CA1283994C - Process for the preparation of cationic coating compositions - Google Patents
Process for the preparation of cationic coating compositionsInfo
- Publication number
- CA1283994C CA1283994C CA000538717A CA538717A CA1283994C CA 1283994 C CA1283994 C CA 1283994C CA 000538717 A CA000538717 A CA 000538717A CA 538717 A CA538717 A CA 538717A CA 1283994 C CA1283994 C CA 1283994C
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- CA
- Canada
- Prior art keywords
- epoxy
- polyglycidyl ether
- ether
- process according
- blend
- 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.)
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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
-
- 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
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1444—Monoalcohols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- 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
Abstract
A B S T R A C T
PROCESS FOR CATIONIC COATING COMPOSITIONS
A process for the preparation of water-thinnable, hydrolytically stable, thermosetting, cationic coating compositions, which comprises blending:
1) 5-35 %w of a carboxylated crosslinking compound, and 2) 65-95 %w of an amino group-containing resin binder, which binder comprises the reaction product of a) ammonia, and b) a blend of b1) a polyglycidyl ether having n epoxy groups per molecule, wherein 1<n<1.9, said polyglycidyl ether being the reaction product of a multifunctional polyglycidyl ether having x epoxy groups per molecule, wherein x>2, and (x-n) mol of a monofunct-ional phenol per mol of the multifunctional polyglycidyl ether, and b2) a diglycidyl ether having an epoxy group concentration in the range of from 1 to 5.5 the average molar epoxy functionality of the glycidyl ethers, present in the blend of polyglycidyl ether and diglycidyl ethers, being <1.75.
and wherein 1) and 2) are blended before or after neutral-ization of 2).
PROCESS FOR CATIONIC COATING COMPOSITIONS
A process for the preparation of water-thinnable, hydrolytically stable, thermosetting, cationic coating compositions, which comprises blending:
1) 5-35 %w of a carboxylated crosslinking compound, and 2) 65-95 %w of an amino group-containing resin binder, which binder comprises the reaction product of a) ammonia, and b) a blend of b1) a polyglycidyl ether having n epoxy groups per molecule, wherein 1<n<1.9, said polyglycidyl ether being the reaction product of a multifunctional polyglycidyl ether having x epoxy groups per molecule, wherein x>2, and (x-n) mol of a monofunct-ional phenol per mol of the multifunctional polyglycidyl ether, and b2) a diglycidyl ether having an epoxy group concentration in the range of from 1 to 5.5 the average molar epoxy functionality of the glycidyl ethers, present in the blend of polyglycidyl ether and diglycidyl ethers, being <1.75.
and wherein 1) and 2) are blended before or after neutral-ization of 2).
Description
~2~33~
T 1~4 PROCESS FO~ CATIONIC COATING COMPOSITIONS
This invention relates to a process for the preparation of hydrolytically stable cationic coating compositions, to the coating compositions prepared by said process and to the use thereof, particularly to their use as aqueous thermosetting coating compositions for application via electrodeposition.
In European Patent Application EP 0127915 aqueous thermosetting coating compositions have been disclosed, based on polyaddition products of defunctionàl;zed multifunc-tional polyglycidyl ethers, diglycidyl ethers and selected i0 amino group-containing compounds. Such defunctionalized polyglycidyl ethers are those having on average n epoxy groups per molecule, wherein l~n<2. They comprise the reaction products of multifunctional polyglycidyl ethers having on average x epoxy groups per molecule, wherein x>2, and (x-n) mol of a monofunctional phenol per mol of multifunc-tional polyglycidyl ether. The coating compositions, based on combinations of these polyaddition products with cocurring resins, when applied by electrodeposition and after stoving yield coatings which have very good flow and flexibility properties as well as a good resistance to sterilization.
This combination of performance properties makes them very suitable for use as the internal lining of cans for many different applications. However when used as the internal coating of cans for applications where taste performance requirements are very critical, such as in certain beverage cans, some of these coatings failed to pass the most severe taste performance tests. Thus the taste performance properties of such coatings leaves room for further improvement.
Therefore the problem underlying the present invention is the improvement of the taste performance properties of these coatings based on the cationic coating compositions, whilst maintaining the high level of the other performance properties.
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To solve this problem, the applicant now proposes to replace, in said cationic coating compositions, the herein-before mentioned amino compound based polyadditions products, by a novel amino group-containing polyaddition product.
The invention provides therefore a process for the preparation of a water-thinnable, hydrolytically stable, thermosetting, cationic coating composition, which comprises blending:
1) 5-35 %w of a carboxylated crosslinking compound, and 2) 65-95 ~w of an amino group-containing resin binder, which binder comprises the reaction product of a) ammonia, and b) a blend of bl) a polyglycidyl ether having n epoxy groups per molecule, wherein l<n<l.9, said polyglycidyl ether being the reaction product of a multifunctional polyglycidyl ether having x epoxy group per molecule, wherein x>2, and (x-n) mol of a monofunc-tional phenol per mol of the multifunctional poly-glycidyl ether, and b2) a diglycidyl ether, having an Epoxy Group Concen-tration in the range of from 1.0 to 5.5, the average molar epoxy functionality of the glycidyl ethers present in the blend of polyglycidyl ether and diglycidyl ether being <1.75.
and wherein 1) and 2) are blended before or after neutral-ization of 2).
The term Epoxy Group Concentration (EGC) as used in this Specification stands for the e~uation EGC = 103 eq. kg~l, in EE
which EE is the epoxy equivalent weight, in g. eq~l, calculated in accordance with I sostandard method 3001-1~7~E).
The multifunctional polyglycidyl ether from which the polyglycidyl ether having n epoxy groups per molecule is .
derived, may conveniently be a polyglycidyl ether prepared by reaction of a polyhydric phenol having a phenolic hydroxyl functionality greater than 2, with an epihalodrin, preferably epichlorohydrin, in the presence of a hydrogen halide S acceptor, e.g. an alkali metal hydroxide.
