CA2058371A1 - Water-thinnable paint binders based on acrylate copolymers - Google Patents
Water-thinnable paint binders based on acrylate copolymersInfo
- Publication number
- CA2058371A1 CA2058371A1 CA002058371A CA2058371A CA2058371A1 CA 2058371 A1 CA2058371 A1 CA 2058371A1 CA 002058371 A CA002058371 A CA 002058371A CA 2058371 A CA2058371 A CA 2058371A CA 2058371 A1 CA2058371 A1 CA 2058371A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- meth
- koh
- component
- water
- 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.)
- Abandoned
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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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
Abstract
ABSTRACT OF THE DISCLOSURE
Water-thinnable paint binders based on alkyl (meth)acrylate copolymers obtained by a partial condensation of a polycarboxyl component with a polyhydroxyl component and a subsequent, at least partial, neutralization of the carboxyl groups are described. A proportion of the alkyl (meth)acrylates can be replaced by aromatic vinyl compounds.
The condensation products contain 0.5 to 2% by weight of monomers containing two or more reactive double bonds, for example diol di(meth)acrylates or divinylbenzene, 0.5 to 2%
by weight of polyol polythioglycolic acid esters and 0.5 to 3.5% by weight of fluorine-containing monomers. The paint binders are particularly suitable for the formulation of high-grade heat-curable finishes with a low content of auxiliary organic solvents.
Water-thinnable paint binders based on alkyl (meth)acrylate copolymers obtained by a partial condensation of a polycarboxyl component with a polyhydroxyl component and a subsequent, at least partial, neutralization of the carboxyl groups are described. A proportion of the alkyl (meth)acrylates can be replaced by aromatic vinyl compounds.
The condensation products contain 0.5 to 2% by weight of monomers containing two or more reactive double bonds, for example diol di(meth)acrylates or divinylbenzene, 0.5 to 2%
by weight of polyol polythioglycolic acid esters and 0.5 to 3.5% by weight of fluorine-containing monomers. The paint binders are particularly suitable for the formulation of high-grade heat-curable finishes with a low content of auxiliary organic solvents.
Description
~8371 FIELD OF INVENTION
The present invention relates to water-thinnable paint binders based on acrylate copolymers; to the process for the preparation of these binders, and to the use of these binders in the Eormulation of water-thinnable finishes with a low auxiliary organic solvent content.
BACKGROUND OF INVENTION
Water-thinnable binders which are obtained by the mixing or partial condensation of a polycarboxyl component r water-soluble after neutralization of the carboxyl groups, with a resin-like, essentially non-water-thinnable polyhy-droxyl component, havin~ favorable viscosity characteristics on dilution with water, are disclssad in a number of patents, for example in Austrian Patent Nos. 328,587; 379,607;
388,738, and 388,382. Although Austrian Patent No. 328,587 specifies acrylate copolymers as a coreactant, commercially useful paints cannot be formulated on the basis of the mono-mer composition described in the Austrian patent since their application properties have disadvantages such as a tendency to form blisters and to sag during the stoving process, even at low film thicknesses.
It has now been found that acrylate-based binder systems, suitable for practical use, are obtained by a , , ~ 2666/US3595 337~L
careful choice of the monomer composition of the poly-carboxyl and p~lyhydroxyl components.
SUMMARY OF INVENTION
Accordingly, the present invention relates to water-thinnable paint binders based on acrylate copolymers obtained by a partial condensation of a polycarboxyl compo-nent with a polyhydroxyl component and a subsequent, at least partial, neutralization of the carboxyl groups, with said binders being characterized in that 10 to 40% by weight, based on the solids content, of an acrylate copoly-mer having an acid value of 70 to 240 mg KOH/g, preferably 100 to 200 mg KOH/g, which contains -(Aa) 57 to 90% by weight of alkyl (meth)acrylates con-taining an alkyl radical of 1 to 12 carbon atoms, these esters being capable of replacement, in an amount of up to 50% by weight, by aromatic vinyl compounds, preferably styrene, (Ab) 10 to 33% by weight of ~,~-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, (Ac) up to 2% by weight of monomers containing two or more reactive double bonds, ~Ad) up to 2% by weight of polyfunctional chain termination regulators of the pol~ol polythioglycolic acid esters type, and 2666/US3595 2~5~7~
(Ae) up to 8% by weight of fluorine-containing monomers copolymerizable with (Aa) to (Ad) is used as the polycarboxyl component (A), and 90 to 60% by weight, based on the solids content, of an acrylate copoly-mer having a hydroxyl value of 90 to 250 mg KOH/g, prefer-ably of 110 to 1~0 mg KOH/g, and optionally having an acid value of 10 to 30 mg KO~I/g, which contains -(Ba) 40 to 80~ by weight of alkyl (meth)acrylates contain-ing an alkyl radical of 1 to 12 carbon atoms, these esters being capable of replacement, in an amount of up to 50% by weight, by aromatic vinyl compounds, preferably styrene, (Bb) 20 to 60% by weight of monoesters of (meth)acrylic acid with diols containing an alkylene radical of 2 to 4 carbon atoms or an oxyalkylene radical of 6 to 12 carbon atoms, (~c) up to 2% by weight o~ monomers containing two or more reactive double bonds, (Bd) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythioglycolic acid ester type, (Be) up to 4% by weight of fluorine-containing monomers co-polymerizable with (Ba) to (Bd), and, if de-sired, (Bf) 1 to 5% by weight of a,~-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, . .
, :
2666/US35g5 ~ 337~
is used as the polyhydroxyl component (B), at least one of the components (A~ and (B) containing a monomer (Ac) or (Bc) and a regulator (Ad) or (Bd) a~d a fluorine-containing mono-mer (Ae) or (~e) and the proportions of the components (A) and ~B) being chosen so that the condensation product con-tains ~
0.5 to 2~ by weight of the monomer (Ac) or (Bc), 0.5 to 2~ by weight of the regulator (Ad) or (~3d), and 0.5 to 3.5% by weight of the fluorine-containing monomers (Ae) or (Be), and has an acid value of 30 to 65 my KOH/g, a hydroxyl value of 70 to 150 mg KOH/g, and an intrinsic viscosity of 12 to 18 ml/g, preferably of 13 to 16 ml/g, measured in chloroform at 20C.
The invention further relates to the process for the preparation of these binders and to the use of the bin-ders in the formulation of water-thinnable finishes with a low content of auxiliary organic solvents.
The binders according to the present invention permit the formulation of paints having good application properties, such as a minimum tendency to sag, rapid solvent release, and very good flow-out. The paints are resistant to yellowing, and the weathering resistance of the stoved films meets the requirements of industry, especially of the automotive industry.
i , 2666/US3595 ~ 37~
The components (A) and (B) ~re prepared in a known manner by solution polymerization, with the monomers being employed in the proportions stated above. (Meth)acrylic acid esters of alkanols containing 1 to 12 carbon atoms and, if desired, a proportionate amount, i.e., up to 50% by weight, of aromatic vinyl monomers as well, in particular styrene, are employed as the monomer component (Aa) or (Ba).
The components (Ab) and (Bf) preferably consist of acrylic or methacrylic acid, but other ~ ethylenically unsaturated carboxylic acids, such as maleic acid, can also be used if degired.
Monoesters of (meth)acrylic acid with diols con-taining 2 to 4 carbon atoms, such as ethylene glycol, propy-lene glycol and butylene glycol or the corresponding iso-meric compounds, are employed as the component (Bb). In addition, monoesters of ether group-containing alkanediols having 6 to 12 carbon atoms, for example triethylene glycol mono(meth)acrylate or the corresponding polyethylene glycol mono(meth)acrylates or dipropylene glycol mono(meth)acrylate or the corresponding polypropylene glycol mono(meth)acryl-ates, can also be used.
The components (Ac) and (Bc) consist of polyfunc-tional copolymerizable monomers, such as butanediol di-(meth)acrylate, hexanediol di(meth)acrylate, trimethylol-propane tri(meth)acrylate, or divinylbenzene.
... . . . ..
' , . . .
-~ 2666/US3595 2~ 7~
Thioglycolic acid esters, such as pentaerythritol tetrathioglycolate or glycerol trithioglycolate, are used as the polyfunctional chain termination regulators (Ad) and (8d).
Perfluoroctylethyl me-thacrylate or similar mono-mers are preferably employed as the fluorine-containing monomers for the components (Ae) and (~3e).
The binders of the present invention use a poly-carboxyl component (A) which must have an acid value of 70 to 240 mg KOH/g, preferably of 100 to 200 mg KOH/g. The hydroxyl value of the polyhydroxyl component (B) is between 90 and 250 mg KOH/g, preferably between 110 and 180 mg KOH/g; and the acid value, if appropriate, is between 10 and 30 mg KOH/g.
The components (A) and (B) are mixed in a ratio, based on the solids content, o~ between 10:90 and 40:60.
The solvent of the polymers is then substantially removed in vacuo and, if required, replaced by a water-tolerant, high-boiling auxiliary solvent, such as the alcohols or glycol ethers. The partial condensation is performed at 100 to 150C, pre~erably at 110 to 130C, until the intrinsic vis-cosity ~measured in chloroform at 20C) has risen to 12 to 18 ml/g, preferably to 13 to 16 ml/g. The ratio of the intrinsic viscosity values of the condensation product to the starting mixture should be 1.1:1 to 1.7:1, preferably 1.2:1 to 1.5:1. When the terminal values have been reached, - 2666/US3595 2~371 a suitable neutralizing agent, such as ammonia, secondary and tertiary amines or alkanolamines, is added and the mix-ture is diluted with deionized water to the desired solids content.
In a special embodiment, as crosslinking component (C) a hydrophobic amino resin, preferably a melamine-form-aldehyde resin, is admixed in an amount of 15 to 35% by weight, preferably of 20 to 30% by weight, based on the solids content of the binder as a whole, to the substantial-ly nonaqueous, optionally partially or completely neutra-lized condensation product of components (~) and (B) at a maximum temperature of 85C, and the mixture is thoroughly homogenized before the addition of the balance of the neu-tralizing agent which may be required and before diluting with water. According to this embodiment, the degree of gloss and the water resistance of the stoved paint films can be even further improved in the case of paints based on bin-der combinations of this type.
The hydrophobic amino resins used according to the invention as component (C) are selected by means of a simple dilutability test. Suitable melamine resins, benzoguanamine resins and urea resins are those which exhibit greater tur-bidity or separation in a mixture of 25 parts by weight of the resin as supplied, 15 parts by weight of ethylene glycol monobutyl ether, and 85 parts by weight of water at room temperature at most 5 minutes a~ter mixing. A large number ~ 2666/US3595 2~5~3~7~
of products of this kind are commercially available. Exam-ples of products which have proved suitable are melamine-formaldehyde condensates such as CYMEL~ 1158/80, CYMEL~
245/80 (both from American Cyanamid Company), VIAMIN~
MF 514/60 (Vianova-Kunstharz, A.G.), and MAPRENAL~ MF 915/75 (Hoechst A.G.).
The formulation of water-thinnable paints, using the binders according to the invention, and the application thereo~ is known to the person skilled in the art and has been extensively described in the literature.
The binders according to the present invention are suitable for forced-drying finishes, such as automotive fin-ishes, electrical equipment finishes, and similar arPas of application. They can also be used for the formulation of clear-coats according to the base-coat/clear-coat process for automotive finishing. Of substantial advantage is the possibility of formulating paints with a very low ccntent of auxiliary organic solvents using the binders according to the invention.
The following examples illustrate the invention in detail without limiting its scope. All parts and percen-tages are by weight, unless stated otherwise.
Preparation of the Polycarboxyl Components (A) and PolyhydroxYl comPonents (B) Used in the Examples The copolymers were prepared in a known manner by solution polymerization in isopropanol corresponding to ~C~5837~
a calculated solids content of 50% by weight for the compo-n~nts (A) and 65% by weight for the components (B). The proportions and properties are summarized in Table 1. A
carboxyl-containing water-thinnable copolymer (Cl) and a combination of acrylate copolymers according to Austrian Patent No. 328,587 (C2), whose composition is also described in Table 1, are used as comparison examples.
Table 1 is as follows:
~C`5~37~l.
~1 ~ ~ I I
~.7 O` . N ' ' `~ r'7 .. . . . . . O ~ N
_ ¦ r~7 N ro . . . . .. . N . _ ~ 7 ~7 . _ rll ~ r~7 r~ ' N U7 ' . . .. . . _ . V7 ~ _ h7 V
n7 t.: ¦ N _ r~7 N . .. . . _ . . _ . . U7 ._ V C
l_ ¦ ~_ _ r~7 _ _ ~ N . . . . . N O 0 0 _ N`:t ~ ' N U7 C7 . . . . . ~ . C7 . N . 7 r~ _ v W C
V V L ~ ~ ~Ll L L U
0 0 ~ ~ hl ~ ~ 8 ~ _ --O ~ C a _ . _ ~ ~ O L
r~ h7 ~ 8 V U L V ~~ Q n 1~ v v v ~ _ N e > ~ ~ E ,_ N C
:.` >. ~ C >~ L ~ 0 ~ ~,~, L h7 0 X0 8 _ > ~ r_ c7 u ~ L ~ ~ ~I cW
W ~7 N I n7 r7 L v N ~ N 1L ~ 3 ~ ~L--L c~ E ~ ~ ~ ~, e o a: ~ L ~ î~ e o ~ ~ L I ~1 L -7 `' _ 337~
ou~ l l N . . . . . . . . _ q ~ o .`n . . ~O . ~J . . . . . .. . _ . _ ~t N
L U~ ~01 N . _ . . ~,~ . . _ . _ . . -- O` O
O . O O . ~ . ~ t_ . . _ . . . N . . O~ _ 0~U~i3 J ~ ~ ~ . . N . . _ . ~ . . ~ o~
O~ ~ .,. . . V'' ' . _ .. . . t'~ .0 I
._~ ~ . . O . N . . . 10 ~ . . _ . . . N . . . _ c m ` ~N~ ' ' ' ~' ~ ' ' ' ' O . ~r '0~ _' W ~ V~ I`J N . . ~ . ~ U~ . . I~J . . _ . .
m ~ ~o.~.. , . ..~ ' .... . N . .0 ~ C~
~ 1~1 . ~? Vl u~ _ . . ~ ~ . . . ~ , ,. _ ~ N V1 N
~. . . 00~ ~ . . . ~ . . ~ . . . . _ . ' ~ 0~ ~ ~ æ
_ r.J ~ ' _ l l ~ ~ ' ' . . . ~ ~ . . tO . V
~ ~ 0 U ~ ~ ~ ~ Y ~.~ ~ U
" ~ al U ~ --U U 9~ , U U 3. ~1 O ~/ I ~ --C , ~ , ~ ~ U ' ~ L ~ ~ ~ ~ L 1 ~ ~ ~ Y ' ~ ~ ~
~: n O n ~~ o ~ ~ o L
2~`S~337~
Examples 1 to 10 The compon~nts (A) and (B) are mixed in the pro-portions stated in Table 2. The isopropanol is removed in vacuo until the solids content of the mixture is at least 95% by weight. The mixture is diluted with dipropylene glycol dimethyl ether to a solids content of 85 to 94% by weight and condensation is effected at 110 to 120'C until the desired intrinsic viscosity is reached. At the end of the condensation reaction the reaction mixture is cooled to 95C, neutralized with amine, and thoroughly dispersed using deionized water.
Examples 11 and 12 The preparation method is the same as used for Examples 1 to 10, except that, after neutralization with the amine, component (C) is added, and the mixture is homogen-ized for at least ten minutes at a maximum of 85C and sub-sequently brought to the desired solids content using deion-ized water.
The characteristics for the products from the examples and the comparison examples are listed in Table 2 as follows:
2666/US3595 ;~ 37~
ûN . ûN ~
N O N N I O . 0,, ~ ~ ~ co U I . . . O ~ . . . . . .. . O~ . N ~: . O
~ 0 I ~ . N i . ~0 ~ ' 0 N N . ~, ~ 1~ ~ ~ O N N ~ c , o ' ~ .
~ m ~ , . . N . ~ I ~ , co W
C <t ` ~U~ O r"
C u~ o ~ o N ~ ~, ~, ~i co J~
U N . ~_ . .O. ~ ~.1 .' .-- . . . O . E
~0 N ~ , . . n N O` ~ ~ ~ N ~ ~
O V~ . o ~ ~ . O ~ . O ~ o C
o ~ . m, , y~ O u~ O O~ CD
V , ' . ` ` `~ , CO ~ ~ ~ COo O V
The present invention relates to water-thinnable paint binders based on acrylate copolymers; to the process for the preparation of these binders, and to the use of these binders in the Eormulation of water-thinnable finishes with a low auxiliary organic solvent content.
BACKGROUND OF INVENTION
Water-thinnable binders which are obtained by the mixing or partial condensation of a polycarboxyl component r water-soluble after neutralization of the carboxyl groups, with a resin-like, essentially non-water-thinnable polyhy-droxyl component, havin~ favorable viscosity characteristics on dilution with water, are disclssad in a number of patents, for example in Austrian Patent Nos. 328,587; 379,607;
388,738, and 388,382. Although Austrian Patent No. 328,587 specifies acrylate copolymers as a coreactant, commercially useful paints cannot be formulated on the basis of the mono-mer composition described in the Austrian patent since their application properties have disadvantages such as a tendency to form blisters and to sag during the stoving process, even at low film thicknesses.
It has now been found that acrylate-based binder systems, suitable for practical use, are obtained by a , , ~ 2666/US3595 337~L
careful choice of the monomer composition of the poly-carboxyl and p~lyhydroxyl components.
SUMMARY OF INVENTION
Accordingly, the present invention relates to water-thinnable paint binders based on acrylate copolymers obtained by a partial condensation of a polycarboxyl compo-nent with a polyhydroxyl component and a subsequent, at least partial, neutralization of the carboxyl groups, with said binders being characterized in that 10 to 40% by weight, based on the solids content, of an acrylate copoly-mer having an acid value of 70 to 240 mg KOH/g, preferably 100 to 200 mg KOH/g, which contains -(Aa) 57 to 90% by weight of alkyl (meth)acrylates con-taining an alkyl radical of 1 to 12 carbon atoms, these esters being capable of replacement, in an amount of up to 50% by weight, by aromatic vinyl compounds, preferably styrene, (Ab) 10 to 33% by weight of ~,~-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, (Ac) up to 2% by weight of monomers containing two or more reactive double bonds, ~Ad) up to 2% by weight of polyfunctional chain termination regulators of the pol~ol polythioglycolic acid esters type, and 2666/US3595 2~5~7~
(Ae) up to 8% by weight of fluorine-containing monomers copolymerizable with (Aa) to (Ad) is used as the polycarboxyl component (A), and 90 to 60% by weight, based on the solids content, of an acrylate copoly-mer having a hydroxyl value of 90 to 250 mg KOH/g, prefer-ably of 110 to 1~0 mg KOH/g, and optionally having an acid value of 10 to 30 mg KO~I/g, which contains -(Ba) 40 to 80~ by weight of alkyl (meth)acrylates contain-ing an alkyl radical of 1 to 12 carbon atoms, these esters being capable of replacement, in an amount of up to 50% by weight, by aromatic vinyl compounds, preferably styrene, (Bb) 20 to 60% by weight of monoesters of (meth)acrylic acid with diols containing an alkylene radical of 2 to 4 carbon atoms or an oxyalkylene radical of 6 to 12 carbon atoms, (~c) up to 2% by weight o~ monomers containing two or more reactive double bonds, (Bd) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythioglycolic acid ester type, (Be) up to 4% by weight of fluorine-containing monomers co-polymerizable with (Ba) to (Bd), and, if de-sired, (Bf) 1 to 5% by weight of a,~-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, . .
, :
2666/US35g5 ~ 337~
is used as the polyhydroxyl component (B), at least one of the components (A~ and (B) containing a monomer (Ac) or (Bc) and a regulator (Ad) or (Bd) a~d a fluorine-containing mono-mer (Ae) or (~e) and the proportions of the components (A) and ~B) being chosen so that the condensation product con-tains ~
0.5 to 2~ by weight of the monomer (Ac) or (Bc), 0.5 to 2~ by weight of the regulator (Ad) or (~3d), and 0.5 to 3.5% by weight of the fluorine-containing monomers (Ae) or (Be), and has an acid value of 30 to 65 my KOH/g, a hydroxyl value of 70 to 150 mg KOH/g, and an intrinsic viscosity of 12 to 18 ml/g, preferably of 13 to 16 ml/g, measured in chloroform at 20C.
The invention further relates to the process for the preparation of these binders and to the use of the bin-ders in the formulation of water-thinnable finishes with a low content of auxiliary organic solvents.
The binders according to the present invention permit the formulation of paints having good application properties, such as a minimum tendency to sag, rapid solvent release, and very good flow-out. The paints are resistant to yellowing, and the weathering resistance of the stoved films meets the requirements of industry, especially of the automotive industry.
i , 2666/US3595 ~ 37~
The components (A) and (B) ~re prepared in a known manner by solution polymerization, with the monomers being employed in the proportions stated above. (Meth)acrylic acid esters of alkanols containing 1 to 12 carbon atoms and, if desired, a proportionate amount, i.e., up to 50% by weight, of aromatic vinyl monomers as well, in particular styrene, are employed as the monomer component (Aa) or (Ba).
The components (Ab) and (Bf) preferably consist of acrylic or methacrylic acid, but other ~ ethylenically unsaturated carboxylic acids, such as maleic acid, can also be used if degired.
Monoesters of (meth)acrylic acid with diols con-taining 2 to 4 carbon atoms, such as ethylene glycol, propy-lene glycol and butylene glycol or the corresponding iso-meric compounds, are employed as the component (Bb). In addition, monoesters of ether group-containing alkanediols having 6 to 12 carbon atoms, for example triethylene glycol mono(meth)acrylate or the corresponding polyethylene glycol mono(meth)acrylates or dipropylene glycol mono(meth)acrylate or the corresponding polypropylene glycol mono(meth)acryl-ates, can also be used.
The components (Ac) and (Bc) consist of polyfunc-tional copolymerizable monomers, such as butanediol di-(meth)acrylate, hexanediol di(meth)acrylate, trimethylol-propane tri(meth)acrylate, or divinylbenzene.
... . . . ..
' , . . .
-~ 2666/US3595 2~ 7~
Thioglycolic acid esters, such as pentaerythritol tetrathioglycolate or glycerol trithioglycolate, are used as the polyfunctional chain termination regulators (Ad) and (8d).
Perfluoroctylethyl me-thacrylate or similar mono-mers are preferably employed as the fluorine-containing monomers for the components (Ae) and (~3e).
The binders of the present invention use a poly-carboxyl component (A) which must have an acid value of 70 to 240 mg KOH/g, preferably of 100 to 200 mg KOH/g. The hydroxyl value of the polyhydroxyl component (B) is between 90 and 250 mg KOH/g, preferably between 110 and 180 mg KOH/g; and the acid value, if appropriate, is between 10 and 30 mg KOH/g.
The components (A) and (B) are mixed in a ratio, based on the solids content, o~ between 10:90 and 40:60.
The solvent of the polymers is then substantially removed in vacuo and, if required, replaced by a water-tolerant, high-boiling auxiliary solvent, such as the alcohols or glycol ethers. The partial condensation is performed at 100 to 150C, pre~erably at 110 to 130C, until the intrinsic vis-cosity ~measured in chloroform at 20C) has risen to 12 to 18 ml/g, preferably to 13 to 16 ml/g. The ratio of the intrinsic viscosity values of the condensation product to the starting mixture should be 1.1:1 to 1.7:1, preferably 1.2:1 to 1.5:1. When the terminal values have been reached, - 2666/US3595 2~371 a suitable neutralizing agent, such as ammonia, secondary and tertiary amines or alkanolamines, is added and the mix-ture is diluted with deionized water to the desired solids content.
In a special embodiment, as crosslinking component (C) a hydrophobic amino resin, preferably a melamine-form-aldehyde resin, is admixed in an amount of 15 to 35% by weight, preferably of 20 to 30% by weight, based on the solids content of the binder as a whole, to the substantial-ly nonaqueous, optionally partially or completely neutra-lized condensation product of components (~) and (B) at a maximum temperature of 85C, and the mixture is thoroughly homogenized before the addition of the balance of the neu-tralizing agent which may be required and before diluting with water. According to this embodiment, the degree of gloss and the water resistance of the stoved paint films can be even further improved in the case of paints based on bin-der combinations of this type.
The hydrophobic amino resins used according to the invention as component (C) are selected by means of a simple dilutability test. Suitable melamine resins, benzoguanamine resins and urea resins are those which exhibit greater tur-bidity or separation in a mixture of 25 parts by weight of the resin as supplied, 15 parts by weight of ethylene glycol monobutyl ether, and 85 parts by weight of water at room temperature at most 5 minutes a~ter mixing. A large number ~ 2666/US3595 2~5~3~7~
of products of this kind are commercially available. Exam-ples of products which have proved suitable are melamine-formaldehyde condensates such as CYMEL~ 1158/80, CYMEL~
245/80 (both from American Cyanamid Company), VIAMIN~
MF 514/60 (Vianova-Kunstharz, A.G.), and MAPRENAL~ MF 915/75 (Hoechst A.G.).
The formulation of water-thinnable paints, using the binders according to the invention, and the application thereo~ is known to the person skilled in the art and has been extensively described in the literature.
The binders according to the present invention are suitable for forced-drying finishes, such as automotive fin-ishes, electrical equipment finishes, and similar arPas of application. They can also be used for the formulation of clear-coats according to the base-coat/clear-coat process for automotive finishing. Of substantial advantage is the possibility of formulating paints with a very low ccntent of auxiliary organic solvents using the binders according to the invention.
The following examples illustrate the invention in detail without limiting its scope. All parts and percen-tages are by weight, unless stated otherwise.
Preparation of the Polycarboxyl Components (A) and PolyhydroxYl comPonents (B) Used in the Examples The copolymers were prepared in a known manner by solution polymerization in isopropanol corresponding to ~C~5837~
a calculated solids content of 50% by weight for the compo-n~nts (A) and 65% by weight for the components (B). The proportions and properties are summarized in Table 1. A
carboxyl-containing water-thinnable copolymer (Cl) and a combination of acrylate copolymers according to Austrian Patent No. 328,587 (C2), whose composition is also described in Table 1, are used as comparison examples.
Table 1 is as follows:
~C`5~37~l.
~1 ~ ~ I I
~.7 O` . N ' ' `~ r'7 .. . . . . . O ~ N
_ ¦ r~7 N ro . . . . .. . N . _ ~ 7 ~7 . _ rll ~ r~7 r~ ' N U7 ' . . .. . . _ . V7 ~ _ h7 V
n7 t.: ¦ N _ r~7 N . .. . . _ . . _ . . U7 ._ V C
l_ ¦ ~_ _ r~7 _ _ ~ N . . . . . N O 0 0 _ N`:t ~ ' N U7 C7 . . . . . ~ . C7 . N . 7 r~ _ v W C
V V L ~ ~ ~Ll L L U
0 0 ~ ~ hl ~ ~ 8 ~ _ --O ~ C a _ . _ ~ ~ O L
r~ h7 ~ 8 V U L V ~~ Q n 1~ v v v ~ _ N e > ~ ~ E ,_ N C
:.` >. ~ C >~ L ~ 0 ~ ~,~, L h7 0 X0 8 _ > ~ r_ c7 u ~ L ~ ~ ~I cW
W ~7 N I n7 r7 L v N ~ N 1L ~ 3 ~ ~L--L c~ E ~ ~ ~ ~, e o a: ~ L ~ î~ e o ~ ~ L I ~1 L -7 `' _ 337~
ou~ l l N . . . . . . . . _ q ~ o .`n . . ~O . ~J . . . . . .. . _ . _ ~t N
L U~ ~01 N . _ . . ~,~ . . _ . _ . . -- O` O
O . O O . ~ . ~ t_ . . _ . . . N . . O~ _ 0~U~i3 J ~ ~ ~ . . N . . _ . ~ . . ~ o~
O~ ~ .,. . . V'' ' . _ .. . . t'~ .0 I
._~ ~ . . O . N . . . 10 ~ . . _ . . . N . . . _ c m ` ~N~ ' ' ' ~' ~ ' ' ' ' O . ~r '0~ _' W ~ V~ I`J N . . ~ . ~ U~ . . I~J . . _ . .
m ~ ~o.~.. , . ..~ ' .... . N . .0 ~ C~
~ 1~1 . ~? Vl u~ _ . . ~ ~ . . . ~ , ,. _ ~ N V1 N
~. . . 00~ ~ . . . ~ . . ~ . . . . _ . ' ~ 0~ ~ ~ æ
_ r.J ~ ' _ l l ~ ~ ' ' . . . ~ ~ . . tO . V
~ ~ 0 U ~ ~ ~ ~ Y ~.~ ~ U
" ~ al U ~ --U U 9~ , U U 3. ~1 O ~/ I ~ --C , ~ , ~ ~ U ' ~ L ~ ~ ~ ~ L 1 ~ ~ ~ Y ' ~ ~ ~
~: n O n ~~ o ~ ~ o L
2~`S~337~
Examples 1 to 10 The compon~nts (A) and (B) are mixed in the pro-portions stated in Table 2. The isopropanol is removed in vacuo until the solids content of the mixture is at least 95% by weight. The mixture is diluted with dipropylene glycol dimethyl ether to a solids content of 85 to 94% by weight and condensation is effected at 110 to 120'C until the desired intrinsic viscosity is reached. At the end of the condensation reaction the reaction mixture is cooled to 95C, neutralized with amine, and thoroughly dispersed using deionized water.
Examples 11 and 12 The preparation method is the same as used for Examples 1 to 10, except that, after neutralization with the amine, component (C) is added, and the mixture is homogen-ized for at least ten minutes at a maximum of 85C and sub-sequently brought to the desired solids content using deion-ized water.
The characteristics for the products from the examples and the comparison examples are listed in Table 2 as follows:
2666/US3595 ;~ 37~
ûN . ûN ~
N O N N I O . 0,, ~ ~ ~ co U I . . . O ~ . . . . . .. . O~ . N ~: . O
~ 0 I ~ . N i . ~0 ~ ' 0 N N . ~, ~ 1~ ~ ~ O N N ~ c , o ' ~ .
~ m ~ , . . N . ~ I ~ , co W
C <t ` ~U~ O r"
C u~ o ~ o N ~ ~, ~, ~i co J~
U N . ~_ . .O. ~ ~.1 .' .-- . . . O . E
~0 N ~ , . . n N O` ~ ~ ~ N ~ ~
O V~ . o ~ ~ . O ~ . O ~ o C
o ~ . m, , y~ O u~ O O~ CD
V , ' . ` ` `~ , CO ~ ~ ~ COo O V
3 e ' m ~ ` '~ ' ` ~ u~ ' o~, ~ ' e, coO ~i,~
8 e . m . . N O . . ~O O . ~ ~ V O
a N . ~ . , C CO` "~ ~ N ~ ' . ~ . N ' E ' 0 O
N U~ .S . m . . o o ~ ~ O ~_ UN~ ~ o I ~ ~ ca 8 O ~o~ N I . Cl~ ~; V
W N .r~ ~ . O . . . . . ~ V W
m ~ U~ cO W ~D ~D
. ' ' ' ' ' ~a ca >~ U
,c ~ N ' ~ , ~ "~ 0O~ X X 8 L
N o o I -- o ~ ~ $ ~ ~ r E E s ~ c7~ ct~ o ~ ~ ~ cn ~
W E
' ~ ' ci N . ~ ~, ~, ~ v I ~. a c , ~ ~ D ~ E
e m , ~ :8~ n ~ v ~ ,~ ~ ~D a _~> E
v ~ c ~ Y ' ~D ' . v o ~ ~ ~ C ~ E
I J . U . U,v,~, ~, , ~, ~ O cn ~ e c ~, ~ .vc .C . . > . X . ~a ~ ~D ~ ~ ~ ~ w ~ E E U ~ O F~ C~ ~ ~ D ~ cD ~
. e . .c . c~ c,a u . ~ ~ ~ . <c . = . 2 ~ O--2666/US3595 ~`5~337~
o ~ . , , o~
~ 0 .
0 : O O : 0 ~ ~ O ~ rl 1~ co O ro ~ O O O U~
O` `O CO O ~,~ ~ N
I o ~ ~ 1~ o co O 1~ 0 N
O ¦ ~o c O ~ v~ O~ E e wl ¦ o 1~ o o co o~ 11 s e o ,~ . _ o ~ e ~
~1 0 COO `
~ ~ ~o ~' ~o~n 0~ :E
I N N O ~O COCO U
_ CO ~ 0 U~ O N , ~ ~
_ ~ ~ ~ _ _ _ L 8 8 I U ~ " " ,, ,., ., V V .. ., ., V .. ~
Iv 'V C ~ U 0 L ~C L :~ C_ IC 3 C ~--¦~ O S N ~ L L L O ~}
O ~ U ~ t~ ~tl. X cl. ~'c ~ 0 0 . 2666/US3595 ~5837~.
Testing of the Binders in Examples 1 to 12 and the Comparison Exam~les C~ and C2 The binders according to the present invention were tested as clear-coats in a metallic base-coat/clear-coat system and as white paint. The formulations are sum-marized in Tables 3 (clear-coat) and 4 (white paint~, the ratio of the combination of acrylate copolymers or the acrylate copolymer of C1 to melamine resin referring in each case to the solids content.
Tables 3 and 4 are as follows:
, 2666/US3595 2(~ 3q~l.
1~1 1.7 ~'I N -- Il ~ 0 0 0 ~t U,N ' ' O -- O ` o ~ r-- N
..,, .. ,~ ,I~O, U 1~ ~ _ O O 0 0 o N ~ W N
O` N N N `O N _ I~
N I~ ~ . O _ O I o ~ 0 0 0 ~--N N N -- 0 ~ O~ 0 r_ -- 0 ~ ~ N
N . N 1~1 ~O 0 ~o 0 ~ o ~ ~ ~-- O : O ~t o O~ 10 1~ O~ u~
o~ ~ ~O N N ~ In O b'~ _ 0 o~ o~ ~o ~ o -- o r~ 0 1.~ Oo W o ~
O` N O~ N N `O N _ _ t~ I_ 0 f~ ~ _ o N 00 ~-- 0 0 1.7 O` N -- 1~ 0 .l r_ ~ ~ N -- N O 0 ~
~11 O
J ~ ~ 0 M ~1 ~ O~ 0 -- 0 ~
~ ~ _ ~0~ N O ~ o ~ $ N
,_ ~ N 01 ~O -- N O O N
V~ ~ ~_ _ 0 17 o ~N
O ~ "~ ., N 0~
' O -- ~ o ~ W N
O N 0 ~ O O ~1 1 ) _ r~l O` ~ N O _ O `O Oo ~ ~ W
~ N N _ 1/1 u~ _ _ o~
N ~ ~ 1'i 0 -- O O~ o ~ oo t_ N U~
0 N _ N .~ _ W 1 _ ~ _ - ~ O ~ $ 0 o u~
u ~c o~
a s 1 ~ r ~ U~ ~ ~ a ~-- X O ~ ~ L ~ ~ > ~, U
Z~'~83~
~ ~ o ~O ~ O o ~t O N o~ ~ t `r ~. ~ R ~- ~ ~
O NO~ `O N ~t 0` 0 `O ~ 0 O U~ ~_ ~t O O 0 o 11~ l~'t 0 O` 0 ~o ~t o O V~o U~ ,, ~
N N0 O . ~ t 7 0 0 N
0 ~ ~0 t O O r~oO ~t o~ ~ ~ ~t ~ 00 N : ~t `O 0 O 0 N
1~ 0 ~_ ~ N O o 0 o o ~ 0 0~ ~N ~ N ~ 0 `O t~l 0 0 o _ Ul O O N o U~ 1 111 N ~0 `O O . ~ ~ ~ ~ 0 0 U~ N ~O ~ O O N o ~t ~ I~ 1.1 N
~~ N ~t ~ ~t 0~ 0 1 t ~_ N ~ I~
I _ N ~ M N ~t _ ~t 0 O` N
t~1 0 1~ N _ 0 V~ 1~1 ~ O t~
N ~t 1~. _ N r~ 0 U~ oN r_ ~ ~ t l~t N ~t 1~-- ~t-- 0 ~ ~J O
1~ N ~ U~ oN ~ U'~ ~t .~ C _ 8~ - ô 4c ~ ~ c ~ v ~-n _ N N ~ 0 `O ~-- 0 O. O ~-- N ~ '-- V~ -- '~ 0 ~
L _ V) L._ ._ O O -- -- O O~
~ ~ E ~-- J O V ~JV U > _ U
-- X O 'o ~ '~ ~ U ~ ~ 'j ~n ~- . .
.
' ' "
.
2666/US359~
Z~`5~3~7~.
The superscripts 1) to 10) in Tables 3 and ~ have the following significance:
(1) commercial melamine resin, medium-reactive, 85% in water (CYMEL~ 373, American Cyanamid Company);
(2) commercial silicone flow-out agent for water-thinnable paints (ADDITOL~ XW 329, Hoechst);
(3) commercial light stabilizer combination of benzotri-azole/UV absorber (TINUVIN~ 1130, Ciba-Geigy), with a sterically hindered am.ine (TINUVIN~ 292, Ciba-Geigy) in the ratio 1:1;
8 e . m . . N O . . ~O O . ~ ~ V O
a N . ~ . , C CO` "~ ~ N ~ ' . ~ . N ' E ' 0 O
N U~ .S . m . . o o ~ ~ O ~_ UN~ ~ o I ~ ~ ca 8 O ~o~ N I . Cl~ ~; V
W N .r~ ~ . O . . . . . ~ V W
m ~ U~ cO W ~D ~D
. ' ' ' ' ' ~a ca >~ U
,c ~ N ' ~ , ~ "~ 0O~ X X 8 L
N o o I -- o ~ ~ $ ~ ~ r E E s ~ c7~ ct~ o ~ ~ ~ cn ~
W E
' ~ ' ci N . ~ ~, ~, ~ v I ~. a c , ~ ~ D ~ E
e m , ~ :8~ n ~ v ~ ,~ ~ ~D a _~> E
v ~ c ~ Y ' ~D ' . v o ~ ~ ~ C ~ E
I J . U . U,v,~, ~, , ~, ~ O cn ~ e c ~, ~ .vc .C . . > . X . ~a ~ ~D ~ ~ ~ ~ w ~ E E U ~ O F~ C~ ~ ~ D ~ cD ~
. e . .c . c~ c,a u . ~ ~ ~ . <c . = . 2 ~ O--2666/US3595 ~`5~337~
o ~ . , , o~
~ 0 .
0 : O O : 0 ~ ~ O ~ rl 1~ co O ro ~ O O O U~
O` `O CO O ~,~ ~ N
I o ~ ~ 1~ o co O 1~ 0 N
O ¦ ~o c O ~ v~ O~ E e wl ¦ o 1~ o o co o~ 11 s e o ,~ . _ o ~ e ~
~1 0 COO `
~ ~ ~o ~' ~o~n 0~ :E
I N N O ~O COCO U
_ CO ~ 0 U~ O N , ~ ~
_ ~ ~ ~ _ _ _ L 8 8 I U ~ " " ,, ,., ., V V .. ., ., V .. ~
Iv 'V C ~ U 0 L ~C L :~ C_ IC 3 C ~--¦~ O S N ~ L L L O ~}
O ~ U ~ t~ ~tl. X cl. ~'c ~ 0 0 . 2666/US3595 ~5837~.
Testing of the Binders in Examples 1 to 12 and the Comparison Exam~les C~ and C2 The binders according to the present invention were tested as clear-coats in a metallic base-coat/clear-coat system and as white paint. The formulations are sum-marized in Tables 3 (clear-coat) and 4 (white paint~, the ratio of the combination of acrylate copolymers or the acrylate copolymer of C1 to melamine resin referring in each case to the solids content.
Tables 3 and 4 are as follows:
, 2666/US3595 2(~ 3q~l.
1~1 1.7 ~'I N -- Il ~ 0 0 0 ~t U,N ' ' O -- O ` o ~ r-- N
..,, .. ,~ ,I~O, U 1~ ~ _ O O 0 0 o N ~ W N
O` N N N `O N _ I~
N I~ ~ . O _ O I o ~ 0 0 0 ~--N N N -- 0 ~ O~ 0 r_ -- 0 ~ ~ N
N . N 1~1 ~O 0 ~o 0 ~ o ~ ~ ~-- O : O ~t o O~ 10 1~ O~ u~
o~ ~ ~O N N ~ In O b'~ _ 0 o~ o~ ~o ~ o -- o r~ 0 1.~ Oo W o ~
O` N O~ N N `O N _ _ t~ I_ 0 f~ ~ _ o N 00 ~-- 0 0 1.7 O` N -- 1~ 0 .l r_ ~ ~ N -- N O 0 ~
~11 O
J ~ ~ 0 M ~1 ~ O~ 0 -- 0 ~
~ ~ _ ~0~ N O ~ o ~ $ N
,_ ~ N 01 ~O -- N O O N
V~ ~ ~_ _ 0 17 o ~N
O ~ "~ ., N 0~
' O -- ~ o ~ W N
O N 0 ~ O O ~1 1 ) _ r~l O` ~ N O _ O `O Oo ~ ~ W
~ N N _ 1/1 u~ _ _ o~
N ~ ~ 1'i 0 -- O O~ o ~ oo t_ N U~
0 N _ N .~ _ W 1 _ ~ _ - ~ O ~ $ 0 o u~
u ~c o~
a s 1 ~ r ~ U~ ~ ~ a ~-- X O ~ ~ L ~ ~ > ~, U
Z~'~83~
~ ~ o ~O ~ O o ~t O N o~ ~ t `r ~. ~ R ~- ~ ~
O NO~ `O N ~t 0` 0 `O ~ 0 O U~ ~_ ~t O O 0 o 11~ l~'t 0 O` 0 ~o ~t o O V~o U~ ,, ~
N N0 O . ~ t 7 0 0 N
0 ~ ~0 t O O r~oO ~t o~ ~ ~ ~t ~ 00 N : ~t `O 0 O 0 N
1~ 0 ~_ ~ N O o 0 o o ~ 0 0~ ~N ~ N ~ 0 `O t~l 0 0 o _ Ul O O N o U~ 1 111 N ~0 `O O . ~ ~ ~ ~ 0 0 U~ N ~O ~ O O N o ~t ~ I~ 1.1 N
~~ N ~t ~ ~t 0~ 0 1 t ~_ N ~ I~
I _ N ~ M N ~t _ ~t 0 O` N
t~1 0 1~ N _ 0 V~ 1~1 ~ O t~
N ~t 1~. _ N r~ 0 U~ oN r_ ~ ~ t l~t N ~t 1~-- ~t-- 0 ~ ~J O
1~ N ~ U~ oN ~ U'~ ~t .~ C _ 8~ - ô 4c ~ ~ c ~ v ~-n _ N N ~ 0 `O ~-- 0 O. O ~-- N ~ '-- V~ -- '~ 0 ~
L _ V) L._ ._ O O -- -- O O~
~ ~ E ~-- J O V ~JV U > _ U
-- X O 'o ~ '~ ~ U ~ ~ 'j ~n ~- . .
.
' ' "
.
2666/US359~
Z~`5~3~7~.
The superscripts 1) to 10) in Tables 3 and ~ have the following significance:
(1) commercial melamine resin, medium-reactive, 85% in water (CYMEL~ 373, American Cyanamid Company);
(2) commercial silicone flow-out agent for water-thinnable paints (ADDITOL~ XW 329, Hoechst);
(3) commercial light stabilizer combination of benzotri-azole/UV absorber (TINUVIN~ 1130, Ciba-Geigy), with a sterically hindered am.ine (TINUVIN~ 292, Ciba-Geigy) in the ratio 1:1;
(4) commercial antifoam based on acetylene diols (SURFINOL~E
104/50%, ~ir Products);
104/50%, ~ir Products);
(5) demineralized water;
(6) solids content in % by weight;
(7) The HS value is a measure of the content of volatile organic solvents and is calculated from the following formula:
HS value =
% by wt. of ~aint solids conten~ (PS) x 100 % by wt. of PS + % by wt. of aux. solvent + % by wt. of amine (8) efflux time according to DIN 53 211/23C in seconds;
HS value =
% by wt. of ~aint solids conten~ (PS) x 100 % by wt. of PS + % by wt. of aux. solvent + % by wt. of amine (8) efflux time according to DIN 53 211/23C in seconds;
(9) content of auxiliary organic solvents and amine in ~ by weight;
(10) commercial titanium dioxide (KRONOS~ CL 310, Kronos Corporation).
The pH of the formulated paints was adjusted to 7.5 to 9.0 with dimethylethanolamine and thinned with deion~
ized water to a viscosity corresponding to an efflux time according to DIN 53 211/23GC of 27 to 30 seconds.
2666/US3595 ~'5~
The clear-coats were applied onto coated steel panels (zinc phosphate coating, cathodically deposited electrocoating paint (a), body filler (b), metallic base-coat (c), the products (a) to (c) being those used in the automotive industry) by spraying at 23C and 60~ relative atmospheric humidity. ~fter a flash-off time of 10 minutes and a preliminar~ drying time of lO minutes at 80C, the paints were stoved for 30 minutes at 140C.
The white paints were applied in a similar manner to coated steel panels (zinc phosphate coating, cathodically deposited electrocoating paint (a), body filler (b), the products (a) and (b) being those used in the automotive industry) and stoved.
The results are summarized in Tables 5 and 6, the significance of the superscripts (1) to (4) being -(1~ measured in a Byk Type Colourgloss 2 glossmeter atan angle of 60.
(2) a wad of cotton wool saturated with acetone is placed on the paint film and the time required for the film to soften is measured.
(3) + : the paint film is unaffected after 240 hours of immersion in water at 40C.
(+) : the paint film is softened a~ter 240 hours of immersion in water at 40C, but its hardness is restored after storage for about 2 hours at room temperature.
(4) the paint fi.lm, applied in the form of a wedge (60 ~m max., 15 ~m min.), exhibits, after stoving, blister formation or running from the specified film thickness.
Z~ 7~.
A repeat of the tests of film characteristics on paint formulations based on the binders according to the invention which have been stored for 3 months at room temp-erature shows virtually no change in the results.
Tables 5 and 6 are as follows:
~3r~
2666/US3595 ~C~ f ~.
N U'~ _. ~ N ~ Ir~ O
L ' , ' _, t`J ' `O
. , . . ~ ..
CJ o, , ~ .N ~ " ~ ON ' N
~ . I I I I
N ~0~ ~ ~' cO~ ~ N ~ N
. ' ~,, '. , ~, O, ~, ~, +, ~0, N
.~
. ', 1, ~
tn . ~ . r~l . N + O . N
. ' ~ ~, .
O` O ' O, ~ 'N, + ~ N, CSS N ' O, N ' 1:~ ' , t'~
' ~
t_ ~, N, O~, N, +, ~, t tt'l W ~o~ . O .r~J . ~ . " . N . ~
~C
o ~ n Ir~~ , tO' ' ~ ~
~ ' ,O ~ , N
~ U~ ~ ~ ' t~~ I ~ . + ~CO, ~
N O ~ t~ CO ~ .
U~, o C~
' . ~ ~ , , , O
COO ~ CO ~ t~ ~ +, ~ ~ ~
' ~~
tV
0 y Y C~ E
tV t~, t ,, ~ , ~5 ~ o ~ ~
ts., . ~ t~ ~ to O F O
tS t C~ ~ ^ L _ to ~ ~1 V
t,l ~ . ~ M -- 5/ . C~ CJ L y L ~ t~ tn to o -- L ttl V
v ~ z ' O 'C 0 ~1 ~a t~ ~ t" ~ _ Ct ~ . L Q _ ~ _ tO V ~ ~ ~E
' , z~
. : : : :
. . . . . .
~ : ' : ' :
UIr~ . N ~ ~ ~ N, N
. ~ ', , .
UO~, N, ~_ ~ N, + ~ N ' N
., O0 . N . ~0 N f . ~.1 ~
~1~0 ' N ~ N
.' , , . , ~~,~, ~ +
~Irl, N, ~0 N, , 11 'O . ~, , , , , ~
W `O. I ol ~, ~ +, e . , , , , , .
I_ U~1/`1 ' N tO ~ 11~1 ~ + ~ N ~ ~
. . , ~ ~ , .
0, ~ ' 0 ' ~ ' + ' ~ ' ~
~0 Vl ~ ~ ; 3 ~ N
N. , , ~ , , +
. I I I I
~ . N . F~. I N I + I ~O
V V ' v ' ' C ' ~ ' ~^ ' C
~ c U~ IU . ~ _ . L
C C ~, C 1~, V N . '-- .
V ~ ~ ' C ~ , C C L ' ~ V C ~
.
2666/US3595 z~ 7~
As will be apparent to one skilled in the art, various modifications can be made within the scope of the aforesaid description. Such modifications being within the ability of one skilled in the art form a part of the present invention and are embraced by the appended claims.
The pH of the formulated paints was adjusted to 7.5 to 9.0 with dimethylethanolamine and thinned with deion~
ized water to a viscosity corresponding to an efflux time according to DIN 53 211/23GC of 27 to 30 seconds.
2666/US3595 ~'5~
The clear-coats were applied onto coated steel panels (zinc phosphate coating, cathodically deposited electrocoating paint (a), body filler (b), metallic base-coat (c), the products (a) to (c) being those used in the automotive industry) by spraying at 23C and 60~ relative atmospheric humidity. ~fter a flash-off time of 10 minutes and a preliminar~ drying time of lO minutes at 80C, the paints were stoved for 30 minutes at 140C.
The white paints were applied in a similar manner to coated steel panels (zinc phosphate coating, cathodically deposited electrocoating paint (a), body filler (b), the products (a) and (b) being those used in the automotive industry) and stoved.
The results are summarized in Tables 5 and 6, the significance of the superscripts (1) to (4) being -(1~ measured in a Byk Type Colourgloss 2 glossmeter atan angle of 60.
(2) a wad of cotton wool saturated with acetone is placed on the paint film and the time required for the film to soften is measured.
(3) + : the paint film is unaffected after 240 hours of immersion in water at 40C.
(+) : the paint film is softened a~ter 240 hours of immersion in water at 40C, but its hardness is restored after storage for about 2 hours at room temperature.
(4) the paint fi.lm, applied in the form of a wedge (60 ~m max., 15 ~m min.), exhibits, after stoving, blister formation or running from the specified film thickness.
Z~ 7~.
A repeat of the tests of film characteristics on paint formulations based on the binders according to the invention which have been stored for 3 months at room temp-erature shows virtually no change in the results.
Tables 5 and 6 are as follows:
~3r~
2666/US3595 ~C~ f ~.
N U'~ _. ~ N ~ Ir~ O
L ' , ' _, t`J ' `O
. , . . ~ ..
CJ o, , ~ .N ~ " ~ ON ' N
~ . I I I I
N ~0~ ~ ~' cO~ ~ N ~ N
. ' ~,, '. , ~, O, ~, ~, +, ~0, N
.~
. ', 1, ~
tn . ~ . r~l . N + O . N
. ' ~ ~, .
O` O ' O, ~ 'N, + ~ N, CSS N ' O, N ' 1:~ ' , t'~
' ~
t_ ~, N, O~, N, +, ~, t tt'l W ~o~ . O .r~J . ~ . " . N . ~
~C
o ~ n Ir~~ , tO' ' ~ ~
~ ' ,O ~ , N
~ U~ ~ ~ ' t~~ I ~ . + ~CO, ~
N O ~ t~ CO ~ .
U~, o C~
' . ~ ~ , , , O
COO ~ CO ~ t~ ~ +, ~ ~ ~
' ~~
tV
0 y Y C~ E
tV t~, t ,, ~ , ~5 ~ o ~ ~
ts., . ~ t~ ~ to O F O
tS t C~ ~ ^ L _ to ~ ~1 V
t,l ~ . ~ M -- 5/ . C~ CJ L y L ~ t~ tn to o -- L ttl V
v ~ z ' O 'C 0 ~1 ~a t~ ~ t" ~ _ Ct ~ . L Q _ ~ _ tO V ~ ~ ~E
' , z~
. : : : :
. . . . . .
~ : ' : ' :
UIr~ . N ~ ~ ~ N, N
. ~ ', , .
UO~, N, ~_ ~ N, + ~ N ' N
., O0 . N . ~0 N f . ~.1 ~
~1~0 ' N ~ N
.' , , . , ~~,~, ~ +
~Irl, N, ~0 N, , 11 'O . ~, , , , , ~
W `O. I ol ~, ~ +, e . , , , , , .
I_ U~1/`1 ' N tO ~ 11~1 ~ + ~ N ~ ~
. . , ~ ~ , .
0, ~ ' 0 ' ~ ' + ' ~ ' ~
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2666/US3595 z~ 7~
As will be apparent to one skilled in the art, various modifications can be made within the scope of the aforesaid description. Such modifications being within the ability of one skilled in the art form a part of the present invention and are embraced by the appended claims.
Claims (13)
1. Water-thinnable paint binders based on acry-late copolymers obtained by a partial condensation of a polycarboxyl component (A) with a polyhydroxyl component (B) and a subsequent, at least partial, neutralization of the carboxyl groups, characterized in that 10 to 40% by weight, based on the solids content, of an acrylate copolymer having an acid value of 70 to 240 mg KOH/g which contains -(Aa) 57 to 90% by weight of alkyl (meth)acrylates containing an alkyl radical of 1 to 12 carbon atoms, or said acrylates being replaced, in an amount of up to 50% by weight, by aromatic vinyl compounds, (Ab) 10 to 33% by weight of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, (Ac) up to 2% by weight of monomers containing two or more reactive double bonds, (Ad) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythiogly-colic acid esters type, and (Ae) up to 8% by weight of fluorine-containing monomers copolymerizable with said (Aa) to (Ad), is used as the polycarboxyl component (A), and 90 to 60% by weight, based on the solids content, of an acrylate copoly-mer having a hydroxyl value of 90 to 250 mg KOH/g which contains -(Ba) 40 to 80% by weight of alkyl (meth)acrylates con-taining an alkyl radical of 1 to 12 carbon atoms, or said acrylates being replaced, in an amount of up to 50% by weight, by aromatic vinyl compounds, (Bb) 20 to 60% by weight of monoesters of (meth)acrylic acid with diols containing an alkylene radi-cal of 2 to 4 carbon atoms or an oxyalkylene radical of 6 to 12 carbon atoms, (Bc) up to 2% by weight of monomers containing two or more reactive double bonds, (Bd) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythiogly-colic acid esters type, (Be) up to 4% by weight of fluorine-containing monomers copolymerizable with (Ba) to (Bd), and (Bf) 0 to 5% by weight of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, is used as the polyhydroxyl component (B), at least one of the components (A) and (B) containing a monomer (Ac) or (Bc) and a regulator (Ad) or (Bd) and a fluorine-containing mono-mer (Ae) or (Be) and the proportions of the components (A) and (B) being chosen so that the condensation product con-tains -0.5 to 2% by weight of the monomer (Ac) or (Bc), 0.5 to-2% by weight of the regulator (Ad) or (Bd), and 0.5 to 3.5% by weight of the fluorine-containing monomers (Ae) or (Be), and has an acid value of 30 to 65 mg KOH/g, a hydroxyl value of 70 to 150 mg KOH/g, and an intrinsic viscosity of 12 to 18 ml/g measured in chloroform at 20°C.
2. The binders according to claim 1 wherein the acrylate copolymer has an acid value of 100 to 200 mg KOH/g;
the aromatic vinyl compounds of (Aa) and (Ba) are styrene;
the .alpha.,.beta.-ethylenically unsaturated carboxylic acid of (Ab) is (meth)acrylic acid; the acrylate copolymer of component (B) has a hydroxyl value of 110 to 180 mg KOH/g, and the conden-sation product has an intrinsic viscosity of 13 to 16 ml/g.
the aromatic vinyl compounds of (Aa) and (Ba) are styrene;
the .alpha.,.beta.-ethylenically unsaturated carboxylic acid of (Ab) is (meth)acrylic acid; the acrylate copolymer of component (B) has a hydroxyl value of 110 to 180 mg KOH/g, and the conden-sation product has an intrinsic viscosity of 13 to 16 ml/g.
3. The water-thinnable paint binders further characterized in that the condensation product of components (A) and (B) according to claim 2 contains a hydrophobic amino resin in an amount of 15 to 35% by weight based on the solids content of the binder as a whole, as added crosslink-ing component (C).
4. The water-thinnable paint binder according to claim 2 or 3 wherein the polyhydroxyl component (B) has an acid value of from 10 to 30 mg KOH/g.
5. Process for the preparation of water-thinnable paint binders based on acrylate copolymers which are ob-tained by a partial condensation of a polycarboxyl component with a polyhydroxyl component and a subsequent, at least partial, neutralization of the carboxyl groups, character-ized in that -(A) 10 to 40% by weight, based on the solids content, of an acrylate copolymer representing the polycarboxyl component (A), which has an acid value of 70 to 240 mg KOH/g and contains in the form of a solution polymer, (Aa) 57 to 90% by weight of alkyl (meth)acrylates con-taining an alkyl radical of 1 to 12 carbon atoms, said acrylates being replaced, in an amount of up to 50% by weight, by aromatic vinyl compounds, (Ab) 10 to 33% by weight of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, (Ac) up to 2% by weight of monomers containing two or more reactive double bonds, (Ad) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythiogly-colic acid esters type, and (Ae) up to 8% by weight of fluorine-containing monomers copolymerizable with said (Aa) to (Ad) is mixed with -(B) 90 to 60% by weight, based on the solids content, of an acrylate copolymer representing the poly-carboxyl component (B), which has a hydroxyl value of 90 to 250 mg KOH/g, and contains in the form of a solution polymer, (Ba) 40 to 80% by weight of alkyl (meth)acrylates con-taining an alkyl radical of 1 to 12 carbon atoms, said acrylates being replaced, in an amount of up to 50% by weight, by aromatic vinyl compounds, (Bb) 20 to 60% by weight of monoesters of (meth)acrylic acid with diols containing an alkylene radi-cal of 2 to 4 carbon atoms or an oxyalkylene radical of 6 to 12 carbon atoms, (Bc) up to 2% by weight of monomers containing two or more reactive double bonds, (Bd) up to 2% by weight of polyfunctional chain termina-tion regulators of the polyol polythiogly-colic acid esters type, (Be) up to 4% by weight of fluorine-containing monomers copolymerizable with (Ba) to (Bd), and (Bf) 0 to 5% by weight of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, at least one of the components (A) and (B) containing a monomer (Ac) or (Bc) and a regulator (Ad) or (Bd) and a fluorine-containing monomer (Ae) or (Be) and the proportions of the components (A) and (B) being chosen so that the condensation product contains -0.5 to 2% by weight of the monomer (Ac) or (Bc), 0.5 to 2% by weight of the regulator (Ad) or (Bd), and 0.5 to 3.5% by weight of the fluorine-containing monomer (Ae) or (Be), the solvent is removed in vacuo until the solids content of the mixture is at least 95% by weight, the mixture is di-luted with a water-tolerant, high-boiling auxiliary solvent to a solids content of 85 to 94% by weight and the mixture is then partially condensed at 100 to 150°C until the in-trinsic viscosity (measured in chloroform at 20°C) has in-creased to 12 to 18 ml/g, and the acid value has reached 30 to 65 mg KOH/g and the hydroxyl value 70 to 150 mg KOH/g, and the reaction mixture is neutralized.
6. The process according to claim 5 wherein said polycarboxyl component (A) has an acid value of 100 to 200 mg KOH/g, the aromatic vinyl compounds of (Aa) and (Ba) are styrene, the unsaturated carboxylic acid of (Bf) is (meth)-acrylic acid, the partial condensation is carried out at a temperature of 110 to 130°C, and the reaction mixture is neutralized with ammonia or an amine or an alkanolamine and thereafter diluted with deionized water.
7. The process according to claim 6, character-ized in that butanediol di(meth)acrylate or hexanediol di(meth)acrylate or trimethylolpropane tri(meth)acrylate or divinylbenzene or a mixture thereof are used as the compo-nent (Ac) or (Bc).
8. The process according to claim 6, character-ized in that perfluoroctylethyl methacrylate is used as the component (Ae) or (Be).
9. The process according to claim 6, character-ized in that dipropylene glycol monomethyl ether is used as the high-boiling auxiliary solvent containing secondary hydroxyl groups.
10. The process according to claim 6, character-ized in that the ratio of the intrinsic viscosity values (measured in chloroform at 20°C) of the condensation product to the starting mixture is 1.1:1 to 1.7:1, preferably 1.2:1 to 1.5:1.
11. The process according to claim 5 wherein said polyhydroxyl component (B) has an acid value of from 10 to 30 mg KOH/g.
12. Process for the preparation of water-thinnable paint binders, characterized in that as crosslinking compo-nent (C) a hydrophobic amino resin is admixed in an amount of 15 to 35% by weight, based on the solids content of the binder as a whole, to a substantially nonaqueous condensa-tion product of a polycarboxyl component (A) and a polyhy-droxyl component (B) at a maximum temperature of 85°C, and the mixture is thoroughly homogenized before the addition of neutralizing agent and before diluting with water.
13. A water-thinnable finish containing the binder according to claim 1 and a low content of auxiliary organic solvents.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT263790A AT396244B (en) | 1990-12-27 | 1990-12-27 | Water-dilutable paint binders based on acrylate copolymers, and their use |
| AT2637/90 | 1990-12-27 | ||
| AT0079091A AT397508B (en) | 1990-12-27 | 1991-04-16 | WATER-THINNABLE VARNISH BINDING AGENTS BASED ON ACRYLATE COPOLYMERS AND THEIR USE |
| AT790/91 | 1991-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2058371A1 true CA2058371A1 (en) | 1992-06-28 |
Family
ID=25593920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058371A Abandoned CA2058371A1 (en) | 1990-12-27 | 1991-12-23 | Water-thinnable paint binders based on acrylate copolymers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0496079A3 (en) |
| JP (1) | JPH04304277A (en) |
| KR (1) | KR920012342A (en) |
| AT (1) | AT397508B (en) |
| CA (1) | CA2058371A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228931B1 (en) | 1998-03-11 | 2001-05-08 | Vianova Resins Ag | Water-dilutable film-forming binders |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09511263A (en) * | 1993-12-23 | 1997-11-11 | ヴィアノヴァ レジンズ アクチエンゲゼルシャフト | Preparation of water-dilutable acrylate copolymer-based lacquer binders and their use |
| JPH08328251A (en) * | 1995-03-31 | 1996-12-13 | W R Grace & Co | Aqueous photosensitive resin composition |
| JPH08328252A (en) * | 1995-03-31 | 1996-12-13 | W R Grace & Co | Aqueous photosensitive resin composition |
| AT407253B (en) * | 1997-10-06 | 2001-02-26 | Vianova Kunstharz Ag | WATER-THINNABLE RESINS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US6613826B2 (en) * | 2001-09-01 | 2003-09-02 | Toyota Technical Center, U.S.A., Inc. | Aqueous coating composition |
| WO2022107402A1 (en) * | 2020-11-18 | 2022-05-27 | 三菱ケミカル株式会社 | (meth)acrylic copolymer, (meth)acrylic copolymer composition, and ink |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT328587B (en) * | 1973-08-20 | 1976-03-25 | Vianova Kunstharz Ag | PROCESS FOR THE MANUFACTURING OF AQUATIC COATING AGENTS |
-
1991
- 1991-04-16 AT AT0079091A patent/AT397508B/en not_active IP Right Cessation
- 1991-12-16 EP EP19910121525 patent/EP0496079A3/en not_active Withdrawn
- 1991-12-23 CA CA002058371A patent/CA2058371A1/en not_active Abandoned
- 1991-12-26 JP JP3345611A patent/JPH04304277A/en not_active Withdrawn
- 1991-12-27 KR KR1019910024696A patent/KR920012342A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228931B1 (en) | 1998-03-11 | 2001-05-08 | Vianova Resins Ag | Water-dilutable film-forming binders |
Also Published As
| Publication number | Publication date |
|---|---|
| ATA79091A (en) | 1993-09-15 |
| KR920012342A (en) | 1992-07-25 |
| EP0496079A3 (en) | 1993-02-03 |
| EP0496079A2 (en) | 1992-07-29 |
| AT397508B (en) | 1994-04-25 |
| JPH04304277A (en) | 1992-10-27 |
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