CA2018574A1 - Liquid coating composition including, as a crosslinking agent, an unblocked monoprimary amine - Google Patents
Liquid coating composition including, as a crosslinking agent, an unblocked monoprimary amineInfo
- Publication number
- CA2018574A1 CA2018574A1 CA002018574A CA2018574A CA2018574A1 CA 2018574 A1 CA2018574 A1 CA 2018574A1 CA 002018574 A CA002018574 A CA 002018574A CA 2018574 A CA2018574 A CA 2018574A CA 2018574 A1 CA2018574 A1 CA 2018574A1
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- CA
- Canada
- Prior art keywords
- alkyl
- group
- binder
- liquid coating
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Materials For Medical Uses (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
ABSTRACT
A liquid coating composition is provided which comprises, as a binder, a compound containing at least two pendant activated unsaturated groups and, as a crosslinking agent For the activated unsaturated groups, a particular unblocked monoprimary amine compound. The liquid coating compositions of the present invention provide the particular advantage of surprisingly good potlife without blocking the crosslinking agent, with the resulting coating compositions displaying good properties such as, for example, solvent resistance.
A liquid coating composition is provided which comprises, as a binder, a compound containing at least two pendant activated unsaturated groups and, as a crosslinking agent For the activated unsaturated groups, a particular unblocked monoprimary amine compound. The liquid coating compositions of the present invention provide the particular advantage of surprisingly good potlife without blocking the crosslinking agent, with the resulting coating compositions displaying good properties such as, for example, solvent resistance.
Description
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Liqui~ Coati~ Co~ )osi~ion InclllclirltJ, as ~I Crossl;nkirlg Agent, an Unblockecl l~lonol)rilllary Al~ e Back~round oF the Inven-tion The present invention relates generally to a liquid coating compositioll whicll comprises, as a binder, a compound containing at least two pendant activated unsaturated yroups and, as a crosslinkiny agent For the activated unsaturated groups of the binder, a particular unblocked nlonoprimary amine.
A coatiny composition comprising, as a binder, a compound containing at least two pendant activated unsaturated groups and an amine crosslinkiny agent is generally known from EP-A-0203296 and EP-A-0346982, which are both incorporated by reference herein for all purposes. The amine crosslinking agent may contain only one primary amino group, but it is taught that this primary amino group must be blocked with, For example, an aldehyde or ke-tone.
As is well-known, the~reactive groups oF crosslinking agents are often blocked to prevent unwanted early reaction and, consequently, decreased potiiFe of the .coatiny compositiorl. Amine crosslinking ayents normally are blocked with, for example, aldehydes and/or ketones The use of such blockiny a~ents can have a number oF disadvantages~
For example, elevate-l temperatures are oFten require(l to unblock the crosslinkiny agents and, particularly for the above blocking agents, water is required to remove the:aldehyde or ketone. With very low relative humidities, therefore, the cross-linkiny reaction can be delayed or proceed only very slowly. Further, once the crosslinkiny ayent is unblocked, the blocking agent must be removed or it will remain in the coating~composition:as ~an ;mpurity. This can lead to the previously applied coatiny, or the coated substrate itselF
~(particularly plastics), beiny attacked.
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Su~ lary o-f the Invention In accordance with the presen-t invention, there is provided a liquid coating coml)os;tion whicll comprises, as a binder, a compouncl containiny at least two pendant activated unsaturated groups and a crosslinkin(J agent -for the activated unsaturated groups of lhe binder, whereill the crosslinking ayent for the activated unsa-tura-ted groups of the binder comprises an unblocked monoprimary amine of the general formula (I) H2N- (CH2 ) n-NRR ' ( I ) wherein n is a number from 1 to ~;
R is selected from an H atom, a Cl-C3 alkyl and a mono hydroxy substituted C1-C3 alkyl; and Rl is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl.
It has been surprisingly discovered that the use of this narrow class oF monopr;mary amines as crosslinking agents allows the formulation of coatings with good solvent resistance as well as good potlife.
Additionally, without the aldehyde and/or ke-tone blockin~ a~ent, the production and use of such coating compos;tions are greatly simpl;fied - not only ls the en-tire step of blockint~ the crossl;nk;n~
a~ent no longer necessary, but also the crossl;nk;ng oF the system becomes in~epen(lent oF relative hu~ni(lity.
These and other features and advantages of the present invention will be more readily understood by those skilled in the ar-t from a reading of the following detailed description.
Detailed Description of the Preferred Embodiments As just indicated, the liquid coating composit ions in accordance with the present invention comprise, as a binder, a compound containing at least two pendant activated unsaturated groups and, as a crosslinking ., ~ , .
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agent -ror such activa-ted unsaturated groups, a particular unblocked monoprilllary amine.
As suitable a-t leas-t two pendant activated unsaturated groups for thebinder may be mentioned ~roups oF the formulas (II), (III), (IV) and/or (V) -OOC-C=CH2 (II) -OOC-CH=CII-COOR3 (III) -ooc-CH2-CI=c~l2 (IV) -OC-r=CH2 (V) COOR3 1~2 ~herein RZ is selected from an H atom or a methyl group, R3 is selected from an H atom, a group R4, a yroup of the formula (VI) and a group of -the formula (VII) -CH(OH)-CH2-CH2Rs (VI) -CH2-CH(OH)-CH2Rs (VII) R3 is selec-ted from an alkyl group, a cycloalkyl yroup and an aryl group, which groups may be substituted or not wi-th an alkyl, and Rs ;s seiected from an ll a~om, a group R4, a qroup of the Forlllula (VIII) and a group of the Fornlula (IX) -OR4 (VIII) -OOC-R4 i (IX).
As an example of suitable binders containing pendant activated unsaturated groups of the formula (II) may be mentioned those disclosed in previously incorporated EP-A-0203296, and reFerence may be had thereto for further details. In general, these bind:ers may be referred to simply as acryloyl and metllacryloyl groups-containiny binders.
As an example of suitable binders containing pendant activated unsaturated groups of the formula (III), ~IV) ancl/or (V) may be mentioned those disclosed in previously incorporated EP-A-0346982, and reference may be had thereto For further details.
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As a firs-t speci-Fic example o-f suitable binders containin~ pendantactivated unsaturated grollps ~lII), (IV) and/or (V) may be mentioned compounds resultin(J -from the addition of maleic anhy(lride and/or itaconic anhydride to an OH groups-containing copolymer.
Such an OH groul)s con-taining copolymer is pre-ferably an addition copolymer obtained by radical polymerization of a mononler mixture of:
~l) 5-90% by weight, more preferably 10-50% by weight, of a metllylol (meth)acrylalnide and/or a hydroxy(cyclo)alkyl (metll)acrylate with the (cyclo)alkyl group containing 1-18 carbon atoms, and (2) 10-95~ by weight, more pre-ferably 50-90% by weight, of another copolymerizable comonolner.
Suitable o-ther copolymerizable comonomers include acrylic and methacrylic esters of monoal cohol s having l-24 carbon atoms, such as methyl acrylate, methyl methacrylate, e-thyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate and ole~yl acrylate; dialkyl maleates, such as dimethyl maleate and d;ethyl maleate; vinyl esters of alkane carboxylic acids, such as vinyl acetate an(l vinyl propionate; and monovinyl aromatic compourlds, such as styrene, villyl toluene, and a-me~hyl styrene. Of course use may also be nlade of mixtures of 2 or more oF the aforemelltioned comonomers.
Other suitable OH groups-containing copolymers include copolymers of styrene and allyl alcohol, partially hydrolyzed copolymers of vinyl chloride and vinyl acetate, and partially hydrolyzed copolymers of vinyl acetate and vinyl versatate. These copolymers and their preparative processes are known to one skilled in the art and need no -further elucidation here.
The addition of maleic anhydride and/or itaconic anhydride to the above-described Oll groups-containing copolymers may generally be .
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carried out at a temperature in -the range o-f 50-120CI preferably in the range of 70-120~C. During the addition there may optionally be present a catalyst such as a tertiary amine ~e.y., pyridine) or an organic tin compound (e.g., dibutyl tin oxide) -in a conventional amount, for instance, 0.1% by weight calculated on the reaction components.
After the addition of the maleic anhydride and/or itaconic anhydr-ide to the OH groups-containing copolymer, the resulting carboxylic acid groups o-F the addition polymer may optionally be neutralized wholly or in part with an inorganic or organic base. As examples of suitable bases may be mentioned sodium hydroxide, potassium hydroxide and tertiary amines such as triethylamine and dimethyl aminoethanol.
Depending on the acid number.and the degree of neutralization, the bi~der may become water-dilutable and useable in water-dilutable coating COlllpOS i tions.
Al-ternatively, however, -the carboxylic acid ~roups present in the binder may optionally be reacted wholly or in part with a d~FFerent appropriate compound, such as a morloFurlctional epoxy compound or a molloal cohol .
Suitable monvFunctiorlal epoxy compounds include ethylene ox;de, propylene oxide, butylene oxide, and the higher alkylene oxides; alkyl glycidyl ethers, such as butyl glycidyl ether or hexyl glycidyl ether;
and the ~lycidyl esters of preferably branched alkane carboxylic acids, for instance the glycidyl esters oF a,a-dimetllyl octanoic acid, which last-men;tioned ester is commercially available under the trade designation Cardura E from Shell Chemical.
Esterification with the epoxy compound generally takes place at a temperature in the range of 80-140C, preferably in the range of 100-120C. Esteri-Fication may optionally be carried out in the presence of a catalyst such as an organic ammonium salt or an organic .
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CrIII salt (e.g., Cr~ 2-ethyl hexanoate) in conventional amoun~s, such as 0.01-2.0% by weight calculated on the reaction components.
Suitable monoalcollols include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, cyclohexanol, n-decyl alcohol, n-dodecyl alcohol, tricyclodecyl methanol (TCDM), oleyl alcohol and stearyl alcohol.
Esterification with the monoalcohol generally takes place at a temperature in the range of 100-180CI preferably in the range of 120-160C. Esterification may optionally be carried out in the presence of a catalyst such as p-toluene sulfonic acid or an organic tin compound (e.g., butylchlorotindihydroxide) in conventional amounts, such as 0.01-2.0% by weight calcula-ted on the reaction components.
As a second speci-Fic example of suitable binders containing pendant activated unsakurated groups (III), (IV) and/or (V) may be mentioned compounds obkained by reacking a monoester of maleic acid, fumaric acid and/or itaconic acid with an at least difunctional epoxy compound.
As examples o-F sllitable difunctional or polyFunctional epoxy compounds, which as such may be solid or liquid, may be mentioned khe diglycidyl or polyglycidyl ethers of (cyclo)aliphakic or aromatic hydroxyl compounds, such as ethylene ~lycol, glycerol, cyclohexane diol, and mononuclear or polynuclear difunctional or kriFunctional phenols and b;sphenols such as bisphenol-A and bisphenol-F;
polyglycidyl ethers~ of phenol formaldehyde novolak; polymers o-f ethylenically unsatura-ted compounds containing epoxy groups, such as glycidyl (meth)acrylate, N-glycidyl (meth)acrylamidet and/or allyl glycidyl ether, and optional~ly of one or more different copolymerizable ethylenically unsaturated monomers; cycloaliphatic epoxy compounds, such a~ epoxidized and optionally subsequently ~ -' ',. '" " '' ' . ' ~ '' ,,'; ;,'" ~ , . 1~
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hydrogenated styrene or divinyl benzene; glycidyl esters of fatty acids having for instance 6-24 carbon atoms; glyci(lyl (meth)acrylate;
isocyanurate group-containing epoxy COlllpOUIl~S; an epoxidized polyalkadiene, sucll as epoxidized polybutadiene; hyclantoin epoxy resins; epoxy resins obtained by epoxi(lizing aliphatic ~nd/or cycloaliphatic alkenes, such as dipentene dioxide, dicyclopentadiene dioxide and vinyl cyclohexene dioxide; glycidyl groups-containing resins, such as polyesters or polyurethanes containing one or more glycidyl groups per molecule; and mixtures of the epoxy resins reFerred to above. Ihese epoxy resins are generally known to one skilled in the art and need no further elucidation here.
Examples of suitable monoesters include fumaric, maleic and/or itaconic monoesters of alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, cyclohexanol, n-decyl alcohol, n-dodecyl alcohol, tricyclodecyl me-th~nol (TCDM), oleyl alcohol and stearyl alcohol; and the monoesters of monoalkylene or polyalkylene glycols, the monoalkyl ethers and/or the monoalkane carboxylic esters thereof, such as mono(di)(propylene) ethylene 01ycol monomethyl(ethyl)ether, mono(di)(propylene) e-thylene glycol acetate and hiyher analoyous compounds.
The reaction oF ~he monoester of male;c ac;d, Fumaric acid and/oritaconic acid with the dlFunctional or polyfunctional epoxy compound is generally carried out at a temperature in the range o-f ~0-140C, preferably in the range of 100-120C. During the reaction use may be made of a catalyst~such as an ammonium salt or an organic chromium compound (e.g., Cr~ 2-ethyl hexanoate) in conventional amounts, such as 0.01-2.0% by weight calculated on the reaction components.
As a third specific example of suitable binders containing pendan-t activated unsaturated groups (IIIj, (IV) and/or (V) may be mentioned those obtained by reacting a monofunctional epoxy compound with a monoester of fumaric acid, maleic acid and/or itaconic acid, then . , 201~
~3 reacting the resulting compound througll the hydroxyl group with an at least cii runctional isocyanate compound.
Suitai~le isocyanate conlpounds include aliphatic, cycloalipl1atic or aromatic di-, tri- or tetraisocyanates wnich may l)e ethylenically unsaturated or not, such as 1,2-propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylen~ cliisocyanate, hexanletllylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyl hexanlethylene diisocyanate, 2,~,4-trimethyl hexametilylene diisocyanate, dodecamethylene diisocyanate, dipropyl ether diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane cliisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, ~-methyl-1,3-diisocyanatocyclohexane, transvinylidene diisocyanate, dicyclohexyl methane-'1,4'-diisocyanate,
AC0 ~18G US
Liqui~ Coati~ Co~ )osi~ion InclllclirltJ, as ~I Crossl;nkirlg Agent, an Unblockecl l~lonol)rilllary Al~ e Back~round oF the Inven-tion The present invention relates generally to a liquid coating compositioll whicll comprises, as a binder, a compound containing at least two pendant activated unsaturated yroups and, as a crosslinkiny agent For the activated unsaturated groups of the binder, a particular unblocked nlonoprimary amine.
