CA2203103A1 - Method for the two-stage preparation of aqueous autocrosslinking copolymer dispersions and their use for coating materials - Google Patents
Method for the two-stage preparation of aqueous autocrosslinking copolymer dispersions and their use for coating materialsInfo
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- CA2203103A1 CA2203103A1 CA002203103A CA2203103A CA2203103A1 CA 2203103 A1 CA2203103 A1 CA 2203103A1 CA 002203103 A CA002203103 A CA 002203103A CA 2203103 A CA2203103 A CA 2203103A CA 2203103 A1 CA2203103 A1 CA 2203103A1
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Classifications
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of 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
- 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
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
Abstract
The invention concerns a two-stage method for the preparation of aqueous, self-crosslinking copolymer dispersions made from acrylate copolymers having acetoacetyl and carboxylic groups, the copolymers being neutralized with polyamines which act as crosslinking agents. The invention also concerns the use of such copolymers in paints as binders which crosslink at room temperature or at elevated temperatures.
Description
~ ' CA 02203103 1997-04-18 wo 96/i6998 'YT Tr= PCT/AT95/00227 Method for the two-staqe preparation of aqueous autocrosslinkinq copolymer dispersions and their use for coatinq materials :
The invention relates to a two-stage method of preparing aqueous, autocrosslinking copolymer dispersions based on acrylate copolymers which have acetoacetyl groups and carboxyl groups and which are neutralized with polyamines which act as a crosslinking component, and to their use as binders for storage-stable one-component coating materials and, in combination with low molecular mass polyisocyanates, as binders for two-component coating materials which crosslink at room temperature or at elevated temperature.
EP 0555774 A1 discioses a one-stage method of preparing such copolymer dispersions. The products, however, have a disadvantage. Firstly, a high proportion of acetoacetyl groups is required in order to achieve a sufficient crosslinking density of the coating films;
secondly, this high proportion of appropriate monomers brings about the formation, during the copolymerization, o~ bits and coagulum which can be removed again only at great length and using complex apparatus.
It has surprisingly now been found that films of aqueous copolymer dispersions with small proportions of acetoacetyl groups also have a high crosslinking density if the emulsion copolymerization takes place by a two-stage method in which monomers having in each case aceto-acetyl or carboxyl groups are employed only in the first stage.
The invention relates accordingly to a method of preparing aqueous, autocrosslinking copolymer dispersions whose monomer composition is (Aa) from 3 to 35~ by weight, preferably from 8 to 15~
by weight, of (meth)acrylate monomers containing acetoacetyl groups, A(b) from 1 to 20~ by weight, preferably from 3 to 16 by weight, o~ ethylenically unsatu-rated carboxylic acids, preferably (meth)acrylic acid, A(c) from 11 to 96~ by weight, preferably from 30 to 70~
by weight, of (meth)acrylic alkyl esters and, if desired, diesters of maleic or fumaric acid, and A(d) from 0 to 40~ by weight, preferably from 0 to 25~
by weight, of other free-radically polymerizable monomers, such as vinyl aromatic compounds, vinyl esters, hydroxyalkyl (meth)acrylates and (meth)acrylamide, the sum of the percentages of components (Aa) to (Ad) necessarily being 100, and the dispersions being neutral-ized with polyamines which act as a crosslinking com-ponent, which method is characterized in that A) a two-stage free-radical emulsion polymerization is carried out, with the proviso that in the first stage from 60 to 90~ by weight of a mixture of the monomers (Aa) to (Ad) and in the second stage from 10 to 40~ by weight of a mixture of the monomers (Ac) and (Ad) are copolymerized, the sum of the percentages again necessarily being 100 and the condition holding that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-~, preferably from 80 to 90 mol-~, relative to the acetoacetyl groups, and subsequently B) the carboxyl groups of the copolymer dispersions (A) are reacted with polyamines which contain at least ~ CA 02203103 1997-04-18 Wo 96/i6998 - 3 - PCT/AT95/00227 two primary amino groups in the molecule, in a pro-portion of from 50 to loO mol-~, preferably from 9o to 100 mol-~, relative to the total primary amino groups, with salts being formed.
5The invention additionally relates to the copolymer dispersions prepared in accordance with the invention and to their use as binders for storage-stable one-component coating materials and, in combination with low molecular mass polyisocyanates, as binders for two-component coating materials which crosslink at room temperature or at elevated temperature.
The primary polyamines serve as neutralizing agents for stabilizing the aqueous copolymer dispersions and, finally, as a crosslinking component during film 1', formation.
In accordance with the invention the copolymer dispersions are prepared by the method of a two-stage free-radical emulsion copolymerization in a known manner.
In this method the monomer components Aa) to Ad) defined in the main claim are employed in the stated proportions.
As monomer component (Aa) use is made of (meth)-acrylate monomers containing acetoacetyl groups, such as N-diacetone(meth)acrylamide, or (meth)acrylic aceto-acetoxyalkyl esters, preferably the ethyl ester.
25As monomer component (Ad) examples of vinyl-aromatic compounds are styrene and p-methylstyrene and an example of vinyl esters is vinyl acetate.
The condition holds that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 30to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-~, preferably from 80 to 90 mol-~, relative to the aceto-acetyl groups.
Subsequently, the carboxyl groups of the copolymer dispersions (A) even reacted with polyamines which have at least two primary amino groups in the molecule, in a proportion of from 50 to 100 mol-~, CA 02203l03 l997-04-l8 ... .
preferably from 90 to 100 mol-~, relative to the total primary amino groups, with salts being formed.
Examples of polyamines are alkylenediamines, such as ethylenediamine and its homologs and isomers, and also diprimary polyalkylenepolyamines, such as diethylenetri-amine, and other polyamines, such as trimethylolpropane-hexaethoxytriamine or diprimary polyethoxydiamines.
The copolymer dispersions prepared in accordance with the invention have an excellent storage stability and give films having good resistance properties. They can be employed as binders for industrial coatings and primers. In addition, they can be used to formulate clearcoats which are used for coating wood, plastic, leather or paper.
The copolymer dispersions are crosslinked by reacting the primary amino groups of the polyamines with the keto groups of the acetoacetyl groups of the copolymer dispersions (A) even at room temperature following the evaporation of a substantial proportion of the water.
With the proviso that hydroxyalkyl (meth)-acrylates are among those monomers used as component (Ad), the copolymer dispersions can also be combined advantageously with low molecular mass polyisocyanates.
Polyisocyanates employed are customary commercial oligomers, for example isocyanurates, biuret types or allophanate types of aliphatic diisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, in a binder/polyiso-cyanate ratio of from 90:10 to 60:40 (based on solids).
Two-component coating materials of this kind have relatively long pot lives and, in comparison with one-component coating materials, in the form of coating films after a drying period of 4 weeks they possess not only 3!, the expected higher crosslinking density but also a markedly reduced tendency to bring about yellow discoloration of light-colored woods.
The formulation of water-th;nn~hle coating materials using the binders prepared in accordance with Wo 96/16998 - 5 - PCT/AT95/00227 the invention, and the application of such coating materials, are known to the skilled worker.
The examples which follow illustrate the inven-tion without re~tricting it in its scope. All data in parts or percentages relate, unless specified otherwise, to units of weight.
1. Examples 1 to 7 and Comparison ExamPle Vl Example 1 In a reactor suitable for emulsion copolymeriz-ation, with reflux condenser, thermometer and two feed vessels, a mixture of 360 parts of demineralized water, 24 parts of Triton X 200 (sodium alkylaryl polyether-sulfonate, manufacturer: Rohm & Haas, USA) and 5.4 parts -of Triton X 165 (octylphenol ethoxylate, manufacturer:
Rohm & Haas, USA) is homogenized with stirring.
The feed vessel I is charged with a homogeneous emulsion consisting of 1150 parts of demineralized water, 24 parts of Triton X 200, 10 parts of Triton X 165, 3.2 parts of ammonium peroxodisulfate, 165 parts of butyl methacrylate, 280 parts of butyl acrylate, 275 parts of styrene, 140 parts of acetoacetoxyethyl methacrylate and 40 parts of methacrylic acid. 5% of this preemulsion is run into the reactor. The contents of the reactor are heated to 85~C with stirring and held at this temperature for 10 minutes. The remaining contents of feed vessel I
are then metered into the reactor at a uniform rate over the course of 120 minutes at 85~C.
Subsequently, a homogeneous emulsion of 100 parts of demineralized water, 3.1 parts of Triton X 200, 2.4 parts of Triton X 165, 30 parts of butyl acrylate, 70 parts of styrene and 0.8 parts of ammonium per-oxodisulfate is metered in from feed vessel II over the course of 30 minutes at 85~C. After the end of the feed, the contents of the reactor are heated to 88~C and held at this temperature for 120 minutes. Finally, they are cooled to 25~C, and 115 parts of a 20% strength aqueous diethylenetriamine solution are added with stirring over ~ CA 02203l03 l997-04-l8 the course of one hour. A 38.8~ opalescent dispersion is obtained having a mean particle size of 90 nanometres.
~ The pH is 7.9.
Example 2 to 7 are prepared in analogy to Example 1. The compositions of the initial reactor charges and of the feeds, and altered polymerization parameters, are given in Table 1, in which the following abbreviations are used:
A~EMA acetoacetoxyethyl methacrylate 1() APS ammonium peroxodisulfate AA acrylic acid BA butyl acrylate BMA butyl methacrylate BV Hostapal BV conc. (Hoechst AG, DE) 15 DAMA diacetonemethacrylamide DBF dibutyl fumarate DETA diethylenetriamine DW demineralized water EHA 2-ethylhexyl acrylate 20 HBA 4-hydroxybutyl acrylate HDA 1,6-hexamethylenediamine HEMA 2-hydroxyethyl methacrylate MA methacrylic acid pMST p-methylstyrene 25 ST styrene X 165 (Triton X 165) Rohm & Haas, USA) X 200 (Triton X 200) Rohm & Haas, USA) X 305 (Triton X 305) Rohm & Haas, USA) (alkylaryl polyether alcohol) Comparison Example V1 One-stage copolymer dispersion with high acetoacetoxy functionality (corresponding to Example 7 of EP 0555774 A1) In a reactor suitable for emulsion poly-merization, 40 parts of DW and 27 parts of a liquor containing 80 parts of DW, 100 parts of a mixture of ~ ~ CA 02203l03 l997-04-l8 WO 96/16998 - 7 - PCT/AT95/bO227 45 parts of AAEMA, 10.9 parts of AA, 28.1 parts of BA and 16 parts of sMA, 0.5 part of Triton x 305, 1 part of dodecylsulfonate, 0.2 part of tert-dodecyl mercaptan and 1 part of APS are heated to 85~C. The rem~;n;ng 155.7 parts of the liquor are added uniformly over the course of 2 hours from a feed vessel which is provided with a stirrer. The theoretical solids content of 45~ is reached after a subsequent reaction time of 2 hours. The batch is cooled to 25~C and neutralized with 31.2 parts of a 20 lo strength aqueous solution of DETA. The copolymer disper-sion prepared in one stage contains fractions of bits and coagulum which require removal by filtration The characteristic data for the copolymer disper-sions prepared in accordance with Examples 1 to 7 and Comparison Example Vl are summarized in Table 2.
.
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11'1 0 1' 0 0 LO 11'1 0 11~ O 11~ 0 111 N ~1 0 0 0 ~
N .-1 0 ~1 IJ7 CO N ~r U') O 11') ~11 N
(~) O N N r-l N r-l .-1 :~ o u~ 3 o u~ 5 ~ 3 o u~
N r'( N ~1 .¢ L~ m ~ N ~I fS ~3 X X X X Ul OX X
r ~ ~r 0 u~
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N~I N ~1 1~ N ~1 .¢ M
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-- v ~ E ~ E -r ~ 4~ o - CA 02203l03 l997-04-l8 Table 1 continued 3 > u~ 3 ~ 3 ~
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m o r o o u~ m o ~ o o u~ o u~ ~ ~ o o _~ o ,~ o ~) ~ In ~ N ~
3 0 u~ e O u~ m ~ m ~ 3 0 U~
X X X X X X
~D ~ O U~
In ~ r o In In Ln U~ O O O O In o ~D ~1 0 0 0 ~ C~ o ~ ~ ~ U~ O O ~ O ~ U~ C~
3 ~ u~ g ~ u~ ; 3 ~ Lr~ cn E~ ,¢
a m o ~ m o ~ m !~ ~ m o ~ u~ m ~ E~
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2. Coatinqs performance testinq of the coPolYmer disper-sions prepared in accordance with Examples 1 to 5 and prepared in accordance with Comparison ExamPle V1 in clearcoats The clearcloats 1 to 5 and V1 were prepared from 100 parts of binder (as solids), 0.8 part of a customary commercial antifoam, 0.2 part of a customary commercial leveling agent, an optional rheology additive (e.g.
PU thickener) and deionized water, and these clearcoats were subjected to the following coatings performance tests whose results are summarized in Table 3:
Freedom from tack: drYing recorder, glass strips, 150 ~m wet film thickness, at 20~C (stated in minutes) Sandability: veneered wood, 150 ~m wet film thickness;
the parameter tested is the clogging of sandpaper (grade 320) after 10 strokes following a drying time of 60 minutes at room temperature (0 = no clogging, MIN = minimal clogging.
KONIG pendulum hardness (DIN 53157): glass plates, 120 ~m wet film thickness, drying time of 24 hours at 20~C.
Resistance to acetone, ethanol and water: glass plates, 120 ~m wet film thickness, drying time of 24 hours at 20~C. A cotton wool pad impregnated with the solvent is placed on the film and covered with a glass beaker. The time is measured until the film softens.
02203103 1997-04-l8 Table 3 Clearcoat 1 2 3 4 5 Vl ;
Freedom from tack in minutes 20 15 20 15 20 15 .~An~h; 1; ty 0 0 MIN 0 0 MIN
Pendulum hardness in seconds 65 80 90 65 60 45 Acetone resistance in seconds ~60 >60 >60 >60 >60 >60 Ethanol resistance in seconds >2 >2 >2 >2 >2 < 0.25 Water resistance in seconds>24 ,24 ,24 ,24 ,24 ~ 1 3. Coatinqs performance testinq of the copolymer disper-sions prepared in accordance with Examples 6 and 7 inclearcoats and in two-component coatinq materials Clearcoats 6 and 7 were prepared in analogy to clearcoats 1 to 5, but additionally received per 100 parts in each case 10 or 20 parts of Bayhydur~ LS 2032 (polyisocyanate 1.5 based on hexamethylene diisocyanate with a free iso-cyanate group content of about 17~ and a solids content of lOO~, manufacturer: BAYER AG).
Two-component coatinq materials (6a and 7a) Binder: polyisocyanate = 79.5 : 20.5 (based on solids) Solids content of the coating materials: 44.5 Two-comPonent coatinq materials (6b and 7b) Binder: polyisocyanate = 66 : 34 (based on solids) Solids content of the coating materials: 49.2~
The clearcoats and two-component coating materials were subjected to the coatings tests already mentioned and those indicated below, the results of which are summar-ized in Table 4:
Pot life: The two-component coating material is stirred once an hour. This operation is repeated until gelling begins.
CA 02203l03 l997-04-l8 Yellow discoloration: 200 ~m wet film thickness on maple (veneered). Assessment is made after storage for 4 weeks at room temperature (1 = no measurable discoloration, 5 = very severe discoloration) Table 4 Clearcoat 6 7 Two~ t coating material 6a 6b 7a 7b Freedom from tack in minutes20 25 S0 20 25 40 SAn~Ahility o MIN o o MIN
1 0 Pendulum hardness in seconds75 70 50 70 65 45 Acetone resistance in seconds ,60 80 80 ,60 70 go Ethanol resistance in seconds >2 ~5 ~8 ~2 ~6 ~ 10 ~ater resistance in seconds ~24 ,36 ~48 ~24 ,86 ~48 Potlife in hours - ~48 20 - ~48 25 Yellow discoloration 4 2 1-2 4 2 1-2 In addition to Table 4, the coating films of the two-component coating materials 6a, 6b and 7a, 7b exhibit, in comparison with the clearcoats 6 and 7, after a drying time of 4 weeks at room temperature, as expected, markedly better results in their resistance to acetone, ethanol and water.
The invention relates to a two-stage method of preparing aqueous, autocrosslinking copolymer dispersions based on acrylate copolymers which have acetoacetyl groups and carboxyl groups and which are neutralized with polyamines which act as a crosslinking component, and to their use as binders for storage-stable one-component coating materials and, in combination with low molecular mass polyisocyanates, as binders for two-component coating materials which crosslink at room temperature or at elevated temperature.
EP 0555774 A1 discioses a one-stage method of preparing such copolymer dispersions. The products, however, have a disadvantage. Firstly, a high proportion of acetoacetyl groups is required in order to achieve a sufficient crosslinking density of the coating films;
secondly, this high proportion of appropriate monomers brings about the formation, during the copolymerization, o~ bits and coagulum which can be removed again only at great length and using complex apparatus.
It has surprisingly now been found that films of aqueous copolymer dispersions with small proportions of acetoacetyl groups also have a high crosslinking density if the emulsion copolymerization takes place by a two-stage method in which monomers having in each case aceto-acetyl or carboxyl groups are employed only in the first stage.
The invention relates accordingly to a method of preparing aqueous, autocrosslinking copolymer dispersions whose monomer composition is (Aa) from 3 to 35~ by weight, preferably from 8 to 15~
by weight, of (meth)acrylate monomers containing acetoacetyl groups, A(b) from 1 to 20~ by weight, preferably from 3 to 16 by weight, o~ ethylenically unsatu-rated carboxylic acids, preferably (meth)acrylic acid, A(c) from 11 to 96~ by weight, preferably from 30 to 70~
by weight, of (meth)acrylic alkyl esters and, if desired, diesters of maleic or fumaric acid, and A(d) from 0 to 40~ by weight, preferably from 0 to 25~
by weight, of other free-radically polymerizable monomers, such as vinyl aromatic compounds, vinyl esters, hydroxyalkyl (meth)acrylates and (meth)acrylamide, the sum of the percentages of components (Aa) to (Ad) necessarily being 100, and the dispersions being neutral-ized with polyamines which act as a crosslinking com-ponent, which method is characterized in that A) a two-stage free-radical emulsion polymerization is carried out, with the proviso that in the first stage from 60 to 90~ by weight of a mixture of the monomers (Aa) to (Ad) and in the second stage from 10 to 40~ by weight of a mixture of the monomers (Ac) and (Ad) are copolymerized, the sum of the percentages again necessarily being 100 and the condition holding that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-~, preferably from 80 to 90 mol-~, relative to the acetoacetyl groups, and subsequently B) the carboxyl groups of the copolymer dispersions (A) are reacted with polyamines which contain at least ~ CA 02203103 1997-04-18 Wo 96/i6998 - 3 - PCT/AT95/00227 two primary amino groups in the molecule, in a pro-portion of from 50 to loO mol-~, preferably from 9o to 100 mol-~, relative to the total primary amino groups, with salts being formed.
5The invention additionally relates to the copolymer dispersions prepared in accordance with the invention and to their use as binders for storage-stable one-component coating materials and, in combination with low molecular mass polyisocyanates, as binders for two-component coating materials which crosslink at room temperature or at elevated temperature.
The primary polyamines serve as neutralizing agents for stabilizing the aqueous copolymer dispersions and, finally, as a crosslinking component during film 1', formation.
In accordance with the invention the copolymer dispersions are prepared by the method of a two-stage free-radical emulsion copolymerization in a known manner.
In this method the monomer components Aa) to Ad) defined in the main claim are employed in the stated proportions.
As monomer component (Aa) use is made of (meth)-acrylate monomers containing acetoacetyl groups, such as N-diacetone(meth)acrylamide, or (meth)acrylic aceto-acetoxyalkyl esters, preferably the ethyl ester.
25As monomer component (Ad) examples of vinyl-aromatic compounds are styrene and p-methylstyrene and an example of vinyl esters is vinyl acetate.
The condition holds that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 30to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-~, preferably from 80 to 90 mol-~, relative to the aceto-acetyl groups.
Subsequently, the carboxyl groups of the copolymer dispersions (A) even reacted with polyamines which have at least two primary amino groups in the molecule, in a proportion of from 50 to 100 mol-~, CA 02203l03 l997-04-l8 ... .
preferably from 90 to 100 mol-~, relative to the total primary amino groups, with salts being formed.
Examples of polyamines are alkylenediamines, such as ethylenediamine and its homologs and isomers, and also diprimary polyalkylenepolyamines, such as diethylenetri-amine, and other polyamines, such as trimethylolpropane-hexaethoxytriamine or diprimary polyethoxydiamines.
The copolymer dispersions prepared in accordance with the invention have an excellent storage stability and give films having good resistance properties. They can be employed as binders for industrial coatings and primers. In addition, they can be used to formulate clearcoats which are used for coating wood, plastic, leather or paper.
The copolymer dispersions are crosslinked by reacting the primary amino groups of the polyamines with the keto groups of the acetoacetyl groups of the copolymer dispersions (A) even at room temperature following the evaporation of a substantial proportion of the water.
With the proviso that hydroxyalkyl (meth)-acrylates are among those monomers used as component (Ad), the copolymer dispersions can also be combined advantageously with low molecular mass polyisocyanates.
Polyisocyanates employed are customary commercial oligomers, for example isocyanurates, biuret types or allophanate types of aliphatic diisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, in a binder/polyiso-cyanate ratio of from 90:10 to 60:40 (based on solids).
Two-component coating materials of this kind have relatively long pot lives and, in comparison with one-component coating materials, in the form of coating films after a drying period of 4 weeks they possess not only 3!, the expected higher crosslinking density but also a markedly reduced tendency to bring about yellow discoloration of light-colored woods.
The formulation of water-th;nn~hle coating materials using the binders prepared in accordance with Wo 96/16998 - 5 - PCT/AT95/00227 the invention, and the application of such coating materials, are known to the skilled worker.
The examples which follow illustrate the inven-tion without re~tricting it in its scope. All data in parts or percentages relate, unless specified otherwise, to units of weight.
1. Examples 1 to 7 and Comparison ExamPle Vl Example 1 In a reactor suitable for emulsion copolymeriz-ation, with reflux condenser, thermometer and two feed vessels, a mixture of 360 parts of demineralized water, 24 parts of Triton X 200 (sodium alkylaryl polyether-sulfonate, manufacturer: Rohm & Haas, USA) and 5.4 parts -of Triton X 165 (octylphenol ethoxylate, manufacturer:
Rohm & Haas, USA) is homogenized with stirring.
The feed vessel I is charged with a homogeneous emulsion consisting of 1150 parts of demineralized water, 24 parts of Triton X 200, 10 parts of Triton X 165, 3.2 parts of ammonium peroxodisulfate, 165 parts of butyl methacrylate, 280 parts of butyl acrylate, 275 parts of styrene, 140 parts of acetoacetoxyethyl methacrylate and 40 parts of methacrylic acid. 5% of this preemulsion is run into the reactor. The contents of the reactor are heated to 85~C with stirring and held at this temperature for 10 minutes. The remaining contents of feed vessel I
are then metered into the reactor at a uniform rate over the course of 120 minutes at 85~C.
Subsequently, a homogeneous emulsion of 100 parts of demineralized water, 3.1 parts of Triton X 200, 2.4 parts of Triton X 165, 30 parts of butyl acrylate, 70 parts of styrene and 0.8 parts of ammonium per-oxodisulfate is metered in from feed vessel II over the course of 30 minutes at 85~C. After the end of the feed, the contents of the reactor are heated to 88~C and held at this temperature for 120 minutes. Finally, they are cooled to 25~C, and 115 parts of a 20% strength aqueous diethylenetriamine solution are added with stirring over ~ CA 02203l03 l997-04-l8 the course of one hour. A 38.8~ opalescent dispersion is obtained having a mean particle size of 90 nanometres.
~ The pH is 7.9.
Example 2 to 7 are prepared in analogy to Example 1. The compositions of the initial reactor charges and of the feeds, and altered polymerization parameters, are given in Table 1, in which the following abbreviations are used:
A~EMA acetoacetoxyethyl methacrylate 1() APS ammonium peroxodisulfate AA acrylic acid BA butyl acrylate BMA butyl methacrylate BV Hostapal BV conc. (Hoechst AG, DE) 15 DAMA diacetonemethacrylamide DBF dibutyl fumarate DETA diethylenetriamine DW demineralized water EHA 2-ethylhexyl acrylate 20 HBA 4-hydroxybutyl acrylate HDA 1,6-hexamethylenediamine HEMA 2-hydroxyethyl methacrylate MA methacrylic acid pMST p-methylstyrene 25 ST styrene X 165 (Triton X 165) Rohm & Haas, USA) X 200 (Triton X 200) Rohm & Haas, USA) X 305 (Triton X 305) Rohm & Haas, USA) (alkylaryl polyether alcohol) Comparison Example V1 One-stage copolymer dispersion with high acetoacetoxy functionality (corresponding to Example 7 of EP 0555774 A1) In a reactor suitable for emulsion poly-merization, 40 parts of DW and 27 parts of a liquor containing 80 parts of DW, 100 parts of a mixture of ~ ~ CA 02203l03 l997-04-l8 WO 96/16998 - 7 - PCT/AT95/bO227 45 parts of AAEMA, 10.9 parts of AA, 28.1 parts of BA and 16 parts of sMA, 0.5 part of Triton x 305, 1 part of dodecylsulfonate, 0.2 part of tert-dodecyl mercaptan and 1 part of APS are heated to 85~C. The rem~;n;ng 155.7 parts of the liquor are added uniformly over the course of 2 hours from a feed vessel which is provided with a stirrer. The theoretical solids content of 45~ is reached after a subsequent reaction time of 2 hours. The batch is cooled to 25~C and neutralized with 31.2 parts of a 20 lo strength aqueous solution of DETA. The copolymer disper-sion prepared in one stage contains fractions of bits and coagulum which require removal by filtration The characteristic data for the copolymer disper-sions prepared in accordance with Examples 1 to 7 and Comparison Example Vl are summarized in Table 2.
.
Tabl e Q ~ ~ a m ,~
~:~ o o O
~D
11'1 0 1' 0 0 LO 11'1 0 11~ O 11~ 0 111 N ~1 0 0 0 ~
N .-1 0 ~1 IJ7 CO N ~r U') O 11') ~11 N
(~) O N N r-l N r-l .-1 :~ o u~ 3 o u~ 5 ~ 3 o u~
N r'( N ~1 .¢ L~ m ~ N ~I fS ~3 X X X X Ul OX X
r ~ ~r 0 u~
N N O N ~~ N O t' N ~ ~D ~ O O O ~--.I N _I
3 ~ ~ o ~ 3 ~
X XX X X
N U~ O
~D ~P
O U) t' ~ N
~r N
Q3 0 3 O U) CQ g~ a o ~
N~I N ~1 1~ N ~1 .¢ M
X X X X ~ O X X
Ul N O
~ N r~ ~ ~
o ~ ') o ~r o 1'~ u) o 111 o o o ~1 N O O O r~l ~D N If ~ N ~ ~ ~ ~ O ~ ~~ N
~) r~ ~I N N ~1 ~1 J ~: ~v Et~- .
E -- ~ . ~ ~G 1 H
S~ ~8 .
-- v ~ E ~ E -r ~ 4~ o - CA 02203l03 l997-04-l8 Table 1 continued 3 > u~ 3 ~ 3 ~
a m ~ ~ m ~D ~ m m . ~ ~ m ~o ~ ~ m Q
X X ~ X
r o o O
m o r o o u~ m o ~ o o u~ o u~ ~ ~ o o _~ o ,~ o ~) ~ In ~ N ~
3 0 u~ e O u~ m ~ m ~ 3 0 U~
X X X X X X
~D ~ O U~
In ~ r o In In Ln U~ O O O O In o ~D ~1 0 0 0 ~ C~ o ~ ~ ~ U~ O O ~ O ~ U~ C~
3 ~ u~ g ~ u~ ; 3 ~ Lr~ cn E~ ,¢
a m o ~ m o ~ m !~ ~ m o ~ u~ m ~ E~
~ a ~ ~ ~C n ~3 X X ~ X
~., o o O
~ a~ w o o r o ~ u~ u~ o u~ o In o r ~ ~ o o o ~
~~ ~1 0 Ln O CO ~D O O O O r~7 v E H E ~
H -- -- H
H H
~ ID
c ~ E E --~ o v v -- ~~~, - ' CA 02203l03 l997-04-l8 Table 2 ~D ~ In Ln -- Ln O O ~ ~D
o c~ ~
CO U~ O O N ~' ~) ~ I
~7 O
O
V
o a 0~ ~' O O O ~ Ut ~1 S~ ~
~ ~ O
CQ
(~ o\~ N ~1 V I ~ ~ I
.~ ~ ~ V_ a ~
~q ~ U ~ - U>1 4~ ~
--I ~ -~1c) ~ ~x' o o 5- C v ,¢ N G
a ~ ~ 0~O 0~O
r O O
0\o 0\o ~ ~ ~ ~
X ~ C~ ~ ~ O O O O ~ ~ ~ --_ ~_ _ _ _ _ _ _ _ W0 96/16998 ~ PCT/AT95/00227 Table 2 continued m ~ o~ o ~ ~ ~ o d~ GO c~ ~
n O O ~ ~D
~ o a~
t' ~D In ~
~D O O O ~ O
~~ cn ~ cn ~ o l:I; L) S) ~
~D ~ ~ V
L-- O O O O ~ a O O~
~1 -, ~
$~
S~
U2 ~
~ ~ O
o\~ N
v J Q
~- a ~
C L ~ ~ x O o a ~, ~ ~ V - - v - o\~ o\~
CJ ~ QJ ~) tJ) C ) f~ ~, I O O
o\O o\O
X r O ~ O O O O O ~ ~ ~ ~
- ' - CA 02203l03 l997-04-l8 ~ . .
2. Coatinqs performance testinq of the coPolYmer disper-sions prepared in accordance with Examples 1 to 5 and prepared in accordance with Comparison ExamPle V1 in clearcoats The clearcloats 1 to 5 and V1 were prepared from 100 parts of binder (as solids), 0.8 part of a customary commercial antifoam, 0.2 part of a customary commercial leveling agent, an optional rheology additive (e.g.
PU thickener) and deionized water, and these clearcoats were subjected to the following coatings performance tests whose results are summarized in Table 3:
Freedom from tack: drYing recorder, glass strips, 150 ~m wet film thickness, at 20~C (stated in minutes) Sandability: veneered wood, 150 ~m wet film thickness;
the parameter tested is the clogging of sandpaper (grade 320) after 10 strokes following a drying time of 60 minutes at room temperature (0 = no clogging, MIN = minimal clogging.
KONIG pendulum hardness (DIN 53157): glass plates, 120 ~m wet film thickness, drying time of 24 hours at 20~C.
Resistance to acetone, ethanol and water: glass plates, 120 ~m wet film thickness, drying time of 24 hours at 20~C. A cotton wool pad impregnated with the solvent is placed on the film and covered with a glass beaker. The time is measured until the film softens.
02203103 1997-04-l8 Table 3 Clearcoat 1 2 3 4 5 Vl ;
Freedom from tack in minutes 20 15 20 15 20 15 .~An~h; 1; ty 0 0 MIN 0 0 MIN
Pendulum hardness in seconds 65 80 90 65 60 45 Acetone resistance in seconds ~60 >60 >60 >60 >60 >60 Ethanol resistance in seconds >2 >2 >2 >2 >2 < 0.25 Water resistance in seconds>24 ,24 ,24 ,24 ,24 ~ 1 3. Coatinqs performance testinq of the copolymer disper-sions prepared in accordance with Examples 6 and 7 inclearcoats and in two-component coatinq materials Clearcoats 6 and 7 were prepared in analogy to clearcoats 1 to 5, but additionally received per 100 parts in each case 10 or 20 parts of Bayhydur~ LS 2032 (polyisocyanate 1.5 based on hexamethylene diisocyanate with a free iso-cyanate group content of about 17~ and a solids content of lOO~, manufacturer: BAYER AG).
Two-component coatinq materials (6a and 7a) Binder: polyisocyanate = 79.5 : 20.5 (based on solids) Solids content of the coating materials: 44.5 Two-comPonent coatinq materials (6b and 7b) Binder: polyisocyanate = 66 : 34 (based on solids) Solids content of the coating materials: 49.2~
The clearcoats and two-component coating materials were subjected to the coatings tests already mentioned and those indicated below, the results of which are summar-ized in Table 4:
Pot life: The two-component coating material is stirred once an hour. This operation is repeated until gelling begins.
CA 02203l03 l997-04-l8 Yellow discoloration: 200 ~m wet film thickness on maple (veneered). Assessment is made after storage for 4 weeks at room temperature (1 = no measurable discoloration, 5 = very severe discoloration) Table 4 Clearcoat 6 7 Two~ t coating material 6a 6b 7a 7b Freedom from tack in minutes20 25 S0 20 25 40 SAn~Ahility o MIN o o MIN
1 0 Pendulum hardness in seconds75 70 50 70 65 45 Acetone resistance in seconds ,60 80 80 ,60 70 go Ethanol resistance in seconds >2 ~5 ~8 ~2 ~6 ~ 10 ~ater resistance in seconds ~24 ,36 ~48 ~24 ,86 ~48 Potlife in hours - ~48 20 - ~48 25 Yellow discoloration 4 2 1-2 4 2 1-2 In addition to Table 4, the coating films of the two-component coating materials 6a, 6b and 7a, 7b exhibit, in comparison with the clearcoats 6 and 7, after a drying time of 4 weeks at room temperature, as expected, markedly better results in their resistance to acetone, ethanol and water.
Claims (4)
1. Method of preparing aqueous, autocrosslinking copolymer dispersions whose monomer composition is (Aa) from 3 to 35% by weight, preferably from 8 to 15%
by weight, of (meth)acrylate monomers containing acetoacetyl groups, A(b) from 1 to 20% by weight, preferably from 3 to 16%
by weight, of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, A(c) from 11 to 96% by weight, preferably from 30 to 70%
by weight, of (meth)acrylic alkyl esters and, if desired, diesters of maleic or fumaric acid, and A(d) from 0 to 40% by weight, preferably from 0 to 25%
by weight, of other free-radically polymerizable monomers, such as vinylaromatic compounds, vinyl esters, hydroxyalkyl (meth)acrylates and (meth)acrylamide, the sum of the percentages of components (Aa) to (Ad) necessarily being 100, and the dispersions being neutralized with polyamines which act as a crosslinking component, which method is characterized in that A) a two-stage free-radical emulsion polymerization is carried out, with the proviso that in the first stage from 60 to 90% by weight of a mixture of the monomers (Aa) to (Ad) and in the second stage from 10 to 40% by weight of a mixture of the monomers (Ac) and (Ad) are copolymerized, the sum of the percentages again necessarily being 100 and the condition holding that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-%, preferably from 80 to 90 mol-%, relative to the acetoacetyl groups, and subsequently B) the carboxyl groups of the copolymer dispersions (A) are reacted with polyamines which contain at least two primary amino groups in the molecule, in a proportion of from 50 to 100 mol-%, preferably from 90 to 100 mol-%, relative to the total primary amino groups, with salts being formed.
by weight, of (meth)acrylate monomers containing acetoacetyl groups, A(b) from 1 to 20% by weight, preferably from 3 to 16%
by weight, of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, preferably (meth)acrylic acid, A(c) from 11 to 96% by weight, preferably from 30 to 70%
by weight, of (meth)acrylic alkyl esters and, if desired, diesters of maleic or fumaric acid, and A(d) from 0 to 40% by weight, preferably from 0 to 25%
by weight, of other free-radically polymerizable monomers, such as vinylaromatic compounds, vinyl esters, hydroxyalkyl (meth)acrylates and (meth)acrylamide, the sum of the percentages of components (Aa) to (Ad) necessarily being 100, and the dispersions being neutralized with polyamines which act as a crosslinking component, which method is characterized in that A) a two-stage free-radical emulsion polymerization is carried out, with the proviso that in the first stage from 60 to 90% by weight of a mixture of the monomers (Aa) to (Ad) and in the second stage from 10 to 40% by weight of a mixture of the monomers (Ac) and (Ad) are copolymerized, the sum of the percentages again necessarily being 100 and the condition holding that the acrylate copolymers (A) contain acetoacetyl groups in an amount of from 0.2 to 1.7 mol/kg, preferably from 0.4 to 0.8 mol/kg, and carboxyl groups in an amount of from 0.15 to 1.6 mol/kg, preferably from 0.4 to 0.75 mol/kg, and that the carboxyl groups are present in an amount of from 50 to 95 mol-%, preferably from 80 to 90 mol-%, relative to the acetoacetyl groups, and subsequently B) the carboxyl groups of the copolymer dispersions (A) are reacted with polyamines which contain at least two primary amino groups in the molecule, in a proportion of from 50 to 100 mol-%, preferably from 90 to 100 mol-%, relative to the total primary amino groups, with salts being formed.
2. Aqueous, autocrosslinking copolymer dispersions prepared according to claim 1.
3. Use of the aqueous, autocrosslinking copolymer dispersions prepared according to claim 1 as binders for storage-stable one-component coating materials which crosslink at room temperature or at elevated temperature.
4. Use of the aqueous, autocrosslinking copolymer dispersions prepared according to claim 1, in combination with low molecular mass polyisocyanates, where a ratio of copolymer dispersions to polyisocyanates of from 90 : 10 to 60 : 40 (based on solids) is chosen, as binders for two-component coating materials.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA2210/94 | 1994-11-29 | ||
| AT221094A AT402504B (en) | 1994-11-29 | 1994-11-29 | Process for preparing aqueous self-crosslinking copolymer dispersions and their use as binders for storage-stable one-component coating materials |
| ATA1833/95 | 1995-11-08 | ||
| AT183395A AT403478B (en) | 1995-11-08 | 1995-11-08 | Prodn. of aq. self-crosslinking copolymer dispersions for paint binders - by two-stage emulsion polymerisation of acrylic monomer mixt. contg. acetoacetyl and carboxyl gps., followed by neutralisation with poly:amine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2203103A1 true CA2203103A1 (en) | 1996-06-06 |
Family
ID=25596931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002203103A Abandoned CA2203103A1 (en) | 1994-11-29 | 1995-11-23 | Method for the two-stage preparation of aqueous autocrosslinking copolymer dispersions and their use for coating materials |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5939482A (en) |
| EP (1) | EP0794970B1 (en) |
| JP (1) | JP3455225B2 (en) |
| AT (1) | ATE170883T1 (en) |
| CA (1) | CA2203103A1 (en) |
| DE (1) | DE59503548D1 (en) |
| DK (1) | DK0794970T3 (en) |
| ES (1) | ES2122695T3 (en) |
| NO (1) | NO308954B1 (en) |
| PL (1) | PL320422A1 (en) |
| WO (1) | WO1996016998A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19609509B4 (en) * | 1996-03-11 | 2006-11-02 | Celanese Emulsions Gmbh | Aqueous polymer dispersions as a binder for elastic block and scratch resistant coatings |
| DE69709859T2 (en) * | 1996-05-10 | 2002-09-19 | Du Pont | ACRYLIC POLYMERS |
| US6028155A (en) * | 1997-05-21 | 2000-02-22 | Eastman Chemical Company | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
| US6417267B1 (en) | 1996-05-28 | 2002-07-09 | Eastman Chemical Company | Adhesive compositions containing stable amino-containing polymer latex blends |
| DE69715404T2 (en) | 1996-05-28 | 2003-01-09 | Eastman Chem Co | SURFACE-ACTIVE AGENT-CONTAINING ACETOACETOXY FUNCTIONAL AND ENAMINE FUNCTIONAL POLYMERS |
| US5998543A (en) * | 1996-05-28 | 1999-12-07 | Eastman Chemical Company | Stable amino-containing polymer latex blends |
| US5891950A (en) * | 1996-05-28 | 1999-04-06 | Eastman Chemical Company | Use of stable amino-functional latexes in water-based inks |
| US5962556A (en) * | 1996-10-22 | 1999-10-05 | Eastman Chemical Company | Functional latexes resistant to hydrolysis |
| US6262169B1 (en) | 1998-05-14 | 2001-07-17 | Eastman Chemical Company | Protonated amines for controlled crosslinking of latex polymers |
| CN1265117A (en) * | 1997-05-21 | 2000-08-30 | 伊斯曼化学公司 | Process for preparing reactive latex blends which are chemically and physically stable until film formation |
| US6649679B1 (en) | 1997-09-18 | 2003-11-18 | Eastman Chemical Company | Stable waterborne polymer compositions containing poly(alkylenimines) |
| AT407045B (en) | 1998-10-19 | 2000-11-27 | Vianova Kunstharz Ag | AQUEOUS, SELF-CROSS-LINKING COPOLYMER DISPERSIONS, A METHOD FOR THE PRODUCTION AND THEIR USE IN BINDERS FOR VARNISHES |
| JP3654820B2 (en) * | 2000-06-20 | 2005-06-02 | 大日本塗料株式会社 | Resin composition for water-based paint |
| AU2002301310B2 (en) | 2001-10-17 | 2007-12-20 | Rohm And Haas Company | Polymer composition |
| US20030134973A1 (en) * | 2002-01-15 | 2003-07-17 | Chen Robert Gow-Sheng | Waterborne latexes for anti-corrosive and solvent-resistant coating compositions |
| WO2004090020A1 (en) | 2003-04-02 | 2004-10-21 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| US8465844B2 (en) * | 2004-02-13 | 2013-06-18 | Henkel Ag & Co. Kgaa | Elastic attachment adhesive containing radial block copolymer |
| US20050182194A1 (en) * | 2004-02-13 | 2005-08-18 | Qiwei He | Adhesive containing radial block copolymer |
| EP1819789B1 (en) | 2004-10-20 | 2011-06-15 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| ES2595990T3 (en) | 2009-04-09 | 2017-01-04 | Valspar Sourcing, Inc. | Polymer having unsaturated cycloaliphatic functionality and coating compositions formed therefrom |
| US8486574B2 (en) * | 2009-07-14 | 2013-07-16 | Ford Global Technologies, Llc | Method and system for power control in an automotive vehicle |
| US8754614B2 (en) * | 2009-07-17 | 2014-06-17 | Tesla Motors, Inc. | Fast charging of battery using adjustable voltage control |
| WO2011009040A1 (en) | 2009-07-17 | 2011-01-20 | Valspar Sourcing, Inc. | Coating composition and articles coated therewith |
| BR112012006030A2 (en) | 2009-09-18 | 2016-03-22 | Valspar Sourcing Inc | method coated article and composition |
| CN102115513B (en) * | 2009-12-30 | 2014-05-28 | 罗门哈斯公司 | Dispersion system for low-odor styrenic polymer |
| DE102010029930A1 (en) | 2010-06-10 | 2011-12-15 | Evonik Röhm Gmbh | Preparing acetoacetoxyalkyl(meth)acrylate compounds, useful e.g. in adhesives, comprises reacting acetoacetic acid alkyl ester- with hydroxyalkyl(meth)acrylate-compounds in presence of catalyst and optionally in presence of stabilizer |
| CN102746601B (en) * | 2011-04-18 | 2014-11-26 | 罗门哈斯公司 | Water whitening resistance copolymer dispersion for coating material |
| CN105377703B (en) | 2013-07-02 | 2017-09-08 | 威士伯采购公司 | Coating composition for packing articles such as food and beverage container |
| KR101884537B1 (en) | 2013-07-02 | 2018-08-01 | 발스파 소싱 인코포레이티드 | Coating compositions for packaging articles such as food and beverage containers |
| CN105085788B (en) * | 2015-09-07 | 2018-01-30 | 山东天庆科技发展有限公司 | A kind of water-based nonionic acrylic resin and its synthetic method |
| US9796873B2 (en) | 2016-02-02 | 2017-10-24 | Ennis Paint, Inc. | Linear polyglycidyl amine additives for controlled crosslinking of latex polymers |
| US10913811B2 (en) | 2016-03-18 | 2021-02-09 | Basf Se | Finely divided aqueous multistage polymer dispersion, method for the production thereof, and use thereof as a binder |
| WO2018063095A1 (en) * | 2016-09-29 | 2018-04-05 | Nipsea Technologies Pte Ltd | Crosslinking agent for polymer emulsions |
| CN117511286A (en) * | 2016-09-30 | 2024-02-06 | 广东华润涂料有限公司 | Water-dispersible copolymers for formaldehyde scavenging |
| CN110317502B (en) * | 2019-06-04 | 2021-05-14 | 嘉宝莉化工集团股份有限公司 | Water-based woodware seal primer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997772A (en) * | 1987-09-18 | 1991-03-05 | Eastman Kodak Company | Water-insoluble particle and immunoreactive reagent, analytical elements and methods of use |
| US5116895A (en) * | 1988-12-30 | 1992-05-26 | Union Oil Company Of California | Polymer systems and methods for their production |
| US5055506A (en) * | 1988-12-30 | 1991-10-08 | Union Oil Company Of California | Polymer systems and methods for their production |
| DE3902103A1 (en) * | 1989-01-25 | 1990-08-02 | Roehm Gmbh | BINDER FOR WAESSED GLOSSY COLORS |
| US5391624A (en) * | 1992-02-10 | 1995-02-21 | S. C. Johnson & Son, Inc. | Thermosettable compositions |
| AT396934B (en) * | 1992-02-14 | 1993-12-27 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF AQUEOUS, SELF-CROSSLINKING POLYMER DISPERSIONS AND THEIR USE AS A BINDING AGENT FOR STORAGE-COMPONENT VARNISHES |
| GB9221222D0 (en) * | 1992-10-09 | 1992-11-25 | Ici Plc | Coating composition |
| US5369163A (en) * | 1992-11-13 | 1994-11-29 | Rohm And Haas Company | Process for preparing large dimension emulsion polymer particles, polymer product and uses thereof |
| US5306744A (en) * | 1992-12-18 | 1994-04-26 | Rohm And Haas Company | Functionalized multistage polymers |
| US5308890A (en) * | 1993-02-26 | 1994-05-03 | Rohm And Haas Company | Emulsion polymer blend of a multi-stage latex and a non-film forming latex |
-
1995
- 1995-11-23 PL PL95320422A patent/PL320422A1/en unknown
- 1995-11-23 WO PCT/AT1995/000227 patent/WO1996016998A1/en active IP Right Grant
- 1995-11-23 DK DK95937711T patent/DK0794970T3/en active
- 1995-11-23 ES ES95937711T patent/ES2122695T3/en not_active Expired - Lifetime
- 1995-11-23 JP JP51714196A patent/JP3455225B2/en not_active Expired - Fee Related
- 1995-11-23 AT AT95937711T patent/ATE170883T1/en not_active IP Right Cessation
- 1995-11-23 EP EP95937711A patent/EP0794970B1/en not_active Expired - Lifetime
- 1995-11-23 CA CA002203103A patent/CA2203103A1/en not_active Abandoned
- 1995-11-23 DE DE59503548T patent/DE59503548D1/en not_active Expired - Lifetime
- 1995-11-23 US US08/836,304 patent/US5939482A/en not_active Expired - Fee Related
-
1997
- 1997-05-22 NO NO972352A patent/NO308954B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0794970A1 (en) | 1997-09-17 |
| JP3455225B2 (en) | 2003-10-14 |
| ES2122695T3 (en) | 1998-12-16 |
| JPH10509206A (en) | 1998-09-08 |
| DK0794970T3 (en) | 1999-06-07 |
| US5939482A (en) | 1999-08-17 |
| ATE170883T1 (en) | 1998-09-15 |
| EP0794970B1 (en) | 1998-09-09 |
| NO972352D0 (en) | 1997-05-22 |
| PL320422A1 (en) | 1997-09-29 |
| NO308954B1 (en) | 2000-11-20 |
| DE59503548D1 (en) | 1998-10-15 |
| NO972352L (en) | 1997-05-22 |
| WO1996016998A1 (en) | 1996-06-06 |
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