CA2022101A1 - Process for the preparation of self-crosslinking cationic paint binders - Google Patents
Process for the preparation of self-crosslinking cationic paint bindersInfo
- Publication number
- CA2022101A1 CA2022101A1 CA002022101A CA2022101A CA2022101A1 CA 2022101 A1 CA2022101 A1 CA 2022101A1 CA 002022101 A CA002022101 A CA 002022101A CA 2022101 A CA2022101 A CA 2022101A CA 2022101 A1 CA2022101 A1 CA 2022101A1
- Authority
- CA
- Canada
- Prior art keywords
- stage
- process according
- employed
- primary
- diamines
- 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
Links
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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
ABSTRACT OF DISCLOSURE
The preparation of self-crosslinking, cationic paint binders which can be diluted with water after protona-tion, based on reaction products formed from aminoalkylation products of phenols with epoxy resins wherein the diepoxy resins employed in a final processing stage are modified proportionally with monoamines and diamines is described.
The modification of the invention provides further means for influencing the application and rheological properties of the binders, the paints formulated therewith, and the deposited films when the latter are crosslinked.
The preparation of self-crosslinking, cationic paint binders which can be diluted with water after protona-tion, based on reaction products formed from aminoalkylation products of phenols with epoxy resins wherein the diepoxy resins employed in a final processing stage are modified proportionally with monoamines and diamines is described.
The modification of the invention provides further means for influencing the application and rheological properties of the binders, the paints formulated therewith, and the deposited films when the latter are crosslinked.
Description
2404~US3420 2 ~ 2 2 ~J'~ ~ ~
PROCESS FOR THE PREPARATION OF
SELF-CROSSLINKING CATIONIC PAINT BINDERS
_ELATED PATENTS
This application relates to the subject matter of commonly assigned U.S. Patent Nos. 4,711,934; 4,711,935;
4,845,170, and 4,845,171.
FIELD OF INVENTION
The present invention relates to a process for the preparation of self-crosslinking, cationic paint binders which can be diluted with water after protonation and to the binders obtained. More particularly, the binders are based on reaction products formed from aminoalkylation products of phenols with epoxy resins wherein the diepoxy resins employ-ed in the final processing stage are modi~ied proportionally with monoamines and diamines.
BACKGROUND OF INVENTION
Processes for the preparation of reaction products formed from aminoalkylation products of phenols with epoxy resins are described in U.S. Patent Nos. 4,711,934;
4,711,935; 4,845,170 and 4,845,171, corresponding substan-tially to Austrian Patent Nos. 382,160; 384~232; 384,818;
385,048; 386,220; 386,221, and 390,071. Austrian Patent No. 382,160 and U.S. Patent Nos. 4,711,934 and 4,845,170 - , . .. ~:
.' ' ' ', ~
-- ~ .-: .
. .
PROCESS FOR THE PREPARATION OF
SELF-CROSSLINKING CATIONIC PAINT BINDERS
_ELATED PATENTS
This application relates to the subject matter of commonly assigned U.S. Patent Nos. 4,711,934; 4,711,935;
4,845,170, and 4,845,171.
FIELD OF INVENTION
The present invention relates to a process for the preparation of self-crosslinking, cationic paint binders which can be diluted with water after protonation and to the binders obtained. More particularly, the binders are based on reaction products formed from aminoalkylation products of phenols with epoxy resins wherein the diepoxy resins employ-ed in the final processing stage are modi~ied proportionally with monoamines and diamines.
BACKGROUND OF INVENTION
Processes for the preparation of reaction products formed from aminoalkylation products of phenols with epoxy resins are described in U.S. Patent Nos. 4,711,934;
4,711,935; 4,845,170 and 4,845,171, corresponding substan-tially to Austrian Patent Nos. 382,160; 384~232; 384,818;
385,048; 386,220; 386,221, and 390,071. Austrian Patent No. 382,160 and U.S. Patent Nos. 4,711,934 and 4,845,170 - , . .. ~:
.' ' ' ', ~
-- ~ .-: .
. .
2~2~ ~ ~
disclose a process for the preparation of self-crosslink-ing, cationic paint binders which can be diluted with water after protonation based on reaction products formed from aminoalkylation products of phenols with epoxy resins, char-acterized in that -(1) an aminoalkylation product which contains on averageat 12ast one NH group per molecule and has been formed from phenol and/or a substituted phenol, preferably a monoalkylphenol or monoarylphenol or monoaralkylphenol having one or, if appropriate, two phenolic hydroxyl groups, a primary alkylamine and/or primary alkanol-amine and/or primary/tertiary alkyldiamine and formal-dehyde or a formaldehyde donor, is reacted with (2) a half-masked diisocyanate and, in a further reaction stage, (3) 50 to 100% of the phenolic hydroxyl groups of the product of (1) and (2) are reacted with epoxy com-pounds, preferably diepoxy resins having an epoxide equivalent weight between 50 and 2000.
According to the present invention, it has now been found that the application and rheological properties of the coating agents based on tha products of the aforesaid patents can be improved if the diepoxy resins employed in the final processing stage are modified by a partial reac-tion with monoamines or diamines.
~ . .. . .
... . ..
. . .
2404/US3420 2 ~ 2 2 ~ ~ ~
SUMMARY OF INVENTlON AND GENERAL DESCRIPTION
Accordingly, the present invention relates to a process for the preparation of self-crosslinking, cationic paint binders which can be diluted with water after protona-tion and are based on reaction products formed from amino-alkylation products of phenols and epoxy resins, which have been obtained by reacting (l) an aminoalkylation product which contains on average at least one NH group per molecule and has been formed from phenol and/or a substituted phenol, preferably a monoalkylphenol or monoarylphenol or monoaralkylphenol having one or, if appropriate, two phenolic hydroxyl groupsj a primary alkylamine and~or primary alkanol-amine and/or primary/tertiary alkyldiamine and formal-dehyde or a formaldehyde donor, with (2) a half-masked diisocyanate, and subsequently reacting (3) 50 to 100% of the phenolic hydroxyl groups of the product of (1) and (2) with epoxy compounds, preferably diepoxy resins having an epoxide equivalent weight between 50 and 2000, which is characterized in that 5 to 70 mole ~, preferably 10 to 40 mole %, of the glycidyl groups of the epoxy com-pounds employed in stage (3) are reacted with monoamines and/or diamines before they are reacted with the inter-mediate product obtained in stage (2) or, if appropriate, - ~ -,. ... ..
: : - "
2404/US3420 2~2~ ~ ~
at the same time as they are reacted in accordance with stage (3). The invention also embraces the modified cross-linking cationic paint binders obtained by practicing the process. The modification of the binders according to the present invention provides further means for influencing the application and rheological properties of the binders, the paints formulated therewith, and the deposited films when the latter are crosslinked.
The preparation of the precursors and intermediate products employed is carried out in accordance with the man-ner descrihed in U.S. Patent Nos. 4,711,934 and 4,845,170.
Monoamines which can be employed for reaction with the epoxy component according to the present invention are essentially all primary and secondary amines, such as the homologous monoalkyl monoamines or dialkyl monoamines or the homologous monoalkanol monoamines or dialkanol monoamines. The di-amines employed are preferably reaction products of dipri-mary amines with 2 mole of monoepoxy compound. Primary-tertiary diamines, such as dimethylaminopropylamine and homologues, are also preferred.
In a particular embodiment, the amine-functional compounds employed according to this inven-tion are the oxa-zolidine amines described in U.S. Patent No~ 4,431,781, cor-responding to European Patent No. 0,076,955, which have the genaral formulae -. . . ~
, , . : : .:.
- ` 2~12~ ~ ~3-l4 R3 ~ ÇH ~ CH ~ NH - R1 ~ N--- CH - R4 OH l l R2~ \
and/or II) R4 ~ CH N ~ ( CHz ) n NH ~ X
o~ ~ R
and/or (III) R5 - NH ~ R1 ~ N I H - R"
R ~ ~O ~ 6 wherein -R1 denotes a linear or branched or cyclic alkylene radical having 2 to 12 carbon atoms or an aralkylene radical, R2 denotes a linear or branched alkyl radical having l to 4 carbon atoms, an aryl radical or an H atom or, for both R2 groups jointly, a ring-forming alkylene radical which is optionally substituted by alkyl, aryl, or alkoxy radicals, '; ; ! ~, , , . , ' : , .' . ' ' ' , ,, ' . :
" 'i' ' ~ ~ "~
2~2~ ~ ~
R3 denotes a saturated or unsaturated, aliphatic or cyclo-aliphatic or aromatic hydrocarbon radical which option-ally contains ether or ester groupings, R4 denotes H or CH3-, R5 denotes a radical remaining after reaction with an active hydrogen atom of an acrylic or methacrylic monomer which is monofunctional in respect of the double bonds of the monomer, R6 denotes a hydrogen atom or an alkyl radical, n denotes a numerical 2, 3 or 4, and X denotes either -( CH2 ) n ~ N CH - R4 R "' ~0 ~ 3 or ;
(CH2) n ~ NH - CH ~ fH - R3 OH
The reaction of the diepoxy or polyepoxy compounds with the amines is carried out either before or at the same time as the reaction of the epoxy compounds with the phenol component. In either case, the reaction is carried out at 60C - 100C, and the ratios and the reaction conditions ars chosen in order that the end products do not contain ~ - . - :
,.
. .~ , . ~ : ~; .; .
2404/US3420 2~22~ ~
free epoxy groups. There is no essential di~ference between the end products prepared by the two process variants.
In order to achieve dilutability with water, the basic groups of the reaction product are neutralized par-tially or completely with acids, preferably with formic acid, acetic acid, or lactic acid. Usually neutralization of 20 - 60% of the basic groups or an amount of approxi-mately 20 t.o 60 millimole of acid per 100 g of solid resin is sufficient for a dilutability which is suitable or prac-tical use. The bindexs are then diluted with deionized water to the desired concentration. If desired, they are processed with crosslinking catalysts, pigments, filler, and other additives to give pigmented paints before neutra-lization or before dilution, or in a partly diluted state.
- The formulation of such paints and their appli-cation in the electrocoating process are known to those skilled in the art and are described in the literature. The curing of the deposited coatings is carried out, when used as primer, at temperatures between 150C and 170C for 10 to 30 minutes. If the binders do not contain self-crosslinking structures in an adequate amount, concomitantly additional crosslinking agents can be used, such as masked isocyanates or amino resins or phenolic resins. If suitably formulated, the products can also be applied by other processes, such as dipping, rolling, or spraying. If desired, the binders can : . .;
, 2404/US3420 C~ 2 ~
also be processed in organic solvents.
ILLUSTRATIVE EXAMPLES AND PREFERRED EMBODIMENTS
The following examples illustrate the invention without limiting its scope. Unless otherwise specified, all data in parts or percentages relate to units of weight.
The following abbreviations are used in the e~am-ples:
PH........ phenol NPH....... nonylphenol BPA....... bisphenol A
DMAPA... N,N-dimethylaminopropylamine DEAPA... N,N-diethylaminopropylamine EHA....... 2-ethylhexylamine EGL....... monoethylglycol monoethylether MIC I... toluylene diisocyanate, half-masked with EGL
MIC II.. toluylene diisocyanate, half-masked with 2-ethylhexanol EPH I... diepoxy resin based on bisphenol A and epichlorohydrin (epoxide equivalent weight approximately 190) EPH II.~. diepoxy resin based on bisphenol A and epichlorohydrin tepoxide e~uivalent weight approximately 480) EPH III.. glycidyl ether of tertiary C9/C11-mono-carboxylic acids (epoxide equivalent weight 250) : , -` 2~22~
OXAM I.. oxazolidine amine formed from 1 mole of aminoethylethanolamine, 1 mole of 2-ethyl hexyl acrylate, and l mole of formaldehyde (MW = 300) OXAM II. oxazolidine amine formed from 1 mole of di-ethylenetriamine, 2 mole of octene oxide, and 2 mole of formaldehyde ~MW = 231) DIAM...... reaction product of 1 mole of pentamethylene-diamine with 2 mole of EPH III (MW = 602) DOLA...... diethanolamine DGDM...... diethyleneglycol dimethylether MOP....... methoxypropanol The preparation of the modified aminoalkylation products (VP 1 to 4~ is effected in accordance with the examples in U.S. Patent No. 4,711,934, in the ratios indi-cated in Table 1 as follows:
.
, ~
. .;
2404/US3420 . 2~22~
C) .,, O ~
I
I
oo ~ o ~
a) ~d t a~
~1 ~- I ~ ~D O
o -' I , X 0~
~ _ o\ o\ o\o o\o ~_ o o o o U~ CO t` t` ~
a~ ~ _ _ _ _ ., a a 5a Xa o o ~ ~ ~ w ~n a a a a a ,~
_ o o o o I
o _ _, _ _ _ H H H
O
H H H H H
~~ I X ~ X ~ , ~r co d' ~D O ~ O
~ ~ ~'1 Il~ ) a ,i ,i ~
~ , _ _ _ _ _ E~~ 5 ¦ ~ a a ~a I ~ O O
~ O 7 D O
~ _ Q) 1~ o o o o ~ I
~ _ , I
l I o o o o o ~ ~ ~ ~o ~
~ I
,_ _ o o o o I
~1 ~1 ~1 ~1 ~1 ,~ I ~ _ _ _ ~ _ a Z m ~ P~
I o ~ co ~r P~
P~
~ ,~ ~ ~ ~P ' , :. : : -: . :-: . ~ . :
- ::
.
2404/US3420 2 ~ 2 2 ~ O ~
Preparation of the Binders Accordin~ to the Invention Examples 1 - 6 The reaction of the starting materials indicated in Table 2 can be carried out either in a one-stage process or in a two-stage process. There is no difference in the properties of the products prepared by the two processes which go beyond customary variations.
In the one-stage process, the components are reacted in a 70% strength solution in the solvent indicated in Table 2 at 95C to 100C until the epoxy groups have been completely reacted. Monoglycidyl compounds which can be employed are in this case preferably not reacted until after the reaction of the diepoxy resins with the amine compounds.
In the two-stage process, the diepoxy resin is reacted in the first stage at 60C to 80C with the amine compound until the amount of epoxy groups corresponding stoichiometrically to the aminohydrogens has reacted. After the modified aminoalkylation product (VP) and the monogly-cidyl compound, if employed, have been added and after the solids content has been adjusted with solvent to 70 to 75%, further reaction is carried out at 90C to 100C until an epoxide value of virtually zero i5 reached.
For further processing, the products are adjusted to th~ solids content indicated in Table 2. The solvents used are the glycol ethers, preferably methoxypropanol.-:
, The column "Solubility" in Table 2 indicates theamount of formic acid (in millimole) per lO0 g of solid resin, which is required in order to give a stable clear lacquer after dilution with water to a solids content of 15~.
Table 2 is as follows:
"
' . . :' , ; : ~
.
2404/US3~20 2 ~ 2 2 .
~o~
o o o ~ o U~O
o\ o~ o\ ~o o~o o\O
n o ~ o ~ U) ~ ~ ~ t` ~ ~O ~D
o o o ~ ~ ~o o~
cn x ~ a ~: x ~ ~ _ ~ ~ ~
~ ln o o ~ o ~ I O ~ ~i O ~i 00 ~1 C H ~i ~ i~ 1_1 ~i ~
~ I xO a ~ ~ o ~ ~
I ~ ~ o ~ ~ ~t~
~ .
E~ cô,~ ô ô c~ o ô
I ~ ~ ~ o ~ ~i ~_O ~ _ ~ _~ ~_ _ ,1 ~ ~ ~r ~ ~
P~
~ U~ ~ :>
I ~D ~O ~ ~ ~ O O
r~ c~ l` ~ ~ ~ ~r r~ ~ ~ U~ o o _ _ ~ ~ ~ ~ ~_ ~ I C~ O O OO OO
0~ a ) ~ ~ ,i ~1~ ~1 ~ ~1 -E ' HH H H H H H H H
_ ~ ~ ~5 ~ ~ ~C~
I U~ ~ ~ ~ ~ ~ IY :q o o o o o o o ~r co c~ In o ~
,~ ~ ~ ,I~r I -I ~ ~ ~P U.
..
:.
:' '' ` :
2404/US3420 2 ~ ~ 2 ~J ~ ~
The binders prepared in accordance with Examples 1 to 6 were deposited by electrical means in the form o a clear lacquer onto steel sheets. The clear lacquer was pre-pared by adding an amount of dibutyltindilaurate correspond-ing to 0.8% of metal (relative to solid resin) to the resin solution obtained in accordance with the example, and the mixture was diluted to a solids content of 15~ with deion-ized water. The films were stoved for 20 minutes at 160C, and, at a film thickness o~ 20 + 2 ~m, had a resistance to methylethylketone of at least 150 double rubs.
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.
. , :
: ~ ~
., :
,, :. - ,: :: :, , ;'~'
disclose a process for the preparation of self-crosslink-ing, cationic paint binders which can be diluted with water after protonation based on reaction products formed from aminoalkylation products of phenols with epoxy resins, char-acterized in that -(1) an aminoalkylation product which contains on averageat 12ast one NH group per molecule and has been formed from phenol and/or a substituted phenol, preferably a monoalkylphenol or monoarylphenol or monoaralkylphenol having one or, if appropriate, two phenolic hydroxyl groups, a primary alkylamine and/or primary alkanol-amine and/or primary/tertiary alkyldiamine and formal-dehyde or a formaldehyde donor, is reacted with (2) a half-masked diisocyanate and, in a further reaction stage, (3) 50 to 100% of the phenolic hydroxyl groups of the product of (1) and (2) are reacted with epoxy com-pounds, preferably diepoxy resins having an epoxide equivalent weight between 50 and 2000.
According to the present invention, it has now been found that the application and rheological properties of the coating agents based on tha products of the aforesaid patents can be improved if the diepoxy resins employed in the final processing stage are modified by a partial reac-tion with monoamines or diamines.
~ . .. . .
... . ..
. . .
2404/US3420 2 ~ 2 2 ~ ~ ~
SUMMARY OF INVENTlON AND GENERAL DESCRIPTION
Accordingly, the present invention relates to a process for the preparation of self-crosslinking, cationic paint binders which can be diluted with water after protona-tion and are based on reaction products formed from amino-alkylation products of phenols and epoxy resins, which have been obtained by reacting (l) an aminoalkylation product which contains on average at least one NH group per molecule and has been formed from phenol and/or a substituted phenol, preferably a monoalkylphenol or monoarylphenol or monoaralkylphenol having one or, if appropriate, two phenolic hydroxyl groupsj a primary alkylamine and~or primary alkanol-amine and/or primary/tertiary alkyldiamine and formal-dehyde or a formaldehyde donor, with (2) a half-masked diisocyanate, and subsequently reacting (3) 50 to 100% of the phenolic hydroxyl groups of the product of (1) and (2) with epoxy compounds, preferably diepoxy resins having an epoxide equivalent weight between 50 and 2000, which is characterized in that 5 to 70 mole ~, preferably 10 to 40 mole %, of the glycidyl groups of the epoxy com-pounds employed in stage (3) are reacted with monoamines and/or diamines before they are reacted with the inter-mediate product obtained in stage (2) or, if appropriate, - ~ -,. ... ..
: : - "
2404/US3420 2~2~ ~ ~
at the same time as they are reacted in accordance with stage (3). The invention also embraces the modified cross-linking cationic paint binders obtained by practicing the process. The modification of the binders according to the present invention provides further means for influencing the application and rheological properties of the binders, the paints formulated therewith, and the deposited films when the latter are crosslinked.
The preparation of the precursors and intermediate products employed is carried out in accordance with the man-ner descrihed in U.S. Patent Nos. 4,711,934 and 4,845,170.
Monoamines which can be employed for reaction with the epoxy component according to the present invention are essentially all primary and secondary amines, such as the homologous monoalkyl monoamines or dialkyl monoamines or the homologous monoalkanol monoamines or dialkanol monoamines. The di-amines employed are preferably reaction products of dipri-mary amines with 2 mole of monoepoxy compound. Primary-tertiary diamines, such as dimethylaminopropylamine and homologues, are also preferred.
In a particular embodiment, the amine-functional compounds employed according to this inven-tion are the oxa-zolidine amines described in U.S. Patent No~ 4,431,781, cor-responding to European Patent No. 0,076,955, which have the genaral formulae -. . . ~
, , . : : .:.
- ` 2~12~ ~ ~3-l4 R3 ~ ÇH ~ CH ~ NH - R1 ~ N--- CH - R4 OH l l R2~ \
and/or II) R4 ~ CH N ~ ( CHz ) n NH ~ X
o~ ~ R
and/or (III) R5 - NH ~ R1 ~ N I H - R"
R ~ ~O ~ 6 wherein -R1 denotes a linear or branched or cyclic alkylene radical having 2 to 12 carbon atoms or an aralkylene radical, R2 denotes a linear or branched alkyl radical having l to 4 carbon atoms, an aryl radical or an H atom or, for both R2 groups jointly, a ring-forming alkylene radical which is optionally substituted by alkyl, aryl, or alkoxy radicals, '; ; ! ~, , , . , ' : , .' . ' ' ' , ,, ' . :
" 'i' ' ~ ~ "~
2~2~ ~ ~
R3 denotes a saturated or unsaturated, aliphatic or cyclo-aliphatic or aromatic hydrocarbon radical which option-ally contains ether or ester groupings, R4 denotes H or CH3-, R5 denotes a radical remaining after reaction with an active hydrogen atom of an acrylic or methacrylic monomer which is monofunctional in respect of the double bonds of the monomer, R6 denotes a hydrogen atom or an alkyl radical, n denotes a numerical 2, 3 or 4, and X denotes either -( CH2 ) n ~ N CH - R4 R "' ~0 ~ 3 or ;
(CH2) n ~ NH - CH ~ fH - R3 OH
The reaction of the diepoxy or polyepoxy compounds with the amines is carried out either before or at the same time as the reaction of the epoxy compounds with the phenol component. In either case, the reaction is carried out at 60C - 100C, and the ratios and the reaction conditions ars chosen in order that the end products do not contain ~ - . - :
,.
. .~ , . ~ : ~; .; .
2404/US3420 2~22~ ~
free epoxy groups. There is no essential di~ference between the end products prepared by the two process variants.
In order to achieve dilutability with water, the basic groups of the reaction product are neutralized par-tially or completely with acids, preferably with formic acid, acetic acid, or lactic acid. Usually neutralization of 20 - 60% of the basic groups or an amount of approxi-mately 20 t.o 60 millimole of acid per 100 g of solid resin is sufficient for a dilutability which is suitable or prac-tical use. The bindexs are then diluted with deionized water to the desired concentration. If desired, they are processed with crosslinking catalysts, pigments, filler, and other additives to give pigmented paints before neutra-lization or before dilution, or in a partly diluted state.
- The formulation of such paints and their appli-cation in the electrocoating process are known to those skilled in the art and are described in the literature. The curing of the deposited coatings is carried out, when used as primer, at temperatures between 150C and 170C for 10 to 30 minutes. If the binders do not contain self-crosslinking structures in an adequate amount, concomitantly additional crosslinking agents can be used, such as masked isocyanates or amino resins or phenolic resins. If suitably formulated, the products can also be applied by other processes, such as dipping, rolling, or spraying. If desired, the binders can : . .;
, 2404/US3420 C~ 2 ~
also be processed in organic solvents.
ILLUSTRATIVE EXAMPLES AND PREFERRED EMBODIMENTS
The following examples illustrate the invention without limiting its scope. Unless otherwise specified, all data in parts or percentages relate to units of weight.
The following abbreviations are used in the e~am-ples:
PH........ phenol NPH....... nonylphenol BPA....... bisphenol A
DMAPA... N,N-dimethylaminopropylamine DEAPA... N,N-diethylaminopropylamine EHA....... 2-ethylhexylamine EGL....... monoethylglycol monoethylether MIC I... toluylene diisocyanate, half-masked with EGL
MIC II.. toluylene diisocyanate, half-masked with 2-ethylhexanol EPH I... diepoxy resin based on bisphenol A and epichlorohydrin (epoxide equivalent weight approximately 190) EPH II.~. diepoxy resin based on bisphenol A and epichlorohydrin tepoxide e~uivalent weight approximately 480) EPH III.. glycidyl ether of tertiary C9/C11-mono-carboxylic acids (epoxide equivalent weight 250) : , -` 2~22~
OXAM I.. oxazolidine amine formed from 1 mole of aminoethylethanolamine, 1 mole of 2-ethyl hexyl acrylate, and l mole of formaldehyde (MW = 300) OXAM II. oxazolidine amine formed from 1 mole of di-ethylenetriamine, 2 mole of octene oxide, and 2 mole of formaldehyde ~MW = 231) DIAM...... reaction product of 1 mole of pentamethylene-diamine with 2 mole of EPH III (MW = 602) DOLA...... diethanolamine DGDM...... diethyleneglycol dimethylether MOP....... methoxypropanol The preparation of the modified aminoalkylation products (VP 1 to 4~ is effected in accordance with the examples in U.S. Patent No. 4,711,934, in the ratios indi-cated in Table 1 as follows:
.
, ~
. .;
2404/US3420 . 2~22~
C) .,, O ~
I
I
oo ~ o ~
a) ~d t a~
~1 ~- I ~ ~D O
o -' I , X 0~
~ _ o\ o\ o\o o\o ~_ o o o o U~ CO t` t` ~
a~ ~ _ _ _ _ ., a a 5a Xa o o ~ ~ ~ w ~n a a a a a ,~
_ o o o o I
o _ _, _ _ _ H H H
O
H H H H H
~~ I X ~ X ~ , ~r co d' ~D O ~ O
~ ~ ~'1 Il~ ) a ,i ,i ~
~ , _ _ _ _ _ E~~ 5 ¦ ~ a a ~a I ~ O O
~ O 7 D O
~ _ Q) 1~ o o o o ~ I
~ _ , I
l I o o o o o ~ ~ ~ ~o ~
~ I
,_ _ o o o o I
~1 ~1 ~1 ~1 ~1 ,~ I ~ _ _ _ ~ _ a Z m ~ P~
I o ~ co ~r P~
P~
~ ,~ ~ ~ ~P ' , :. : : -: . :-: . ~ . :
- ::
.
2404/US3420 2 ~ 2 2 ~ O ~
Preparation of the Binders Accordin~ to the Invention Examples 1 - 6 The reaction of the starting materials indicated in Table 2 can be carried out either in a one-stage process or in a two-stage process. There is no difference in the properties of the products prepared by the two processes which go beyond customary variations.
In the one-stage process, the components are reacted in a 70% strength solution in the solvent indicated in Table 2 at 95C to 100C until the epoxy groups have been completely reacted. Monoglycidyl compounds which can be employed are in this case preferably not reacted until after the reaction of the diepoxy resins with the amine compounds.
In the two-stage process, the diepoxy resin is reacted in the first stage at 60C to 80C with the amine compound until the amount of epoxy groups corresponding stoichiometrically to the aminohydrogens has reacted. After the modified aminoalkylation product (VP) and the monogly-cidyl compound, if employed, have been added and after the solids content has been adjusted with solvent to 70 to 75%, further reaction is carried out at 90C to 100C until an epoxide value of virtually zero i5 reached.
For further processing, the products are adjusted to th~ solids content indicated in Table 2. The solvents used are the glycol ethers, preferably methoxypropanol.-:
, The column "Solubility" in Table 2 indicates theamount of formic acid (in millimole) per lO0 g of solid resin, which is required in order to give a stable clear lacquer after dilution with water to a solids content of 15~.
Table 2 is as follows:
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2404/US3~20 2 ~ 2 2 .
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I ~D ~O ~ ~ ~ O O
r~ c~ l` ~ ~ ~ ~r r~ ~ ~ U~ o o _ _ ~ ~ ~ ~ ~_ ~ I C~ O O OO OO
0~ a ) ~ ~ ,i ~1~ ~1 ~ ~1 -E ' HH H H H H H H H
_ ~ ~ ~5 ~ ~ ~C~
I U~ ~ ~ ~ ~ ~ IY :q o o o o o o o ~r co c~ In o ~
,~ ~ ~ ,I~r I -I ~ ~ ~P U.
..
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2404/US3420 2 ~ ~ 2 ~J ~ ~
The binders prepared in accordance with Examples 1 to 6 were deposited by electrical means in the form o a clear lacquer onto steel sheets. The clear lacquer was pre-pared by adding an amount of dibutyltindilaurate correspond-ing to 0.8% of metal (relative to solid resin) to the resin solution obtained in accordance with the example, and the mixture was diluted to a solids content of 15~ with deion-ized water. The films were stoved for 20 minutes at 160C, and, at a film thickness o~ 20 + 2 ~m, had a resistance to methylethylketone of at least 150 double rubs.
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.
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Claims (12)
1. Process for the preparation of self-crosslink-ing, cationic paint binders which can be diluted with water after protonation, based on reaction products formed from aminoalkylation products of phenols and epoxy resins ob-tained by reacting -(1) an aminoalkylation product which contains on average at least one NH group per molecule and has been formed from phenol having at least one phenolic hydroxyl group, a primary alkylamine and/or primary alkanol-amine and/or primary/tertiary alkyldiamine and formal-dehyde or a formaldehyde donor, and (2) a half-masked diisocyanate and, in a further reaction stage, reacting (3) 50 to 100% of the phenolic hydroxyl groups of the reaction product of (1) and (2) with epoxy compounds having an epoxide equivalent weight between 50 and 2000, characterized in that 5 to 70 mole % of the glycidyl groups of the epoxy compound employed in stage (3) are reacted with monoamines and/or diamines before they are reacted with the intermediate product obtained in stage (2) or at the same time as they are reacted in accordance with stage (3).
2. The process according to claim 1 wherein said phenol of stage (1) is a substituted phenol.
3. The process according to claim 1 wherein the phenol of stage (1) is a member of the group consisting of a monoalkylphenol, a monoarylphenol, or a monoaralkylphenol.
4. The process according to claim 1 wherein the phenol of stage (1) is a diphenol.
5. The process according to claim 1 wherein the epoxy compound of stage (3) is a diepoxy resin.
6. The process according to claim l wherein from 10 to 40 mole % of the glycidyl groups of the epoxy compound employed in stage (3) are reacted with the monoamine and/or diamines.
7. The process according to claim 1 characterized in that the monoamines employed are primary and secondary amines.
8. The process according to claim 1 characterized in that the monoamines employed are primary and secondary alkanolamines.
9. The process according to claim 1 characterized in that the diamines employed are reaction products of diprimary amines with 2 mole of monoepoxy compound.
10. The process according to claim 1 characterized in that the diamines employed are primary-tertiary diamines.
11. The process according to claim 1 characterized in that the amine-functional compounds employed are oxazoli-dine amines of the general formulae -(I) and/or (II) and/or (III) wherein -R1 is a linear or branched or cyclic alkylene radical having 2 to 12 carbon atoms or an aralkylene radical, R2 is a linear or branched alkyl radical having 1 to 4 carbon atoms, an aryl radical or an H atom or, for both R2 groups jointly, a ring-forming alkylene radical which is optionally substituted by alkyl, aryl, or alkoxy radicals, R3 is a saturated or unsaturated, aliphatic or cycloali-phatic or aromatic hydrocarbon radical which option-ally contains ether or ester groupings, R4 is H or CH3-, R5 is a moiety remaining after reaction with an active hydrogen atom of an acrylic or methacrylic monomer which is monofunctional in respect of the double bonds of the monomer, R6 is a hydrogen atom or an alkyl radical, n is a number 2, 3 or 4, and X is either - or .
12. The self-crosslinking cationic paint binders made by the process of any of claims 1-11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT181989A AT392075B (en) | 1985-07-22 | 1989-07-28 | Process for the preparation of self-crosslinking cationic paint binders |
| ATA1819/89 | 1989-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2022101A1 true CA2022101A1 (en) | 1991-01-29 |
Family
ID=3521677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002022101A Abandoned CA2022101A1 (en) | 1989-07-28 | 1990-07-27 | Process for the preparation of self-crosslinking cationic paint binders |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0410365B1 (en) |
| JP (1) | JPH0374477A (en) |
| KR (1) | KR910003048A (en) |
| CA (1) | CA2022101A1 (en) |
| DE (1) | DE59005069D1 (en) |
| ES (1) | ES2051416T3 (en) |
| HR (1) | HRP920982A2 (en) |
| YU (1) | YU138090A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958141A (en) * | 2022-05-31 | 2022-08-30 | 紫荆花涂料（上海）有限公司 | Single-component water-based epoxy primer for curtain coating and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69406904T2 (en) * | 1993-01-12 | 1998-05-14 | Cytec Tech Corp | SINGLE COMPONENT POLYURETE LAYER COMPOSITION |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT376229B (en) * | 1982-03-11 | 1984-10-25 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF RADIATION-curable synthetic resin binders |
| DE3666451D1 (en) * | 1985-07-22 | 1989-11-23 | Vianova Kunstharz Ag | Process for the manufacture of self-cross-linking, cationic varnish binders |
| DE3728762A1 (en) * | 1987-08-28 | 1989-03-09 | Basf Lacke & Farben | BINDING AGENT FOR CATHODIC ELECTRIC DIP PAINTING |
-
1990
- 1990-07-16 YU YU138090A patent/YU138090A/en unknown
- 1990-07-24 EP EP90114133A patent/EP0410365B1/en not_active Expired - Lifetime
- 1990-07-24 ES ES90114133T patent/ES2051416T3/en not_active Expired - Lifetime
- 1990-07-24 DE DE90114133T patent/DE59005069D1/en not_active Expired - Fee Related
- 1990-07-26 JP JP2196408A patent/JPH0374477A/en active Pending
- 1990-07-27 KR KR1019900011459A patent/KR910003048A/en not_active Application Discontinuation
- 1990-07-27 CA CA002022101A patent/CA2022101A1/en not_active Abandoned
-
1992
- 1992-10-02 HR HRP920982AA patent/HRP920982A2/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958141A (en) * | 2022-05-31 | 2022-08-30 | 紫荆花涂料（上海）有限公司 | Single-component water-based epoxy primer for curtain coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0410365A3 (en) | 1992-06-10 |
| YU138090A (en) | 1992-09-07 |
| ES2051416T3 (en) | 1994-06-16 |
| DE59005069D1 (en) | 1994-04-28 |
| JPH0374477A (en) | 1991-03-29 |
| EP0410365A2 (en) | 1991-01-30 |
| KR910003048A (en) | 1991-02-26 |
| HRP920982A2 (en) | 1994-04-30 |
| EP0410365B1 (en) | 1994-03-23 |
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