A coatiny composition comprising, as a binder, a compound containing at least two pendant activated unsaturated groups and an amine crosslinkiny agent is generally known from EP-A-0203296 and EP-A-0346982, which are both incorporated by reference herein for all purposes. The amine crosslinking agent may contain only one primary amino group, but it is taught that this primary amino group must be blocked with, For example, an aldehyde or ke-tone.
As is well-known, the~reactive groups oF crosslinking agents are often blocked to prevent unwanted early reaction and, consequently, decreased potiiFe of the .coatiny compositiorl. Amine crosslinking ayents normally are blocked with, for example, aldehydes and/or ketones The use of such blockiny a~ents can have a number oF disadvantages~
For example, elevate-l temperatures are oFten require(l to unblock the crosslinkiny agents and, particularly for the above blocking agents, water is required to remove the:aldehyde or ketone. With very low relative humidities, therefore, the cross-linkiny reaction can be delayed or proceed only very slowly. Further, once the crosslinkiny ayent is unblocked, the blocking agent must be removed or it will remain in the coating~composition:as ~an ;mpurity. This can lead to the previously applied coatiny, or the coated substrate itselF
~(particularly plastics), beiny attacked.
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Su~ lary o-f the Invention In accordance with the presen-t invention, there is provided a liquid coating coml)os;tion whicll comprises, as a binder, a compouncl containiny at least two pendant activated unsaturated groups and a crosslinkin(J agent -for the activated unsaturated groups of lhe binder, whereill the crosslinking ayent for the activated unsa-tura-ted groups of the binder comprises an unblocked monoprimary amine of the general formula (I) H2N- (CH2 ) n-NRR ' ( I ) wherein n is a number from 1 to ~;
R is selected from an H atom, a Cl-C3 alkyl and a mono hydroxy substituted C1-C3 alkyl; and Rl is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl.
It has been surprisingly discovered that the use of this narrow class oF monopr;mary amines as crosslinking agents allows the formulation of coatings with good solvent resistance as well as good potlife.
Additionally, without the aldehyde and/or ke-tone blockin~ a~ent, the production and use of such coating compos;tions are greatly simpl;fied - not only ls the en-tire step of blockint~ the crossl;nk;n~
a~ent no longer necessary, but also the crossl;nk;ng oF the system becomes in~epen(lent oF relative hu~ni(lity.
These and other features and advantages of the present invention will be more readily understood by those skilled in the ar-t from a reading of the following detailed description.
Detailed Description of the Preferred Embodiments As just indicated, the liquid coating composit ions in accordance with the present invention comprise, as a binder, a compound containing at least two pendant activated unsaturated groups and, as a crosslinking ., ~ , .
. . .. .
2 ~
agent -ror such activa-ted unsaturated groups, a particular unblocked monoprilllary amine.
As suitable a-t leas-t two pendant activated unsaturated groups for thebinder may be mentioned ~roups oF the formulas (II), (III), (IV) and/or (V) -OOC-C=CH2 (II) -OOC-CH=CII-COOR3 (III) -ooc-CH2-CI=c~l2 (IV) -OC-r=CH2 (V) COOR3 1~2 ~herein RZ is selected from an H atom or a methyl group, R3 is selected from an H atom, a group R4, a yroup of the formula (VI) and a group of -the formula (VII) -CH(OH)-CH2-CH2Rs (VI) -CH2-CH(OH)-CH2Rs (VII) R3 is selec-ted from an alkyl group, a cycloalkyl yroup and an aryl group, which groups may be substituted or not wi-th an alkyl, and Rs ;s seiected from an ll a~om, a group R4, a qroup of the Forlllula (VIII) and a group of the Fornlula (IX) -OR4 (VIII) -OOC-R4 i (IX).
As an example of suitable binders containing pendant activated unsaturated groups of the formula (II) may be mentioned those disclosed in previously incorporated EP-A-0203296, and reFerence may be had thereto for further details. In general, these bind:ers may be referred to simply as acryloyl and metllacryloyl groups-containiny binders.
As an example of suitable binders containing pendant activated unsaturated groups of the formula (III), ~IV) ancl/or (V) may be mentioned those disclosed in previously incorporated EP-A-0346982, and reference may be had thereto For further details.
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As a firs-t speci-Fic example o-f suitable binders containin~ pendantactivated unsaturated grollps ~lII), (IV) and/or (V) may be mentioned compounds resultin(J -from the addition of maleic anhy(lride and/or itaconic anhydride to an OH groups-containing copolymer.
Such an OH groul)s con-taining copolymer is pre-ferably an addition copolymer obtained by radical polymerization of a mononler mixture of:
~l) 5-90% by weight, more preferably 10-50% by weight, of a metllylol (meth)acrylalnide and/or a hydroxy(cyclo)alkyl (metll)acrylate with the (cyclo)alkyl group containing 1-18 carbon atoms, and (2) 10-95~ by weight, more pre-ferably 50-90% by weight, of another copolymerizable comonolner.
Suitable o-ther copolymerizable comonomers include acrylic and methacrylic esters of monoal cohol s having l-24 carbon atoms, such as methyl acrylate, methyl methacrylate, e-thyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate and ole~yl acrylate; dialkyl maleates, such as dimethyl maleate and d;ethyl maleate; vinyl esters of alkane carboxylic acids, such as vinyl acetate an(l vinyl propionate; and monovinyl aromatic compourlds, such as styrene, villyl toluene, and a-me~hyl styrene. Of course use may also be nlade of mixtures of 2 or more oF the aforemelltioned comonomers.
Other suitable OH groups-containing copolymers include copolymers of styrene and allyl alcohol, partially hydrolyzed copolymers of vinyl chloride and vinyl acetate, and partially hydrolyzed copolymers of vinyl acetate and vinyl versatate. These copolymers and their preparative processes are known to one skilled in the art and need no -further elucidation here.
The addition of maleic anhydride and/or itaconic anhydride to the above-described Oll groups-containing copolymers may generally be .
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carried out at a temperature in -the range o-f 50-120CI preferably in the range of 70-120~C. During the addition there may optionally be present a catalyst such as a tertiary amine ~e.y., pyridine) or an organic tin compound (e.g., dibutyl tin oxide) -in a conventional amount, for instance, 0.1% by weight calculated on the reaction components.
After the addition of the maleic anhydride and/or itaconic anhydr-ide to the OH groups-containing copolymer, the resulting carboxylic acid groups o-F the addition polymer may optionally be neutralized wholly or in part with an inorganic or organic base. As examples of suitable bases may be mentioned sodium hydroxide, potassium hydroxide and tertiary amines such as triethylamine and dimethyl aminoethanol.
Depending on the acid number.and the degree of neutralization, the bi~der may become water-dilutable and useable in water-dilutable coating COlllpOS i tions.