Examples of suitable such polyhydric phenols are novolac resins of general formula H H H
(- ~ O ':
wherein R represents an alkylene, e.g. CH2 group, Rl represents an alkyl group, e.g. a methyl, p-t-butyl, octyl or nonyl group, q and p are numbers having average values O<q<6 and O<p<2, or of general formula H H H
R2 o R2 o H H H
q wherein R2 represents an alkylene, e g. CH2 group, R3 .. . . .
. ~ ..
`
.
', ' , . .
represents an alkylene, e.g. CH2 or C(CH3)2 group, a carbonyl group, a~ oxygen or sulphur atom and q' is a number having an average value in the range of from 0 to 2.
3ther examples of suitable polyhyd~ic polynuclear phenols are 1,1-2 2-tetra(4-hydroxyphenyl)ethane and the tetra-phenol derived -from diphenolic acid having the general formula H H
O O
CH3C-CH2-CH2Co-R4-CoCH2-CH2-C-CH3 (III) O O
H H
wherein R4 represents the residue of a diol. Polyglycidyl ethers derived from polyhydric phenols of formulae I, II and III are known and are described, together with processes for their preparation, in, for example, US Patent 2,844,553, British Patent Application 2,070,020, W. German Patent Application 2,656,867 and British Patent Application 2,001,991.
Preferably the multifunctional polyglycidyl ether is an epoxy novolac resin wherein x is in -the range from 2.5 to 3.5.
The monofunctional phenol may be a single phenol or a mixture of phenols. For example the phenol may conveniently be phenol optionally substituted by one or more o-f one or more sub-stituents selected from C1_16 alkyl, C3_16 alkenyl, Cl_4 hydroxy-.
: ': ' ' ' .: ~ - . . .
;~ . .
- 4a - 63293~2809 alkyl, C2_13 alkoxycarbonyl and C1_16 alkoxy groups. Examples of such compounds include phenol, the c.resols, salicyl alcohol, 2-allyl phenol 2,4,6-triallyl phenol, dimethyl phenol, 4-hydroxymethyl-2,6 dimethyl --: ~ , . .
~' " ' ' . ' ' ' ~':
T 1~4 PROCESS FO~ CATIONIC COATING COMPOSITIONS
This invention relates to a process for the preparation of hydrolytically stable cationic coating compositions, to the coating compositions prepared by said process and to the use thereof, particularly to their use as aqueous thermosetting coating compositions for application via electrodeposition.
In European Patent Application EP 0127915 aqueous thermosetting coating compositions have been disclosed, based on polyaddition products of defunctionàl;zed multifunc-tional polyglycidyl ethers, diglycidyl ethers and selected i0 amino group-containing compounds. Such defunctionalized polyglycidyl ethers are those having on average n epoxy groups per molecule, wherein l~n<2. They comprise the reaction products of multifunctional polyglycidyl ethers having on average x epoxy groups per molecule, wherein x>2, and (x-n) mol of a monofunctional phenol per mol of multifunc-tional polyglycidyl ether. The coating compositions, based on combinations of these polyaddition products with cocurring resins, when applied by electrodeposition and after stoving yield coatings which have very good flow and flexibility properties as well as a good resistance to sterilization.
This combination of performance properties makes them very suitable for use as the internal lining of cans for many different applications. However when used as the internal coating of cans for applications where taste performance requirements are very critical, such as in certain beverage cans, some of these coatings failed to pass the most severe taste performance tests. Thus the taste performance properties of such coatings leaves room for further improvement.
Therefore the problem underlying the present invention is the improvement of the taste performance properties of these coatings based on the cationic coating compositions, whilst maintaining the high level of the other performance properties.
~ ~ .
.
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To solve this problem, the applicant now proposes to replace, in said cationic coating compositions, the herein-before mentioned amino compound based polyadditions products, by a novel amino group-containing polyaddition product.
The invention provides therefore a process for the preparation of a water-thinnable, hydrolytically stable, thermosetting, cationic coating composition, which comprises blending:
1) 5-35 %w of a carboxylated crosslinking compound, and 2) 65-95 ~w of an amino group-containing resin binder, which binder comprises the reaction product of a) ammonia, and b) a blend of bl) a polyglycidyl ether having n epoxy groups per molecule, wherein l<n<l.9, said polyglycidyl ether being the reaction product of a multifunctional polyglycidyl ether having x epoxy group per molecule, wherein x>2, and (x-n) mol of a monofunc-tional phenol per mol of the multifunctional poly-glycidyl ether, and b2) a diglycidyl ether, having an Epoxy Group Concen-tration in the range of from 1.0 to 5.5, the average molar epoxy functionality of the glycidyl ethers present in the blend of polyglycidyl ether and diglycidyl ether being <1.75.
and wherein 1) and 2) are blended before or after neutral-ization of 2).
The term Epoxy Group Concentration (EGC) as used in this Specification stands for the e~uation EGC = 103 eq. kg~l, in EE
which EE is the epoxy equivalent weight, in g. eq~l, calculated in accordance with I sostandard method 3001-1~7~E).
The multifunctional polyglycidyl ether from which the polyglycidyl ether having n epoxy groups per molecule is .
derived, may conveniently be a polyglycidyl ether prepared by reaction of a polyhydric phenol having a phenolic hydroxyl functionality greater than 2, with an epihalodrin, preferably epichlorohydrin, in the presence of a hydrogen halide S acceptor, e.g. an alkali metal hydroxide.
Examples of suitable such polyhydric phenols are novolac resins of general formula H H H
(- ~ O ':
wherein R represents an alkylene, e.g. CH2 group, Rl represents an alkyl group, e.g. a methyl, p-t-butyl, octyl or nonyl group, q and p are numbers having average values O<q<6 and O<p<2, or of general formula H H H
R2 o R2 o H H H
q wherein R2 represents an alkylene, e g. CH2 group, R3 .. . . .
. ~ ..
`
.
', ' , . .
represents an alkylene, e.g. CH2 or C(CH3)2 group, a carbonyl group, a~ oxygen or sulphur atom and q' is a number having an average value in the range of from 0 to 2.
3ther examples of suitable polyhyd~ic polynuclear phenols are 1,1-2 2-tetra(4-hydroxyphenyl)ethane and the tetra-phenol derived -from diphenolic acid having the general formula H H
O O
CH3C-CH2-CH2Co-R4-CoCH2-CH2-C-CH3 (III) O O
H H
wherein R4 represents the residue of a diol. Polyglycidyl ethers derived from polyhydric phenols of formulae I, II and III are known and are described, together with processes for their preparation, in, for example, US Patent 2,844,553, British Patent Application 2,070,020, W. German Patent Application 2,656,867 and British Patent Application 2,001,991.
Preferably the multifunctional polyglycidyl ether is an epoxy novolac resin wherein x is in -the range from 2.5 to 3.5.
The monofunctional phenol may be a single phenol or a mixture of phenols. For example the phenol may conveniently be phenol optionally substituted by one or more o-f one or more sub-stituents selected from C1_16 alkyl, C3_16 alkenyl, Cl_4 hydroxy-.
: ': ' ' ' .: ~ - . . .
;~ . .
- 4a - 63293~2809 alkyl, C2_13 alkoxycarbonyl and C1_16 alkoxy groups. Examples of such compounds include phenol, the c.resols, salicyl alcohol, 2-allyl phenol 2,4,6-triallyl phenol, dimethyl phenol, 4-hydroxymethyl-2,6 dimethyl --: ~ , . .
~' " ' ' . ' ' ' ~':
3~
phenol, 2-hydroxyphenethyl alcohol, 4-hydroxybenzyl alcohol and ethyl 4-hydroxybenzoate. Preferably the monofunctional phenol i8 phenol substituted in the para-position by a C4_12 alkyl substituent. ~xamples of such alkyl substituents include n-, iso- and t-butyl, n- and iso-octyl, n-and iso-nonyl and n-and iso-dodecyl groups. Branched alkyl substituents are particularly suitable. P-iso-octyl phenol has been found to be a very suitable monofunctional phenol.
The diglycidyl ether will generally be a diglycidyl ether of a dihydric phenol such as 2,2-bis(4-hydroxyphenyl)-propane. Examples of diglycidyl ethers based on such a dihydric phenol are "EPIKOTE lO01" (registered trade mark) (EGC 2000 to 2220) and "EPIKOTE 3003" (registered trade mark) (EGC 1~10 to 1380). Preferred diglycidyl ethers have a EGC
in the range of from 1.8 to 2.4.
The reaction beeween ammonia and epoxy groups is known.
This reaction i5 hereinafter referred to as amidation. From British Patent Specification 1221906 it can be concluded that with the amidation of diglycidyl ethers, the content of secondary and tertiary amino groups present in the reaction product, is related to the excess of ammonia over epoxy used. A smaller excess will increase the content of secondary and tertiary amino groups as well as the molecular weight of the reaction product and the risk of gelation.
It can be expected that the presence of such higher molecular weight polyaddition products will contribute positively towards the performance of the ultimate coating.
Although it might be possible to prepare such higher molecular weight reaction products by carefully controlled process conditions, in the process of the present invention it has been found advantageous to reduce the omnipresent risk of gelation by restricting the average number of epoxy groups per molecule of glycidyl ether. For the polyglycidyl ether the average molar epoxy functionality is restricted to , .
~ . .. . . . .
,~ ' . .
, - . : .
~ ' , ' . .
.~ :
1<n<1.9 preferably 1.3<n<1.6, while the average molar epoxy functionality for the glycidyl ethers present in the blend of polyglycidyl ethers and diglycidyl ether is set at <1.75.
It is preferred that the polyglycidyl ether and diglycidyl ethers are present in said blend in a weight ratio in the range of from 75:25 to 45:55.
In the preparation of the hereinbefore mentioned amino group-containing binders, it is preferred that on average 0.45 to 0.6 mol of ammonia is reacted per equivalent of epoxy, for which at least 4.5 equivalents of amino-hydrogen per equivalent of epoxy is generally employed.
In the preparation of the amino group-containing binders, the blend of the polyglycidyl ether and diglycidyl ether may conveniently be contacted with ammonia while dissolved in an organic solvent. Preferably said solvent is a water-miscible solvent and includes mono Cl_6 alkyl ethers of mono- or polyethylene glycol or mono- or polypropylene glycol, and cyclic ethers such as tetrahydrofuran (THF) or dioxane. A
preferred water-miscible solvent is 2-n-butoxyethanol.
The glycidyl ether content of these solutions may conveniently be in the range of from 50 to 90 %w and preferably in the range of from 60 to 70 %w. Ammonia may be introduced into the reactor as supplied e.g. as a 25 %w aqueous solution.
The resulting mixture will generally be inhomogeneous and may as such be used for preparing the amino group containing binder. It has however proven to be advantageous to carry out the amidation in the presence of one or more solvents, which when present in a sufficient concentration will convert the reactor contents into a more or less homogeneous mixture.
Suitable such solvents include lower alcohols such as methanol and ethanol as well as lower ethers, especially ~ cyclic ethers such as THF and dioxane. Very promising results ; have been obtained with a ~:1 w/w blend of THF and ethanol.
~ The amidation is carried out at a temperature in the .
"~. ` : '. ` ' : ' . ' . ~: . ` ` -range of from 20 to 120C and at atmospheric or slightly above atmospheric pressure. It is believed that the amino group-containing resin binders as prepared by the method as hereinbefore described are novel compounds.
The carboxylated crosslinking compound may be a carboxy-lated melamine-, urea- or phenolformaldehyde resin and is preferably a carboxylated melamine formaldehyde type resin.
Cymel 1141 (trade mark) is such a carboxylated melamine formaldehyde resin. The carboxylated crosslinking compound is preferably present in a ratio of amino group-containing resin binder to carboxylated crosslinking compound of ~5:15 to 75:25 (w/w).
Pigments, fillers, dispersing agents, and other components known in the art of paint formulation may further be added.
Addition of small amounts (up to 1 %w) of non-ionic surfactant may be useful for further stabilization of aqueous composi-tions or improvement of the wetting during application.
Co-solvents, such as 2-n-butoxyethanol and, especially, 2-n-hexyloxyethanol, may advantageously be included. The water for use in the aqueous compositions is preferably purified, such as by distillation or demineralization.
The water-dilutable compositions may be applied by a variety of methods known in the art, onto a variety of substrates, in particular metals such as bare steel, phosphated steel, chromate-treated steel~ zinc tin plate (for can coating), and aluminium (also e.g. for can coating), to produce cured coatings of desireable thickness, from 2 micrometres upwards up to in general 40 micrometres.
Curing of the coating compositions made according to the process of the present invention can be performed by stoving, for example, at temperatures of from 170 to 220DC, with curing times varying form 3 to 20 minutes.
The thermosetting coating compositions may generally be applied by electrodeposition and other methods such as :
. . . -.
' . . ` ' - :
. ' ~ -. ~ .
~3~L
spraying or dipping, and are particularly suitable for coating cans by electrodeposition.
The invention will be further understood from the following examples, in which parts and percentages are by weight, unless otherwise indicated, and various terms are defined as follows:
Polyether I is a multifunctional epoxy diphenylolpropane novolac resin, having an average molecular weight 615 and on average 3.1 epoxy groups per molecule.
Polyether II is a multifunctional epoxy diphenylolpropane novolac resinJ having an average molecular weight 660 and on average 3.3 epoxy groups per molecule.
Polyether III is a multifunctional epoxy novolac resin, having an average molecular weight 665 and on average 3.5 epoxy groups per molecule.
Polyether IV is a multifunctional epoxy novolac resin3 having an average molecular weight 732 and on average 3.5 epoxy groups per molecule.
Polyether E-l is a solid diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having an EGC of 2.13.
Polyether E-2 is a solid diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having an EGC of 2.04.
Polyether E-3 is a solid diglycidyl ether of 2 2-bis(4-hydroxyphenyl)propane having an EGC of 2.06.
CYMEL 1141 (trade mark) is a highly alkylated melamine-formaldehyde curing resin containing methoxy and isobutoxy substituents and acidic chelating groups, 85% w solids in isobutanol, and having an acid value of 22 + 3 mg KOH/g.
"Amine value" is expressed in milli-equivalents (amino) nitrogen per gram.
"Ep fav": average epoxy functionality.
Polyglycidyl ether preparation Four different polyglycidyl ethers were prepared by heating a multifunctional polyether and a monofunctional -: ~
-':' :. ~ ' ' :, . . . .
~ .
.
; . --, phenol with stirring to 140C, whereupon tetramethylammonillm chloride (TMAC~ was added as a 50% solution in water. The reactor contents were maintained at 140 C until the reaction had been completed, i.e. the calculated EGC had been obtained.
AEter a slight cooling 2-n-butoxyethanol was added to arrive at a solution eontaining 66.7 %w solids. Process details and product characteristics are given in Table 1.
Y~
v ~ I _, I c~i ~a 0 ?I l ,~
?l l :1 ~I I
~0 w I u~
1~ ~, I _ _ ~ _ I
l ~ ~ ~ l l ~1 i ~ l o o U~ o C~
ll ~ e _ I I I
rd I . .
E~ I g ~ ' ~ ~
~ l W O I
~ C ~ ~ ~ V - -~ ~ o 1-~ O u~ O
V
o P~ V
' ~ l ~ l ~
0~) h ~ ~ l l r l I
P~
- - , ~ : ., :
.
~ : , : , '. " .
~ , : . : . ~. ' . . .
~L2~33~
~V
Preparation of amino group-containing resin binders ,__ The binders were prepared according the following procedure:
An amount of a Polyether solution, 66.7 ~w in 2-n-butoxyethanol, corresponding with 1.5 eq epoxy, an amount of diglycidyl ether E-l or E-2 corresponding with 1.5 eq epoxy and additional 2-n-butoxyethanol were homogenized by heating to 90C with stirring. After cooling to 25~C a 25 ~w aqueous solution of ammonia was added in an amount as indicated hereinafter together with a suf~icient amount of a ~/1 w/w blend of THF/ethanol to arrive at a clear "solution". Thereupon the temperature of the reactor contents was gradually raised to about 60 C in approximately 6 hours during which period virtually all the epoxy groups had reacted. Subsequently the temperature in the reactor was increased to 120 CJ in as short a time as was possible, and maintained at that tempera-ture to remove excess ammonia, water, THF and ethanol by distillation using a nitrogen purge. The ammonia removal was checked with the aid of a vet paper-pH-indicator.
Process details and product characteristics are given in Table 2.
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Preparation of 2-amino-2-methyl-1-propanol based amino-_ group containing binder A 95% aqueous solution of 2-amino-2-methyl-1-propanol (154.6 g, 1.65 mol), water (40 g) and 2-n-butoxyethanol (100 g) were heated with stirring to 100 C. To the resulting mixture was added a homogeneous mixture of Polyglycidyl ether 4 (1638 g; 66.7~ solids; 1.5 epoxy equivalents~ polyether E-3 (727.5 g, 1.5 epoxy equivalents) and 2-n-butoxyethanol (197 g), over a period of 2 hours, with stirring, while the temperature was maintained at 100 to 110 C. After the addition was complete, the mixture was kept at 100 to 120 C with stirring for a further 8 hours, until reaction was complete (amine value 0.84 on solids). The resulting product had a 15 solids content of 68.8 %w while the viscosity at 25 C of the 40 %w solution in 2-n-butoxyethanol was 1.8 Pa.s.
Examples VI-VIII
Preparation of aqueous lacquers for electrodeposition The 2-n-butoxyethanol solutions of the amino group-containing resin binders as prepared in examples I IV and V were blended respectively with the appropriate amounts of Cymel 1141 and 2-n-hexyloxyethanol, neutralized with lactic acid and finally diluted with demineralized water to arrive at lacquers having a solids content of ]5 ~DW. l`he quantities of each of the components used are given in Table 3 together with the characteristics of the lacquers thus prepared.
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Table 3 ___________ ____________________.________________________ ___________ Example VI VII VIII
_______._________________________.__________________________________ Binder solution from Ex. I IV V
Binder solution g 1000 ~57 1000 Cymel 1141 208 176.5176.5 2-n-hexyloxyethanol g 61 178 60 Lactic acid (90 %w) g 39 41 41 Demineralized water g 39293747.5 3722.5 Lacquer characteristics Binder/cocuring resin ratio 77.5/22.5 80/20 80/20 Degree of neutralization 0.67 0.75 0.75 pH 5.5 5.04.9 Conductivity ms 700 634 -Comparative Example B
Preparation of_a~ueous lacquer for electrodeposition The adduct of comparative Example A (321.6 g), "CYMEL 1141"
(60 g) and 2-n-hexyloxyethanol (61.2 g) were mixed together at ambient temperature (20 C). The resulting homogeneous mixture was neutralized with 90 %w lactic acid in water (12.5 g, = 0.7) and thinned with demineralized water (2267.4 g).
The resulting coating composition had a solids content of 10 70w, pH 4.2 and conductivity 650 s/cm at 20C.
Examples IX-XI
Cathodic electrodeposition The lacquers as prepared in examples VI-VIII were used to coat 330 ml tin-plate cans (2-piece DWI cans) by cathodic electrodeposition. The can formed the cathode of an electro-depositon cell, the anode being a stainless steel memberinserted within the can at a substantially uniform separation of 2 millimetres from the can. A potential difference of 100 120V, which resulted after baking in a coating weight per , . . . . : .
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can in the range of 200-250 mg, corresponding with an average dry film thickness in the range of 5 to 6 m, was applied between the can and the anode for 1-2 seconds. After removal from the electrodeposition cell, the coated can was vigorously rinsed with demineralized water and the coating was cured by stoving for 5 minutes at 200C.
After curing and measuring the weight of the coating, the porosity was tested by using a WAC0 ~AMEL RATER (ex Wilkens-Anderson Co. USA). The principle of this method is that when a potential difference (6.2V) is applied between the can filled with an electrolytic solution and an electrode inserted in said electrolytic solution, a current will pass between the electrode and the inner surface of the can only if the coating has insufficient insulating power, i.e. when the film contains pores. Hence the current measured is a yard stick for the film quality. A current < 0.6 mA is con-sidered to correspond with a non porous film.
Results are given in Table 4 following, in which solvent resistance is expressed in terms of "MEK rubs", i.e. the number of double rubs with a methylethylketone-moistened cloth necessary to remove the coatings, while the film appearance (flow) is expressed as a numerical rating resulting from a visual assessment (5: smooth surface, excellent flow, no defects, 4: orange-peel type surface, 3: orange-peel type surface and few bubbles and/or pinholes, 2: many bubbles and/or pinholes).
The sterilisation resistance of the coatings was determined by exposure to water at 121C for 90 minutes and rated according to a numerical scale ranging from 5: no blushing to 0: very heavy blushing.
The coatings were tested for taste by a taste panel employing mineral water as the taste sensitive beverage.
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Comparative Example C
Cathodic electrodeposition of aqueous lacquer composition from comparative example B
The aqueous lacquer composition from comparative example B was applied by electrodeposition onto a 330 ml tin-plate can by the same method as for the lacquer compositions from exarnples VI-VIII. The results have been incorporated in Table 4.
The results in Table 4 indicate that the cationic coating compositions, made according to the process of the present invention, are superior in taste perforrnance compared with the ammonia-free based system while simultaneously maintain-ing the high level of other performance properties.
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phenol, 2-hydroxyphenethyl alcohol, 4-hydroxybenzyl alcohol and ethyl 4-hydroxybenzoate. Preferably the monofunctional phenol i8 phenol substituted in the para-position by a C4_12 alkyl substituent. ~xamples of such alkyl substituents include n-, iso- and t-butyl, n- and iso-octyl, n-and iso-nonyl and n-and iso-dodecyl groups. Branched alkyl substituents are particularly suitable. P-iso-octyl phenol has been found to be a very suitable monofunctional phenol.
The diglycidyl ether will generally be a diglycidyl ether of a dihydric phenol such as 2,2-bis(4-hydroxyphenyl)-propane. Examples of diglycidyl ethers based on such a dihydric phenol are "EPIKOTE lO01" (registered trade mark) (EGC 2000 to 2220) and "EPIKOTE 3003" (registered trade mark) (EGC 1~10 to 1380). Preferred diglycidyl ethers have a EGC
in the range of from 1.8 to 2.4.
The reaction beeween ammonia and epoxy groups is known.
This reaction i5 hereinafter referred to as amidation. From British Patent Specification 1221906 it can be concluded that with the amidation of diglycidyl ethers, the content of secondary and tertiary amino groups present in the reaction product, is related to the excess of ammonia over epoxy used. A smaller excess will increase the content of secondary and tertiary amino groups as well as the molecular weight of the reaction product and the risk of gelation.
It can be expected that the presence of such higher molecular weight polyaddition products will contribute positively towards the performance of the ultimate coating.
Although it might be possible to prepare such higher molecular weight reaction products by carefully controlled process conditions, in the process of the present invention it has been found advantageous to reduce the omnipresent risk of gelation by restricting the average number of epoxy groups per molecule of glycidyl ether. For the polyglycidyl ether the average molar epoxy functionality is restricted to , .
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1<n<1.9 preferably 1.3<n<1.6, while the average molar epoxy functionality for the glycidyl ethers present in the blend of polyglycidyl ethers and diglycidyl ether is set at <1.75.
It is preferred that the polyglycidyl ether and diglycidyl ethers are present in said blend in a weight ratio in the range of from 75:25 to 45:55.
In the preparation of the hereinbefore mentioned amino group-containing binders, it is preferred that on average 0.45 to 0.6 mol of ammonia is reacted per equivalent of epoxy, for which at least 4.5 equivalents of amino-hydrogen per equivalent of epoxy is generally employed.
In the preparation of the amino group-containing binders, the blend of the polyglycidyl ether and diglycidyl ether may conveniently be contacted with ammonia while dissolved in an organic solvent. Preferably said solvent is a water-miscible solvent and includes mono Cl_6 alkyl ethers of mono- or polyethylene glycol or mono- or polypropylene glycol, and cyclic ethers such as tetrahydrofuran (THF) or dioxane. A
preferred water-miscible solvent is 2-n-butoxyethanol.
The glycidyl ether content of these solutions may conveniently be in the range of from 50 to 90 %w and preferably in the range of from 60 to 70 %w. Ammonia may be introduced into the reactor as supplied e.g. as a 25 %w aqueous solution.
The resulting mixture will generally be inhomogeneous and may as such be used for preparing the amino group containing binder. It has however proven to be advantageous to carry out the amidation in the presence of one or more solvents, which when present in a sufficient concentration will convert the reactor contents into a more or less homogeneous mixture.
Suitable such solvents include lower alcohols such as methanol and ethanol as well as lower ethers, especially ~ cyclic ethers such as THF and dioxane. Very promising results ; have been obtained with a ~:1 w/w blend of THF and ethanol.
~ The amidation is carried out at a temperature in the .
"~. ` : '. ` ' : ' . ' . ~: . ` ` -range of from 20 to 120C and at atmospheric or slightly above atmospheric pressure. It is believed that the amino group-containing resin binders as prepared by the method as hereinbefore described are novel compounds.
The carboxylated crosslinking compound may be a carboxy-lated melamine-, urea- or phenolformaldehyde resin and is preferably a carboxylated melamine formaldehyde type resin.
Cymel 1141 (trade mark) is such a carboxylated melamine formaldehyde resin. The carboxylated crosslinking compound is preferably present in a ratio of amino group-containing resin binder to carboxylated crosslinking compound of ~5:15 to 75:25 (w/w).
Pigments, fillers, dispersing agents, and other components known in the art of paint formulation may further be added.
Addition of small amounts (up to 1 %w) of non-ionic surfactant may be useful for further stabilization of aqueous composi-tions or improvement of the wetting during application.
Co-solvents, such as 2-n-butoxyethanol and, especially, 2-n-hexyloxyethanol, may advantageously be included. The water for use in the aqueous compositions is preferably purified, such as by distillation or demineralization.
The water-dilutable compositions may be applied by a variety of methods known in the art, onto a variety of substrates, in particular metals such as bare steel, phosphated steel, chromate-treated steel~ zinc tin plate (for can coating), and aluminium (also e.g. for can coating), to produce cured coatings of desireable thickness, from 2 micrometres upwards up to in general 40 micrometres.
Curing of the coating compositions made according to the process of the present invention can be performed by stoving, for example, at temperatures of from 170 to 220DC, with curing times varying form 3 to 20 minutes.
The thermosetting coating compositions may generally be applied by electrodeposition and other methods such as :
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spraying or dipping, and are particularly suitable for coating cans by electrodeposition.
The invention will be further understood from the following examples, in which parts and percentages are by weight, unless otherwise indicated, and various terms are defined as follows:
Polyether I is a multifunctional epoxy diphenylolpropane novolac resin, having an average molecular weight 615 and on average 3.1 epoxy groups per molecule.
Polyether II is a multifunctional epoxy diphenylolpropane novolac resinJ having an average molecular weight 660 and on average 3.3 epoxy groups per molecule.
Polyether III is a multifunctional epoxy novolac resin, having an average molecular weight 665 and on average 3.5 epoxy groups per molecule.
Polyether IV is a multifunctional epoxy novolac resin3 having an average molecular weight 732 and on average 3.5 epoxy groups per molecule.
Polyether E-l is a solid diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having an EGC of 2.13.
Polyether E-2 is a solid diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane having an EGC of 2.04.
Polyether E-3 is a solid diglycidyl ether of 2 2-bis(4-hydroxyphenyl)propane having an EGC of 2.06.
CYMEL 1141 (trade mark) is a highly alkylated melamine-formaldehyde curing resin containing methoxy and isobutoxy substituents and acidic chelating groups, 85% w solids in isobutanol, and having an acid value of 22 + 3 mg KOH/g.
"Amine value" is expressed in milli-equivalents (amino) nitrogen per gram.
"Ep fav": average epoxy functionality.
Polyglycidyl ether preparation Four different polyglycidyl ethers were prepared by heating a multifunctional polyether and a monofunctional -: ~
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; . --, phenol with stirring to 140C, whereupon tetramethylammonillm chloride (TMAC~ was added as a 50% solution in water. The reactor contents were maintained at 140 C until the reaction had been completed, i.e. the calculated EGC had been obtained.
AEter a slight cooling 2-n-butoxyethanol was added to arrive at a solution eontaining 66.7 %w solids. Process details and product characteristics are given in Table 1.
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Preparation of amino group-containing resin binders ,__ The binders were prepared according the following procedure:
An amount of a Polyether solution, 66.7 ~w in 2-n-butoxyethanol, corresponding with 1.5 eq epoxy, an amount of diglycidyl ether E-l or E-2 corresponding with 1.5 eq epoxy and additional 2-n-butoxyethanol were homogenized by heating to 90C with stirring. After cooling to 25~C a 25 ~w aqueous solution of ammonia was added in an amount as indicated hereinafter together with a suf~icient amount of a ~/1 w/w blend of THF/ethanol to arrive at a clear "solution". Thereupon the temperature of the reactor contents was gradually raised to about 60 C in approximately 6 hours during which period virtually all the epoxy groups had reacted. Subsequently the temperature in the reactor was increased to 120 CJ in as short a time as was possible, and maintained at that tempera-ture to remove excess ammonia, water, THF and ethanol by distillation using a nitrogen purge. The ammonia removal was checked with the aid of a vet paper-pH-indicator.
Process details and product characteristics are given in Table 2.
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Preparation of 2-amino-2-methyl-1-propanol based amino-_ group containing binder A 95% aqueous solution of 2-amino-2-methyl-1-propanol (154.6 g, 1.65 mol), water (40 g) and 2-n-butoxyethanol (100 g) were heated with stirring to 100 C. To the resulting mixture was added a homogeneous mixture of Polyglycidyl ether 4 (1638 g; 66.7~ solids; 1.5 epoxy equivalents~ polyether E-3 (727.5 g, 1.5 epoxy equivalents) and 2-n-butoxyethanol (197 g), over a period of 2 hours, with stirring, while the temperature was maintained at 100 to 110 C. After the addition was complete, the mixture was kept at 100 to 120 C with stirring for a further 8 hours, until reaction was complete (amine value 0.84 on solids). The resulting product had a 15 solids content of 68.8 %w while the viscosity at 25 C of the 40 %w solution in 2-n-butoxyethanol was 1.8 Pa.s.
Examples VI-VIII
Preparation of aqueous lacquers for electrodeposition The 2-n-butoxyethanol solutions of the amino group-containing resin binders as prepared in examples I IV and V were blended respectively with the appropriate amounts of Cymel 1141 and 2-n-hexyloxyethanol, neutralized with lactic acid and finally diluted with demineralized water to arrive at lacquers having a solids content of ]5 ~DW. l`he quantities of each of the components used are given in Table 3 together with the characteristics of the lacquers thus prepared.
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Table 3 ___________ ____________________.________________________ ___________ Example VI VII VIII
_______._________________________.__________________________________ Binder solution from Ex. I IV V
Binder solution g 1000 ~57 1000 Cymel 1141 208 176.5176.5 2-n-hexyloxyethanol g 61 178 60 Lactic acid (90 %w) g 39 41 41 Demineralized water g 39293747.5 3722.5 Lacquer characteristics Binder/cocuring resin ratio 77.5/22.5 80/20 80/20 Degree of neutralization 0.67 0.75 0.75 pH 5.5 5.04.9 Conductivity ms 700 634 -Comparative Example B
Preparation of_a~ueous lacquer for electrodeposition The adduct of comparative Example A (321.6 g), "CYMEL 1141"
(60 g) and 2-n-hexyloxyethanol (61.2 g) were mixed together at ambient temperature (20 C). The resulting homogeneous mixture was neutralized with 90 %w lactic acid in water (12.5 g, = 0.7) and thinned with demineralized water (2267.4 g).
The resulting coating composition had a solids content of 10 70w, pH 4.2 and conductivity 650 s/cm at 20C.
Examples IX-XI
Cathodic electrodeposition The lacquers as prepared in examples VI-VIII were used to coat 330 ml tin-plate cans (2-piece DWI cans) by cathodic electrodeposition. The can formed the cathode of an electro-depositon cell, the anode being a stainless steel memberinserted within the can at a substantially uniform separation of 2 millimetres from the can. A potential difference of 100 120V, which resulted after baking in a coating weight per , . . . . : .
:~, ' :: . . ~ : .
can in the range of 200-250 mg, corresponding with an average dry film thickness in the range of 5 to 6 m, was applied between the can and the anode for 1-2 seconds. After removal from the electrodeposition cell, the coated can was vigorously rinsed with demineralized water and the coating was cured by stoving for 5 minutes at 200C.
After curing and measuring the weight of the coating, the porosity was tested by using a WAC0 ~AMEL RATER (ex Wilkens-Anderson Co. USA). The principle of this method is that when a potential difference (6.2V) is applied between the can filled with an electrolytic solution and an electrode inserted in said electrolytic solution, a current will pass between the electrode and the inner surface of the can only if the coating has insufficient insulating power, i.e. when the film contains pores. Hence the current measured is a yard stick for the film quality. A current < 0.6 mA is con-sidered to correspond with a non porous film.
Results are given in Table 4 following, in which solvent resistance is expressed in terms of "MEK rubs", i.e. the number of double rubs with a methylethylketone-moistened cloth necessary to remove the coatings, while the film appearance (flow) is expressed as a numerical rating resulting from a visual assessment (5: smooth surface, excellent flow, no defects, 4: orange-peel type surface, 3: orange-peel type surface and few bubbles and/or pinholes, 2: many bubbles and/or pinholes).
The sterilisation resistance of the coatings was determined by exposure to water at 121C for 90 minutes and rated according to a numerical scale ranging from 5: no blushing to 0: very heavy blushing.
The coatings were tested for taste by a taste panel employing mineral water as the taste sensitive beverage.
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Comparative Example C
Cathodic electrodeposition of aqueous lacquer composition from comparative example B
The aqueous lacquer composition from comparative example B was applied by electrodeposition onto a 330 ml tin-plate can by the same method as for the lacquer compositions from exarnples VI-VIII. The results have been incorporated in Table 4.
The results in Table 4 indicate that the cationic coating compositions, made according to the process of the present invention, are superior in taste perforrnance compared with the ammonia-free based system while simultaneously maintain-ing the high level of other performance properties.
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Claims (8)
1. A process for the preparation of a water-thinnable, hydrolytically stable, thermosetting, cationic coating composi-tion, which comprises blending:
1) 5-35 %w of a carboxylated crosslinking compound, and
1) 5-35 %w of a carboxylated crosslinking compound, and
2) 65-95 %w of an amino group-containing resin binder, which binder comprises the reaction product of a) ammonia, and b) a blend of b1) a polyglycidyl ether having n epoxy groups per molecule, wherein 1<n<1.9, said polyglycidyl ether being the reaction product of a multifunctional polyglycidyl ether having x epoxy groups per mole-cule,wherein x>2, and (x-n)mol of a monofunctional phenol per mol of the multifunctional polyglycidyl ether, and b2) a diglycidyl ether, having an EGC in the range of from 1.0 to 5.5, the average molar epoxy functionality of the glycidyl ethers present in the blend of poly-glycidyl ether and diglycidyl ether being <1.75.
and wherein 1) and 2) are blended before or after neutralization of 2).
2. A process according to claim 1, wherein the multi-functional polyglycidyl ether is an epoxy novolac resin wherein 2.5 < x < 3.5.
and wherein 1) and 2) are blended before or after neutralization of 2).
2. A process according to claim 1, wherein the multi-functional polyglycidyl ether is an epoxy novolac resin wherein 2.5 < x < 3.5.
3. A process according to claim 1, wherein the monofunc-tional phenol is a phenol substituted in the para position by a C4-12 alkyl substituent.
4. A process according to claim 1, 2 or 3, wherein the diglycidyl ether is a diglycidyl ether of 2,2-bis(4-hydroxy-phenyl)propane, having an epoxy group concentration (EGC) in the range of from 1.8 to 2.4.
5. A process according to claim 1, 2 or 3, wherein the polyglycidyl ether and the diglycidyl ether are present in the blend as mentioned under b) in a weight ratio in the range of from 75:25 to 45:55.
6. A process according to claim 1, 2 or 3, wherein the amino group-containing binder is prepared reacting ammonia with blend as mentioned under b) at a temperature in the range of from 20 to 120°C and at atmospheric or slightly above atmospheric pressure.
7. A process according to claim 6, wherein at least 4.5 eq of amino-hydrogen per equivalent of epoxy is employed.
8. A process according to claim 1, 2 or 3, wherein the crosslinking compound and the amino group-containing binder are present in a weight ratio in the range of from 15:85 to 25:75.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868616162A GB8616162D0 (en) | 1986-07-02 | 1986-07-02 | Cationic coating compositions |
| GB8616162 | 1986-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283994C true CA1283994C (en) | 1991-05-07 |
Family
ID=10600462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000538717A Expired - Fee Related CA1283994C (en) | 1986-07-02 | 1987-06-03 | Process for the preparation of cationic coating compositions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4772669A (en) |
| EP (1) | EP0251360B1 (en) |
| JP (1) | JP2525610B2 (en) |
| KR (1) | KR960006083B1 (en) |
| CA (1) | CA1283994C (en) |
| DE (1) | DE3785251T2 (en) |
| ES (1) | ES2053520T3 (en) |
| GB (1) | GB8616162D0 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8621491D0 (en) * | 1986-09-05 | 1986-10-15 | Shell Int Research | Cationic coating compositions |
| DE3909593A1 (en) * | 1989-03-23 | 1990-09-27 | Hoechst Ag | BINDERS, THEIR PRODUCTION AND APPLICATION IN curable mixtures |
| CN1802603A (en) | 2003-07-17 | 2006-07-12 | 霍尼韦尔国际公司 | Planarization films for advanced microelectronic applications and devices and methods of production thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2844553A (en) * | 1953-04-24 | 1958-07-22 | Sherwin Williams Co | Polyhydric phenol-aldehyde-epihalo-hydrin resins |
| AT288025B (en) * | 1967-12-08 | 1971-02-25 | Reichhold Albert Chemie Ag | Process for the preparation of new ammonia and / or amine salts of phenoplasts containing carboxyl groups |
| GB1221906A (en) * | 1968-09-23 | 1971-02-10 | Shell Int Research | Amino-type curing agents for epoxy resins, and their preparation and use |
| IT1051397B (en) * | 1975-12-19 | 1981-04-21 | S I R S P A | PROCESS FOR THE PREPARATION OF EPOXY NOVOLACHE RESINS |
| US4066525A (en) * | 1975-12-22 | 1978-01-03 | Scm Corporation | Cathodic electrocoating process |
| GB2001991B (en) * | 1977-06-30 | 1982-01-06 | Shell Int Research | Preparation of polyglycidyl ethers of polyhydric phenols |
| US4174333A (en) * | 1978-11-02 | 1979-11-13 | Ppg Industries, Inc. | Carboxylated amide polymers and coating compositions containing same |
| DE2914297C2 (en) * | 1979-04-09 | 1981-10-01 | Basf Ag, 6700 Ludwigshafen | Process for the production of polyadducts from ammonia and epoxy compounds and their use |
| JPS56116717A (en) * | 1980-02-20 | 1981-09-12 | Yuka Shell Epoxy Kk | Preparation of novolak-type epoxy resin |
| GB8405139D0 (en) * | 1984-02-28 | 1984-04-04 | Shell Int Research | Binders for thermosetting coating compositions |
| GB8315230D0 (en) * | 1983-06-03 | 1983-07-06 | Shell Int Research | Polyglycidyl ethers |
| DE3475524D1 (en) * | 1983-06-03 | 1989-01-12 | Shell Int Research | Novel polyglycidyl ethers, their preparation and their use as thermosetting coating compositions |
| US4686248A (en) * | 1984-02-28 | 1987-08-11 | Shell Oil Company | Preparation of binders for coatings, thermosetting coating compositions and their use |
| JPS62100520A (en) * | 1985-10-25 | 1987-05-11 | Hitachi Ltd | Epoxy resin composition |
-
1986
- 1986-07-02 GB GB868616162A patent/GB8616162D0/en active Pending
-
1987
- 1987-05-18 DE DE8787200925T patent/DE3785251T2/en not_active Expired - Fee Related
- 1987-05-18 ES ES87200925T patent/ES2053520T3/en not_active Expired - Lifetime
- 1987-05-18 EP EP87200925A patent/EP0251360B1/en not_active Expired - Lifetime
- 1987-06-03 CA CA000538717A patent/CA1283994C/en not_active Expired - Fee Related
- 1987-06-22 US US07/064,475 patent/US4772669A/en not_active Expired - Fee Related
- 1987-06-30 JP JP62161423A patent/JP2525610B2/en not_active Expired - Lifetime
- 1987-06-30 KR KR87006732A patent/KR960006083B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3785251D1 (en) | 1993-05-13 |
| GB8616162D0 (en) | 1986-08-06 |
| JPS6323979A (en) | 1988-02-01 |
| KR880001783A (en) | 1988-04-26 |
| ES2053520T3 (en) | 1994-08-01 |
| EP0251360B1 (en) | 1993-04-07 |
| EP0251360A3 (en) | 1989-10-18 |
| KR960006083B1 (en) | 1996-05-08 |
| JP2525610B2 (en) | 1996-08-21 |
| DE3785251T2 (en) | 1993-07-15 |
| US4772669A (en) | 1988-09-20 |
| EP0251360A2 (en) | 1988-01-07 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |