed into tl1e a-lueous copolymer dispersion~ An example of a typical p1g-ment for mal-uf~cturincJ white lacquers ;s titanium dioxide.
It has been fourld fulthermore, that the copolymer dispersions prepared according to the invention have al1 1D ;nl1erent pi~ment-wetting capacity ~h;ch is particularly pronounced~ 1hus it has been demonstrated, in part;cula,, that these ~i;spersiorls with inor3anic ~hite p;gments~ such as ti.aniu-,m d;oxide up to a we;ght ra~io of binder : p;gment = 1 : 1, can be processed as baking coatin~s of hioh Qloss and rree o, blooll1in~. neactive copolymer dispersions cross linkin~ -foreign substances and having a similar polymeric structure u!1ictl are h;therto known SilO~r~ at th;s level of pi~lnentation, either a marked blooming or they can orlly be use~ with severe losses of gloss~ The graph;cal repre~
sentation i~ in.~nded to ;llustrate th;s in more detail (cf.. Fi~ure~.
Lacquers ha~e been prepared as in use exanlple 1 usin~ a d;spers;on prepared accordin~ to the ;nvent;on ~s in example 3 and various dispers;ons accord;ng to Gerlnan Offenlerlul)gsschrift 2,70~30&. The lacquers ~/ere tes~ed for bloomil1g and gloss~ In tre F;gure, the reflection (,0) is plott2d as a rUnGt;On o~ the level of pigmer,tation (~
~n~ the assess~ent of the bloom is indic~ted at each ~eas ured point (numbers ;n bra~kets. 0 - best ~alue poss;ble~
5 - lo~,Jes~ val-le poss;ble)4 Curve A sl~o~s the mea~ured point:s for the laccluer prepared accordirlg to the inven~ion~
whi 1st curves ~1 to E represent th~ meas(lrecl point s l or the lacquers ob~ained according to the state of ttle art.
Apart from the aminoplast resins, various pro~ucts car. be employed as the pi~ment ~etting a~en-l; natural or synthetic polymers~ llhich are di lu~able w;tll water or solubl.e in waterr are mostly used, the ~ffin;ty for water of which is achieved by a relat;vel~ large number oF hydro-. . 10 phi li c çomponents in the molecule. Accordir)g to GerMan Offenlegurlgsscl1rift 2,505~2~, for example, high-boil1ng adductsl~ving a m31e~u].~ weight of 300-6,~00 of a1:iphat:lc polyh~dric alcohols and epoxides are e~pl.oyed.
In the formulation of pigmented coat;n~ compo~
s;tions, i. is frequently necessary aLso to en,ploy so-called oispersants. In tl1is context~ the aclion of the dispersant on the properties of tho finished film must be taken ;nto account~ for example the action on the ~ater-res;stance. The dispersants employed arer for exampLe, the a.~nmoniunl salts or alkali metal salts of polyrner;c carboxylic acids. The amount of dispersants used depends on the type and the amount of the p;gments employed and the kinders.
The fin;shed formulations of the coating a~ent can a~so have a tertiary amine added to increase the stora~e siab;l;ty. The preferred pH range is 7-~.
In order to decrease the baking temperature~ the coatin~ agent can also ke m;Y~ed l~itl1 a curing catalyst.
catalyst which is fre~uently used ;s paratoluenesuLfonic .
~ 13 ec;d.
rhe coating agcnt based on the co~)olyrner ~i~s~)ctrs1on ohtairled accord;ng 1o ~he ;nvelltloll can be applTel:l to a ~arge numrJel~ of substrates~ which must~ o~ course, be stable at the bak;ng .emperature~ For this reaxon, metallic substrates are particularly suitable, for example objects ~ade of ;ronf steel, aluminum, copper, bronze and brass~
Cerami~ surfaces, glass and ~lood can also be coa~ed..
Di~rs:ion lacquers carl, for example, be applied to the sub~
13 strates using spray gunsf or by brush, squeegee~ roLler or by dip~ing. ~n practice, the coated object is principally aired and dried in air at room tempcrature or at ~
temperature ~hich is only slightly elevated. Then the coat;ng ;s cured by "baking" at a temperature ~rorn 8~-1~0C~ Thc- co3tings are baked, as a ru;e, ~or a period o~ 10~30 m;nutes~ The layer thicknessns of the baked coatin0s are in th~ range from 15 to 8D )Im, preferahly 25 ~o 60 ~m.
Baked transparerit lacquer films and pigmented lacq;ler filns based on the copolymer dispersion prepared according to the ;nvention are distinguished by good level ing, good covering power, smoothness, elasticity, gloss~
adhesion and resistance to weathering and yellowing~
The following examples serve to illustrat~ the invent;on in more detail. Percentages and rat;os relate$
;n each case, to the ~eight, the amounts of solu~ions and dispersions relate~ in each case, to the solid material~
The polymeri2ation experiments were carr;ed out ;n a rnultineck flask hav;ng a stirr-er, thermometer, 72~3~
dropp;ng furlncl and a -lherrllosta~ed L~
~ f ~ mercap~al) ;s use(l as ~he r(cJulc~tc)r~ car~3 shoul~
be ~aken tllat thc mercaptall is adcled to tlle rnixtlJr~ o~ mono-mers or the pre entuision of monolil(?rs orlly shor1ly before 5 the s~art o~ 1he meter;ncJ~ ,, s;nce ;f the m;xture or pre emulsion of Monorners contain;rlg th~ mercaptan is allo~Jed to stand for an,v lerlytil of tirne~ a yellow or brown color ation occursO
Example 1 ___ A monorner emulsion ~ S prepared from 1,150 g of methyl rnethacrylate 1rt50 g of 2-ethylhexyl acrylate ~5U 9 of i~ydroxyethyl methacryla'ce 3n y of N--methylolacrylam;de 'L~J 9 of- me-hacry.al,l;de ~0 g of rnethacrylic acid ~0 9 of sodium lauryl sulfate 6 g of ammoniuM peroxyd;sulfate and 1,330 g of ~ater.
This emuLsion was metered into a solution of S0 9 cf sodium lauryl su~fate and 3 9 of ammoniurn peroxydisul-fate in 1,100 9 of ~ater~ The addition tirne at ~80C uas 2 hours and the subsequent heating ~ime at ~5C was 3 hours~ ~he copolyrner d;spers;on was adjusted to pH 8 wi~h an aqueous Z5 solution of dimethylam;noetllanol (25% strength~. The co~
polynmer dispers;on had a sol-ids content o~ 5~%~
T~ = ~14C, MFT = ~11C.
EY~am~le 2 A rn~nomer eMulsion composed of - . .
w 15 12~7283 10~ ~ of ~tyrene 1fl~ ~ o~ mcthyl ~nethacrylate 1,060 g of 2-ethylhexyl acrylate 250 9 of hydroxyethyl me~hacryla~e 50 g of methacryl;c acid ~30 8 of N-methylolacrylam;de - 50 9 of sod;um laurylethoxylate sul~ate ~Z~S
moles of ethylene oxide) 5 g of ammon;um peroxydisulfate an~
1,400 9 of water ~as metered into a solut;on of 30 9 of sodiurn laurylethoxy-late sulfat ~ith 2-~ moles of ethylene oxide and 3 ~ of amlnorlium peroxydisulfate in 1,100 9 of watera The addi~iort tirne ano the subsequent heating time ~ere set as in Example 1 The neu-r~li7ed copolyrner dispersion had a soli~s con.ent of 50X
r~ =+12~C, MFT =~10C~
Exa~ple 3 The procedure was carried out as in Example 1~ bu~
Z0 the fo~lo~lir~g mixture was used:
138 9 of methyl methacrylate 138 g of 2-ethylhexyl acrylatc 35 g of hydroxyethyl methacrylate 7 g o~ methacrylic acid
rhe er,luls;f;el employed is pret'eral~ly a s;n~le an;orlic enluls;fiel or a mixture of several anionic cmulsi fiersO Examples of an;onic elnulsifiers are the alkal; metal salts OT the hem-isulfates of alkylphenols or alcohols~
and also the hem;sulfates of oxethyLate~l alkylphenols or oxethylated alcohols, pre~erably the alkal; metal salts of the heM;sulfate of a nonylpherlol ~hich has been re-acted ~iith 4-5 moles of ethylene oxide per mole, and also alkyl sulfonate or aryl sulfonate~ sodium lauryl sulfate~
sodium laur~lethoxylate sulfate and secondary sodium alkane~
sutfonates, the carbon chains of which contain 8~20 carbon atoms. The amount of the anionic emulsifier ;s 0~1-5.0%
by weight, preferably 0.5-3.0X by wei~htr relative to the monomers~ In addition~ in order to increase the stab;lity of the aqueous copolyn\er ~isp~rsion, it is possible also tv employ a non^-ionic emulsi-fier oF the type of an ethoxyl-ated alkylphenol or fatty alcohol, for example the addit;on product of 1 mole of nonylphenol and 4 30 moles of ethylene oxide mixed with an anion;c emulsifier~ also in an amount of 0~l-5.0, preferably 0~5-3~0% by ~eicght, relati~e to the monomersu ~ he process accord;ng to the invention is carried out in ~he presence of a radical--Forming ini~ia~orr in part;cular a perox;de compound~ The init;ator is soluble in water or in monomers. A ~ater soluble ir,itia~or is prefera~ly used~
Suieable initiators are the customary inorc~lnic .
Z~3 per--compounds, e;pec;aLLy a~non;um peroxydislllrcl~c~ or al~al; r~tal ~eroxydic;lJlfatcs, for ex;inlple s;odium peroxy-disulfate and potassium peroxycl;slJlfatc, also ammon;uln or alkali metal peroxycliphosphate and organ;c peroxides~ for example~ benzoyl peroxide, and 2lso organic peresters, such as perisopivalate~ to some extent in combination with reducing agents, such as sodium disulfite~ hydrazine, hydroxylamine and llith catalytic amounts of accel~rators, su~h as iron, cobalt~ cerium and vanadyl salts.
In order to re~ulate the rnolecular weight, com-pounds arr~ employed ~hiCil can be used as cha;n terminators in the polymerizat;on of acrylate monoraers. Apart from perhalo~enated hydrocarbons~ any compound having the general formllla R-SH (R = alky~ aryl or aralkyl~ can be used. R is pre~erabiy an aliphati~ hydrocarbon rad;cal hav;ng 2-18 carbon atoms; examples of suitable regulators are ethyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, laury' mercap~an and t-dodecyl mercaptan. The reglllator is empLoyed in an amount of 0~01~5nO% by weight, preferably Zo nf 0~5-3nO% by ~leight~ relcltive to the total of the IDOI10-mers. If a particularly high molecular ~eight is deManded for certain areas of use, the emulsion polymerizat;on is carried out without a regulator.
After conlplet;on of the add;t;on of the m;xture of ~5 monomers, the total batch is stirred for a further 1-3 hours at ~0-90c, preferably at 70-85DC. subsequently, the dispersion is adjusted to a pH of 7.5-~5 w;th a tertiary am7ne, for example triethylamine, die~hal1olMorlo-.nethylalaine, trietllanolam;ne, dirnethyLisopropylhydroY~y-s~ lZ~7~33 metllylamill~,. dimt?tl'lylcln~ 0ethanol~ dimethylaminoprbpclnol or d;etr~ rilirloe~ olO A particularly qood ~ merlt wel y of ~he dlspelsit)rls, and tllus l300d technologil.~l coat~
in~ propert;esr are obtaineAcl particularly by the use o~
dieth2nolmonometllylalll;ne~ dimeth>laminoethanol and dirnetllyl~
a~lino~rop~nolO
The copol)~mers obtained by the process accord;n~
tD the in:t7~tiC(l ~ve g]~s~ ~-c~lsltio~ t~r~lt~ s (TG) in th~ rc~ng~
from 0 to +~0C, preferdbly from ~S to ~35~. The minimllm fiLm-fornat;on temperatures tMFT) of the preserlt aqu*ous copolymer dispersions correlate very ~lell with the measured T~ values which are measured by the method of dif~erential thermal arlalysis (DTA) on dried dispersion ~ilmsO The pro~
cess according to the ;nvent;on leads to copolymers \~hich ?5 have a mean partic;e si~e tparticle diameter3 ot 0u05 to 0~15jurn, preferably of 0.07 to 0.12 ,um.
The aqueous copol)mer dispersion o~ta;ned accord-in~ to the inventiorl when mixed with a water-solu~le and/or water-dispersible aminoplast resin, provides thermcsetting Z0 coa~in~s which provide fillers, textur;ng coat1ngs~ top coats and sin~le-layer coatings which are particularly elastic and have particulally high adhesionr corros;on resistance and ~eathering resistance.
Aminoplast resins are understood to be ~hcrnlo-setting reactioll products of aldehydes, preferably form-aldehyder w;th polyfunctional aminesO for example urea~and tria~;nesr such as melaM;ne or benzoguanam;ne. These resins are frequently etherified~ for exarnp;e with me.hanol, in ordeï to promote the solubility in water~ A melamille resin ~L2~72~33 1 !V - . .
which i~ frequen~l~ used is h~x~unethoxynlethylrilelamineO
which ~ (?s clear sol~ltions in wcl~el and tl~us can be metcred especially ~asily and leads to b;nder ~r,i~t-lr~s hav;ng good stora~e stability.
S In additlcrl~ conventional alkylatedO for example butyla~ed~ melamirle-formaldehyde resins can be used~
prov;ded that they satisfy the requ;remel1ts of water-~olub;lity, of compatib;l;ty or of dispersibil;t~ in the finished formulation of the coating system~
?U The aqueous copolymer dlspersions obta;ned accord~
ing to the ;nvention are mixed with the aminoplast resin in sllch a manner that trelative to tlle total resin solids) 5-~OX b~ ~e;ght of am;noplast resin~ preferably 10 30% by weight~ 2re contained in the~ binder m;xture.
t5 The cvpolyrîer d;~pers;ons can be fvrmui~ed ~ith .am;noplast resins to ~ive transparent lac~uers or p;gmented l~c~uers~ The procedure for the manufacture of the lacquers is frequently such th~t pi~ments andtor f71lers, to~ether with custor~ary lacquer aux;liar;es, opt7Onally curing catalysts and optionally ncutraLizers~ are ground ~o a p;g~-rnent paste ~h;ch is then m;~ed with the b;nder system.
However~ it is frequcntly also poss;ble ~or the aminoplast resin to serve as grinding res;n ~pigMent wettin~ agent~
;n ~he manufacture of the pigment pasteO
All the products customary in the paint and varnish ;ndustry carl be employed as pigments and/or f;llers, pro~
vid;ng that they are sufficiently stable under al~al;ne cond;t;ons~ so that the finished coating agent can be stored for several months. The p;gmcnt can be added to . ., ~Z4'72~3 the ~atch in ttle m.rlrler custom~ry in lllc manufaclure of p;tJmerll:ecJ a~ucous er~ lsion pairl1; In l~c~lu~r for~nulat1Ons w;th aqueous copolymer d;spers;(~ns, ~:ilC ~Jloss ;S ~requc~ntl,yimp~oved if thc p;.Jme~t is rnilled ;nto the am1noplast res;n and tl1en the aqueous p;gm~l1t paste i5 miJ~ed into tl1e a-lueous copolymer dispersion~ An example of a typical p1g-ment for mal-uf~cturincJ white lacquers ;s titanium dioxide.
It has been fourld fulthermore, that the copolymer dispersions prepared according to the invention have al1 1D ;nl1erent pi~ment-wetting capacity ~h;ch is particularly pronounced~ 1hus it has been demonstrated, in part;cula,, that these ~i;spersiorls with inor3anic ~hite p;gments~ such as ti.aniu-,m d;oxide up to a we;ght ra~io of binder : p;gment = 1 : 1, can be processed as baking coatin~s of hioh Qloss and rree o, blooll1in~. neactive copolymer dispersions cross linkin~ -foreign substances and having a similar polymeric structure u!1ictl are h;therto known SilO~r~ at th;s level of pi~lnentation, either a marked blooming or they can orlly be use~ with severe losses of gloss~ The graph;cal repre~
sentation i~ in.~nded to ;llustrate th;s in more detail (cf.. Fi~ure~.
Lacquers ha~e been prepared as in use exanlple 1 usin~ a d;spers;on prepared accordin~ to the ;nvent;on ~s in example 3 and various dispers;ons accord;ng to Gerlnan Offenlerlul)gsschrift 2,70~30&. The lacquers ~/ere tes~ed for bloomil1g and gloss~ In tre F;gure, the reflection (,0) is plott2d as a rUnGt;On o~ the level of pigmer,tation (~
~n~ the assess~ent of the bloom is indic~ted at each ~eas ured point (numbers ;n bra~kets. 0 - best ~alue poss;ble~
5 - lo~,Jes~ val-le poss;ble)4 Curve A sl~o~s the mea~ured point:s for the laccluer prepared accordirlg to the inven~ion~
whi 1st curves ~1 to E represent th~ meas(lrecl point s l or the lacquers ob~ained according to the state of ttle art.
Apart from the aminoplast resins, various pro~ucts car. be employed as the pi~ment ~etting a~en-l; natural or synthetic polymers~ llhich are di lu~able w;tll water or solubl.e in waterr are mostly used, the ~ffin;ty for water of which is achieved by a relat;vel~ large number oF hydro-. . 10 phi li c çomponents in the molecule. Accordir)g to GerMan Offenlegurlgsscl1rift 2,505~2~, for example, high-boil1ng adductsl~ving a m31e~u].~ weight of 300-6,~00 of a1:iphat:lc polyh~dric alcohols and epoxides are e~pl.oyed.
In the formulation of pigmented coat;n~ compo~
s;tions, i. is frequently necessary aLso to en,ploy so-called oispersants. In tl1is context~ the aclion of the dispersant on the properties of tho finished film must be taken ;nto account~ for example the action on the ~ater-res;stance. The dispersants employed arer for exampLe, the a.~nmoniunl salts or alkali metal salts of polyrner;c carboxylic acids. The amount of dispersants used depends on the type and the amount of the p;gments employed and the kinders.
The fin;shed formulations of the coating a~ent can a~so have a tertiary amine added to increase the stora~e siab;l;ty. The preferred pH range is 7-~.
In order to decrease the baking temperature~ the coatin~ agent can also ke m;Y~ed l~itl1 a curing catalyst.
catalyst which is fre~uently used ;s paratoluenesuLfonic .
~ 13 ec;d.
rhe coating agcnt based on the co~)olyrner ~i~s~)ctrs1on ohtairled accord;ng 1o ~he ;nvelltloll can be applTel:l to a ~arge numrJel~ of substrates~ which must~ o~ course, be stable at the bak;ng .emperature~ For this reaxon, metallic substrates are particularly suitable, for example objects ~ade of ;ronf steel, aluminum, copper, bronze and brass~
Cerami~ surfaces, glass and ~lood can also be coa~ed..
Di~rs:ion lacquers carl, for example, be applied to the sub~
13 strates using spray gunsf or by brush, squeegee~ roLler or by dip~ing. ~n practice, the coated object is principally aired and dried in air at room tempcrature or at ~
temperature ~hich is only slightly elevated. Then the coat;ng ;s cured by "baking" at a temperature ~rorn 8~-1~0C~ Thc- co3tings are baked, as a ru;e, ~or a period o~ 10~30 m;nutes~ The layer thicknessns of the baked coatin0s are in th~ range from 15 to 8D )Im, preferahly 25 ~o 60 ~m.
Baked transparerit lacquer films and pigmented lacq;ler filns based on the copolymer dispersion prepared according to the ;nvention are distinguished by good level ing, good covering power, smoothness, elasticity, gloss~
adhesion and resistance to weathering and yellowing~
The following examples serve to illustrat~ the invent;on in more detail. Percentages and rat;os relate$
;n each case, to the ~eight, the amounts of solu~ions and dispersions relate~ in each case, to the solid material~
The polymeri2ation experiments were carr;ed out ;n a rnultineck flask hav;ng a stirr-er, thermometer, 72~3~
dropp;ng furlncl and a -lherrllosta~ed L~
~ f ~ mercap~al) ;s use(l as ~he r(cJulc~tc)r~ car~3 shoul~
be ~aken tllat thc mercaptall is adcled to tlle rnixtlJr~ o~ mono-mers or the pre entuision of monolil(?rs orlly shor1ly before 5 the s~art o~ 1he meter;ncJ~ ,, s;nce ;f the m;xture or pre emulsion of Monorners contain;rlg th~ mercaptan is allo~Jed to stand for an,v lerlytil of tirne~ a yellow or brown color ation occursO
Example 1 ___ A monorner emulsion ~ S prepared from 1,150 g of methyl rnethacrylate 1rt50 g of 2-ethylhexyl acrylate ~5U 9 of i~ydroxyethyl methacryla'ce 3n y of N--methylolacrylam;de 'L~J 9 of- me-hacry.al,l;de ~0 g of rnethacrylic acid ~0 9 of sodium lauryl sulfate 6 g of ammoniuM peroxyd;sulfate and 1,330 g of ~ater.
This emuLsion was metered into a solution of S0 9 cf sodium lauryl su~fate and 3 9 of ammoniurn peroxydisul-fate in 1,100 9 of ~ater~ The addition tirne at ~80C uas 2 hours and the subsequent heating ~ime at ~5C was 3 hours~ ~he copolyrner d;spers;on was adjusted to pH 8 wi~h an aqueous Z5 solution of dimethylam;noetllanol (25% strength~. The co~
polynmer dispers;on had a sol-ids content o~ 5~%~
T~ = ~14C, MFT = ~11C.
EY~am~le 2 A rn~nomer eMulsion composed of - . .
w 15 12~7283 10~ ~ of ~tyrene 1fl~ ~ o~ mcthyl ~nethacrylate 1,060 g of 2-ethylhexyl acrylate 250 9 of hydroxyethyl me~hacryla~e 50 g of methacryl;c acid ~30 8 of N-methylolacrylam;de - 50 9 of sod;um laurylethoxylate sul~ate ~Z~S
moles of ethylene oxide) 5 g of ammon;um peroxydisulfate an~
1,400 9 of water ~as metered into a solut;on of 30 9 of sodiurn laurylethoxy-late sulfat ~ith 2-~ moles of ethylene oxide and 3 ~ of amlnorlium peroxydisulfate in 1,100 9 of watera The addi~iort tirne ano the subsequent heating time ~ere set as in Example 1 The neu-r~li7ed copolyrner dispersion had a soli~s con.ent of 50X
r~ =+12~C, MFT =~10C~
Exa~ple 3 The procedure was carried out as in Example 1~ bu~
Z0 the fo~lo~lir~g mixture was used:
138 9 of methyl methacrylate 138 g of 2-ethylhexyl acrylatc 35 g of hydroxyethyl methacrylate 7 g o~ methacrylic acid
4 g of N-methylolacrylam;de 3 g of sodium laurylet5~oxylate sulfate ~2-5 moles of ethylene oxide) 1 g o-; ammonium peroxydisulfate and 157 9 of l~aterO
i2~7~2133 ~ 16 - , .
The mixt-lre was meter~d into a soluti~n oF 2 g of sod;urn laLIr~le~lloxylate sulfa~e arld O.S ~ of alnrnoniuln per-oxydisulfate in 13ti g of water. The rnixture w~s ~djl.lsted to p~l 8.2 w-itll dinlethylaln;noethanol. The copolynlcr dis-S pers;on had a solids content of SGX. The mean particled;ameter of ~he copolymer was 0.080 ~m.
TG ~ tC, I~FT =~12C~
Example 4 An emulsion was prépared frorn 540 g of methyl methacrylate 360 9 of 2-ethylhexyl acrylate 70 9 of hydroxyethyl metllacrylate 30 9 of methacrylic acid 8 g of methacrylamide ~S 10 g of sod;um lauryl sulfate .3 9 of lauryl mercaptan 2 9 of ammoniurn peroxyd;sulfate and ~ t70 9 of water and metered ;nto a sol.ution of 6 9 o~ so~ium lauryl sul~
zn fa~e and 1 g of ammonium peroxydisulfa~e in 43~ g of ~ater~
The dispersion was brought to pH 8 ~ith d;metllyliso-propylhydroxymethylam;ne and had a solids content of S0~.
TG = ~3~C, MFT - t32 - Example 5 2~ h monomer emuls;on was prepared fron 3~n 9 of methyl methacrylate ~20 9 of butyl acrylate 70 y of hydroxyethyl methacryLate 20 g of methacryl;c ~c;d ~Z~'7~33 2n cf ~ n~t~lylo~ cl~yl~
2f~ ~ o~ m~h~l~r~al~ 0 12 ~ ~f sodium laurylethoxylatc sulfa~e ~ 5 mol.es oF ~1:hyl~1le. OX;df!) 1~ g of lauryl mercaptan and 900 g of wa.er and meter~d ;r,to a solut;on of 1Z g of sod;um lauryl sul-fate ;rl hO0 g o~ water. As tlle irlit;ator" a sol.ut;on o~
2 g of ammonium peroxydisulfate in 40 g of ~later was added in parailel to the morlomer emuls;or,. After adiust;ng the pH to 8v5 with c'f;methylam;noethanol, a dispcrsion llaving a solid~ content o~ 35% was obta;ne~. The mean particle diametel~ of the copolymer ~las 0.12 ~m.
Use l~alnple 1 Prepar~tion of a wh;te lacquer paint based vn rche dispersioll according to Example 5-A~ Pigmellt paste ~to82 g oF hexamethoxymethylmelarfline (50X in water~
~-~.8'> g of wa~r ~de;onized) 20 - 'i.20 g o~ sodium nitri~e (5% in ~fater~
0.36 g o-F sodium polyacrylate (25,' ;n water~
Ovl~ g of a~dit;on product of 1 mole of nonyl phenol and 6--'lO moles oF ethylene oxide 0~07 ~ of cornmerc;al defoamer and 19.2~ g o~F titanium d;ox;de trutile ty?e~
B) Binder o2 9 of d;spersion accordincf to Example 5 t35X
strength) and -7.25 9 of water :~2~7;~33 ' Part A) w~s ;nitially milled ;n a ball mil~ for 1~ hours, t~en ;)art ~) was m;xecl in ancl th~ m;xture ~las a~a;n ground fol a fultl1er 16 hours ;rl a b~ll mill~
The wh;te lacquer hacl a flow v;scorneter t;me of 30 seconds (DIN cop, PIN 53,.Z11, 4 mm no;zle~ and was adjus ted to a f~ow viscometer t;me of 1S~2D seconds ~J;th a rn;x-ture of ~!ater and butylglycol t7 ~. rhe lacquer; ready for spraying had a binder/pignlent ratio of 1:0~8 and a solids ratio oF dispersion to melamine resin of 9:1 w;th a sol-vent content of lcss than Z~. Lacquer films on steel plat:e exhibited a gloss of 85% (measured at an an3le of ~o ~e~ree~ m accordance utth DIN 67,~30). All tests of adhesion on slow and ~den deformation of the substlai-e and by the ~rid 1~ cutting process led to very good values~
1~ Use Example 2 ,_ Preparat;on of a yray spray f;ller based on the polymer d;spersion according to lxample 3:
A) P;gment paste 80 g oF t;tan;um dioxide ~rutile type) 4~ ~ ~f talc 8U g of zinc sulficle/barium sulfate 60 g of chalk 1~ g of si~;ca gel 10 9 of strontium chromate ~5 1.5 9 of flarne soot 1~ g of lead s;licochromate 8 ~ of sod;um polyacr~late ~25X in water~
9 of addition product of 1 mole of l~onylpl1enol and o to 10 moles o, ethylene ox;de . , .
:12472B3 - 15' - ' ' I ~ of commcrcial defoalrler 10 ~ ol` sodium nitl~ite ~ ;n ~later) ?U 9 of butylglycol and 8~5 g of water ~de;onized
i2~7~2133 ~ 16 - , .
The mixt-lre was meter~d into a soluti~n oF 2 g of sod;urn laLIr~le~lloxylate sulfa~e arld O.S ~ of alnrnoniuln per-oxydisulfate in 13ti g of water. The rnixture w~s ~djl.lsted to p~l 8.2 w-itll dinlethylaln;noethanol. The copolynlcr dis-S pers;on had a solids content of SGX. The mean particled;ameter of ~he copolymer was 0.080 ~m.
TG ~ tC, I~FT =~12C~
Example 4 An emulsion was prépared frorn 540 g of methyl methacrylate 360 9 of 2-ethylhexyl acrylate 70 9 of hydroxyethyl metllacrylate 30 9 of methacrylic acid 8 g of methacrylamide ~S 10 g of sod;um lauryl sulfate .3 9 of lauryl mercaptan 2 9 of ammoniurn peroxyd;sulfate and ~ t70 9 of water and metered ;nto a sol.ution of 6 9 o~ so~ium lauryl sul~
zn fa~e and 1 g of ammonium peroxydisulfa~e in 43~ g of ~ater~
The dispersion was brought to pH 8 ~ith d;metllyliso-propylhydroxymethylam;ne and had a solids content of S0~.
TG = ~3~C, MFT - t32 - Example 5 2~ h monomer emuls;on was prepared fron 3~n 9 of methyl methacrylate ~20 9 of butyl acrylate 70 y of hydroxyethyl methacryLate 20 g of methacryl;c ~c;d ~Z~'7~33 2n cf ~ n~t~lylo~ cl~yl~
2f~ ~ o~ m~h~l~r~al~ 0 12 ~ ~f sodium laurylethoxylatc sulfa~e ~ 5 mol.es oF ~1:hyl~1le. OX;df!) 1~ g of lauryl mercaptan and 900 g of wa.er and meter~d ;r,to a solut;on of 1Z g of sod;um lauryl sul-fate ;rl hO0 g o~ water. As tlle irlit;ator" a sol.ut;on o~
2 g of ammonium peroxydisulfate in 40 g of ~later was added in parailel to the morlomer emuls;or,. After adiust;ng the pH to 8v5 with c'f;methylam;noethanol, a dispcrsion llaving a solid~ content o~ 35% was obta;ne~. The mean particle diametel~ of the copolymer ~las 0.12 ~m.
Use l~alnple 1 Prepar~tion of a wh;te lacquer paint based vn rche dispersioll according to Example 5-A~ Pigmellt paste ~to82 g oF hexamethoxymethylmelarfline (50X in water~
~-~.8'> g of wa~r ~de;onized) 20 - 'i.20 g o~ sodium nitri~e (5% in ~fater~
0.36 g o-F sodium polyacrylate (25,' ;n water~
Ovl~ g of a~dit;on product of 1 mole of nonyl phenol and 6--'lO moles oF ethylene oxide 0~07 ~ of cornmerc;al defoamer and 19.2~ g o~F titanium d;ox;de trutile ty?e~
B) Binder o2 9 of d;spersion accordincf to Example 5 t35X
strength) and -7.25 9 of water :~2~7;~33 ' Part A) w~s ;nitially milled ;n a ball mil~ for 1~ hours, t~en ;)art ~) was m;xecl in ancl th~ m;xture ~las a~a;n ground fol a fultl1er 16 hours ;rl a b~ll mill~
The wh;te lacquer hacl a flow v;scorneter t;me of 30 seconds (DIN cop, PIN 53,.Z11, 4 mm no;zle~ and was adjus ted to a f~ow viscometer t;me of 1S~2D seconds ~J;th a rn;x-ture of ~!ater and butylglycol t7 ~. rhe lacquer; ready for spraying had a binder/pignlent ratio of 1:0~8 and a solids ratio oF dispersion to melamine resin of 9:1 w;th a sol-vent content of lcss than Z~. Lacquer films on steel plat:e exhibited a gloss of 85% (measured at an an3le of ~o ~e~ree~ m accordance utth DIN 67,~30). All tests of adhesion on slow and ~den deformation of the substlai-e and by the ~rid 1~ cutting process led to very good values~
1~ Use Example 2 ,_ Preparat;on of a yray spray f;ller based on the polymer d;spersion according to lxample 3:
A) P;gment paste 80 g oF t;tan;um dioxide ~rutile type) 4~ ~ ~f talc 8U g of zinc sulficle/barium sulfate 60 g of chalk 1~ g of si~;ca gel 10 9 of strontium chromate ~5 1.5 9 of flarne soot 1~ g of lead s;licochromate 8 ~ of sod;um polyacr~late ~25X in water~
9 of addition product of 1 mole of l~onylpl1enol and o to 10 moles o, ethylene ox;de . , .
:12472B3 - 15' - ' ' I ~ of commcrcial defoalrler 10 ~ ol` sodium nitl~ite ~ ;n ~later) ?U 9 of butylglycol and 8~5 g of water ~de;onized
5 B~ 6;nder ~40 9 o~ d;spers;on accord~ng to Example :~, 50Y
strerl~th~ and 30 ~ of hexamethoYymetllylmelaminc.
P spray filler~ which had a rac;o of copolymer to rnelamine resin o-F 9:1 and a rat;o of b;nder ~o p;gment of 1:1r uas prepared by t~,~ process according to Use Example 1~ The ~iller paint was sprayed onto steel plate and baked at ~150~'C for 20 minutes~ The d;spersion filler films showed yood mechanical properties and good resistance pro-perties on tes1;ng w;ih chemicals (solvents an~i salt sol-tions)~ The adhesion to ronvenlional bak;ny substr~tes corresponded to the state of the artu Use Ex~rnple ~
Pr~paration of a ~hite lacquer paint fo single-2~ ~ayer coating ~ased on the copolyrner dispersion according ~o Example 3:
A) P;gsnen~ paste 1D0 y of titanium d;oxide (rut-ile type) 40 9 of hexarr~ethoxymethylmelamine (SOY in water) 3 y of sodium polyacrylate t25% in water) 1.6 y of add;tion product of 1 mole of nony!-phenol and 6-10 moles of ethylene oxide 0O6 ~ of commercial defoalner :124'7~3 l of sodiun~ nitrite tSX in water~etl1anol 1.1) ~nd 23 ~ oF butylglycol/cthyld~glycol ~12 ~) Binder 360 g of copolymer dispersion accordin0 to Example 3, 50~ strength~ and 70 g of water/butylglycol t7:3~
A white lacquer paint was prepared by the process according to Use Example 1~ which paint had a flo~/ visco~
meter time of 30 seconds (according to DiN 53,211), a sol;ds content of 4'9% and a solvent content of less than 10X. The baked lacquer filrns on steel plate showed out-standing adhes;on and elasticity properties:
Erichsen cupping test (DIN 53,156~: 9.8 mm Imp3ct cuppin3 test ~AS1M G 14~: ~Z cm-5~g Grid cutting test tDIN 53,151~: a 1he white lacquer films had smooth flaw-free sur~
faces and a yloss o~ 85X tDIN 67,530).
Use Example 4 Preparat;on of a gray tex.uring lacquer lased on the copolymer dispersion according to Example 3:
A) Pigment paste 12 ~ of titanium d;oxide trutile type~
1.5 g of talc 17 g of calcium carbonate 0.2 g o~ soot 0.3 g of red iron oxide 1.5 g of sodium nitrite (10X in wacer) and 1~2 y o~ ethylene ~ly&ol , ~17Z133 ~ 21 -B) Binder 61 c~ Or copolylner d;spers;on and S.3 ~ of hexamethoxym~th~lrnelaMine ~63~ in watert ~thylene glycolO 1:1).
The ~exturing lacquer had a solids ~ontelt~ of 65 and a flow ViSCOnleter time o-f Z10 seconds ~according to DIN 53rZ11)~ The ra-tio of binder ~o pigment was 1~
In order to form opt;nlum texturesr the lacq~er ~as sprayed on in two layersO The undercoat was d;luted with water to a flow visco~eter time of 2U seconds (according to DIN
S3,211) 3nd then applied. After an airing period, the actual texturing lacquer was sprayed on undiluted~ The format;ol-~ of texture l~;th the copolymer dispers;on accord in~ to Example 3 as the binder W3S significantly better than that ~ th co Yentional al~yd resin t;nders.
Use Example 5 Preparation of a recJ sin~le-~layer lacquer base~l cn ~he copolyrner dispersion accord;ng to Exarr~ple 4:
A) Pigment paste ~8 g of molybdate red 1~ g of per~anent red 3 ~ o sodium polyacrylate (25 % in ~at~r3 15 y o-f sodium nitrite (10X in water) ~S g of ethylene glycol ~ 9 of dimetl)ylaminoethanol and 105 g o~ water (de;onized~
B) Binder - 6g4 9 of~ copolymer dispersion ~0 9 oS hexamethoxymethylmelamine (c~3X ;n ~later/
~2~ 33 , ~
etl1ylglycol, l:1) ancl ~ ~ of commerc;al silicone~based levelin~
- . auxiliary CSOX ;n solvcnt) A red lacquer paint~ which had a ratio of polymer to meLamine resin of 9:1 .and a ratio of b;nder to p;gment of 1 ~lSr was prepared b)~ the process according to Use Exalllple 1r At a sol;ds content of 44X and ~ pH of ~.5, the flo~ vi.scometer time of the dispersion wa~. 17 seconds tDIN 53,211). The proportion of organic solvents was ~%u 10The lacquer films baked at 130C (30 minlltes) had gloss values of 86-88% (DIN 67,530)~ 1he exceptional adl1esion ~as also dem(.)nstrated by a value of 9.Z mm in the Erichsen cupping test (~J.N 53,156~.
Comparison Example to Use Example 3 1~Preparation of rlhite lacquer paints for single~
layer coatin~s based on copolymer dispersions accordil1~ ~o German Offenlegungsschriften 2,211,169 ~Example 2) and 2,709,308 (Example S, ~7% strength):
A~ Pi~ment paste 64 ~ o~ titanium dioxide trutiLe type) 16 9 of l-examethoxylne~hylmelamine (50~ in water) 1.2 9 of sodium polyacrylate ~25X in water) 0.64 l3 of addition product of 1 mole of nonyl~
phenol and 6-10 moles of e~hylene oxide 0.24 9 of commercial defoamer and 4 ~ of sodium nitrite ~5% in water/ethanol, - 1:1S.
B) Binder 152 9 o~ copolymer dispersion.
;
~7~
- ~3 -In the process of prel~aration of the white lac~uers in a hall m;ll, with the d;spersion accordin~ to Gerrnan Offenlegur1cJsschr1~t 2~211,16'~, stable lacquer pa;nts were not obta;ned~ Thc p;gment wett;ng ~Jas insuf-F;cient and the S Lacquer paint contained p;gmel1t agglomerates. Spray appli~
cat;on ~las not possible because of the deficient homo-~eneity of the lacquer.
With the dispersion according to German OfFenle ~gungsschri~t 2~,70~308, a stable ~hite lacquer was obtained~
1n but this~ after spray application and baking~ led to lacquer surfaces which were very irre~Jular ~pits, bl;sters and p;n-holes) and wl1ich had inadequate res;stance to chemicals and ~loss values of 70% (accord;n~ to DIN 67,530)~
strerl~th~ and 30 ~ of hexamethoYymetllylmelaminc.
P spray filler~ which had a rac;o of copolymer to rnelamine resin o-F 9:1 and a rat;o of b;nder ~o p;gment of 1:1r uas prepared by t~,~ process according to Use Example 1~ The ~iller paint was sprayed onto steel plate and baked at ~150~'C for 20 minutes~ The d;spersion filler films showed yood mechanical properties and good resistance pro-perties on tes1;ng w;ih chemicals (solvents an~i salt sol-tions)~ The adhesion to ronvenlional bak;ny substr~tes corresponded to the state of the artu Use Ex~rnple ~
Pr~paration of a ~hite lacquer paint fo single-2~ ~ayer coating ~ased on the copolyrner dispersion according ~o Example 3:
A) P;gsnen~ paste 1D0 y of titanium d;oxide (rut-ile type) 40 9 of hexarr~ethoxymethylmelamine (SOY in water) 3 y of sodium polyacrylate t25% in water) 1.6 y of add;tion product of 1 mole of nony!-phenol and 6-10 moles of ethylene oxide 0O6 ~ of commercial defoalner :124'7~3 l of sodiun~ nitrite tSX in water~etl1anol 1.1) ~nd 23 ~ oF butylglycol/cthyld~glycol ~12 ~) Binder 360 g of copolymer dispersion accordin0 to Example 3, 50~ strength~ and 70 g of water/butylglycol t7:3~
A white lacquer paint was prepared by the process according to Use Example 1~ which paint had a flo~/ visco~
meter time of 30 seconds (according to DiN 53,211), a sol;ds content of 4'9% and a solvent content of less than 10X. The baked lacquer filrns on steel plate showed out-standing adhes;on and elasticity properties:
Erichsen cupping test (DIN 53,156~: 9.8 mm Imp3ct cuppin3 test ~AS1M G 14~: ~Z cm-5~g Grid cutting test tDIN 53,151~: a 1he white lacquer films had smooth flaw-free sur~
faces and a yloss o~ 85X tDIN 67,530).
Use Example 4 Preparat;on of a gray tex.uring lacquer lased on the copolymer dispersion according to Example 3:
A) Pigment paste 12 ~ of titanium d;oxide trutile type~
1.5 g of talc 17 g of calcium carbonate 0.2 g o~ soot 0.3 g of red iron oxide 1.5 g of sodium nitrite (10X in wacer) and 1~2 y o~ ethylene ~ly&ol , ~17Z133 ~ 21 -B) Binder 61 c~ Or copolylner d;spers;on and S.3 ~ of hexamethoxym~th~lrnelaMine ~63~ in watert ~thylene glycolO 1:1).
The ~exturing lacquer had a solids ~ontelt~ of 65 and a flow ViSCOnleter time o-f Z10 seconds ~according to DIN 53rZ11)~ The ra-tio of binder ~o pigment was 1~
In order to form opt;nlum texturesr the lacq~er ~as sprayed on in two layersO The undercoat was d;luted with water to a flow visco~eter time of 2U seconds (according to DIN
S3,211) 3nd then applied. After an airing period, the actual texturing lacquer was sprayed on undiluted~ The format;ol-~ of texture l~;th the copolymer dispers;on accord in~ to Example 3 as the binder W3S significantly better than that ~ th co Yentional al~yd resin t;nders.
Use Example 5 Preparation of a recJ sin~le-~layer lacquer base~l cn ~he copolyrner dispersion accord;ng to Exarr~ple 4:
A) Pigment paste ~8 g of molybdate red 1~ g of per~anent red 3 ~ o sodium polyacrylate (25 % in ~at~r3 15 y o-f sodium nitrite (10X in water) ~S g of ethylene glycol ~ 9 of dimetl)ylaminoethanol and 105 g o~ water (de;onized~
B) Binder - 6g4 9 of~ copolymer dispersion ~0 9 oS hexamethoxymethylmelamine (c~3X ;n ~later/
~2~ 33 , ~
etl1ylglycol, l:1) ancl ~ ~ of commerc;al silicone~based levelin~
- . auxiliary CSOX ;n solvcnt) A red lacquer paint~ which had a ratio of polymer to meLamine resin of 9:1 .and a ratio of b;nder to p;gment of 1 ~lSr was prepared b)~ the process according to Use Exalllple 1r At a sol;ds content of 44X and ~ pH of ~.5, the flo~ vi.scometer time of the dispersion wa~. 17 seconds tDIN 53,211). The proportion of organic solvents was ~%u 10The lacquer films baked at 130C (30 minlltes) had gloss values of 86-88% (DIN 67,530)~ 1he exceptional adl1esion ~as also dem(.)nstrated by a value of 9.Z mm in the Erichsen cupping test (~J.N 53,156~.
Comparison Example to Use Example 3 1~Preparation of rlhite lacquer paints for single~
layer coatin~s based on copolymer dispersions accordil1~ ~o German Offenlegungsschriften 2,211,169 ~Example 2) and 2,709,308 (Example S, ~7% strength):
A~ Pi~ment paste 64 ~ o~ titanium dioxide trutiLe type) 16 9 of l-examethoxylne~hylmelamine (50~ in water) 1.2 9 of sodium polyacrylate ~25X in water) 0.64 l3 of addition product of 1 mole of nonyl~
phenol and 6-10 moles of e~hylene oxide 0.24 9 of commercial defoamer and 4 ~ of sodium nitrite ~5% in water/ethanol, - 1:1S.
B) Binder 152 9 o~ copolymer dispersion.
;
~7~
- ~3 -In the process of prel~aration of the white lac~uers in a hall m;ll, with the d;spersion accordin~ to Gerrnan Offenlegur1cJsschr1~t 2~211,16'~, stable lacquer pa;nts were not obta;ned~ Thc p;gment wett;ng ~Jas insuf-F;cient and the S Lacquer paint contained p;gmel1t agglomerates. Spray appli~
cat;on ~las not possible because of the deficient homo-~eneity of the lacquer.
With the dispersion according to German OfFenle ~gungsschri~t 2~,70~308, a stable ~hite lacquer was obtained~
1n but this~ after spray application and baking~ led to lacquer surfaces which were very irre~Jular ~pits, bl;sters and p;n-holes) and wl1ich had inadequate res;stance to chemicals and ~loss values of 70% (accord;n~ to DIN 67,530)~
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of an aqueous dispersion of copolymers, which can be crosslinked with aminoplasts by the action of heat, by copolymerization of (A) styrene and/or methyl methacryl-ate, (B) 2-ethylhexyl acrylate and/or butyl acrylate and/or ethyl acrylate, (C) hydroxyethyl (meth)acrylate and/or hydroxypropyl (meth)-acrylate, (D) acrylic acid and/or methacrylic acid and (E) an amide and/or an N- methylolamide and/or an etherified N-methylolamide of an .alpha.,.beta.-unsaturated carboxylic acid in the aqueous phase in the pre-sence of an emulsifier and a radical-forming initiator, which com-prises copolymerizing a mixture of I. 30-60% by weight of methyl methacrylate or styrene or a mixture of these monomers, II. 30 50% by weight of ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate or a mixture of these monomers, III. 5-15% by weight of hydroxyethyl acrylate, hydroxy-ethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate or a mixture of these monomers, IV. 1-5% by weight of acrylic acid or methacrylic acid or a mixture of these monomers and V. 0.5-5% by weight of an amide or N-methylolamide or an etherified N-methylolamide of an .alpha.,.beta.-unsaturated carboxylic acid or a mixture of monomers of this type.
2. A process according to claim 1 wherein component I is methyl methacrylate.
3. A process according to claim 1 wherein component I is styrene alone which is present in an amount not more than 30% by weight relative to the total amount of monomers.
4. A process according to claim 1, 2 or 3 wherein the ratio of the amounts of monomers and water is selected so that the resulting copolymer dispersion has a solids content of 30 to 60% by weight.
5. A process according to claim 1, 2 or 3 wherein the ratio of the amounts of monomers and water is selected so that the resulting copolymer dispersion has a solids content of 35 to 50% by weight.
6. A process according to claim 1, 2 or 3 wherein after com-pletion of addition of the monomers the total batch is stirred for a further 1-3 hours at 60° - 90°C and the pH is then adjusted to a value in the range 7.5-9.5 with a tertiary amine.
7. A process according to claim 1, 2 or 3 wherein after com-pletion of addition of the monomers the total batch is stirred for a further 1-3 hours at 60° - 90°C and the pH is then adjusted to a value in the range 7.5-9.5 with a tertiary amine selected from the group consisting of triethylamine, diethanolmonomethylamine, tri-ethanolamine, dimethylisopropylhydroxymethylamine, dimethylamino-ethanol, dimethylaminopropanol and diethylaminoethanol.
8. A coating composition which can be crosslinked by the action of heat, which composition comprises an aqueous dispersion of copoly-mers made by a process according to claim 1 and a water-soluble or water dispersible aminoplast resin.
9. A process for preparing a coating composition which can be crosslinked by the action of heat, which comprises admixing an aqueous dispersion of copolymers made by a process according to claim 1 with a water-soluble or water-dispersible aminoplast resin.
10. A method of coating a substrate which comprises applying to the substrate a coating composition as claimed in claim 8, drying the coated substrate and then curing the coating by baking at a temperature of from 80 to 180°C for 10-30 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813128025 DE3128025A1 (en) | 1981-07-16 | 1981-07-16 | METHOD FOR PRODUCING AQUEOUS COPOLYMERISAT DISPERSIONS AND USE OF THE DISPERSIONS |
| DEP3128025.0 | 1981-07-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1247283A true CA1247283A (en) | 1988-12-20 |
Family
ID=6136998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407386A Expired CA1247283A (en) | 1981-07-16 | 1982-07-15 | Aqueous acrylic interpolymer coating dispersion |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0071071B2 (en) |
| JP (1) | JPS5819301A (en) |
| AT (1) | ATE34755T1 (en) |
| AU (1) | AU8605782A (en) |
| BR (1) | BR8204134A (en) |
| CA (1) | CA1247283A (en) |
| DE (2) | DE3128025A1 (en) |
| DK (1) | DK318582A (en) |
| ES (1) | ES8305014A1 (en) |
| FI (1) | FI822503L (en) |
| NO (1) | NO822455L (en) |
| PT (1) | PT75260B (en) |
| ZA (1) | ZA825034B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005010065A1 (en) * | 2003-07-23 | 2005-02-03 | Orica Australia Pty Ltd | Aqueous polymer dispersion |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1230198A (en) * | 1982-07-26 | 1987-12-08 | Joseph V. Koleske | High solids primer-guidecoats based on t-butyl acrylate and styrene |
| CA1230199A (en) * | 1982-08-05 | 1987-12-08 | Joseph V. Koleske | Highly weatherable coatings |
| AT381499B (en) * | 1985-02-27 | 1986-10-27 | Vianova Kunstharz Ag | WATER-DISCOVERABLE COATING AGENTS, METHOD FOR THE PRODUCTION AND THEIR USE FOR BASE LAYERS WITH TWO-LAYER TOP COATING |
| GB2172292A (en) * | 1985-03-08 | 1986-09-17 | Mitsubishi Rayon Co | Acrylic copolymer coatings |
| DE3628124A1 (en) * | 1986-08-19 | 1988-03-03 | Herberts Gmbh | AQUEOUS COATING AGENT, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF |
| DE3724858A1 (en) * | 1987-07-28 | 1989-02-09 | Texaco Ag | WAESSED PLASTIC DISPERSION |
| EP0484399A1 (en) * | 1989-07-28 | 1992-05-13 | Rohm And Haas Company | Water-resistant polymeric emulsions |
| US5202375A (en) * | 1989-07-28 | 1993-04-13 | Rohm And Haas Company | Water-resistant polymeric emulsions |
| US4998975A (en) * | 1989-10-30 | 1991-03-12 | Siemens-Pacesetter, Inc. | Travenously placed defibrillation leads |
| US6498202B1 (en) * | 1999-12-14 | 2002-12-24 | Lexmark International, Inc | Ink jet ink compositions including latex binder and methods of ink jet printing |
| US7241830B2 (en) | 2004-05-07 | 2007-07-10 | Ppg Industries Ohio, Inc. | Organic solvent-free film-forming compositions, multi-layer composite coatings, and related methods |
| US7717992B2 (en) * | 2004-11-03 | 2010-05-18 | Basf Corporation | Color enhancing emulsions |
| CN104231824B (en) * | 2014-09-18 | 2016-08-24 | 苏州圣谱拉新材料科技有限公司 | A kind of metal surface decorative paint and preparation method thereof |
| CN104449175A (en) * | 2014-12-22 | 2015-03-25 | 王道扬 | Water-based environment-friendly paint and preparation method thereof |
| CN105254798A (en) * | 2015-10-17 | 2016-01-20 | 佛山市顺德区巴德富实业有限公司 | Inner-wall stain-resistant pure acrylic emulsion |
| CN105385280A (en) * | 2015-12-25 | 2016-03-09 | 上海金狮化工有限公司 | Leather finishing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1519144C3 (en) * | 1965-02-22 | 1975-11-27 | Bayer Ag, 5090 Leverkusen | coating agents in the form of aqueous solutions |
| DE1644993C3 (en) * | 1968-02-01 | 1974-06-20 | Basf Ag, 6700 Ludwigshafen | Process for the production of coatings by applying coating agents in powder form |
| DE2556327A1 (en) * | 1975-12-13 | 1977-06-23 | Hoechst Ag | FINE PARTICLE COPOLYMER DISPERSIONS AND THE PROCESS FOR THEIR PRODUCTION |
-
1981
- 1981-07-16 DE DE19813128025 patent/DE3128025A1/en not_active Withdrawn
-
1982
- 1982-07-09 ES ES513836A patent/ES8305014A1/en not_active Expired
- 1982-07-13 AT AT82106242T patent/ATE34755T1/en not_active IP Right Cessation
- 1982-07-13 DE DE8282106242T patent/DE3278563D1/en not_active Expired
- 1982-07-13 EP EP82106242A patent/EP0071071B2/en not_active Expired - Lifetime
- 1982-07-14 FI FI822503A patent/FI822503L/en not_active Application Discontinuation
- 1982-07-15 CA CA000407386A patent/CA1247283A/en not_active Expired
- 1982-07-15 ZA ZA825034A patent/ZA825034B/en unknown
- 1982-07-15 BR BR8204134A patent/BR8204134A/en unknown
- 1982-07-15 PT PT75260A patent/PT75260B/en unknown
- 1982-07-15 JP JP57122256A patent/JPS5819301A/en active Pending
- 1982-07-15 AU AU86057/82A patent/AU8605782A/en not_active Abandoned
- 1982-07-15 DK DK318582A patent/DK318582A/en not_active Application Discontinuation
- 1982-07-15 NO NO822455A patent/NO822455L/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005010065A1 (en) * | 2003-07-23 | 2005-02-03 | Orica Australia Pty Ltd | Aqueous polymer dispersion |
| AU2004259044B2 (en) * | 2003-07-23 | 2010-07-22 | Duluxgroup (Australia) Pty Ltd | Aqueous polymer dispersion |
| AU2004259044B8 (en) * | 2003-07-23 | 2010-09-02 | Duluxgroup (Australia) Pty Ltd | Aqueous polymer dispersion |
| US7858695B2 (en) | 2003-07-23 | 2010-12-28 | Duluxgroup (Australia) Pty Ltd | Aqueous polymer dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA825034B (en) | 1983-05-25 |
| DE3278563D1 (en) | 1988-07-07 |
| PT75260B (en) | 1985-01-07 |
| EP0071071B2 (en) | 1994-11-17 |
| DK318582A (en) | 1983-01-17 |
| FI822503A0 (en) | 1982-07-14 |
| DE3128025A1 (en) | 1983-02-03 |
| ES513836A0 (en) | 1983-04-16 |
| AU8605782A (en) | 1983-02-03 |
| ATE34755T1 (en) | 1988-06-15 |
| EP0071071A1 (en) | 1983-02-09 |
| PT75260A (en) | 1982-08-01 |
| ES8305014A1 (en) | 1983-04-16 |
| EP0071071B1 (en) | 1988-06-01 |
| BR8204134A (en) | 1983-07-12 |
| NO822455L (en) | 1983-01-17 |
| FI822503L (en) | 1983-01-17 |
| JPS5819301A (en) | 1983-02-04 |
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