Al-ternatively, however, -the carboxylic acid ~roups present in the binder may optionally be reacted wholly or in part with a d~FFerent appropriate compound, such as a morloFurlctional epoxy compound or a molloal cohol .
Suitable monvFunctiorlal epoxy compounds include ethylene ox;de, propylene oxide, butylene oxide, and the higher alkylene oxides; alkyl glycidyl ethers, such as butyl glycidyl ether or hexyl glycidyl ether;
and the ~lycidyl esters of preferably branched alkane carboxylic acids, for instance the glycidyl esters oF a,a-dimetllyl octanoic acid, which last-men;tioned ester is commercially available under the trade designation Cardura E from Shell Chemical.
Esterification with the epoxy compound generally takes place at a temperature in the range of 80-140C, preferably in the range of 100-120C. Esteri-Fication may optionally be carried out in the presence of a catalyst such as an organic ammonium salt or an organic .
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CrIII salt (e.g., Cr~ 2-ethyl hexanoate) in conventional amoun~s, such as 0.01-2.0% by weight calculated on the reaction components.
Suitable monoalcollols include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, cyclohexanol, n-decyl alcohol, n-dodecyl alcohol, tricyclodecyl methanol (TCDM), oleyl alcohol and stearyl alcohol.
Esterification with the monoalcohol generally takes place at a temperature in the range of 100-180CI preferably in the range of 120-160C. Esterification may optionally be carried out in the presence of a catalyst such as p-toluene sulfonic acid or an organic tin compound (e.g., butylchlorotindihydroxide) in conventional amounts, such as 0.01-2.0% by weight calcula-ted on the reaction components.
As a second speci-Fic example of suitable binders containing pendant activated unsakurated groups (III), (IV) and/or (V) may be mentioned compounds obkained by reacking a monoester of maleic acid, fumaric acid and/or itaconic acid with an at least difunctional epoxy compound.
As examples o-F sllitable difunctional or polyFunctional epoxy compounds, which as such may be solid or liquid, may be mentioned khe diglycidyl or polyglycidyl ethers of (cyclo)aliphakic or aromatic hydroxyl compounds, such as ethylene ~lycol, glycerol, cyclohexane diol, and mononuclear or polynuclear difunctional or kriFunctional phenols and b;sphenols such as bisphenol-A and bisphenol-F;
polyglycidyl ethers~ of phenol formaldehyde novolak; polymers o-f ethylenically unsatura-ted compounds containing epoxy groups, such as glycidyl (meth)acrylate, N-glycidyl (meth)acrylamidet and/or allyl glycidyl ether, and optional~ly of one or more different copolymerizable ethylenically unsaturated monomers; cycloaliphatic epoxy compounds, such a~ epoxidized and optionally subsequently ~ -' ',. '" " '' ' . ' ~ '' ,,'; ;,'" ~ , . 1~
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hydrogenated styrene or divinyl benzene; glycidyl esters of fatty acids having for instance 6-24 carbon atoms; glyci(lyl (meth)acrylate;
isocyanurate group-containing epoxy COlllpOUIl~S; an epoxidized polyalkadiene, sucll as epoxidized polybutadiene; hyclantoin epoxy resins; epoxy resins obtained by epoxi(lizing aliphatic ~nd/or cycloaliphatic alkenes, such as dipentene dioxide, dicyclopentadiene dioxide and vinyl cyclohexene dioxide; glycidyl groups-containing resins, such as polyesters or polyurethanes containing one or more glycidyl groups per molecule; and mixtures of the epoxy resins reFerred to above. Ihese epoxy resins are generally known to one skilled in the art and need no further elucidation here.
Examples of suitable monoesters include fumaric, maleic and/or itaconic monoesters of alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, cyclohexanol, n-decyl alcohol, n-dodecyl alcohol, tricyclodecyl me-th~nol (TCDM), oleyl alcohol and stearyl alcohol; and the monoesters of monoalkylene or polyalkylene glycols, the monoalkyl ethers and/or the monoalkane carboxylic esters thereof, such as mono(di)(propylene) ethylene 01ycol monomethyl(ethyl)ether, mono(di)(propylene) e-thylene glycol acetate and hiyher analoyous compounds.
The reaction oF ~he monoester of male;c ac;d, Fumaric acid and/oritaconic acid with the dlFunctional or polyfunctional epoxy compound is generally carried out at a temperature in the range o-f ~0-140C, preferably in the range of 100-120C. During the reaction use may be made of a catalyst~such as an ammonium salt or an organic chromium compound (e.g., Cr~ 2-ethyl hexanoate) in conventional amounts, such as 0.01-2.0% by weight calculated on the reaction components.
As a third specific example of suitable binders containing pendan-t activated unsaturated groups (IIIj, (IV) and/or (V) may be mentioned those obtained by reacting a monofunctional epoxy compound with a monoester of fumaric acid, maleic acid and/or itaconic acid, then . , 201~
~3 reacting the resulting compound througll the hydroxyl group with an at least cii runctional isocyanate compound.
Suitai~le isocyanate conlpounds include aliphatic, cycloalipl1atic or aromatic di-, tri- or tetraisocyanates wnich may l)e ethylenically unsaturated or not, such as 1,2-propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylen~ cliisocyanate, hexanletllylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyl hexanlethylene diisocyanate, 2,~,4-trimethyl hexametilylene diisocyanate, dodecamethylene diisocyanate, dipropyl ether diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane cliisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, ~-methyl-1,3-diisocyanatocyclohexane, transvinylidene diisocyanate, dicyclohexyl methane-'1,4'-diisocyanate,
3,3'-dimethyl-dicyclohexyl metllane-~,4'-diisocyanate, a toluene diisocyanate, 1,3-bis(l-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, 1,3-bis(isocyanatomethyl)benzene, a xylylene diisocyanate, 1,5-dimethyl-2,~1-bis(isocyanatomeil1yl)benzene, 1,5-dimel;llyl-2,'~-bis(2-isocyanatoethyl)benzene, 1,3,5-triethyl-2,~-bis(lsocyanatomethyl)uenzene, '
4,4'-diisocyanatodiphenyl, 3,3'-dichloro-4,4'-diisocyallatodipllenyl, 3,3'-diphenyl-~,4'-diisocyanatodiphenyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 4,4'-diisocyanatodiphenyl methane, 3,3'-dimethyl-~,4'-diisocyanatodiphenyl methane, - a diisocyanatonaphthalene, polyisocyanates having isocyanurate structural units, the adduct of 2 molecules of a diisocyanate, e.y.
hexamethylene diisocyanate or isophorone diisocyanate, to a dlol, such as ethylene glycol, the adduct of 3 molecules of hexamethylene diisocyanate to 1 molecule of water (available under the trade designation Desmodur N from Bayer AG), the adduct of 1 molecule of trimethylol propane to 3 molecules of toluene diisocyanate (available under the trade designatlon Desmodur L from 8ayer AG) j the adduct of 1 ~: ' :
2~85~
ACO Z1~6 US
molecule of trimet!lylol propane -to 3 molecules oF isophorone diisocyanate, compounds such as 1,3,5-triisocyanatobenzene and 2,~,6-triisocyanatotoluene, and the adduct o-f 1 molecule of pentaerythritol to 4 molecules oF toluene diisocyanate.
