CA1279431C - Process for producing urea group containing resol-curable paint binders - Google Patents
Process for producing urea group containing resol-curable paint bindersInfo
- Publication number
- CA1279431C CA1279431C CA000515551A CA515551A CA1279431C CA 1279431 C CA1279431 C CA 1279431C CA 000515551 A CA000515551 A CA 000515551A CA 515551 A CA515551 A CA 515551A CA 1279431 C CA1279431 C CA 1279431C
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- primary
- epoxy
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- amine
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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
- 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
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
ABSTRACT OF DISCLOSURE
A process is described for producing urea group con-taining paint binders, curable with resols, particularly suited for the formulation of top grade CED-primers. The pro-ducts are resol-modified epoxy resin amine adducts, the resol segments of which are obtained through reaction of NH-group containing aminoalkylation products of phenols with isocyanate compounds. The substituted urea groups improve the adhesion properties and, in particular, to the adhesion of additional layers of paint.
A process is described for producing urea group con-taining paint binders, curable with resols, particularly suited for the formulation of top grade CED-primers. The pro-ducts are resol-modified epoxy resin amine adducts, the resol segments of which are obtained through reaction of NH-group containing aminoalkylation products of phenols with isocyanate compounds. The substituted urea groups improve the adhesion properties and, in particular, to the adhesion of additional layers of paint.
Description
~;~t794~
FIELD OF INVENTION
The invention is directed to a process for producing paint binders curable with resols and to the binders made by the process which are particularly well suited for the formulation of top grade electrodeposition primers for cathodic electrodeposition (CED-primers).
BACKGROUND OF INVENTION
Commonly assigned U.S. Patent No. 4,568,709, corresponding in part to AT-PS 378 537, discloses a process for the preparation of cathodically depositable paint binders based on modified epoxy resins. According to the disclosed process, an epoxy resin is .reacted with a primary amine and the resulting adduct, carrying secondary amine groups, is reacted with a phenol and formaldehyde. If a sufficient excess of formaldehyde is used, the binders are self-crosslinking as a result of the resol constitution. In a special embodiment, as described in the aforesaid U.S. Patent No. 4,568,709 and disclosed in Canadian Application No. 476,617 filed March 15, 1985, the phenol can be totally or partly replaced by aminoalkylation products of phenols to give better solubility to the products, which means that the quantity of acid necessary for achieving water-dilutability is reduced; and, moreover, additional flexibilizing and leveling enhancing groups are introduced into the binder molecule.
Although the known products when used as paint binders, particularly in the formulation of cathodically depositable 7 ~ ~3 1 elecrodeposition paints (CED-paints), give excellent results, such binders are unsatisfactory for special uses where particularly high standards with regard to adhesion, particularly to a subsequent coat of paint, is required.
It is recognized in the art that the incorporation of amide, urethane, or urea groups to the binders will improve the - adhesion properties of the binder. However, the addition of such groups leads to the reduction of the quality of other properties such as corrosion resistance and resistance to water and solvents.
This invention relates to a process for producing cathodically depositable electrodeposition paint binders comprising reacting cvmponents A and B, component A being a modified epoxy compound obtained by reacting an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available expoxy group to provide an epoxy resin-amino adduct having an epoxy value of substantially zero;
and component B being an aminoalkylation product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a : product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B being such that for each mole of NH-groups ~b ' ~
7~431 on component A, 0.5 to 1 mole of component B are used to provide a reaction produc~ upon partial or total neutralization with acids which is dilutable with water.
This invention further relates to cathodically depositable electrodepositi~n paint binders comprising the reaction product of components A and B, component A being a modified epoxy compound obtained by reacting an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available epoxy group to provide an epoxy resin-aminO adduct having an epoxy value of substantially zero;
and component B being an aminoal]cylation product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partlal or total neutralization with acids which is dilutable with water.
It has now been found that the products obtained according to the teaching of U.S. Patent No. 4,568,709, can be Substantially improved in their adhesion characteristics without negative influences on - 3a -...,~
~1 ~7~4;~1 I S - ~. 7 3 0 other properties if the phenols used in the reaction are phe-nol condensates carrying urea groups.
Accordingly, the invention is directed to a process ~- for producing urea group containing resol-curable paint bin-:~: 5 ders based on resol-modified epoxy resin-amine adducts charac-terized in that an aminoalkylation product of a monosubsti-tuted mono- or dinuclear phenol, a primary monoamine, and/or diamine and formaldehyde is utilized as the phenolic component for the reaction with the epoxy amine adduct and formaldehyde wherein the amino-hydrogens of the aminoalkylation product have been reacted in the presence of an aprotic solvent at 30 to 50C with mono- and/or diisocyanate compounds to form a product with a maximum oE four, and preferably two, phenolic hydroxyl groups. Through the reaction of the amino-hydrogens with the isocyanate groups, urea groups are formed essential for the properties of the final products.
The invention is also directed to the paint binders made by the presently disclosed process and to the use of the binders in paint systems r particularly CED-systems.
The aminoalkylation products carrying the urea groups used in the process of the present invention are obtained through reaction of mono- or po~ynuclear phenols with primary ,. : ,' .. ~ . . .". :
, ~ , . ' , ~ ;~794;~
lt' 'l9/US-2730 amines and formaldehyde, and subsequent reaction of the amino-hydrogens with isocyanate compounds. In the schematic reac-tion schemes set forth hereinbelow, the reaction is presented for a simple example where scheme I shows the reaction with a ~ 5 primary monoamine, whereas in scheme II a primary diamine is - ~ used. Radicals X, Y, and R of the schemes are radicals evi-dent from the list of starting materials.
The reaction schemes are as follows:
.
( I ) OH OH
~ [~OE12 -- NH -- X
- CH2 -- NH -- X + OCN~NCO
' ~
.
~ ` S
' .
: '', . ' ' - :. . ..
1;~7~4;31 19~19/US-2730 OH
R NH
NH
OH C = O
[~--CH2--N -- X
I ~ R
` ` (II) OH OH OH
+ NH2 X -- NH2 ~ CH2 -- NH -- X -- NH -- CH
` ~ 2 ~J + 2CH20 , - 2H20 . R R R
. ~ + 2 OCN - Y
OH OH
. ~
FIELD OF INVENTION
The invention is directed to a process for producing paint binders curable with resols and to the binders made by the process which are particularly well suited for the formulation of top grade electrodeposition primers for cathodic electrodeposition (CED-primers).
BACKGROUND OF INVENTION
Commonly assigned U.S. Patent No. 4,568,709, corresponding in part to AT-PS 378 537, discloses a process for the preparation of cathodically depositable paint binders based on modified epoxy resins. According to the disclosed process, an epoxy resin is .reacted with a primary amine and the resulting adduct, carrying secondary amine groups, is reacted with a phenol and formaldehyde. If a sufficient excess of formaldehyde is used, the binders are self-crosslinking as a result of the resol constitution. In a special embodiment, as described in the aforesaid U.S. Patent No. 4,568,709 and disclosed in Canadian Application No. 476,617 filed March 15, 1985, the phenol can be totally or partly replaced by aminoalkylation products of phenols to give better solubility to the products, which means that the quantity of acid necessary for achieving water-dilutability is reduced; and, moreover, additional flexibilizing and leveling enhancing groups are introduced into the binder molecule.
Although the known products when used as paint binders, particularly in the formulation of cathodically depositable 7 ~ ~3 1 elecrodeposition paints (CED-paints), give excellent results, such binders are unsatisfactory for special uses where particularly high standards with regard to adhesion, particularly to a subsequent coat of paint, is required.
It is recognized in the art that the incorporation of amide, urethane, or urea groups to the binders will improve the - adhesion properties of the binder. However, the addition of such groups leads to the reduction of the quality of other properties such as corrosion resistance and resistance to water and solvents.
This invention relates to a process for producing cathodically depositable electrodeposition paint binders comprising reacting cvmponents A and B, component A being a modified epoxy compound obtained by reacting an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available expoxy group to provide an epoxy resin-amino adduct having an epoxy value of substantially zero;
and component B being an aminoalkylation product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a : product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B being such that for each mole of NH-groups ~b ' ~
7~431 on component A, 0.5 to 1 mole of component B are used to provide a reaction produc~ upon partial or total neutralization with acids which is dilutable with water.
This invention further relates to cathodically depositable electrodepositi~n paint binders comprising the reaction product of components A and B, component A being a modified epoxy compound obtained by reacting an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available epoxy group to provide an epoxy resin-aminO adduct having an epoxy value of substantially zero;
and component B being an aminoal]cylation product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partlal or total neutralization with acids which is dilutable with water.
It has now been found that the products obtained according to the teaching of U.S. Patent No. 4,568,709, can be Substantially improved in their adhesion characteristics without negative influences on - 3a -...,~
~1 ~7~4;~1 I S - ~. 7 3 0 other properties if the phenols used in the reaction are phe-nol condensates carrying urea groups.
Accordingly, the invention is directed to a process ~- for producing urea group containing resol-curable paint bin-:~: 5 ders based on resol-modified epoxy resin-amine adducts charac-terized in that an aminoalkylation product of a monosubsti-tuted mono- or dinuclear phenol, a primary monoamine, and/or diamine and formaldehyde is utilized as the phenolic component for the reaction with the epoxy amine adduct and formaldehyde wherein the amino-hydrogens of the aminoalkylation product have been reacted in the presence of an aprotic solvent at 30 to 50C with mono- and/or diisocyanate compounds to form a product with a maximum oE four, and preferably two, phenolic hydroxyl groups. Through the reaction of the amino-hydrogens with the isocyanate groups, urea groups are formed essential for the properties of the final products.
The invention is also directed to the paint binders made by the presently disclosed process and to the use of the binders in paint systems r particularly CED-systems.
The aminoalkylation products carrying the urea groups used in the process of the present invention are obtained through reaction of mono- or po~ynuclear phenols with primary ,. : ,' .. ~ . . .". :
, ~ , . ' , ~ ;~794;~
lt' 'l9/US-2730 amines and formaldehyde, and subsequent reaction of the amino-hydrogens with isocyanate compounds. In the schematic reac-tion schemes set forth hereinbelow, the reaction is presented for a simple example where scheme I shows the reaction with a ~ 5 primary monoamine, whereas in scheme II a primary diamine is - ~ used. Radicals X, Y, and R of the schemes are radicals evi-dent from the list of starting materials.
The reaction schemes are as follows:
.
( I ) OH OH
~ [~OE12 -- NH -- X
- CH2 -- NH -- X + OCN~NCO
' ~
.
~ ` S
' .
: '', . ' ' - :. . ..
1;~7~4;31 19~19/US-2730 OH
R NH
NH
OH C = O
[~--CH2--N -- X
I ~ R
` ` (II) OH OH OH
+ NH2 X -- NH2 ~ CH2 -- NH -- X -- NH -- CH
` ~ 2 ~J + 2CH20 , - 2H20 . R R R
. ~ + 2 OCN - Y
OH OH
. ~
2 ~) R NH NEI R
Y ' Y
,, , .
.
. , ,:
~794;~1 l~i9/US-2730 -In order to avoid gelation, in both cases isocyanates with a functionality corresponding to the phenol/amine/formal-dehyde product must be used. Further, the aminoalkylation product should not carry more than an average of four phenolic hydroxyl groups. The preferred products carry two phenolic hydroxyl groups. There is a possibility of overlap between the two forms as will be apparent to one skilled in the art.
Suitable phenols for the process are all phenols with more than one formaldehyde-reactive site. For achieving a sufficient crosslinking density for self-crosslinking products, the aminoalkylation products should also carry at least two formaldehyde-reactive sites. In addition to simple phenol, alkyl phenols, such as the butyl phenols and their homologues, diphenols and diphenylolalkanes such as bis-(4-hydroxyphenyl)-methane or 2,2-bis-(4-hydroxyphenyl)-propane can be used.
Suitable primary amines for use according to the pro-cess are the alkyl amines, preferably the higher homologues with four or more C-atoms, and alkanolamines such as mono- -ethanolamine and its homologues~ For the simultaneous intro-duction of basic groups in the form of tertiary amine groups, preferably dialkylaminoalkylamines, such as dimethylaminopro-pylamine and the like, are used. The primary diamines pre-.~ , .
~ :' 19~9/~S-2730 ferably are the alkylenediamines, such as ethylenediamine and its homologues.
Formaldehyde can be used in any of the commercially available forms, and preferably is a solution of paraformalde-hyde with a CH2O-content of more than 90~.
According to the reaction schemes as above set forth, when using primary monoamines, diisocyanates are preferably used such as toluylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyan-ate, and the like; or the reaction products of diols withdiisocyanates in a mole ratio of 1 : 2. If primary diamines are used for the aminoalkylation, monoisocyanates are prefer-ably used such as phenylisocyanate or semi-blocked diisocyan-ates.
The preparation of the intermediates of the inven - tion, as shown in the reaction schemes, is carried out in a first step through joint reaction of a phenol~ an amine and formaldehyde, at 80 to 130C, the reaction water being removed azeotropically with an entraining agent. The further reaction with the isocyanate compound is carried ou$ at 30 to 50C, .
preferably in the presence of an aprotic solvent, the iso-~-~ cyanate compound being added in portions while cooling, until an NCO-value of zero is attained.
.
,' ~ . . .
.
~79~1 19~9/~S-2730 The further reaction of the intermediate products with the modified epoxy resins is carried out as described in ~J.S. Patent No. 4,568,709. In accordance with the procedure set forth therein, the epoxy resin amine adducts are reacted S with the intermediate of the invention and formaldehyde at 50 to 90C until the formaldehyde has reacted completely. For each mole o NH-groups on the epoxy resin amine adduct, 0.5 to 1 mole of the intermediate are used. Further, if portions of other phenols or aminoalkylated phenols are optionally em-ployed, for each mole of formaldehyde-reactive site on the phenol compound 0.4 to 0.9 mole of formaldehyde are used.
, In the preparation of the epoxy resin amine adducts, ` the epoxy resins are reacted in the presence of an aprotic solvent~ with a primary amine to give an epoxy resin amine adduct carrying secondary amino groups. For each available epoxy group on the epoxy resin, 0.6 to 1.0 mole of primary amino groups are used. The amines are primary monoalkyl-amines, preferably those with an alkyl radical with four or more C-atoms, or primary alkylene diamines or diamines which~
: 20 carry a tertiary amino group in addition to the primary amino group such as a dialkyamino group. The preferred amines are ' n- or isobutyl amine, hexyl amines, 2-ethylamine, ethylene diamine and its homologues and primary-tertiary diamines, such , ~ . ~,~ ' . .
_g_ ,' ~ ~ ' :: ' '' ' '' :
':
~;~7~4~ .
19~'~9/US-2730 as dimethylaminopropylamine, diethylaminopropylamine and the homologues of this series. Especially preferred are mixtures of alkyl amines and alkylene diamines with dialkylaminoalkyl-amines~ The reaction is carried out at 50 to 90C.
:
Suitable solvents which in some cases are useful for the reaction are the aromatic hydrocarbons such as toluol or xylol, or diethyleneglycol dimethylether. The quantity of solvent lies between 10 and 50~! calculated on the epoxy resin amine adduct.
, The epoxy resin amine adduct may optionally be modi-fied to contain up ko 40 mole-%, calculated on the available epoxy groups, with carboxy compounds such as the saturated or unsatura~ed fatty acids, carboxy group containing polyester resins or corresponding pre-polymers such as polymers based on the acrylics or acrylates. Other effective modifiers are the secondary amines, particularly secondary alkyl amines. The tertiary amino groups provided by reaction of the secondary amine will influence the solubility of the system. The reac-. .
~ tion is carried to an epoxy value of practically zero, meaning : .
that the resulting epoxy amino adducts are free from epoxy groups.
The epoxy resins su;table for the process of the pre-sent invention are the commercially available di~ or polyepoxy ~ ~? ~ 0 '.~ ' ' ~;~7~34;~
compounds, such as those obtained through reaction of poly-nuclear phenols, particularly bisphenol A, i.e., 2,2-bis(4-hydroxyphenyl)-propane or phenol novolaks and epichlorohydrin.
Optionally, other epoxy resins such as those based on polyols can be used. Products of this type are known to one skilled in the art and are described in the literature. The epoxy resins preferred ~or the present process are based on bisphe-nol A or phenol novolaks and epichlorohydrin with an epoxy equivalent weight of ~rom about 180 to 1000.
To obtain water-dilutability, the basic groups of the reaction product are partially or totally neutralized with acids, preferably formic acid, acetic acid, or lactic acid.
For the dilutability needed in formulating paints, it is suf-ficient to neutralize between about 10 to 40% of the basic groups or use a quantity of about 20 to 60 millimoles acid per 100 g resin solids. The binders are diluted with deionized water to the desired concentration. Optionally, prior to neutralization or dilution or in the partially diluted con-dition~ the binders are combined with pigments, extenders, and other paint additives to provide pigmented paints. The for-mulation of such paints and their application in the electro-deposition process are known to one skilled in the art and are described in the literature.
' ~:~irl --1 1-- ' 79~
When the binders of this invention are used as pri-mers, the deposited films are cured at 150 to 170C for 10 to 30 minutes. If the binders do not have a sufficient degree of self-crosslinking structure, additional crosslinking agents such as blocked isocyanates, amino resins, or phenolic resins can be coemployed. With suitable adjustment to the formula-tion, the products can also be applied by other methods, such as dipping, roller coating, or spraying. Optionally, the bin-ders can be processed in organic solventsO
; 10 The ~ollowing examples illustrate the invention with-out limiting the scope thereof. Parts and percentages refer to weight unless otherwise stated.
The following abbreviations are used in the examples:
BPA..... Bisphenol A
BPF..... Bisphenol F
DEAPA... Diethylaminopropylamine DEGM.... Diethyleneglycol dimethylether DGDE~... Diethyleneglycol diethylether DODAM... Dodecane diamine EGL..... Ethyleneglycol monoethylether EHA..... 2-Ethylhexylamine EHX..... 2-Ethylhexanol :
.~
~ '',~`'`' ~
~;~79~
19~9/~S-2730 B-180.... A liquid polybutadiene oil (about 75% 1,4-cis, about 24%, 1,4-trans, and about 1% vinyl configuration; molecular weight about 1500 +
15%; iodine number 450 g/1000 g) EPH I... ..Diepoxy resin based on the reaction of bisphenol A with epichlorohydrin (epoxy equivalent weight about 190) EPH II.. ..Diepoxy resin based on bisphenol A with epi-chlorohydrin (epoxy equivalent weight about 475 HEMA.... ~. Hydroxyethyl methacrylate HMDA.... ..Hexamethylene diamine HMDI.... ..Hexamethylene diisocyanate IBA..... ..Isobutylamine IPDI.... ..Isophorone diisocyanate M I..... ..TDI semi-blocked with EHX
M II.... ..Reaction product of 1 mole IPDI and l mole EGL
M III.... Reactlon product of l mole TDI and l mole HEMA
MIBK.... ..Methylisobutyl ketone MIPA.... ..Monoisopropanol amine MOL~.... ..Monoethanol amine MSA..... ..Maleic acid anhydride `~ NPH..... ..Nonyl phenol (commercially available) - ~ PF 91... ..Paraformaldehyde (91% CH2O) PH...... ..Phenol PPD..... ..Reaction product of l mole polypropylene glycol ; (molecular weight about 600~ and 2 moles TDI to `~ provide the monoisocyanate ; PME..... ..Propyleneglycol monomethylether .
.
79~3~
19~9/US-2730 TsP~..... p-tert.-butylphenol TDI. .... Toluylene diisocyanate X........ Xylol Val.~.... Equivalent weight in grams for the designated functional group and, accordingly, is equivalent `~ to groups Preparation Of The Urea Group Carrying Inter-mediates Used In The Process Of The Invention A reaction vessel is equipped with a water separator, cooler, thermometer, and stirrer. The amine and the phenol are added to the vessel and heated to 70C and paraformalde- ~
hyde is added in portions, the temperature resulting from the exothermic reaction being controlled so as not to surpass 80C. The reaction water is removed with an entraining agent having a boiling range of from 80 to 130C, such as a special ; benzine. The reaction is carried until the theoretical quan-tity of reaction water has separated. The entraining agent is vacuum stripped, and the product is diluted with an aprotic solvent. The reaction is continued at 30 to 50C while adding the isocyanate in portions until an NCO-value of zero is ob-` tained. Weight ratios and reaction conditions are listed in Table 1 as followss ~ ~ .
: '.
, ~.~7~4~
s~ $ ~ o ~o r- ~ o ~_ I_ ci~ a~ Lr~ ~ c~ , ", ~r ul u~ Ln u~ u~ u~
v h ~ l l l l l l ~ In O ~) Ir~ 0~ ~) . ~ _ ~ _~ ~ ~ ~ ~
: I_ a ~ o o o o o o o H H t~ H H æ
~3 H ~ ~ ~ H H H ~
~ O 0~ 00 ~ CO O C~
.C r-l U~ O ~1 O ~ d' ~J N ~1 ~O ~) ~C) ~`1 cn 1:: ~ d~ D~ dP dP d~ dP
H a)-- Ul O Lr) Il~) O O ~ U~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ C ' ~. ~ ~ ~ ..
m . ~ _ Q~ 'O O O O O O O
~ ~ ~ :~ ~ ~ ~ _, ~ ~i C~ o ., ~ ~ O
. .~ ~ ~ ~ ~9 ~ ~ U7 ~D ~ O
:
. ~ ~ ~ ~ ~ ~ _ ~ ~ _ ~ ~ O O O O O O~ O
~ o ~ ~ ~ ~ _, ~ ~ ~, ~
~ ~ C ~ ~ ~ ~ ~ ~ ~ ~
O (`1 OC~ ~00 O ~0 0 U~ o - ~ ~ ~_ _ ~ ~ ~ _~ ~ ~P~
., ._~ o o o o O oo o ~ _ _ _ _ _ __ _ .~
,~ ~ C~ U~ ~ t~ o ~o ~ U~
.
~1 ~`d ~ ~ U~ ~ I_ : :
: ' 7~3~3~
/u~-~130 Preparation of the Epoxy Resin Amine Adducts A-l to A-5 ~sed in the Examples Adduct A-l: A reaction vessel is equipped with a thermom-eter, stirrer, and reflux condensor. 190 parts EPH I (1 Val) are dissolved in 132 parts toluol in the vessel and heated to 60C. Then a blend of 59 parts DEAPA (0.45 mole) and 58 parts EHA (0.45 mole) are slowly added, the reaction temperature being held at 75 to 80C, with cooling if necessary. The tem-` perature is held until an epoxy value of practically zero is , obtained. The adduct solution can be ~urther processed with-out modification. The adduct contains 0.8 mole NH-groups based on resin solids.
. . .
Adduct ~-2: Using the conditions of A-l, a solution of 475 parts EPH II (1 Val) in 254 parts toluol is reacted with 59 parts DEAPA and 58 parts EHA leach 0.45 mole). The product contains 0.8 mole NH-groups based on resin solids.
Adduct A-3: Using the conditions of A-l, a solution of 760 parts EPH I (4 Val~ in 362 parts toluol is reacted with 260 parts DEAP~ (2 moles) and 114 parts HMDA (1 mole). The prpduct contains 4.0 moles NH-groups in 1134 9 resin solids.
Adduct A-4: 700 parts B-180 are reacted in known manner ; in the presence of 0.05 parts diphenylparaphenylene diamine .
,;;, "
~ 16 .
.
.. . .
~.' 794;~
19~9/~S-2730 (inhibitor) at 200C with 100 parts MSA until the MSA has reacted completely. After cooling to 100C, 130 parts ÉHX are added and esterfied at 120~C until the theoretical acid value of the semiester is reached t~5AD-A). 110 parts MAD-A (corres-,~ 5 ponding to about 0.12 COOH-groups) are reacted with 212 parts EPH I in 80~ solution in DEGM at 120C to an acid value of practically zero. After addition of 108 parts DEGM, 59 part~
DEAPA (0.45 mole) and 59 parts EHA (0.45 mole), the batch is reacted at 65 - 70C to an epoxy value of practically zero.
.~
Examples 1 to 7 .. . . .
According to the weight ratios listed in Table 2, the epoxy resin amine adducts are reacted with the intermediates according to Table 1 and, optionally, with a,further phenol compound and with formaldehyde at 60 to 80C until the content of free formaldehyde is below 0.3% (calculated on the formal-dehyde used).
The resin is mixed with the listed quantity of acid and dispersed in water. The solids content of the resulting dispersion is listed in Table 2 as follows:
., ~
:
'~ -17-.
.~7943~
o C~ o L~ o o o .,1 . ~D U~ ~ ~ U~ ~D
~, ~ ~ ~ ~ ~ ~ ~
'o o O O O U~ O Lr~ O
~--1 C h ~ ~S~ ~ ~r ~ ~r eJ~
~) ~
~ U~ Lr~ Lt') O Lr) O L~') ~'. ,~ u~ ~ _ ~ ~ ~ ~
._ a) u~ Lr) r~ ~ ~ O
~ ~ _ _ _ _ _ N
;. ~ ~ u~ Lfl ~ ~ a~ o .~ l~ ~r d' ~ -1 ~ ~D ~1 . ~ .
:, r- ~ U~ _~ _ ~ _ _ ~ ,_ .~ ~ l ~ a) ~ l ~ ~ ~ d1 ~ ul ," ~ ~1 ' ~ ~ O O O ri O O O
m L~ ~ ~ ~! ~ ~ ~ ~ i~i ~!
E~ ~ ~ ,~ l oo ~r o ~ ~ o ~ P~ a~ ~D ~ CO a~ c~
-:' U~ ~ .
. a)~ ~ ~ ~ ô ~ er ~o o o o ~ o o o 3.
.
~_ ~ ~ ~ ~ o ~ ~ ~ U~ ô ~ ~ ~ ~ ~ o ~
o~ P~ ~ ~ r- Ln~ ~ L ~1 ~ ~ ~ ~ ~ ~ r-l ~
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,:' o o o ~r o o o . ~ ~ ~ ~r ~ _ I J~ U~ ~ ~ O O ~ ~ O O 0~ O ~-~
~-~1 ~ ~ ~ u~ ~ c h u~ ~ _ _ _ _ _ _ _ . ~ a~
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`'';`~'',~' L~ ~ ~ ~ cr U~ ~D r~
:
~ ~7~4;~
1 9 ~-. 9/11S-27 3~) EVALUATION OF THE sINDERs ; PROD~CED ACCORDING TO THE INVENTION
Paints were prepared using the binders made according . to Examples 1 to 7 according to the following formulation:
-80 parts coloring paste (see below3 75 parts resin (100%) according to Examples 1-7 used as an aqueous dispersion (See Table 2) Deionized water was used for dilution of the formulation to 18% resin solids.
The paints were cathodically deposited to zinc phos-phated steel panels at conditions giving a dry film thickness of 20 ~ 2Jum and cured at the temperature listed in Table 2 for 30 minutes. In all cases, in the salt spray resistance test ASTM B-117-64/ with a test duration of 700 hours, the : 15 cross incision shows corrosion of less than 2 mm~ In the hu-midity chamber (100~ relative air humidity at 50C~ the coat-ings are unaffected after 500 hours. Testing of the solvent resistance according to the MEK-RubTest gives more than 100 double rubs in all cases.
20 The coloring paste has the following composition:
100 parts milling resin (100%) : 1 parts carbon black : ~ 12 parts basic lead silicate ; 14i parts titanium dioxide `'~ -19-:
.
.
~79fl;~
19~ S-~7~0 The milling resin is prepared as follows: 500 parts of an epoxy resin based on bisphenol A (epoxy equivalent weight about 500) are dissolved in 214 parts PME and, at 110C, are reacted with 83 parts of a semiester of phthalic acid anhydride and EHX in the presence of 0.5 g triethylamine as catalyst to an acid value of below 3 mg KOH/g. Then, 120 parts of an NH-functional oxazolidine of aminoethylethanol-amine, 2-ethylhexylacrylate and formaldehyde, and 26 parts DEAPA are added, and the batch is held at 80C to react to an epoxy value of practically zero, The batch is diluted with 200 parts propyleneglycol monomethylether and partially neu-tralized with 97 parts 3~N formic acid. The resulting solids content is 58.8~.
As will be apparent to one skilled in the art, var-ious modifications can be made within the scope of the afore-said 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.
,, ~ ' ~
,~ .
~ : -20-` ~ ' . ' .
Y ' Y
,, , .
.
. , ,:
~794;~1 l~i9/US-2730 -In order to avoid gelation, in both cases isocyanates with a functionality corresponding to the phenol/amine/formal-dehyde product must be used. Further, the aminoalkylation product should not carry more than an average of four phenolic hydroxyl groups. The preferred products carry two phenolic hydroxyl groups. There is a possibility of overlap between the two forms as will be apparent to one skilled in the art.
Suitable phenols for the process are all phenols with more than one formaldehyde-reactive site. For achieving a sufficient crosslinking density for self-crosslinking products, the aminoalkylation products should also carry at least two formaldehyde-reactive sites. In addition to simple phenol, alkyl phenols, such as the butyl phenols and their homologues, diphenols and diphenylolalkanes such as bis-(4-hydroxyphenyl)-methane or 2,2-bis-(4-hydroxyphenyl)-propane can be used.
Suitable primary amines for use according to the pro-cess are the alkyl amines, preferably the higher homologues with four or more C-atoms, and alkanolamines such as mono- -ethanolamine and its homologues~ For the simultaneous intro-duction of basic groups in the form of tertiary amine groups, preferably dialkylaminoalkylamines, such as dimethylaminopro-pylamine and the like, are used. The primary diamines pre-.~ , .
~ :' 19~9/~S-2730 ferably are the alkylenediamines, such as ethylenediamine and its homologues.
Formaldehyde can be used in any of the commercially available forms, and preferably is a solution of paraformalde-hyde with a CH2O-content of more than 90~.
According to the reaction schemes as above set forth, when using primary monoamines, diisocyanates are preferably used such as toluylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyan-ate, and the like; or the reaction products of diols withdiisocyanates in a mole ratio of 1 : 2. If primary diamines are used for the aminoalkylation, monoisocyanates are prefer-ably used such as phenylisocyanate or semi-blocked diisocyan-ates.
The preparation of the intermediates of the inven - tion, as shown in the reaction schemes, is carried out in a first step through joint reaction of a phenol~ an amine and formaldehyde, at 80 to 130C, the reaction water being removed azeotropically with an entraining agent. The further reaction with the isocyanate compound is carried ou$ at 30 to 50C, .
preferably in the presence of an aprotic solvent, the iso-~-~ cyanate compound being added in portions while cooling, until an NCO-value of zero is attained.
.
,' ~ . . .
.
~79~1 19~9/~S-2730 The further reaction of the intermediate products with the modified epoxy resins is carried out as described in ~J.S. Patent No. 4,568,709. In accordance with the procedure set forth therein, the epoxy resin amine adducts are reacted S with the intermediate of the invention and formaldehyde at 50 to 90C until the formaldehyde has reacted completely. For each mole o NH-groups on the epoxy resin amine adduct, 0.5 to 1 mole of the intermediate are used. Further, if portions of other phenols or aminoalkylated phenols are optionally em-ployed, for each mole of formaldehyde-reactive site on the phenol compound 0.4 to 0.9 mole of formaldehyde are used.
, In the preparation of the epoxy resin amine adducts, ` the epoxy resins are reacted in the presence of an aprotic solvent~ with a primary amine to give an epoxy resin amine adduct carrying secondary amino groups. For each available epoxy group on the epoxy resin, 0.6 to 1.0 mole of primary amino groups are used. The amines are primary monoalkyl-amines, preferably those with an alkyl radical with four or more C-atoms, or primary alkylene diamines or diamines which~
: 20 carry a tertiary amino group in addition to the primary amino group such as a dialkyamino group. The preferred amines are ' n- or isobutyl amine, hexyl amines, 2-ethylamine, ethylene diamine and its homologues and primary-tertiary diamines, such , ~ . ~,~ ' . .
_g_ ,' ~ ~ ' :: ' '' ' '' :
':
~;~7~4~ .
19~'~9/US-2730 as dimethylaminopropylamine, diethylaminopropylamine and the homologues of this series. Especially preferred are mixtures of alkyl amines and alkylene diamines with dialkylaminoalkyl-amines~ The reaction is carried out at 50 to 90C.
:
Suitable solvents which in some cases are useful for the reaction are the aromatic hydrocarbons such as toluol or xylol, or diethyleneglycol dimethylether. The quantity of solvent lies between 10 and 50~! calculated on the epoxy resin amine adduct.
, The epoxy resin amine adduct may optionally be modi-fied to contain up ko 40 mole-%, calculated on the available epoxy groups, with carboxy compounds such as the saturated or unsatura~ed fatty acids, carboxy group containing polyester resins or corresponding pre-polymers such as polymers based on the acrylics or acrylates. Other effective modifiers are the secondary amines, particularly secondary alkyl amines. The tertiary amino groups provided by reaction of the secondary amine will influence the solubility of the system. The reac-. .
~ tion is carried to an epoxy value of practically zero, meaning : .
that the resulting epoxy amino adducts are free from epoxy groups.
The epoxy resins su;table for the process of the pre-sent invention are the commercially available di~ or polyepoxy ~ ~? ~ 0 '.~ ' ' ~;~7~34;~
compounds, such as those obtained through reaction of poly-nuclear phenols, particularly bisphenol A, i.e., 2,2-bis(4-hydroxyphenyl)-propane or phenol novolaks and epichlorohydrin.
Optionally, other epoxy resins such as those based on polyols can be used. Products of this type are known to one skilled in the art and are described in the literature. The epoxy resins preferred ~or the present process are based on bisphe-nol A or phenol novolaks and epichlorohydrin with an epoxy equivalent weight of ~rom about 180 to 1000.
To obtain water-dilutability, the basic groups of the reaction product are partially or totally neutralized with acids, preferably formic acid, acetic acid, or lactic acid.
For the dilutability needed in formulating paints, it is suf-ficient to neutralize between about 10 to 40% of the basic groups or use a quantity of about 20 to 60 millimoles acid per 100 g resin solids. The binders are diluted with deionized water to the desired concentration. Optionally, prior to neutralization or dilution or in the partially diluted con-dition~ the binders are combined with pigments, extenders, and other paint additives to provide pigmented paints. The for-mulation of such paints and their application in the electro-deposition process are known to one skilled in the art and are described in the literature.
' ~:~irl --1 1-- ' 79~
When the binders of this invention are used as pri-mers, the deposited films are cured at 150 to 170C for 10 to 30 minutes. If the binders do not have a sufficient degree of self-crosslinking structure, additional crosslinking agents such as blocked isocyanates, amino resins, or phenolic resins can be coemployed. With suitable adjustment to the formula-tion, the products can also be applied by other methods, such as dipping, roller coating, or spraying. Optionally, the bin-ders can be processed in organic solventsO
; 10 The ~ollowing examples illustrate the invention with-out limiting the scope thereof. Parts and percentages refer to weight unless otherwise stated.
The following abbreviations are used in the examples:
BPA..... Bisphenol A
BPF..... Bisphenol F
DEAPA... Diethylaminopropylamine DEGM.... Diethyleneglycol dimethylether DGDE~... Diethyleneglycol diethylether DODAM... Dodecane diamine EGL..... Ethyleneglycol monoethylether EHA..... 2-Ethylhexylamine EHX..... 2-Ethylhexanol :
.~
~ '',~`'`' ~
~;~79~
19~9/~S-2730 B-180.... A liquid polybutadiene oil (about 75% 1,4-cis, about 24%, 1,4-trans, and about 1% vinyl configuration; molecular weight about 1500 +
15%; iodine number 450 g/1000 g) EPH I... ..Diepoxy resin based on the reaction of bisphenol A with epichlorohydrin (epoxy equivalent weight about 190) EPH II.. ..Diepoxy resin based on bisphenol A with epi-chlorohydrin (epoxy equivalent weight about 475 HEMA.... ~. Hydroxyethyl methacrylate HMDA.... ..Hexamethylene diamine HMDI.... ..Hexamethylene diisocyanate IBA..... ..Isobutylamine IPDI.... ..Isophorone diisocyanate M I..... ..TDI semi-blocked with EHX
M II.... ..Reaction product of 1 mole IPDI and l mole EGL
M III.... Reactlon product of l mole TDI and l mole HEMA
MIBK.... ..Methylisobutyl ketone MIPA.... ..Monoisopropanol amine MOL~.... ..Monoethanol amine MSA..... ..Maleic acid anhydride `~ NPH..... ..Nonyl phenol (commercially available) - ~ PF 91... ..Paraformaldehyde (91% CH2O) PH...... ..Phenol PPD..... ..Reaction product of l mole polypropylene glycol ; (molecular weight about 600~ and 2 moles TDI to `~ provide the monoisocyanate ; PME..... ..Propyleneglycol monomethylether .
.
79~3~
19~9/US-2730 TsP~..... p-tert.-butylphenol TDI. .... Toluylene diisocyanate X........ Xylol Val.~.... Equivalent weight in grams for the designated functional group and, accordingly, is equivalent `~ to groups Preparation Of The Urea Group Carrying Inter-mediates Used In The Process Of The Invention A reaction vessel is equipped with a water separator, cooler, thermometer, and stirrer. The amine and the phenol are added to the vessel and heated to 70C and paraformalde- ~
hyde is added in portions, the temperature resulting from the exothermic reaction being controlled so as not to surpass 80C. The reaction water is removed with an entraining agent having a boiling range of from 80 to 130C, such as a special ; benzine. The reaction is carried until the theoretical quan-tity of reaction water has separated. The entraining agent is vacuum stripped, and the product is diluted with an aprotic solvent. The reaction is continued at 30 to 50C while adding the isocyanate in portions until an NCO-value of zero is ob-` tained. Weight ratios and reaction conditions are listed in Table 1 as followss ~ ~ .
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s~ $ ~ o ~o r- ~ o ~_ I_ ci~ a~ Lr~ ~ c~ , ", ~r ul u~ Ln u~ u~ u~
v h ~ l l l l l l ~ In O ~) Ir~ 0~ ~) . ~ _ ~ _~ ~ ~ ~ ~
: I_ a ~ o o o o o o o H H t~ H H æ
~3 H ~ ~ ~ H H H ~
~ O 0~ 00 ~ CO O C~
.C r-l U~ O ~1 O ~ d' ~J N ~1 ~O ~) ~C) ~`1 cn 1:: ~ d~ D~ dP dP d~ dP
H a)-- Ul O Lr) Il~) O O ~ U~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ C ' ~. ~ ~ ~ ..
m . ~ _ Q~ 'O O O O O O O
~ ~ ~ :~ ~ ~ ~ _, ~ ~i C~ o ., ~ ~ O
. .~ ~ ~ ~ ~9 ~ ~ U7 ~D ~ O
:
. ~ ~ ~ ~ ~ ~ _ ~ ~ _ ~ ~ O O O O O O~ O
~ o ~ ~ ~ ~ _, ~ ~ ~, ~
~ ~ C ~ ~ ~ ~ ~ ~ ~ ~
O (`1 OC~ ~00 O ~0 0 U~ o - ~ ~ ~_ _ ~ ~ ~ _~ ~ ~P~
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,~ ~ C~ U~ ~ t~ o ~o ~ U~
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/u~-~130 Preparation of the Epoxy Resin Amine Adducts A-l to A-5 ~sed in the Examples Adduct A-l: A reaction vessel is equipped with a thermom-eter, stirrer, and reflux condensor. 190 parts EPH I (1 Val) are dissolved in 132 parts toluol in the vessel and heated to 60C. Then a blend of 59 parts DEAPA (0.45 mole) and 58 parts EHA (0.45 mole) are slowly added, the reaction temperature being held at 75 to 80C, with cooling if necessary. The tem-` perature is held until an epoxy value of practically zero is , obtained. The adduct solution can be ~urther processed with-out modification. The adduct contains 0.8 mole NH-groups based on resin solids.
. . .
Adduct ~-2: Using the conditions of A-l, a solution of 475 parts EPH II (1 Val) in 254 parts toluol is reacted with 59 parts DEAPA and 58 parts EHA leach 0.45 mole). The product contains 0.8 mole NH-groups based on resin solids.
Adduct A-3: Using the conditions of A-l, a solution of 760 parts EPH I (4 Val~ in 362 parts toluol is reacted with 260 parts DEAP~ (2 moles) and 114 parts HMDA (1 mole). The prpduct contains 4.0 moles NH-groups in 1134 9 resin solids.
Adduct A-4: 700 parts B-180 are reacted in known manner ; in the presence of 0.05 parts diphenylparaphenylene diamine .
,;;, "
~ 16 .
.
.. . .
~.' 794;~
19~9/~S-2730 (inhibitor) at 200C with 100 parts MSA until the MSA has reacted completely. After cooling to 100C, 130 parts ÉHX are added and esterfied at 120~C until the theoretical acid value of the semiester is reached t~5AD-A). 110 parts MAD-A (corres-,~ 5 ponding to about 0.12 COOH-groups) are reacted with 212 parts EPH I in 80~ solution in DEGM at 120C to an acid value of practically zero. After addition of 108 parts DEGM, 59 part~
DEAPA (0.45 mole) and 59 parts EHA (0.45 mole), the batch is reacted at 65 - 70C to an epoxy value of practically zero.
.~
Examples 1 to 7 .. . . .
According to the weight ratios listed in Table 2, the epoxy resin amine adducts are reacted with the intermediates according to Table 1 and, optionally, with a,further phenol compound and with formaldehyde at 60 to 80C until the content of free formaldehyde is below 0.3% (calculated on the formal-dehyde used).
The resin is mixed with the listed quantity of acid and dispersed in water. The solids content of the resulting dispersion is listed in Table 2 as follows:
., ~
:
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.~7943~
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~ U~ Lr~ Lt') O Lr) O L~') ~'. ,~ u~ ~ _ ~ ~ ~ ~
._ a) u~ Lr) r~ ~ ~ O
~ ~ _ _ _ _ _ N
;. ~ ~ u~ Lfl ~ ~ a~ o .~ l~ ~r d' ~ -1 ~ ~D ~1 . ~ .
:, r- ~ U~ _~ _ ~ _ _ ~ ,_ .~ ~ l ~ a) ~ l ~ ~ ~ d1 ~ ul ," ~ ~1 ' ~ ~ O O O ri O O O
m L~ ~ ~ ~! ~ ~ ~ ~ i~i ~!
E~ ~ ~ ,~ l oo ~r o ~ ~ o ~ P~ a~ ~D ~ CO a~ c~
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.
~_ ~ ~ ~ ~ o ~ ~ ~ U~ ô ~ ~ ~ ~ ~ o ~
o~ P~ ~ ~ r- Ln~ ~ L ~1 ~ ~ ~ ~ ~ ~ r-l ~
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,:' o o o ~r o o o . ~ ~ ~ ~r ~ _ I J~ U~ ~ ~ O O ~ ~ O O 0~ O ~-~
~-~1 ~ ~ ~ u~ ~ c h u~ ~ _ _ _ _ _ _ _ . ~ a~
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`'';`~'',~' L~ ~ ~ ~ cr U~ ~D r~
:
~ ~7~4;~
1 9 ~-. 9/11S-27 3~) EVALUATION OF THE sINDERs ; PROD~CED ACCORDING TO THE INVENTION
Paints were prepared using the binders made according . to Examples 1 to 7 according to the following formulation:
-80 parts coloring paste (see below3 75 parts resin (100%) according to Examples 1-7 used as an aqueous dispersion (See Table 2) Deionized water was used for dilution of the formulation to 18% resin solids.
The paints were cathodically deposited to zinc phos-phated steel panels at conditions giving a dry film thickness of 20 ~ 2Jum and cured at the temperature listed in Table 2 for 30 minutes. In all cases, in the salt spray resistance test ASTM B-117-64/ with a test duration of 700 hours, the : 15 cross incision shows corrosion of less than 2 mm~ In the hu-midity chamber (100~ relative air humidity at 50C~ the coat-ings are unaffected after 500 hours. Testing of the solvent resistance according to the MEK-RubTest gives more than 100 double rubs in all cases.
20 The coloring paste has the following composition:
100 parts milling resin (100%) : 1 parts carbon black : ~ 12 parts basic lead silicate ; 14i parts titanium dioxide `'~ -19-:
.
.
~79fl;~
19~ S-~7~0 The milling resin is prepared as follows: 500 parts of an epoxy resin based on bisphenol A (epoxy equivalent weight about 500) are dissolved in 214 parts PME and, at 110C, are reacted with 83 parts of a semiester of phthalic acid anhydride and EHX in the presence of 0.5 g triethylamine as catalyst to an acid value of below 3 mg KOH/g. Then, 120 parts of an NH-functional oxazolidine of aminoethylethanol-amine, 2-ethylhexylacrylate and formaldehyde, and 26 parts DEAPA are added, and the batch is held at 80C to react to an epoxy value of practically zero, The batch is diluted with 200 parts propyleneglycol monomethylether and partially neu-tralized with 97 parts 3~N formic acid. The resulting solids content is 58.8~.
As will be apparent to one skilled in the art, var-ious modifications can be made within the scope of the afore-said 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.
,, ~ ' ~
,~ .
~ : -20-` ~ ' . ' .
Claims (15)
1. Process for producing cathodically depositable electrodeposition paint binders comprising reacting components A and B, component A being a modified epoxy compound obtained by reacting an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available epoxy group to provide an epoxy resin-amino adduct having an epoxy value of substantially zero; and component B being an aminoalkyla-tion product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a product with a maximum of four phanolic hydroxyl groups; the ratio of components A and B
being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partial or total neutralization with acids which is dilutable with water.
being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partial or total neutralization with acids which is dilutable with water.
2. The process according to claim 1 wherein the said phenol compound is a mono- or polynuclear phenol.
3. The process according to claim 1 wherein the said phenol compound has two phenolic hydroxyl groups.
4. The process according to claim 2 wherein said mono- or polynuclear phenol is substituted with an alkyl group.
5. The process according to claim 2 wherein the amine of the aminoalkylation product is a primary monoalkyl-amine with at least four carbon atoms.
6. The process according to claim 1 wherein the epoxy resin is based on bisphenol A or a phenol novolak.
7. The process according to claim 1 wherein the amine of the epoxy resin amino adduct is a blend of primary monoalkylamines and primary alkylene diamines.
8. The process according to claim 1 wherein the reaction of the epoxy groups with the amines is carried out at 50 to 90°C.
9. Cathodically depositable electrodeposition paint binders comprising the reaction product of components A and B, component A being a modified epoxy compound obtained by react-ing an epoxy resin having at least two epoxy groups and having an epoxy equivalent weight of from about 180 to 1000, with 0.6 to 1.0 mole of primary amino groups on a primary monoalkyl amine or a primary alkylene diamine or a primary-tertiary alkylene diamine per each.
available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available epoxy group to provide an epoxy resin-amino adduct having an epoxy value of substantially zero; and component B being an aminoalkyla-tion product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B
being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partial or total neutralization with acids which is dilutable with water.
available epoxy group and 0 to 0.4 mole of a carboxylic compound or a secondary amine per each available epoxy group to provide an epoxy resin-amino adduct having an epoxy value of substantially zero; and component B being an aminoalkyla-tion product of a phenol compound, a primary mono- or diamine and formaldehyde, the amino-hydrogens thereof having been reacted in the presence of an aprotic solvent with a mono- or diisocyanate compound to provide a product with a maximum of four phenolic hydroxyl groups; the ratio of components A and B
being such that for each mole of NH-groups on component A, 0.5 to 1 mole of component B are used to provide a reaction product upon partial or total neutralization with acids which is dilutable with water.
10. The binder according to claim 9 wherein the said phenol compound is a mono- or polynuclear phenol.
11. The binder according to claim 9 wherein the said phenol compound has two phenolic hydroxyl groups.
12. The binder according to claim 10 wherein said mono- or polynuclear phenol is substituted with an alkyl group.
13. The binder according to claim 10 wherein the amine of the aminoalkylation product is a primary monoalkyl-amine with at least four carbon atoms.
14. The binder according to claim 9 wherein the epoxy resin is based on bisphenol A or a phenol novolak.
15. The binder according to claim 9 wherein the amine of the epoxy resin-amino adduct is a blend of primary mono-alkylamines and primary alkylene diamines.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT233185A AT382633B (en) | 1985-08-09 | 1985-08-09 | METHOD FOR PRODUCING RESOL curable paint binders containing urea groups |
| ATA2331/85 | 1985-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1279431C true CA1279431C (en) | 1991-01-22 |
Family
ID=3532368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000515551A Expired - Lifetime CA1279431C (en) | 1985-08-09 | 1986-08-08 | Process for producing urea group containing resol-curable paint binders |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0214442B1 (en) |
| AT (1) | AT382633B (en) |
| CA (1) | CA1279431C (en) |
| DE (1) | DE3675477D1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT387974B (en) * | 1987-04-17 | 1989-04-10 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF SELF-CROSSING CATIONIC LACQUERS CONTAINING BIURET GROUPS AND THE USE THEREOF |
| DE20210502U1 (en) * | 2002-07-06 | 2003-11-20 | Braun Melsungen Ag | Peristaltic peristaltic pump |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3963663A (en) * | 1974-04-26 | 1976-06-15 | Desoto, Inc. | Electrodeposition of thermosetting coatings at the cathode |
| DE2711385A1 (en) * | 1977-03-16 | 1978-09-21 | Basf Ag | CATHODICALLY SEPARABLE ELECTRO-DIP PAINT BINDING AGENT |
| DE3311516A1 (en) * | 1983-03-30 | 1984-10-04 | Basf Farben + Fasern Ag, 2000 Hamburg | HEAT-CURABLE COATING AGENTS AND THEIR USE |
-
1985
- 1985-08-09 AT AT233185A patent/AT382633B/en not_active IP Right Cessation
-
1986
- 1986-07-30 DE DE8686110498T patent/DE3675477D1/en not_active Expired - Fee Related
- 1986-07-30 EP EP19860110498 patent/EP0214442B1/en not_active Expired - Lifetime
- 1986-08-08 CA CA000515551A patent/CA1279431C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATA233185A (en) | 1986-08-15 |
| EP0214442A3 (en) | 1988-02-24 |
| EP0214442B1 (en) | 1990-11-07 |
| DE3675477D1 (en) | 1990-12-13 |
| EP0214442A2 (en) | 1987-03-18 |
| AT382633B (en) | 1987-03-25 |
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