The reaction o-F the adduct oF the nlonofunctional epoxy compound and the monoester of maleic acid, fumaric acid and/or itaconic acid ~ith the difunctional or polyfunctional isocyanate compound is carried out, as a rule, at a temperature in the range of 2~-lOO~C, and preferably in the range of 50-80C. Optionally, use may be made of a catalyst such as a t-amine (e.g., triethylamine) or an organic tin compound (e.g., dibutyl tin oxide or dibutyl tin stearate) in a concentration of 0.01-1% by weight calculated on the constituents present.
The number average molecular weight of the addition polymers as described above should generally be in the range of 800 to 100 000, preFerably in the range of 800 to 15 000.
As mentioned above, suitable crosslinkin~ agents in accordance with the present invention comprise unblocked monopr;lllary amines of the general fornlula (I) ll2N (C~l2)n-NRR~
wherein n is a number From 1 to 4;
R is selected from an ll atom, a Cl-C3 alkyl and a monohydroxy substituted Cl-C3 alkyl; and Rl is selected from a C1-C3 alkyl and a monahydroxy substituted C1-C3 alkyl.
More preferred are those wherein n is 2 or 3, R is a C1-C3 alkyl, and Rl is a C1-C3 alkyl or monohydroxy substituted C1-C3 alkyl, such as N-methyl-N-(3-aminopropyl) ethanolamine, N-ethyl-N-(2-aminoethyl) ethylamine, N-methyl-N-(2-aminoethyl) methylamine and N-methyl-N-(3-aminopropyl) methylamine.
.
I
.
7 ~
AC() 21~ US
The coating compositions generally contain so mucll binder and crosslinking agent as to give a ratio of the nulnber of equivalents o-F
tlle ethylellically unsaturated double bonds o-F the binder to the number of equivalents o-f the primary amino groups of the crosslinking agent in the range of 1.5 -to 2.5, preferably in the range o-f 1.9 to 2.1, most preFerably 2.0 (stoichiollletric).
The coating compositions usually also contain an organic solvent. ~s suitable examples may be mentioned aliphatic or aromatic hydrocarbons, esters, ethers, alcohols, ketones, diketo compounds such as acetyl ketone, nitroalkanes such as nitropropane, and (cyclo)aliphatic or aromatic esters of acetylacetic acid of which the (cyclo)alkyl group or the aromatic group has 1-20 carbon atoms, such as ethyl acetoacetate, cyclohexyl acetoacetate and phenyl acetoacetate. I-F, however; the binder is water-dilutable, the above-mentioned solvents may be replaced wholly or in part with water.
In addition, -the coating compositions may contain the usual addit;ves,such as pigments, Fillers, levelllng ayents, emulsiflers, anti--foaming agents and other rheology control agents, antioxidants, UV
stabilizers, anti-sag agents and catalysts such as organic carboxylic acids. Optiorlally, the composition may contaih a non-functional polymer, such as an acrylate (co)polymer, cellulose acetopropionate, cellulose acetobutyrate, nitrocellulose or a vinyl polynler.
. .
The coating composition may be applied to a substrate in any suitable manner, such as by roller coating, spraying, brushing, sprinkling, flow coating or dipping. It is preFerred that the composition should be applied by spraying. ~
.:' Suitable substrates include those of me-tals which may be pretreated or not, wood, synthetic materials, paper, glass or leather. Suitable metals include iron, steel and aluminium. Curiny of the coating may be carried out at a temperature of 0-30C. Optionally, a curing .
, ~8~7~
temperature above 30C may be used, so that the curing time may be recluced. For instance, the coating composition may be baked at a temperature in the range o-f 60-120C.
The invention will be further described in the -following examples, whicll are not to be construed as limiting the scope o-f the present invention.
EXAMPLES
Preparation oF Binder A
Into a reactor were charged 500.0 g of white spirit (boiling range 140-165C) and 500 9 of Solvesso 100, which were heated to boiling temperature. Next, there were added separately, over a period of three hours, a first mixture of:
460.0 9 of glycidyl methacrylate, 1071.0 9 of styrene, 369.0 9 oF butyl acrylate and 100.0 g of lauryl methacrylate, and a second mixtùre of:
300.0 9 xylene an(l 140.0 y of tert. butylperoxy-3,5,5-tr;methyl hexanoate.
The reaction mixture was kept at boiling temperature until a conversion of over 98~ was attained.
To 500.0 g of the composition thus prepared were added:
52.8 g of monomethyl maleate,
hexamethylene diisocyanate or isophorone diisocyanate, to a dlol, such as ethylene glycol, the adduct of 3 molecules of hexamethylene diisocyanate to 1 molecule of water (available under the trade designation Desmodur N from Bayer AG), the adduct of 1 molecule of trimethylol propane to 3 molecules of toluene diisocyanate (available under the trade designatlon Desmodur L from 8ayer AG) j the adduct of 1 ~: ' :
2~85~
ACO Z1~6 US
molecule of trimet!lylol propane -to 3 molecules oF isophorone diisocyanate, compounds such as 1,3,5-triisocyanatobenzene and 2,~,6-triisocyanatotoluene, and the adduct o-f 1 molecule of pentaerythritol to 4 molecules oF toluene diisocyanate.
The reaction o-F the adduct oF the nlonofunctional epoxy compound and the monoester of maleic acid, fumaric acid and/or itaconic acid ~ith the difunctional or polyfunctional isocyanate compound is carried out, as a rule, at a temperature in the range of 2~-lOO~C, and preferably in the range of 50-80C. Optionally, use may be made of a catalyst such as a t-amine (e.g., triethylamine) or an organic tin compound (e.g., dibutyl tin oxide or dibutyl tin stearate) in a concentration of 0.01-1% by weight calculated on the constituents present.
The number average molecular weight of the addition polymers as described above should generally be in the range of 800 to 100 000, preFerably in the range of 800 to 15 000.
As mentioned above, suitable crosslinkin~ agents in accordance with the present invention comprise unblocked monopr;lllary amines of the general fornlula (I) ll2N (C~l2)n-NRR~
wherein n is a number From 1 to 4;
R is selected from an ll atom, a Cl-C3 alkyl and a monohydroxy substituted Cl-C3 alkyl; and Rl is selected from a C1-C3 alkyl and a monahydroxy substituted C1-C3 alkyl.
More preferred are those wherein n is 2 or 3, R is a C1-C3 alkyl, and Rl is a C1-C3 alkyl or monohydroxy substituted C1-C3 alkyl, such as N-methyl-N-(3-aminopropyl) ethanolamine, N-ethyl-N-(2-aminoethyl) ethylamine, N-methyl-N-(2-aminoethyl) methylamine and N-methyl-N-(3-aminopropyl) methylamine.
.
I
.
7 ~
AC() 21~ US
The coating compositions generally contain so mucll binder and crosslinking agent as to give a ratio of the nulnber of equivalents o-F
tlle ethylellically unsaturated double bonds o-F the binder to the number of equivalents o-f the primary amino groups of the crosslinking agent in the range of 1.5 -to 2.5, preferably in the range o-f 1.9 to 2.1, most preFerably 2.0 (stoichiollletric).
The coating compositions usually also contain an organic solvent. ~s suitable examples may be mentioned aliphatic or aromatic hydrocarbons, esters, ethers, alcohols, ketones, diketo compounds such as acetyl ketone, nitroalkanes such as nitropropane, and (cyclo)aliphatic or aromatic esters of acetylacetic acid of which the (cyclo)alkyl group or the aromatic group has 1-20 carbon atoms, such as ethyl acetoacetate, cyclohexyl acetoacetate and phenyl acetoacetate. I-F, however; the binder is water-dilutable, the above-mentioned solvents may be replaced wholly or in part with water.
In addition, -the coating compositions may contain the usual addit;ves,such as pigments, Fillers, levelllng ayents, emulsiflers, anti--foaming agents and other rheology control agents, antioxidants, UV
stabilizers, anti-sag agents and catalysts such as organic carboxylic acids. Optiorlally, the composition may contaih a non-functional polymer, such as an acrylate (co)polymer, cellulose acetopropionate, cellulose acetobutyrate, nitrocellulose or a vinyl polynler.
. .
The coating composition may be applied to a substrate in any suitable manner, such as by roller coating, spraying, brushing, sprinkling, flow coating or dipping. It is preFerred that the composition should be applied by spraying. ~
.:' Suitable substrates include those of me-tals which may be pretreated or not, wood, synthetic materials, paper, glass or leather. Suitable metals include iron, steel and aluminium. Curiny of the coating may be carried out at a temperature of 0-30C. Optionally, a curing .
, ~8~7~
temperature above 30C may be used, so that the curing time may be recluced. For instance, the coating composition may be baked at a temperature in the range o-f 60-120C.
The invention will be further described in the -following examples, whicll are not to be construed as limiting the scope o-f the present invention.
EXAMPLES
Preparation oF Binder A
Into a reactor were charged 500.0 g of white spirit (boiling range 140-165C) and 500 9 of Solvesso 100, which were heated to boiling temperature. Next, there were added separately, over a period of three hours, a first mixture of:
460.0 9 of glycidyl methacrylate, 1071.0 9 of styrene, 369.0 9 oF butyl acrylate and 100.0 g of lauryl methacrylate, and a second mixtùre of:
300.0 9 xylene an(l 140.0 y of tert. butylperoxy-3,5,5-tr;methyl hexanoate.
The reaction mixture was kept at boiling temperature until a conversion of over 98~ was attained.
To 500.0 g of the composition thus prepared were added:
52.8 g of monomethyl maleate,
5.5 9 oF hydroquinone monomethyl ether and 0.3 9 of chromium (III)-2-ethyl hexanoate, and the resulting mixture was heated to 100C with air being passed through. The mixture was kept at 100C until an acid number of 2.3 was reached (the theoretical average maleic acid functionality was ~), then diluted with 66.0 g xylene.
~8~7~
Ob-tained was a 56.~% solution oF the Binder A with a viscosity oF 352 cPa.s (measured at 20C with a Rheomat 15 rotation viscometer) and a nullll)er average molecular weight o-F 3480.
For use in the following examples, Binder A was hlrtller diluted with butyl acetate to a ~0% solids content.
Binder B
Into a reactor was charged 2073.0 g o-f xylene, which was heated to boiling temperature. Next, there were added separately, over a period of three hours, a first mixture of:
3~63.0 9 of glycidyl methacrylate 2831.0 g of s-tyrene, 3676.0 g of butyl acrylate and 521.0 g of decyl methacrylate, and a second mixture of:
735.0 g oF xylene and 735.0 g of tert. butylperoxy-3,5,5-trimethyl hexanoa-te.
The resultiny reaction mixture was kept at boiling temperature until a conversion of over 98% was obtained, at which kime a Further ~00.0 q of xylene was added.
To the cornposition thus prepared were added:
1528.0 g of acrylic acid, 3.8 g oF chromium(III)-2-ethylhexanoate and 5.0 g of hydroquinone, and the resulting mixture was heated to 110C with air being passed through until the acid number decreased to below 2, at which time the mixture was diluted with 500.0 g of xylene.
Obtained was a 79.~% soluton of the Binder B, which had an acid number of O.8, -2 f~ 7 ~
ACO 21~6 US
For use in the following ex2nlples, einder B was further diluted with butyl acetate to a 40% solids content.
Examples 1-5 and Comp~rat e Examples 1 and 2 Coatin~ compositions on the basis of the above-described binders and crosslinking agents, as set forth in Table 1 below, were prepared by admixing stoichiometric amounts (Z equivalents ethylencially unsaturated double bond per equivalent primary amine) of the two connponents to attain a theoretical crosslinkin~ of 100%.
The abbreviations of the crosslinking agents, as used in Table 1, are as follows:
(1) N-metllyl-N-(3-aminopropyl) ethanolanline (2) N-methyl-N-(2-aminoethyl) methylamine (3) N-methyl-N-(3-aminopropyl) methylanline (4) N-ethyl-N-(2-arninoethyl) ethylamine (5) 2,2,4-trimethylhexalnethylene diamine .~. . ~
The pok life of such coat~ng compositions was measured, after the mixing of the components, as the increase in the viscosity in conFormance with the DIN cup method. The initial viscosity was set at 15 sec., measured with the aid of a DIN cup ~, and the pot liFe was the number of hours for the viscosity to increase by 100%. The results are presented below in Table 1.
- :
To measure solvent resistance, immediately after mixing the resulting coating compositions were applied to glass .panels, using a doctor blade, to a wet film thickness of 120~rn. A -first set of panels was stoved for 30 minu-tes at 110C (drying condition I), and another set was allowed to dry for 7 days at room temperature (drying condition II). The cured films were all clear and exhibited high gloss. Solvent resistance to ethanol (EtOH) and methyl ethyl ketone (MEK) was measured by soaking~a 0.5 cm diameter roll oF cellulose paper in the : :
' , .
.
AC~ Z186 US
1'1 , solvent and rubbing back and forth (1 D-Rub) with about ~00 g pressure on the film. The results aFter a set number o-f D-Rubs is assesse~
according to DIN53230 (O = unchanged; 5 = very s-trongly attacked). The results are also presented below in Table 1.
Cross. Drying No. of Solvent Potlife Ex. Binder Agent Solvent Cond. D-Rubs Resist. (hours) la A (1) E-tOH- I 100 2-3 >18 lb MEK 100 3 1c EtOH II 100 3 ld MEK 100 4 2a A (2) EtOH I lOO O ~24 2b MEK 100 , 2 2c EtOH II 100 2-3 2d MEK 100 2-3 3a A (3) EtOH I 100 0-1 >24 3b MEK 100 1-2 3c EtOH II 100 2 3d MEK 100 3 4a B (2) EtOH I 100 0 2-4 5 ~b MEK 100 0 4c E-tOH II 100 1-2 4d MEK ~ 100 3 5a B (~) EtOH I 100 1-2 2-~ 5 5b MEK 100 1 3-4 5c EtOII II 100 1-2 5d MEK 100 3 Cla A (5) EtOH I 100 1 3 min.
Clb MEK 100 1-2 C2a B (5) EtOH I 100 0 5 min.
C2b MEK 100 3-4 These resul-ts demons-trate that a good combination of crosslinking asshown by the solvent resistance in combination with a good potliFe can be obtained by the use of the particular unblocked monoprimary amines in accordance with the present invention. This is most evident from the coating compositions including Binder A but it should also be noted that the potlife of the coating compositions comprising Binder B are acceptable and comparable -to those described in previouly 2~:~857~
incorporated EP-A-0203296 and EP-A-03~6982, which re~uires the use of blockecl amines.
Comparative Examples 1 and 2 demonstrate that, althougll other unblocked amines outside the scope oF the present invention can be used successfully to crosslink the ~inders A and B, the resulting potlife renders such a system totally impractical for commercial purposes.
Many modiflcations and variations may be made to the embodiments specifically mentioned here without departing substantially from the concept of the present invention. Accordingly, it should be clearly understood that the preferred form o-f the invention described herein is exemplary only, and not intended as a limitation on the scope thereof.
-- .
~8~7~
Ob-tained was a 56.~% solution oF the Binder A with a viscosity oF 352 cPa.s (measured at 20C with a Rheomat 15 rotation viscometer) and a nullll)er average molecular weight o-F 3480.
For use in the following examples, Binder A was hlrtller diluted with butyl acetate to a ~0% solids content.
Binder B
Into a reactor was charged 2073.0 g o-f xylene, which was heated to boiling temperature. Next, there were added separately, over a period of three hours, a first mixture of:
3~63.0 9 of glycidyl methacrylate 2831.0 g of s-tyrene, 3676.0 g of butyl acrylate and 521.0 g of decyl methacrylate, and a second mixture of:
735.0 g oF xylene and 735.0 g of tert. butylperoxy-3,5,5-trimethyl hexanoa-te.
The resultiny reaction mixture was kept at boiling temperature until a conversion of over 98% was obtained, at which kime a Further ~00.0 q of xylene was added.
To the cornposition thus prepared were added:
1528.0 g of acrylic acid, 3.8 g oF chromium(III)-2-ethylhexanoate and 5.0 g of hydroquinone, and the resulting mixture was heated to 110C with air being passed through until the acid number decreased to below 2, at which time the mixture was diluted with 500.0 g of xylene.
Obtained was a 79.~% soluton of the Binder B, which had an acid number of O.8, -2 f~ 7 ~
ACO 21~6 US
For use in the following ex2nlples, einder B was further diluted with butyl acetate to a 40% solids content.
Examples 1-5 and Comp~rat e Examples 1 and 2 Coatin~ compositions on the basis of the above-described binders and crosslinking agents, as set forth in Table 1 below, were prepared by admixing stoichiometric amounts (Z equivalents ethylencially unsaturated double bond per equivalent primary amine) of the two connponents to attain a theoretical crosslinkin~ of 100%.
The abbreviations of the crosslinking agents, as used in Table 1, are as follows:
(1) N-metllyl-N-(3-aminopropyl) ethanolanline (2) N-methyl-N-(2-aminoethyl) methylamine (3) N-methyl-N-(3-aminopropyl) methylanline (4) N-ethyl-N-(2-arninoethyl) ethylamine (5) 2,2,4-trimethylhexalnethylene diamine .~. . ~
The pok life of such coat~ng compositions was measured, after the mixing of the components, as the increase in the viscosity in conFormance with the DIN cup method. The initial viscosity was set at 15 sec., measured with the aid of a DIN cup ~, and the pot liFe was the number of hours for the viscosity to increase by 100%. The results are presented below in Table 1.
- :
To measure solvent resistance, immediately after mixing the resulting coating compositions were applied to glass .panels, using a doctor blade, to a wet film thickness of 120~rn. A -first set of panels was stoved for 30 minu-tes at 110C (drying condition I), and another set was allowed to dry for 7 days at room temperature (drying condition II). The cured films were all clear and exhibited high gloss. Solvent resistance to ethanol (EtOH) and methyl ethyl ketone (MEK) was measured by soaking~a 0.5 cm diameter roll oF cellulose paper in the : :
' , .
.
AC~ Z186 US
1'1 , solvent and rubbing back and forth (1 D-Rub) with about ~00 g pressure on the film. The results aFter a set number o-f D-Rubs is assesse~
according to DIN53230 (O = unchanged; 5 = very s-trongly attacked). The results are also presented below in Table 1.
Cross. Drying No. of Solvent Potlife Ex. Binder Agent Solvent Cond. D-Rubs Resist. (hours) la A (1) E-tOH- I 100 2-3 >18 lb MEK 100 3 1c EtOH II 100 3 ld MEK 100 4 2a A (2) EtOH I lOO O ~24 2b MEK 100 , 2 2c EtOH II 100 2-3 2d MEK 100 2-3 3a A (3) EtOH I 100 0-1 >24 3b MEK 100 1-2 3c EtOH II 100 2 3d MEK 100 3 4a B (2) EtOH I 100 0 2-4 5 ~b MEK 100 0 4c E-tOH II 100 1-2 4d MEK ~ 100 3 5a B (~) EtOH I 100 1-2 2-~ 5 5b MEK 100 1 3-4 5c EtOII II 100 1-2 5d MEK 100 3 Cla A (5) EtOH I 100 1 3 min.
Clb MEK 100 1-2 C2a B (5) EtOH I 100 0 5 min.
C2b MEK 100 3-4 These resul-ts demons-trate that a good combination of crosslinking asshown by the solvent resistance in combination with a good potliFe can be obtained by the use of the particular unblocked monoprimary amines in accordance with the present invention. This is most evident from the coating compositions including Binder A but it should also be noted that the potlife of the coating compositions comprising Binder B are acceptable and comparable -to those described in previouly 2~:~857~
incorporated EP-A-0203296 and EP-A-03~6982, which re~uires the use of blockecl amines.
Comparative Examples 1 and 2 demonstrate that, althougll other unblocked amines outside the scope oF the present invention can be used successfully to crosslink the ~inders A and B, the resulting potlife renders such a system totally impractical for commercial purposes.
Many modiflcations and variations may be made to the embodiments specifically mentioned here without departing substantially from the concept of the present invention. Accordingly, it should be clearly understood that the preferred form o-f the invention described herein is exemplary only, and not intended as a limitation on the scope thereof.
-- .
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A liquid coating composition which comprises, as a binder, a compound containing at least two pendant activated unsaturated groups and a crosslinking agent for the activated unsaturated groups of the binder, wherein the crosslinking agent for the activated unsaturated groups of the binder comprises an unblocked monoprimary amine of the general formula (I) H2N-(CH2)n-NRR1 (I) wherein n is a number from 1 to 4;
R is selected from an H atom, a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl; and R1 is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl.
R is selected from an H atom, a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl; and R1 is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl.
2. The liquid coating composition of claim 1, wherein the binder contains at least two pendant activated unsaturated groups of the formulas (II), (III), (IV) and/or (V) (II) -OOC-CH=COOR3 (III) (IV) (V) wherein R2 is selected from an H atom or a methyl group, R3 is selected from an H atom, a group R4, a group of the formula (VI) and a group of the formula (VII) -CH(OH)-CH2-CH2R5 (VI) -CH2-CH(OH)-CH2R5 (VII) R4 is selected from an alkyl group, a cycloalkyl group and an aryl group, which groups may be substituted or not with an alkyl, and R5 is selected from an H atom, a group R4, a group of the formula (VIII) and a group of the formula (IX) -OR4 (VIII) -OOC-R4 (IX).
3. The liquid coating composition of claim 2 wherein the binder containing pendant activated unsaturated groups of the Formula (II) comprises an acryloyl and/or methacryloyl groups-containing compound.
4. The liquid coating composition of claim 2 wherein the binder containing pendant activated unsaturated groups of the formulas (III), (IV) and/or (V) comprises compounds obtained by the addition of maleic anhydride or itaconic anhydride to an OH
groups-containing copolymer.
groups-containing copolymer.
S. The liquid coating composition of claim 2 wherein the binder containing pendant activated unsaturated groups of the formulas (III), (IV) and/or (V) comprises compounds obtained by the reaction of a monoester of maleic acid fumaric acid and/or itaconic acid with an at least difunctional epoxy compound.
6. The liquid coating composition of claim 2 wherein the binder containing pendant activated unsaturated groups of the formulas (III), (IV) and/or (V) comprises compounds obtained by reacting a monofunctional epoxy compound with a monoester of fumaric acid maleic acid and/or itaconic acid, then reacting the resulting compound through the hydroxyl group with an at least difunctional isocyanate compound.
7. The liquid coating composition of claim 1 wherein the ratio of the number of equivalents of ethylenically unsaturated double bonds of the binder to the number of equivalents of the primary amino groups of the crosslinking agent is in the range of 1.5 to 2.5.
8. The liquid coating composition of claim 7, wherein such ratio is in the range of 1.9 to 2.1.
9. Use of an unblocked monoprimary amine of the general formula (I) H2N-(CH2)n-NRR1 (I) wherein n is a number from 1 to 4;
R is selected from an H atom, a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl; and R1 is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl, as a crosslinking agent for activated unsaturated groups of a compound containing at least two pendant activated unsaturated groups.
R is selected from an H atom, a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl; and R1 is selected from a C1-C3 alkyl and a monohydroxy substituted C1-C3 alkyl, as a crosslinking agent for activated unsaturated groups of a compound containing at least two pendant activated unsaturated groups.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP89201497 | 1989-06-09 | ||
| EP89201497.8 | 1989-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2018574A1 true CA2018574A1 (en) | 1990-12-09 |
Family
ID=8202406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002018574A Abandoned CA2018574A1 (en) | 1989-06-09 | 1990-06-08 | Liquid coating composition including, as a crosslinking agent, an unblocked monoprimary amine |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5112904A (en) |
| EP (1) | EP0401898B1 (en) |
| JP (1) | JPH0331381A (en) |
| AT (1) | ATE111500T1 (en) |
| BR (1) | BR9002747A (en) |
| CA (1) | CA2018574A1 (en) |
| DE (1) | DE69012432T2 (en) |
| DK (1) | DK0401898T3 (en) |
| ES (1) | ES2060929T3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589534A (en) * | 1990-10-16 | 1996-12-31 | Akzo Nobel N.V. | Aqueous coating compositions including a reactive emulsifier |
| MY108731A (en) * | 1992-04-16 | 1996-11-30 | Akzo Nv | Aqueous coating compositions |
| CN1070199C (en) * | 1993-01-06 | 2001-08-29 | 阿克佐诺贝尔公司 | Oligomeric sterically hindered polyamide crosslinkers and coating compositions containing the same |
| JP2005526293A (en) * | 2002-05-17 | 2005-09-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Flattening element for thermal printing of color filters |
| US9057182B1 (en) * | 2009-07-06 | 2015-06-16 | Adam Friedman | Spatially reactive water system incorporating a non tactile control module |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759913A (en) * | 1952-05-20 | 1956-08-21 | Hercules Powder Co Ltd | Copolymers of compounds containing activated ethylene double bonds with active hydrogen compounds |
| US3778418A (en) * | 1970-09-24 | 1973-12-11 | Y Nakayama | Maleinization process |
| US4343915A (en) * | 1981-08-12 | 1982-08-10 | Scm Corporation | Polyspirolactone polymers |
| US4755623A (en) * | 1983-09-06 | 1988-07-05 | American Cyanamid Company | Polyfunctional amine crosslinker, process for making same, and compositions containing same |
| US4544732A (en) * | 1984-12-24 | 1985-10-01 | Shell Oil Company | Heat-curable composition |
| DE3661834D1 (en) * | 1985-03-29 | 1989-02-23 | Akzo Nv | A liquid coating composition and a process for coating a substrate with such coating composition |
| ATE46712T1 (en) * | 1985-03-29 | 1989-10-15 | Akzo Nv | LIQUID COATING COMPOSITION AND METHOD OF COATING SUBSTRATES THEREOF. |
| DE3540464A1 (en) * | 1985-11-14 | 1987-05-21 | Polychemie Gmbh | REACTIVE BINDERS |
| ATE63110T1 (en) * | 1986-04-03 | 1991-05-15 | Akzo Nv | COLORLESS KETIMINE, THEIR PRODUCTION AND USE AS CROSSLINKING AGENTS. |
| ES2021017B3 (en) * | 1986-09-24 | 1991-10-16 | Akzo Nv | AQUEOUS COATING COMPOSITION AND PROCESS FOR COATING A SUBSTRATE WITH SUCH COATING COMPOSITION |
| JP2639534B2 (en) * | 1986-09-24 | 1997-08-13 | アクゾ・ナームローゼ・フェンノートシャップ | Aqueous coating composition |
| US4871806A (en) * | 1987-11-16 | 1989-10-03 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| EP0346982B1 (en) * | 1988-06-15 | 1992-07-29 | Akzo N.V. | Liquid coating composition curable at ambient temperatures |
-
1990
- 1990-05-30 ES ES90201372T patent/ES2060929T3/en not_active Expired - Lifetime
- 1990-05-30 DE DE69012432T patent/DE69012432T2/en not_active Expired - Fee Related
- 1990-05-30 AT AT90201372T patent/ATE111500T1/en not_active IP Right Cessation
- 1990-05-30 EP EP90201372A patent/EP0401898B1/en not_active Expired - Lifetime
- 1990-05-30 DK DK90201372.1T patent/DK0401898T3/en active
- 1990-06-08 CA CA002018574A patent/CA2018574A1/en not_active Abandoned
- 1990-06-08 JP JP2148819A patent/JPH0331381A/en active Pending
- 1990-06-08 US US07/535,930 patent/US5112904A/en not_active Expired - Fee Related
- 1990-06-11 BR BR909002747A patent/BR9002747A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69012432D1 (en) | 1994-10-20 |
| EP0401898A1 (en) | 1990-12-12 |
| EP0401898B1 (en) | 1994-09-14 |
| US5112904A (en) | 1992-05-12 |
| BR9002747A (en) | 1991-08-20 |
| DE69012432T2 (en) | 1995-04-20 |
| DK0401898T3 (en) | 1995-01-09 |
| ATE111500T1 (en) | 1994-09-15 |
| JPH0331381A (en) | 1991-02-12 |
| ES2060929T3 (en) | 1994-12-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |